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A WILEY-INTERSCIENCE PUBLICATION JOHN WILEY & SONS, INC. New York • Chichester • Weinheim • Brisbane • Singapore • Toronto
G R U L K E
This book is printed on acid-free paper. @ Copyright © 1999 by John Wiley & Sons, Inc. All rights reserved. Published simultaneously in Canada. No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or by any means, electronic, mechanical, photocopying, recording, scanning or otherwise, except as permitted under Sections 107 or 108 of the 1976 United States Copyright Act, without either the prior written permission of the Publisher, or authorization through payment of the appropriate per-copy fee to the Copyright Clearance Center, 222 Rosewood Drive, Danvers, MA 01923, (978) 750-8400, fax (978) 750-4744. Requests to the Publisher for permission should be addressed to the Permissions Department, John Wiley & Sons, Inc., 605 Third Avenue, New York, NY 10158-0012, (212) 850-6011, fax (212) 850-6008, E-Mail: PERMREQ @ WILEY.COM. Library of Congress Cataloging-in-Puhlication Data: Polymer Handbook / Editors: J. Brandrup, E. H. Immergut, and E. A. Grulke; Associate Editors, A. Abe, D. R. Bloch. - 4th ed. p. cm. "A Wiley-Interscience Publication." Includes index. ISBN 0-471-16628-6 (cloth : alk. paper) 1. Polymers—Tables. 2. Polymerization—Tables. I. Brandrup, J. II. Immergut, E. H. III. Grulke, Eric A. QD388.P65 1999 547.7-dc21 98-37261 Printed in the United States of America. 10 9 8 7 6 5 4 3 2
Contributors Abe, A. Tokyo Institute of Polytechnics, Atsugi, Japan Allegra, G. Dipartimento di Chimica del Politecnico, Milano, Italy Andreeva, L. N. Institute of High Molecular Weight Compounds, Russian Academy of Sciences, St. Petersburg, Russian Federation Andrews, R, J. Chemical and Materials Engineering Department, University of Kentucky, Lexington, Kentucky, USA Bai, F. The Maurice Morton Institute of Polymer Science, Univeristy of Akron, Akron, USA Bareiss, R. E. Editorial Office, Macromolecular Chemistry and Physics, Mainz, FR Germany Barrales-Rienda, J. M. Instituto de Ciencia y Tecnologia de Polfmeros, Madrid, Spain Bello, A. Instituto de Ciencia y Tecnologia de Polfmeros, Madrid, Spain Bello, P. Instituto de Ciencia y Tecnologia de Polfmeros, Madrid, Spain Bloch, D. R. Lakeshore Research, Racine, Wisconsin, USA Brandrup, J. Wiesbaden, FR Germany Calhoun, B. H. The Maurice Morton Institute of Polymers Science, University of Akron, Akron USA Casassa, E. F. Department of Chemistry, Carneagfe-Mellon University, Pittsburgh, Pennsylvania, USA Cheng, S. Z. D. The Maurice Morton Institute of Polymer Science, University of Akron, Akron, Ohio, USA Chiu, F.-C. The Maurice Morton Institute of Polymer Science, University of Akron, Akron, Ohio, USA Cho, J. Polymer Science and Engineering Department, Dankook University, Seoul, South Korea Collins, E. A. Avon Lake, Ohio, USA Daniels, C. A. The Geon Company, Avon Lake, Ohio, USA DeLassus, P. T. The Dow Chemical Company, Freeport, Texas, USA Dixon, K. W. Akzo Nobel Chemicals, Inc., Dobbs Ferry, New York, USA
Elias, H.-G. Michigan Molecular Institute, Midland, Michigan, USA Fink, G. Max-Planck-Institut fur Kohlenforschung, Miilheim an der Ruhr, FR Germany Fink, H.-P. Fraunhofer Institut fiir angewandte Polymerforschung, TeltowSeehof, FR Germany Fouassier, J. P. Laboratoire de Photochimie Generate, Ecole Nationale Superieure de Chimie, Mulhouse, France Fu, Q. The Maurice Morton Institute and Department of Polymer Science, University of Akron, Akron, Ohio, USA Furuta, I. Japan Synthetic Rubber Company Ltd., Yokkaichi, Mie, Japan Ganster, J. Fraunhofer Institute for Applied Polymer Research, TeltowSeehof, Germany Greenley, R. Z. Monsanto Corporation (retired), St. Louis, Missouri, USA Grulke, E. A. Chemical and Materials Engineering, University of Kentucky, Lexington, Kentucky, USA Goh, S. H. Department of Chemistry, National University of Singapore, Singapore Guzman G. M. Instituto de Ciencia y Tecnologfa de Polfmeros, Madrid, Spain Hill, D. J. T. Department of Chemistry, University of Queensland, St. Lucia, Australia Hiltner, A. Department of Macromolecular Science, School of Engineering Case Western University, Cleveland, Ohio, USA Inomata, K. Department of Polymer Chemistry, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo, Japan Iwama, M. Japan Synthetic Rubber Company Ltd., Yokkaichi, Mie, Japan Jenkins, A. D. School of Chemistry, Physics and Environmental Science, University of Sussex, Brighton, Sussex, UK Jenkins, J. School of Chemistry, Physics and Environmental Science, University of Sussex, Brighton, Sussex, UK
Johnson, M. Chemistry/Physics Library, University of Kentucky, Lexington, Kentucky, USA Kamachi, M. Department of Applied Physics and Chemistry, Fukui University of Technology, Gakuen, Fukui, Japan Kerbow, D. L. DuPont Fluoroproducts, Wilmington, Delaware, USA Kimura, S.-L Japan Synthetic Rubber Company Ltd., Yokkaichi, Mie, Japan Korte, S. Zentrale Ferschung, Bayer AG, Leverkunsen, FR Germany Krause, S. Department of Chemistry, Rensselaer Polytechnic Institute, Troy, New York, USA Kurata, M. Institute for Chemical Research, Kyoto University, Uji, Kyoto, Japan Lechner, M. D. Physikalische Chemie, Universitat Osnabriick, Osnabriick, FR Germany Leonard, J. Department de Chimie and CERSIM, Universite Laval, Quebec, Canada Li, F. The Maurice Morton Institute of Polymer Science, University of Akron, Akron, Ohio, USA
Muck, K.-F. Ticona GmbH, Kelsterbach, FR Germany Nagai, S. Plastics Technical Association, Osaka, Japan Nordmeier, E. Physikalische Chemie, Universitat Osnabriick, Osnabriick FR Germany Ogo, Y. Research Institute for Solvothermal Technology, Hayashi, Takamatsu, Kagawa, Japan Orwoll, R. A. College of William and Mary, Williamsburg, Virginia, USA Pauly, S. Fachlaboratorium fur Permeationspriifung, Wiesbaden, FR Germany Peebles, L. H., Jr. Chemistry Division, Naval Research Laboratory, Washington, DC, USA Perera, M. C. S. Magnetic Resonance Facility, School of Science, Griffith University, Nathan, Australia Porzio, W. Instituto di Chimica delle Macromolecole del C.N.R., Milano, Italy Pyda, M. Department of Chemistry, University of Tennessee, Knoxville, Tennessee, USA
Liggat, J. Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, Scotland
Quirk, R. P. The Maurice Morton Institute of Polymer Science, University of Akron, Akron, Ohio, USA
Lindemann, M. Greenville, South Carolina, USA Luft, G. Institut fur Chemische Technologie, Technische Hochschule, Darmstadt, FR Germany
Riande, E. Instituto de Ciencia y Tecnologia de Polimeros, Madrid, Spain
Magill, J. H. School of Engineering, University of Pittsburgh, Pittsburgh, Pennsylvania, USA McKenna, T. F. Centre Nationale de Ia Recherche Scientifique, Laboratoire de Chimie et Procedes de Polymerisation/Departement Genie des Procedes, Villeurbanne, France Mehta, R. H. Dupont Nylon, Chattanooga, Tennessee, USA Mettle, S. V. Dipartimento di Chimica del Politecnico, Milano, Italy Metanomski, W. V. Chemical Abstracts Service, Columbus, Ohio, USA Michielsen, S. School of Textile and Fiber Engineering, Georgia Institute of Technology, Atlanta, Georgia, USA Miller, R. L. Michigan Molecular Institute, Midland, Michigan, USA Morita, Y. Japan Atomic Energy Research Institute, Takasaki, Gunma-ken, Japan
Richter, W. J. Max-Planck-Institut fur Kohlenforschung, Miilheim an der Ruhr, FR Germany Rothe, M. University of UIm, UIm, FR Germany Rule, M. Coca Cola Company, Atlanta, Georgia, USA Salort, J. F. Madrid, Spain Salom, C. Escuela Tecnica Superior de Ingenieros Aeronauticos, Universidad Politecnica, Madrid, Spain Sanchez, I. C. Chemical Engineering Department, University of Texas at Austin, Austin, Texas, USA Santos, A. M. Faculdade de Engenharia Quimica de Lorena - FAENQUIL, Lorena, Sao Paulo, Brazil Schoff, C. K. PPG Industries, Allison Park, Pennsylvania, USA Schuld, N. Institut fur Physikalische Chemie, Universitat Mainz, Mainz, FR Germany
Seferis, J. C. Chemical Engineering Department, University of Washington, Seattle, Washington, USA Seguchi, T. Japan Atomic Energy Research Institute, Takasaki, Gunma-ken, Japan
Wagener, K. B. Department of Chemistry and Center for Macromolecular Science and Engineering, University of Florida, Gainesville, Florida, USA Whiteman, N. F. The Dow Chemical Company, Freeport, Texas, USA
Schrader, D. The Dow Chemical Company, Midland, Michigan, USA
Witenhafer, D. E. Dublin, Ohio, USA
Sperati, C. A. Chemical Engineering Department, Ohio University, Athens, Ohio, USA
Wolf, B. A. Institut fur Physikalische Chemie, Universitat Mainz, Mainz, FR Germany
Steinmeier, D. G. Physikalische Chemie, Universitat Osnabriick, Osnabruck, FR Germany
Wu, S. E. I. DuPont de Nemours, Central Research and Development Department, Experimental Station, Wilmington, Delaware
Tsunashima, Y. Institute for Chemical Research, Kyoto University, Uji, Kyoto, Japan
Wunderlich, B. Department of Chemistry, University of Tennessee, Knoxville, Tennessee, USA
Tsvetkov, N. V. Institute of High Molecular Weight Compounds, Russian Academy of Science, St. Petersburg, Russian Federation
Wunderlich, W. ROHM GmbH, Darmstadt, FR Germany
Tsvetkov, V. N. Institute of High Molecular Weight Compounds, Russian Academy of Science, St. Petersburg, Russian Federation
Yamada, B. Department of Applied Chemistry, Faculty of Technology, Osaka City University, Sumiyoshi, Osaka, Japan
Ueda, A. Osaka Municipal Technical Research Institute, Morinomiya, Joto-ku, Osaka, Japan
Zhu, L. The Maurice Morton Institute of Polymer Science, University of Akron, Akron, Ohio, USA
Preface The purpose of the Polymer Handbook is to bring together the data and constants needed in theoretical and experimental polymer research. All polymer researchers have experienced the frustration of searching for data in the everexpanding polymer literature and know the difficulties involved in trying to locate a particular constant that is buried in a long journal article. The contributors to this Handbook have taken on the arduous task of searching the literature and compiling the data and constants that polymer chemists, polymer physicists, and polymer engineers are likely to need. The 520 and odd tables in this Handbook are divided into eight sections. The first lists the IUPAC nomenclature rules for polymers and the International System of Units. Although several naming conventions exist in the technical literature, IUPAC names permit a consistent listing of all polymers. Section II contains data and constants needed for polymer synthesis, kinetic mechanisms, and thermodynamic studies of polymerization and depolymerization reactions. Sections III and IV contain physical constants of monomers, solvents, and oligomers. Section V lists the physical constants of many important commercial polymers. Section VI and VII cover the solid state properties of polymers and the properties of polymer solutions. Section VIII of the Handbook lists the commonly used abbreviations or acronyms for polymers and Chemical Abstract Registry Numbers, and gives suggestions for electronic data searching for polymer information. This section should also be consulted in the few cases where contributors have not used IUPAC nomenclature. As in the previous editions, the Polymer Handbook concentrates on synthetic polymers, poly(saccharides) and derivatives, and oligomers. Few data on biopolymers are included. Spectroscopic data as well as data needed by engineers and designers, such as mechanical and rheological data, are minimized, since many excellent compilations exist elsewhere. Only fundamental constants and parameters that refer to the polymer molecule, that describe the solid state of polymer molecules, or that describe polymer solutions, were compiled. Constants that depend on processing conditions or on sample history were not emphasized, as they can be found in existing plastics handbooks and encyclopedias.
A critical evaluation of the values published in the literature was not attempted, since such a task would have required an inordinate amount of time and a sizable staff. Therefore, the users of this Handbook should consult the original literature for details when in doubt about the validity of any data. (The authors of the individual tables were nevertheless requested to eliminate obviously erroneous data from otherwise complete compilations.) The Fourth Edition revisions have focused on data generated in the ten years since the publication of the Third Edition. Therefore, a completely revised Polymer Handbook has been prepared. We have added new tables and incorporated a large amount of new data into existing tables. As a result, the Fourth Edition contains approximately twenty-five percent more data, and the number of pages has increased from about 1850 in the Third Edition to about 2250. We hope that this new edition will be as useful to the polymer research community as the three earlier editions and that many of the Polymer Handbook's previous users will also obtain the Fourth Edition for their laboratory and library. The publisher plans a CD-ROM for the Polymer Handbook in the near future. We would be grateful if our contributors and users send us any new data they accumulate in the course of their research, and any errors, misprints, omissions and other flaws. We will pass on such data to the publisher, for the polymer database, and for future editions of this Handbook. We would like to thank all of the contributors to the Polymer Handbook for their help and continued patience. The staff at John Wiley, especially Carla Fjerstad, Shirley Thomas, and Jacqueline Kroschwitz, have provided excellent help and support in getting all the work done. We hope that the outstanding efforts of all these people will find due appreciation among the users of this Handbook. July, 1998
J. Brandrup E. H. Immergut E. A. Grulke A. Abe D. R. Bloch
Contents
Contributors .............................................................................................................................
v
Preface ....................................................................................................................................
ix
I.
Nomenclature Rules – Units
Nomenclature ...............................................................................................................................................
I/1
A. Introduction ........................................................................................................................
I/1
B. IUPAC Recommendations .................................................................................................. 1. Source-based Nomenclature .................................................................................. 1.1 Homopolymers ........................................................................................ 1.2 Copolymers ............................................................................................. 1.3 Nonlinear Macromolecules and Macromolecular Assemblies ................ 2. Structure-based Nomenclature ............................................................................... 2.1 Regular Single-strand Organic Polymers ............................................... 2.2 Regular Double-strand Organic Polymers .............................................. 2.3 Regular Single-strand Inorganic and Coordination Polymers ................. 2.4 Regular Quasi-single-strand Coordination Polymers .............................. 2.5 Irregular Single-strand Organic Polymers ...............................................
I/1 I/2 I/2 I/2 I/3 I/3 I/3 I/6 I/6 I/7 I/7
C. Use of Common and Semisystematic Names .....................................................................
I/8
D. Chemical Abstracts (CA) Index Names ...............................................................................
I/8
E. Polymer Class Names ........................................................................................................
I/11
F. References .........................................................................................................................
I/12
Units .............................................................................................................................................................
I/13
A. Introduction ........................................................................................................................
I/13
B. International Units ..............................................................................................................
I/13
C. SI-prefixes ..........................................................................................................................
I/14
D. Conversion Factors ............................................................................................................
I/14
E. Conversion Table for SI vs. English-american Units ...........................................................
I/17
II.
Polymerization and Depolymerization
Decomposition Rates of Organic Free Radical Initiators ............................................................................
II/1
A. Introduction ........................................................................................................................
II/1
B. Tables of Decomposition Rates of Organic Free Radical Initiators ..................................... Table 1. Azonitriles ............................................................................................................... Table 2. Miscellaneous Azo-derivatives ................................................................................
II/2 II/2 II/9
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xi
xii
Contents Table 3. Table 4. Table 5. Table 6. Table 7.
Alkyl Peroxides ....................................................................................................... Acyl Peroxides ........................................................................................................ Hydroperoxides and Ketone Peroxides .................................................................. Peresters and Peroxycarbonates ............................................................................ Miscellaneous Initiators ...........................................................................................
II/23 II/29 II/43 II/48 II/67
C. Notes ..................................................................................................................................
II/69
D. References .........................................................................................................................
II/70
Propagation and Termination Constants in Free Radical Polymerization ..................................................
II/77
A. Introduction ........................................................................................................................
II/77
B. Tables of Table 1. Table 2. Table 3. Table 4. Table 5. Table 6. Table 7. Table 8. Table 9. Table 10. Table 11. Table 12. Table 13.
Propagation and Termination Constants ............................................................. Dienes ..................................................................................................................... Olefins ..................................................................................................................... Acrylic Derivatives ................................................................................................... Methacrylic Derivatives ........................................................................................... Itaconic Derivatives ................................................................................................. Fumaric Derivatives ................................................................................................ Vinyl Halides ........................................................................................................... Vinyl Esters ............................................................................................................. Vinyl Ethers ............................................................................................................. Styrene Derivatives ................................................................................................. Vinyl Heteroaromatics ............................................................................................. Aldehydes ............................................................................................................... Others .....................................................................................................................
II/79 II/79 II/79 II/80 II/82 II/85 II/87 II/87 II/87 II/88 II/88 II/90 II/90 II/90
C. References .........................................................................................................................
II/91
Transfer Constants to Monomers, Polymers, Catalysts and Initiators, Solvents and Additives, and Sulfur Compounds in Free Radical Polymerization ...........................................................................
II/97
A. Introduction ........................................................................................................................
II/97
B. Tables of Transfer Constants ............................................................................................. Table 1. Transfer Constants to Monomers ........................................................................... Table 2. Transfer Constants to Polymers ............................................................................. Table 3. Transfer Constants to Catalysts and Initiators ........................................................ Table 4. Transfer Constants to Solvents and Additives ........................................................ Table 5. Transfer Constants to Sulfur Compounds ...............................................................
II/98 II/98 II/103 II/106 II/110 II/150
C. Remarks .............................................................................................................................
II/157
D. References .........................................................................................................................
II/159
Photopolymerization Reactions ...................................................................................................................
II/169
A. Introduction ........................................................................................................................
II/169
B. Tables ................................................................................................................................ Table 1. Rate Constants of Cleavage, Electron Transfer and Monomer Quenching in Radical Photoinitiators ............................................................................................ Annex to Table 1. Photoinitiator Compound Chemistries ......................................
II/170
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II/170 II/173
Contents Table 2. Bimolecular Rate Constants for the Reaction of Phosphonyl Radicals with Various Monomers in Cyclohexane at Room Temperature .................................... Table 3. Bimolecular Rate Constants for the Reaction of Various Radicals with Various Olefinic Monomers at Room Temperature ................................................. Table 4. Bimolecular Rate Constants for the Reaction of Ph2P = O and Ph2P = S with Various Monomers .................................................................................................. Table 5. Electron Transfer Reaction of Radicals with Diphenyliodonium Salts .................... Table 6. Electron Transfer Rate Constants (ke) between Photosensitizers and Cationic Photoinitiators and Quenching Rate Constants (kq) for Cyclohexene Oxide in Methanol (M) and Acetonitrile (AN) .......................................................... Table 7. Excitation Transfer Rate Constants (kT) for Thioxanthones and Photoinitiators ......................................................................................................... Annex to Table 7. Compound Chemistries ............................................................ Table 8. Triplet State Lifetimes (τT) of the Sensitizer (TXI) in Different Media, and Rate Constant (kT) of the Interaction between TXI and TPMK ............................... Table 9. Some Values of the Triplet State Energy Levels of Photoinitiators and Monomers ............................................................................................................... Table 10. Values of τ0T, τT, and kba in Solution ........................................................................ Table 11. Rate Constant of Interaction of Ketones and Light Stabilizers in Solution .............. Annex to Table 11 ...................................................................................................
xiii II/176 II/176 II/176 II/176
II/177 II/178 II/178 II/179 II/179 II/179 II/179 II/179
C. References .........................................................................................................................
II/180
Free Radical Copolymerization Reactivity Ratios .......................................................................................
II/181
A. Introduction ........................................................................................................................
II/181
B. Tables ................................................................................................................................ Table 1. Copolymer Reactivity Ratios ................................................................................... Acenaphthalene to Fumarate, bis(3-chloro-2-butyl) ................................................ Fumarate, di-(2-chloroethyl) to N-N-divinylaniline ................................................... N-vinylimidazole to Styrene, p-2-(2-hydroxypropyl)- ............................................... Styrene, p-4-methoxyphenyl ketone to Vinylbenzoate, p-, sodium ......................... Vinylbenzoic acid, p- to Xanthate, S-methacryloyl O-ethyl ..................................... Table 2. Listing of Quick Basic (Microsoft) Program for Calculating Reactivity Ratios .........
II/182 II/182 II/182 II/212 II/241 II/268 II/285 II/288
C. References .........................................................................................................................
II/290
Q and e Values for Free Radical Copolymerizations of Vinyl Monomers and Telogens ...........................
II/309
A. Introduction ........................................................................................................................
II/309
B. Q and e Table 1. Table 2. Table 3. Table 4.
Values for Free Radical Copolymerizations .......................................................... Monomers ............................................................................................................... Telogens ................................................................................................................. Monomers Arranged by Q Values ........................................................................... Monomers Arranged by e Values ...........................................................................
II/310 II/310 II/314 II/314 II/317
C. References .........................................................................................................................
II/319
Patterns of Reactivity (U,V) Parameters for the Prediction of Monomer Reactivity Ratios and Transfer Constants in Radical Polymerization ...................................................................................
II/321
A. Introduction ........................................................................................................................
II/321
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xiv
Contents B. Example .............................................................................................................................
II/322
C. Transfer Constants .............................................................................................................
II/322
D. Tables of Parameters ......................................................................................................... Table 1. Monomers ............................................................................................................... Table 2. Transfer Agent ........................................................................................................
II/323 II/323 II/326
E. References .........................................................................................................................
II/327
Copolymerization Parameters of Metallocene-catalyzed Copolymerizations ............................................
II/329
A. Introduction ........................................................................................................................
II/329
B. A Brief Theoretical Outline of Copolymerization Reactions ................................................. 1. First-order Markov Model ........................................................................................ 2. Second-order Markov Model ...................................................................................
II/329 II/330 II/330
C. Calculation of the Copolymerization Parameters ................................................................ 1. First-order Markov Model ........................................................................................ 1.1. Copolymerization Parameters Deduced from the Mayo-lewis Equation .................................................................................................. 1.2. Determination of Copolymerization Parameters from the Sequence Distribution (Triad Distribution) .............................................. 2. Second-order Markov Model ................................................................................... 3. Example ..................................................................................................................
II/331 II/331
D. Table of Copolymerization Parameters ...............................................................................
II/333
E. List of Catalysts/Cocatalysts Used .....................................................................................
II/336
F. References .........................................................................................................................
II/336
Rates of Polymerization and Depolymerization, Average Molecular Weights, and Molecular Weight Distribution of Polymers .........................................................................................................
II/339
A. Introduction ........................................................................................................................
II/339
B. Reference Tables for the Calculation of Rates of Polymerization, Average Molecular Weights, and Molecular Weight Distributions of Polymers for Various Types of Polymerization .................................................................................................................... Table 1. Addition Polymerization with Termination ............................................................... Table 2. Addition Polymerization - "Living" Polymers with Partial Deactivation .................... Table 3. Linear Condensation Polymerization without Ring Formation ................................ Table 4. Equilibrium Polymerization ...................................................................................... Table 5. Nonlinear Polymerization Systems ......................................................................... Table 6. Degradation of Polymers - May Be Accompanied by Crosslinking ......................... Table 7. Influence of Reactor Conditions and Design on the Molecular Weight Distribution ..............................................................................................................
II/340 II/341 II/344 II/346 II/347 II/348 II/350
C. Some Distribution Functions and Their Properties .............................................................. 1. Normal Distribution Function (Gaussian Distribution) ............................................. 2. Logarithmic Normal Distribution Function ............................................................... 3. Generalized Exponential Distribution ...................................................................... 4. Poisson Distribution ................................................................................................
II/352 II/353 II/353 II/354 II/354
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II/331 II/331 II/332 II/332
II/352
Contents
xv
D. Molecular Weight Distribution in Condensation Polymers: the Stockmayer Distribution Function ...........................................................................................................
II/354
E. References .........................................................................................................................
II/356
Heats and Entropies of Polymerization, Ceiling Temperatures, Equilibrium Monomer Concentrations, and Polymerizability of Heterocyclic Compounds ...................................................
II/363
A. Heats of Polymerization ...................................................................................................... Table 1. Monomers Giving Polymers Containing Carbon Atoms Only in the Main Chain ....................................................................................................................... 1.1 With Acyclic Carbons Only in the Main Chain ........................................
II/365
1.1.1 Dienes ..............................................................................................
II/365
1.1.2 Monomers Giving Polymers with or without Aliphatic Side Chains That Contain Only C, H ........................................................
II/365
1.1.3 Monomers Giving Polymers with Aliphatic Side Chains That Contain Heteroatoms .......................................................................
II/368
1.1.4 Monomers Giving Polymers with Aromatic Side Chains That Contain Only C, H ............................................................................
II/371
1.1.5 Monomers Giving Polymers with Aromatic Side Chains and That Contain Heteroatoms ............................................................... 1.2 With Aromatic or Cyclic Carbons in the Main Chain ............................... Table 2. Monomers Giving Polymers Containing Heteroatoms in the Main Chain ............... 2.1 Monomers Giving Polymers Containing O in the Main Chain, Bonded to Carbon Only ..........................................................................
II/365 II/365
II/371 II/372 II/373 II/373
2.1.1 Ethers and Acetals ...........................................................................
II/373
2.1.2 Cyclic Esters ..................................................................................... 2.2 Monomers Giving Polymers Containing O in the Main Chain, Bonded to Other Heteroatoms (S, Si, P) ................................................ 2.3 Monomers Giving Polymers Containing S in the Main Chain, Bonded in the Chain to Carbon Only ...................................................... 2.4 Monomers Giving Polymers Containing N in the Main Chain, Bonded in the Chain to Carbon Only ...................................................... 2.5 Monomers Giving Polymers Containing N in the Main Chain, Bonded to Other Heteroatoms (P) .......................................................... 2.6 Other Monomers Giving Polymers Not Listed Above ............................. Table 3. Copolymers .............................................................................................................
II/376 II/377 II/378 II/378 II/379 II/379 II/380
B. Entropies of Polymerization ................................................................................................ Table 4. Monomers Giving Polymers Containing Main Chain Carbon Only ......................... 4.1 Main Chain Acyclic Carbon Only ............................................................
II/381 II/382 II/382
4.1.1 Dienes ..............................................................................................
II/382
4.1.2 Monomers Giving Polymers without or with Aliphatic Side Chains That Contain Only C, H ........................................................
II/382
4.1.3 Monomers Giving Polymers with Aliphatic Side Chains That Contain Heteroatoms .......................................................................
II/384
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Contents 4.1.4 Monomers Giving Polymers with Aromatic Side Chains That Contain Only C, H ............................................................................
II/385
4.1.5 Monomers Giving Polymers with Aromatic Side Chains That Contain Heteroatoms .......................................................................
II/385
4.1.6 Other Monomers Giving Polymers Not Listed Above ...................... 4.2 With Aromatic or Cyclic Carbons in the Main Chain ............................... Table 5. Monomers Giving Polymers Containing Heteroatoms in the Main Chain ............... 5.1 Monomers Giving Polymers Containing O in the Main Chain, Bonded to Carbon Only ..........................................................................
II/386 II/386 II/387
5.1.1 Ethers and Acetals ...........................................................................
II/387
5.1.2 Cyclic Esters ..................................................................................... 5.2 Monomers Giving Polymers Containing O in the Main Chain, Bonded to Other Heteroatoms (S, Si, P) ................................................ 5.3 Monomers Giving Polymers Containing N in the Main Chain, Bonded in the Chain to Carbon Only ...................................................... 5.4 Other Monomers Giving Polymers Not Listed Above ............................. Table 6. Copolymers .............................................................................................................
II/390
C. Ceiling Temperatures and Equilibrium Monomer Concentrations ....................................... 1. Equilibria Involving Pure Liquid Monomers ............................................................. Table 7. Monomers Giving Polymers Containing Main Chain Acyclic Carbon Only ............................................................................................ Table 8. Monomers Giving Polymers Containing Heteroatoms in the Main Chain ...................................................................................................... 8.1
II/391 II/391 II/392 II/392 II/393 II/394 II/394 II/395
Monomers Giving Polymers Containing O in the Main Chain, Bonded to Carbon Only ....................................................................
II/395
Monomers Giving Polymers Containing O in the Main Chain, Bonded to Other Heteroatoms (S, P, Si) .........................................
II/396
Monomers Giving Polymers Containing S in the Main Chain, Bonded in the Chain to Carbon Only ...............................................
II/396
Monomers Giving Polymers Containing N in the Main Chain, Bonded in the Chain to Carbon Only ...............................................
II/397
8.5 Other Monomers Giving Polymers Not Listed Above ...................... Equilibria Involving Gaseous Monomers ................................................................. Equilibria Involving Monomers in Solution .............................................................. Table 9. Monomers Giving Polymers Containing Main Chain Carbon Only .........
II/397 II/397 II/398 II/398
8.2 8.3 8.4
2. 3.
II/387
9.1
Monomers Giving Polymers Containing Main Chain Acyclic Carbon Only .....................................................................................
II/398
9.2
Monomers Giving Polymers Containing Main Chain Cyclic Carbon .............................................................................................. Table 10. Monomers Giving Polymers Containing Heteroatoms in the Main Chain ......................................................................................................
II/399
10.1 Monomers Giving Polymers Containing O in the Main Chain, Bonded to Carbon Only ....................................................................
II/399
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II/399
Contents
xvii
10.2 Monomers Giving Polymers Containing O in the Main Chain, Bonded to Other Heteroatoms (Si, P) ..............................................
II/400
10.3 Monomers Giving Polymers Containing S in the Main Chain, Bonded in the Chain to Carbon Only ...............................................
II/400
10.4 Monomers Giving Polymers Containing N in the Main Chain, Bonded in the Chain to Carbon Only ............................................... Table 11. Copolymers .............................................................................................
II/400 II/401
11.1 1:1 Copolymers ................................................................................
II/401
11.2 General Copolymers ........................................................................
II/401
D. Polymerizability of 5-, 6-, and 7-membered Heterocyclic Ring Compounds ........................ Table 12. 5-membered Ring Compounds ............................................................................... Table 13. 6-membered Ring Compounds ............................................................................... Table 14. 7-membered Ring Compounds ............................................................................... Table 15. Comparison of Polymerizability (+ or -)of Unsubstituted 5-, 6- and 7-membered Ring Compounds ...............................................................................
II/401 II/402 II/403 II/404
E. Notes ..................................................................................................................................
II/406
F. References .........................................................................................................................
II/407
Activation Energies of Propagation and Termination in Free Radical Polymerization ...............................
II/415
A. Introduction ........................................................................................................................
II/415
B. Tables ................................................................................................................................ Table 1. Dienes ..................................................................................................................... Table 2. Olefins ..................................................................................................................... Table 3. Acrylic Derivatives ................................................................................................... Table 4. Methacrylic Derivatives ........................................................................................... Table 5. Vinyl Halogens ........................................................................................................ Table 6. Vinyl Ethers and Vinyl Esters .................................................................................. Table 7. Styrene and Derivatives .......................................................................................... Table 8. Vinyl Heteroaromatics ............................................................................................. Table 9. Miscellaneous Compounds .....................................................................................
II/416 II/416 II/416 II/417 II/418 II/420 II/421 II/421 II/422 II/423
C. References .........................................................................................................................
II/424
Activation Volumes of Polymerization Reactions ........................................................................................
II/429
A. Introduction ........................................................................................................................
II/429
3
II/405
B. Activation Volumes (sm /mol) of Some Polymerization Reactions ......................................
II/432
C. Activation Volumes of Initiator Decomposition ....................................................................
II/435
D. Activation Volumes of Chain Propagation ...........................................................................
II/435
E. Activation Volumes of Chain Termination ...........................................................................
II/436
F. Activation Volumes of Chain Transfer Reactions ................................................................
II/436
G. Influence of Pressure on Copolymerization ........................................................................ Table 1. Copolymerization Parameters ................................................................................. Table 2. Reactivity Ratios of Terpolymerization .................................................................... Table 3. Activation Volumes ................................................................................................. Table 4. Q, e Values .............................................................................................................
II/437 II/437 II/438 II/439 II/440
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xviii
Contents H. References .........................................................................................................................
II/440
Activation Enthalpies and Entropies of Stereocontrol in Free Radical Polymerizations .............................
II/445
A. Introduction ........................................................................................................................
II/445
B. Tables ................................................................................................................................ Table 1. Ratios of Some i-ADS for Different Mechanisms .................................................... Table 2. Ratios of Rate Constants for Markov First Order Mechanisms ............................... Table 3. ∆H++s/i - ∆H++i/s and ∆S++s/i - ∆S++i/s of Free Radical Polymerizations in Different Solvents .................................................................................................... Table 4. Activation Enthalpy Differences (∆H++A - ∆H++B) Calculated from Various Literature Data ........................................................................................................ Table 5. Activation Entropy Differences (∆S++A - ∆S++B) Calculated from Various Literature Data ........................................................................................................ Table 6. Calculated Compensation Temperatures T0 and Compensation Enthalpies ∆∆H++0 for Various Monomers and Modes of Addition, Assuming Markov First Order Trials .....................................................................................................
II/446 II/446 II/446
C. References .........................................................................................................................
II/450
Products of Thermal Degradation of Polymers ...........................................................................................
II/451
A. Introduction ........................................................................................................................
II/451
B. Tables ................................................................................................................................ Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... Table 2. Main-chain Carbocyclic Polymers ........................................................................... Table 3. Main-chain Heteroatom Polymers ........................................................................... Table 4. Main-chain Heterocyclic Polymers .......................................................................... Table 5. Cellulose and Its Derivatives ...................................................................................
II/451 II/451 II/464 II/465 II/473 II/475
C. References .........................................................................................................................
II/475
Radiation Chemical Yields: G Values ..........................................................................................................
II/481
A. Introduction ........................................................................................................................
II/481
B. Tables of G Values ............................................................................................................. Table 1. Homopolymers ........................................................................................................ 1.1 Polydienes .............................................................................................. 1.2 Polyolefins .............................................................................................. 1.3 Polyacrylates .......................................................................................... 1.4 Poly(methacrylates) ................................................................................ 1.5 Poly(styrenes) ......................................................................................... 1.6 Poly(vinyls) .............................................................................................
II/481 II/482 II/482 II/482 II/483 II/484 II/485 II/486
1.6.1 Acrylamides and Nitriles ...................................................................
II/486
1.6.2 Vinyl Monomers ................................................................................ Miscellaneous Polymers .........................................................................
II/486 II/487
1.7.1 Cellulose and Derivatives .................................................................
II/487
1.7.2 Poly(siloxanes) .................................................................................
II/487
1.7.3 Poly(amino Acids) ............................................................................
II/487
1.7.4 Polyesters .........................................................................................
II/488
1.7
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II/447 II/448 II/449
II/449
Contents
III.
xix
1.7.5 Polysulfones .....................................................................................
II/488
1.7.6 Polyketones ......................................................................................
II/488
1.7.7 Fluoropolymers .................................................................................
II/488
1.7.8 Others ............................................................................................... Table 2. Copolymers ............................................................................................................. 2.1 Copolymers with Ethylene ...................................................................... 2.2 Copolymers with Methyl Methacrylate .................................................... 2.3 Copolymers with Styrene ........................................................................ 2.4 Copolymers with Sulfur Dioxide .............................................................. 2.5 Other Copolymers ................................................................................... Table 3. Polymers Blends ..................................................................................................... Table 4. Composites .............................................................................................................
II/489 II/490 II/490 II/490 II/491 II/491 II/492 II/493 II/493
C. References .........................................................................................................................
II/493
Physical Properties of Monomers and Solvents
Physical Properties of Monomers ................................................................................................................
III/1
A. Introduction ........................................................................................................................
III/1
B. Tables of Table 1. Table 2. Table 3. Table 4.
Table 5.
Table 6.
Table 7. Table 8. Table 9.
Table 10.
Table 11.
Physical Properties ............................................................................................. Acetylenes .............................................................................................................. Acid Dichlorides ...................................................................................................... Acroleins ................................................................................................................. Acrylamides/Methacrylamides ................................................................................ 4.1 Acrylamides ............................................................................................ 4.2 Methacrylamide ...................................................................................... Acrylates/Methacrylates .......................................................................................... 5.1 Acrylate, Acids/Esters ............................................................................. 5.2 Methacrylate, Acids/Esters ..................................................................... Alcohols .................................................................................................................. 6.1 Alkanediols ............................................................................................. 6.2 Ether Diols .............................................................................................. Allyl Functional ........................................................................................................ Amines, Difunctional ............................................................................................... Anhydrides .............................................................................................................. 9.1 Monoanhydrides ..................................................................................... 9.2 Dianhydrides ........................................................................................... Butadienes .............................................................................................................. 10.1 1,2-butadienes ........................................................................................ 10.2 1,3-butadienes ........................................................................................ Butenes ................................................................................................................... 11.1 1-butenes ................................................................................................ 11.2 2-butenes ................................................................................................
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III/4 III/4 III/4 III/4 III/4 III/4 III/6 III/8 III/8 III/12 III/16 III/16 III/18 III/18 III/20 III/20 III/20 III/24 III/24 III/24 III/24 III/26 III/26 III/26
xx
Contents Table 12. Epoxides ................................................................................................................. 12.1 Monoepoxides ........................................................................................ 12.2 Diepoxides .............................................................................................. Table 13. Ethylene Halides ..................................................................................................... Table 14. Fumaric, Acids/Esters ............................................................................................. Table 15. lsocyanates ............................................................................................................. Table 16. Lactams .................................................................................................................. Table 17. Lactones ................................................................................................................. Table 18. Maleate, Acids/Esters ............................................................................................. Table 19. Propenes ................................................................................................................. Table 20. Styrenes .................................................................................................................. Table 21. Vinyl Functional ....................................................................................................... 21.1 Aryl .......................................................................................................... 21.2 Esters ...................................................................................................... 21.3 Ethers ..................................................................................................... 21.4 N-substituted ........................................................................................... 21.5 Sulfonates ...............................................................................................
III/26 III/26 III/28 III/28 III/30 III/30 III/32 III/32 III/32 III/32 III/34 III/36 III/36 III/36 III/38 III/38 III/40
Isorefractive and Isopycnic Solvent Pairs ....................................................................................................
III/43
A. Introduction ........................................................................................................................
III/43
B. Table of Isorefractive and Isopycnic Solvent Pairs ..............................................................
III/43
Refractive Indices of Common Solvents .....................................................................................................
III/55
A. Introduction ........................................................................................................................
III/55
B. Table of Refractive Indices of Common Solvents ...............................................................
III/55
Physical Constants of the Most Common Solvents for Polymers ...............................................................
III/59
IV.
Physical Data of Oligomers
Physical Data of Oligomers .........................................................................................................................
IV/1
A. Introduction ........................................................................................................................
IV/2
B. Oligomers Containing Main Chain Acyclic Carbon Only ..................................................... Table 1. Oligo(olefins) ........................................................................................................... 1.1. Oligo(methylenes) and Oligo(ethylenes) ................................................ 1.2. Oligo(perfluoromethylenes) and Oligo(perfluoroethylenes) .................... 1.3. Oligo(isobutenes) .................................................................................... 1.4. Oligo(1-alkenylenes) ............................................................................... References .............................................................................................................. Table 2. Oligo(dienes) ........................................................................................................... 2.1. Oligomers of 1,3-butadiene .................................................................... 2.2. Oligomers of lsoprene ............................................................................. 2.3. Oligomers of 1,3-butadiene Derivatives .................................................. 2.4. 1,4-oligo(alkadienes) .............................................................................. 2.5. Oligomers of Cyclopentadiene and 1,3-cyclohexadiene .........................
IV/3 IV/3 IV/3 IV/6 IV/8 IV/9 IV/9 IV/14 IV/14 IV/15 IV/16 IV/16 IV/17
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Contents
xxi
2.6. Oligomers of Allene ................................................................................ References .............................................................................................................. Table 3. Oligo(acetylenes) .................................................................................................... 3.1. Linear Oligomers of Acetylene ................................................................ 3.2. Polyenyne Oligomers .............................................................................. 3.3. Oligomeric α-ω-diynes ............................................................................ 3.4. Oligo(alkynes) ......................................................................................... 3.5. Cyclic Oligo(alkynes) .............................................................................. 3.6. Pericyclynes ............................................................................................ References .............................................................................................................. Table 4. Oligomers with Aliphatic Side Chains Which in Addition Contain Heteroatoms ........................................................................................................... 4.1. Oligomeric Acrylic Derivatives ................................................................ 4.2. Oligomeric Methacrylic Derivatives ......................................................... 4.3. Oligomers of β-alkyl Substituted Vinyl Derivatives ................................. 4.4. Oligo(vinyl) Derivatives ........................................................................... References .............................................................................................................. Table 5. Oligo(styrenes) ........................................................................................................ References ..............................................................................................................
IV/17 IV/18 IV/19 IV/19 IV/20 IV/20 IV/20 IV/20 IV/21 IV/21
C. Oligomers Contaning Heteroatoms in the Main Chain ........................................................ Table 6. Oligomers Containing O in the Main Chain ............................................................. 6.1. Oligo(ethers) and Oligo(acetals) .............................................................
IV/33 IV/33 IV/33
6.2.
References .................................................................................................. Oligo(carbonates) ...................................................................................
IV/43 IV/47
6.3.
References .................................................................................................. Oligo(esters) ...........................................................................................
IV/47 IV/48
6.4.
References .................................................................................................. Oligo(urethanes) .....................................................................................
IV/56 IV/58
References .................................................................................................. Table 7. Oligo(sulfides) and Oligo(selenides) ....................................................................... 7.1. Cyclic Oligo(thiomethylenes) and Oligo(Selenomethylenes) .................. 7.2. Cyclic Oligo(thioalkylenes) ...................................................................... 7.3. Substituted Cyclic(thioethylenes) ............................................................ 7.4. Cyclic Co-oligomers of Formaldehyde and Thioformaldehyde ............... 7.5. Cyclic Oligo(ether Sulfides) .................................................................... 7.6. Thiacyclophanes ..................................................................................... References .............................................................................................................. Table 8. Oligomers Containing N in the Main Chain ............................................................. 8.1. Oligo(amides) .........................................................................................
IV/61 IV/62 IV/62 IV/62 IV/62 IV/62 IV/63 IV/63 IV/63 IV/64 IV/64
References .................................................................................................. Oligo(peptides) .......................................................................................
IV/70 IV/72
References ..................................................................................................
IV/84
8.2.
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IV/22 IV/22 IV/24 IV/26 IV/27 IV/28 IV/30 IV/32
xxii
Contents 8.3.
Oligo(imines) ...........................................................................................
IV/88
8.4.
References .................................................................................................. Oligo(ureas) ............................................................................................
IV/89 IV/89
References ..................................................................................................
IV/90
D. Carbon Chain Oligomers Containing Main Chain Cyclic Units ............................................ Table 9. Oligo(cyclopentylenes) ............................................................................................ Table 10. Oligo(spiranes) ........................................................................................................ Table 11. Oligo(xylylenes) ...................................................................................................... 11.1. Linear Oligo(xylenes) .............................................................................. 11.2. Cyclic Oligo(xylylenes) ............................................................................ Table 12. Oligo(stilbenes) ....................................................................................................... Table 13. Oligo(benzyls) ......................................................................................................... Table 14. Oigo(2,5-dimethyl-benzyls) ..................................................................................... Table 15. Oligo(2,3,5,6-tetramethyl-benzyls) .......................................................................... Table 16. Oligo(p-phenylene Oxides) ..................................................................................... Table 17. Oligo(p-phenylene Sulfides) .................................................................................... Table 18. Oligo(p-phenoxyphenylmethanes) .......................................................................... Table 19. Oligo(diphenylmethanes) ........................................................................................ References .............................................................................................................. Table 20. Phenol-formaldehyde and Related Oligomers ........................................................ 20.1. Linear Phenol-formaldehyde Oligomers ................................................. 20.2. Oligomeric Phenol Alcohols .................................................................... 20.3. Cyclic Phenol-formaldehyde Oligomers .................................................. 20.4. Branched Phenol-formaldehyde Oligomers ............................................ 20.5. Hydroquinone Oligomers ........................................................................ References .............................................................................................................. Table 21. Oligo(phenylenes) ................................................................................................... 21.1. o-oligo(phenylenes) ................................................................................ 21.2. m-oligo(phenylenes) ............................................................................... 21.3. p-oligo(phenylenes) ................................................................................ 21.4. Oligo(p-quinones) ................................................................................... References ..............................................................................................................
IV/90 IV/90 IV/90 IV/90 IV/90 IV/90 IV/91 IV/91 IV/91 IV/91 IV/91 IV/91 IV/91 IV/91 IV/91 IV/92 IV/92 IV/93 IV/94 IV/94 IV/95 IV/95 IV/96 IV/96 IV/96 IV/97 IV/98 IV/98
E. Oligomers Containing Heterocyclic Rings in the Main Chain .............................................. Table 22. Heterocyclic Oligomers ........................................................................................... 22.1 Oligo(furan) Derivatives .......................................................................... 22.2. Oligo(thiophene) Derivatives .................................................................. 22.3. Oligo(pyrrole) Derivatives ....................................................................... 22.4. Oligo(pyridine) Derivatives ...................................................................... 22.5. Cyclic Oligo(heterocyclics) ...................................................................... References .............................................................................................................. Table 23. Oligo(saccharides) .................................................................................................. 23.1. Oligomeric Pentoses ...............................................................................
IV/99 IV/99 IV/99 IV/100 IV/100 IV/100 IV/101 IV/101 IV/102 IV/102
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xxiii
23.2. Oligomeric Hexoses ................................................................................ IV/102 23.3. Oligomeric Amino Sugars ....................................................................... IV/103 References .............................................................................................................. IV/104
V.
Physical Constants of Some Important Polymers
Physical Constants of Rubbery Polymers ...................................................................................................
V/1
A. Introduction ........................................................................................................................
V/1
B. Tables ................................................................................................................................ Table 1. 1,4-cis(96-98%)Poly(butadiene) ............................................................................. Table 2. Poly(butadiene-co-acrylonitrile) .............................................................................. Table 3. Poly(butadiene-co-styrene) ..................................................................................... Table 4. Poly(chloroprene)(CR Neoprene) ........................................................................... Table 5. Poly(isobutene)-co-isoprene) Butyl Rubber (IIR) .................................................... Table 6. Polyisoprene, Natural Rubber ................................................................................. Table 7. Ethylene-propylene-diene-terpolymer (EPDM) .......................................................
V/1 V/1 V/2 V/3 V/3 V/4 V/5 V/6
C. References .........................................................................................................................
V/6
Physical Constants of Poly(ethylene) ..........................................................................................................
V/9
A. Crystallographic Data and Crystallographic Modifications ..................................................
V/9
B. Molecular Parameters and Solution Properties ...................................................................
V/9
C. Crystallinity, Crystal Size and Crystallization Kinetics .........................................................
V/10
D. Equilibrium Thermodynamic Properties ..............................................................................
V/11
E. Other General Physical Properties .....................................................................................
V/12
F. Effect of Chain Branching (Short) on Physical Properties ...................................................
V/15
G. Properties of a Series of Selected Poly(ethylene) Samples ................................................
V/16
H. Properties of Typical Poly(ethylenes) .................................................................................
V/17
I.
References .........................................................................................................................
V/17
Physical Constants of Poly(propylene) ........................................................................................................
V/21
A. Crystallographic Data and Modifications of Isotactic Polypropylenes ..................................
V/21
B. Crystallographic Data and Modifications of Syndiotactic Polypropylenes ............................
V/21
C. Dimensions of Poly(propylene) Molecules ..........................................................................
V/22
D. Crystallinity and Crystallization Kinetics ..............................................................................
V/22
E. Equilibrium Thermodynamic Properties ..............................................................................
V/23
F. Other General Properties ...................................................................................................
V/24
G. Properties of Typical Mainly Isotactic Poly(propylenes) ......................................................
V/26
H. Properties of Some Commercial Poly(propylene) Grades ...................................................
V/26
I.
Mechanical Properties of Poly(propylene) Homopolymers ..................................................
V/27
J. Mechanical Properties of Poly(propylene) Random Copolymers ........................................
V/28
K. Mechanical Properties of Poly(propylene) Impact Copolymers ...........................................
V/28
L. References .........................................................................................................................
V/28
Physical Constants of Fluoropolymers ........................................................................................................
V/31
A. Introduction ........................................................................................................................
V/31
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xxiv
Contents B. Physical Constants of Poly(tetrafluoroethylene) ................................................................. Notes ....................................................................................................................................... Infrared Absorption Spectrum of Poly(tetrafluoroethylene) ..................................................... References ..............................................................................................................................
V/31 V/37 V/38 V/39
C. Physical Constants of Melt Processible Fluorocarbon Polymers PFA and FEP .................. Notes ....................................................................................................................................... References ..............................................................................................................................
V/41 V/44 V/45
D. Physical Constants of Modified Poly(ethylene-co-tetrafluoroethylene) ................................ Notes ....................................................................................................................................... References ..............................................................................................................................
V/45 V/48 V/48
E. Physical Constants of Poly(vinylidene Fluoride) ................................................................. Notes ....................................................................................................................................... References ..............................................................................................................................
V/48 V/51 V/52
F. Physical Constants of Amorphous Fluoropolymers ............................................................. Notes ....................................................................................................................................... References ..............................................................................................................................
V/52 V/54 V/54
G. Physical Constants of Poly(chlorotrifluoroethylene) ............................................................ Notes ....................................................................................................................................... References ..............................................................................................................................
V/55 V/57 V/58
Physical Constants of Poly(acrylonitrile) .....................................................................................................
V/59
A. Tables of Table 1. Table 2. Table 3. Table 4. Table 5. Table 6. Table 7. Table 8. Table 9.
Physical Constants ............................................................................................. Crystallinity/Crystallization Behavior ....................................................................... Electric and Electronic Properties ........................................................................... Fiber Properties ...................................................................................................... Further Properties of Acrylic Fibers ........................................................................ Optical Properties ................................................................................................... Polymerization: Kinetic and Thermodynamic Data ................................................. Solubility/Solution Properties .................................................................................. Special Solid State Properties ................................................................................ Thermal and Thermodynamic Data ........................................................................
V/59 V/59 V/60 V/61 V/61 V/61 V/62 V/62 V/63 V/64
B. References .........................................................................................................................
V/64
Physical Constants of Poly(vinyl Chloride) ..................................................................................................
V/67
Physical Constants of Poly(vinyl Acetate) ...................................................................................................
V/77
Physical Constants of Poly(methyl Methacrylate) .......................................................................................
V/87
Physical Constants of Poly(styrene) ............................................................................................................
V/91
Physical Constants of Poly(oxymethylene) .................................................................................................
V/97
Physical Constants of Poly(oxyethylene-oxyterephthaloyl), (Poly(ethylene Terephthalate)) .....................
V/113
Physical Constants of Poly(oxytetramethylene-oxyterephthaloyl) and Copolymers with Tetramethylene Oxide Thermoplastic Elastomers .............................................................................
V/119
Physical Constants of Various Polyamides: Poly[imino(1-oxohexamethylene)], (Polyamide 6) Poly(iminoadipoyl-iminohexamethylene), (Polyamide 66), Poly(iminohexamethyleneiminosebacoyl), (Polyamide 610), Poly[imino(1-oxododecamethylene)], Poly(amide 12) ................
V/121
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Contents
xxv
Physical Constants of Cellulose ..................................................................................................................
V/135
A. Introduction ........................................................................................................................
V/135
B. Solid State Properties ......................................................................................................... Table 1. Unit Cell Dimensions ............................................................................................... Table 2. Density .................................................................................................................... Table 3. Average Ordered Fraction of Cotton and Linters Measured by Various Techniques ............................................................................................................. Table 4. Average Ordered Fraction Measured by Various Techniques ................................ Table 5. Degree of Crystallinity ............................................................................................. Table 6. Crystallite Sizes ...................................................................................................... Table 7. X-ray Orientation of Cellulose Fibers ...................................................................... Table 8. Heat Capacity ......................................................................................................... Table 9. Thermal Expansion Coefficient ............................................................................... Table 10. Other Thermal Properties ....................................................................................... Table 11. Refractive Index and Birefringence ......................................................................... Table 12. Resistivity ................................................................................................................ Table 13. Dielectric Constant and Loss Factor at 1 kHz ......................................................... Table 14. Other Electrical Properties ...................................................................................... Table 15. Crystal Elastic Modulus E1 in Chain Direction ......................................................... Table 16. Fiber Strength, Elongation and Modulus .................................................................
V/136 V/136 V/136
C. Solution Properties ............................................................................................................. Table 17. Typical Non-aqueous Cellulose Solvents ............................................................... Table 18. Other Solvents ........................................................................................................ Table 19. Viscosity - Molecular Weight Relationships ............................................................ Table 20. Second Virial Coefficients ....................................................................................... Table 21. Sedimentation and Diffusion Coefficients ............................................................... Table 22. Partial Specific Volumes, ν2 .................................................................................... Table 23. Geometrical Chain Characteristics ......................................................................... Table 24. Polymer-solvent Interaction Parameters .................................................................
V/147 V/147 V/148 V/148 V/150 V/150 V/151 V/151 V/152
D. References .........................................................................................................................
V/152
Physical and Mechanical Properties of Some Important Polymers ............................................................
V/159
A. Introduction ........................................................................................................................
V/159
B. Narrative Descriptions ........................................................................................................ 1. Multipurpose Polymers ........................................................................................... 2. Polyolefins and Barrier Polymers ............................................................................ 3. Styrenics and Engineering Thermoplastics ............................................................. 4. Elastomers ..............................................................................................................
V/159 V/159 V/160 V/160 V/161
C. Properties of Commercial Polymers ................................................................................... Table 1. Multipurpose Thermoplastics .................................................................................. Table 2. Polyolefins and Barrier Polymers ............................................................................ Table 3. Styrenics and Engineering Thermoplastics ............................................................. Table 4. Elastomers ..............................................................................................................
V/162 V/162 V/164 V/166 V/168
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V/136 V/137 V/137 V/138 V/140 V/140 V/141 V/141 V/144 V/144 V/145 V/146 V/146 V/147
xxvi VI.
Contents Solid State Properties
Crystallographic Data and Melting Points for Various Polymers ................................................................
VI/1
A. Introduction ........................................................................................................................ 1. Nomenclature .......................................................................................................... 2. Examples of Polymer Names .................................................................................. 2.1. Polymer Names Based on Source .......................................................... 2.2. Polymer Names Based on Structure ...................................................... References for Introduction .....................................................................................
VI/1 VI/1 VI/2 VI/2 VI/3 VI/5
B. Crystallographic Data for Various Polymers ....................................................................... Table 1. Poly(olefins) ............................................................................................................ Table 2. Poly(vinyls) and Poly(vinylidenes) .......................................................................... Table 3. Poly(aromatics) and Poly(imides) ........................................................................... Table 4. Poly(dienes) and Poly(diynes) ................................................................................ Table 5. Poly(peptides) ......................................................................................................... Table 6. Poly(amides) ........................................................................................................... Table 7. Poly(esters) ............................................................................................................. Table 8. Poly(urethanes) and Poly(ureas) ............................................................................ Table 9. Poly(ethers) ............................................................................................................. Table 10. Poly(oxides) ............................................................................................................ Table 11. Poly(sulfides) and Poly(sulfones) ............................................................................ Table 12. Poly(saccharides) ................................................................................................... Table 13. Other Polymers .......................................................................................................
VI/5 VI/6 VI/13 VI/15 VI/22 VI/26 VI/33 VI/40 VI/49 VI/51 VI/52 VI/57 VI/59 VI/64
C. Melting Points of Polymers ................................................................................................. Cellulose, see Poly (1,4-β-D-glucose) to Poly(4,4'-methylenediphenylene isophthalamide) ....................................................................................................... Poly(4,4'-methylenediphenylene octadecamethylenediurea) to Poly(p-xylylene undecanediamide) ..................................................................................................
VI/71 VI/71 VI/94
D. Appendix: Formula Index to the Tables .............................................................................. VI/113 0 to 4 ....................................................................................................................................... VI/114 5 to 30 ..................................................................................................................................... VI/133 E. References ......................................................................................................................... VI/159 1 to 839 ................................................................................................................................... VI/159 840 to 1946 ............................................................................................................................. VI/174 Glass Transition Temperatures of Polymers ............................................................................................... VI/193 A. Introduction ........................................................................................................................ VI/194 1. Example of a Property Change at Tg ...................................................................... VI/194 2. Tg: a "Non-Equilibrium" Transition ........................................................................... VI/195 B. Tg Measurement Methods .................................................................................................. VI/195 1. Data Interpretation .................................................................................................. VI/195 2. Oscillating Load Methods ........................................................................................ VI/196 C. Other Factors Affecting Tg .................................................................................................. VI/196 1. Structure ................................................................................................................. VI/196 This page has been reformatted by Knovel to provide easier navigation.
2. 3. 4. 5. 6.
Contents
xxvii
Crystallinity/Crosslinking ......................................................................................... Diluents ................................................................................................................... Molecular Weight .................................................................................................... Thermal History ....................................................................................................... Pressure ..................................................................................................................
VI/196 VI/197 VI/197 VI/197 VI/197
D. Estimation Methods for the Glass Transition Temperature ................................................. VI/197 E. Classification, Nomenclature, and Abbreviations ................................................................ VI/197 1. Naming Conventions ............................................................................................... VI/198 2. Abbreviations .......................................................................................................... VI/198 F. Tables of Glass Transition Temperatures of Polymers ....................................................... VI/198 Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... VI/198 1.1 Poly(acrylics) and Poly(methacrylics) ..................................................... VI/198 1.1.1 Poly(acrylic acid) and Poly(acrylic Acid Esters) ............................... VI/198 1.1.2 Poly(acrylamides) ............................................................................. VI/201 1.1.3 Poly(methacrylic Acid) and Poly(methacrylic Acid Esters) .............. VI/201 1.1.4 Poly(methacrylamides) ..................................................................... VI/205 1.1.5 Other α- and β-substituted Poly(acrylics) and Poly(methacrylics) ............................................................................ 1.2 Poly(alkenes) .......................................................................................... 1.3 Poly(dienes) ............................................................................................ 1.4 Poly(styrenes) ......................................................................................... 1.5 Poly(vinyl Alcohol) and Poly(vinyl Ketones) ............................................ 1.6 PoIy(vinyl Esters) .................................................................................... 1.7 Poly(vinyl Ethers) and Poly(vinyl Thioethers) ......................................... 1.8 Poly(vinyl Halides) and Poly(vinyl Nitriles) .............................................. 1.9 Others ..................................................................................................... Table 2. Main-chain Carbocyclic Polymers ........................................................................... 2.1 Poly(phenylenes) .................................................................................... 2.2 Others ..................................................................................................... Table 3. Main-chain Acyclic Heteroatom Polymers .............................................................. 3.1 Main-chain –C–O–C– Polymers .............................................................
VI/205 VI/205 VI/207 VI/209 VI/212 VI/213 VI/214 VI/215 VI/216 VI/218 VI/218 VI/218 VI/219 VI/219
3.1.1 Poly(anhydrides) .............................................................................. VI/219 3.1.2 Poly(carbonates) .............................................................................. VI/219 3.1.3 Poly(esters) ...................................................................................... VI/221 3.1.4 Poly(ether Ketones) ......................................................................... VI/226 3.1.5 Poly(oxides) ...................................................................................... VI/226 3.2
3.1.6 Poly(urethanes) ................................................................................ VI/229 Main-chain O-heteroatom Polymers ....................................................... VI/231 3.2.1 Nitroso-polymers .............................................................................. VI/231 3.2.2 PoIy(siloxanes) ................................................................................. VI/231 3.2.3 Poly(sulfonates) ................................................................................ VI/233
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Contents 3.3
Main-chain –C–(S)n–C- and –C–S–N– Polymers ................................... VI/233 3.3.1 Poly(sulfides) .................................................................................... VI/233 3.3.2 Poly(sulfones) and Poly(sulfonamides) ........................................... VI/234
3.4
3.3.3 Poly(thioesters) ................................................................................ VI/235 Main-chain –C–N–C Polymers ............................................................... VI/235 3.4.1 Poly(amides) .................................................................................... VI/235 3.4.2 Poly(anilines) .................................................................................... VI/241 3.4.3 Poly(imides) ...................................................................................... VI/241 3.4.4 Poly(imines) ...................................................................................... VI/241
3.4.5 Poly(ureas) ....................................................................................... 3.5 Poly(phosphazenes) ............................................................................... 3.6 Poly(silanes) and Poly(silazanes) ........................................................... Table 4. Main-chain Heterocyclic Polymers .......................................................................... 4.1 Carbohydrates ........................................................................................ 4.2 Liquid Crystals ........................................................................................ 4.3 Natural Polymers .................................................................................... 4.4 Poly(acetals) ........................................................................................... 4.5 Poly(anhydrides) ..................................................................................... 4.6 Poly(benzimidazoles) .............................................................................. 4.7 Poly(benzothiazinophenothiazines) ........................................................ 4.8 Poly(benzothiazoles) .............................................................................. 4.9 Poly(benzoxazlnes) ................................................................................ 4.10 Poly(benzoxazoles) ................................................................................ 4.11 Poly(carboranes) .................................................................................... 4.12 Poly(dibenzofurans) ................................................................................ 4.13 Poly(dioxoisoindolines) ........................................................................... 4.14 Poly(fluoresceins) ................................................................................... 4.15 Poly(furan Tetracarboxylic Acid Diimides) .............................................. 4.16 Poly(oxabicyclononanes) ........................................................................ 4.17 Poly(oxadiazoles) ................................................................................... 4.18 Poly(oxindoles) ....................................................................................... 4.19 Poly(oxoisoindolines) .............................................................................. 4.20 Poly(phthalazines) .................................................................................. 4.21 Poly(phthalides) ...................................................................................... 4.22 Poly(piperazines) .................................................................................... 4.23 Poly(piperidines) ..................................................................................... 4.24 Poly(pyrazinoquinoxalines) ..................................................................... 4.25 Poly(pyrazoles) ....................................................................................... 4.26 Poly(pyridazines) .................................................................................... 4.27 Poly(pyridines) ........................................................................................ 4.28 Poly(pyromellitimides) ............................................................................. 4.29 Poly(pyrrolidines) ....................................................................................
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VI/242 VI/242 VI/243 VI/243 VI/243 VI/244 VI/244 VI/244 VI/244 VI/245 VI/245 VI/245 VI/245 VI/245 VI/245 VI/246 VI/246 VI/247 VI/247 VI/247 VI/248 VI/248 VI/248 VI/248 VI/248 VI/248 VI/249 VI/249 VI/249 VI/249 VI/249 VI/249 VI/250
Contents 4.30 Poly(quinones) ........................................................................................ 4.31 Poly(quinoxalines) .................................................................................. 4.32 Poly(triazines) ......................................................................................... 4.33 Poly(triazoles) ......................................................................................... Table 5. Copolymers .............................................................................................................
xxix VI/250 VI/250 VI/252 VI/252 VI/252
G. References ......................................................................................................................... VI/253 1 to 953 ................................................................................................................................... VI/253 954 to 1560 ............................................................................................................................. VI/268 Rates of Crystallization of Polymers ............................................................................................................ VI/279 A. Introduction ........................................................................................................................ 1. Background ............................................................................................................. 1.1 General Remarks .................................................................................... 1.2 Background ............................................................................................. 1.3 Morphological Outline/Growth Features ................................................. 2. General Principles and Techniques Involved in Crystallization Rate Studies ......... 2.1 Kinetics of Bulk Transformations ............................................................ 2.2 Thermodynamic Crystallization Models .................................................. 2.3 Growth Kinetics of Lamellar Structures: Crystals and Spherulites ......... 3. Other Significant Aspects of Crystallization ............................................................ 3.1 Nonisothermal Crystallization ................................................................. 3.2 Crystallization of Blends ......................................................................... 3.3 Solvent and Pressure-induced Crystallization ........................................ 3.4 Crystallization of Mesophases ................................................................ 3.5 Flow Induced Crystallization ................................................................... 3.6 Epitaxial Crystallization ........................................................................... 3.7 Orientational Crystallization .................................................................... 3.8 Crystallization of Copolymers ................................................................. 3.9 Computer Simulations ............................................................................
VI/280 VI/280 VI/280 VI/280 VI/281 VI/282 VI/282 VI/284 VI/284 VI/286 VI/286 VI/287 VI/288 VI/288 VI/289 VI/289 VI/289 VI/290 VI/290
B. Tables of Rates of Crystallization of Various Polymers ....................................................... VI/291 1. Rates of Crystal Growth .......................................................................................... VI/291 Table 1. Poly(alkenes), Poly(dienes), Poly(vinyls) ................................................ VI/291 1.1
2.
Homopolymer Melts ......................................................................... VI/291
1.2 Solutions ........................................................................................... Table 2. Poly(oxides) ............................................................................................ Rates of Radial Spherulitic Growth ......................................................................... Table 3. Poly(dienes), Poly(alkenes), Poly(vinyls) ................................................ 3.1
VI/296 VI/300 VI/304 VI/304
Homopolymer Melts ......................................................................... VI/304
3.2 Blends ............................................................................................... VI/312 Table 4. Poly(oxides) ............................................................................................ VI/315 4.1
Homopolymer Melts ......................................................................... VI/315
4.2
Complexes ....................................................................................... VI/318
4.3
Blends ............................................................................................... VI/319
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xxx
Contents Table 5. Poly(carbonates) ..................................................................................... VI/326 Table 6. Poly(esters) ............................................................................................. VI/327 6.1
Homopolymer Melts ......................................................................... VI/327
6.2
Blends ............................................................................................... VI/329
6.3 Copolymers ...................................................................................... VI/331 Table 7. Poly(amides) ........................................................................................... VI/331 Table 8. Poly(siloxanes) ....................................................................................... VI/334 8.1
Homopolymer Melts ......................................................................... VI/334
8.2 Copolymers ...................................................................................... VI/334 Table 9. Others ..................................................................................................... VI/336 9.1 3.
Homopolymers Melts ....................................................................... VI/336
9.2 lonomers ........................................................................................... VI/340 Rates of Bulk Crystallization (Avrami Constants) ................................................... VI/341 Table 10. Poly(dienes), Poly(alkenes), Poly(vinyls) ................................................ VI/341 10.1 Melts and Solutions .......................................................................... VI/341 10.2 Blends and Copolymers ................................................................... VI/353 Table 11. Poly(oxides) ............................................................................................ VI/365 11.1 Homopolymer Melts ......................................................................... VI/365 11.2 Blends ............................................................................................... VI/371 Table 12. Poly(carbonates) ..................................................................................... VI/372 Table 13. Poly(esters) ............................................................................................. VI/373 13.1 Homopolymer melts ......................................................................... VI/373 13.2 Blends and Copolymers ................................................................... VI/377 Table 14. Poly(amides) ........................................................................................... VI/379 14.1 Blends of Poly(amides) .................................................................... VI/382 Table 15. Poly(urethanes) ...................................................................................... VI/383 Table 16. Table 17. Table 18. Table 19.
15.1 Blends of Poly(urethanes) ................................................................ Poly(siloxanes) ....................................................................................... Poly(phosphazenes) ............................................................................... Others ..................................................................................................... Composites .............................................................................................
VI/383 VI/384 VI/384 VI/385 VI/389
19.1 Composites of Blends ...................................................................... VI/390 C. References ......................................................................................................................... VI/391 Isomorphous Polymers Pairs ....................................................................................................................... VI/399 A. Introduction ........................................................................................................................ VI/399 B. Techniques ......................................................................................................................... VI/400 C. Tables of lsomorphous Pairs of Monomer Units ................................................................. Table 1. lsomorphous Units Within the Same Macromolecules (Copolymers) ..................... 1.1 lsomorphous Units with Different Chemical Constitution ........................ 1.2 lsomorphous Units with Different Configurations and/or with Headto-head, Head-to-tail Constitutional Disorder ..........................................
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VI/401 VI/401 VI/401 VI/405
Contents
xxxi
Table 2. Isomorphism of Macromolecules ............................................................................ VI/405 D. References ......................................................................................................................... VI/406 Miscible Polymers ........................................................................................................................................ VI/409 A. Definition of Miscibility ........................................................................................................ VI/409 B. Data Collection ................................................................................................................... VI/410 C. Arrangement of the Tables ................................................................................................. VI/410 D. Tables ................................................................................................................................ Table 1. Chemically Dissimilar Polymer Pairs Miscible in the Amorphous State at Room Temperature ................................................................................................. Table 2. Polymer Pairs Containing One Monomer in Common, Miscible in the Amorphous State at Room Temperature ................................................................ Table 3. Chemically Dissimilar Polymer Triads (and Tetrads) Miscible in the Amorphous State at Room Temperature ................................................................ Table 4. Polymer Pairs Miscible in the Amorphous State at Room Temperature; Molecular Weight Dependence Investigated .......................................................... Table 5. Polymer Pairs That Appear to Have High Temperature Miscibility Although Immiscible at or Below Room Temperature ............................................................ Table 6. Polymer Pairs Miscible at Room Temperature That Appear to Have a Lower Critical Solution Temperature (LCST) Above Room Temperature ......................... Table 7. Polymer Pairs That Appear to Have Both a Lower Critical Solution Temperature and a Upper Critical Solution Temperature ....................................... Table 8. Polymer Pairs That Cocrystallize ............................................................................
VI/411 VI/411 VI/444 VI/448 VI/450 VI/452 VI/454 VI/458 VI/459
E. References ......................................................................................................................... VI/461 Heat Capacities of High Polymers ............................................................................................................... VI/483 A. Introduction ........................................................................................................................ VI/483 B. Experimental Curves .......................................................................................................... VI/485 C. Data Tables for Solids and Liquids ..................................................................................... Table 1. cis-1,4-Poly(butadiene) (PBDc) .............................................................................. Table 2. trans-1,4-Poly(butadiene) (PBDt) ............................................................................ Table 3. cis-1,4-Poly(2-methylbutadiene) (PMBD) ............................................................... Table 4. Poly(ethylene) (PE) ................................................................................................. Table 5. Poly(propylene) (PP) ............................................................................................... Table 6. PoIy(1-butene) (PB) ................................................................................................ Table 7. PoIy(1-pentene) (PPE) ............................................................................................ Table 8. PoIy(1-hexene) (PHE) ............................................................................................. Table 9. Poly(isobutene) (PIB) .............................................................................................. Table 10. Poly(4-methyl-1-pentene) (P4MPE) ........................................................................ Table 11. Poly(tetrafluoroethylene) (PTFE) ............................................................................ Table 12. Poly(vinyl Fluoride) (PVF) ....................................................................................... Table 13. Poly(vinylidene Fluoride) (PVF2) ............................................................................ Table 14. Poly(trifluoroethylene) (P3FE) ................................................................................. Table 15. Poly(vinyl Chloride) (PVC) ......................................................................................
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VI/486 VI/486 VI/487 VI/488 VI/488 VI/489 VI/490 VI/490 VI/491 VI/492 VI/492 VI/493 VI/494 VI/494 VI/495 VI/496
xxxii
Contents Table 16. Table 17. Table 18. Table 19. Table 20. Table 21. Table 22. Table 23. Table 24. Table 25. Table 26. Table 27. Table 28. Table 29. Table 30. Table 31. Table 32. Table 33. Table 34. Table 35. Table 36. Table 37. Table 38. Table 39. Table 40. Table 41. Table 42. Table 43. Table 44. Table 45. Table 46. Table 47. Table 48. Table 49. Table 50.
Poly(vinylidene Chloride) (PVC2) ........................................................................... Poly(chlorotrifluoroethylene) (PC3FE) .................................................................... Poly(vinyl Alcohol) (PVA) ........................................................................................ Poly(vinyl Acetate) (PVAc) ...................................................................................... Poly(styrene) (PS) ................................................................................................... Poly(α-methylstyrene) (PMS) .................................................................................. Poly(vinyl Benzoate) (PVBZ) .................................................................................. Poly(methyl Acrylate) (PMA) ................................................................................... Poly(ethyl Acrylate) (PEA) ...................................................................................... Poly(n-butyl Acrylate) (PnBA) ................................................................................. Poly(iso-butyl Acrylate) (PIBA) ................................................................................ Poly(methacrylic Acid) (PMAA) ............................................................................... Poly(methyl Methacrylate) (PMMA) ........................................................................ Poly(ethyl Methacrylate) (PEMA) ............................................................................ Poly(n-butyl Methacrylate) (PnBMA) ....................................................................... Poly(iso-butyl Methacrylate) (PIBMA) ..................................................................... Poly(hexyl Methacrylate) (PHMA) ........................................................................... Poly(acrylonitrile) (PAN) .......................................................................................... Poly(methacrylamide) (PMAM) ............................................................................... Poly(oxy-1-oxoethylene) (PCL) ............................................................................... Poly(oxy-1-oxohexamethylene) (PCL) .................................................................... Poly(oxyethyleneoxyterephthaloyl) (PET) ............................................................... Poly(imino-(1-oxohexamethylene)) (Nylon 6) ......................................................... Poly(iminoadipoyliminohexamethylene) (Nylon 66) ................................................ Poly(iminoadipoyliminododecamethylene) (Nylon 612) .......................................... Poly(oxymethylene) (POM) ..................................................................................... Poly(oxyethylene) ................................................................................................... Poly(oxytrimethylene) (PO3M) ................................................................................ Poly(oxytetramethylene) (PO4M) ............................................................................ Poly(oxypropylene) (POPr) ..................................................................................... Poly(oxy-1,4-phenylene) (POPh) ............................................................................ Poly(oxy-2,6-dimethyl-1,4-phenylene) (PPO) ......................................................... Poly(oxy-2,6-diphenyl-1,4-phenylene) (POPPO) .................................................... Poly(oxycarbonyloxy-1,4-phenylene-isopropylidene- 1,4-phenylene) (PC) ............ Trigonal Selenium (SeT) .........................................................................................
VI/496 VI/497 VI/498 VI/498 VI/499 VI/500 VI/500 VI/501 VI/502 VI/502 VI/503 VI/504 VI/504 VI/505 VI/506 VI/506 VI/507 VI/508 VI/508 VI/509 VI/510 VI/510 VI/511 VI/512 VI/512 VI/513 VI/514 VI/514 VI/515 VI/515 VI/516 VI/517 VI/517 VI/518 VI/519
D. References ......................................................................................................................... VI/519 Surface and Interfacial Tensions of Polymers, Oligomers, Plasticizers, and Organic Pigments ............... VI/521 A. Introduction ........................................................................................................................ 1. Definition ................................................................................................................. 2. Temperature Dependence ...................................................................................... 3. Macleod's Relation .................................................................................................. 4. Molecular Weight Dependence ............................................................................... 5. Effects of Glass and Crystal-melt Transitions ......................................................... This page has been reformatted by Knovel to provide easier navigation.
VI/521 VI/521 VI/522 VI/522 VI/522 VI/522
Contents 6. 7.
xxxiii
Effect of Surface Chemical Constitution ................................................................. VI/523 Dispersion (Nonpolar) and Polar Components ....................................................... VI/523
B. Tables ................................................................................................................................ VI/523 Table 1. Surface Chemical Constitution and Surface Tension ............................. VI/524 1.1
Hydrocarbon Surfaces ..................................................................... VI/524
1.2
Fluorocarbon Surfaces ..................................................................... VI/524
1.3
Chlorocarbon Surfaces .................................................................... VI/524
1.4 Silicane Surfaces .............................................................................. VI/524 Table 2. Surface Tension, Polarity, and Macleod's Exponent for Amorphous Surfaces .............................................................................. VI/524 2.1
Hydrocarbon Polymers ..................................................................... VI/524
2.2
Styrene Polymers ............................................................................. VI/525
2.3
Halogenated Hydrocarbon Polymers ............................................... VI/525
2.4
Vinyl Polymers - Esters .................................................................... VI/526
2.5
Vinyl Polymers - Others ................................................................... VI/526
2.6
Acrylic Polymers - Nonfluorinated .................................................... VI/526
2.7
Acrylic Polymers - Fluorinated ......................................................... VI/527
2.8
Methacrylic Polymers - Nonfluorinated ............................................ VI/527
2.9
Methacrylic Polymers - Fluorinated ................................................. VI/527
2.10 Methacrylic Hydrogels ...................................................................... VI/527 2.11 Poly(ethers) ...................................................................................... VI/528 2.12 Poly(ether) Copolymers ................................................................... VI/529 2.13 Poly(esters) ...................................................................................... VI/529 2.14 Poly(carbonates) .............................................................................. VI/530 2.15 Poly(sulfones) ................................................................................... VI/530 2.16 Phenoxy Resins ............................................................................... VI/530 2.17 Epoxy Resins ................................................................................... VI/530 2.18 Poly(amides) .................................................................................... VI/530 2.19 Poly(imides) ...................................................................................... VI/531 2.20 Poly(imines) ...................................................................................... VI/531 2.21 Poly(urethanes) ................................................................................ VI/531 2.22 Poly(siloxanes) ................................................................................. VI/531 2.23 Organosilanes - Hydrolyzed and Condensed Films ........................ VI/532 2.24 Cellulosics ........................................................................................ VI/533 2.25 Poly(peptides) .................................................................................. VI/533 2.26 Miscellaneous ................................................................................... VI/533 Table 3. lnterfacial Tension for Amorphous Interfaces ......................................... VI/535 3.1
Hydrocarbon Polymers vs. Others ................................................... VI/535
3.2
Styrene Polymers vs. Others ........................................................... VI/537
3.3
Vinyl Polymers vs. Others ................................................................ VI/537
3.4
Acrylic Polymers vs. Others ............................................................. VI/538
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Contents 3.5
Methacrylic Polymers vs. Others ..................................................... VI/538
3.6
Poly(ethers) vs. Others .................................................................... VI/539
3.7
Poly(esters) vs. Others ..................................................................... VI/539
3.8
Poly(amides) vs. Others ................................................................... VI/539
3.9
Epoxy Resins vs. Others .................................................................. VI/539
3.10 Poly(Siloxanes) vs. Others ............................................................... VI/539 3.11 Miscellaneous ................................................................................... VI/540 C. References ......................................................................................................................... VI/540 Permeability and Diffusion Data .................................................................................................................. VI/543 A. Introduction ........................................................................................................................ VI/543 B. Conversion Factors for Various Units of the Permeability Coefficient ................................. VI/545 C. Tables ................................................................................................................................ Table 1. Permeability Coefficients, Diffusion Coefficients, and Solubility Coefficients of Polymers ............................................................................................................. 1.1 Poly(alkanes) .......................................................................................... 1.2 Poly(styrenes) ......................................................................................... 1.3 Poly(methacrylates) ................................................................................ 1.4 Poly(nitriles) ............................................................................................ 1.5 Poly(vinyls) ............................................................................................. 1.6 Fluorine Containing Polymers ................................................................. 1.7 Poly(dienes) ............................................................................................ 1.8 Poly(xylylenes) ........................................................................................ 1.9 Poly(oxides) ............................................................................................ 1.10 Poly(esters), Poly(carbonates) ............................................................... 1.11 PoIy(siloxanes) ....................................................................................... 1.12 Poly(amides), Poly(imides) ..................................................................... 1.13 Poly(urethanes) ...................................................................................... 1.14 Poly(sulfones) ......................................................................................... 1.15 Poly(aryl Ether Ether Ketone) ................................................................. 1.16 Cellulose and Derivatives ....................................................................... Table 2. Permeability Coefficients of Six Different Fluorinated Hydrocarbons through Polymers ................................................................................................................. Table 3. Permeability Coefficients of Various Organic Compounds through Lowdensity Poly(ethylene) ............................................................................................. Table 4. Permeability Coefficients and Diffusion Coefficients of an Equimolar Mixture of Various Compounds (1.25 M Each) through High-density Poly(ethylene) .......... Table 5. Permeability Coefficients of Various Organic Compounds through Highdensity Poly(ethylene) and Poly(propylene) ........................................................... Table 6. Permeability Coefficients of Various Organic Compounds through Irradiation Crosslinked Low-density Poly(ethylene) ................................................................. Table 7. Permeability Coefficients of Cases through Irradiation Crosslinked Lowdensity Poly(ethylene) .............................................................................................
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VI/545 VI/545 VI/545 VI/547 VI/548 VI/549 VI/549 VI/552 VI/553 VI/555 VI/555 VI/555 VI/558 VI/559 VI/560 VI/560 VI/561 VI/561 VI/562 VI/562 VI/564 VI/564 VI/564 VI/565
Contents
xxxv
Table 8. Permeability Coefficients of Chemically Crosslinked Poly(oxypropylene) .............. Table 9. Permeability Coefficients of Gases through Various Elastomers ............................ Table 10. Permeability Coefficients of Gases through Various Commercial Elastomers at 35°C. ................................................................................................................... Table 11. Permeability, Diffusion and Solubility Coefficients of Alkanes through Santoprene™ (Blend of Ethylene-propylene Copolymer and lsotactic Poly(propylene)) ...................................................................................................... Table 12. Permeability, Diffusion and Solubility Coefficients of Esters through Poly(epichlorohydrin) (ECO) ...................................................................................
VI/565 VI/566 VI/566
VI/566 VI/567
D. References ......................................................................................................................... VI/568 Refractive Indices of Polymers .................................................................................................................... VI/571 A. Introduction ........................................................................................................................ VI/571 B. Molar Refraction ................................................................................................................. VI/571 C. Refractive Indices of Heterogeneous Polymers .................................................................. VI/572 D. Optical Anisotropy .............................................................................................................. VI/572 E. Applications ........................................................................................................................ Table 1. Intrinsic Optical Properties of Selected Polymers ................................................... Table 2. Average Refractive Indices of Polymers (in Order of Increasing n) ........................ Table 3. Average Refractive Indices of Polymers (in Alphabetical Order) ............................
VI/573 VI/573 VI/574 VI/578
F. References ......................................................................................................................... VI/582 Radiation Resistance of Plastics and Elastomers ....................................................................................... VI/583 A. Introduction ........................................................................................................................ 1. General Comments ................................................................................................. 2. Criterion for Radiation Resistance .......................................................................... 3. Factors of Influence and Their Consideration in Tables ......................................... 3.1 Type of Polymer and Formulation ........................................................... 3.2 Type of Radiation and Dosimetry ........................................................... 3.3 Dose Rate and the Atmosphere ............................................................. 3.4 Temperature ........................................................................................... 3.5 Other Stresses ........................................................................................
VI/583 VI/583 VI/583 VI/583 VI/583 VI/584 VI/584 VI/584 VI/584
B. List of Symbols Used .......................................................................................................... VI/584 C. Tables of Table 1. Table 2. Table 3. Table 4.
Radiation Resistance .......................................................................................... Thermoplastics ........................................................................................................ Elastomers .............................................................................................................. Aromatic Polymers .................................................................................................. Organic Composite Materials ..................................................................................
VI/585 VI/585 VI/586 VI/587 VI/588
D. References ......................................................................................................................... VI/588 PVT Relationships and Equations of State of Polymers ............................................................................. VI/591 A. Introduction ........................................................................................................................ VI/591 B. Isothermal Compressibility Equations ................................................................................. VI/592 C. Empirical or Semiempirical 3-Parameter Equations of State ............................................... VI/593 D. Lattice or Quasi Lattice Models .......................................................................................... VI/593 This page has been reformatted by Knovel to provide easier navigation.
xxxvi
Contents E. Continuum Models .............................................................................................................. VI/594 F. Tables ................................................................................................................................ Table 1. Zero Pressure Volume V0(T) and Bulk Modulus B0(T) ............................................ Table 2. Abbreviations of Polymer Names and the Experimental TemperaturePressure Range for Polymer Liquids ...................................................................... Table 3. PVT Properties of Other Polymers .......................................................................... Table 4. Characteristic Parameters for the Sanchez-cho Equation of State ......................... Table 5. Characteristic Parameters for the Hartmann-haque Equation of State ................... Table 6. Characteristic Parameters for the Simple Cell Model Equation of State ................. Table 7. Characteristic Parameters for the Flory, Orwoll and Vrij Equation of State ............ Table 8. Characteristic Parameters for the Simha-somcynsky Equation of State ................ Table 9. Characteristic Parameters for the Sanchez-lacombe Equation of State ................. Table 10. Characteristic Parameters for the AHS + vdW Equation of State ...........................
VI/595 VI/595 VI/596 VI/597 VI/597 VI/597 VI/598 VI/599 VI/599 VI/600 VI/600
G. References ......................................................................................................................... VI/601
VII. Solution Properties Viscosity – Molecular Weight Relationships and Unperturbed Dimensions of Linear Chain Molecules ............................................................................................................................................
VII/1
A. Introduction ........................................................................................................................ 1. The Viscosity - Molecular Weight Relationship ....................................................... 2. Unperturbed Dimensions of Linear Chain Molecules ..............................................
VII/2 VII/2 VII/4
B. Effect of Molecular Weight Distribution on the Viscosity Constant K ...................................
VII/5
a
C. Tables of Viscosity - Molecular Weight Relationships, [η] = KM ........................................ Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... 1.1 Poly(dienes) ............................................................................................ 1.2 Poly(alkenes), Poly(acetylenes) ............................................................. 1.3 Poly(acrylic Acid) and Derivatives .......................................................... 1.4 Poly(α-substituted Acrylic Acid) and Derivatives .................................... 1.5 Poly(vinyl Ethers) .................................................................................... 1.6 Poly(vinyl Alcohol), Poly(vinyl Halides) ................................................... 1.7 Poly(vinyI Esters) .................................................................................... 1.8 Poly(styrene) and Derivatives ................................................................. 1.9 Other Compounds .................................................................................. 1.10 Copolymers ............................................................................................. Table 2. Main-chain Carbocyclic Polymers ........................................................................... Table 3. Main-chain Heteroatom Polymers ........................................................................... 3.1 Poly(oxides), Poly(ethers) ....................................................................... 3.2 Poly(esters), Poly(carbonates) ............................................................... 3.3 Poly(amides) ........................................................................................... 3.4 Poly(amino Acids) ................................................................................... 3.5 Poly(ureas), Poly(urethanes), Poly(imines) ............................................ 3.6 Poly(sulfides) .......................................................................................... 3.7 Poly(phosphates) .................................................................................... This page has been reformatted by Knovel to provide easier navigation.
VII/5 VII/5 VII/5 VII/7 VII/10 VII/13 VII/17 VII/17 VII/18 VII/19 VII/24 VII/27 VII/31 VII/32 VII/32 VII/34 VII/36 VII/38 VII/39 VII/39 VII/39
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3.8 Poly(siloxanes), Poly(silsesquioxanes) ................................................... 3.9 Poly(heterocyclics) .................................................................................. 3.10 Copolymers (Maleic Anhydride, Sulfones) .............................................. 3.11 Other Compounds .................................................................................. Table 4. Cellulose and Derivatives, Poly(saccharides) ......................................................... Table 5. Miscellaneous .........................................................................................................
VII/40 VII/41 VII/42 VII/42 VII/43 VII/46
D. Calculated Unperturbed Dimensions of Freely Rotating Chains .........................................
VII/46
E. Unperturbed Dimensions of Linear Polymer Molecules ...................................................... Table 6. Main-chain Acyclic Carbon Polymers ..................................................................... 6.1 Poly(dienes) ............................................................................................ 6.2 Poly(alkenes), Poly(acetylenes) ............................................................. 6.3 Poly(acrylic Acid) and Derivatives .......................................................... 6.4 Poly(α-substituted Acrylic Acid) and Derivatives .................................... 6.5 Poly(vinyl Ethers), Poly(vinyl Alcohol), Poly(vinyl Esters), Poly(vinyl Halides) .................................................................................. 6.6 Poly(styrene) and Derivatives ................................................................. 6.7 Other Compounds .................................................................................. 6.8 Copolymers ............................................................................................. Table 7. Main-chain Carbocyclic Polymers ........................................................................... Table 8. Main-chain Heteroatom Polymers ........................................................................... 8.1 Poly(oxides), Poly(ethers) ....................................................................... 8.2 Poly(esters), Poly(carbonates) ............................................................... 8.3 Poly(amides) ........................................................................................... 8.4 Poly(amino Acids) ................................................................................... 8.5 Poly(urethanes) ...................................................................................... 8.6 Poly(sulfides) .......................................................................................... 8.7 Poly(phosphates) .................................................................................... 8.8 Poly(siloxanes), Poly(silsesquioxanes), Poly(silmethylenes) ................. 8.9 Poly(heterocyclics) .................................................................................. 8.10 Copolymers (Maleic Anhydride, Sulfones, Siloxanes) ............................ 8.11 Other Compounds .................................................................................. Table 9. Cellulose and Derivatives, Poly(saccharides) .........................................................
VII/47 VII/47 VII/47 VII/48 VII/49 VII/50
F. References .........................................................................................................................
VII/68
Sedimentation Coefficients, Diffusion Coefficients, Partial Specific Volumes, Frictional Ratios, and Second Virial Coefficients of Polymers in Solution ............................................................................
VII/85
A. Sedimentation Coefficients, Diffusion Coefficients, Partial Specific Volumes, and Frictional Ratios of Polymers in Solution ............................................................................ 1. Introduction ............................................................................................................. 1.1. Sedimentation Coefficient ....................................................................... 1.2. Diffusion Coefficient ................................................................................ 1.3. Molar Mass Averages Determined from Sedimentation and Diffusion Coefficients .............................................................................. 1.4. Partial Specific Volumes ......................................................................... This page has been reformatted by Knovel to provide easier navigation.
VII/53 VII/54 VII/56 VII/58 VII/60 VII/60 VII/60 VII/61 VII/63 VII/63 VII/63 VII/63 VII/64 VII/64 VII/64 VII/65 VII/66 VII/66
VII/86 VII/86 VII/86 VII/87 VII/89 VII/89
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Contents 1.5. 1.6. 1.7.
Frictional Ratios ...................................................................................... List of Symbols and Abbreviations .......................................................... Miscellaneous .........................................................................................
B. Tables of Sedimentation Coefficients, Diffusion Coefficients, Partial Specific Volumes, and Frictional Ratios of Polymers in Solution ...................................................... Table 1. Poly(alkenes) .......................................................................................................... Table 2. Poly(dienes) ............................................................................................................ Table 3. Acrylic Polymers ..................................................................................................... Table 4. Vinyl Polymers ........................................................................................................ Table 5. Styrene Polymers .................................................................................................... Table 6. (O, C)-Heterochain Polymers [Poly(ethers), Poly(esters), Poly(carbonates)] ......... Table 7. (N, C)- and (O, N, C)-Heterochain Polymers [Poly(amides), Poly(ureas), Poly(urethanes)] ...................................................................................................... Table 8. Other Synthetic Polymers ....................................................................................... Table 9. Inorganic Polymers ................................................................................................. Table 10. Poly(saccharides) ................................................................................................... Table 11. Other Biopolymers [Proteins, Poly(nucleotides)] ....................................................
VII/89 VII/90 VII/91 VII/92 VII/92 VII/94 VII/96 VII/105 VII/109 VII/134 VII/137 VII/140 VII/141 VII/144 VII/157
C. Second Virial Coefficients of Polymers in Solution .............................................................. 1. Introduction ............................................................................................................. 1.1. Colligative Properties .............................................................................. 1.2. Scattering Methods ................................................................................. 1.3. Sedimentation Velocity ........................................................................... 1.4. Sedimentation Equilibrium ...................................................................... 1.5. p–V–T Measurements ............................................................................ 1.6. Averages of the Second Virial Coefficient .............................................. 1.7. Second Virial Coefficient – Molar Mass Relationship ............................. 1.8. Temperature Dependence, Pressure Dependence ................................ 1.9. Abbreviations .......................................................................................... 1.10. Miscellaneous .........................................................................................
VII/163 VII/163 VII/163 VII/163 VII/163 VII/164 VII/164 VII/164 VII/164 VII/164 VII/164 VII/164
D. Tables of Table 12. Table 13. Table 14. Table 15. Table 16. Table 17. Table 18.
VII/165 VII/165 VII/168 VII/170 VII/177 VII/179 VII/188
Table 19. Table 20. Table 21. Table 22.
Second Virial Coefficients of Polymers in Solution .............................................. Poly(alkenes), Poly(alkynes) ................................................................................... Poly(dienes) ............................................................................................................ Poly(acrylics) ........................................................................................................... Poly(vlnyls) .............................................................................................................. Poly(styrenes) ......................................................................................................... (O, C)-heterochain Polymers [Poly(ethers), Poly(esters), Poly(carbonates)] ......... (N, C)- and (O, N, C)-heterochain Polymers [Poly(amides), Poly(ureas), Poly(urethanes)] ...................................................................................................... Other Synthetic Polymers ....................................................................................... Inorganic Polymers ................................................................................................. Poly(saccharides) ................................................................................................... Other Biopolymers [Proteins, Poly(nucleotides)] ....................................................
VII/191 VII/192 VII/192 VII/194 VII/196
E. References ......................................................................................................................... VII/198 This page has been reformatted by Knovel to provide easier navigation.
Contents
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Polymolecularity Correction Factors ............................................................................................................ VII/215 A. List of Symbols Used .......................................................................................................... VII/216 B. Introduction ........................................................................................................................ VII/217 Table 1 .................................................................................................................................... VII/223 C. Polymolecularity Correction Factors for Intrinsic Viscosity Versus Molecular Weight Relationship ....................................................................................................................... Table 2 .................................................................................................................................... Table 3 .................................................................................................................................... Table 4 .................................................................................................................................... Table 5 .................................................................................................................................... Table 6 .................................................................................................................................... Table 7 .................................................................................................................................... Table 8 .................................................................................................................................... Table 9 .................................................................................................................................... Table 10 .................................................................................................................................. Table 11 .................................................................................................................................. Table 12 .................................................................................................................................. Table 13 .................................................................................................................................. Table 14 .................................................................................................................................. Table 15 .................................................................................................................................. Table 16 .................................................................................................................................. Table 17 .................................................................................................................................. Table 18 .................................................................................................................................. Table 19 ..................................................................................................................................
VII/223 VII/223 VII/223 VII/223 VII/224 VII/224 VII/224 VII/224 VII/224 VII/225 VII/225 VII/225 VII/225 VII/225 VII/226 VII/226 VII/226 VII/226 VII/226
D. Polymolecularity Correction Factors for Sedimentation Coefficient Versus Molecular Weight Relationship ........................................................................................................... Table 20 .................................................................................................................................. Table 21 .................................................................................................................................. Table 22 .................................................................................................................................. Table 23 .................................................................................................................................. Table 24 .................................................................................................................................. Table 25 .................................................................................................................................. Table 26 .................................................................................................................................. Table 27 ..................................................................................................................................
VII/227 VII/227 VII/227 VII/227 VII/227 VII/228 VII/228 VII/228 VII/229
E. Polymolecularity Correction Factors for Diffusion Coefficient Versus Molecular Weight Relationship ........................................................................................................... Table 28 .................................................................................................................................. Table 29 .................................................................................................................................. Table 30 .................................................................................................................................. Table 31 .................................................................................................................................. Table 32 .................................................................................................................................. Table 33 .................................................................................................................................. Table 34 ..................................................................................................................................
VII/229 VII/229 VII/229 VII/229 VII/230 VII/230 VII/230 VII/230
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Contents Table 35 Table 36 Table 37 Table 38 Table 39 Table 40 Table 41
.................................................................................................................................. .................................................................................................................................. .................................................................................................................................. .................................................................................................................................. .................................................................................................................................. .................................................................................................................................. ..................................................................................................................................
VII/230 VII/231 VII/231 VII/231 VII/231 VII/232 VII/232
F. Polymolecularity Correction Factors for Mean-Square Radius of Gyration versus Molecular Weight Relationship ........................................................................................... Table 42 .................................................................................................................................. Table 43 .................................................................................................................................. Table 44 .................................................................................................................................. Table 45 .................................................................................................................................. Table 46 .................................................................................................................................. Table 47 ..................................................................................................................................
VII/232 VII/232 VII/233 VII/233 VII/233 VII/234 VII/234
G. Polymolecularity Correction Factors for Second Virial Coefficient Versus Molecular Weight Relationship ........................................................................................................... Table 48 .................................................................................................................................. Table 49 .................................................................................................................................. Table 50 .................................................................................................................................. Table 51 ..................................................................................................................................
VII/234 VII/234 VII/235 VII/235 VII/235
H. Polymolecularity Correction Factors for the Determination of the Dimensions of Macromolecules ................................................................................................................. 1. Fox-flory Relationship ............................................................................................. Table 52 .................................................................................................................. Table 53 .................................................................................................................. Table 54 .................................................................................................................. Table 55 .................................................................................................................. 2. Interconversion of Different Averages of the Mean-square Radius of Gyration .................................................................................................................. Table 56 .................................................................................................................. Table 57 .................................................................................................................. Table 58 .................................................................................................................. Table 59 .................................................................................................................. 3. Interconversion of Different Averages of the Mean-square End-to-end Distance .................................................................................................................. Table 60 .................................................................................................................. Table 61 .................................................................................................................. Table 62 .................................................................................................................. Table 63 .................................................................................................................. Table 64 .................................................................................................................. Table 65 ..................................................................................................................
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VII/235 VII/235 VII/235 VII/236 VII/236 VII/236 VII/236 VII/236 VII/237 VII/237 VII/238 VII/238 VII/238 VII/238 VII/239 VII/239 VII/239 VII/239
Contents 4.
I.
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The Effect of Polymolecularity on the Radius of Gyration of Stiff Polymer Chains ..................................................................................................................... VII/240 Table 66 .................................................................................................................. VII/240 Table 67 .................................................................................................................. VII/240
Polymolecularity Correction Factors for the Determination of Unperturbed Dimensions of Macromolecules .......................................................................................... 1. Burchard-stockmayer-fixman Procedure ................................................................ Table 68 .................................................................................................................. Table 69 .................................................................................................................. Table 70 .................................................................................................................. 2. Cowie-bywater Procedure ....................................................................................... Table 71 .................................................................................................................. Table 72 .................................................................................................................. Table 73 .................................................................................................................. Table 74 .................................................................................................................. 3. Baumann-stockmayer-fixman Procedure ................................................................ Table 75 .................................................................................................................. Table 76 .................................................................................................................. Table 77 .................................................................................................................. Table 78 .................................................................................................................. 4. Baumann-kurata-stockmayer Procedure ................................................................ Table 79 .................................................................................................................. Table 80 .................................................................................................................. Table 81 .................................................................................................................. Table 82 ..................................................................................................................
VII/240 VII/240 VII/240 VII/240 VII/241 VII/241 VII/241 VII/241 VII/241 VII/241 VII/242 VII/242 VII/242 VII/242 VII/242 VII/243 VII/243 VII/243 VII/243 VII/244
J. References ......................................................................................................................... VII/244 Polymer-solvent Interaction Parameters ..................................................................................................... VII/247 A. Introduction ........................................................................................................................ VII/247 B. Concentration Variables ..................................................................................................... VII/247 C. Conversion of Concentration Variables .............................................................................. VII/247 D. Basic Equations .................................................................................................................. VII/247 E. Methods of Determination .................................................................................................. VII/248 F. Temperature Dependence .................................................................................................. VII/249 G. Concentration Dependence ................................................................................................ VII/249 H. Molecular Weight Dependence ........................................................................................... VII/250 I.
Polymer-solvent Interaction Parameters, χ ......................................................................... VII/250
J. References ......................................................................................................................... VII/262 Concentration Dependence of the Viscosity of Dilute Polymer Solutions: Huggins and Schulzblaschke Constants ............................................................................................................................ VII/265 A. Introduction ........................................................................................................................ VII/265 B. Tables ................................................................................................................................ VII/266
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xlii
Contents Table 1. Huggins Constants ................................................................................................. 1.1 Poly(dienes) and Poly(alkenes) .............................................................. 1.2 Poly(acrylic Acid) and Poly(methacrylic Acid) Derivatives ...................... 1.3 Vinyl Polymers ........................................................................................ 1.4 Poly(oxides) ............................................................................................ 1.5 Poly(esters) ............................................................................................. 1.6 Polyamides ............................................................................................. 1.7 Other Compounds .................................................................................. 1.8 Cellulose, Cellulose Derivatives, and Polysaccharides .......................... Table 2. Schulz-blaschke Constants .....................................................................................
VII/266 VII/266 VII/268 VII/272 VII/277 VII/278 VII/279 VII/280 VII/282 VII/284
C. References ......................................................................................................................... VII/285 Theta Solvents ............................................................................................................................................. VII/291 A. Introduction ........................................................................................................................ 1. Fundamentals ......................................................................................................... 1.1 Thermodynamics .................................................................................... 1.2 Unperturbed Dimensions ........................................................................ 2. Methods to Determine Theta Solvents .................................................................... 2.1 Phase Equilibrium (PE) ........................................................................... 2.2 Second Virial Coefficient (A) ................................................................... 2.3 Cloud Point Titration (CP) ....................................................................... 2.4 Cloud Temperature Titration (CT) ........................................................... 2.5 Unperturbed Dimensions (RGM, VM, DM, SM) ...................................... 2.6 Other Methods ........................................................................................
VII/291 VII/291 VII/291 VII/292 VII/293 VII/293 VII/293 VII/294 VII/294 VII/294 VII/294
B. Tables of Theta Solvents for Polymers ............................................................................... Table 1. Homochain Polymers .............................................................................................. 1.1 Poly(alkanes) .......................................................................................... 1.2 Poly(alkenes) .......................................................................................... 1.3 Poly(styrenes) ......................................................................................... 1.4 Poly(vinyls) ............................................................................................. 1.5 Poly(acrylics) and Related Compounds .................................................. 1.6 Poly(methacrylics) and Related Compounds .......................................... 1.7 Other Carbon Chains .............................................................................. Table 2. Heterochain Polymers ............................................................................................. 2.1 Poly(acetals) and Poly(ethers) ................................................................ 2.2 Poly(esters) ............................................................................................. 2.3 Poly(amides) ........................................................................................... 2.4 Polyureas and Polyurethanes ................................................................. 2.5 Polysaccharides ...................................................................................... 2.6 Carbon-sulfur Chains .............................................................................. 2.7 Silicon-oxygen Chains ............................................................................ 2.8 Phosphorus-oxygen Chains ....................................................................
VII/295 VII/295 VII/295 VII/299 VII/300 VII/305 VII/307 VII/308 VII/312 VII/313 VII/313 VII/315 VII/316 VII/316 VII/316 VII/317 VII/317 VII/318
C. References ......................................................................................................................... VII/318
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Fractionation of Polymers ............................................................................................................................ VII/327 A. Principles of Polymer Fractionation .................................................................................... VII/327 B. Fractionation Methods ........................................................................................................ 1. Fractionation by Solubility ....................................................................................... 2. Fractionation by Chromatography ........................................................................... 3. Cross Fractionation ................................................................................................. 4. Fractionation by Sedimentation .............................................................................. 5. Fractionation by Diffusion ....................................................................................... 6. Fractionation by Ultrafiltration through Porous Membranes .................................... 7. Fractionation by Zone Melting ................................................................................. 8. Electron Microscopic Counting Method ..................................................................
VII/328 VII/328 VII/330 VII/332 VII/333 VII/333 VII/333 VII/333 VII/333
C. Tables of Fractionation Systems for Different Polymers ..................................................... Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... 1.1 Poly(dienes) ............................................................................................ 1.2 Poly(alkenes) .......................................................................................... 1.3 Poly(acrylic Acid) and Derivatives .......................................................... 1.4 Poly(methacrylic Acid) and Derivatives .................................................. 1.5 Other α- and β-Substituted Poly(acrylics) and Poly(methacrylics) ......... 1.6 Poly(vinyl Ethers) .................................................................................... 1.7 Poly(vinyl Alcohol), Poly(vinyl Ketones), Poly(vinyl Halides), Poly(vinyl Nitriles) ................................................................................... 1.8 Poly(vinyl Esters) .................................................................................... 1.9 Poly(styrenes) ......................................................................................... 1.10 Other Compounds .................................................................................. 1.11 Random and Alternating Copolymers ..................................................... 1.12 Block Copolymers ................................................................................... 1.13 Graft Copolymers .................................................................................... 1.14 Mixture of Polymers ................................................................................ Table 2. Main-chain Carbocyclic Polymers ........................................................................... 2.1 Poly(phenylenes) .................................................................................... 2.2 Formaldehyde Resins ............................................................................. Table 3. Main-chain Heteroatom Polymers ........................................................................... 3.1 Poly(oxides) ............................................................................................ 3.2 Poly(carbonates) ..................................................................................... 3.3 Poly(esters) ............................................................................................. 3.4 Poly(urethanes) and Poly(ureas) ............................................................ 3.5 Poly(amides) and Poly(imines) ............................................................... 3.6 Poly(amino Acids) ................................................................................... 3.7 Poly(sulfides), Poly(sulfones), Poly(sulfonamides) ................................. 3.8 Poly(silanes) and Poly(siloxanes) ........................................................... 3.9 Poly(phosphazenes) and Related Polymers ........................................... 3.10 Other Compounds .................................................................................. 3.11 Random Copolymers ..............................................................................
VII/333 VII/333 VII/333 VII/336 VII/344 VII/346 VII/351 VII/353
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VII/353 VII/355 VII/356 VII/363 VII/366 VII/382 VII/389 VII/395 VII/397 VII/397 VII/397 VII/398 VII/398 VII/404 VII/405 VII/410 VII/411 VII/414 VII/416 VII/418 VII/422 VII/423 VII/425
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Contents 3.12 Block Copolymers ................................................................................... 3.13 Graft Copolymers .................................................................................... Table 4. Poly(saccharides) ................................................................................................... 4.1 Poly(saccharides) ................................................................................... 4.2 Graft Copolymers .................................................................................... 4.3 Mixtures of Polymers ..............................................................................
VII/427 VII/430 VII/431 VII/431 VII/436 VII/438
D. References ......................................................................................................................... 1 to 1188 ................................................................................................................................. 1189 to 2452 ........................................................................................................................... 2453 to 3608 ...........................................................................................................................
VII/438 VII/438 VII/458 VII/478
Solvents and Non Solvents for Polymers .................................................................................................... VII/497 A. Introduction ........................................................................................................................ VII/498 B. Abbreviations ..................................................................................................................... VII/498 C. Tables of Solvents and Nonsolvents ................................................................................... Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... 1.1 Poly(dienes), Poly(acetylenes) ............................................................... 1.2 Poly(alkenes) .......................................................................................... 1.3 Poly(acrylics), Poly(methacrylics) ...........................................................
VII/499 VII/499 VII/499 VII/500 VII/501
1.3.1 Poly(acrylic Acids) ............................................................................ VII/501 1.3.2 Poly(acrylates) .................................................................................. VII/501 1.3.3 Poly(methacrylates) ......................................................................... VII/501 1.3.4 Poly(disubstituted Esters) ................................................................ VII/502 1.3.5 Poly(acrylamides), Poly(methacrylamides) ..................................... 1.4 Poly(vinyl Ethers) .................................................................................... 1.5 Poly(vinyl Alcohols), Poly(acetals), Poly(vinyl Ketones) ......................... 1.6 Poly(vinyl Halides) .................................................................................. 1.7 Poly(vinyl Nitrites) ................................................................................... 1.8 Poly(vinyl Esters) .................................................................................... 1.9 Poly(styrenes) ......................................................................................... 1.10 Other Compounds .................................................................................. Table 2. Main-chain Carbocyclic Polymers ........................................................................... 2.1 Poly(phenylenes) .................................................................................... 2.2 Other Compounds .................................................................................. Table 3. Main-chain Carbonyl Polymers ............................................................................... Table 4. Main-chain Acyclic Heteroatom Polymers .............................................................. 4.1 Main-chain –C–O–C– Polymers .............................................................
VII/503 VII/503 VII/504 VII/505 VII/506 VII/506 VII/507 VII/508 VII/509 VII/509 VII/510 VII/510 VII/511 VII/511
4.1.1 Poly(oxides) ...................................................................................... VII/511 4.1.2 Poly(carbonates) .............................................................................. VII/513 4.1.3 Poly(esters) ...................................................................................... VII/513 4.1.4 Poly(anhydrides) .............................................................................. VII/515 4.1.5 Poly(urethanes) ................................................................................ VII/515
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Contents 4.2
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Main-chain –O– Heteroatom Polymers ................................................... VII/515 4.2.1 Poly(sulfonates) ................................................................................ VII/515
4.3
4.2.2 Poly(siloxanes) ................................................................................. VII/516 Main-chain –C–S–C– and –C–S–N– Polymers ...................................... VII/516 4.3.1 Poly(sulfides) .................................................................................... VII/516 4.3.2 Poly(sulfones) ................................................................................... VII/517
4.4
4.3.3 Others ............................................................................................... VII/518 Main-chain –C–N–C– Polymers ............................................................. VII/518 4.4.1 Poly(amides) .................................................................................... VII/518 4.4.2 Poly(hydrazides) ............................................................................... VII/520 4.4.3 Poly(ureas) ....................................................................................... VII/521 4.4.4 Poly(carbodiimides) .......................................................................... VII/521
4.4.5 Other Compounds ............................................................................ 4.5 Poly(phosphazenes) and Related Compounds ...................................... 4.6 Poly(silanes), Poly(silazanes) ................................................................. Table 5. Main-chain Heterocyclic Polymers .......................................................................... 5.1 Poly(benzoxazoles), Poly(oxadiazoles), Poly(oxadiazolidines) .............. 5.2 Poly(dithiazoles), Poly(benzothiazoles) .................................................. 5.3 Poly(imides) ............................................................................................
VII/521 VII/522 VII/522 VII/523 VII/523 VII/524 VII/524
5.3.1 Poly(benzimides) .............................................................................. VII/524 5.3.2 Poly(pyromellitides) .......................................................................... VII/525 5.3.3 Others ............................................................................................... 5.4 Poly(quinoxalines) .................................................................................. 5.5 Poly(benzimidazoles) .............................................................................. 5.6 Poly(piperazines) .................................................................................... 5.7 Poly(anhydrides) ..................................................................................... 5.8 Poly(thiophenes) ..................................................................................... 5.9 Others ..................................................................................................... Table 6. Formaldehyde Resins ............................................................................................. Table 7. Natural Polymers and Modified Natural Polymers .................................................. 7.1 Natural Rubber and Derivatives .............................................................. 7.2 Cutta Percha ........................................................................................... 7.3 Cellulose and Derivatives .......................................................................
VII/525 VII/526 VII/526 VII/526 VII/527 VII/527 VII/527 VII/528 VII/528 VII/528 VII/529 VII/529
7.3.1 Cellulose ........................................................................................... VII/529 7.3.2 Cellulose Ethers ............................................................................... VII/529 7.3.3 Cellulose Esters ............................................................................... VII/530 7.3.4 Cellulose Nitrate and Sulfate ........................................................... 7.4 Starch and Derivatives ............................................................................ 7.5 Other Poly(saccharides) ......................................................................... 7.6 Natural Resins ........................................................................................ Table 8. Inorganic Polymers ................................................................................................. Table 9. Poly(electrolytes) .................................................................................................... This page has been reformatted by Knovel to provide easier navigation.
VII/531 VII/531 VII/531 VII/532 VII/532 VII/533
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Contents Table 10. Block Polymers ....................................................................................................... VII/533 Table 11. Dendrimers ............................................................................................................. VII/534 D. References ......................................................................................................................... VII/536
Specific Refractive Index Increments of Polymers in Dilute Solution ......................................................... VII/547 A. Introduction ........................................................................................................................ VII/547 B. Introduction from the Third Edition ...................................................................................... VII/547 C. Refractometric Calibration Data .......................................................................................... VII/550 D. Tables of Specific Refractive Index Increments of Polymer Solutions ................................. Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... 1.1 Poly(dienes) ............................................................................................ 1.2 Poly(alkenes) .......................................................................................... 1.3 Poly(acrylic Acid) and Derivatives .......................................................... 1.4 Poly(methacrylic Acid) and Derivatives .................................................. 1.5 Other α- or β-Substituted Poly(acrylics) and Poly(methacrylics) ............ 1.6 Poly(styrenes) ......................................................................................... 1.7 Other Compounds .................................................................................. Table 2. Main-chain Cyclic Carbon Polymers ....................................................................... Table 3. Main-chain Heteroatom Polymers ........................................................................... 3.1 C–O–C Polymers (Poly(oxides), Poly(esters), and Others) .................... 3.2 C–S–C Polymers (Poly(sulfones) and Others) ....................................... 3.3 C–N–C Polymers (Poly(amides), Poly(isocyanates), Poly(urethanes), and Others) ................................................................. 3.4 Poly(amino Acids) ................................................................................... 3.5 Poly(silanes) and Poly(silazanes) ........................................................... 3.6 Poly(heterocyclics) and Others ............................................................... Table 4. Cellulose and Derivatives ....................................................................................... Table 5. Poly(saccharides) ...................................................................................................
VII/551 VII/551 VII/551 VII/553 VII/557 VII/561 VII/573 VII/574 VII/588 VII/594 VII/594 VII/594 VII/599 VII/599 VII/604 VII/606 VII/608 VII/609 VII/611
E. References ......................................................................................................................... VII/615 Particle Scattering Factors in Rayleigh Scattering ...................................................................................... VII/629 A. Introduction: General Relations for a Homogeneous Solute ............................................... VII/629 B. Scattering Factors for Various Molecular Models ................................................................ VII/630 C. Effects of Dispersion in Molecular Weight .......................................................................... VII/631 D. Determination of Molecular Weight and Radius of Gyration ................................................ VII/632 E. Calculation of Scattering Factors ........................................................................................ VII/633 F. Particle Scattering Factors and Dissymmetries .................................................................. VII/633 Table 1. Dissymmetries for Monodisperse Systems ............................................................. VII/634 Table 2. Dissymmetries for Monodisperse and Polydisperse Coils ...................................... VII/634 G. References ......................................................................................................................... VII/635 Dipole Moments of Polymers in Solution ..................................................................................................... VII/637 A. Introduction ........................................................................................................................ VII/637 B. Dipole Moments of Polymers In Solution ............................................................................ VII/638 Table 1. Polyoxides (Polyethers) .......................................................................................... VII/638 This page has been reformatted by Knovel to provide easier navigation.
Contents Table 2. Table 3. Table 4. Table 5. Table 6. Table 7. Table 8. Table 9. Table 10. Table 11. Table 12. Table 13.
Polysulfides (Polythioethers) ................................................................................... Hydroxyl Terminated Oxide/Sulfide Copolymers .................................................... Polyesters Derived from Aromatic Diacids .............................................................. Aliphatic and Cycloaliphatic Polyesters .................................................................. Polycarbonates ....................................................................................................... Vinyl Polymers ........................................................................................................ Acrylic Polymers ..................................................................................................... Methacrylic Polymers .............................................................................................. Itaconate Polymers ................................................................................................. Polydienes .............................................................................................................. Silicon Based Polymers .......................................................................................... Styrene Copolymers ...............................................................................................
xlvii VII/639 VII/640 VII/640 VII/641 VII/641 VII/642 VII/643 VII/644 VII/644 VII/644 VII/645 VII/645
C. References ......................................................................................................................... VII/646 Heat, Entropy and Volume Changes for Polymer-liquid Mixtures .............................................................. VII/649 A. Introduction ........................................................................................................................ VII/649 1. Scope of the Table .................................................................................................. VII/649 2. Experimental Methods ............................................................................................ VII/649 B. Key for the Tables .............................................................................................................. VII/650 C. Tables of Literature References for Heat, Entropy, and Volume Changes for Polymer-solvent Mixtures ................................................................................................... Table 1. Main-chain Carbon Polymers .................................................................................. 1.1 Poly(dienes) ............................................................................................ 1.2 Poly(alkenes) .......................................................................................... 1.3 Poly(acrylics) .......................................................................................... 1.4 Vinyl Polymers ........................................................................................ 1.5 Poly(styrenes) ......................................................................................... 1.6 Other Compounds .................................................................................. Table 2. Main-chain Carbon Heteroatom Polymers .............................................................. 2.1 Poly(oxides) and Poly(esters) ................................................................. 2.2 Poly(amides) ........................................................................................... 2.3 Poly(siloxanes) ....................................................................................... 2.4 Derivatives of Cellulose .......................................................................... 2.5 Other Compounds ..................................................................................
VII/650 VII/650 VII/650 VII/651 VII/654 VII/655 VII/657 VII/659 VII/659 VII/659 VII/661 VII/661 VII/662 VII/663
D. References ......................................................................................................................... VII/663 Heats of Solution of Some Common Polymers ........................................................................................... VII/671 A. Introduction ........................................................................................................................ VII/671 B. Table of Heats of Solution .................................................................................................. VII/671 C. References ......................................................................................................................... VII/673 Solubility Parameter Values ......................................................................................................................... VII/675 A. Introduction ........................................................................................................................ VII/675 B. Miscibility of Solvents and Polymers ................................................................................... VII/676 1. Cohesive Energy Density and the Solubility (Hildebrand) Parameter ..................... VII/676 This page has been reformatted by Knovel to provide easier navigation.
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Contents 2. 3.
Cohesive Energy Parameters for Polar Systems .................................................... VII/677 Relationship Between Solubility Parameters and Other Thermodynamic Parameters ............................................................................................................. VII/677
C. Solubility Parameter Measurements, Calculations, and Correlations .................................. 1. Solvents .................................................................................................................. 2. Polymers ................................................................................................................. 2.1 Indirect Measurements ........................................................................... 2.2 Correlation Methods ............................................................................... Table 1. Selected Solvents for Use in Polymer Solvency Testing ........................................ Table 2. Group Contribution to Cohesive Energy Density .................................................... 2.1 Carbon-containing Groups ...................................................................... 2.2 Oxygen-containing Groups ..................................................................... 2.3 Nitrogen-containing Groups .................................................................... 2.4 Other Groups .......................................................................................... 2.5 Structural Features ................................................................................. Table 3. Contribution to Ecoh and V ....................................................................................... Table 4. Solubility Parameter I: Component Group Contributions ........................................ Table 5. Solubility Parameter II: Component Group Contributions ....................................... Table 6. Equations to be Used for Hoy's System .................................................................
VII/679 VII/679 VII/680 VII/680 VII/682 VII/683 VII/684 VII/684 VII/684 VII/684 VII/684 VII/685 VII/685 VII/686 VII/686 VII/687
D. Solubility Table 7. Table 8. Table 9.
VII/688 VII/688 VII/694 VII/698 VII/698 VII/698 VII/698 VII/699 VII/699 VII/699 VII/699 VII/700 VII/700 VII/700 VII/700 VII/701 VII/701 VII/701 VII/701 VII/702 VII/702 VII/708 VII/709 VII/710
Parameter Tables ................................................................................................ Solubility Parameters of Solvents in Alphabetical Order ......................................... Solubility Parameters of Solvents in Increasing Order of δ ..................................... Hansen Solubility Parameters of Liquids at 25°C ................................................... 9.1 Paraffinic Hydrocarbons ......................................................................... 9.2 Aromatic Hydrocarbons .......................................................................... 9.3 Halohydrocarbons ................................................................................... 9.4 Ethers ..................................................................................................... 9.5 Ketones ................................................................................................... 9.6 Aldehydes ............................................................................................... 9.7 Esters ...................................................................................................... 9.8 Nitrogen-containing Compounds ............................................................ 9.9 Sulfur-containing Compounds ................................................................ 9.10 Acid Halides and Anhydrides .................................................................. 9.11 Alcohols .................................................................................................. 9.12 Acids ....................................................................................................... 9.13 Phenols ................................................................................................... 9.14 Water ...................................................................................................... 9.15 Polyhydric Alcohols ................................................................................. Table 10. Solubility Parameters of Polymers .......................................................................... 10.1 Main Chain Carbon Polymers ................................................................. 10.2 Main Chain C–O Polymers ..................................................................... 10.3 Main Chain C–N Polymers ..................................................................... 10.4 Other Polymers ....................................................................................... This page has been reformatted by Knovel to provide easier navigation.
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E. References ......................................................................................................................... VII/711 Optically Active Polymers ............................................................................................................................ VII/715 A. Abbreviations Used ............................................................................................................ VII/715 B. Optically Active Polymers from Chiral Monomers ............................................................... Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... 1.1 Poly(alkenes) .......................................................................................... 1.2 Poly(acrylics) and Related Polymers ...................................................... 1.3 Poly(methacrylics) and Related Polymers .............................................. 1.4 Poly(vinyl Ethers), Poly(vinyl Ketones), and Poly(vinyl Esters) .............. 1.5 Poly(styrenes), Poly(carbazoles) ............................................................ 1.6 Poly(dienes) ............................................................................................ 1.7 Poly(isonitriles) ....................................................................................... 1.8 Poly(alkynes) .......................................................................................... 1.9 Poly(maleimides) and Related Polymers ................................................ 1.10 Other Compounds .................................................................................. Table 2. Main-chain Acyclic Heteroatom Polymers .............................................................. 2.1 Poly(oxides) ............................................................................................ 2.2 Poly(esters) ............................................................................................. 2.3 Poly (sulfides), Poly(thioesters) .............................................................. 2.4 Poly(urethanes), Poly(ureas) .................................................................. 2.5 Poly(amides) ........................................................................................... 2.6 Poly(isocyanates) ................................................................................... 2.7 Poly(imines) ............................................................................................ 2.8 Poly(amino Acids) ................................................................................... Table 3. Poly(saccharides) ...................................................................................................
VII/716 VII/716 VII/716 VII/716 VII/717 VII/718 VII/719 VII/720 VII/720 VII/721 VII/722 VII/723 VII/723 VII/723 VII/724 VII/725 VII/725 VII/726 VII/728 VII/728 VII/729 VII/732
C. Optically Active Polymers from Achiral Monomers .............................................................. Table 4. Main-chain Acyclic Carbon Polymers ..................................................................... 4.1 Poly(acrylics) and Related Polymers ...................................................... 4.2 Poly(methacrylics) and Related Polymers .............................................. 4.3 Poly(vinyl Ethers) .................................................................................... 4.4 Poly(styrenes) ......................................................................................... 4.5 Poly(dienes) ............................................................................................ 4.6 Poly(isonitriles) ....................................................................................... 4.7 Poly(maleimides) .................................................................................... 4.8 Other Compounds .................................................................................. Table 5. Main-chain Acyclic Heteroatom Polymers .............................................................. 5.1 Poly(oxides) and Poly(sulfides) .............................................................. 5.2 Poly(isocyanates) ...................................................................................
VII/733 VII/733 VII/733 VII/734 VII/735 VII/735 VII/735 VII/736 VII/736 VII/737 VII/737 VII/737 VII/738
D. References ......................................................................................................................... VII/739 Anisotropy of Segments and Monomer Units of Polymer Molecules ......................................................... VII/745 A. Introduction ........................................................................................................................ VII/745
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l
Contents B. Tables of Anisotropy of Segments and Monomer Units of Polymer Molecules ................... Table 1. Main-chain Acyclic Carbon Polymers ..................................................................... 1.1 Poly(dienes) ............................................................................................ 1.2 Poly(alkenes) .......................................................................................... 1.3 Poly(acrylic Acid) and Derivatives .......................................................... 1.4 Poly(methacrylic Acid) and Derivatives .................................................. 1.5 Poly(acrylic Acid) Derivatives with Mesogenic Side Groups ................... 1.6 Poly(methacrylic Acid) Derivatives with Mesogenic Side Groups ........... 1.7 Vinyl Polymers ........................................................................................ 1.8 Poly(vinyl) Derivatives with Mesogenic Side Groups .............................. 1.9 Copolymers, Graft and Block Copolymers .............................................. Table 2. Main-chain Carbocyclic Polymers ........................................................................... Table 3. Main-chain Heteroatom Polymers ........................................................................... 3.1 Poly(oxides) ............................................................................................ 3.2 Poly(esters) ............................................................................................. 3.3 Poly(amides) ........................................................................................... 3.4 Poly(peptides) and Nucleic Acids ........................................................... 3.5 Poly(phosphazenes) ............................................................................... 3.6 Poly(siloxanes) ....................................................................................... Table 4. Main-chain Heterocyclic Polymers .......................................................................... 4.1 Poly(imides) ............................................................................................ 4.2 Poly(pyrromellitimides) ........................................................................... 4.3 Poly(quinoxalines) .................................................................................. 4.4 Poly(benzimidazoles), Poly(benzoxazoles) ............................................ 4.5 Poly(saccharides) ...................................................................................
VII/746 VII/746 VII/746 VII/747 VII/747 VII/748 VII/748 VII/749 VII/750 VII/751 VII/751 VII/752 VII/752 VII/752 VII/752 VII/755 VII/755 VII/755 VII/756 VII/756 VII/756 VII/756 VII/757 VII/757 VII/758
C. References ......................................................................................................................... VII/760 Gelation Properties of Polymer Solutions .................................................................................................... VII/765
VIII. Abbreviations of Polymer Names and Chemical Abstract Numbers Abbreviations for Thermoplastics, Thermosets, Fibers, Elastomers and Additives ...................................
VIII/1
A. Introduction ........................................................................................................................
VIII/1
B. Abbreviations in Alphabetical Order ....................................................................................
VIII/2
C. Abbreviations and Acronyms Based on Poly(monomer) Names ......................................... VIII/15 D. Abbreviations for Polymers Named after a Characteristic Polymer Croup .......................... VIII/17 E. Abbreviations for Polymers Produced by Chemical Transformation of Other Polymers ............................................................................................................................ VIII/18 F. Abbreviations for Blends, Reinforced Polymers, etc. .......................................................... VIII/19 G. ISO Codes for Thermoplastic Materials .............................................................................. 1. Codes for ISO Data Blocks 1-5 ............................................................................... 1.1 ISO and DIN Codes for Data Block 1 ..................................................... 1.2 ISO Codes for Items in Data Block 2 ...................................................... 1.3 ISO Codes for Items in Data Block 3 ......................................................
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VIII/19 VIII/19 VIII/19 VIII/20 VIII/20
Contents 1.4 1.5
li
ISO Codes for Extending and Reinforcing Fillers (Data Block 4) ........... VIII/20 ISO Codes for Data Block 5 .................................................................... VIII/21
H. SPI Codes for the Recycling of Plastics .............................................................................. VIII/21 I.
Recommended Abbreviations and Acronyms for Names of Elastomers ............................. VIII/21
J. Abbreviations for Textile Fibers .......................................................................................... VIII/22 Chemical Abstract Registry Numbers and Online Database Searching for Polymer Literature ................ VIII/25 A. Nomenclature ..................................................................................................................... VIII/25 B. CAS Registry Numbers ...................................................................................................... VIII/25 C. Indexing and CAS Registry Number Assignment ................................................................ VIII/26 D. Example Searches ............................................................................................................. 1. Example of a Search Using the Polymer CAS Registry Number ............................ 2. Example of a Search Using the Monomer CAS Registry Number .......................... 3. Example of a Combined Search ............................................................................. 4. Example of a Copolymer Search ............................................................................ 5. Example of an Engineering Database Search ........................................................ 6. Example of a Search with Punctuation in the Polymer Name ................................. 7. Example of an Engineering Materials Abstracts Search ......................................... 8. Example of a Polymer Trademark Search ..............................................................
VIII/26 VIII/26 VIII/26 VIII/26 VIII/28 VIII/29 VIII/29 VIII/29 VIII/29
E. List of CAS Regisry Numbers of Common Polymers .......................................................... VIII/32
Index .......................................................................................................................................
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W . V. Metanomski Chemical Abstracts Service, Columbus, Ohio, USA
A. Introduction B. IUPAC Recommendations 1. Source-Based Nomenclature 1.1. Homopolymers 1.2. Copolymers 1.3. Nonlinear Macromolecules & Macromolecular Assemblies 2. Structure-Based Nomenclature 2.1. Regular Single-Strand Organic Polymers 2.2. Regular Double-Strand Organic Polymers 2.3. Regular Single-Strand Inorganic and Coordination Polymers 2.4. Regular Quasi-Single-Strand Coordination Polymers 2.5. Irregular Single-Strand Organic Polymers C. Use of Common and Semisystematic Names D. Chemical Abstracts (CA) Index Names E. Polymer Class Names F. References A.
1-1 1-1 I-2 I-2 I-2 I-3 I-3 I-6 I-6 I-7 I-7 I-8 I-8 1-11 1-12
INTRODUCTION
Macromolecular (polymer) nomenclature has an almost 50-year history. As early as 1949 there existed a Subcommission on Nomenclature within the International Union of Pure and Applied Chemistry (IUPAC) under the chairmanship of Maurice L. Huggins. The Subcommission was part of the IUPAC Commission on Macromolecules, chaired then by Herman F. Mark. Other notable pioneers in polymer science, Jan Joseph Hermans, Otto Kratky, Harry W. Melville, and George J. Smets, were members of the Commission. The Subcommission produced its first official report in 1952. It recognized then, what is just as true today, that the practice in the field of small molecules of providing rigorous definitions is impractical for polymers. The latter consist of molecules not necessarily exactly of the same size, chemical composition, or structure. The differences result from the presence of end groups, branches, variation in orientation of monomeric units, and irregularity in the sequence of different types of units. The American Chemical Society (ACS) Division of Polymer Chemistry established its Nomenclature Commit-
tee in 1963 to try to unify earlier attempts to name polymers in some coherent way. Their first major project resulted in a structure-based nomenclature for regular linear polymers, first published in ACS Polymer Preprints in 1967, adopted by Chemical Abstracts in 1968, and incorporated in IUPAC recommendations in 1975 [I]. When the IUPAC Commission on Macromolecules was elevated to become the IUPAC Division of Macromolecular Chemistry, the latter in turn established its Commission on Macromolecular Nomenclature in 1968. The Commission in the course of its nearly 30 years of existence produced a series of major documents that have shaped modern nomenclature and terminology of polymer science. The recommendations are being published in the IUPAC official journal, Pure and Applied Chemistry, and occasionally are republished in the form of a "Compendium" which groups all the currently valid documents in a single volume. The Commission published its "Compendium of Macromolecular Nomenclature" in 1991 [2]. The book, which IUPAC has designated the "Purple Book", in analogy to other IUPAC books ("Blue" - organic, "Red" - inorganic, "Orange" - analytical, "Green"- physical, and "Gold" - overall chemistry), has the two most basic macromolecular nomenclature recommendations: "nomenclature of regular single-strand organic polymers" and "source-based nomenclature for copolymers". In more recent years, the Commission extended that basic nomenclature to double-strand (ladder and spiro) organic polymers, irregular and crosslinked polymers, and polymer blends and interpenetrating networks. In this article, the basic structure-based and source-based nomenclature of polymers is explained and illustrated in some detail. The continuing use of common and semisystematic nomenclature with reference to specific tables in this Handbook is highlighted. The current Chemical Abstracts (CA) index names [3] are compared and contrasted with the IUPAC practice and typical names employed in the polymer journals and textbooks. B.
IUPAC RECOMMENDATIONS
Since polymers, unlike low-molecular-weight compounds, have no uniform structure and are mixtures of macromolecules of different length and different structural
arrangement, their graphical representation and their names require a special approach. Often enough, the structure of the polymer has not been sufficiently characterized and the researcher cannot draw its chemical structure. Consequently, no name of the polymer reflecting its structure is possible. A polymerization reaction for a polymer formed from a monomer such as vinyl chloride can schematically be represented by
polybutadiene polyethylene poly(methyl methacrylate) poly(methyl vinyl ether) polystyrene poly(tetrafluoroethylene) poly(vinyl alcohol) poly(vinyl acetate) poly(vinyl chloride) poly(vinylidene dichloride)
That shows an idealized product. In fact, however, the polymer consists of long-chains of various lengths. The repeating units, - C H 2 - C H C l - , are not necessarily all uniquely oriented and joined in a regular fashion as shown in the idealized structure above. In addition to "head-totail" links
Parentheses are used when the name of the monomer consists of two or more words, and when the monomer has substituents. These are all olefinic type reactants, from which two carbon atoms originally linked by a double bond form a bivalent group:
other links such as "head-to-head"
where R and R [ represent a hydrogen atom or a substituent group. Many of these are joined, in turn, to each other but their exact orientation or sequence is seldom known. On the other hand, different polymers derived from a single monomer and having identical constitutional units can still be differentiated by additional information, such as average molecular weight and other chemical and physical characteristics.
and "tail-to-tail"
can occur, and the exact sequence of all these repeating units usually is not known. This becomes even more complicated when a copolymer is derived from more than one monomer, such as styrene and methyl acrylate, which contribute two constitutional or monomeric units:
They can combine into a polymeric chain, resulting in many types such as unspecified, statistical, random, alternating, periodic, block, or graft copolymers. Because the exact structure of the polymer is not always known, two systems of naming polymers exist: source-based nomenclature, structure-based nomenclature. 1.
Source-Based Nomenclature
1.1. Homopolymers Homopolymers are derived from only one species of monomer, which may be the actual starting reactant (or source), or be a hypothetical monomer if the homopolymer is formed by a modification of another homopolymer. The name of the polymer is formed by attaching the prefix "poly" to the name of the actual or assumed monomer, or the starting reactant (source), from which the polymer is derived. Examples: poly (acrylic acid) polyacrylonitrile
1.2. Copolymers For copolymers, the names of monomers are cited after the prefix "poly". In addition, an italicized connective (infix) is placed between the names of monomers to denote the kind of sequential arrangement by which the constitutional (monomeric) units, derived from each monomer, are related in the structure [4]. Seven types of sequence arrangements are listed with their corresponding connectives:
Type
Connective
unknown or unspecified statistical (obeying known statistical laws) random (obeying Bernoullian distribution) alternating (for two monomeric units) periodic (ordered sequence of more than two) block (linear arrangement of blocks) graft (side blocks chains connected to main chain)
Examples:
-co-stat-raft-alt-per-block-graft-
poly[styrene-C(?-(methyl methacrylate)! poly^tyrene-statf-acrylonitrile-statf-butadiene) poly[ethylene-ran-(vinyl acetate)] poly[(ethylene glycol)-tf/r-(terephthalic acid)] poly[formaldehyde-/?er-(ethylene oxide)-per(ethylene oxide)] polystyrene-&/oc&-polybutadiene polybutadiene-gra/f-polystyrene
The names of the monomers are those common or semisystematic names that are encountered most often in the literature of polymer science. The order of citation of monomers in copolymer names is arbitrary. An equally acceptable alternative scheme for naming copolymers utilizes the prefix "copoly", followed by citation of the names of the monomers, separated by an oblique stroke (a solidus). Parentheses are not needed to enclose monomer names consisting of two or more words. Examples:
the constituent macromolecules with an italicized connective between them. Examples:
copoly(styrene/methyl methacrylate) j"tatf-copoly(styrene/acrylonitrile/butadiene) ran-copoly(ethylene/vinyl acetate) a/f-copoly(ethylene glycol/terephthalic acid) per-copoly(formaldehyde/ethyleneoxide/ethylene oxide) Wtfc/:-copoly(styrene-butadiene) gra/£-copoly(butadiene-styrene)
1.3. Nonlinear Macromolecules and Macromolecular Assemblies Most recently, the source-based nomenclature has been extended for non-linear macromolecules and macromolecular assemblies [5], The non-linear macromolecules comprise branched, graft, comb, star, cyclic, and network macromolecules. The macromolecular assemblies comprise polymer blends, interpenetrating polymer networks, and polymer-polymer complexes. The following italicized qualifiers can be used as both prefixes (e.g., blend-, net-) and infixes (connectives) (e.g., -blend-, -net-) to designate the skeletal structure of nonlinear macromolecules or macromolecular assemblies:
Type cyclic branched, unspecified short-chain-branched long-chain-branched branched with branch point of functionality / comb star star with / arms network crosslink polymer blend interpenetrating polymer network semi-interpenetrating polymer network polymer-polymer complex
Connective cyclo branch sh-branch l-branch f-branch comb star f-star net t (Greek iota) blend ipn sipn compl
2.
poly styrene-com£>-poly aery lonitrile com&-poly(styrene~statf-acrylonitrile) poly styrene-comZ?- [poly acrylonitrile; poly(methyl methacrylate)] 4-sfar-polystyrene star-(po\yA-block-polyB-block-polyC) star-(polyA; polyB; polyC) star-(polyacrylonitrile; polystyrene) (M1 100000:20000) fte£-polystyrene-£-divinylbenzene n^-poly[styrene-<3/Kmaleic anhydride)]^-(ethylene glycol) polystyrene-Weftd-poly(2,6-dimethylphenol) poly(methyl methacrylate)-We?i(i-poly(tt-butyl acrylate) (net-polystyrene)-sipn-poly(vinyl chloride) [net-poly(styrenQ-stat-butSidiene]-ipn-[netpoly(ethyl acrylate)
Structure-Based Nomenclature
2.1. Regular Single-Strand Organic Polymers For regular organic polymers which have only one species of constitutional repeating unit (CRU) in a single sequential arrangement and consist of single strands only, the name is poly(constitutional repeating unit), wherein the repeating group is named as a bivalent organic group according to the IUPAC nomenclature rules for organic compounds [I]. Each such repeating group can consists of simple or substituted subunits such as: methylene ethylene vinylene hexane-l,6-diyl 1-chloroethylene 1 -oxopropane-1,3-diyl adipoyl 1,4-phenylene cyclohexane-1,4-diyl oxy thio sulfonyl imino methylimino hydrazo piperidine-1,4-diyl
In naming non-linear homopolymer molecules, the italicized prefix for the skeletal structure of the macromolecule is placed before the source-based name of the constituent linear chain. Assemblies of macromolecules held together by noncovalent bonds are named by a combination of the names of
silanediyl dimethylsilanediyl Before the total constitutional repeating unit (CRU) can be given a unique name, a single preferred CRU must be selected. References page 1-12
For instance, in a polymer such as
it is immediately evident that a three-atom group (oxygen, chlorine-substituted methylene group, and methylene group) are being regularly repeated. Yet, the CRU can be identified in at least three ways
d. for carbon-only acyclic chains, seniority is determined first by length, then by the number of substituents, by the ascending order of locants, and, finally, by the alphabetical order of the names of the substituent groups.
c. carbocycles, e.g., 1,4-phenylene:
In all cases, the basic seniority rules apply only to those atoms or groups of atoms that are in the main chain. The kinds of substituents on the main chain (whether acyclic carbon-only groups, or hetero-atom-containing groups, or any ring systems) do not affect the selection of the CRU, unless identical basic subunits in the chain have to be further differentiated by the number of substituents and their alphabetical order, but not by the type of the substituent. If completely identical subunits are separated by other subunits, the direction of citation is determined by the shorter part between them. The preferred CRU is the one beginning with the subunit of highest seniority. To establish direction, one proceeds from this subunit to the neighboring subunit of the same or next in seniority. In the example of a poly(chloroethylene oxide), shown above, where a regularly repeating structure has been assumed, the subunit of the highest seniority is the oxygen atom and the subunit next in seniority is a substituted - C H 2 - C H 2 - . The substituted subunit, - C H C l - C H 2 - , is oriented in such a way that the substituent, chlorine atom, is assigned the lowest locant (1 rather than 2). The CRU is written to read from left to right. Thus, the preferred CRU is
cyclobutane-1,3-diyl: d. carbon-containing acyclic groups, e.g., 1-chloroethylene: - C H C l - C H 2 propane-1,3-diyl: - C H 2 - C H 2 - C H 2 -
and the polymer
To obtain a unique name based on a preferred CRU, several rules have to be applied. Rules have been developed to specify both seniority among subunits, that is, the point at which to begin writing the CRU, and also the direction in which to move along the chain from left to right to reach the end of the chain. The order of seniority among the types of bivalent groups that are parts of the chain of a single-strand polymer is a.
heterocycles, e.g., piperidine-l,4-diyl: thiophene-2,5-diyl:
b. heteroatomic acyclic groups, e.g., oxy: - O - , sulfonyl: - S O 2 - , imino: - N H -
Within each structural type, the seniority is established by further criteria: a.
for heterocycles, a ring system containing nitrogen is senior to a system containing a hetero atom other than nitrogen, with further descending order of seniority governed by the greatest number of rings in the ring system, the largest individual ring in the ring system, the largest number of hetero atoms, and the greatest variety of hetero atoms; b. for heteroatomic acyclic chains, oxygen is senior to sulfur, sulfur to nitrogen, nitrogen to phosphorus, phosphorus to silicon, silicon to germanium, etc.; c. for carbocycles, a three-ring system is senior to a two-ring system, a two-ring system containing two 6-membered rings is senior to one containing a 5and a 6-membered rings, a fused two-ring system (two atoms common to both rings) is senior to a spiro two-ring system (one atom in common), and an unsaturated ring is senior to a saturated ring of the same size;
is named poly [oxy (1 -chloroethylene)] The second example:
poly [(methylimino)methyleneimino-1,3-phenylene] illustrates a polymer whose CRU starts with a substituted nitrogen atom and proceeds through the shortest path to the unsubstituted nitrogen atom and then through a carbocycle. The chemical structure of the CRU is enclosed in parentheses or brackets. While dashes representing chemical bonds may be omitted within the formula unless necessary for clarity, at the ends of the CRU, dashes must be shown. They are drawn across the enclosing marks.
symbol a denoting the left-hand end group and the symbol co denoting the other end group.
The third example:
Example: poly(pyridine-3,5-diylcarbonyloxymethylene) shows a polymer, whose CRU starts with a heterocycle and then proceeds through a substituted carbon atom to a hetero atom. If the end groups of the chain are known, they may be specified by adding prefixes to the polymer name, with the
Structure
a-(trichloromethyl)-co-chloropoly (1,4-phenylenemethylene) The following table compares and contrasts structurebased and source-based names of some common polymers.
Structure-based name
Source-based or trivial name
Poly(methylene) Poly(propylene)
Polyethylene Polypropene
Poly (1,1 -dimethylethylene) Poly (1 -methyl-1 -butenylene)
Polyisobutylene Polyisoprene
Poly (1 -phenylethylene)
Polystyrene
PoIy(I -chloroethylene)
Poly(vinyl chloride)
Poly (1 -cyanoethylene)
Poly aery lonitrile
PoIy(I-acetoxyethylene)
Poly(vinyl acetate)
PoIy(1,1-difluoroethylene) Poly(difluoromethylene)
Poly(vinylidene fluoride) Polytetrafluoroethylene
Poly[(2-propyl-1,3-dioxane-4,6-diyl)methylene]
Poly(vinyl butyral)
Poly[ 1 -(methoxycarbonyl)-1 -methylethylene]
Poly(methyl methacrylate)
Poly(oxyethylene)
Poly(ethylene oxide)
Poly(oxy-1,4-phenylene)
Poly(phenylene oxide)
Poly[imino(l-oxohexane-1,6-diyl)]
Poly(e-caprolactam)
Poly(oxyethyleneoxyterephthaloyl)
Poly(ethylene terephthalate)
Poly(iminoadipoyliminohexamethylene)
Poly(hexamethylenediamine-a/?-adipic acid) or poly(hexamethylene adipamide) Poly(maleic anhydride-a/r-styrene)
Poly[(2,5-dioxotetrahydrofuran-3,4-diyl)( 1 -phenylethylene)]
References page 1-12
2.2. Regular Double-Strand Organic Polymers In a double-strand polymer, the macromolecules consist of an uninterrupted sequence of rings with adjacent rings having two or more atoms in common (a ladder polymer) or one atom in common (a spiro polymer). As for a single-strand polymer, a single preferred constitutional repeating unit (CRU) must be selected in order to obtain a unique name [6]. The CRU is usually a tetravalent group denoting attachment to four atoms and is named according to the usual rules of organic nomenclature. Again, the name of the polymer is in the form of
common at each junction:
the name based on the preferred CRU is
poly(constitutional repeating unit) Since the polymer has a sequence of rings, in order to identify a preferred CRU, the rings must be broken by observing the following criteria in decreasing order of priority: a. minimize the number of free valences in the CRU, b. maximize the number of most preferred hetero atoms in the ring system, c. retain the most preferred ring system, and d. choose the longest chain for acyclic CRU. Further decisions are based on the seniority of ring systems (indicated in the preceding section), on the orientation of the CRU to give the lowest free valence locant at the lower left of the structural diagram, and on placing the acyclic subunits, if any, on the right side of the ring system within the CRU. For a polymer consisting of adjacent 6-membered saturated carbon rings:
the name of the preferred CRU, which in this case is an acyclic chain of four carbon atoms with four free valences at each atom (the lowest at the lower left), is
poly (butane-1,4: 3,2-tetrayl)
poly(l,4-dithiin-2,3:5,6-tetrayl-5,6-dicarbonyl) Here, by applying the seniority of the rings system, the heterocycle was left intact, but the carbocycle was broken. That left two bivalent acyclic subunits (carbonyl groups), which according to the rule, have been placed on the right side of the cyclic subunit, with attachments as in the original polymer. Another, still more complex ladder polymer, derived from the polycondensation of 1,4,5,8-naphthalenetetracarboxylic dianhydride with 1,2,4,5-benzenetetramine:
poly[(7-oxo-7//,10//-benz[
the preferred CRU and the name are:
The free valence locants are always placed just in front of the corresponding ending of the tetravalent unit and are cited in the order lower-left, upper-left: upper-right, lower-right that is, in a clockwise direction, the left locants being separated from the right locants by a colon. For a more complex ladder polymer consisting of an alternating sequence of 6-membered sulfur-containing rings and keto-group containing carbocycles, with two atoms in
poly(2,4,8,10-tetraoxaspiro[5.5]undecane-3,3:9,9-tetrayl-9,9-diethylene)
2.3. Regular Single-Strand Inorganic and Coordination Polymers The names of inorganic and coordination polymers are based on the fundamentals developed for organic polymers [7]. As in the nomenclature of organic polymers, these rules apply to structural representations
which may at times be idealized and do not take into account irregularities, chain imperfections, or random branching. A constitutional repeating unit (CRU) is selected and named. However, because of the basic difference between the organic and inorganic nomenclature, the subunits of the CRU are not named as bivalent groups, but as inorganic or coordination groups indicating covalent and/or coordinate bonding. The name of the polymer is the name of the CRU prefixed by the term "poly", "catena", or other structural indicator. In order to arrive at the preferred CRU, seniorities of the constitutent subunits are considered as well as the preferred direction for the sequential citation. The constituent subunit of the highest seniority must contain one or more central atoms; bridging groups between central atoms in the backbone of the polymer are of lower seniority. This is consistent with the principle of coordination nomenclature which puts the emphasis on the coordination center. Examples of homoatomic backbones are
catena-poly [dimethyltin]
caterca-poly[(difluorosilicon) (dimethylsilicon)]
More common coordination polymers consist of a mononuclear central atom with a bridging ligand. The CRU of such a polymer cites the central atom first, which is prefixed by its associated non-bridging ligands, followed in turn by the name of the bridging ligand prefixed by the Greek letter \i:
2.4. Regular Quasi-Single-Strand Coordination Polymers In a regular quasi-single-strand coordination polymer, the preferred CRU has one terminal constituent subunit connected through a single atom to the next CRU [7]. Such polymers are named as single-strand coordination polymers:
catena-poly [palladiumdi-u-chloro]
catena-polyfsilicondi-u-thio]
catena-poly[platinum(ubromo-u-chloro)]
catena-poly [titaniumtri-u-chloro]
2.5. Irregular Single-Strand Organic Polymers Irregular polymers are named by placing the prefix "poly" before the structure-based names of the constitutional units, collectively enclosed in parentheses or brackets, with the individual constitutional units separated by an oblique stroke (a solidus) [8]. The stroke indicates the irregular or unknown sequential arrangement of these units. The dashes at each end of the formula are drawn fully inside the enclosing marks to denote that these are not necessarily terminal bonds of the macromolecule. For instance, a partially hydrolyzed poly(vinyl acetate) containing units:
is represented graphically and named:
catena-poly [(amminechlorozinc)-u-chloro]
catena-pory[(dihydroboron)-ju-(dimethylamido)] poly( 1 -acetoxyethylene/1 -hydroxyethylene)
Multiple bridging ligands between the pair of central atoms are cited in alphabetic order. Italicized element symbols indicating the coordinating atoms in bridging ligands are cited in the order of direction of the CRU and are separated by a colon:
A copolymer of vinyl chloride and styrene joined head-totail is
poly (1 -chloroethy lene/1 -pheny lethylene) A chlorinated polyethylene consisting of units
catena-poly [copper-[|i-chloro-bis-u-(diethyl S')] -copper- u-chloro]
disulfide-S: References page 1-12
is shown and named as
poly(chloromethylene/dichloromethylene/methylene) C.
USE OF COMMON AND SEMISYSTEMATIC NAMES
The main purpose of chemical nomenclature is to identify a chemical species by means of written or spoken words for a useful communication among chemists. A systematic nomenclature arose from the need to provide a relationship between the structure and the name. In other words, the reader should be able to deduce and identify the structure from the name. Traditional names, however, not necessarily based on structures, have been widely used for many common compounds. These are the so-called common, trivial, or semisystematic names, which are satisfactory for communication within a given special chemical field. It was earlier stated that in the macromolecular nomenclature IUPAC is recommending the use of common and semisystematic names for monomers in the sourcebased polymer names. The structure-based names, on the other hand, are more related to the structural characteristic of the polymers. But even there, IUPAC allows for a limited number of common names for such substituent groups as "allyl" and "vinyl", and for bivalent groups such as "adipoyl" and "terephthaloyl". The authors in this Handbook for the most part are using the IUPAC-recommended names, or very close variants thereof. On the other hand, in some compilations such as "Crystallographic Data for Various Polymers" (in Section VI), the author provides an excellent introduction and explanation of the names used. For some structure-based names, reflecting constitutional repeating units (CRU), especially for those with a center of symmetry, the naming of linking bivalent groups begins with the central subunit and proceeds in both directions. The IUPAC method selects the most senior bivalent group and proceeds naming from left to right.
In no case, there is any misunderstanding in either case as to which structure is associated with each name. Abbreviations and acronyms are also extensively used in the chemical literature for monomers, polymers, as well as for additives, modifiers, and fillers. Their extensive list is provided in Section VIII of this Handbook. As is clearly stated there, the same abbreviation is often used for different monomers and polymers, and the same polymer may have different abbreviations or acronyms. Examples: 1. DPP 2. PVA 3. trioctyl phosphate 4. polyacrylonitrile
diphenyl phthalate dipropyl phthalate poly(vinyl alcohol) poly(vinyl acetate) TOF TOP PAC PAN
The IUPAC policy [9] on the use of abbreviations in the chemical literature states that there are great advantages in defining all abbreviations in a single conspicuous place in each paper, preferably near the beginning of the paper in a single list. An alternative is to define each abbreviation fully the first time it appears in the text. No abbreviations should be used in the titles of publications. A chapter of this Handbook contains a set of abbreviations recognized by international organizations. D.
CHEMICAL ABSTRACTS (CA) INDEX NAMES
Chemical Abstracts Service (CAS), the publisher of printed Chemical Abstracts (CA) and corresponding products and services in microform, online databases, CD-ROM, and World Wide Web also names the polymers, selected for inclusion in the CAS Chemical Registry System and in the CA Chemical Substance Indexes, in two ways: a.
Examples:
Handbook name: poly(4,4'-sulfonyldiphenylene carbonate) IUPAC name: poly(oxycarbonyloxy-l,4-phenylenesulfonyl-1,4-phenylene) 2.
Handbook name: poly (oxy die thy lene succinate) IUPAC name: poly(oxyethyleneoxyethyleneoxysuccinyl)
in terms of the component monomer(s) from which they are prepared b. in terms of the final structure of the resulting polymer. There are definitive rules that govern when each type of structure is recorded and named [3], The primary, comprehensive representation of polymers by CAS is by citation of the component monomer(s) because, in many cases, the structure of the final polymer is either not known or is not described in sufficient detail by the author. When the polymer structure is well documented by the author or can be confidently assumed, because one and only one structure is chemically possible, then a supplementary representation with a corresponding systematic name is added to the CAS Registry System and included in the printed indexes and online files.
The chemical nomenclature used by CAS has developed in parallel, and generally in accordance, with the rules and recommendations published by IUPAC. However, their rules of systematic nomenclature do not necessarily lead to a unique name for each compound, but do lead to an unambiguous one. This causes no difficulty in normal scientific communication, but is unacceptable in a formal, rigidly controlled, alphabetic listing such as the CA Chemical Substance Index. The CA index names must not only be unambiguous, unique, and totally reproducible, but also selected so as to bring the names of structurally related substances into juxtaposition in the alphabetic index. CAS has always recognized that, while a unique name is needed for an index and for substance identification, the use of such invariant name in scientific papers is neither practicable nor desirable. In this section, it is intended to highlight the characteristics of the CA index names for polymers and compare them with some of the typical names used in the scientific community. a. b.
c. d.
e.
IUPAC rules have been adapted to the specific needs of a highly ordered alphabetical index. Most common names were eliminated and exceptional treatment for various classes of substances was discontinued. A single preferred name is determined for each identifiable substance. A strict order of precedence of chemical functions and compound classes is followed to determine the preferred "index heading parent". A total name is "inverted" by citing first the index heading parent (usually, basic skeleton name with a locant and suffix denoting the principal function), followed by the comma of inversion, the substituents, and the modification (derivative of the principal function), e.g., 2-propenoic acid, 2-methyl-, methyl ester
As mentioned above, most common names, including those still sanctioned by IUPAC, have been replaced by fully systematic names. The following is a short list of most common monomers with both common names and CA Index names: Common acrylamide acrylic acid acrylonitrile adipic acid 8-caprolactam 8-caprolactone ethylene glycol ethylene oxide fumaric acid
CA Index names (inverted form) 2-propenamide 2-propenoic acid 2-propenamide hexanedioic acid 2//-azepin-2-one, hexahydro2-oxepanone 1,2-ethanediol oxirane 2-butenedioic acid, (E)-
glycolic acid hydroquinone isophthalic acid lactic acid maleic acid maleic anhydride melamine methacrylic acid methyl acrylate phthalic anhydride propylene oxide styrene terephthalic acid vinyl alcohol vinyl chloride vinylidene chloride
acetic acid, hydroxy1,4-benzenediol 1,3-benzenedicarboxylic acid propanoic acid, 2-hydroxy2-butenedioic acid, (Z)2,5-furandione 1,3,5-triazine-2,4,6-triamine 2-propenoic acid, 2-methyl2-propenoic acid, methyl ester 1,3-isobenzofurandione oxirane, methylbenzene, ethenyl1,4-benzenedicarboxylic acid ethenol ethene, chloroethene, 1,1-dichloro-
Similarly, commonly named substituent and multiplying groups have their systematic equivalents in CA Indexes: adipoyl allyl tert-butyl ethylene hexamethylene isopropyl succinyl vinyl vinylene
1,6-dioxo-1,6-hexanediyl 2-propenyl 1,1 -dimethylethyl 1,2-ethanediyl 1,6-hexanediyl 1-methylethyl 1,4-dioxo-1,4-butanediyl ethenyl 1,2-ethenediyl
Homopolymers are described by the term "homopolymer" cited in the modification under the monomer name in the index. In the structural diagram derived from the CAS Registry System records, the structure of the monomer is enclosed in parentheses followed by a subscript "x". The corresponding empirical formula is also expressed in a similar way. Examples: 1. Poly (methacrylic acid): (CH 2 =CH-COOH) x CH3 (C 4 H 6 O 2 ), CA name: 2-Propenoic acid, 2-methyl-, homopolymer 2. Polystyrene: (CH2=CH)x C6H5 (C 8 H 8 ), CA name: Benzene, ethenyl-, homopolymer 3. PoIy(11-aminoundecanoic acid): (H 2 N-(CH 2 )Io-COOH), (C 11 H 23 NO 2 ), CA name: Undecanoic acid, 11-amino-, homopolymer References page 1-12
4. Poly (lac tic acid): (CH3-CH-COOH)x OH (C3H6O3)* CA name: Propanoic acid, 2-hydroxy-, homopolymer Copolymers formed from two or more monomers are described by the term "polymer with" (followed by the other monomers in alphabetical order) cited in the modification under each monomer name. In the structural diagram derived from the CAS Registry System records, the structures of monomers, separated by a period or periods, are enclosed in parentheses followed by a subscript ' V . The corresponding empirical formulas are similarly expressed. The descriptors alternating, block, and graft are cited whenever applicable. Examples: 1. Butadiene-vinyl ethyl ether copolymer: (CH2=CH-CH=CH2•CH2=CH-O-CH2CH3)X (C4H8OC4H6)Jt (in Formula Index order) CA names: 1,3-Butadiene, polymer with ethoxyethene Ethene, ethoxy-, polymer with 1,3butadiene 2. Isophthalic acid-terephthalic acid-ethylene glycol polyester: (HOOC-m-C6H4-COOHHOOC-p-C6H4-COOHOH-(CH2)2-OH)X (C 8 H 6 O 4 C 8 H 6 O 4 C 2 H 6 O 2 ), CA names: 1,3-Benzenedicarboxylic acid, polymer with 1,4-benzenedicarboxylic acid and 1,2-ethanediol 1,4-Benzenedicarboxylic acid, polymer with 1,3-benzenedicarboxylic acid and 1,2-ethanediol 1,2-Ethanediol, polymer with 1,3-benzenedicarboxylic acid and 1,4-benzenedicarboxylic acid Telomers are named as copolymers with the term "telomer with" cited in the modification under both the monomer (taxogen) and the chain-transfer agent (telogen). In the structural representation, the monomer is enclosed in parentheses with a subscript "*", followed by the telogen structure. The corresponding empirical formula is expressed in the same way. Examples: 1. Vinylpyrrolidone homopolymer terminated with mercaptopropionic acid:
CA names: 2-Pyrrolidinone, 1-ethenyl-, telomer with 3-mercaptopropanoic acid Propanoic acid, 3-mercapto-, telomer with l-ethenyl-2-pyrrolidinone 2. Acrylic acid-vinyl choride copolymer terminated with carbon tetrachloride: (CH 2 =CH-COOH-CI-CH=CH 2 )X-CCI 4
(C3H4O2C2H3Cl)xCCl4 CA names: 2-Propenoic acid, telomer with chloroethene and tetrachloromethane Ethene, chloro-, telomer with 2-propenoic acid and tetrachloromethane Methane, tetrachloro-, telomer with chloroethene and 2-propenoic acid Structural repeating units (SRU), equivalent to IUPAC constitutional repeating units (CRU), are selected and named for polymers that have well documented regular structure, or can confidently be assumed. Assumptions are made for a. polyamides formed from a dibasic acid (ester or halide) and a diamine; from an amino acid (ester or halide); from a lactam; b. polyesters formed from a dibasic acid (anhydride, ester, or halide) and a dihydric alcohol (phenol); from a hydroxy acid (ester, halide); from a lactone; c. polycarbonates formed from carbonic acid (ester, dihalide) and a dihydric alcohol (phenol); d. polyurethanes formed from a diisocyanate and a dihydric alcohol (phenol). The structural repeating unit is named by citation of one or more multivalent radicals of regular substitutive nomenclature. The selection of the preferred SRU, its orientation, and the construction of the name, proceeding from left to right, follows the same rules as those in the IUPAC recommendations for the CRU. In CA names, however, the names of the radicals are fully systematic, as explained and contrasted above. The empirical formula is enclosed in parentheses followed by a subscript "n". Examples: 1. Nylon 11:
CA name: Poly[imino(l-oxo-l,ll-undecanediyl)] 2. Poly(ethylene adipate):
CA name: Poly[oxy-1,2-ethanediyloxy(1,6-dioxo1,6-hexanediyl)]
3. Poly (ether ether ketone) (PEEK):
CA name: Poly(oxy-1,4-phenyleneoxy-1,4-phenylenecarbonyl-1,4-phenylene) Poly(alkylene glycols) and their ethers and esters are indexed in CA as structural repeating units with the specified end groups, if aplicable. Examples: 1. Poly(ethylene glycol): HfO-CH 2 -CH 2 ^ n OH CA name: Poly(oxy-l,2-ethanediyl), a-hydroco-hydroxy2. Poly(trimethylene glycol) dimethyl ether: CH3 4 0 - C H 2 - C H 2 - C H 2 ^ O - C H 3 CA name: Poly(oxy-1, 3-propanediyl), a-methylco-methoxy3. Poly(tetramethylene glycol) diacrylate: CH2=CH-C(O) 40-CH 2 -CH 2 -CH 2 -CH 2 ^ n 0-C(O)-CH=CH 2 CA name: Poly(oxy-1, 4-butanediyl), a-(l-oxo2-propenyl)-co- [(1 -oxo-2-propenyl)oxy ] E. POLYMER CLASS NAMES In most textbooks, handbooks, encyclopedias, and indexes to polymer nomenclature, information on polymer is grouped under polymer class names. The following is a list of such terms extracted from these sources. Acrylic Polymers Alkyd resins Aminoplasts Coumarone-indene-resins Epoxy resins Fluoropolymers Phenolic resins Polyacetals Polyacetylenes Polyacrylics Polyalkylenes Polyalkenylenes Polyalkynylenes Polyamic acids Polyamides Polyamines Polyanhydrides Polyarylenealkenylenes Polyarylenealkylenes Polyarylenes Polyazomethines
Polybenzimidazoles Polybenzothiazoles Polybenzoxazinones Polybenzoxazoles Polybenzyls Polycarbodiimides Polycarbonates Polycarboranes Polycarbosilanes Polycyanurates Polydienes Polyester-polyurethanes Polyesters Polyetheretherketones Polyether-polyurethanes Polyethers Polyhydrazides Polyimidazoles Polyimides Polyimines Polyisocyanurates Polyketones Polyolefins Polyoxadiazoles Polyoxides Polyoxyalkylenes Polyoxyarylenes Polyoxymethylenes Polyoxyphenylenes Polyphenyls Polyphosphazenes Polypyrroles Polypyrrones Polyquinolines Polyquinoxalines Polysilanes Polysilazanes Polysiloxanes Polysilsesquioxanes Polysulfides Polysulfonamides Polysulfones Polythiazoles Polythioalkylenes Polythioarylenes Polythioethers Polythiomethylenes Polythiophenylenes Polyureas Polyurethanes Polyvinyl acetals Polyvinyl butyrals Polyvinyl formals Vinyl polymers
These classes are not mutually exclusive, some are relatively generic and some more specific. Some of them References page 1-12
could be grouped and arranged in a hierarchy, e.g., Polyacetals Polyvinyl acetals polyvinyl butyrals polyvinyl formals Polyesters polycarbonates
Polyethers epoxy resins polyetheretherketones polyoxyalkylenes polyoxymethylenes polyoxyarylenes polyoxyphenylenes
Some are synonymous or near synonymous, e.g., polyalkenylenes and polydienes, polyalkynylenes and polyacetylenes, polyethers and polyoxides, polythioethers and polysulfides. F. REFERENCES 1. IUPAC, "Nomenclature of Regular Single-Strand Organic Polymers (Recommendations 1975)", Pure Appl. Chem. 48, 373 (1976). Reprinted as Chapter 5 in Ref. 2. 2. IUPAC, "Compendium of Macromolecular Nomenclature". W. V. Metanomski, (Ed.), Blackwell Scientific, Oxford, 1991.
3. Chemical Abstracts Service, "CA Index Guide 1997", Appendix IV, "Chemical Substance Index Names", Chemical Abstracts Service, Columbus, Ohio, 1997. 4. IUPAC, "Source-Based Nomenclature for Copolymers (Recommendations 1985)", Pure Appl. Chem. 57, 1427 (1985). Reprinted as Chapter 7 in Ref. 2. 5. IUPAC, "Source-Based Nomenclature for Non-Linear Macromolecules and Macromolecular Assemblies (Recommendations 1997)", Pure Appl. Chem. 69, 2511 (1997). 6. IUPAC, "Nomenclature of Regular Double-Strand (Ladder and Spiro) Organic Polymers (Recommendations 1993)", Pure Appl. Chem. 65, 1561 (1993). 7. IUPAC, "Nomenclature for Regular Single-Strand and Quasi-Single-Strand Inorganic and Coordination Polymers (Recommendations 1984)", Pure Appl. Chem. 57, 149 (1985). Reprinted as Chapter 6 in Ref. 2. 8. IUPAC, "Structure-Based Nomenclature for Irregular Single-Strand Polymers (Recommendations 1994)", Pure Appl. Chem. 66, 873 (1994). 9. IUPAC, "Use of Abbreviations in the Chemical Literature (Recommendations 1979)", Pure Appl. Chem. 52, 2229 (1980).
U n i t s J. Brandrup Wiesbaden, FR Germany
A. B. C. D. E.
A.
Introduction International Units Si-Prefixes Conversion Factors Conversion Table for SI vs. English-American Units
1-13 1-13 1-14 1-14 1-17
INTRODUCTION
The International System of Units (1) is used in this Handbook as far as possible, since this system has become obligatory in many European countries and since it is supported by the National Bureau of Standards (2) and the American Society for Testing and Materials (3). Only
cursory information is given here for units needed in this Handbook. Detailed information may be found in the following References: 1. "Si-units and recommendations for the use of their multiples and of certain other units'', ISO 1000-1973. 2. "The International System of Units (SI)", Eds. C. H. Page, P. Vigoreux, Natl. Bur. Std. Spec. Publ., 1981, 330. 3. "Standard Metric Practice Guide", ASTM E-380-85. 4. Manual of Symbols and Terminology for Physicochemical Quantities and Units; Pergamon Press, Oxford 1979 (Pure Appl. Chem., 51, 1 (1979). 5. F. S. Conant, using the SI units, Polym. Eng. ScL, 17, 222 (1977) (further references).
B. INTERNATIONAL UNITS Selection of multiples of the Si-unit
Quantity
Si-unit
Length Area Volume Time Frequency Mass Density Force
m (metre) m2 m3 s (second) Hz (hertz) kg (kilogram) kg/m3 N (newton)
km, cm, mm, jum, nm km2, dm2, cm2, mm2 dm3, cm3, mm3 ks, ms, us, ns THz, GHz, MHz, kHz Mg, g, mg, jag mg/m3; kg/dm3; g/cm3 MN, kN, mN, uN
Pressure
Pa (pascal) or N/m2
GPa, MPa, kPa, mPa, uPa
Stress Viscosity (dynamic) Viscosity (kinematic) Surface tension Energy, work, heat
Pa or N/m2 Pas m2/s N/m J (joule)
Power Temperature Thermal conductivity Heat capacity Specific heat Entropy Amount of substance Electrical resistance Electrical conductivity
W (watt) K (kelvin), 0C W/mK J/K J/(kgK) J/K mol (mole) ft S (I/ft)
GPa; MPa or N/mm2; kPa mPas mm2/s mN/m TJ, GJ, MJ, kJ, mJ GW, MW, kW, mW, uW
Accepted units used with SI
Units accepted temporarily 1A = 10 ~10 m
Non SI units that should not be used 1 JJ. = 10 ~6 m
litre (1, L) (1 1= 1 dm3) d, h, min Iy= 10 ~9 kg
t t/m3; kg/1 1 bar = 105 Pa 1 atm = 101325 Pa
Electronvolt (eV) IeV«1.602 x 10" 19 J
1 dyn = 10 ~5 N; pond, kilopond 101325 1 Torr = Pa /OU = 133.32Pa poise; 1P = 0.1 Pas stokes; 1 St= 1 cm2/s dyn/cm lerg=10~ 7 J lcal = 4.1868J I0K=IK 0.86kcal/(mhgrd)
kJ/K kJ/(kgK) kJ/K Mole
1/13
C
SI-PREFIXES
Factor
Prefix
Symbol
Factor
Prefix
Symbol
10 18 10 15 10 12 10 9 10 6 10 3 10 2 10 l
exa peta tera giga mega kilo hecto deca
E P T G M k h da
10 ~l 10 ~2 10 ~3 10 " 6 10 ~9 10 " 1 2 10 ~15 10 ~18
deci centi milli micro nano pico femto atto
d c m \i n p f a
in
ft
yd
thou or mil
3.281 8.333 x 10~2 1 3 8.334 xlO~ 5
1.094 2.778 x 10~2 3.333XlO" 1 1 2.778 x 10" 5
3.937 x 104 1.0 x l O 3 1.2 x 104 3.6 x 104 1
D.
CONVERSION FACTORS
Length
m
Im in ft yd thou or mil
1 2.540 xlO~ 2 3.048XlO- 1 9.144X10" 1 2.540 xlO~ 5
Area
m2
Im2 sq. in sq. ft sq. yd ar
1 6.452 x 10 ~4 9.29OxIO" 2 8.361 x KT 1 1.0 x l O 2
Volume
m3
1 m3 1 (lit) cu. in cu. ft cu. yd gal (US) gal (UK)
Mass lkg lbm ton (metric) ton (UK) cwt (UK) ton (US) ounce grain Density lkg/m 3 Mg/m 3 =g/cm 3 lbm/cu. ft lbm/cu. in lbm/gal (UK) lbm/gal (US)
3.937XlO 1 1 12 36 1.0 x l O " 3 sq. in 1.55OxIO3 1 1.44OxIO2 1.296 x 103 1.55OxIO5 1 (lit)
1 10~3 1.639 x 10 ~5 2.832 x 10~2 7.646XlO" 1 3.785 x 10~3 4.546 xlO~ 3
sq. ft
103 1 1.639 x 10 ~2 2.832 x 101 7.645 x 102 3.785 4.546
kg
lbm
1 4.536 x 10" 1 1 x 103 1.016 x l O 3 5.080 x 101 9.072 x 102 2.835 x 10~2 6.480 x 10 " 5
2.205 1 2.205 x 103 2.24OxIO 3 1.120 x 102 2.0 x 103 6.250 x 10~2 1.429 x 10 ~8
kg/m3 1 1.OxIO3 1.602 x 101 2.768 x 104 9.978XlO 1 1.198 x 102
1.076XlO1 6.994 x 10 ~3 1 9 1.076 x 103
sq. yd
ar
1.196 7.716 x 10 ~4 1.111 x 10" 1 1 1.196 x l O 2
l.OxlO" 2 6.452 x 10 ~6 9.29OxIO" 4 8.361 x 10" 3 1
cu. in
cu. ft
cu. yd
gal (US)
gal (UK)
6.102 x 104 6.102 x 101 1 1.728 x 103 4.666 x 104 2.31OxIO2 2.774 x 102
3.531 x 10l 3.531 x 10~2 5.787 x 10 ~4 1 2JxIO1 1.337 xlO" 1 1.605 x 10 - 1
1.308 1.308 x 10~3 2.143 x 10~5 3.703 x 10" 2 1 4.951 x 10~3 5.946 x 10~3
2.642 x 102 2.642 x 10" 1 4.329 x 10 ~3 7.481 2.02OxIO2 1 1.201
2.20 x 102 2.20 x 10" 1 3.605 x 10~3 6.229 1.682 xlO 2 8.327 x 10"1 1
ton (UK) (long ton) 9.842xlO~ 4 4.464 x 10~4 9.842XlO" 1 1 5.0 x 10~2 8.929 x 10" 1 2.790 x 10~5 6.378 x 10 ~8
Mg/m3 = g/cm3 1.0 XlO" 3 1 1.602 x 10" 2 2.768 x 101 9.978 x 10~2 1.198 x 10" 1
cwt (UK) (long cwt)
ton (US) (short ton)
ounce
grain
1.968xlO~ 2 8.929 x 10~3 19.68 2.OxIO 1 1 1.786 x 101 5.580 x 10" 4 1.276 x 10 ~6
1.102xl0~ 3 5.0 x 10~4 1.102 1.120 5.600 x 10" 2 1 3.125 x 10~5 7.143 x 10 ~8
3.527XlO 1 1.6 x 101 3.527 x 104 3.584 x 104 1.792 x 103 3.2 x 104 1 2.286 x 10 " 3
1.543 x 104 7.0 x 103 1.543 x 107 1.568 x 107 7.840 x 105 1.4 x 107 4.375 x 102 1
lbm/cu.ft 6.243 XlO" 2 6.243XlO 1 1 1.728 x 103 6.229 7.480
lbm/cu.in
lbm/gal (UK)
lbm/gal (US)
3.613 x 10" 5 3.613xlO~ 2 5.789 x 10~4 1 3.605 x 10~3 4.329 x 10~3
1.002 x 10~2 1.002XlO1 1.605 x 10" 1 2.774 x 102 1 1.201
8.345 x 10" 3 8.345 1.337 x 10" 1 2.310 x 102 8.327XlO" 1 1
Force IN kp lbf dyn tonf (UK) tonf (US)
N (kg m/s2)
kgf, kp
lbf
dyn
tonf (UK) (long ton)
tonf (US) (short ton)
1 9.807 4.448 1.0 x IO"5 9.964 x 103 8.896 x 103
1.02OxIO-1 1 4.536 x 10~! 1.020 x 10~6 1.016 x 103 9.072 x 102
2.248 x HT 1 2.205 1 2.248 x 10~6 2.240 x 103 2.0 x 103
1.0 xlO 5 9.807 x 105 4.448 x 105 1 9.964 x 108 8.896 x 108
1.004 x 10~4 9.842 x 10~4 4.464 x 10~4 1.004 x 10~9 1 8.929 x 10"1
1.124 x 10" 4 1.102 x 10~3 5.0 x 10~4 1.124 x 10~9 1.120 1
Pressure lPa(=lN/m2) IkPa 1 MPa (=1 N/mm2 1 bar ( = 0.1 MPa) lp/cm 2 t lkp/m 2 t lat^lkp/cm2)+ 1 atm( = 760Torr)t lTorr(= 1/760atm)f Psi (lbf/sq. in) f
Pa
MPa (N/mm 2 )
kPa
1 103 106 105 9.8IxIO 1 9.81 9.8IxIO 4 1.01325 x 105 1.33 x 102 6.895 x 103
10~3 1 103 102 9.8IxIO" 2 9.8IxIO" 3 9.8IxIO 1 1.01325 xlO 2 1.33XlO"1 6.895
10- 6 10" 3 1 10"1 9.8IxIO" 5 9.8IxIO" 6 9.81 x 10~2 1.01325XlO"1 1.33 x 10" 4 6.895 x 10" 3
bar
p/cm 2
kp/m 2
at+
atm*
Torrt
Psi (lbf/sq. in)t
10" 5 10" 2 10 ! 1 9.81 x 10"4 9.8IxIO" 5 9.8IxIO" 1 1.013 1.33 x 10" 3 6.895 xlO" 2
1.02 x 10" 2 1.02x10' 1.02 xlO 4 1.02 xlO 3 1 10" ! 103 1.033 x 103 1.36 7.03IxIO" 5
1.02XlO-1 1.02 xlO 2 1.02 x 105 1.02 xlO 4 10] 1 104 1.033 x 104 1.36XlO1 7.03IxIO" 6
1.02 x 10~5 1.02 xlO" 2 1.02x10" 1.02 10" 3 10~4 1 1.033 1.36 x 10" 3 7.031 x 10~2
9.87 x 10" 6 9.87 x 10" 3 9.87 9.87 xlO" 1 9.68 x 10 " 4 9.68 x 10" 5 9.68 xlO" 1 1 1.32 x 10" 3 6.805 xlO" 2
7.50xl0~ 6 7.50 7.5OxIO3 7.5OxIO2 7.36x10"' 7.36 x 10"2 7.36 xlO 2 7.6OxIO2 1 5.17IxIO" 1
1.450xl0~ 4 1.45OxIO-1 1.45OxIO2 1.45OxIO1 1.422 x 10 ~2 1.422 x 10~3 1.422XlO1 1.47OxIO1 1.934 x 10"2 1
Non SI units.
Stress l P a ( = lN/m 2 ) lN/mm 2 (= IMPa) lkp/cm2 ( = 1 at)t lkp/mm 2 t Psi lbf/sq. in
Pa
N/mm2
kp/cm 2t
kp/mm2t
Psi (lbf/sq. in)1
1 106 9.8IxIO 4 9.8IxIO 6 6.895 x 103
10" 6 1 9.8IxIO- 2 9.81 6.895 x 10~3
1.02 XlO" 5 1.02XlO1 1 102 7.031 x 10~2
1.02 xlO" 7 1.02XlO-1 10~2 1 7.031 x 10~4
1.45OxIO-4 1.45OxIO2 1.422XlO1 1.422 xlO 3 1
Non SI units.
Viscosity (dynamic) lPas mPas cP kps/m2 kph/m2 lbm/(fts) lbm/(fth) lbf s/sq. ft
Viscosity (kinematic) Im2Zs mm2/s m2/h cSt sq. ft/s sq. ft/h
Pas (Ns/rcm2) (kg/(sm)) 1 1.0 x 10- 3 1.0 xlO" 3 9.807 3.530 x 104 1.488 4.134 x 10~4 4.788XlO 1
mPas (mNs/m2)
cP
1.0 xlO 3 1.0 xlO 3 1 1 1 1 9.807 x 103 9.807 x 103 3.530 x 107 3.530 x 107 1.488 x 103 1.488 x 103 1 4.134 x 10" 4.134 x 10" 1 4.788 x 104 4.788 x 104
m2/s 1 1.0 x 10" 6 2.778 x 10~4 1.0 x IO' 6 9.290 x 10~2 2.581 x 10" 5
mm2/s 1.0 xlO 6 1 2.778 x 102 1.0 9.290 x 104 2.581 x 10" 1
kps/m 2
kph/m2
lbm/(fts)
1.02OxIO-1 1.020 x 10" 4 1.02OxIO-4 1 3.60 x 103 1.518 x 10"1 4.215 x 10~5 4.882
2.833 x 10 ~5 2.833 x 10~8 2.833 xlO~ 8 2.778 x 10" 4 1 4.215 x 10" 5 1.171 x IO"8 1.356 x l O " 3
6.720 x KT 1 6.720 x 10~4 6.72OxIO- 4 6.590 2.372 x 104 1 2.778 x 10" 4 3.2HxIO 1
m2/h 3.6OxIO3 3.60 x 10" 3 1 3.60 x 10- 3 3.345 x 102 9.290 x 10~2
cSt 1.0 x 106 1.0 2.778 x 102 1 9.290 x 104 2.581 x IO1
lbm/(fth) 2.419 x 103 2.419 2.419 2.372 x 104 8.540 x 107 3.60 x 103 1 1.158 x 105
sq. ft/s 1.076 x 10l 1.076 x 10~5 2.990 x 10"3 1.076 x 10~5 1 2.778 x 10~4
lbf s/sq. ft 2.089XlO" 2 2.089 x 10~5 2.089 x 10~5 2.048XlO- 1 7.373 x 102 3.103 x 10~2 8.634 x 10" 6 1
sq. ft/h 3.875 x 104 3.875 x 10~2 1.076 x 101 3.875 x 10" 2 3.60 x IO3 1
N/m (kg/s2)
Surface tension lN/m mN/m kp/m dyn/cm
Energy IJ kWh kpm PSh lbfft erg HPh kcal BTU a
J(Nm) (kgm 2 /s 2 ) 1 3.6OxIO6 9.807 2.648 x 106 1.356 1.0 x 10" 7 2.685 x 106 4.187 xlO 3 1.055 x 103
dyn/cm
1.02OxIO-1 1.020 xlO~ 4 1 1.020 x 10 ~4
1.0 xlO 3 1.0 9.807 x 103 1
kgfm kpm
Psh
lbfft
erg
HPh
kcal
BTUa
1.02OxIO-1 3.67IxIO 5 1 2.70 x 105 1.363 x 10"1 1.020 x 10 " 8 2.737 x 105 4.269 X^ 102 1.076 x 102
3.777xlO~ 7 1.360 3.704 xlO~ 6 1 5.120 x 10"7 3.777 x 10~14 1.014 1.581 x 10" 3 3.985 x 10" 4
7.376X10" 1 2.655 x 106 7.233 1.953 x 106 1 7.375 x 10" 8 1.980 x 106 3.088 x 103 7.782 x 102
1.OxIO7 3.6OxIO13 9.807 x 107 2.648 x 1013 1.356 x 107 1 2.685 x 1013 4.187 xlO 1 0 1.055 x 1010
3.725xlO~ 7 1.341 3.653 x 10~6 9.863 x 10"1 5.051 x 10~7 3.725 x 10~14 1 1.560 xlO~ 3 3.930 x 10~4
2.388xlO~ 4 8.598 x 102 2.342 x 10~3 6.324 x 102 3.238 x 10~4 2.388 x IO' 11 6.412 x 102 1 2.520 x 10"1
9.478xlO~ 4 3.412 x 103 9.295 x 10~3 2.510 x 103 1.285 x 10~3 9.478 x 10"11 2.544 x 103 3.968 1
kWh 2.778xlO~ 7 1 2.724 xlO" 6 7.355 x 10"1 3.766 x 10~7 2.778 x 10"14 7.457 x 10"1 1.163 xlO~ 3 2.931 x 10" 4
kgf/m (kp/m)
1.0 xlO 3 1 9.807 x 103 1.0
1 1.0 xlO~ 3 9.807 1.0 x 10 ~3
British thennal unit.
J (Nm) (kgm 2 /s 2 )
Heat 1J kcal BTU CHU Wh a
mN/m
kca! 2.388 x 10" 4 1 2.520 x 10" 1 4.539XlO" 1 8.598XlO" 1
1 4.187 xlO 3 1.055 x 103 1.90OxIO3 3.6OxIO3
BTU
CHU°
9.478 x 10~A 3.968 1 1.80 3.412
5.262 x 10" 4 2.203 5.552 x 10" 1 1 1.894
Centigrade heat unit.
Power
W (J/s) (kgm 2 /s 3 )
kgf m/s kpm/s
1W kpm/s PS HP erg/s ft lbf/s kcal/h BTU/h
1 1.020 x IO"1 9.807 1 7.355 x IO2 7.5 x IO1 7.457 x IO2 7.604 x 10l 1.0 x 10" 7 1.020 x 10~8 1.356 1.383 x 10" 1 1.163 1.186 x 10"1 2.931 x 10" 1 2.988 x 10~2
PS HP (metr) 1.360 x 10" 3 1.333 x 10~2 1 1.014 1.360 x IO"10 1.843 x 10" 3 1.581 x 10" 3 3.985 x 10" 4
HP 1.341 x 1.315 x 9.863 x 1 1.341 x 1.818 x 1.560 x 3.930 x
erg/s 10~3 10" 2 10" 1 10" 10 10" 3 10" 3 10" 4
1.0 x 107 9.807 x 107 7.355 x 109 7.457 x IO9 1 x 10~8 1.356 x IO7 1.163 x IO7 2.931 x IO6
ft lbffs 7.376 x 10"1 7.233 5.425 x IO2 5.50 x IO2 7.375 1 8.578 x 10" 1 2.162 x 10" 1
kcal/h
BTU/h
8.598 x 10" 1 8.432 6.324 x 102 6.412 x IO2 8.598 x 10~8 1.166 1 2.520 x 10" 1
3.412 3.346XlO1 2.510 x IO3 2.544 x IO3 3.412 x 10" 7 4.626 3.968 1
Thermal conductivity
W/mK (kgm/(s3K))
kcal/(mh°C)
BTU/(fth°F)
BTU/(inh°F)
BTU in/ (sq.fth°F)
1 W/(mK) kcal/(mh°C) BTU/(fth°F) BTU/(inh°F) BTU in/(sq. fth°F)
1 1.163 1.731 2.077 x IO1 1.442 x 10" 1
8.598 x 10~! 1 1.488 1.786 x IO1 1.24 x 10" 1
5.778 x 10~J 6.72OxIO" 1 1 1.2 x IO1 8.333 x 10~2
4.815 x 10~2 5.6OxIO" 2 8.333 x 10" 2 1 6.944 x 10~3
6.933 8.064 1.2XlO1 1.44 x IO2 1
Specific heat, heat capacity
J/kgK (m2Z(S2K))
kJ/(kgK)
kcal/(kg°C)
BTU/(lbm°F)
1 J/(kgK) kJ/(kgK) kcal/(kg°C) BTU/(lbm°F) Wh/(kgK)
1 1.0 x IO3 4.187 xlO 3 4.187 x IO3 3.6OxIO3
1.0 x 10 ~3 1 4.187 4.187 3.60
2.389 x 10 " 4 2.389 x 10" 1 1 1.0 8.598XlO" 1
2.389 x 10 ~4 2.389 x 10"1 1.0 1 0.8598
E.
C O N V E R S I O N TABLE FOR SI vs. E N G L I S H - A M E R I C A N U N I T S
SI to English-American unit
English-American unit to SI
Length I m = 1.0936 yd = 3.28 ft = 39.37 in 1 mm = 0.03937 in
lyd = 3 ft = 0.9144m l f t = 12 in = 0.3048 m Im = 25.4 mm
lkg = 2.20461b
lib = 0.45359 kg
1 N = l(kgm)/s 2 = 2.248 x 10" 1 lbf
I M = 4.448 N
1 Pa = 1 N/m 2 = 1.450 x 1O-4 lbf/in2
1 lbf /in 2 = 1 psi = 6.89475 x 103 Pa
Mass, weight
Force
Pressure 4
= 6.89475 x 10 ~2 bar
= 2.953 x 10 ~ in Hg = 4.015 x 10~ 3 inH 2 O
HnHg = 3.38638 x 103Pa = 3.38638 x 10"2 bar
1 bar = 105 Pa = 1.450 x 10l lbf /in 2 = 2.953 x 101UiHg
ImH 2 O = 2.49089 x 102Pa
2
= 4.015 x 10 HiH 2 O
= 2.49089 x 10 " 3 bar
Tension, stress lN/mm 2 = 1.450 x 10 2 lbf/in 2
1 lbf/in2 = 6.89475 x 10 " 3 N/mm 2
Dynamic viscosity IPas = (Ns)/m 2 = 2.089 x 10~2 (lbf s)/ft2 1
= lkg/(ms) = 6.72x 10" lbf/(ft s)
1 (lbf s)/ft2 = 4.78802 x 101 Pas llb/(fts) = 1.488 Pa s
Kinematic viscosity I m 2 / s = 1.076 x 101 ft 2 /s
Ift 2 /s = 9.29x 10~ 2 m 2 /s
U = I W s = INm = 7.376 x 10"1 ftlbf
1 ft lbf = 1.35582 J
Energy, quantity of heat
1
IkJ = 9.478 x 10- BTU
IBTU= 1.05506 kJ
Power, heat flow rate I W = I Nm/s = 7.367 x 10 - 1 (ftlbf)/s 1
= 1 J/s = 4.425 x 10 (ftlbf)/min = 3.412 BTU/h
l(ftlbf)/s= 1.35582 W 1 (ftlbf)/min = 2.25969 x 10~2 W 1 BTU/h = 2.93072 x 10" 1 W
Specific heat capacity 1 J/(kg K) = 2.388 x 10~ 4 BTU/(lb/ 0 F) 3
5
1 J/(m K) = 1.491 x 10~ BTU/(ft
3 0
F)
IBTU/(Ib 0F) =4.1868 x 10 3 J/(kgK) IBTU/(ft 3 0F) =6.71 x 10 4 J/(m 3 K)
Thermal conductivity 1 W/(mK) = 6.933 (BTUin)/(ft 2 h °F) = 5.778 x 10~ 1 BTU/(fth°F) = 4.815 x 10 " 2 BTU/(inh 0F)
1 (BTUin)/(ft2h °F) = 1.442 x 10^1 W/(mK) lBTU/(fth°F) = 1.7307 W/(m K) 1 BTU/(in h °F) = 2.07689 x 101 W/(mK)
English-American unit to SI
SI to English-American unit Heat flux density
lBTU/(ft 2 h) = 3.1546 W/m 2
l W / m 2 = 3.17x 10- 1 BTU/(ft 2 h)
1BTU/(in2 h) =4.54263 x 10 2 W/m 2
= 2.201 x Kr 3 BTU/(in 2 h) Heat transfer coefficient lW/(m 2 K) = 1.761 x 10- 1 BTU/(ft 2 h°F)
1 BTU/(ft2 h °F) = 5.678 W/(m 2 K)
1 (m2 K)/W = 5.678 (ft2 h °F)/BTU
1 (ft2h °F)/BTU = 1.761 x 10- 1 (m 2 /K)/W
I K = I 0 C = 1.8 0 F
1 0F = 5.555 x 10" 1 K = 5.555 x 10" 1 0C
Thermal resistance
Temperature
Conversion: Tc= ^(rF-32)
r F = | r c + 32
7 K = ^ Tp+ 255.372
TF = I (TK- 255.372)
TQ - Temperature in Celsius ( 0 C); T? - Temperature in fahrenheit (0F); TK -
Temperature in kelvin (K).
S E C T I O N
P
O
L
Y
M
E
R
I
D
E
P
O
L
Y
M
Z E
A R
T I
Il
I Z
O A
N T
A I
O
N N
D
D e c o m p o s i t i o n F r e e
R a t e s
R a d i c a l
o f
O r g a n i c
I n i t i a t o r s
K. W . D i x o n Akzo Nobel Chemicals Inc., Dobbs Ferry, NY, USA A. Introduction 11-1 B. Tables of Decomposition Rates of Organic Free Radical Initiators II-2 Table 1. Azonitriles II-2 Table 2. Miscellaneous AzoDerivatives M-9 Table 3. Alkyl Peroxides II-23 Table 4. Acyl Peroxides II-29 Table 5. Hydroperoxides and Ketone Peroxides II-43 Table 6. Peresters and Peroxy Carbonates II-48 Table 7. Miscellaneous Initiators II-68 C. Notes II-69 D. References II-70 A.
INTRODUCTION
The decomposition of most organic free radical initiators follows first order kinetics. With certain peroxides, however, higher order decompositions are observed. Generally, the higher order reaction is caused by a reaction of radicals with the initiator (induced decomposition). The value of the rate for unimolecular decomposition may be determined either by extrapolation of the rate back to zero initiator concentration or by use of a monomer or other radical "trap". Some of the peroxides may also decompose by non-radical routes. Acids, bases, and polar solvents favor ionic intermediates. Koenig (296) presents an excellent discussion of azo and peroxide decomposition pathways. Decomposition rate (kd) data in these tables are reported for first order kinetics:
where / is the initiator concentration (mol/1) and t is the time (s). The decomposition rate constant k^ is related to half-life (t ^ 2 ) by the following equation:
Fig. 1 relates kd in s" 1 to half-life for the range of k^ found in the tables. For some of the initiators listed, the enthalpy (AH *) is given (Note h) rather than the Arrhenius activation energy
(E2). The two quantities are related by the equation £ a = AH* +RT, where R is the gas constant (in kJ/moldeg.) and T is the absolute temperature (94). Assuming that k& is linear with respect to \/T and that the activation energy, £ a , and the decomposition rate constant, kd, for one temperature are known, kd for any temperature can be calculated from the following expression:
Where given by the author, the overall equation for kd in terms of the frequency factor (A) and activation energy (£ a ) has been included. Thus for any temperature (converted to K) the kd may be calculated:
Although a wide range of initiators is reported in the tables, the author admits that the compilation is far from complete. There are several purposeful omissions: (a) azo compounds, where the azo group is part of a ring structure - these recombine almost exclusively; (b) compounds that decompose at appreciable rates only above 200 degrees. Neither class would be expected to be useful initiators. The data have been arranged into seven tables. Within each table the individual initiators are listed according to the following criteria: 1. Initiators: (a) according to increasing number of carbon atoms; (b) alphabetically (neglecting trivial prefixes), for compounds containing equal number of carbons; (c) miscellaneous initiators are listed alphabetically in Table 7. 2. For each initiator, solvents are listed alphabetically. 3. For a given solvent, all measurements reported by one investigator are listed in a series, with the activation energy listed opposite the lowest temperature. Abbreviations: DMSO - dimethyl sulfoxide; DMAC dimethylacetamide; DMF - dimethylformamide; THF tetrahydrofuran; DCB - 1,2-dichlorobenzene.
20hrs. 100 days
120 min.
12 min.
10 days
100 sec. 200 min.
10 sec.
1 sec. 0.12 sec.
20 min.
40hrs. 200 days _200 sec.
60 min.
1 year 50 days
100 hrs.
10 hrs.
40 sec.
0.5 sec.
5 sec.
10 min. Rate constant (*d)
Figure 1. Relationship of half life to rate constant (k^) (half lives are to the right of each vertical line)
B.
TABLES O F D E C O M P O S I T I O N RATES O F O R G A N I C FREE R A D I C A L I N I T I A T O R S
TABLE 1. AZONITRILES Number of C atoms 5
Initiator
Solvent
N-Acetyl N'-oc-cyanoethyl diimide
Toluene
2-Cyano-2-propyl-azo-formamide
Chlorobenzene Toluene
Xylene
8
2-(Carbamoylazo)isobutyronitrile N-Acetyl N'-ot-cyanocyclopentyldiimide
Toluene Toluene
2,2/-Azo-bis-isobutyronitrile (2,2'-azo-bis-2-methylpropionitrile)
Acetic acid
Acetonitrile tert-Amyl alcohol Aniline Benzene
T( 0 C) 60.8 68.6 82.0 100 100 110 104 100 120 104 65.7 76.8 91.5 79.9 79.9 79.9 80 82 82 79.9 79.9 80.2 80.2 40.0 45.2 50.0 55.0 60.5 69.5
^d(S"1) 2.46 x 10 " 5 5.45 x l 0 ~ 5 2.49 xlO~ 4 1.5 x 10 " 5 2.1 x 10 ~5 6.8 x l O " 5 1.9 XlO" 5 2.IxIO-5 2.4xlO-4 1.93 x 10 ~5 1.82 x l O " 5 7.29 x 10 ~5 3.65 x l O " 4 1.43 x 10 ~4 1.48 x 10 ~4 1.62 XlO" 4 1.52 x l O - 4 1.50xl0" 4 1.49 XlO" 4 1.25 x 10 " 4 1.24 xlO~ 4 1.40 x 10~4 1.68 x l O " 4 5.44 x l O " 7 1.12 XlO" 6 2.64 XlO" 6 5.19 x l O " 6 1.16 x l O " 5 3.78 x l 0 ~ 5
Ea (kj/mol)
Notes
110.2
144.3 a 144.3 a 120.3
V2 V3 a a a v2
128.4
a,t2 a,t2 a,t2 a,t2 a,t2 a,t2
Refs. 322 322 322 93 93 93 339 93 93 340 322 322 322 146 146 146 62 2 175 146 146 61 61 69 69 69 69 69 69
TABLE 1. cont'd Number of C atoms S (cont'd)
Initiator 2,2'-Azo-bis-isobutyronitrile
Solvent Benzene
Benzene or Toluene
H-Butanol Isobutanol Di-n-butyl phthalate
Carbon tetrachloride
Chlorobenzene
Cyclohexanone Dichloroethane Dichloroethane: propionitrile (1:1) Diethylene glycol monobutylether DMF DMF DMF/methyl methacrylate (9/1) (8/2) (7/3) (6/4) (5/5) (4/6) (3/7) (2/8) (1/9) N,iV-Dimethylaniline
Dioxane/Water (80/20) pH7.0
Dioxane/Water (80/20) pH 10.7 Dodecanethiol
T( 0 C) 40 50 60 70 78 37 43 50 60 100 T (K) 82 82 82 80.2 80 90 100 110 120 127 137 145 80 90 100 110 120 40 60 77 64 82 101 T (K) 82 70
^d(S"1)
Ea (kj/mol)
4.83 x 10~7 2.085 XlO" 6 8.45 xlO~ 6 3.166 XlO" 5 8.023 x l O " 5 2.83 x 10 ~7 7.35 x l O - 7 2.16 x l O " 6 9.15 x l O - 6 1.52 x l O - 3 1.58 x 1015 1.54 x 10~4 1.55 XlO" 4 1.66 x 10~4 (1.67-1.76) x 10~4 2.64 x 10 ~4 6.47 x l O - 4 1.78 XlO" 3 4.88 x l O - 3 1.43 XlO" 2 2.48 x l O " 2 5.43 XlO" 2 1.24XlO- 1 2.22 x l O " 4 4.23 XlO" 4 1.99 x l O - 3 5.3 x l O " 3 1.48 x l O - 2 2.15XlO" 7 4.0OxIO- 6 1.2IxIO- 4 1.93 x 10 ~5 1.93 x l O - 4 1.93 x l O - 3 2.89 x 1015 1.43 x 10 ~4 2.0IxIO- 5 1.64 x l O - 5
123.4
Notes
128.9
exp[- 128.9/#7] a a a 122.2
y4 y4 y4 y4 y4 y 16 y 16 y 32
128.4
a,t2 a,t2 a
exp[- 130.23//?7] a m8
Refs. 66 66 66 66 66 39 39 39 19 39 39 175 2 2,175 61 236 236 236 236 236 236 236 236 375 375 375 375 375 69 69 62 344 344 344 344 2,175 293 293
1.94 x 10~5 2.442 x 10 ~5
293 26
6.2096 x l O - 5 6.45 x l O - 4
294 355
60 60 60 60 60 60 60 60 60 66.82 72.27 80 65.3 70.0 75.0 80.0
5.55 x 10~4 5.1OxIO- 4 5.1OxIO- 4 5.3OxIO- 4 5.65 x 10 ~A 5.35 x l O - 4 5.65 x l O - 4 6.25 x l O - 4 6.5OxIO- 4 3.483 x 10~5 6.914 XlO" 5 1.83 x l O - 4 2.53 x 10 " 5 3.20xl0~ 5 8.5 x l O - 5 1.62 x l O - 4
355 355 355 355 355 355 355 355 355 26 26 62 186 186 186 186
75.0 80
1.72 x l O " 4 1.46 x 10 ~4
70 66.82 71.2 60
a 141.0
a
186 62
Notes page 11-69; References page 11-70
TABLE 1. cont'd Number of C atoms S (cont'd)
Initiator 2,2'-Azo-bis-isobutyronitrile
Solvent Ethyl acetate Ethyl acetate/ SnCl4 (1:1) Glycerol/DMF 95/5, (v/v) Maleimide (solid state) Methyl methacrylate
Nitrobenzene 1-Nitrobutane Propionitrile/SnCl4 (1:1) Propylene carbonate Styrene
Toluene
Toluene/SnCl4 (1:1) Xylene
o-Xylene
3,6-Dicyano-3,6-dimethyl1,2-diazacyclohexene-l
Water Dichloromethane
2,2/-Azo-bis[2-(hydroxymethyl)propionitrile
Methyl cellosolve
9
N-Acetyl W-a-cyanocyclohexyldiimide
Toluene
10
N-Acetyl N'-oc-cyanocycloheptyldiimide
Toluene
4,4/-Azo-bis-(4-cyanopentanol) 4,4/-Azo-bis-(4-cyanovaleric acid) l,r-Azo-bis-l-cyclobutanenitrile
Acetone Acetone Mesitylene
2,2'-Azo-bis-2-methylbutyronitrile
Xylene Toluene Xylene
T( 0 C) 40 60 T (K) 71.2 65 72 50 50 60 70 70 80 100 82 T (K) 72.27 50 70 T (K) 68.4 60.00 60 65 70 80.4 90.0 100.0 105.0 69.8 80.2 80.3 60 50 77 82 80 80 82 85 95 105 T(K) 50 -6.06 0.03 2.52 77
82.0 92.8 100.6 59.4 66.1 79.6 70 70 130.4 141.6 120.4 69.8 80.2 80
kA (s^1) 4.7 x l O " 7 9.36 XlO- 6 8.56 x 1015 2.6054 x 10~5 4.97 x 10 ~5 2.07 x l O - 4 9.7 x 10 ~7 7.5 x l O - 6 7.2OxIO- 4 3.1 x 10" 5 1.27 x l O - 4 1.98 x l O " 4 2.24 x l O - 3 1.45 x l O " 4 9.10 x 1015 5.821 x 10 ~5 2.97 x 10~6 4.72 x l O - 5 1.29 x 1015 3.8 x l O - 5 9.03 x 10~6 9.8 x l O " 6 1.9 x l O - 5 4.OxIO- 5 1.55 x l O - 4 4.86 x 10- 4 1.6OxIO- 3 2.61 x 10 - 3 3.8 x l O - 5 (1.72-1.60) x 10- 4 1.3OxIO- 4 4.0 x 10" 5 2.OxIO- 6 9.46 x l O - 5 1.44 x l O - 4 1.53 xlO~ 4 1.5OxIO- 4 1.45 x l O " 5 2.75IxIO- 4 9.58IxIO- 4 2.782 x l O - 3 3.16xl0 1 5 1.56 x 10 ~6 4.6OxIO- 4 1.14 x l O " 3 1.64 x l O - 3 1.93 x 10 ~5
5.2IxIO- 5 1.7OxIO- 4 3.74 XlO" 4 4.44 x 10 ~5 9.82 x 10 ~5 4.51 x 10- 4 4.26 x 10~5 4.58 x 10 ~5 5.20xl0"5 1.6OxIO- 4 2.05 x 10 ~5 2.3 x IO"5 8.4-9.OxIO- 5 9.97 x 10~5
Ea (kj/mol)
Notes
128.5
a,t2 a,t2
exp[- 121 A/RT]
a a a a,v20
132.2
V4 a a a
exp[- 121.0/RT] 127.6
a a
exp[- 127.6/RT] c,m3 a 121.3
142.3 m2
131.0
a a a a a,t4 a
131.8
exp[-131.8//?7] 88.8
h
a
114.8
112.0
m7 ni7 134.3
129.7 123.0
a
Refs. 69 69 290 294 185 185 289 289 355 216 216 226 226 2,175 290 26 132 132 132 234 291 290 339 47 47 47 47 47 61 61 234 290 175 175 175 62 62 2 332 332 332 332 285 252 252 252 339
322 322 322 322 322 322 305 305 101 101 101 61 61 62
TABLE 1. cont'd Number of C atoms
Initiator
10 (cont'd)
2,2'-Azo-bis-2-ethylpropionitrile
Nitrobenzene
2,2'-Azo-bis-2-methylbutyronitrile
Cyclohexanone
Solvent
Chlorobenzene
Ethanol
Ethylbenzene
N-benzoyl iV'-a-cyanoethyldiimide
4-Bromophenyl-azo-2-methyl2-propionitrile 4-Bromophenyl-azo-(methylpropanedinitrile)
DCB
4-Nitrophenyl-azo-2-methyl2-propionitrile 4-Nitrophenyl-azo-2-(methylpropanedinitrile)
DCB
Phenyl-azo-2-methyl-2propionitrile Phenyl-azo-2-(methylpropanedinitrile)
11
Toluene Toluene
DCB
DCB
DCB DMF 1,2,4-Trimethylbenzene DCB
Phenyl-azo-2-(methylpropanedinitrile)
DCB
4-Bromophenyl-azo-2-(ethylpropanedinitrile)
DCB
4-Methoxyphenylazo-2(methylpropanedinitrile)
Butanol Chlorobenzene DCB Decane DMSO Heptane Hexanol Octane Octanol Propanol Toluene Chlorobenzene
4-Methoxyphenyl-azo2-(methylpropanedinitrile)
DCB
T( 0 C) 80 100 79.9 90.0 100.1 66 84 104 T (K) 80.0 90.0 100.0 80.0 90.0 100.0 67 69.2 83.2 90.0 160 80 85 90 T (K) 160 80 85 90 T(K) 160 160 160 80 85 90 T (K) 80 85 90 T (K) 80 85 90 T (K) 85 85 85 85 85 85 85 85 85 85 85 78.1 85.3 90.2 75.0 85.1 95.1 104.9
kd (s"1) 8.3 x 10~5 1.08 x l O - 3 1.06 x l O " 4 3.7IxIO-4 1.27xlO- 3 1.93 x 10 ~5 1.93 x l O - 4 1.93 XlO" 3 1.38 x 1015 1.05 x 10 " 4 3.23 x l O - 4 9.87 x l O - 4 8.22 x l O " 5 2.94 x l O - 4 1.02 x l 0 ~ 3 1.9 x l O " 5 1.31 x 10 ~5 7.96 x l O - 5 1.744 xlO~ 4 2.85 x 10 ~5 2.4xlO" 5 4.8xlO-5 9.4 x 10 ~5 7.23 xlO 1 6 2.3 x 10 " 5 3.1 x 10~5 6.0xl0"5 1.14 x l O - 4 1.35 xlO 1 6 5.65 x 10~5 6.9xlO" 5 5.35 x 10 ~5 4.45 x 10 ~5 8.0xl0"5 1.42 x l O - 4 8.48 x 1013 2.4xlO~ 5 4.8xlO" 5 9.4 x l O - 5 7.23 x 1016 1.85 x 10 " 5 3.65 x 10 ~5 7.05 x l O - 5 3.00 x 1016 2.9xlO" 4 9.5 x 10" 5 8.35 x l 0 ~ 5 3.8xl0"5 4.87 XlO" 4 5.15 x l 0 ~ 5 1.6 x l O " 4 4.4xlO~ 5 1.5xlO~ 4 3.1 x 10~4 6.75 x l 0 ~ 5 5.76 x 10 ~5 9.52 x 10 ~5 1.307 xlO~ 4 2.73 x l 0 ~ 5 8.35 x l 0 ~ 5 2.236 xlO~ 4 6.397 xlO~ 4
Ea (kj/mol)
Notes
143.1 131.6
a a h
exp[- 129.93//?7] 119.8
h
134.9
h
a 127.9
145.0
exp[-U5.0/RT]
139.1
exp[-139.1 /RT]
123.2
exp[- 123.2/RT] 145.0
exp[- 145.0/RT] 142.9
exp[- 142.9/RT] 110 71 115 142 114 136 102 140 112 103 137 71.5
116
Refs. 226 226 336 336 336 344 344 344 344 336 336 336 336 336 336 339 322 322 322 329 329 329 329 329 329 329 329 329 329 329 329 329 329 329 329 329 329 329 329 329 329 329 329 329 331 331 331 331 331 331 331 331 331 331 331 330 330 330 330 330 330 330
Notes page 11-69; References page 11-70
TABLE 1. confd Number of C atoms 11 {confd)
Initiator 4-Methoxyphenyl-azo2-(methylpropanedinitrile)
DCB
Phenyl-azo-2-(2-methylbutyronitrile)
DCB DMF 1,2,4-Trimethylbenzene DCB
4-Tolyl-azo-2-(methylpropanedinitrile)
12
13
14
Solvent
4,4/-Azo-bis-(l-bromo4-cyanopentane) 4,4/-Azo-bis-4-cyanopentanoic acid 4,4'-Azo-bis-(4-cyanopentanol)
Toluene
U'-Azo-bis-l-cyclopentanenitrile
Toluene
2,2'-Azo-bis-2-cyclopropylpropionitrile (mp 64-65)
Toluene
2,2'-Azo-bis-2-cyclopropylpropionitrile (mp 76-77)
Toluene
2,2'-Azo-bis-2,3dimethylbutyronitrile 2,2/-Azo-bis-2-methylvaleronitrile 4-Bromophenyl-azo-2(isopropylpropanedinitrile)
Toluene
T(K) 80 85 90 T (K) 160 160 160 80 85 90 T(K) T(K)
kd (s"1) 5.67 x 1012 4.7xlO~ 5 8.1 x 10 " 5 1.38 x l O " 4 2.94 x 1012 5.OxIO" 5 5.2xl0~ 5 5.05 x 10 " 5 4.5xlO" 5 7.9xl0~5 1.365 XlO" 5 1.21 x 1013 1.OxIO11 1.9 x l O " 5 8.97 x 10 " 5 2.55 x 10 " 4 7.99 XlO" 4 2.81 x 10" 3 8.99 x l O " 3 2.6xlO-2 5.2 XlO" 2 7.45 x l O " 5 2.43 x 10 " 4 5.18 xlO~ 4 3.50 x 10~5 7.53 x 10 ~5 2.68 XlO" 4 3.90 x 10 ~5 8.17 x 10 " 5 2.46 XlO" 4 2.6 x l O " 5 1.02 x 10 " 4 4.2xlO~ 5 (1.65-1.74) x 10" 4 1.4xl0~ 5 2.80xl0"5 5.4 XlO" 5 1.73 xlO 1 6 3.06 x 10 " 5 1.177 x 10 ~A 4.594 XlO" 4 7.320xl0" 4 2.06 xlO 1 7 1.62 x l O " 5 3.17 x 10 " 5 2.252 XlO" 4 1.12 x l O " 4 2.21 x 10 " 4 4.26 XlO" 4 1.19 xlO 1 7 4.85 x 10 " 5
£ a (kj/mol)
Notes
exp[- U6/RT] 114.8
Refs. 330 329 329 329 329 329 329 329 329 329 329 329 307
exp[- 114.S/RT]
117.7
exp[- UlJ/RT] exp[-104.7 /RT]
2,6-Dimethylphenyl-azo2-methylpropanedinitrile
DCB
N-Benzoyl W-a-cyanocyclopentyl diimide
Toluene
4-Bromophenyl-azoisobutylpropanedinitrile
DCB
4-Bromophenyl-azo-2(2-terf-butylpropionitrile) 4-Nitrophenyl-azo-2(2-terf-butylpropionitrile) Phenyl-azo-2-(2-terf-butylpropionitrile)
DCB
69 80 80 90 100 110 120 130 80.3 89.2 95.1 44.2 49.5 59.2 44.2 49.5 59.3 69.8 80.2 69.8 80.2 80 85 90 T(K) 60.1 70.0 80.6 84.5 T(K) 76.7 82.0 98.4 80 85 90 T(K) 160
DCB
160
1.8 x l O " 5
329
DCB 1,2,4-Trimethylbenzene Hexamethylphosphoramide Toluene
160 160 160
9.35 x 10 " 5 9.65 x 10 ~5 9.5xl0~5
329 329 329
2,2'-Azo-bis-2-cyclobutylpropionitrile (mp 38-42) 2,2'-AzO-Ws^-CyClObUIyIpropionitrile (mp 81.5-82.5)
Water
T( 0 C)
Di-w-butyl phthalate
Toluene DCB
Toluene
142.3
a a
141.4
117.2
108.8
w w w w w w
133.9 138.1 142.0
exp[- 142.0/RT] 130.5
exp[-130.5//?7] 131.9
141.6
exp[-141.6kJ//?7]
339 62 375 375 375 375 375 375 101 101 101 57 57 57 57 57 57 61 61 61 61 329 329 329 329 330 330 330 330 330 322 322 322 329 329 329 329 329
80.5
1.51 x 10 " 4
w
104
80.5
1.51 x 10 " 4
w
104
TABLE 1. cont'd Number of C atoms
Initiator
Solvent
14 {cont'd)
U'-Azo-bis-l-cyclohexanenitrile
Chlorobenzene DMSO
Nitrobenzene Toluene
2,2'-Azo-bis-2,4-dimethylvaleronitrile
Dimethyl-4,4'-azo-bis-cyanopentanoate (meso)
Xylene Toluene
Xylene DMAC
(no+)
(nD_)
4,4'-Azo-bis-4-cyano-l-methylpiperidine
DMSO
2,2'-Azo-bis-2-propylbutyronitrile
Nitrobenzene
2,2/-Azo-bis-2,3,3-trimethylbutyronitrile(mp 114-116) 2,2'-Azo-bis-2,3,3-trimethylbutyronitrile (mp 116-118) 2,2/-Azo-bis-2-methylhexylnitrile 2,2'-Azo-bis-2,4-dimethylvaleronitrile
Toluene
2,2/-Azo-bis-2,4-dimethylvaleronitrile (mp 56-57) 2,2/-Azo-bis-2,4-dimethylvaleronitrile (mp 74-76) 2,2/-Azo-bis-2-isopropylbutyronitrile AH4-Chlorobenzoyl) N'-OLcyanocyclohexyl diimide AHl-Cyanocyclohexyl)pentamethyleneketenimine
Toluene Toluene Toluene Toluene Toluene Toluene Toluene
Chlorobenzene Cumene Toluene terf-Butylbenzene
15
2-Phenyl-azo-2,4-dimethyl4-methoxyvaleronitrile JV-Benzoyl N'-ot-cyanocycloheptyl diimide
Xylene Toluene
T( 0 C) 79.97 100.12 80 85 90 95 100 80.3 95.2 102.4 88 77 51 68 T(K) 77 77.9 85.0 90.2 99.7 77.6 85.9 90.0 99.2 77.9 85.4 90.2 99.0 80 85 90 95 80 100 79.9 89.0 79.9 88.9 80.2 69.8 80.2 59.7 69.9 69.8 80.2 80.5 79.1 86.4 99.7 100 100 100 100 100 100 100 100 122 74.6 82.8 89.2
A^(S"1) 8.42 x l O " 6 1.107 XlO" 4 1.01 x l O " 5 2.01 x 10 " 5 3.89 x l O " 5 6.83 x l O " 5 1.14 x l O " 4 6.5 x 10" 6 5.44 x l O " 5 1.26 x l O " 4 1.9 XlO" 5 5.31 x 10 ~6 1.9 x l O " 5 1.9xlO" 4 6.98 xlO 1 4 5.77 x 10 ~4 1.43 x l O " 4 3.76 x 10 " 4 6.8OxIO" 4 2.05 XlO" 3 1.46 x l O " 4 4.03 x l O " 4 6.9OxIO" 4 2.04X10- 3 1.49 XlO" 4 3.90 x 10 ~4 6.95 x l O " 4 1.97xl0- 3 9.7xlO~ 6 1.75 x 10 " 5 3.64 x l O " 5 6.47 XlO" 5 2.55 x 10" 4 2.72 XlO" 5 7.42 x 10 " 5 2.59 x l O " 4 1.05 x 10 " 4 3.09 x 10" 4 1.58 x l O " 4 1.98 xlO~ 4 7.1 x 10 " 4 8.05 x 10 ~5 2.89 x 10 " 4 1.98 x l O " 4 7.IxIO"4 1.01 x 10" 4 8.6 x l O " 6 2.01 x 10 ~5 1.044 x l O - 4 3.85 x 10 " 5 2.07 x 10 " 5 3.93 x 10~5 1.42 x 10 " 5 3.10x 10" 5 1.83 x l O " 5 2.39 x 10 " 5 1.22 x 10- 5 1.9 x 10~5 6.43 x 10 " 5 1.781 x 10" 4 3.519 x l O " 4
E* (kj/mol)
Notes
140.2 135.6
h
121.3
121
a a a a
exp[-121//?7] 133.9
133.5
133.5
136.4
128.9 146.4 125.5
a a a a a a a a a a a a a h
a a w w w w
121.3 121.3 121.3
w w w w
132.7
p,z (1) p,z (3950) p,z (1) p,z (3950) p,z (1) p,z(3950) p,z (1) p,z (3950)
122.8
Refs. 179 179 135 135 135 135 226 101 101 101 339 175 343 343 343 175 205 205 205 205 205 205 205 205 205 205 205 205 135 135 135 135 226 226 57 57 57 57 61 61 61 57 57 57 57 50 322 322 322 299 299 299 299 299 299 299 299 339 322 322 322
Notes page 11-69; References page II - 70
TABLE 1. cont'd Number of C atoms 15 (cont'd)
16
Initiator
Solvent
N-(4-Methoxybenzoyl) N'-OLcyanocyclohexyldiimide
Toluene
JV-(4-Methylbenzoyl) jy'-otcyanocyclohexyl diimide
Toluene
iV-Phenylacetyl W-a-cyanocyclohexyl diimide
Toluene
4-Cyano-l-methylpiperidine-4,4'-azo4'-cyano-l,l'-dimethylpiperidinium nitrate
DMSO
4,4'-Azo-bis-4-cyano-1,1'-dimethylpiperidinium nitrate
DMSO
4,4/-Azo-bis(4-cyanopentanoyl)bis2-aminoethanol
DMF
Toluene
2,2/-Azo-bis-2-methylheptylonitrile
Toluene Xylene Toluene Xylene
80
Toluene
80.5
Toluene
80.5
Toluene
40 1.175 50 4.45 40 6.95 50 2.89 80.5 (1.325±0.35)
l,l'-Azo-bis-l-(2-methylcyclohexane)nitrile l,l'-Azo-bis-l-cyclohexanecarbonitrile 2,2/-Azo-bis-cyclopentylpropionitrile (mp 72.2-74.5) 2,2'-Azo-bis-2-cyclopentylpropionitrile (mp 96.3-97.6) 2,2/-Azo-bis-2,4,4-trimethylvaleronitrile (mp 67.5-69) 2,2'-Azo-bis-2,4,4-trimethylvaleronitrile (mp 94.5-95.5) 2,2'-Azo-bis-2-isopropyl-3-methylbutyronitrile U'-Azo-bis-l-cyano-^' dimethyl cyclohexane
Acetic acid Toluene
Toluene Toluene
133.9
132.6
h
124.7
h
115.1
a a exp[- 115/RT]
a
62
1.31 x 1O -4
w
104
1.30 x 10 ~4
w
104
w w w w
50 50 50 50 50
h
135 135 135 135 61 104 101 101 101 357 357 357 357
x x x x x
10~4 10~4 10~5 10~4 10~4
Toluene
69 74 80
2.83 x l O - 5 4.65 x l O - 5 1.16 x l O " 4
DMF
134.1
322 322 322 322 322 322 322 322 322 135 135 135 135 135 135 135 135 357 357 357 357 357 357 101 101 101 101 343 343 343 50 62 101
166.9
4.7 x l O " 6
DMAC
4,4'-Azo-bis(4-cyanopentanoyl)bis2-(2-aminoethoxy)ethanol
Toluene
142.8
Refs.
a
1.5IxIO- 5 2.79XlO" 5 5.4OxIO- 5 9.77 XlO" 5 8.3 x 10 ~6 2.27 x 10 ~4 5.35 x 10~5 1.45 x l O - 4 2.6OxIO- 4 1.77 x 10~5 2.9OxIO- 5 4.9OxIO- 5 1.74 x l 0 ~ 5
Toluene
Notes
126.4
80 85 90 95 80.3 80.5 36.6 45.4 49.7 65 69 74 65
DMSO
2,2'-AzO-Ms^-CyClOhCXyIpropionitrile l,l'-Azo-bis-l-cyclooctanenitrile
2,2'-Azo-bis-2-benzylpropionitrile
£ a (kj/mol)
7.1 x 1(T6 1.71 x 10 ~5 9.73 XlO- 5 1.06 x l O " 5 2.20 x 10 ~5 1.255 xlO~ 4 3.08 x 10 ~5 9.76 x 10 - 5 2.77xlO- 4 1.76 x 10~5 3.31 x 10~5 6.23 x 10 ~5 1.156xlO- 4 2.84 x l 0 ~ 5 5.1IxIO-5 9.87 x l 0 ~ 5 1.626xlO- 4 1.76 x 10 ~5 2.85 x 10 ~5 4.66 x l 0 ~ 5 1.73 x l O " 5 2.73 x l O - 5 4.53 x l O - 5 3.28 x 10~4 2.69 x l O " 5 9.72 x l O - 5 2.69X10- 4 1.9xlO" 5 1.9 x l O " 4 1.03 x 1015 1.63 x 10 ~4 1.78 x 10~4 7.43 x 10~6
2,2'-Azo-bis-(4-methoxy-2,4dimethylvaleronitrile)
l,r-Azo-bis-l-cycloheptane-nitrile
20
A:d (s"1)
80.8 87.9 101.2 81.4 87.3 101.9 74.3 82.9 91.2 80 85 90 95 80 85 90 95 65 69 74 65 69 74 69.5 48.9 58.9 67.3 30 47 T(K) 80.0 80.0 80.2
DMAC
18
T( 0 C)
113.5 121.3
132.2
108.4
357 357 54
TABLE 1. cont'd Number of C atoms 20 (cont'd)
22
34
Initiator /
2,2 -Azo-bis-2-isobutyl-4-methylvaleronitrile 2,2'-Azo-bis-2-(4-chlorobenzyl)propionitrile / 2,2 -Azo-bis-2-(4-nitrobenzyl)propionitrile l,l'-Azo-bis-l-cyclodecanenitrile
4,4'-Azo-bis-(4-cyanopentanyl)bis(heptadecafluorododecanoate)
Solvent Toluene
0
T( C)
1
kd (s" )
E* (kj/mol)
Notes
4
Refs.
Toluene
60.1 80.5 80
3.78 xlO~ 3 5.28 x 10 " 5 8.8xl0~
50 50 54
Toluene
80
1.00 x 10 ~
4
54
Toluene
50.8 60.2 69.5 90 100 110 120 130
5.4OxIO" 4 1.7OxIO4 5.69xlO4 9.86 x 10 " 3 2.11 x 10 ~ 3 4.4 x l 0 ~ 2 1.1 x 10~ 2 1.42 XlO"
Di-n-butyl phthalate
5
101 101 101 375 375 375 375 375
TABLE 2. MISCELLANEOUS AZO-DERIVATIVES Number of C atoms 2
Initiator l,l'-Azo-bis-formamide
Solvent DMF
DMSO
Formamide
4
Methyl-azo-3-propene
Hexamethylphosphoramide Vapor
5
2,3-Diazobicyclo[2,2,l]hept-2-ene
Isooctane
6
2,2'-AzO-Ws-PrOPaHe
Toluene Vapor
3,3'-Azo-bis-l-propene
Vapor
2,2'-Dichloro-2,2'-azo-bis-propane
Diphenyl ether
Siliconeoil
Methyl-azo-l,l-dimethyl-2-propene (cw) (trans)
Perfluoroazo-2-propane
Acetone
p-DiisopropylBenzene Vapor
T( 0 C)
*d (s" 1 )
86.0 100.3 115.3 86.0 100.3 115.3 86.0 115.3 115.3
1.56 x 10 " 5 5.73 XlO" 5 1.14x10-4 5.48 XlO" 6 2.72 x l O - 5 1.01 XlO" 4 9.25 x 10 ~5 -2.0 x l O " 3 3.83 x 10~5
163.3 169.8 182.8 T (K) 131.5 142.3 164.1 180.8 164.1 250 260 270 280 290 142.65 152.68 167.12 158.5 167.9 178.5 185 199 221 -13.89 -5.04 4.00 114.55 123.83 133.33 T(K)
5.88 x 10 ~4 1.110 x l 0 ~ 3 3.36 XlO" 3 3.2 x 10 1 4 5.44 x 10~6 1.82 XlO" 5 1.66xlO- 4 8.35 x l O " 4 1.64 x l O " 4 7.67 x 10 " 3 1.67xlO- 2 3.35X10- 2 6.52X10- 2 1.28XlO-1 3.88 x l O " 4 1.10 x l O - 3 4.45 x l O - 3 1.03 x 10~4 4.54 x l O - 4 8.08 X l O " 4 4.8xlO"4 2.1 x 10" 3 1.6xlO- 2 3.62 x 10~5 1.7OxIO- 4 6.82 x l O - 4 1.02 x l O " 4 2.68 x l O " 4 8.44 XlO" 4 5.0IxIO16
Ea (kj/mol)
148
Notes C2 C2 C2 c c c
268 268 268 268 268 268 268 268 268
h
298 298 298 298 180 180 180 180 180 110 110 110 110 110 319 319 319 297 297 297 240 240 240 252 252 252 252 252 252 360
exp[- №/RT] 157.7
171.1
a a a a a
151.3
138.3
h,u 4 U4 U4
96.8
h
147.9
h
exp[-189.0//?7]
Refs.
Notes page 11-69; References page 11-70
TABLE 2. cont'd Number of C atoms 6 (cont'd)
Initiator
Solvent
l-Propyl-azo-3'-propene
Vapor
Triazobenzene
Nitrobenzene
Tetralin
7
8
terf-Butyl-azo-3-propene
2,2/-Azo-isobutyramide Azo-bis-isobutyramidine
Azo-bis-isobutyramidine 2HCl (AIBA)
Vapor
Water Water Chloroform DMSO Methanol Water (pH 1.9) Water (pH 5.8) Water (pH 9.5) Water
AIBA
Water
AIBA-kaolin adduct
Water
AIBA-bentonite adduct
Water
Azo-bis(2-amidinopropane) 2HCl 2,2'-Azo-bis(2-amidinopropane) 2HCl Azo-bis-isobutyramidine 2HNO3
Methanol Water Water DMSO-cumene
2,2'-Azo-bis-isobutane
Vapor
2,2'-Azo-bis-isobutane
Diphenyl ether/isoquinoline (90/10)
J( 0 C) 101.32 114.10 126.02 T (K) 105 115 130 145 105 115 130 145 80.88 90.90 106.81 T (K) 88 60 60 60 70 60 50 60 50 60 50 60 60.0 70.0 75.0 80.0 40.15 50.05 60.20 70.10 100.10 70 50.0 60.0 70.0 80.0 50.0 55.0 65.0 70.0 80.0 50 50 56 60 70 160 180 190 210 174.8 188.3 188.8 165 175 185 190
kd (s'1) 1.10 x 10~ 6 5.60 x l O ~ 6 2.11 x l O ~ 5 6.3 x 10 1 4 3.5 x 10~ 7 1.20 x l O ~ 6 6.25 x l O ~ 6 2.5OxIO-5 4.0xl0~7 1.34 x 10~6 6.01 x 10 ~6 2.47 x l 0 ~ 5 2.13 x l O ~ 6 7.27 x l O ~ 6 3.89 x l O ~ 5 5.4 x 10 12 1.9xl0~ 5 3.15 x 10~5 2.80xl0~ 5 7.1 x 10~6 3.68 xlO~ 6 1.45 x 10 ~6 8.3 x 10 ~6 3.42 x 10 ~5 8.0xl0~ 6 3.22 x l 0 ~ 5 4.7 x 10 ~6 2.53 x l 0 ~ 5 3.70 x 10 ~5 1.33 xlO~ 4 2.58 xlO~ 4 5.13 xlO~ 4 2.49 xlO~ 6 9.79 xlO~ 6 4.03 x l 0 ~ 5 1.52 xlO~ 4 4.96 x l 0 ~ 3 1.52 xlO~ 4 1.37 x l 0 ~ 5 6.16 xlO~ 5 2.28 xlO~ 4 9.53 xlO~ 4 1.8OxIO- 5 3.97 xlO~ 5 1.53 xlO~ 4 3.21 x 10~4 1.04 XlO- 3 1.45 x 10 ~5 8.1x 10 ~6 1.93 x 10 ~5 4.86 x l 0 ~ 5 1.53 xlO~ 4 1.9xlO~ 5 5.01 x l 0 ~ 5 1.53 xlO~ 4 1.05 x l 0 ~ 3 6.8 x l 0 ~ 5 1.75 xlO~ 4 1.14 xlO~ 4 2.782 x l 0 ~ 5 8.74 x l 0 ~ 5 2.513 x l O ~ 4 4.143 XlO" 4
Ea (kj/mol)
Notes
149.2
v2i V2I V2I
e x p [ - 149.2/RT] 140.2
136.0
124.9
exp[- 124.9/RT]
v2i V21 V2I v2i a q2 q3
126.5 124.4 151.7 128.9
h
122.6
h
133.9
h
126.4
h
a
a m4 m4 m4
176.6
m4 h
Refs. 298 298 298 298 45 45 45 45 45 45 45 45 298 298 298 298 342 288 288 184 21 184 341 341 341 341 341 341 233 233 233 233 237 237 237 237 237 21 233 233 233 233 233 233 233 233 233 356 356 340 21 21 339 221 221 221 243 243 243 171 171 171 171
TABLE 2. cont'd Number of C atoms 8 (cont'd)
Initiator 2,2'-Azo-bis-isobutane 2,2'-Dimethoxy-2,2'-azopropane
10
Diphenyl ether/isoquinoline (90/10) Diphenyl ether
2,2/-Dimethylmercapto-2,2/azopropane
Diphenyl ether
Isopropyl-azo-l,l-dimethyl-2propene (cis)
Acetone
(trans)
9
Solvent
Diisopropylbenzene
2,2/-Azo-bis(2-methylpropane) 2-(4-Bromophenyl-azo)-2nitropropane
Vapor DCB
rm-Butyl-azo-U-dimethyl2-propene (trans)
Diisopropylbenzene
2-(4-Nitrophenylazo)-2-nitropropane
DCB
oc-Phenylethyl-azo-methane
Diphenyl ether
2,2'-Diacetylthio-2,2'-azopropane
Hexadecane Diphenyl ether
2,2 '-Diacetoxy-2,2 '-azopropane
Diphenyl ether
Siliconeoil Azo-bis( 1,1 -dimethyl-2-propene) (trans)
Xylene
Azo-bis-(l,l-dimethyl)-2-propyne (trans)
Xylene
2,2/-Azo-bis-2-methylbutane
Ethylbenzene
Isoamyl alcohol
2,2'-Azo-bis-2-methylbut-3-ene
n-Decane
2,2'-Azo-bis-2-(methylcarboxy)propane 2,2'-Azo-bis-methyl-2-methylpropionate
Water
2,2'-Azo-bis-methyl-2-methylpropionate
Collidine 1,2-Dichlorobenzene Diethyl oxalate Ethylene glycol Nitrobenzene Undecane Xylene
T( 0 C)
A;d (s *)
195 200 150.1 159.9 174.6 125.0 135.0 145.0 -25.09 -16.65 -8.20 97.41 106.06 115.06 160 130 135 140 T(K) 73.72 80.31 87.08 130 140 145 T(K) 151 161 171 161 130.0 140.0 149.4 190.0 200.1 210.3 258
6.73IxIO- 4 1.093 x 10~3 4.02 x l O " 5 1.50xl0~ 4 6.67 XlO" 4 3.40xl0~ 4 7.10 xlO~ 4 1.15 x l 0 ~ 3 6.30x 10" 5 2.87 x 10 " 4 1.10 x l O - 3 1.15 x 10~4 3.19 x l O - 4 9.22 x l O - 4 1.93 x 10 " 5 1.62 x 10~4 2.59 x 10 ~4 4.3OxIO- 4 1.1 xlO 1 3 8.69 x 10 ~5 1.83 x 10~4 3.80xl0~ 4 LOOx 10~4 2.44 x 10 ~4 4.06 x l O - 4 1.1 x 1013 4.35 x 10 ~5 1.16 x l O - 4 3.48 XlO" 4 1.2OxIO- 4 1.33 x 10~4 4.4OxIO" 4 1.19 x l O - 5 8.23 x 10 ~5 2.6IxIO-4 6.38 x l O " 4 1.46 x 10 ~2
42.03 49.98 57.39 41.32 48.20 57.19 180.0 190.0 200.0 180.0 190.0 200.0 44.90 55.44 63.74 50
5.95 x 10~5 1.73 x l O - 4 4.54 x l O - 4 5.37 x l 0 ~ 5 1.3OxIO- 4 4.39 x l O - 4 1.36 x KT 4 3.89 x l O - 4 1.03 x l O - 3 1.14xlO- 4 3.5IxIO-4 9.26 xlO~ 4 6.73 x 10 ~5 2.631 x 10 ~4 7.045 x l O " 4 3.51 x 10~6
80 80 80 80 80 100 80 80
1.67 x 10 ~A 1.44 x 10 " 4 1.52 x 10 ~4 1.24 x 10 " 4 1.6IxIO- 4 1.73 x 10- 3 1.04 x 10 ~4 1.09 x 10 ~4
Ea (kj/mol)
Notes
171.8
84.6
91.3
h,u5 U5 U5 h
137.8
h
a 130
exp[- 130/RT] 112.3
h
134
exp[- 134/RT] 161.5
151.3
h
171.4
h
109.4
h
111.9
h
176.4
h
176.0
h
107.3
h
129.3
149.8
a a a a a a a a
Refs. 171 171 297 297 297 297 297 297 252 252 252 252 252 252 340 325 325 325 325 252 252 252 325 325 325 325 149 149 149 149 297 297 297 297 297 297 240 252 252 252 252 252 252 336 336 336 336 336 336 278 278 278 285 226 226 226 226 226 226 226 62
Notes page 11-69; References page 11-70
TABLE 2. cont'd Number of C atoms 10 (cont'd)
Initiator
Solvent
N,Af'-Azo-piperidine
Silicone oil
2-(4-Methoxyphenylazo)2-nitropropane
DCB
Dimethyl 2,2'-azo-isobutyrate
Acetic acid
Acetonitrile
Benzene
Cyclohexane
Dimethyl-2,2'-azo-isobutyrate
Methanol
Methanol/SnCl4
Methanol/ZnCl2 Paraffin Toluene
11
2,3,7,8-Tetraazahexacyclo[7.4.1.04'12.0611.01013]tetradeca2,7-diene 2-(2,6-Dimethylphenylazo)2-nitropropane
a-Phenylethyl-azo-2-propane
12
Toluene/SnCl4 Acetonitrile-d3
DCB
Diphenyl ether/ benzoquinone Diphenyl ether
Azo-bis-isobutanoldiacetate
Cyclohexane
Azo-bis-(l-carbomethoxy-3-methylpropane)
Benzene
Carbon tetrachloride
4,4'-Azo-bis-(4-cyanopentanoic acid) (meso)
DMAC
T( 0 C)
kA (s" 1 )
181 228 135 140 150 T(K) 40 50 60 70 40 50 60 70 50 60 70 40 50 60 80 40 50 60 40 50 60 60 99.2 60 60 66 70 80 60 215 230 250 135 140 150 T(K) 143.2
1.7 x l O " 3 4.3 XlO- 2 7.4xlO" 5 1.30 x 10 ~4 3.67 XlO" 4 2.5 XlO 15 8.61 x 10 ~7 3.16 xlO~ 6 1.56 XlO" 5 5.49 x l O " 5 5.44 x 10~7 2.68 XlO" 6 1.01 x 10 " 5 3.57 XlO- 5 2.22 x 10 " 6 8.85 XlO" 6 3.27 x l O " 5 2.89 x 10 " 7 1.38 x l O " 6 5.85 XlO" 6 2.22 x l O - 5 6.86 x 10 " 7 3.12 XlO" 6 1.44 XlO" 5 1.20 x 10 " 6 4.46 x l O " 6 1.98 XlO" 5 1.51 x 10 ~5 1.02 x 10 " 3 8.9xlO- 6 8.11xlO" 6 1.93 x l 0 ~ 5 3.17 x l O " 5 1.19xlO- 4 1.63 x 10 ~4 1.18 x l 0 ~ 5 6.65 x l O " 5 3.4OxIO" 4 9.OxIO" 5 1.44 x 10 ~4 3.86 x l O " 4 4.8 xlO 1 3 1.5OxIO"4
143.0 152.0 165.5 170.0 180.0 189.0 199.0 36 45 55 65 45 55 65 77.6 85.3 90.9 99.8
1.54 x 10 ~4 4.24 xlO~ 4 1.57Ox 10" 3 4.86 x 10 " 5 1.27 XlO" 4 3.47 x l O " 4 1.01 x 10" 3 3.05 x 10 ~7 1.31 x 10 " 6 4.54 x l O " 6 1.82 x l O - 5 7.18 x 10 " 7 3.79 xlO~ 6 1.02 x l O " 5 1.33 x 10 ~4 3.7OxIO" 4 7.17 XlO" 4 2.02 x l O " 3
£ a (kj/mol)
Notes
153
exp[-153//CT] a a a a a a a a a a a a a a a a a a a a a
131.6 a
188.7
Xi X1 Xi
exp[- 13S/RT]
113 ti 3 ti3
133.5
a a a a
Refs. 240 240 325 325 325 325 326 326 326 326 326 326 326 326 326 326 326 326 326 326 326 326 326 326 326 326 326 326 240 290 340 340 340 340 290 174 174 174 325 325 325 325 220 310 310 310 189 189 189 189 68 68 68 68 68 68 68 205 205 205 205
TABLE 2. cont'd Number of C atoms 12 (cont'd)
Initiator
Solvent
4,4'-Azo-bis-(4-cyanopentanoic acid) (nD±)
Azo-bis-(AyV'-dimethylene isobutyramidine) 2HCl Azo-bis-(W-dimethyleneisobutyramidine)
tert-Butyl(2,2,4-trimethyl2-pentyl)diazene
60 70 75 70 60 44
2.06 x 10 " 4 6.64 x 10~4 1.08 XlO" 3 6.97 x 10 ~4 2.13 x 10 ~4 1.9xlO" 5
80 75 80 85 60 61 155 165.7 180.0 120.0 135.0 143.0 145.0 150.0 155.0 160.0 165.0 170.0 60 70 80 60 70 80 60 70 80 58
1.79 x 10~4 8.04 x 10 ~5 1.39 x l O - 4 2.6 x l O " 4 1.09 x 10~5 1.9xl0~ 5 1.6IxIO- 4 4.75 x 10 " 4 1.98 x l O - 3 1.06 x 10 ~4 5.94 x l O - 4 1.42IxIO- 3 7.56 xlO~ 5 1.273 xlO~ 4 2.147 x l O " 4 3.771 x 10~4 6.07 x l O - 4 1.033 x l O - 3 1.6IxIO- 5 5.88 x 10 ~5 2.02 XlO" 4 1.53xl0- 5 5.62 x l O - 5 2.OxIO- 4 1.62 x l O " 5 5.83 x l O - 5 2.066 XlO" 4 1.93 x 10 " 5
Methanol Water
50 50
4.83 x 10 ~5 4.02 x 10 ~5
Methanol «-Decane
50 39.21 50.71 58.95
Chlorobenzene Nitrobenzene Water DMSO
DMSO-cumene DMSO-tetralin Water DMSO DMSO-cumene
DMSO-tetralin Methanol Diphenyl ether
oc-Cumyl-azo-isopropane
Diphenyl ether
2,2/-Dicyclopropyl-2,2/-azopropane
Diphenyl ether/ ^ isoquinoline (90/10)
Di-(2-hydroxyethyl)-2,2'-azobis-isobutyrate
Dioxane
DMF
Toluene
14
2,2/-Azo-bis[AK2-hydroxyethyl)2-methylpropionamidine] 2HCl 2,2'-Azo-bis[2-(imidazoline-2-yl)propane 2HCl 2,2'-Azo-bis[2-(irnidazoline-2-yl)propane 2,2'-Azo-bis-(2-cyclobut1-enylpropane)
(s" 1 )
1.53 x l O - 4 4.1IxIO-4 7.0OxIO- 4 2.09 x l O - 3 1.55 x l O - 4 4.05 x l O " 4 6.98 x l O - 4 2.0OxIO- 3 1.51 x 10" 4 4.34 x l O - 4 7.33 xlO~ 4 2.24 x l O - 3 4.13 x l O " 5 5.93 x 10 ~4 1.56 x 10~4 1.9xl0" 5
(nD_)
2,2-Azo-bis-[2-methyl-J/V(2-hydroxyethyl) propionamide] Azo-bis-(AyV'-dimethyleneisobutyramidine) 2HNO3
fcd
77.9 85.8 90.1 99.1 78.0 85.4 90.0 99.0 77.7 86.0 90.5 99.7 70 92.6 80 86
(n D + )
2,2-Azo-bis-(ethyl-2-methylpropionate)
T( 0 C)
Water
4.7xlO~ 6 1.286 x l O " 4 5.678 x 10 ~4 1.762 XlO" 3
Ea (kj/mol)
Notes
134.3
a a a a a a a a a a a a a a a a
205 205 205 205 205 205 205 205 205 205 205 205 139 139 226 342
a
21 21 21 21 21 339
134.3
134.3
123.0
159.6
a h
158.2
h
125.7
129.9
129.9
a
Refs.
21 21 21 21 21 339 314 314 314 310 310 310 171 171 171 171 171 171 292 292 292 292 292 292 292 292 292 339 356 356
112.3
h
356 278 278 278
Notes page 11-69; References page II - 70
TABLE 2. cont'd Number of C atoms
Initiator
U (cont'd)
2,2'-Azo-bis-(2-methylhex-3-ene)
n-Decane
Di-(2-chloroethyl)-2,2'-azo-bisisobutyrate
Dioxane
Solvent
DMF Di-(2-chloroethyl)-2,2'-azo-bisisobutyrate
Toluene
l,l'-bis-(4-Chlorophenyl) azomethane
Diphenyl ether
Di-(2-hydroxypropyl)2,2/-azo-bis-isobutyrate
Dioxane DMF Toluene
15 16
2,2/,3,3,3',3/-Hexamethyl2,2'-azo-butane
Diphenyl ether
U'-Diphenyl-azo-methane
Diphenyl ether
2,2'-Azo-bis[2-methyl-N-(phenylWater methyl)propionamidine] 2HCl 2,2'- Azo-bis[2-(4-methylimidazoline-2-yl)-propane Methanol 2,2'-Azo-bis[2-(4-methylimidazolineMethanol 2-yl)-propane 2HCl Water 2,2'-Azo-bis[2-(3,4,5-trihydroMethanol pyrimidine-2-yl)propane 2,2'-Azo-bis[2-(3,4,5-trihydroMethanol pyrimidine-2-yl)propane 2HCl Water 1-Methylcyclopentyl-azoterf-Butyl benzene a-cumene l,r-Azo-bis-l-chloro1-phenylethane
Acetophenone Benzophenone Paraffin
Toluene
!,r-Azo-bis-1-chloro-l(3-bromophenyl)ethane l,r-Azo-bis-l-chloro-l(4-bromophenyl)ethane
Toluene Toluene
J(0C)
* d (s" 1 )
39.25 49.52 58.95 60 70 80 60 70 80 60 70 80 145.56 155.56 165.56 175.56 60 70 80 60 70 80 60 70 80 170.0 180.0 190.0 145.0 155.0 165.0 175.0 53
5.33 xlO~ 5 2.256 xlO~ 4 7.584 XlO" 4 1.56 x 10~5 5.55 x 10 " 5 1.9672 x l O - 4 1.25 x l O " 5 4.902 x l O - 5 1.9125 x 10" 4 1.666 x 10 " 5 5.018 x l O - 5 1.99 x l O " 4 2.3OxIO- 4 7.6OxIO" 4 1.49 XlO" 3 4.4OxIO" 3 1.80 x 10 " 5 7.6xlO~ 5 2.22 XlO" 4 1.97 x l O - 5 6.55 x l O " 5 2.3OxIO- 4 1.9Ox 10" 5 7.72 x l O " 5 2.365 x l O - 4 2.37 xlO" 4 5.29 x l O " 4 1.00 x l 0 ~ 3 1.72 x l O " 4 4.93 x l O - 4 1.12 x l O " 3 2.34 x l O - 3 1.93 x 10 " 5
50 50 50 50 50 50 88.3 107.3 117.6 74.8 83 67.8 86.2 98.2 94.5 112.3 120.5 129.3 137 64 74 64 74 59 69 59 69
Ea (kj/mol)
Notes
115.2
h
129.9 134.1 129.9 146.6
h
121.5 121.5 121.5 156.7
h
119.0
h
a
Refs. 278 278 278 292 292 292 292 292 292 292 292 292 297 297 297 297 292 292 292 292 292 292 292 292 292 297 297 297 297 297 297 297 339
10 ~5 10 " 5 10 " 5 10 ~6
356 356 356 356
7.8xlO~ 6 5.9xlO~ 6 5.00xl0" 5 4.95 x 10 " 4 1.43 x l O " 3 8.6xlO~ 4 1.95 x 10 " 3 2.8xlO" 4 3.3 x l O " 3 1.40xl0" 2 2.4xlO" 3 5.2 x l O - 2 1.03XlO"1 1.6XlO" 1 5.OxIO" 1 1.8 x 10 " 4 7.2 x l O " 4 1.79 xlO" 4 7.2OxIO" 4 1.64 x 10~4 6.64 x 10 ~4 1.77 xlO" 4 6.75 x 10 ~4
356 356 327 327 327 240 240 240 240 240 240 240 240 240 240 240 240 239 239 239 239 239 239
1.23 x 7.48 x 6.73 x 1.1 x
132.0
h
135.1
a a a a a a
131.8 127.2
TABLE 2. cont'd Number of C atoms 16 (cont'd)
Initiator U'-Azo-bis-l-chloro-l(4-chlorophenyl)ethane 2,2/-Azo-bis-(2-cyclopent-lenylpropane)
Solvent Toluene n-Decane
l,l'-Azo-bis-l,l-dicyclopropylethane
Diphenyl ether/ isoquinoline (90/10)
2,2/-Azo-bis-{2-methyk/V-[U(bis-hydroxymethyl)-2-hydroxyethyl] propionamide} 2,2/-Azo-bis-{2-methyl-iV-[l,l(bis-hydroxymethyl)ethyl] propionamide} 2,2'-Azo-bis[2-(4, 4-dimethylimidazoline-2-yl) propane 2,2'-Azo-bis[2-(4,4-dimethylimidazoline-2-yl)propane 2HCl 2,2 '-Azo-bis[2-(4,5-dimethylimidazoline-2-yl)propane 2HCl
Water
2,2'-Azo-bis[2-(4,5,6,7-tetrahydrolH-l,3-diazepine-2-yl)propane 2HCl 2,2/-Azo-bis-(2,2,4-trimethylpentane) U'-Azo-bis-l-phenylethane l,r-Azo-bis-l-phenylethane
l,l'-Di-(3-chlorophenyl)-l,razo-ethane l,l'-Di-(4-chlorophenyl)-l,l'azo-ethane
1.97 x 10~4 6.93 x 10 " 4 9.98 x l O " 5 4.593 x 10 " 4 1.528 x l O - 3 6.33 x l O " 5 2.03 x 10 ~4 6.07 XlO" 4 1.695 x l O " 3 1.9 x 10~5
Ea (kj/mol)
Notes
118.8 116.9
a a h
149.0
h
Refs.
a
239 239 278 278 278 171 171 171 171 342
a
342
82
1.9 x l O " 5
Methanol
50
9.3xlO" 6
356
Methanol Water
50 50
9.55 x 10 ~5 9.30xl0"5
356 356
Methanol Water Methanol Water
50 50 50 50
9.21 8.94 1.23 1.04
x 10 " 5 x 10 " 5 x 10~5 xlO"5
356 356 356 356
1.9 x 10~5
Diphenyl ether
110
Dodecane Ethylbenzene Toluene Ethylbenzene
97.3 3.175 x l 0 ~ 5 100.4 (5.45 ± 0.05) x 10~5 110.3 (1.69 ± 0.01) x 10 ~4 105.02 8.473 x 10 " 5 105.28 9.02 x l O - 5 105.28 7.62 x l O " 5 105.02 7.623 x l O " 5 97.3 4.135 x 10 ~5 97.3 3.688 x 10 " 5 97.3 3.995 x 10 " 5 97.3 3.294 x 10 ~5 140.0 1.93 x l O " 4 150.1 5.29 x 10~4 164.8 2.18 x l O " 3 95 4.13 x l O " 5 105 1.218 x l O " 4 85 1.45 x 10~5 95 4.82 x l O " 5 105 1.650xl0~ 4 120.05 7.8xlO-5 130.0 2.63 xlO~ 4 139.0 7.38 XlO" 4 147.0 1.906 x l O - 3 105 1.121 x 10~4
N-Methyl-N-benzyl aniline N-Methyl propionamide Diphenylmethane Propylene carbonate Diphenyl ether
p-Cymene p-Cymene
a,oc-Diethylbenzyl-azo-3-pentane
Diphenyl ether
l,l'-Di-(3-fluorophenyl)1,1'-azo-ethane l,r-Di-(4-fluorophenyl)1,1'-azo-ethane
p-Cymene
Di-(3-hydroxybutyl)-2,2'-azo-bisisobutyrate
59 69 39.21 49.52 58.95 120 130 140 150 80
^d(S" 1 )
Water
(l,l'-d 2 ) (l,l,U',r,l'-d6)
terr-Butyl-(2,2,4,6,6-pentamethyl-4-heptyl)-diazine
T( 0 C)
/?-Cymene
Dioxane
DMF
85 95 105 60 70 80 60 70 80
5.5 x l O " 6 2.35 x 10 " 5 7.85 x l O - 5 2.22 x 10" 5 7.84 x 10 ~5 2.413 x l O " 4 1.83 x l O " 5 7.69 x l O " 5 2.424 XlO" 4
a
136.4
141.6
h
122.3
h
134.1
h
147.0
h
117.3
121.5
339 26 107,98 107,98 152 183 183 152 26 26 26 26 314 314 314 266,313 266,313 266.313 266,313 266,313 310 310 310 310 266,313 266,313 266,313 266,313 292 292 292 292 292 292
Notes page 11-69; References page II - 70
TABLE 2. cont'd Number of C atoms 16 (cont'd)
Initiator
Solvent
Di-(3-hydroxybutyl)-2,2'-azo-bisisobutyrate
Toluene
Di-(4-hydroxybutyl)-azo-bisisobutyrate
Dioxane
DMF
Toluene
l,r-Bis-(4-methoxyphenyl)azo-methane
Diphenyl ether
2,2',4,4,4',4'-Hexamethyl2,2'-azo-pentane
Diphenyl ether
1-Methylcyclohexyl-azo-a-cumene
17
18
terf-Butylbenzene
1,1 '-Diphenyl-l,l'-azo-ethane
p-Cymene
2-(Phenylazo)-2-propyl perbenzoate
Chlorobenzene
(l-Phenylethyl)-azo-diphenylmethane l,l'-Bis(p-tolyl)-azo-methane
Chloroform-d Chlorotoluene Ethylbenzene Diphenyl ether
3,7-Diphenyl-l,2-diaza-l-cycloheptene
l,l'-Azo-bis-cumene
Xylene
Benzene terr-Butylbenzene
Chlorobenzene
Cumene
Dodecane «-Octane
Toluene
T( 0 C) 60 70 80 60 70 80 60 70 80 60 70 80 145.0 155.0 165.0 175.0 130.2 140.0 150.0 102.2 113.1 122.0 95 105 10 35 10 10 58 145.0 155.0 165.0 175.0 61.0 70.0 80.0 89.3 100.2 80 100.2 58.91 60 60 60 55 55 55 55 55 55 60 60 60 60.23 60 60 60 40.04 49.52 59.42 69.23 41.0 44.8 58.5
fcd
(s" 1 ) 2.43 x 10 ~5 8.18 x 10 ~5 2.461xlO~ 4 2.12 x 10 ~5 6.57 x 10 ~5 2.539 x l 0 ~ 4 1.97 x l 0 ~ 5 6.19xlO- 5 2.50xl0~ 4 2.59 x l 0 ~ 5 6.66 XlO- 5 2.628 xlO~ 4 2.23 x 10~A 5.67 x 10 ~4 1.61 x 10~3 3.79 x l 0 ~ 3 1.82 xlO~ 4 4.51 x 10 ~4 1.28 x l 0 ~ 3 2.58 x 10 ~4 9.81xlO~ 4 2.2OxIO- 3 2.74 x l 0 ~ 5 8.21xl0~ 5 4.5 x 10~4 1.9 x l 0 ~ 3 5.IxIO-. 4 6.4xlO~ 4 1.9XlO" 5 2.00 x 10~4 4.69 xlO~ 4 1.22 x l O - 3 3.45 x l 0 ~ 3 3.80xl0~ 5 1.34 xlO~ 4 4.27 XlO" 4 1.59 x l O - 3 4.04 x 10 ~3 4.26 xlO~ 4 3.94 XlO" 3 1.94 xlO~ 4 1.03 x 10 ~4 4.03 x l 0 ~ 5 4.44 x l O - 6 8.50 x 10 " 5 6.88 x l 0 ~ 5 4.42 x l O - 5 8.1OxIO- 5 6.75 x l O " 5 3.83 x l O - 5 1.16 x l O - 4 4.73 x l 0 ~ 5 7.23X10- 6 1.47 x 10~4 1.14 x 10~4 4.44 x l 0 ~ 5 8.32xl0-6 9.46 x 10 ~6 4.33 x l O - 5 1.62 xlO~ 4 5.80xl0~ 4 9.6x10-6 1.98 xlO~ 5 1.28OxIO-4
E* (kj/mol)
Notes
117.3
125.7
125.7
121.5
145.0
h
132.8
h
131.1
h
124.0
h
145.4
a h
a a V5 z (1256) z (3890) z (1013) z (4154) z (1013) z (4154) z (1256) z (3890)
z (1256) z (3890) h
122.8
Refs. 292 292 292 292 292 292 292 292 292 292 292 292 297 297 297 297 297 297 297 327 327 327 266,313 266,313 372 372 372 372 339 297 297 297 297 138 138 138 138 138 44 44 217 333 333 333 280 280 280 280 280 280 333 333 333 217 333 333 333 217 217 217 217 309 309 309
TABLE 2. cont'd Number of C atoms IS (cont'd)
Initiator
Solvent
l,l'-Azo-bis-4-bromocumene
Toluene
lJ'-Azo-bis-S-chlorocumene
Toluene
1,1'- Azo-bis-4-chlorocumene
Toluene
l,r-Azo-bis-l-chloro-l-(4-tolyl)ethane
Acetophenone
Paraffin
Toluene
2,2'-Azo-bis[2-(4-ethyl-4-methylimidazoline-2-yl)propane 2HCl 2,2/-Azo-bis[2-(4-ethyl-5-methylimidazoline-2-yl)propane 2HCl 2,2'-Azo-bis[2-(5,5-dimethyl-3,4,5-trihydropyrimidine-2-yl)propane 2,2/-Azo-bis[2-(5,5-dimethyl-3,4,5-trihydropyrimidine-2-yl)propane2HCl l,l'-Azo-bis-4-fluorocumene
Methanol Water Methanol Water Methanol
l,l'-Di-3-trifluoromethylphenyl)-l,l'-azo-ethane l,l/-Azo-bis-(2-methoxyphenyl)ethane
p-Cymene
Methanol Water Toluene
p-Cymene
l,l'-Azo-bis-(2-methoxyphenyl)ethane
Ethylbenzene
l,l/-Azo-bis-(3-methoxyphenyl)ethane l,r-Azo-bis-(4-methoxyphenyl)ethane l,r-Azo-bis-l-(4-methoxyphenyl)ethane l,r-Azo-bis-l-phenylpropane
p-Cymene
2,2/-Azo-bis-2-phenyl-hexafluoropropane
Toluene
p-Cymene Ethylbenzene Ethylbenzene
U'-Dimethyl-azo-cyclooctane
Benzene
!,l'-Diphenyl-azo-cyclopropane
Benzene
Ethylbenzene
T( 0 C) 42.8 48.6 58.0 36.0 42.8 48.2 61.1 36.0 42.8 48.2 74.8 79.5 86 105 109.5 126 135.5 59 69 59 69 50 50 50 50 50
kd ( s 1 ) 2.72 xlO~ 5 6.28 x l O " 5 2.189 x l O - 4 8.8 x 10~6 2.46 XlO" 5 5.55 x l 0 ~ 5 2.796xlO- 4 1.11 x 10 ~~5 2.9OxIO- 5 6.52 x l 0 ~ 5 2.1 x 10~3 3.OxIO" 3 7.4 x l O - 3 1.66 x l O " 3 2.5 x l O - 2 6.4 x l O - 2 UxlO"1 1.03 x 10 ~4 4.OxIO" 4 1.03 x l O - 4 3.93 XlO" 4 6.8OxIO" 5 7.38 x 10 " 5 9.48 x 10 " 5 1.1 x 10 " 4 9xlO"7
50 8.OxIO- 6 50 7.9xlO" 6 36.0 5.7xlO-6 42.8 1.31 x 10 ~5 48.2 2.94 XlO" 5 61.1 1.880xl0~ 4 95 4.13 x IO" 5 105 1.357 x 10~4 84.6 1.69 x 10~5 95 6.1IxIO-5 105 1.975 x l O - 4 106.06 2.29 x l O " 5 113.81 5.52 x 10~5 133.66 4.87 XlO" 4 95 1.53 x IO" 5 105 6.91 x 10 ~5 95 3.56 x l O " 5 105 1.09OxIO- 4 100.4 (7.15 ±0.1) x 10~5 110.3 (2.48 ± 0.02) x 10 ~4 100.4 (2.35 ±0.1) x 10~5 110.3 (7.2 ±0.2) x 10- 5 45.0 8.36 x l O " 6 50.0 2.16 x l O " 5 55.0 4.92 x l O - 5 60.0 8.81xl0"5 67.0 2.46 x l O - 4 43.8 6.3 x l O - 5 53.8 2.4 x l O - 4 130.0 1.09 x l O " 4 140.0 3.05 x l O - 4 150.0 8.96 x l O " 4 165.0 9.6xlO" 5 175.0 2.2IxIO" 4 185.0 5.09 x l O - 4 170.0 1.67 x 10 ~4 180.0 3.48 x l O " 4
Ea (kj/mol)
Notes
117.7
115.9
112.5
126.8
a
115.9
134.9
h
135.6
h
171.8
a a a h
126.5
h
149.8 135.1 137.2
h
115.5 145.8
h
135.3
h
Refs. 309 309 309 200 200 200 200 200 200 200 240 240 240 240 240 240 240 240 240 239 239 356 356 356 356 356 356 356 200 200 200 200 266,313 266,313 266 266,313 266,313 300 300 300 266,313 266,313 266,313 266,313 98 98 98 98 173 173 173 173 173 42 42 327 327 327 323 323 323 323 323
Notes page 11-69; References page 11-70
TABLE 2. cont'd Number of C atoms IS (cont'd)
19
20
Initiator
Solvent
3,8-Diphenyl-l,2-diaza-lcyclooctene
Tetralin
U'-Di-O-tolyO-U'-azo-ethane l,l'-Di-(4-tolyl)-l,r-azo-ethane
/?-Cymene p-Cymene
Phenyl-azo-diphenylmethane
Decalin
2-(2-Phenyl-4-methylpentyl)azo-2-(4-methylpentane)
Diphenyl ether
l,l'-Azo-bis-l-acetoxy1-phenylethane
Paraffin
U'-Azo-bis-U-dicyclopropylbutane
Diphenyl ether/ isoquinoline (90/10)
9-Azo-bis-decalin (cis)
Ethylbenzene
(trans)
oc,a'-Azo-bis(a-methylbenzyl) diacetate
Dichlorobenzene
Azo-bis-4-methylcumene
Cumene
Toluene
2,2'-Azo-bis[2-(4-ethyl-5-isopropylimidazoline-2-yl)propane 2HCl 2,2'-Azo-bis-2-(4-tolyl)-propane
Methanol Water Toluene
l,r-Azo-bis-l,l,l-tricyclopropylmethane
Diphenyl ether/ isoquinoline (90/10)
l,r~Di-(4-ethylphenyl)1,1-azo-ethane l,l'-Diphenyl-azo-butane
l,l'-Diphenyl-azo-cyclobutane
Decalin/ isoquinoline (90/10) Isoquinoline Cumene/ isoquinoline (90/10) p-Cymene Ethylbenzene
Ethylbenzene
T( 0 C)
^d(S"1)
143 151 165 173 105 95 105 124.5 144.5 103.0 110.0 120.0 130.0 131 142 149.5 120.0 125.0 130.0 135.0 140.0 147.0 180.0 190.0 200.0 180.0 190.0 200.0 65 70 80 90 55 55 55 41.0 49.5 58.5 50 50 36.0 42.8 61.1 105.0 110.0 115.0 120.0 125.0 130.0 135.0
9.52 x 10~5 2.09 x l O " 4 8.77 XlO" 4 1.82 xlO~ 3 8.17 x l O " 5 3.06 x 10~5 9.35 x l O - 5 3.44 x 10 " 5 2.69 x l O - 4 1.17 x l O " 4 2.52 x 10 ~4 8.51 x 10- 4 2.611 x l O " 3 3.2 x l O " 2 4.3 x 10~2 8.OxIO- 2 4.26 x l O " 5 7.94 x l O " 5 1.49 x l O " 4 2.697 x l O - 4 4.774 x l O " 4 1.055 XlO" 3 1.41 x 10" 4 3.95 x l O " 4 1.05 XlO" 3 1.9Ox 10" 4 5.35 XlO" 4 1.41xlO" 3 1.86 x 10 ~5 4.0OxIO" 5 1.592 x l O " 4 5.525 x l O " 4 8.86 x 10 " 5 7.54 XlO" 5 4.47 x 10- 5 1.33 x 10~5 5.02 XlO" 5 1.690xl0" 4 7.72 x 10~5 1.01 x 10 ~4 8.4xlO~ 6 1.62 x l O - 5 2.08 x l O " 4 7.89 x l O " 5 1.374 x l O " 4 2.36 XlO" 4 4.58 x l O " 4 7.76 xlO~ 4 1.38 x l O " 3 2.39 x l O " 3
118.5 118.5
3.60 x 10 " 4 3.30 x l O " 4
118.5 95 105 93.88 105.68 119.55 63.2 73.8 79.1 87.7
445xlO" 4 3.02 x l O " 5 9.14 x l O " 5 1.67 x 10~5 6.96 XlO" 5 3.39 x l O " 4 8.2xlO~ 6 3.5 XlO" 5 6.9 x l O " 5 1.69 XlO" 4
Ea (kj/mol)
Notes
153.6
126.5
h
142.3
159.0
h
175.1
h
175.1
h
z (1013) z (4154) 120.7
110.0
143.5
h
Refs. 137 137 137 137 266,313 266,313 266,313 46 46 310 310 310 310 240 240 240 171 171 171 171 171 171 335 335 335 335 335 335 366 366 366 366 280,333 280,333 280,333 309 309 309 356 356 200 200 200 171 171 171 171 171 171 171 171 171
h 125.3 a a a h 122.3
b,h
171 266,313 266,313 300 300 300 323 323 323 323
TABLE 2. cont'd Number of C atoms 20 (cont'd)
22
24
25
Initiator (-HJ)-I,l'-Diphenyl-lmethyl-azo-methane 2,2'-Azo-bis(2-methyl-A^-phenylpropionamidine) 2HCl 2,2/-Azo-bis[A^-(4-chlorophenyl)2-methylpropionamidine] 2HCl 2,2'-Azo-bis[Af-(4-hydroxyphenyl)2-methylpropionamidine] 2HCl l,r-Azo-bis-l-phenyl-3methylbutane 1,1'-Azo-bis-4-ethylcumene
Solvent
T( 0 C)
^d(S1)
Water
106.0 127.9 45
8.26 x l O " 6 1.18 x l O " 4 1.93 x 10 ~5
Water
45.5
Water
Cumene
Ethylbenzene Toluene
l,r-Azo-bis-4-isopropylcumene
Toluene
U'-Diisopropyl-U'diphenyl-azo-ethane l,l'-Diphenyl-azocyclopentane
Ethylbenzene
2,2'-Azo-bis[2-methyl-N-(phenylmethyl)propionamidine] 2HCl 2,2'-Azo-bis[2-(4-methyl-4-isobutylimidazoline-2-yl)propane 2HCl 2,2'-Azo-bis[2-(4-methyl-5-isobutylimidazoline-2-yl)propane 2HCl 2,2/-Azo-bis[2-(4-ethyl-5-propylimidazoline-2-yl)propane 2HCl U'-Azo-bis-4-terf-butylcumene
Water
oc,a'-Azo-bis(a-methylbenzyl)dimethacrylate
Dichlorobenzene
Bis(2,2,4,6,6-pentamethyl4-heptyl)diazine
Diphenyl ether
l,r-Diphenyl-azo-cyclohexane
Benzene
3-Bromophenyl-azo-triphenylmethane 4-Bromophenyl-azo-triphenylmethane 4-Hydroxyphenyl-azo-triphenylmethane
Toluene
Benzene
Methanol Water Methanol Water Methanol Water Toluene
Toluene Acetic acid Pyridine Toluene
2-Nitrophenyl-azo-9-phenylfluorene
Toluene
4-Nitrophenyl-azo-9-phenylfluorene
Toluene
2,4-Dinitrophenyl-azo-9-phenylfluorene 2-Nitrophenyl-azo-triphenylmethane
Toluene Toluene
3-Nitrophenyl-azo-triphenylmethane
Toluene Benzene terf-Butylbenzene
Ea (kj/mol)
Notes
149.2
b
Refs.
a
318 318 339
1.93 x 10 ~5
a
339
47.5
1.93 x 10~5
a
339
100.4 110.3 42.8 48.6 58.0 42.8 51.2 58.0 50
7.6xl0"5 2.42 x 10 " 4 1.29 x l O " 5 3.29 x l O " 5 1.24Ox 10~4 1.13 x l O " 5 4.26 x l 0 ~ 5 1.078 xlO~ 4 3.52 x l O ' 5
h
98 98 309 309 309 309 309 309 324
a
323 323 323 339
29.5 40.0 50.0 52 50 50 50 50 50 50 42.8 48.6 58.0 65 70 80 90 100.1 109.2 125.0 45.5 54.0 69.7 53.8 64.0 53.35 64.30 54.00 64.00 54.00 64.00 54.00 64.00 45.45 55.55 45.45 55.55 55.55 64.94 64.94 75.06 53.8 64.0 60 60
3.16 1.24 4.68 1.93
x 10~4 x 10 " 3 XlO" 3 x 10 ~5
5.54 x 10 " 5 7.08 x 10 ~5 7.72 x 10 ~5 9.78 x 10 ~5 1.06 x 10 " 4 1.41 x 10~4 1.16 x l 0 ~ 5 2.58 x l 0 ~ 5 1.080xl0" 4 3.65 x 10~5 7.98 x 10 ~5 2.313 xlO~ 4 1.344 XlO" 3 3.03 x 10 ~4 7.62 x l O " 4 3.90xl0~ 3 2.52 x 10~5 8.74 x l O - 5 7.12 xlO~ 4 1.14 x 10 " 4 4.58 x 10 " 4 1.05 x 10 " 4 4.28 x 10 " 4 1.42 x 10~4 6.2xlO~ 4 1.52 x l O " 4 6.7 XlO" 4 1.70 x 10~4 6.4 x l O " 4 1.01 x 10~4 3.71 x 10" 4 2.06 x 10 " 4 7.53 XlO" 4 2.06 x 10 " 4 6.92 x 10 ~4 1.46 x 10 ~4 5.26 XlO" 4 5.8 x 10 ~5 1.99 x l O " 4 9.92 x 10 ~5 9.18 x 10 ~5
139.3 108.9
124.4
113.6 103.1
123.6 h
125.7 h 125.7
125.1 117.2 133.9 133.9 121.3 119.7 111.7 119.2 123.8 110.9
356 356 356 356 356 356 309 309 309 366 366 366 366 314 314 314 323 323 323 42 42 52 52 52 52 52 52 52 52 75 75 75 75 75 75 75 75 42 42 263 263
Notes page 11-69; References page 11-70
TABLE 2. cont'd Number of C atoms 25 (cont'd)
Initiator
Solvent
3-Nitrophenyl-azo-triphenylmethane
Cumene Ethylbenzene Octane Toluene
4-Nitrophenyl-azo-triphenylmethane
Benzene tert-Butylbenzene
Chlorobenzene
Cumene
Decane
1-Decene Dodecane
1-Eicosene Heptane
Hexadecane
1-Hexadecene Hexane 1-Hexene Nonane
Octadecane 1-Octadecene Octane
1-Octene Pentane Tetradecane
4-Nitrophenyl-azo-triphenylmethane
2,4-Dinitrophenyl-azo-triphenylmethane Phenyl-azo-triphenylmethane
1-Tetradecene Toluene
Toluene Acetic acid Anisole
T( 0 C)
A^(S"1)
60 60 60 45 60 60 60 60 60 55 55 55 55 55 55 60 60 60 50 60 70 77.5 60 50 60 70 60 50 60 70 50 60 70 77.5 60 50 60 60 50 60 70
1.04 x 10~4 1.10 x 10~ 4 1.01 x 10~4 1.25 x 10 " 5 1.22 x l O ~ 4 1.09 x 10 " 4 9.7xlO~ 5 4.03 x l O - 5 4.44 x 10 " 6 8.50xl0~ 5 6.88 x l O " 5 4.42 x l O - 5 8.1OxIO- 5 6.75 XlO" 5 2.62 x l O - 5 1.15 x l O " 4 4.73 x l O " 5 7.23 XlO" 6 2.017 x l O " 5 9.988 x l O " 4 3.35OxIO- 4 1.16 XlO" 3 1.038 x l O " 4 1.933 x 10 ~5 9.166 x l O " 5 3.25OxIO- 4 7.6OxIO- 5 2.716 x l O " 5 1.043 x l O - 4 3.900xl0"4 1.716 x l O " 5 8.133 x l O " 5 2.966 x l O - 4 1.09xl0-3 8.25 x 10 ~5 2.75OxIO- 5 1.195 x l O ~ 4 1.143 x 10 ~4 2.20OxIO- 5 9.900 x l O " 5 3.71OxIO- 4
60 70 60 60 70 77.5 60 50 60 50 60 70 60 64.94 75.06 53.35 64.30 75.06 84.98 43.30 64.00 25.0
7.78OxIO- 5 2.783 x l O - 4 7.58 x 10 ~5 1.015 x 10~4 3.65OxIO- 4 1.78 x l O - 3 1.123 x l O ~ 4 3.600xl0"5 1.28OxIO- 4 1.866 x l O " 5 8.80OxIO- 5 3.116 x l O ~ 4 9.02 x 10 " 5 2.58 x 10~4 9.19 x l O - 4 5.7 x l O - 5 2.25 XlO" 4 1.9OxIO- 4 6.13 x 10~4 5.7 x 10~5 8.4 x l O - 4 2.58 x l O " 6
Ea (kj/mol)
Notes
z (1256) z (3890) z (1013) z (4154) z (1013) z (6180) z (1256) z (3890)
123.0 113.0 122.6 117.2 120.5
b,h
Refs. 263 263 263 263 263 263 263 263 263 333 333 333 333 333 333 263 263 263 168,263 168,263 168 168 168 168,263 168,263 168 168 168 168,263 168 168,263 168,263 168 168 168 168,263 168,263 168 168,263 168,263 168 168,263 168 168 168,263 168 168 168 168,263 168,263 168,263 168,263 168 168 75 75 52 52 75 75 52 52 103
TABLE 2. Number of C atoms 25 (cont'd)
cont'd
Initiator Phenyl-azo-triphenylmethane
Solvent Anisole
Benzene
Benzonitrile
/m-Butylbenzene
Chlorobenzene
Cumene
Cyclohexane
Decane Dodecane Diethyl malonate
Ethylbenzene Heptane Hexadecane Hexane Nitrobenzene
Octane
Pyridine Tetradecane Toluene
26
2,2/-Azo-bis[2-(4-ethyl-5-propylimidazoline-2-yl)propane 2HCl Azo-bis-diphenylmethane
Methanol Water Toluene
1,1'-Bis-biphenyl-azo-methane
Diphenyl ether
l,l'-Azo-bis-l-(4-tolyl)-cyclohexane
Toluene
T( 0 C) 50.2 74.7 25.0 74.5 80.1 85.9 25.0 49.6 74.7 50 25.0 50.3 74.7 50 50 50 25.0 49.6 74.7 50 50 50 25.0 49.6 74.7 60 60 25.1 74.5 80.1 85.9 50 60 60 60 25.0 74.5 80.1 85.9 50 50 50 60 53.35 64.00 60 43.8 53.8 45 50 45.45 55.55 43.30 53.35 53.3 50 50 54.0 64.0 135.0 145.0 155.0 165.0 36.0
^d(S1) 1.31 x 10~4 3.03 x l O ~ 3 3.0xl0~6 2.9 x l O ~ 3 6.8 x l 0 ~ 3 1.1 x l O ~ 2 4.29 x l O ~ 6 1.24 x l O - 4 3.12 x l 0 ~ 3 1.37 x l O ~ 4 2.62 x l O ~ 6 1.56 x l O ~ 4 3.14 x l 0 ~ 3 1.33 x 10 ~4 3.83 x l 0 ~ 5 9.53 x l O ~ 6 3.77 x l O ~ 6 1.67 x l O ~ 4 3.93 x l 0 ~ 3 1.50 x 10 ~4 6.82 x l 0 ~ 5 7.65 x l O ~ 6 4.22 x l O ~ 6 9.90 x l 0 ~ 5 1.75 x l 0 ~ 3 5.72 x 10~4 5.35 x 10 ~4 3.1 x 10~6 2.8 x 10 ~3 5.9 x l O " 3 1.0 x l 0 ~ 2 1.58 x 10 ~4 6.60xl0~4 4.76 x 10 ~4 7.60xl0~4 2.6xlO~ 6 3.0xl0~3 5.8 x l 0 ~ 3 9.8 x l 0 ~ 3 1.59 x 10 ~4 7.53 x l O ~ 5 1.17 x l 0 ~ 5 6.41 x l O ~ 4 1.74 x l 0 ~ 4 8.OxIO" 4 4.99 x 10 ~4 6.3 x 10" 5 2.4 x l O - 4 9.23 x l 0 ~ 5 1.73 x l O - 4 8.48 x l 0 ~ 5 3.5IxIO-4 6.0xl0~5 2.25 XlO" 4 2.25 x l O - 4 9.75 x 10 ~5 1.33 x 10 ~4 1.01 x 10 ~4 3.4OxIO- 4 1.23 x 10~4 3.58 x l O " 4 7.76 XlO" 4 2.09 x l O - 3 8.7xlO~ 6
E a (kj/mol)
Notes
Refs.
b b
118.3
112.1
121.3
118.4
102.5
116.6
118.7
129.7
115.5
122.6 113.0 113.0
111.3 134.1
107.1
103 103 114 114 114 114 b,h 103 103 b 103 263 b,h 103 b 103 103 263 z (1140) 263 z (4265) 263 b,h 103 b 103 b 103 263 z (1140) 263 z (4265) 263 h 103 b 103 b 103 263 263 114 114 114 114 263 263 263 263 114 114 114 114 263 z (1140) 263 z (4265) 263 263 52 52 263 42 42 263 263 75 75 52 52 46 356 356 107,312 46,107,312 h 297 297 297 297 200
Notes page 11-69; References page 11-70
TABLE 2. cont'd Number of C atoms 26 (cont'd)
Initiator l,l'-Azo-bis-l-(4-tolyl)-cyclohexane
Toluene
l,r-Diisopropyl-2,2'-dimethyl1,1 '-Diphenyl-azo-propane
Ethylbenzene
4-Methoxyphenyl-azo-triphenylmethane l,r-Diphenyl-azo-cycloheptane
Toluene
3-Tolyl-azo-triphenylmethane
Benzene terf-Butylbenzene Cumene Ethylbenzene Octane Toluene
4-Tolyl-azo-triphenylmethane
27 28
Solvent
4-Acetaminophenyl-azo-triphenylmethane U'-Azo-bis-l,2-diphenylethane (meso)
Benzene
Benzene tert-Butylbenzene Cumene Ethylbenzene Octane Toluene
Toluene Ethylbenzene
(D,L)
30
l,l'-Dibutyl-l,l'-diphenylazo-pentane
Ethylbenzene
34
l,r-Azo-bis-(l,3-diphenylpentane) 3,10,13,20-Tetraphenyl-l,2,ll,12-tetraaza-Ul-cycloeicosadiene
Bromobenzene Xylene Xylene
3,12,15,24-Tetraphenyl-l,2,13,14-tetraaza-l,13-cyclotetracosadiene
Ethylbenzene Xylene
40
44
Poly[oxyethylenexoxy(l-oxo-2,2-dimethylethylene)azo-(2-oxo-1,1 -dimethylethylene)
o-Xylene
T( 0 C) 42.8 61.1 50.0 60.0 70.0 54.00 64.00 16.2 24.8 33.4 41.1 50 50 50 50 45 43.8 53.8 45 50 50 50 50 50 45 43.30 53.35 45 50 54.00 64.00 96.56 106.47 115.28 96.56 106.47 115.28 50.0 60.0 70.0 89.7 118.8 110 120 130 112.95 110.8 119.8 110 120 130 85 95 105 T(K)
* d (s" 1 ) 2.0IxIO" 5 2.009 x l O " 4 6.24 x l O " 5 2.49 x 10 " 4 7.77 XlO" 4 2.13 x l O " 4 7.6xlO" 4 1.65 x 10 " 4 5.52 xlO~ 4 1.66 x l 0 ~ 3 4.52 XlO" 3 1.3OxIO"4 1.3OxIO"4 1.51 x 10 " 4 1.72 x 10 " 4 8.9xl0"5 7.4 x l O " 5 2.77 XlO" 4 9.74 XlO" 5 1.81 x 10" 4 1.26 x 10 ~4 1.35 x 10 ~4 1.4OxIO"4 1.62 x 10 ~4 8.6xl0"5 6.9xlO" 5 2.25 XlO" 4 9.3 x l O " 5 1.52 x l O " 4 1.46 x 10" 4 5.9xlO" 4 2.75 x l O " 5 9.03 x 10" 5 2.42 XlO" 4 3.22 x l O " 5 1.04 XlO" 4 2.84 XlO" 4 5.05 x l O " 5 2.03 x 10~4 6.24 x l O " 4 1.5 x 10" 5 5.6 x 10 " 4 7.2OxIO" 5 2.3OxIO" 4 6.9OxIO" 4 8.76IxIO" 5 8.9 x 10"5 2.2 XlO" 4 7.63 xlO" 5 2.46 x 10"4 7.12 xlO" 4 2.106 x 10"4 7.312 x 10~4 1.995 x 10"3 1.99 x 1014
Ea (kj/mol)
Notes
117.2
113.8
100.4
125.5 138.5
138.9
108.9
145.6
126.4 143.9
124.0
exp[-124.0//?7]
a,h a a a,h a a h
Refs. 200 200 324 324 324 52 52 323 323 323 323 263 263 263 263 263 42 42 263 263 263 263 263 263 263 52 52 263 263 52 52 162 162 162 162 162 162 324 324 324 311 311 38 38 38 158 48 48 38 38 38 332 332 332 332
TABLE 3. ALKYL PEROXIDES Number of C atoms
Initiator
2
Methyl peroxide
4
Ethyl peroxide
Solvent Vapor Methanol Styrene Vapor
Vapor (toluene)
5
2,4-Pentanedione peroxide
Triethyl phosphate
6
Propyl peroxide
Vapor
7
Isopropyl peroxide Allyl tert-butylperoxide
Styrene Toluene
Dimethylaminomethyl peroxide
ter/-butyl
8
tert-Butyl
peroxide
Acetic acid
Acetonitrile
Benzene
Benzhydrol terf-Butanol
2-Butanol n-Butyl mercaptan Tri-n-butylamine
T( 0 C) T(K) T(K) 60 140.2 147.8 160.0 176.5 184.5 145.9 145.9 200 210 218 226 234 245 100 115 125 146.5 155.3 166.8 175.4 60 130 140 150 160 110 120 130 115 120 125 130 95 125 115 120 125 130 80 130 100 100 115 130 120 120 120 120 120 125 130 135 125 120 125 130 135 125 125 125 135
^a(S1)
Ea (kj/mol)
1.6xlO 15 4.IxIO15 1.2xlO" 9 1.75 x 10 ~4 3.6OxIO- 4 1.08 x l O " 3 3.78 x l 0 ~ 3 7.16 x l O " 3 6.69 x l O - 4 5.02 x l O " 4 3.58 x 10 ~2 6.76xlO- 2 1.47XlO- 1 2.23XlO- 1 3.86XlO" 1 6.43XlO- 1 1.9X10" 6 6.IxIO"6 1.4 x l O " 5 2.50xl0~ 4 6.0OxIO- 4 1.95 x l O " 3 4.1OxIO- 3 6. xlO" 1 0 5.76 x l O " 5 1.785 XlO" 4 4.800xl0~ 4 1.27OxIO-3 5.5xl0~ 5 1.9 x l O " 4 4.76 x l O " 4 1.2 x l O " 5 2.19 x l O " 5 2.98 x l O " 5 6.29 x l O - 5 9.53 x 10 " 7 3.89 x l O - 5 1.19 x l O " 5 2.21 x 10~5 3.47 x l O - 5 5.63 x l O " 5 7.81xl0"8 (2.48-3.04) x 10~5 8.8 x l O " 7 8.75 XlO" 7 5.66 x l O " 6 3.0OxIO- 5 1.39 x l O - 5 7.6 x l O - 6 7.5 x l O - 6 3.7 XlO" 6 1.10 x l O - 5 1.99 x l O - 5 3.22 XlO" 5 6.19 x l O " 5 8.7xl0"5 1.41 x 10 ~5 2.49 x l O " 5 4.3OxIO- 5 7.32 x l 0 ~ 5 4.8xlO-5 1.5 x 10 ~5 (1.7±0.3) x 10" 5 (4.2 ±0.4) x 10 " 5
exp[- Ul.l/RT] exp[-153.9//?7] 147.3 131.8
Notes
a a a a a t8
132.6
92
132.2
154.8 139.1
a a a a a a a h,m6
134.5
139.7
h
129.7
d h
142.3 146.9
m 2 ,u 2 m 2 ,u 2 a
147.7
a a z (0.98) z (864) z (1620) z (3480) h
143.5
h
Refs. 72 225 92 127 127 127 127 127 187 187 87 87 87 87 87 87 337 337 337 128 128 128 128 92 321 321 321 321 303 303 303 192 192 192 192 208 208 192 192 192 192 129 129 126,337 197 126,337 126,337 33 33 33 33 192 192 192 192 140 192 192 192 192 140 140 64 64
Notes page II - 69; References page II - 70
TABLE 3. cont'd Number of C atoms 8 (cont'd)
Initiator terf-Butyl
peroxide
Solvent Tri-n-butylamine tert-Butylbenzene
Carbon tetrachloride
Chlorobenzene
Cumene
Cyclohexane
Cyclohexanol Cyclohexene
Cyclohexylamine Decane
Dodecane
Dimethylaniline
Ethyl benzoate
Af-Ethylcyclohexyl amine Heptane Hexadecane
Hexane
T( 0 C) 145 T (K) 125 135 145 T (K) 125 125 125 120 120 120 120 125 150 121 141 164 T (K) 125 135 145 T (K) 95 120 125 130 135 125 120 125 130 135 120 120 120 120 125 80 110 130 115 130 140 80 110 130 120 125 130 135 120 125 130 135 125 80 110 80 110 130 80 110
kd (s~l) (1.60±0.21) x 10~4 2.8 x 1 0 u (1.5 ±0.2) x 10~5 (5.0±0.3)xl0-5 (1.51 ±0.22) xlO~ 4 2.8 x 1014 2.1OxIO- 6 2.49 x l O - 6 2.03 xlO~ 6 9xlO"6 2.4 x l O - 6 2.3 x l O - 6 8.6 x l 0 ~ 7 1.4OxIO- 6 4.45 x 104 1.93 x l 0 ~ 5 1.93 x l O - 4 1.93 XlO" 3 4.20 x 1015 (1.6±0.1) x 10~5 (5.2 ±0.3) x 10- 5 (1.56±0.13)x 10~4 2.8 x 1014 2.48 x 10 ~7 6.3 x l O - 6 1.52 x l O - 5 2.59 XlO" 5 4.64 x l 0 ~ 5 2.4 x l O " 5 7.6 x 10~6 1.38 x l O - 5 2.81 x 10- 5 4.4IxIO-5 8.3 XlO" 6 6.2 XlO" 6 3.77 x l O " 6 2.65 XlO" 6 5.50xl0~ 5 1.39 x 10 ~8 2.0IxIO-6 2.48 XlO" 5 3.00xl0~ 6 2.16 xlO~ 5 6.66 x l 0 ~ 5 1.29 x 10 ~8 1.87 xlO~ 6 2.44 x l 0 ~ 5 9.6xlO~ 6 1.89 x l 0 ~ 5 3.41 x l 0 ~ 5 5.84 x l 0 ~ 5 1.07 x l 0 ~ 5 1.92 x l 0 ~ 5 3.39 x l 0 ~ 5 5.90xl0~ 5 4.01 x 10 ~5 1.44 x 10 ~8 2.19 xlO~ 6 1.07 x 10 ~8 1.82 xlO~ 6 2.33 xlO~ 5 1.64 x 10 ~8 2.17 xlO~ 6
EB (kj/mol)
Notes
exp[- U6A/RT\
exp[- 146A/RT] U1 s s,t6 z (0.98) z (1930) z (2890) z (5525) ui,t 6
exp[- 153.46/RT]
exp[- H6A/RT] 170.7
h
156.1
h
157.3
z (0.98) z (1275) z (2890) z (5725) h
163
a a a
148.5
h
Refs. 64 123 64 64 64 123 301 301 301 33 33 33 33 301 346 344 344 344 344 64 64 64 123 208 192 192 192 192 140 192 192 192 192 33 33 33 33 143 270 270 270 337 337 337 270 270 270 192 192 192 192 192 192 192 192 143 270 270 270 270 270 270 270
TABLE 3. cont'd Number of C atoms S (cont'd)
Initiator terf-Butyl
peroxide
Solvent 2-Methyl-2-butanol
Methyl methacrylate AT-Methylpipendine Mineral oil Nonane
Norbornanol Nujol Octane 2-Octanol Piperidine 1-Propanol Styrene Tetradecane
Tetrahydrofuran
Toluene
Triethylamine
Vapor (acetone)
Vapor (carbon tetrachloride) Vapor (chloroform) Vapor (dichlorodifluoromethane) Vapor (trichloro ethylene) Vapor (methylene chloride) Vapor (3-pentanone) Vapor (silicon tetrafluoride) Vapor (toluene) Vapor
T( 0 C)
^d(S"1)
Ea (kj/mol)
Notes
149.4
h
Refs.
120 125 130 135 T (K) 125 T (K) 80 110 130 125 125 80 110 125 125 125 T(K) 80 110 130 120 125 130 135 125 100 120 120 120 120 125 125 T(K) 120 125 130 135 127.5 131 146 151.5 162 167 145 T (K) 150
1.26 xlO" 5 2.34 XlO" 5 4.47 xlO" 5 6.8OxIO"5 2.8 x 10 14 1.54 xlO" 5 1.31 x 1015 1.36 x 10 ~8 2.0IxIO" 6 2.54 x 10 ~5 4.4xlO" 5 7.8 XlO" 7 1.48 x 10 "8 2.19 xlO" 6 5.5xl0"5 3.49 x 10 ~5 2.8xl0"5 2.8xlO 1 4 1.12 xlO" 8 1.82 xlO" 6 2.38 xlO" 5 9.7xlO" 6 1.84 XlO" 5 3.39 xlO" 5 5.76 xlO" 5 1.5 x l 0 ~ 5 6.82 x 10 ~7 1.34 XlO" 5 9.5 xlO" 6 8.OxIO- 6 5.7 xlO" 6 1.6 xlO" 5 1.62 xlO" 5 1.3OxIO16 7.9xlO~ 6 1.69 xlO" 5 3.15 xlO" 5 5.55 XlO" 5 7.4 xlO" 6 1.13 XlO" 5 6.OxIO" 5 1.03 xlO" 4 3.6 xlO~ 4 5.2 xlO" 4 1.3 xlO" 4 5.9 x 10 16 8.58 x 10 "4
150 150
1.167 xlO" 3 >(2.00 x 10 ~4)
1
130 130
150
2.35 x 10"3
1
130
150
1.017 x 10 ~3
1
130
145 T (K) 160 160 160 148 158 103.2 111.9
1.5 x 10~ 4 6.8 x 10 16 1.05 xlO" 3 1.25 x l 0 ~ 3 1.27 xlO" 3 9.OxIO- 5 2.5 xlO" 4 5.6xlO" 7 2.03 XlO" 6
exp[- U6A/RT] exp[- 154.6/RT]
u
exp[-146.4//?7]
155.2
h
z (0.98) z (2000) z (2850) z (5170)
exp[- 15S3/RT] 169.9
h
165.3 exp[- 1653/RT] 1
165.3 exp[- 1653/RT] 113.0
a,i(2.6) a,i(33) a,i(100)
192 192 192 192 123 143 376 270 270 270 140 301 270 270 140 143 140 123 270 270 270 192 192 192 192 140 197 33 33 33 33 140 143 376 192 192 192 192 238 238 238 238 238 238 125 125 130
125 125 117 117 117 88 88 227 227
Notes page 11-69; References page II - 70
TABLE 3. cont'd Number of C atoms S (cont'd)
Initiator tert-Butyl peroxide
Solvent Vapor
Vapor (He)
KBr pellets
terf-Butyl 2-chloro-l,l-dimethylethylperoxide
Cumene
sec-Butyl peroxide
Toluene Vapor Decane Dodecane Heptane Hexadecane Octane Styrene Tetradecane Chlorobenzene Chlorobenzene Chlorobenzene Chlorobenzene
Butyl peroxide
Bromo-terf-butyl peroxide Chloro-terf-butyl peroxide Bis(chloro-tert-butyl) peroxide 2-terf-Butyl peroxy-2-methyl1-propanol
T( 0 C) 120.2 129.5 138.5 145.4 125 135 145 129.6 141.0 152.5 166.8 130 140 150 160 170 129 138 149 152 139.7 147.2 154.6 159.8 T (K) 145 T(K) 149.5 160 160 160 130 140 150 160 280 290 300 310 320 330 340 350 109 127 149 120 130 140 150 100 100 80 80 80 80 80 60 80 150 150 150 150
A^(S" 1 ) 6.39 x 10 " 6 1.98 XlO- 5 6.0OxIO- 5 1.24 x l O ~ 4 1.1 x K r 5 3.6 XlO- 5 1.15 x l O - 4 1.64 x l 0 ~ 5 6.28 XlO" 5 2.25 x l O - 4 8.92 x l O - 4 1.82 x l O - 5 5.75 x l O " 5 1.75 x l O - 4 4.88 x l O " 4 1.35 x l O - 3 1.97 x l O - 5 4.3 x l O - 5 1.30 x l O ~ 4 1.62 XlO" 4 6.OxIO- 5 1.43 x l O - 4 3.22 x l O - 4 5.53 x l O - 4 3.2 x 10 16 1.3 x l O - 4 1.9xlO 1 6 1.79 XlO" 4 4.0OxIO- 4 4.53 XlO" 4 4.83 x l O - 4 1.91 x 10" 5 5.95 x l 0 ~ 5 1.78 x l O " 4 4.96 x l 0 ~ 4 7.7 1.5IxIO 1 2.77X10 1 4.87XlO 1 8.34XlO 1 1.38 x l O 2 2.13 x l O 2 3.22 x l O 2 3.8 x 10" 7 2.96 x l O - 5 4.4 x l O " 4 8.82 x 10~6 2.8OxIO- 5 9.26 x l 0 ~ 5 2.78 x l O - 4 2.7 x 10 ~6 1.5 x 10" 6 1.43 x 10 " 8 1.17 x l O " 8 2.04 x 10~8 8.8 x 10 ~9 1.58 x l O " 8 3.3 x 10 ~9 9.6xlO-9 3.63 x 10 " 4 4.15 x 10 ~A 3.11 x 10 ~4 1.16 x 10 " 3
Ea (kj/mol)
159.0
Notes
a a a a a
163.6
exp[- 163.6/RT] 161.5 exp[-161.5//?7] 156.5 i(37-132) 154.8 a,i(2.6) a,i(33) a,i(100) 156.7 U3 U3 U3 U3 154.8 i(10) i(10) i(10) i(10) i(10) KlO) i(lO) i(lO) 159.0 h
t6 t6 t6 t6 t6 142.3 t6
Refs. 227 227 227 227 64 64 64 86 86 86 86 96 96 96 96 96 88 88 88 88 63 63 63 63 63 125 175,125 83 117 117 117 277 277 277 277 111 111 111 111 111 111 111 111 241 241 241 363 363 363 363 197 197 270 270 270 270 270 92 270 346 346 346 346
TABLE 3. cont'd Number of C atoms
J(0C)
Initiator
Solvent
2-tert-Buty\ peroxy-2-methyl1-propanol-di l-Hydroxybutyl-«-butyi peroxide
Chlorobenzene
150
a-Methylstyrene
1-Hydroxyisobutyl-isobutyl peroxide
a-Methylstyrene
1-Hydroxyisobutyl-l-di-isobutyll,l-d 2 peroxide
a-Methylstyrene
Dimethylaminomethylterf-amyl peroxide
Styrene
Diethylaminomethylterf-butyl peroxide
Styrene
N-Piperidinomethyltert-buty\ peroxide
Styrene
9
tert-Butyl tert-amyl peroxide
Cumene
10
tert-Amyl peroxide
Bulk
79.4 99.4 109.9 79.4 99.4 109.9 99.5 109.8 122.0 110 120 130 110 120 130 110 120 130 110 120 130 140 125 132.2 108 128 150 T (K) 125 125 125 132.2 136.7 142.2 149.2 136.7 142.2 149.7 110 120 130 140 110 120 130 140 150 127.5 130 132.5 135 137.5 140 142.5 145 147.5 150 80 85 100 115
8 (cont'd)
Chlorobenzene
Decalin Octane Triethylamine Vapor
11 12
tert-Butyl 1,1-dimethylbutyl peroxide
Cumene
ter/-Butyl 1,1,2-trimethylpropyl peroxide
Cumene
2-Methyl-2-tert-butyl-peroxyacetate Ethyl 2-terf-butylperoxymethylpropenoate
Chlorobenzene Triisopropylbenzene
Apocamphane-1-formyl peroxide 2,2-Bis(tert-butylperoxybutane)
Benzene Benzene
A:d (s" 1 )
Ea (kj/mol)
Notes
1.23 x 10" 3 1.7 x 10~5 1.06 x l O - 4 2.9 x l O - 4 3.7 x 10" 5 2.OxIO" 4 4.8 x l O - 4 6.9xlO~ 5 1.8 x 10~4 4.2 x l O - 4 4.9xlO"5 1.19 x 10" 4 3.76 x l O " 4 4.IxIO-5 1.35 x 10~4 3.25 x l O - 4 5.5 x 10" 5 2.66 x 10 ~4 4.16 x l O - 4 3.86 x 10" 6 1.287 x l O - 5 4.3OxIO- 5 1.406 x l O - 4 5.7xlO- 5 1.15 XlO" 4 1.93 x 10 ~5 1.93 x l O " 4 1.93 x 10- 3 4.02 xlO 1 5 2.8xl0-5 3.0xl0"5 3.5 x 10 ~5 7.2 x 10~5 1.15 XlO" 4 2.16 xlO~ 4 4.8 x l O " 4 1.34 x l O - 4 2.4IxIO- 4 5.61 x 10" 4 4.38 x l O " 6 1.537 x l O " 5 4.99 x l 0 ~ 5 1.544 x l O - 4 7.07 x 10 " 6 2.374 x 10 ~5 7.62 x l 0 ~ 5 2.308 xlO~ 4 4.12 x 10 " 4 1.63 x 10~4 1.95 x l O " 4 2.16 x l O " 4 2.56 x l O - 4 3.47 XlO" 4 3.92 x l O - 4 4.68 x l O - 4 5.37 x l O - 4 6.3OxIO- 4 7.76 x l O ~ 4 2.3 x 10 ~4 3.OxIO- 6 1.9 x l 0 ~ 5 9.36 x l 0 ~ 5
Refs. 346
102.9
83.7
c c c
89.5
130.7
132.4
130.7
tn tn tn tn tn tn tn tn tn
exp[- US35/RT]
154.8-171.5
i(200-225) i(200-225) i(200-225) i(100-200) i(440-610) i(440-610) i(440-610)
C2 C2 C2 C2 C2 C2 C2 C2 C2 C2 151
a a a
32 32 32 32 32 32 25 25 25 303 303 303 303 303 303 303 303 303 363 363 363 363 202 202 344 344 344 344 202 202 202 63 63 63 63 63 63 63 363 363 363 363 363 363 363 363 346 353 353 353 353 353 353 353 353 353 353 244 337 337 337
Notes page 11-69; References page II - 70
TABLE 3. cont'd Number of C atoms 12 (cont'd)
13
Initiator
Solvent
tert-Butyl 1,1,3,3-tetramethylbutyl peroxide
Cumene
1-Hydroxy-l-hydroperoxydicyclohexyl peroxide
Benzene
Di-(I -hydroxycyclohexyl)peroxide Diisopropylaminomethyltert-amyl peroxide
Chlorobenzene
1-Phenylethyl terf-butyl peroxide terf-Butyla-cumyl peroxide
Chlorobenzene terf-Butylbenzene
Styrene
Chlorobenzene
Cumene
Dodecane
14
15 16
terf-Butyl />-chlorocumyl peroxide tert-Butyl p-nitrocumyl peroxide tert-Butyl l,l-dimethyl-2-phenylethyl peroxide
Cumene Cumene Cumene
U-Di-(terf-butylperoxy)cyclohexane Ethyl-3,3-di-tert-butylperoxy)-butyrate l-[4-(Dimethylamino)phenyl]ethyl tert-butyl peroxide
Benzene Benzene Chlorobenzene
tert-Butyl /?-methoxycumyl peroxide tert-Butyl p-methylcumyl peroxide terf-Butyl m-methoxycumyl peroxide Bis(l, 1,2,2-tetramethylpropyl) peroxide 2-[4-(Dimethylamino)phenyl]propyl tert-buty\ peroxide l,l-Di-(terf-amylperoxy)cyclohexane tert-Butyl 3-isopropenylcumyl peroxide
Cumene Cumene Cumene Cumene Chlorobenzene
2,5-Dimethyl-2,5-di(tert-butylperoxy)-hexane
Benzene
Benzene Chlorobenzene
Chlorobenzene
2,5-Dimethyl-2,5-di(terr-butylperoxy)-3-hexyne
Benzene
T( 0 C)
kd (s" 1 )
110 120 130 140 85 100 115 130 105 120 110 120 130 129.2 138 158 115 136 159 T(K) 138 158 125 128 138 148 158 125 125 110 120 130 140 93
1.085 x 10~5 3.73 x 10 ~5 1.141 x 10~4 3.40xl0~ 4 9.6xlO~ 6 5.1 x 10 ~5 1.9 xlO~ 4 5.2 x l O - 4 ~1.9xl0~5 ~1.9xlO~4 3.9xl0"5 1.21 x 10~4 3.OxIO" 4 3.09 x 10~5 1.48 xlO~ 4 9.62 XlO" 4 1.93 x 10 ~5 1.93 xlO~ 4 1.93 x l 0 ~ 3 1.17 xlO 1 5 1.44 xlO~ 4 8.88 xlO~ 4 3.04 x l 0 ~ 5 4.44 x 10 ~5 1.39 xlO~ 4 3.21 x 10 ~4 8.88 xlO~ 4 2.42 x 10 ~5 2.20 x 10 ~5 4.35 x 10 ~6 1.458 x 10~5 4.70xl0~ 5 1.463 xlO~ 4 1.9xlO~ 5
111 100.4 110.8 120.9 129.2 129.2 125 125 125 125 129.2
1.9xl0" 5 1.82 xlO~ 6 6.97 x 10 ~6 2.18 x l 0 ~ 5 6.18 x l 0 ~ 5 5.22 x l 0 ~ 5 3.72 x 10 ~5 3.22 x 10 ~5 2.84 x 10 ~5 4.84 xlO~ 4 1.51 x 10~4
90 104 126 152 T(K) 115 130 145 115 134 156 T (K) 115 130 145 160
1.9xl0~ 5 1.93 x 10 ~5 1.93 x 10 ~4 1.93x10-3 1.161xl0 13 1.15 x l 0 ~ 5 6.86 x 10 ~5 4.75 xlO~ 4 1.93 x l 0 ~ 5 1.93 xlO~ 4 1.93 x l 0 ~ 3 1.68 x 1016 3.91 x 10 ~6 2.35 x 10 ~5 1.14 xlO~ 4 6.17 xlO~ 4
Ea (kj/mol)
Notes
a,c2 a,c2 a,c2 a,c2
132.4
tn tn tn a a
exp[-146.98//?7] a a 146.4
a a a a
a a 151.7
m2
m2
a
exp[-128.33/#7] 166.9
exp[- 155.49/RT] 156.9
a a a
a a a a
Refs. 363 363 363 363 337 337 337 337 344 344 303 303 303 282 80 80 344 344 344 344 80 80 352 80 80 80 80 352 352 363 363 363 363 338 338 282 282 282 282 282 352 352 352 352 282
338 344 344 344 344 126,337 126,337 126,337 344 344 344 344 126,337 126,337 126,337 126,337
TABLE 3. cont'd Number of C atoms 16 (cont'd)
17
18
Initiator 2,5-Dimethyl-2,5-di(terf-butylperoxy)-3-hexyne
rc-Butyl-4,4-bis(terf-butylperoxy)valerate
Solvent Chlorobenzene
Dodecane
1,1 -Bis-(terr-butylperoxy)3,3,5-trimethylcyclohexane
Benzene
Cumyl peroxide
Benzene
terr-Butylbenzene Chlorobenzene
Cumene
Dodecane
Diisopropylcarbinol Neat
Bicyclo[2.2.2]octane1-formyl peroxide
20
a,a'-Bis(tert-butyrperoxy)diisopropyl benzene
Carbon tetrachloride
Chlorobenzene Cyclohexane Isooctane Toluene Benzene
Chlorobenzene
Neat
24
TABLE 4. Number of C atoms 4
2,5-Dimethyl-2,5-di-(2-ethylhexanoylperoxy) hexane
Benzene
T( 0 C)
^d(S" 1 )
Ea (kj/mol)
Notes
Refs.
120
1.93 x 10~5
344
141 164 T (K) 100 115 130
1.93 xlO~ 4 1.93 x l O - 3 1.90 x 1015 5.83 x 10" 6 3.53 x 10 ~5 2.9IxIO-4
344 344 344 8 8 8
85 100 115 115 130 145 158 112 132 154 T (K) T (K) 138 158 128 138 148 158 138 150 155 160 165 30
6.9xlO~ 6 138 5.05 x l O - 5 2.7IxIO-4 2.05 x 10 ~5 159 1.05 x l O - 4 6.86 x l O - 4 1.72 x 10 ~3 1.93 x IO" 5 1.93 xlO~ 4 1.93 x l O - 3 9.24 x 1015 exp[- 152.61/RT] 4.31 x 1014 exp[- 1443/RT] 2.57 x l O - 4 1.52 x l O - 3 8.75XlO" 5 2.31 x 10- 4 5.37 xlO~ 4 1.83 x l O - 3 3.16 x 10~4 3.98 x 10~3 4.81 x 10- 3 9.63 x l O - 3 1.16 x l O - 2 1.71 x 10 " 4 1.73 x 10 " 3 1.68 x l O - 4 6.2OxIO" 4 6.IxIO-5 5.OxIO- 5 3.66 x 10 " 4 1.9 x l O " 5 147 4.91 x 10 ~5 9.61 x 10- 5 1.93 x 10~5 1.93 x l O - 4 1.93 x l O - 3 7.65 xlO 1 5 exp[- 152.69 kJ/RT] 3.61 x 10~3 4.44 x l O " 3 4.62 x l O - 3 1.9xlO- 5
30 30 30 30 115 125 130 114 134 156 T(K) 155 160 165 68
exp[- 150.61/RT] a a a a a a a a a a
a a a a a a a a a a a n vi
a a a
a a a a
337 337 337 337 126,337 126,337 80 344 344 344 344 67 80 80 80 80 80 80 80 371 371 371 371 244 244 244 244 244 244 244 337 337 337 344 344 344 344 371 371 371 338
ACYL PEROXIDES
Initiator Acetyl peroxide
Solvent Acetic acid
T( 0 C) 55.2 64.9 75.2 85.2 73.2
kd (s"1) 2.8 x 10~6 9.9xlO~ 6 3.75 x l O - 5 1.3OxIO- 4 2.62 x l O - 5
£ a (kj/mol)
Notes
126.4
d,e d,e d,e d,e a
Refs. 106,176 106,176 106,176 106,176 100
Notes page 11-69; References page II - 70
Table 4. cont'd Number of C atoms 4 (cont'd)
Initiator Acetyl peroxide
Solvent Benzene
H-Butanol seoButanol tert-Butanol Carbon tetrachloride
Chloroform Cyclohexane
Cyclohexene
Cyclopentene
Cumene Decane n-Dodecane Ethanol Heptane Hexadecane «-Hexane 1-Hexene
2-Methyl-l-pentene
rc-Octadecane n-Octane Isooctane
1-Pentene
Propionic acid
J( 0 C) 35 55 65 50 70 85 70 60.3 80 55.2 64.9 75.2 85.2 60.3 60.3 60.3 80.3 26 46 65 80 80.3 55.2 64.9 75.2 85.2 60 70 80 90 100 70 80 90 100 80 80 60 80 60.3 80.3 80 80 60 70 80 90 100 80 90 100 60 60 80 60 55.2 64.9 75.2 85.2 70 80 90 64.9 85.2
A^(S"1) 9.5 x 10 ~7 3.14 XlO" 6 1.27 x l O - 5 1.1 x l O " 6 2.39X10" 5 1.73 x l O " 4 2.38 XlO" 5 5.OxIO" 6 8.7xl0-5 2.6 XlO" 6 1.07x10-5 4.65x10-5 1.62 XlO" 4 3.4xlO" 5 3xl0~5 3.1xl0"6 4.9x10-5 1.08 x 10 " 7 4.84 XlO" 7 2.11 x l O " 6 5.5x10-5 ~5 2.1 x 10"6 8.3 XlO" 6 3.6OxIO- 5 1.27 XlO" 4 4.5xlO~ 6 1.77x10-5 7.0x10-5 2.28 xlO" 4 7.61X10" 4 1.6OxIO-5 7.0x10-5 2.55 XlO" 4 7.25 xlO" 4 7.6xl0-5 6.85 x l 0 ~ 5 2.3xlO" 6 6.15x10-5 1.01 x 10 " 4 1.4OxIO-3 7.72 x 10 " 5 5.39 x l O " 5 3.4xlO~ 6 2.35 x 10" 5 8.7x10-5 3.05 XlO" 4 9.83 x l O " 4 9.OxIO" 5 3.12 XlO" 4 9.81 x 10 " 4 1.9xlO" 6 2.9xlO" 6 7.34x10-5 2.9xlO~ 6 2.35 x l O " 6 9.4 XlO" 6 4.03x10-5 1.49 XlO" 4 2.45 x 10 " 5 9.4 x 10"5 3.22 XlO" 4 1.4 x l O " 5 1.66 XlO" 4
Ea (kj/mol)
Notes
134
a a a a
135.1
c,e c,e c,e c,e
133.9
131.4
c,e c,e c,e c,e
133.5
137.2
129.7
132.6
126.8
134.7
c,e c,e c,e c,e
d,e
Refs. 68 68 68 337 126,337 126,337 16 4 20 106,176 106,176 106,176 106,176 4 4 4 4 68 68 68 20 4 106,176 106,176 106,176 106,176 20 20 20 20 20 20 20 20 20 20 168 70 168 4 4 168 168 70 20 20 20 20 20 20 20 70 70 168 70 106,176 106,176 106,176 106,176 20 20 20 106,176 106,176
Table 4. cont'd Number of C atoms 4 (cont'd)
Initiator Acetyl peroxide
Solvent n-Tetradecane Toluene
Vapor (toluene)
6
Propionyl peroxide
Acetic acid Acetic anhydride Benzene
Benzonitrile Dioxane n-Hexane Isooctane Nitrobenzene Toluene Vapor
2-Iodopropionyl peroxide
Perfluoropropionyl peroxide
8
2,2,3,3-Tetrafluoropropionyl peroxide tert-Butyl permaleic acid Butyryl peroxide
Acetone Benzene
H-Butyl vinyl ether Cyclohexene 95%Ethanol Freon 113
Isooctane Freon 113 Acetone Acetic acid Acetic anhydride
J( 0 C) 60 80 60.3 55.2 64.9 75.2 85.2 73.2 85.5 90 88.0 134.7 150.7 161.7 170.7 184.2 65.0 85.0 65.0 85.0 65.0 85.0 50 70 85 65.0 85.0 65.0 85.0 65.0 85.0 65.0 86.5 65.0 85.0 65.0 85.0 65.0 85.0 99.4 134.4 152.2 176.4 190.9 T (K) 56 62.5 62.5 62.5 62.5 62.5 62.5 20 30 40 T (K) T(K) 25 35 87 65.0 85.0 65.0 85.0
^d(S1) 2.OxIO" 6 5.9OxIO" 5 5xlO"6 2.7 xlO~ 6 1.14 x l O " 5 4.70xl0~ 5 1.59 xlO~ 4 3.06 XlO" 5 1.72 XlO" 4 7.33 x l O " 5 3.12 x l O " 4 3.1 x 10" 2 1.18XlO"1 2.77XlO" 1 6.10X10" 1 1.76 3.8xlO~ 5 4.3 XlO" 4 3.5 x l O " 5 4.5 x l O " 4 1.88 x KT 5 2.4OxIO" 4 2.72 x l O " 6 4.3OxIO" 5 2.89 XlO" 4 3.9xl0"5 5.IxIO"4 4.5 x 10~5 4.5 x l O " 4 1.50x 10" 5 1.72 x l O " 4 9.8 x l O " 6 1.44 x l O " 4 3.7xl0"5 4.1 x 10 " 4 1.87 x l O " 5 2.54 x l O " 4 1.0 x l O " 5 1.6 xlO~ 4 8 xlO"4 2.6 XlO" 2 1.22XlO- 1 8.OxIO" 1 2.33 2.5 x 10 " 4 2.19 x 10 ~4 (2.40-2.81) x 10 ~4 7.12 XlO" 4 (2.36 ±0.07) x 10 ~4 2.47 x 10" 4 2.7xlO" 4 4.OxIO" 4 2.19 x 10 " 5 8.5OxIO- 5 3.26 XlO" 4 1.8 x 109 1.5xlO 17 2.26 x 10 " 4 7.17 x 10 " 4 1.9xlO~ 5 4.7 x 10" 5 5.6 x l O " 4 4.3 x 10 " 5 5.5 x l O " 4
Ea (kj/mol)
129.7 133.9
138.1 129.7 123.4
123.0 128.9 129.3 127.6
130.5 116.7
Notes
c,e c,e c,e c,e a a a
c,e c,e d,e c,e c,e c,e a a a d,e d,e c,e c,e
123.8 130.5 120.9
c,e c,e c,e
130.1 125.5 125.5
exp[- 125.5/RT]
100.1
s s n,s p s s s h
exp[- 83.8//?7] exp[- 121.5/RT} 86.3
h
108.8
125.1
a c,e c,e c,e
Refs. 70 168 4 106,176 106,176 106,176 106,176 100 100 113 105 105 105 105 105 105 51 51 51 51 51 51 126,337 126,337 126,337 51 51 51 51 51 51 51 51 51 51 51 51 51 51 85 85 85 85 85 85 77 77 77 77 77 77 77 283 283 283 304 304 283 283 338 51 51 51 51
Notes page II - 69; References page II - 70
Table 4. cont'd Number of C atoms 8 (cont'd)
Initiator Butyryl peroxide
Solvent Benzene Benzonitrile Dioxane Hexane Isooctane Toluene Vapor
Isobutyryl peroxide
Acetonitrile Benzene
Benzonitrile tert-Butanol Carbon tetrachloride
Chlorobenzene
Chloroform Cyclohexane Fluorobenzene Isooctane
Cyclopropane formyl peroxide
Isopropanol Nitrobenzene Nujol Tetralin Toluene Vapor p-Xylene Carbon tetrachloride
Diacetyl succinoyl diperoxide
Styrene
Succinoyl peroxide
Acetone
T( 0 C) 65.0 85.0 65.0 85.0 65.0 85.0 65.0 85.0 65.0 85.0 65.0 85.0 65.0 85.0 96.7 127.4 158.9 178.9 T(K) 40 20 30 40 40 40 40 40 40 45 50 55 60 40 23 39 57 T (K) 40 40 40 40 25 35 45 55 T (K) 40 40 40 40 40 40 40 40 64.5 70.4 77.8 60 73.5 85 70 85 100
^a(S1) 2.24 x 10~5 3.02 x l O - 4 4.3 x 10~5 5.8 x l O - 4 4.6xlO~ 5 4.6 x l O - 4 1.14 x 10~5 1.53 x l O - 4 1.11 x 10~5 1.56 x l O " 4 2.14 x l O " 5 2.87 x l O - 4 1.6 x l O " 5 2.OxIO- 4 8.6 x l O " 4 1.5 XlO" 2 3.OxIO" 1 1.27 1.9 xlO~ 4 6.81 x 10 " 4 1.6 x l O " 5 6.75 x l O - 5 2.59 x l O - 4 2.38 XlO" 4 2.4OxIO- 4 4.2xlO~ 4 2.5IxIO" 4 7.8xl0"5 1.58 XlO" 4 3.05 x l O - 4 5.61 x 10~4 7.67 xlO~ 4 1.73 x 10 " 4 1.93 x l O - 5 1.93 x l O - 4 1.93 XlO" 3 3.37 xlO 1 4 7.5 x 10 ~5 4.5 x 10 ~5 4.7OxIO- 5 1.23 x 10 " 4 3.35 x 10 ~6 1.54 XlO" 5 6.14 x l O - 5 2.26 x l O - 4 2.8 x 1014 3.2 x l O " 5 3.05 x 10~4 5.8OxIO- 4 4.63 XlO" 5 1.75 x 10 ~4 1.43 x 10 ~4 -1 x 10 ~5 1.4OxIO- 4 4.4xlO" 6 9.3 x 10 ~6 2.31 x 10- 5 5.2xlO~~6 2.3 x l O - 5 9.3 x 10- 5 2.8OxIO- 5 1.21 x 10- 4 4.36 x l O - 4
Ea (kj/mol)
Notes
131.4
d,e c,e d,e
131.4 116.3 131.4 133.5 130.5
c,e c,e c,e c,e c,e c,e d,e c,e
123.8 123.8
exp[-123.8//?7] 109
1113 a a a In3
exp[- 109.06//?7]
114.2
exp[- 1H2/RT]
125.5
99.6
a a a
Refs. 51 51 51 51 51 51 51 51 51 51 51 51 51 51 85 85 85 85 85 167 337 337 337 167 148,244 148 148 148 148 148 148 148 148 344 344 344 344 148 148 167 148 84 84 84 84 84 148 148 148 167 148 148 167 148 34 34 34 215 215 215 126,337 126,337 126,337
Table 4. cont'd Number of C atoms 9
10
11
Initiator Acetyl benzoyl peroxide
T( 0 C)
Chlorobenzene
70 96 96 75 75 75 41 41 65 70 75 14 25 44.5 56.5 44.5 60 73.5 85 50 60 70
5-Bromo-2-thenoyl peroxide 4-Bromo-2-thenoyl peroxide 5-Chloro-2-thenoyl peroxide a-Chloropropionyl m-chlorobenzoylperoxide Cyclobutane formyl peroxide
Carbon tetrachloride Carbon tetrachloride Carbon tetrachloride Acetonitrile Cyclohexane Carbon tetrachloride
Cyclopropane acetyl peroxide
Carbon tetrachloride
Diacetyladipoyl diperoxide
Styrene
Difuroyl peroxide
styrene
2,2,3,3,4,4,5,5-Octafluoropentanoyl peroxide
Freon 113
Perfluoro-2-(2-ethoxysulfinic acid) propionyl peroxide Pivaloyl peroxide 2-Thenoyl peroxide 3-Thenoyl peroxide Benzoyl isobutyryl peroxide
m-Chlorobenzoyl isobutyryl peroxide
12
Solvent
Freon 113 Carbon tetrachloride Carbon tetrachloride Carbon tetrachloride Acetonitrile Cyclohexane
Acetonitrile Cyclohexane
p-Chlorobenzoyl isobutyryl peroxide
Cyclohexane
p-Fluorobenzoyl isobutyryl peroxide
Cyclohexane
5-Methyl-bis-2-thenoyl peroxide p-Nitrobenzoyl isobutyryl peroxide
Carbon tetrachloride Cyclohexane
P-Allyloxypropionyl peroxide
Toluene
p-Xylene
m-Chlorobenzoyl 2-methylbutanoyl peroxide
Acetic acid Acetonitrile
kd (s"1) 2xl0~5 5.12 x l O " 4 4.08 XlO" 4 1.53 x 10 " 5 1.14 x 10 ~5 1.58 x 10 ~5 3.05 x 10 ~5 1.51xl0~ 5 5.15 x 10 " 5 8.95,6.63 x l O " 5 1.41 x 10" 4 9.45 x 10 ~5 9.75,10.57 x 10" 4 5.01 x 10 " 5 2.64 XlO" 4 6.5-8.OxIO" 4 6.6xlO" 6 4.73 XlO" 5 1.84 x l O " 4 7.0xl0"7 2.9 xlO~ 6 1.03 XlO" 5
20 30 40 T(K)
3.29 x 10 " 5 1.27 XlO" 4 5.01 x 10 " 4 2.8xlO 1 4
10 75 75 41 41 70 40 50 60 70 41 40 50 41 50 55 60 65 55 60 65 70 75 40 45 50 55 60 70 80 90 70 80 90 40 40
1.9xlO~ 4 2.21 x 10 ~~5 2.14 x 10 " 5 4.06 x 10 " 4 1.63 x l O " 5 3.05 xlO~ 4 1.45 x l O - 5 5.398 XlO" 5 1.924 x l O " 4 6.872 x l O " 4 1.03 x 10 ~3 3.486 x 10 " 5 1.362 x l O " 4 4.4OxIO- 5 1.029 x 10 ~4 1.651 x 10- 4 3.21 x 10- 4 5.638 x l O - 4 1.117 x 10 " 4 2.038 XlO" 4 4.893 x l O - 4 9.603 x l O " 4 2.92 x 10 " 5 8.1xl0"5 1.336 x l O " 4 2.889 x l O - 4 4.725 X l O ' 4 8.921 x 10 ~4 2.0IxIO" 5 8.62 x l O " 5 2.53 x l O " 4 2.32 x l O " 5 8.88 x l O " 5 2.95 x l O " 4 1.60 x 10 ~3 1.72 x 10 " 3
Ea (kj/mol)
Notes
z(25),vi3 z(19),vi3 a,mi a,mi a,mi ni3 ni3
101.7 n
125.7
h
100.6
h
exp[-95.1//?7]
a,mi a,mi
112.5
h,j j j j
111.3
h,j j j
a
a a a a a a
Refs. 155 284 284 232 232 232 167 167 34 34 34 34 34 24 24 24 215 215 215 287 287 287 283 283 283 304 244 232 232 167 167 167 164 164 164 164 167 164 164 167 164 164 164 164 164 164 164 164 232 164 164 164 164 164 191 191 191 191 191 191 256 256
Notes page II - 69; References page II - 70
Table 4. cont'd Number of C atoms 12 (cont'd)
14
Initiator m-Chlorobenzoyl 2-methylbutanoyl peroxide
Solvent
Cyclobutane acetyl peroxide
2-Butanol Carbon tetrachloride Cyclohexane Carbon tetrachloride
Cyclopentane formyl peroxide
Carbon tetrachloride
Hexanoyl peroxide 5-Hexenoyl peroxide
Toluene Toluene
4-Methoxybenzoyl isobutyrylperoxide
Cyclohexane
4-Methylbenzoyl isobutyrylperoxide
Cyclohexane
4-Methyl-2-thenoyl peroxide 5-Methyl-2-thenoyl peroxide Perfluoro-2-furnanacetyl peroxide Perfluoro-2-propoxypropionylperoxide Perfluoro-2-n-propoxypropionylperoxide
Carbon tetrachloride Carbon tetrachloride Freon 113 Freon 113 perF-ether mix. Freon 113
Perfluoro-2-iso-propoxypropionylperoxide
Freon 113
2-Azidobenzoyl peroxide
Benzene
Benzoyl peroxide
Acetic acid Acetone
Acetonitrile Acetophenone
Allyl alcohol Anisole Benzaldehyde Benzene
T( 0 C) 40 40 40 65 70 75 40 45 50 55 77 60.1 70.4 76.4 85.0 55 60 65 70 40 50 60 70 75 75 T (K) T(K) T (K) 20 30 40 20 30 40 50 80 75 50 70 85 100 70 70 80 94.5 80 30 80 90 25 30 55 60 60 80 70 78 78 79.8 80 66 72.5 78 70
kd (s"1) 9.0xl0~4 1.32 x 10 ~4 6.OxIO" 5 1.37 x 10 ~5 2.13,3.08 x 10- 5 3.83 x l O - 5 1.50 x 10 ~5 2.55 XlO" 5 4.96 XlO" 5 8.17,7.85 x 10" 5 1.186 x 10 ~4 1.06 x 10 " 5 4.15 XlO" 5 8.59 x l O " 5 2.668 x l O - 4 5.465 x 10 ~5 1.024 x l O " 4 1.876 XlO" 4 3.208 XlO" 4 9.6IxIO" 6 3.619 x l 0 ~ 5 1.305 XlO" 4 4.772 x l O " 4 2.92 x 10 " 5 4.21 x 10 ~5 1.2 x 1011 4.4xlO 1 4 8.9 x 1016 4.81 x 10 ~5 1.96 x 10 ~4 7.16 XlO" 4 8.32 x 10 ~5 3.43 x 10 ~4 1.34 x l 0 ~ 3 2.5 x 10~5 9.4 XlO" 4 7.53 x 10 " 5 2.25 x 10 ~6 2.63X10- 5 1.34 xlO~ 4 5.83 xlO~ 4 1.76 x 10 ~5 1.15 x 10~5 4.32xlO- 5 2.30xl0~ 4 3.80 x 10 ~4 1.42 x 10 ~7 5.50xl0~ 5 1.71 x 10- 4 6.4xlO~ 5 4.80 xlO~ 8 1.14 xlO~ 6 2.76 xlO~ 6 2.0xl0~6 2.5xlO-5 1.38x10-5 2.3OxIO- 5 1.67x10-5 3.48x10-5 4.8x10-5 7.72 x 10 ~6 1.87x10-5 3.77x10-5 1.17x10-5
Ea (kj/mol)
129.3
Notes
c c c c
j j j j a,mi ^m1 exp[- 11A/RT] exp[- 9Z.5/RT] exp[-110.2/RT] 100.1
h
102.7
h
111.3
126.4
116.3
124.3
129.7
133.9
d2 d2 a,r a a a a tj a a a a,r a a,r a,r p2 a a,r a,r m2 m2 a c X9
a a a a
Refs. 256 256 256 34 34 34 34 34 34 34 209 209 209 209 209 164 164 164 164 164 164 164 164 232 232 304 304 304 283 283 283 283 283 283 161 161 74 126 126 126 126 124 5 5 5 74 109 74 74 279 109 74 74 14 14 213 230 230 170 20 131 131 131 73
Table 4. cont'd Number of C atoms 14 (cont'd)
Initiator Benzoyl peroxide
Solvent Benzene
Benzyl alcohol Bromobenzene
Butanol Butanone Di-n-butyl phthalate
Carbon tetrachloride Chlorobenzene
Chloroform Cumene
Cyclohexane Decane Decalin Dioxane
J( 0 C) 75 80 80 50.8 54.9 60.9 65.6 71.0 75.8 70 85 100 70 70 75 75 85 85 100 100 79 80 80 80.2
80 80 117 127 137 147 75 79 70 80 80.2 80.2 80.2 80.2 71 91 113 T (K) 30 80 85 90 30 45 60 80 T (K) 100 80 80 80 70 80 80 80
kd (s"1) 2.62 x 10 " 5 4.39 XlO" 5 3.27 XlO" 5 4.28 XlO" 7 8.53 x l O - 7 1.66 x l O - 6 3.22 XlO" 6 5.94 x l O - 6 1.19 XlO" 5 1.27 XlO" 5 8.94 x l O - 5 4.96 x l O - 4 1.03 x l O - 5 1.18 XlO" 5 1.48 x l O - 5 1.66 x l O - 5 4.7 x l O - 5 5.5 XlO" 5 2.28 x l O - 4 2.56 x l O " 4 2.58 x l O - 5 3.35 x l O " 5 4.44 x 10 " 4 8.15 x l O " 5 2.19 x l O " 5 3.84 x l O - 5 3.55 x l 0 ~ 5 4.34 x l O - 5 6.06 x 10 " 4 4.64 x 10 " 5 2.78 x 10 ~3 7.44 X l O " 3 1.72 x l O - 2 3.89 X l O " 2 1.07 x 10 " 5 1.69 X l O " 5 1.35 x 10 ~5 4.64 x l O - 5 2.85 x l O " 5 2.36 x l O - 5 3.52 x l 0 ~ 5 2.62 X l O " 5 1.93 x l O - 5 1.93 x l O " 4 1.93 XlO" 3 6.94 x l O 1 3 5.47 x 10 ~8 3.69 x 10 ~5 6.39 XlO" 5 1.19 x l O - 4 7.3OxIO- 8 1.85 x l O 7 1.45 x l O - 6 1.70 XlO" 5 1.20 x 10 13 2.5 XlO" 4 7.72 x 10 ~5 2.53 x 10 " 5 2.26 x 10 " 4 1.30 x 10 " 5 6.72 x l O - 4 4.2OxIO- 4 4.18 x l 0 ~ 5
Ea (kj/mol)
123.8
130
128.0 124.3
Notes a a a,b 2 a,t2 a,t2 a,t2 a,t2 a,t2 a,t2 a a a a,m2 t2 m3 m3 m3 a,t6 a a,r t9
Hi1 m3 m5
120.1
a,r a,r yi6
a,r t 6 ,a I1 a,r t9 Cm 1 c,m 3
exp[- 12235/RT] a a,r a,r a,r a 120.5
exp[- 120.5/RT] a,t7 a,r a,r ti a,r a,r a,m!
Refs. 73 73 347 69 69 69 69 69 69 337 126,337 126,337 16 124 12 12 12 12 12 12 120 7 74 231 231 231 231 231 74 74 236 236 236 236 74 121 124 74 231 231 231 231 344 344 344 344 109 74 74 74 109 67 67 67 67 122 74 270 74 74 74 6 232
Notes page 11-69; References page 11-70
Table 4. cont'd Number of C atoms 14 (cont'd)
Initiator Benzoyl peroxide
Solvent Ethanol
Ethylbenzene
90% Formic acid H-Heptane
Hexadecane Hexane Isooctane Isopropylbenzene Methyl acetate Methylcyclohexane 4-Methyl-2pentanone a-Methylstyrene Mineral oil Neat Nitrobenzene PEG 400
90% aq. PEG 400
80% aq. PEG 400
70% aq. PEG 400
rt-Pentanol Phenol Propionic acid Propylene glycol
Styrene
T( 0 C) 25 40 50 30 75 80 85 90 80 80 80 80 130 135 140 145 145 145 145 150 155 160 80 80 80 80 80 49.2 53.9 80 80 70 80 105 80 30 25 40 50 70 25 40 50 70 25 40 50 70 25 40 50 70 80 80 80 25 40 50 34.8 49.4 61.0 74.8 100.0
^d(S1) 3.02 x l O ~ 8 2.77 x l O " 7 4.72 x l O - 7 3.61 x 10 " 8 1.8IxIO- 5 3.33 XlO" 5 5.56 XlO" 5 1.01 x 10- 4 3.15 x l 0 ~ 5 6.94 x 10 " 4 3.11 x 10 ~5 2.7IxIO-5 5.73 XlO" 3 1.02 x l O " 2 1.54 x l O - 2 2.25 XlO" 2 2.22xlO-2 2.21 x 10~2 2.12 x l O - 2 3.47 x l O " 2 5.21 x 10- 2 7.87 x l O - 2 2.51 x 10 " 5 2.85 x 10 ~5 2.79 x 10 ~5 2.7OxIO" 5 3.34 x 10~5 6.28 x 10 ~7 1.0 XlO" 6 5.25 x 10 ~5 4.28 x 10 ~5 3.02 x 10 " 5 2.89 x 10~5 7.22 x 10 ~3 4.58 x 10 ~5 6.6IxIO-8 5.0IxIO-7 5.73 x l O - 6 1.15 x l 0 ~ 5 1.15 XlO" 4 3.65 x 10~7 5.35 x l O " 6 1.15 x l O - 5 1.15 x l O " 4 2.77 x 10 ~7 3.09 x l O " 6 7.29 x l O - 6 1.15 x l O - 4 1.71 x 10 ~7 2.1IxIO-6 5.01 x 10- 6 1.15 x l O " 4 1.48 x 10 ~4 6.25 x 10 " 4 3.19 x 10~5 3.25 x 10 ~8 1.51 x l O ~ 7 3.16 x l O - 7 3.89 x 10 ~8 5.28 XlO" 7 2.58 x l O - 6 1.83 x l 0 ~ 5 4.58 x l O " 4
£ a (kj/mol)
Notes a a a a a,r a,r a,r a,r c a,r a,r z (1500) z (1500) z (1500) z (500) z (1000) z (1500) z (2000) z (1500) z (1500) z (1500)
123.8
117.6
m2 c a,t2 a,t2 a,r a,r a m2 a a,r a a a a a a a a a a a a a a a a a a,r a,r a,r a a a a a a a a
Refs. 351 351 351 109 74 74 74 74 239 74 74 270 377 377 377 377 377 377 377 377 377 377 270 270 270 308 229 69 69 74 74 213 308 371 74 109 351 351 351 351 351 351 351 351 351 351 351 352 351 351 351 351 74 74 74 351 351 351 10 10 10 10 10
Table 4. cont'd Number of C atoms 14 (cont'd)
Initiator Benzoyl peroxide
Solvent Poly(styrene)
Tetradecane Tetralin Toluene
Poly(vinylchloride)
Styrene
3-Bromobenzoyl peroxide
4-Bromobenzoyl peroxide 4-terr-Butylbenzoyl peroxide 2-Chlorobenzoyl peroxide 3-Chlorobenzoyl peroxide 4-Chlorobenzoyl peroxide
p-Xylene Benzene
Dioxane Dioxane Dioxane Acetophenone Benzene Acetophenone Dioxane Acetophenone Benzene
Dioxane Styrene
Cyclohexane formyl peroxide
Benzene
Carbon tetrachloride
Cyclopentane acetyl peroxide
Carbon tetrachloride
Diacetylsebacoyl diperoxide
Carbon tetrachloride
T( 0 C) 56.4 64.6 76.7 83.4 98.5 70.9 80.1 89.5 80 80 30 49.0 55.1 60.2 65.1 70.3 60.00 64.6 76.7 83.4 98.5 50 60 70 80 60 80 80 80 80 80 80 80 80 80 80 80 50 85 100 80 34.8 49.4 61.0 74.8 100.0 30 35 40 45 50 35 45 50 60 35 40 45 65 70 75 60 73.5 85
^d(S"1) 3.8 x 10~7 1.47 x l O - 6 9.27 x l O " 6 2.5OxIO- 5 1.41 x l O " 4 2.86 x l O - 6 1.11 x l O - 5 3.33 x l O - 5 2.64 x 10 ~5 3.72 x 10 " 5 4.94 x l O " 8 6.OxIO- 7 1.31 x 10- 6 2.83 x l O - 6 5.69 x l O - 6 1.10 x l O - 5 2.24 x l O " 6 6.3xlO" 7 5.11 XlO" 6 1.44 x l O - 5 9.33 x l O " 5 7 x IO" 7 7.7 x l O - 6 9.9 x l O " 6 3.1OxIO- 5 1.1 x 10 " 6 1.22 x l O - 5 2.6OxIO- 5 2.57 x 10 ~5 3.23 x 10 ~5 6.06 x 10 ~5 3.88 x 10 " 4 3.12 x 10 " 4 2.85 x 10 ~5 2.63 x 10 ~5 3.83 x 10 " 5 2.17 x 10 ~5 6.2 x l O " 7 6.64 x l O - 5 3.86 x l O - 4 3.62 x 10 " 5 8.3xl0-8 8.3 x l O " 7 3.33 x l O - 6 2.22 x l O - 5 4.17 x l O - 4 9.64 x 10 ~5 1.46 x l O " 4 3.1OxIO- 4 5.11xlO" 4 7.77 x l O - 4 6.6xlO~~5 2.1IxIO-4 4.45 xlO~ 4 1.3OxlO" 3 2.87 x l O - 5 5.22,5.29 x 10 " 5 9.67 x l O - 5 1.48 x 10" 5 3.2OxIO" 5 4.97 x l O - 5 1.04 x 10 ~5 5.20xl0~5 2.3OxIO- 4
E a (kj/mol)
120.5 123.8
Notes
Refs.
a a a a a a a a
17 17 17 17 17 15 15 15 270 74 109 69 69 69 69 69 291 17 17 17 17 287 287 287 229 116 116 7 6,232 6,232 232 5 7 5 6 5 7 126 126 126 6 10 10 10 10 10 219 219 219 219 219 148 148 148 148 34 34 34 34 34 34 215 215 215
a,r a a,t2 a,t2 a,t2 a,t2 a,t2 e,m3 a a a a
125.7
c
123.0 128.4 127.2 128.9
84.5
a a,mi a,mi a,m a a a a,mi a a a a a ^m1 a a a a a a,h
Xi X1 xi
Notes page 11-69; References page II - 70
Table 4. cont'd Number of C atoms 14 (cont'd)
Initiator 2,4-Dichlorobenzoyl peroxide
Solvent Benzene
Styrene
2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoroheptanoyl peroxide Heptanoyl peroxide 6-Heptenoyl peroxide
2-Iodobenzoyl peroxide 2-Iodobenzoyl 4-nitrobenzoyl peroxide
3-Methylbenzoyl peroxide 4-Methylbenzoyl peroxide 2-Nitrobenzoyl peroxide
Freon 113 Toluene Toluene
Chloroform Acetone Acetonitrile Benzene Carbon tetrachloride Chloroform Nitrobenzene Dioxane Dioxane Acetophenone Methyl iodide
15
16
3-Nitrobenzoyl peroxide 4-Nitrobenzoyl peroxide 3,5-Dinitrobenzoyl peroxide Perfluoroheptanoyl peroxide
Acetophenone Acetophenone Acetophenone Freon 113
Benzoyl phenylacetyl peroxide
Benzene
4-terf-Butylbenzoyl isobutyryl peroxide
Cyclohexane
3-Cyanobenzoyl benzoyl peroxide 3-Methoxybenzoyl benzoyl peroxide 4-Methoxybenzoyl benzoyl peroxide 4-Methoxybenzoyl 3-bromobenzoyl peroxide 4-Methoxybenzoyl-3,5-dinitrobenzoyl peroxide
Dioxane Dioxane Dioxane Dioxane Benzene Nitrobenzene
J( 0 C) 70 70 50 70 85 34.8 49.4 61.0 74.8 100.0 30 40 77 70 70 77 85 22 25 25 25 25 25 25 80 80 59.3 80 24.95 45.05 80 80 80 20 30 40 20 25 25 25 30 35 55 60 65 70 80 80 80 80
^d(S" 1 ) 9.7OxIO" 5 1.24 xlO~ 4 1.08 xlO~ 5 1.37 xlO~ 4 7.69 XlO" 4 3.88 x 10 " 6 2.39 x l 0 ~ 5 7.78 xlO~ 5 2.78 xlO~ 4 4.17 x l 0 ~ 3 1.14 x 10~4 4.06 x 10 ~4 1.24 x 10 ~4 5.33 x 10 ~5 5.01 x 10 ~5 1.07 xlO~ 4 2.88 xlO~ 4 1.86 x 10 ~3 3.0xl0~4 2.1x 10 ~4 5.7xl0~5 3.4xl0~5 2.8xlO~ 4 6.2xlO~ 4 4.38 x 10 ~5 6.11 x 10 ~5 5.80xl0~ 5 1.34 x l 0 ~ 3 1.78 xlO~ 5 1.50xl0~ 4 3.80xl0"5 4.33 x 10 " 5 1.87 x l 0 ~ 5 3.01 x 10 ~5 1.11 xlO~ 4 4.20xl0~4 1.10 x 10~4 2.05 xlO~ 4 3.15 xlO~ 4 6.38 xlO~ 4 3.88 xlO~ 4 6.67 xlO~ 4 6.543 x 10 ~5 1.171 x 10~4 2.663 xlO~ 4 5.016 xlO~ 4 2.73 x 10 ~2 4.82 x 10 ~2 7.57 x 10 ~5 4.43 x 10 ~2
£ a (kj/mol)
117.6
100.6
Notes a,j a,k a a a a a a a a h a a,k a,j a,j a,k
119.7 81.2 126.4 126.8 130.5 98.0
a,mi a,mi a a h a a a
90.8 vi n
ti 0 tio t 10 tio a,m\ a,mi a,mi a,mi
Refs. 16 16 126,337 126,337 126,337 10 10 10 10 10 283 283 19 19 19 19 19 82 78 78 78 78 78 78 232 232 5 5 82 82 5 5 5 283 283 283 222 222 222 222 222 222 164 164 164 164 6 6 6 6
51 51 51
1.02 x 10 ~5 9.61 x 10 ~4 1.67 XlO" 3
t5
108 108 108
a a
89 89
a a a
95 116 116 126 126 126
4-Methoxybenzoyl 4-nitrobenzoyl peroxide
Benzene
70 70
2.08 x 10 ~5 8.03 x l 0 ~ 5
3,5-Dibromo-4-methoxybenzoyl peroxide
Benzene
Caprylyl peroxide
Benzene
60 60 80 50 70 85
9.5 x 10 ~7 6.1 xlO~ 7 9.4 x 10 ~6 3.44 x 10 ~6 5.78 x l 0 ~ 5 3.78 xlO~ 4
128.9
Table 4. cont'd Number of C atoms 16 (cont'd)
Initiator
Solvent
Caprylyl peroxide /7-(Chloromethyl)benzoyl peroxide
Mineral oil Acetone
3-Cyanobenzoyl peroxide 4-Cyanobenzoyl peroxide Cycloheptane formyl peroxide
THF Toluene Dioxane Acetophenone Dioxane Carbon tetrachloride
Cyclohexane acetyl peroxide
Carbon tetrachloride
2-Ethyl-4-methyl-2-pentenoyl peroxide 2-Ethylhexanoyl peroxide 2-Ethyl-2-hexenoyl peroxide 2-Iodophenylacetyl peroxide
2-Methoxybenzoyl peroxide 3-Methoxybenzoyl peroxide 4-Methoxybenzoyl peroxide 2-Methylbenzoyl peroxide 3-Methylbenzoyl peroxide 4-Methylbenzoyl peroxide Endo-norbornane-2-carbonylperoxide
Mineral oil Mineral oil Mineral oil Acetone Chloroform Toluene Acetophenone Acetophenone Dioxane Acetophenone Dioxane Acetophenone Acetophenone Dioxane Acetophenone Dioxane Carbon tetrachloride
Exo-norbornane-2-carbonylperoxide
Carbon tetrachloride
Endo-norbornene-5-carbonylperoxide
Carbon tetrachloride
Exo-norbornene-5-carbonylperoxide
Carbon tetrachloride
Dioctanoyl peroxide
w-Heptane
T( 0 C) T (K) 70 70 70 70 80 80 80 35 40 45 65 70 75 54.4 64.3 71.8 T(K) T(K) T (K) 0 0 0 50 80 80 80 80 80 70 80 80 80 80
A^(S"1)
Ea (kj/mol)
9.8 x 1015 2.07 x 10 ~5 1.82 x l O " 5 1.15 XlO" 5 8.8xl0"6 1.70 x 10 ~2 2.43 x 10 ~5 2.03 x 10 " 5 7.85 x 10 ~5 1.63,1.34XlO"5 2.02 XlO" 4 1.27 x 10 " 5 2.76 XlO" 5 3.61 x 10 " 5 3.1 x 10 " 6 1.19 x l O " 5 2.95 XlO" 5
exp[- UOA/RT]
7.IxIO16 1.2xlO 14 1.6 x 1016 2.6OxIO" 5 3.98 x 10 ~5 1.3xlO" 5 6.0xl0"5 2.15 XlO" 3 6.42 x 10 " 5 5.75 x 10 ~5 1.56 x 10 " 4 1.18 x 10 ~A 9.02 x 10 " 5 4.7OxIO" 5 4.4OxIO" 5 5.92 x 10 " 5 6.13 x 10~5
exp[-138.4//?7] exp[- 106A/RT] exp[-136.3//?7]
Notes
m7
a,mi a a,mi
113.8 120.9 120.1 126.4 126.4 125.1
Refs. 1 307 307 307 307 6 5 6 34 34 34 34 34 34 24 24 24
c,e,q q a a a a,mi a a,mi a a a,mi a a,mi
1 1 1 79 79 79 5 5 5 6 5 6 5 5 6 5 6
44.5 53.9 65.9
6.IxIO"6 2.83 XlO" 5 1.25 XlO" 4
j j j
23 23 23
44.5 53.9 65.9 44.5 53.9 65.9 44.5 53.9 65.9 44.5 53.9 65.9 445 53.9 65.9 44.5 53.9 65.9 44.5 53.9 65.9 70 80 80
9.1 x 10" 6 4.33 x l O " 5 1.28 x l O " 4 4.68 x 10 " 5 2.05 x 10 " 4 8.18 xlO~ 4 7.2 XlO" 5 1.6OxIO"4 8.48 XlO" 4 6.30xl0~ 5 1.2IxIO" 4 7.18 x l O " 4 2.22 x l O " 5 4.52 XlO" 5 2.37 x l O " 4 6.58 x 10 " 5 1.2IxIO- 4 8.42 XlO" 4 2.58 xlO~ 5 1.2OxIO"4 7.1OxIO- 4 1.70xl0" 5 7.0IxIO-5 6.8OxIO- 5
j,m 2 j , m2 j,m 2 j j j j , m2 j,m 2 j , m2 j j j j,m 2 j,m 2 j,m 2 j j j j,m 2 j,m 2 j,m 2 z (1500) z (500) z (1000)
23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 23 377 377 377
Notes page 11-69; References page 11-70
Table 4. Number of C atoms 16 (cont'd)
18
cont'd
Initiator
Solvent
T( 0 C)
^d(S1)
Ea (kj/mol)
Notes
Refs.
80 80 80 90 95 100 63 80 100 T (K) 20 20 20 20 0 0 18 80 80 80
6.27 x 10~5 6.01 x l 0 ~ 5 5.77xlO-5 2.13 x l O ~ 4 3.8OxIO- 4 6.79 x l O ~ 4 1.93 x 10 ~5 1.93 x l O - 4 1.93 x l O - 3 2.30 x 10 15 1.02 x 10 ~3 4.76 x 10 ~4 1.86 x 10 ~4 1.6OxIO- 4 7.8xl0~5 2.5OxIO- 5 3.34 XlO" 4 1.42 x 10 ~4 1.4 x l O ~ 4 2.3 x 10 ~4
Acetonitrile 2-Butanol Carbon tetrachloride Cyclohexane
40 40 40 40
5.9xl0~3 4.4xlO~ 3 6.7 x 10 ~4 4.4xlO~ 4
256 256 256 256
5-terf-Butylthenoyl peroxide Cinnamoyl peroxide
Acetonitrile 2-Butanol Carbon tetrachloride Cyclohexane Carbon tetrachloride Styrene
Dibenzoyl succinoyl diperoxide
Unknown
Nonanoyl peroxide Isononanoyl peroxide (3,5,5trimethylhexanoyl peroxide)
Mineral oil
40 40 40 40 75 50 70 70 75 85 T(K)
4.2xlO~ 3 2.8 x 10 ~3 6.5 x 10 ~4 3.9xlO~ 4 4.03 x 10 ~5 1.2OxIO- 5 1.67 x l O - 4 7.7 x 10 ~6 1.42 x l O - 5 5.4 x l O - 5 8.4xlO 1 4
256 256 256 256 232 316 316 214 214 214 1
50 70 85 60 59 77 96 T (K) 60 70 80 80 80 80 80 80 90 100 120 125 130 135 140 145 150 T (K)
6.IxIO-6 8.02 x l 0 ~ 5 5.3OxIO- 4 1.9 x l O - 5 1.93 x 10 ~5 1.93 XlO" 4 1.93 x l O - 3 2.84 x 1015 5.28 x 10 ~6 2.06 x l 0 ~ 5 9.53 x l O - 5 9.1OxIO- 5 8.62 x l O - 5 8.24 x l O - 5 7.86 x l O - 5 7.46 x l O - 5 2.52 x l O - 4 8.8IxIO-4 6.98 x l O - 3 1.27xl0- 2 2.15 XlO" 2 2.6OxIO- 2 5.7IxIO- 2 8.62xl0-2 1.17XlO- 1 1.6 x 1015
Dioctanoyl peroxide
^-Heptane
Dioctanoyl peroxydicarbonate
Chlorobenzene
Phenylacetyl peroxide
Acetonitrile Benzene Carbon tetrachloride Cyclohexane Styrene Toluene
Triptoyl peroxide
Benzene
Apocamphoyl peroxide ds-5-rm-Butylcyclohexylformylm-chlorobenzoyl peroxide
Benzene
fra«5-4-^rf-Butylcyclohexylformylm-chlorobenzoyl peroxide
Benzene
Chlorobenzene
n-Heptane
2-Nonenoyl peroxide
Mineral oil
z z z z z z
(1500) (2000) (2500) (1500) (1500) (1500)
exp[- 129.05/RT]
96.2
f,u2 f,uj
a,mi
125.5
X1 xi xi
exp[-121A/RT] 126
a a a a
exp[- 128.34/^7] z (1500) z (1500) z(l) z (500) z (1000) z (1500) z (2000) z (2500) z (1500) z (1500) z (1500) z (1500) z (1500) z (1500) z (1500) z (1500) z (1500) exp[-128.8//?7]
377 377 377 377 377 377 344 344 344 344 167 167 167 167 316 59 59 102 244 102
337 337 337 338 344 344 344 344 377 377 377 377 377 377 377 377 377 377 377 377 377 377 377 377 377 1
Table 4. cont'd Number of C atoms
Initiator
18 (cont'd)
3-Nonenoyl peroxide 2-Phenylpropionyl peroxide
19
Dibenzoyl itaconyl diperoxide
Solvent Mineral oil Cyclohexane On silica Styrene Unknown
J(0C) T (K) 55.8 49.4 70 70 75 85
Dibenzoyl a-methylsuccinoyldiperoxide
Unknown
70 75 85
20
Decanoyl peroxide
Benzene
Chlorobenzene
Dioctanoyl a-bromosuccinoyldiperoxide
Mineral oil Unknown
60 70 85 63 80 100 T (K) T(K) 70 75 85
Dioctanoyl a-chlorosuccinoyldiperoxide
Unknown
70 75 85
21
Dioctanoyl a-chlorosuccinoyldiperoxide 4-Ethyl-2-octenoyl peroxide Dioctanoyl itaconoyl diperoxide
Chlorobenzene
70
Chlorobenzene THF Chlorobenzene
70 70 70
1.18 x 10 " 4 6.2xl0"5 1.54 x 10 " 5
Chlorobenzene
35 70 35 50 55 65 T(K) 55
9.42 x 10 " 5 3.02 x 10" 3 9.77 x 10" 4 7.92 x l O " 5 1.45 x l O " 4 4.13 x l O " 4 1.07 x l O 1 2 1.38 x l O " 4
85 T (K) 70
85 Unknown
70 75 85
22
Benzoyl 2-[mms-2-(3-nitrophenyl)vinyljbenzoyl peroxide Benzoyl 2- [frans-2-(4-nitrophenyI)vinyl]benzoyl peroxide Benzoyl 2-[fra«s-2-(4-nitrophenyI)vinyl]-4-nitrobenzoyl peroxide Benzoyl 2-[frans-2-(phenyl)vinyl]benzoyl peroxide 4-Benzylidenebutyryl peroxide
3.7 x 10 14 6.8xlO~ 6 7.5 x 10 " 5 5.5 x 10" 5 5.63 x 10~ 4 1.87 XlO" 5 8.63xlO- 4 3.62 xl0~ 5 1.69 X l O " 3 1.00 X l O - 4 2.74 x 10 " 4 1.26 x l O " 5 4.26 X l O " 4 2.40xl0~5 9.6OxIO"4 8.7 x l O " 5 1.53 x 10~5 5.67 XlO" 5 3.8OxIO- 4 1.93 x 10 " 5 1.93 x l O - 4 1.93 x l 0 ~ 3 3.64 x 10 15 2.7xl015 1.52 x 10 ~~4 1.82 x l O " 5 2.74 XlO" 4 3.83 xlO- 5 6.97 x l O " 4 1.15 X l O " 4 2.02 x 10 ~A 2.42 x l O " 5 3.23 x l O " 4 4.83 xlO~ 5 8.5OxIO-4 1.58 x 10~ 4 8.2 x 10 1 4 3.23 x 10 ~4 2.8OxIO-5 5.47 x l O " 4 5.6OxIO"5 1.28 x l O " 3 1.92 X l O " 4 5.48 x 10 ~4 5.88 x l 0 ~ 5 9.58 x l O " 4 1.06 x l O " 4 2.61xl0"3 3.84 x l O " 4 1.87 x 10~4
Unknown Mineral oil Unknown
75
Dioctanoyl a-methyl succinoyldiperoxide
* d (s" 1 )
Methanol Acetophenone
E31 (kj/mol)
Notes
exp[- 10S.0/RT]
83.7 115.1
82.8 116.3
127.2
exp[- 130.48//?7] exp[- 131.9/K7] 96.2 126.4
95.4 126.4
X2 X2 X2 X2 X2 X2 X2 X2 X2 X2 X2 x2 a a a
X2 X2 X2 X2 x2 X2 X2 X2 X2 X2 X2 X2
e x p [ - 121A/RT] 92.9 127.6
96.2 131.0
84.5
1 258 258 316 214 214 214 214 214 214 214 214 214 214 214 214 126,337 126,337 126,337 344 344 344 344 1 214 214 214 214 214 214 214 214 214 214 214
X2 X2 X2 X2 X2 X2 X2 x2 X2 x2 x2 x2 t9
214 1 214 214 214 214 214 214 214 214 214 214 214 214 175
t9 t9 t9
175 175 175
h,t 9 t9 t9
175 175 175 133 133 133 133 133
99.6
exp[-99.6//?7] 98.7
Refs.
m2
Notes page II - 69; References page II - 70
Table 4. cont'd Number of C atoms 22 (cont'd)
Initiator 4-Benzylidenebutyryl peroxide
Solvent Acetophenone Benzene
Carbon tetrachloride
Nitrobenzene Propylene carbonate
4-ter/-Butylbenzoyl peroxide cis-4-tert-Butylcyclohexane formylperoxide
Toluene Dioxane Butane Carbon tetrachloride
frarcs-4-te7t-Butylcyclohexane formylperoxide
Carbon tetrachloride
fra«s-4-(4-Chlorobenzylidene)butyryl peroxide
Benzene
Propylene carbonate
frarcs-4-(4-Fluorobenzylidene)butyryl peroxide
Benzene
Propylene carbonate
1-Naphthoyl peroxide
Benzene
4-Nitrobenzoyl-2-[rra«5-2-(4-nitrophenyl)vinyl] benzoyl peroxide 2-Phenylisovaleryl peroxide
Chlorobenzene
5-Phenylpenta-2,4-dienoyl-peroxide 5-Phenylpentanoyl peroxide
Acetonitrile Cyclohexane On silica Styrene Acetophenone Benzene Carbon tetrachloride
Propylene carbonate 24
Dibenzoyl 2-bromosebacoyldiperoxide
Unknown
J( 0 C) 65 T(K) 50 60 70 60 70 T(K) 60 40 50 T (K) 50 40 50 60 70 80 40 40 40.0 45.45 50.7 40.0 44.7 48.9 50 60 70 40 50 60 50 60 70 40 50 60 54.6 59.9 64.5 70 55.0 55.0 50 70 77 77 70 77 85 T(K) 60 60 70 75 85
Dioctanoyl 2-bromosebacoyldiperoxide
Unknown
70 75
A^(S"1) 4.02 x 10 " 4 7.14xlOn 2.40xl0~ 5 6.8OxIO- 5 1.845 x l O - 4 3.47 x 10~5 1.06 XlO" 4 1.42xlO 13 3.38 x 10~4 7.36 x 10~5 2.13 XlO- 4 5.93 x 1010 2.08 XlO" 4 7.23 x l O - 5 2.093 x l O " 4 5.117 x l O - 4 1.64 x 10~4 6.08 x 10 ~2 1.25 x 10 ~5 1.69 x l O " 5 (8.65 ± 0.35) x 10 ~5 (1.32 ±0.04) x 10- 4 (2.35 ±0.05) x 10- 4 (4.25 ±0.23) x 10~5 (7.10 ± 0.38) x 10 ~5 (1.14±0.04)x 10~4 2.10xl0"5 6.56 x 10 ~5 1.75 x l O " 4 5.33 x 10 ~5 1.448 x 10~4 2.791 x 10~4 2.67 x 10 " 5 8.44 x 10 ~5 2.119 x l O - 4 6.53 x 10 ~5 1.685 x l O - 4 4.54OxIO- 4 1.01 x 10~4 1.86 x l O - 4 3.OxIO" 4 6.06 x 10~5 2.27 x 10 " 5 6.4xlO-6 2.56 x 10 ~4 2.18 x l O " 4 2.37 x 10 ~4 1.054 x l O " 5 2.76 x l O " 5 7.19 x l O - 5 1.87 x l O - 4 1.76xlO 15 4.41 x 10 ~5 2.8Ox 10" 5 4.80xl0~4 3.87 x 10~5 7.64 x l O - 4 7.22 XlO" 5 2.0OxIO" 3 2.02 x l O - 4 6.46 x 10 ~4 5.23 x 10~5 1.17IxIO- 3
Ea (kj/mol)
Notes
exp[- 98.1/RT] 91.2
m2 m2 h
112.5 exp[-112.5 /RT]
m2 m2 m2
89.5 exp[- 89.5/RT] 82.0
m2 h
76.1
a,mi z (0.98) z (1010) h
81.6
h
95.0
h
94.1
h
t9
n2
127.6 130.1
exp[-130.1/i?7]
87.9 110.8
99.6 129.7
h,m2 m2 m2 m2 m2 m2 X2 X2 x2 X2 x2 X2 X2 X2 x2
Refs. 133 133 194 194 194 133 133 133 133 133 133 133 133 194 194 194 133 6 145 145 35 35 35 35 35 35 194 194 194 194 194 194 194 194 194 194 194 194 170 170 170 175 258 258 258 316 133 194 133 133 133 133 133 133 214 214 214 214 214 214 214 214 214
Next Page
Table 4. cont'd Number of C atoms 24 (cont'd)
Initiator
Solvent
Dioctanoyl 2-bromosebacoyldiperoxide
Unknown
Lauroyl peroxide
Benzene
Chlorobenzene
Ethyl acetate
Ethyl ether Mineral oil Styrene
26 28 36 x
TABLE 5. Number of C atoms 4
2-Phenoxybenzoyl peroxide Myristoyl peroxide Menthylphthaloyl peroxide Aliphatic polymeric diacyl peroxide
kd(s'1)
Benzene Benzene
Acetophenone Benzene Dioxane Chlorobenzene
Ea (kj/mol)
30 40 50 60 70 60 70 85 70 40 50 60 70 61 79 99 T (K) 40 50 61 70 30 T (K) 34.8 49.4 61.0 74.8 100.0 50 60 65 70 50
1.08 x 10 " 4 3.0OxIO" 3 3.72 x l 0 ~ 4 2.56 x 10 " 7 4.91 x 10~7 2.19 x l O - 6 9.17 xlO~ 6 2.86 x l O - 5 1.51 x 10~5 5.58 x l 0 ~ 5 3.75 x l O - 4 4.33 x l O - 5 2.91 x 10 ~7 1.15 XlO" 6 4.75 x l O - 6 1.87 xlO~ 5 1.93 x 10 ~5 1.93 x l O - 4 1.93 XlO" 3 3.92 xlO 1 4 6.03 x 10 ~7 2.7OxIO- 6 1.05 x l 0 ~ 5 3.99 x l 0 ~ 5 1.97 x 10 " 6 2.2 x 1016 2.06 x 10 ~7 2.25 x l O " 6 1.42 x l 0 ~ 5 1.00 x l O - 4 2.39 x l O - 3 3.1 x 10" 6 1.2OxIO- 5 2.22 x l O - 5 4.32 x l O - 5 2.03 x 10 ~4
50 60 70 65 70 55 75 75 80
6.58 x 10 ~5 1.815 x 10 ~4 4.729 x l O " 4 8.18x10 ~5 3.38 x 10 ~5 1.15 x 10~4 9.04 x 10 ~5 9.00 x 10 " 5 1.720xl0" 4
85
Carbon tetrachloride
rraw5-4-(4-Methoxybenzylidene)butyryl peroxide frarcs-4-(4-Methylbenzylidene)butyryl peroxide
T( 0 C)
Notes X2 X2 X2 a
127.2
a a a a,j
exp[- 12337/RT]
a exp[- 137.9/RT] a a a a a 121.1
90.4
121.3
c,h c c a a Vu Vi5 V 15
Refs. 214 214 214 99 68 68 68 68 126,337 126,337 126,337 16 68 68 68 68 344 344 344 344 68 68 68 68 99 1 10 10 10 10 10 287 287 287 287 194 194 194 194 5 16 65 302 302 302
HYDROPEROXIDES AND KETONE PEROXIDES
Initiator
Solvent
sec-Butyl hydroperoxide
Toluene
ter/-Butyl hydroperoxide
Benzene
T( 0 C) 172.0 182.3 130 145 160 154.5 161.7 169.3 174.6
fcd
(s"1) 2.65 x 10 ~5 4.9 XlO" 5 3 x 10 ~7 1.6 XlO" 6 6.6 x l O - 6 4.29 XlO" 6 9.27 x l O - 6 2.OxIO- 5 4.OxIO- 5
Ea (kj/mol)
138
170.7
Notes
a a a h
Refs. 199 199 337 337 337 76 76 76 76
Notes page 11-69; References page II - 70
Previous Page
Table 4. cont'd Number of C atoms 24 (cont'd)
Initiator
Solvent
Dioctanoyl 2-bromosebacoyldiperoxide
Unknown
Lauroyl peroxide
Benzene
Chlorobenzene
Ethyl acetate
Ethyl ether Mineral oil Styrene
26 28 36 x
TABLE 5. Number of C atoms 4
2-Phenoxybenzoyl peroxide Myristoyl peroxide Menthylphthaloyl peroxide Aliphatic polymeric diacyl peroxide
kd(s'1)
Benzene Benzene
Acetophenone Benzene Dioxane Chlorobenzene
Ea (kj/mol)
30 40 50 60 70 60 70 85 70 40 50 60 70 61 79 99 T (K) 40 50 61 70 30 T (K) 34.8 49.4 61.0 74.8 100.0 50 60 65 70 50
1.08 x 10 " 4 3.0OxIO" 3 3.72 x l 0 ~ 4 2.56 x 10 " 7 4.91 x 10~7 2.19 x l O - 6 9.17 xlO~ 6 2.86 x l O - 5 1.51 x 10~5 5.58 x l 0 ~ 5 3.75 x l O - 4 4.33 x l O - 5 2.91 x 10 ~7 1.15 XlO" 6 4.75 x l O - 6 1.87 xlO~ 5 1.93 x 10 ~5 1.93 x l O - 4 1.93 XlO" 3 3.92 xlO 1 4 6.03 x 10 ~7 2.7OxIO- 6 1.05 x l 0 ~ 5 3.99 x l 0 ~ 5 1.97 x 10 " 6 2.2 x 1016 2.06 x 10 ~7 2.25 x l O " 6 1.42 x l 0 ~ 5 1.00 x l O - 4 2.39 x l O - 3 3.1 x 10" 6 1.2OxIO- 5 2.22 x l O - 5 4.32 x l O - 5 2.03 x 10 ~4
50 60 70 65 70 55 75 75 80
6.58 x 10 ~5 1.815 x 10 ~4 4.729 x l O " 4 8.18x10 ~5 3.38 x 10 ~5 1.15 x 10~4 9.04 x 10 ~5 9.00 x 10 " 5 1.720xl0" 4
85
Carbon tetrachloride
rraw5-4-(4-Methoxybenzylidene)butyryl peroxide frarcs-4-(4-Methylbenzylidene)butyryl peroxide
T( 0 C)
Notes X2 X2 X2 a
127.2
a a a a,j
exp[- 12337/RT]
a exp[- 137.9/RT] a a a a a 121.1
90.4
121.3
c,h c c a a Vu Vi5 V 15
Refs. 214 214 214 99 68 68 68 68 126,337 126,337 126,337 16 68 68 68 68 344 344 344 344 68 68 68 68 99 1 10 10 10 10 10 287 287 287 287 194 194 194 194 5 16 65 302 302 302
HYDROPEROXIDES AND KETONE PEROXIDES
Initiator
Solvent
sec-Butyl hydroperoxide
Toluene
ter/-Butyl hydroperoxide
Benzene
T( 0 C) 172.0 182.3 130 145 160 154.5 161.7 169.3 174.6
fcd
(s"1) 2.65 x 10 ~5 4.9 XlO" 5 3 x 10 ~7 1.6 XlO" 6 6.6 x l O - 6 4.29 XlO" 6 9.27 x l O - 6 2.OxIO- 5 4.OxIO- 5
Ea (kj/mol)
138
170.7
Notes
a a a h
Refs. 199 199 337 337 337 76 76 76 76
Notes page 11-69; References page II - 70
TABLE 5. cont'd Number of C atoms 4 (cont'd)
Initiator tert-Butyl hydroperoxide
Solvent Benzene Chlorobenzene
Cumene Cyclohexane Dodecane Heptane w-Octane
Toluene
Vapor
tert-Butyl hydroperoxide/cobalt 2-Ethyl hexanoate
Chlorohenzene
tert-Butyl hydroperoxide/cobalt stearate Methyl ethyl ketone peroxides
Benzene
5
tert-Amyl hydroperoxide
Ethyl acetate Chlorobenzene
6
Acetone cyclic diperoxide
Benzene
3,3,6,6-Tetramethyl-1,2,4,5tetroxane
Toluene Benzene
Toluene Vapor
Cyclohexyl hydroperoxide
Benzene Benzene/styrene (50/50) Cyclohexane
T( 0 C) 172.3 182.6 171 199 231 182.6 100 172 86.1 98.5 172 149.8 159.9 169.6 179.6 100 172.5 181.5 192.6 204.5 214.9 570 670 773 873 973 0 0 0 25 25 45 45 100 115 130 70 153 190 228 135.5 145.5 165.0 165.0 135.5 140.5 145.5 150.5 165.0 165.0 130.1 150.1 170.1 177.1 185.1 194.1 207.1 215.1 250.1 70 70 130 140 150
#d ( s 1 ) 1.09 x l O " 5 3.1 x 10~5 1.93 x 10~5 1.93 x l O " 4 1.93 x l O " 3 8.1 x 10" 5 1.2xlO- ? 1.4IxIO- 4 1.32 xlO~ 6 5.55 x l O - 6 1.41 x 10" 4 8xlO"6 2.5 XlO" 5 6.9 x l 0 ~ 5 1.82 x l 0 ~ 5 5.7xl0"8 9.2 x l O " 6 2.69 XlO" 5 8.3 x l O " 5 1.52 XlO" 4 3.24 xlO~ 4 3.4XlO 1 4.95 8.4XlO 1 5.66 x 102 2.58 x 103 1.01 x 10" 3 8.29 x 10 ~5 5.4OxIO" 4 2.3 XlO" 3 1.1 x l O " 3 1.4xlO" 3 l.OxlO" 3 1.3 x 10 " 5 4.80xl0"5 1.60xl0" 4 1.28 x 10~6 1.93 x 10 " 5 1.93 x l O " 4 1.93 x l O " 3 6.25 x l O " 7 2.09xl0-6 1.41 x 10" 5 1.37 x l O " 5 6.25 x l O " 7 1.19 x 10~6 2.09 x l O " 6 2.83 XlO" 6 1.41 x 10" 5 1.37 x l O " 5 1.8 x l O " 6 3.4xlO- 6 3.5xl0-6 4.6x10-6 1.3 x l 0 ~ 5 2.4 x l O - 5 8.5 x l O " 5 1.66 x l O " 4 4.88 x l O - 4 0 1.27 x 10~3 2.38 x l 0 ~ 3 1.16 x l O - 2 3.20xl0" 2
Ea (kj/mol)
Notes
c
128.4
163.2
c b b f f f
c
Vi0 V7 V1
101
147.1
Vi a a a
h
a a a a a
Refs. 199 199 344 344 344 199 199 199 41 41 199 118 118 118 118 199 199 199 199 199 199 188 188 188 188 188 190 190 190 198 198 198 198 337 337 337 13 344 344 344 286 286 286 286 373 373 373 373 373 373 365 365 365 365 365 365 365 365 365 91 91 91 91 91
TABLE 5. cont'd Number of C atoms 6 (cont'd)
Initiator Cyclohexyl hydroperoxide
Solvent Benzene
80
Cyclohexane
80
Cyclohexene
80
Dimethylheptadiene
80
1-Octene
80
7
Benzyl hydroperoxide
Styrene
8
1,4-Dimethylcyclohexanehydroperoxide 1,1,3,3-Tetramethylbutylhydroperoxide
1,4-Dimethylcyclohexane
Benzene
Chlorobenzene
2,5-Dimethyl-2,5-di(hydroperoxy)hexane
(S)x
9
Benzene
n-Octyl hydroperoxide 2,4,4-Trimethylpentyl2-hydroperoxide Poly(phenyleneethyl hydroperoxide)/manganese resinate
White oil White oil
Cumene hydroperoxide
Benzene
Chlorobenzene
Chlorobenzene
Cumene
Mesitylene Styrene Toluene
Cumyl hydroperoxide
10
p-Cymene hydroperoxide
T( 0 C)
White oil Acetone-d6
/?-Cymene
^d(S" 1 )
60 60 120
Reaction order varies from 1.5 to 2.0 Reaction order varies from 1.5 to 2.0 Reaction order varies from 1.5 to 2.0 Reaction order varies from 1.5 to 2.0 Reaction order varies from 1.5 to 2.0 9xlO~6 1.8 x l O - 5 1.4xlO" 5
130 145 160 135 153 173
1.7xlO~ 5 7.41 x 10- 5 2.83 XlO" 4 1.93 x 10 ~5 1.93xlO- 4 1.93 x l O - 3
130 145 160 150 150
2.7xlO~ 6 1.0 x l O - 5 3.16 x l O - 5 9.29 x 10 ~5 9.29 x 10 " 5
26 30 35 115 130 145 159 193 253 110 120 132 T(K)
2.0OxIO- 4 2.75 x 10" 4 3.67 XlO" 4 4xlO"7 1.7 x l O - 6 6.6 x l O ~ 6 1.93 x 10 ~5 1.93 x l O " 4 1.93xl0-3 2.742 x 10 ~6 5.194 x l O - 6 9.305 x l O - 6 2.1OxIO 11
125 139 182.3 150 -33.0 -23.0 -12.0 -18.0 -8.0
9xlO~6 3 xlO-5 6.45 x l O " 5 1.34 x 10~4 7.0xl0~5 2.28 XlO" 4 1.2IxIO- 3 8.3 x l O - 5 4.23 x l O - 4
-3.0 110 120 132 T(K)
1.65xlO- 3 5.50OxIO" 6 1.20OxIO- 5 2.089 XlO" 5 1.23 x l O 1 2
Ea (kj/mol)
Notes
Refs. 119
119
119
119
119
C3 C4 c
276 276 224
134
a a a
337 337 337 344 344 344
113
a a a a a
337 337 337 177 177
t3 t3 t3 a a a
212 212 212 337 337 337 344 344 344 367 367 367 367 58 58 199 199 199 177 264 264 264 264 264
137.2
112.5 112.5 46.0
122
exp[- S0.0/RT] 98.7 101.3
121.3 62.0
a
110.2
tu tM tu
exp[-85.48//?71
264 367 367 367 367
Notes page 11-69; References page II - 70
TABLE 5. cont'd Number of C atoms 10 (cont'd)
Initiator Decalin hydroperoxide
Solvent
Pinane hydroperoxide
Acetic acid Chlorobenzene Decalin 1,2-Dichlorobenzene Ethylene glycol Nitrobenzene Pyridine Benzene
2-Phenylbutyl 2-hydroperoxide
sec-Butylbenzene
l-Phenyl-2-methylpropylhydroperoxide
Benzene
l-Phenyl-2-methylpropyl-2hydroperoxide
Benzene
Tetralin hydroperoxide
Poly(butene) n-Butyl stearate 2-Ethyl-l-hexene 1-Hexadecene Mineral oil
/i-Octadecane Isooctane Octyl ether Poly(propylene) «-Tetradecane Tetralin 2,2,4-Trimethyl-l-pentene white oil Toluene
(1O)n
Poly(cumyleneethylhydroperoxide) (MWIlOO)
11
2,2-Bis(terf-butyldioxy)propane
Cumene
l-Methoxy-l-(terf-butylperoxy) cyclohexane
Cumene
s£c-Butyltoluene hydroperoxide
^c-Butyl toluene
2,2-Di-(tert-butylperoxy)butane
Chlorobenzene
2,2-Bis(ter/-butyldioxy)butane Diisopropylbenzene monohydroperoxide
Cumene Chlorobenzene
l-Methoxy-l-(terr-amylperoxy) cyclohexane
Cumene
12
T( 0 C) 130 130 130 130 130 130 130 130 145 160 110 120 132 T(K) 133.8 143.9 153.9 163.7 174 144.2 154.5 165.6 176.0 170 170 130 170 170 135.6 150.6 170 170 170 170 170 170 T(K) 170 150 130 140 150 90 100 110 120 80 90 100 110 100 110 120 T(K) 98 116 136 T(K) 100 150 182 218 80 90
^d(S"1) 5.5xl0~4 10% in 3 h 1.4IxIO- 5 4.48 x l O " 5 1.65 x 10 ~4 4.73 x 10 ~5 (2.31-2.89) x 10 ~4 7.08 x 10 " 6 2.72 x l 0 ~ 5 9.17 x l O - 5 2.944 x 10 ~6 6.61IxIO- 6 1.089 XlO" 5 4.06 xlO 1 2 3.18 x l O " 6 8.95 x 10 " 6 2.OxIO" 5 4.03 XlO" 5 9.77 x l O " 5 5.04 x 10 " 6 1.21 x IO"5 2.92 x l O " 5 6.97 XlO" 5 2.17 x l O " 3 1.47 x l O " 4 1.08 x l O " 4 1.26 x l O " 3 7.92 x l O " 4 4.2 x l O " 5 1.00 XlO" 4 4.82 x l O - 4 2.54 x 10~4 1 31 x 10" 4 1.45 x l 0 ~ 3 2.5OxIO" 3 2.32 x 10~4 2.27 x 109 1.67 x 10~3 1.34 x 10~4 2.79 x 10" 5 4.OxIO- 5 5.78 XlO" 5 2.16 x 10~6 9.14 x l O " 6 2.97 XlO" 5 9.56 x l O " 5 4.79 x 10 ~6 1.898 x 10 ~5 6.57 x l 0 ~ 5 2.139 x l O - 4 4.11IxIO- 6 8.194 XlO" 6 1.9555 x l O - 5 1.02 xlO 1 6 1.93 x 10 ~5 1.93 x l O - 4 1.93 xlO" 3 9.3OxIO 16 1.84 x 10 ~5 1.93XlO" 5 1.93 x 10 ~4 1.93 x l O - 3 7.82 xlO~ 6 3.07 x 10 " 5
£ a (kj/mol)
Notes
124.3 176.4 117.2
123.8
a a a
exp[-87.15//?7] 122.2
h
125.5
h
78.2 125.5 82.8
t3 t3 e,t3 t3 t3 t3 e,t3 t3 t3 t3 t3 t3 t3
117.2 131.4
119.2 121.3
exp[-102.1 /RT] t3 121.3
txp[-\W2/RT]
exp[-154.08/^7]
Refs. 228 228 228 228 228 228 228 18 18 18 367 367 367 367 76 76 76 76 76 76 76 76 76 71 71 71 71 71 71 71 71 71 71 71 71 71 112 71 177 210 210 210 361 361 361 361 348 348 348 348 367 367 367 367 344 344 344 344 361 344 344 344 348 348
TABLE 5. cont'd Number of C atoms 12 (cont'd) 13
14
Initiator
Solvent
l-Methoxy-l-(te/Y-amylperoxy) cyclohexane l-Methoxy-l-(terf-hexylperoxy) cyclohexane
Cumene
U-Bis(tert-butylperoxy)cyclopentane
Cumene
2,2-Bis(terf-butyldioxy)-3-methylbutane
Diphenylmethane
U-Bis(terf-butylperoxy)cyclohexane
Cumene
Cumene Cumene
Chlorobenzene
l,l-Bis(terr-butylperoxy)-2-methylcyclopentane
15
16
17
w-Dodecane n-Hexadecane H-Hexane n-Nonane Cumene
1,1-Diphenylethyl hydroperoxide
Chlorobenzene
l-Methoxy-l-(rm-octylperoxy)cyclohexane
Cumene
U-Bis(^-butylperoxy)-2-methylcyclohexane
Cumene
U-Bis(terf-amylperoxy)cyclohexane
Cumene
l,l-Bis(terf-butylperoxy)cyclooctane
Cumene
l,l-Bis(^rr-butylperoxy)-2-n-propylcyclohexane
Cumene
l,l-Bis(terf-butylperoxy)2-isopropylcyclohexane
Cumene
l,l-Bis(ferf-butylperoxy)3,3,5-trimethylcyclohexane
Cumene
T( 0 C) 100 110 80 90 100 110 80 90 100 110 90 100 110 120 100 80 90 100 110 94 113 134 T (K) 100 100 100 100 80 90 100 110 90 110 130 150 T (K) 70 80 90 100 80 90 100 110 80 90 100 110 90 100 110 120 80 90 100 70 80 90 100 80 90 100 110
A:d (s"1) 1.058 xlO~ 4 3.450 x 10 " 4 8.34 x 10~6 3.17 x l O " 5 1.12Ox 10" 4 3.653 x l O - 4 4.98 x l O " 6 1.80xl0~ 5 6.67 x l O " 5 2.17 XlO" 4 1.08 x 10 ~5 3.75 x 10 ~5 1.29 XlO" 4 4.1IxIO-4 3.17 x l O " 5 3.47 x 10~6 1.45 x 10 ~5 5.06 x l O " 5 1.62 XlO" 4 1.93 x 10 " 5 1.93 x l O " 4 1.93 x l 0 ~ 3 3.47 x 1015 3.51 x 10 ~5 3.15 x l O " 5 3.82 x 10 " 5 3.62 x 10 ~5 1.55 x 10~5 5.82 x 10~5 1.85 x l O " 4 6.0OxIO" 4 2.OxIO" 9 1.007 XlO" 6 1.034 XlO" 6 1.223 XlO" 6 1.38 x 108 5.9xlO~ 6 2.3OxIO" 5 8.18 x l O " 5 2.84OxIO" 4 1.29 x 10~5 4.51 x 10 " 5 1.43 XlO" 4 4.58 x l O " 4 5.34 x l O " 6 2.02 x 10 " 5 7.32 x l O " 5 2.44 XlO" 4 1.11 x 10 " 5 4.15 x 10~5 1.36 x l O - 4 4.24 xlO~ 4 1.2OxIO- 5 4.19 x 10 " 5 1.38 XlO" 4 2.59 x 10" 5 4.86 x 10 ~5 1.98 x l O " 4 7.46 XlO" 4 3.82 x 10~6 1.50 x 10 " 5 5.31 x 10 " 5 1.75 XlO" 4
Ea (kj/mol)
exp[- 142A/RT]
exp[- 105A/RT]
Notes
Refs. 348 348 348 348 348 348 349,364 349,364 349,364 349,364 358 358 358 358 361 349,350 349,350 349,350 348,349,350 344 344 344 344 364 364 364 364 349 349 349 349 374 374 374 374 374 348 348 348 348 349 349 349 349 348 348 348 348 364 364 364 364 349 349 349 349 349 349 349 349,364 349,364 349,364 349,364
Notes page 11-69; References page 11-70
TABLE 5. cont'd Number of C atoms Il (cont'd)
Initiator
Solvent
U-Bis(tert-butylperoxy)3,3,5-trimethylcyclohexane
Chlorobenzene
rc-Butyl 4,4-di-(terf-butylperoxy) valerate
Chlorobenzene
18
l,l-Bis(terr-hexylperoxy)cyclohexane
Cumene
20
U-Bis(tert-butylperoxy)cyclododecane
Cumene
22
U-Bis(tert-octylperoxy)cyclohexane
Cumene
31
2,2-Bis[4,4-di-(tert-butylperoxycyclohexyl)propane
Chlorobenzene
TABLE 6. Number of C atoms 4 5
85 105 128 T (K) 102 121 143 T(K) 80 90 100 110 90 100 110 80 90 100 110 87 106 128 T(K)
kd (s"1) 1.93 x ICT5 1.93 x 10 ~4 1.93 X l O - 3 7.59 x 10 13 1.93 x 10 " 5 1.93 x 10 ~4 1.93 XlO- 3 1.91 x 1015 5.38 x 10~6 2.06 x 10 ~5 7.48 XlO" 5 2.48 XlO- 4 8.14 x l O " 6 3.22 x 10~5 9.93 XlO" 5 1.513 x 10~5 5.62 x 10 ~5 1.983 X l O - 4 6.26 x l O - 4 1.93 x 10 ~5 1.93 x 10 ~4 1.93 x l O - 3 8.79 x l O 1 4
Ea (kj/mol)
Notes
Refs. 344 344 344 344 344 344 344 344 348 348 348 348 364 364 364 348 348 348 348 344 344 344 344
exp[- 127.52/RT]
exp[- 143.51/RT]
exp[-135.56//?7]
PERESTERS AND PEROXYCARBONATES
Initiator Dimethyl peroxalate tert-Butyl percarbamate tert-Butyl performate
Solvent
J( 0 C)
Pentane Chlorobenzene Chlorobenzene
25 90 130.8 140.8 140.6 140 140 140.6 140 140.6 140 79.5 88.4 92.8 64 64 64 64 79.6 87.8 92.6 88.2 92.8 99.4 75 85 85 100 115 130 75
4-Chlorotoluene Cumene 6
J( 0 C)
Isobutyl peracetate
a-Methylstyrene
tt-Butyl peracetate
a-Methylstyrene
sec-Butyl peracetate
terr-Butyl peracetate
a-Methylstyrene
terf-Amyl
alcohol Benzene
n-Butanol
A^(S"1) 1.7xlO~ 5 6.6xlO" 6 5.43 x 10 ~5 1.7OxIO- 4 1.8OxIO- 4 2.12 XlO" 3 5.06 x l O - 4 1.61 x 10~4 1.62 x l O - 3 1.77 x 10~4 1.02 XlO" 3 1.36 x l O " 5 3.61xl0" 5 5.58 x l O - 5 ~9.6xl0~3 8.2 x l O - 3 6.5 x l O - 4 1.2 x l O - 3 1.57 x l O - 5 3.27 x l O - 5 5.38 x l O - 5 1.79XlO"5 3.19 x l O - 5 5.37 x l O - 5 2.8 x 10 " 6 1.2xlO~ 6 2.18 x l O - 6 1.54 x 10- 5 1.02 XlO" 4 5.69 x l O - 4 2.65 x 10 ~5
Ea (kj/mol)
Notes
159.0
h
64.0
m2 V8 V1 v8 b b,v6
115.2
g2,vi6 g2,vi7 g2,vi8 g2,vi9 101.0
104.3
151.9
a a a a
Refs. 203 141 218 218 218 218 218 218 218 218 218 253 253 253 253 253 253 253 253 253 253 253 253 253 193 193 126,337 126,337 126,337 126,337 193
TABLE 6. cont'd Number of C atoms 6 (cont'd)
Initiator rm-Butyl peracetate
Solvent 2-Butanol
Chlorobenzene
Decane
rm-Butyl trichloroperacetate
Diethyl peroxydicarbonate
Dodecane Hexadecane Hexane Octane Paraffin Tetradecane Chlorobenzene
terr-Butanol 2,2'-Oxydiethylene bis(allyl carbonate)
7
Diethyl peroxalate ten-Amyl peracetate
Pentane Chlorobenzene
tert-Butyl methoxyperacetate
Ethylbenzene
terf-Butyl peracrylate
Benzene
terr-Butylperoxy isopropyl
Chlorobenzene
terr-Butyl perpropionate carborate
Benzene Decane Dodecane Hexadecane a-Methylstyrene
8
rm-Butyl 2-acetoxyperacetate tert-Buty\ cyclopropanepercarboxylate
Octane Tetradecane Ethylbenzene «-Dodecane rc-Hexadecane 2,2,4-Trimethylpentane
ferf-Butyl ethoxyperacetate
Ethylbenzene
T (0C)
£ d (s" 1 )
75 75 75 60 100 119 139 T (K) 100 115 125 100 100 100 130.1 100 130.1 100 60 66.8 77.0 45 55 40 50 60 25 90 108 129 T(K) 40.0 39.6 50.2 60.1 90 100 110 98 117 137 T(K) 80 90 100 100 100 70 90 100 100 91.8
1.13 x 10" 4 5.3 XlO" 5 4 xlO-7 2.3IxIO"8 1.93 XlO" 5 1.93 XlO" 4 1.93 x l O " 3 1.57 x 10 16 1.5 x IO" 5 7.9IxIO-5 2.45 XlO" 4 1.95 x 10- 5 1.78 x 10 ~5 1.55 x 10 " 5 5.08 x 10~4 2.07 x 10 ~5 3.13 x 10~4 1.55 x 10 ~5 1.19 x 10 " 5 2.75 x l O - 5 1.00 XlO" 4 1.25 x 10 " 5 5.7 x l 0 ~ 5 6.94 x l O " 6 2.86 x 10 " 5 1.28 x l O - 4 2.6xlO"5 1.93 x 10 " 5 1.93 x l O " 4 1.93xl0- 3 4.13 x l O 1 5 2.2xlO"4 1.94 x l O - 4 8.24 x l O - 4 2.35 x l O - 3 1.12 x l O " 5 1.5IxIO- 5 4.85 x l O - 5 1.93 x 10 " 5 1.93 XlO" 4 1.93 x l O - 3 2.49 x l O 1 6 1.53 x 10~6 6.04 x 10 " 6 1.82 x 10 ~5 1.78 x IO" 5 1.58 x 10 ~5 3.02 x 10~7 4.85 x l O " 6 2.03 x 10 ~5 1.68 x 10 ~5 2.73 x 10 ~5
113.0 102.6 113.0 102.6 113.0 120.4 40.0 40.6 46.0 55.6
5.48 x 10 ~5 1.28XlO" 5 4.92 x l O - 5 1.7IxIO- 5 6.19 x 10~5 1.505 XlO" 4 2.96 x 10 ~4 2.89 x l O - 4 5.58 x l O - 4 1.94 XlO" 3
E31 (kj/mol)
Notes
159.0
c t7 m3 a,h
exp[- 149.36/RT] 134
125.9 126.8
a,h h
133.9-138.1
c c a a a
127.2
exp[-141.1/#n 104.7 103.9
86.2
a,h h
a a a
exp[-150.15//?7] a a
a a
b
153.8
h
146.2
h
105 102.7
a m 2 ,h
Refs. 193 193 193 81 344 344 344 344 337 337 337 270 270 270 169 270 169 270 81 28 28 18 18 90 90 90 203 344 344 344 344 315 328 328 328 211 211 211 344 344 344 344 213 213 270 270 270 213 213 270 270 328 255 255 255 255 255 255 315 328 328 328
Notes page 11-69; References page 11-70
TABLE 6. cont'd Number of C atoms 8 (cont'd)
Initiator tert-Butyl heptafluoroperoxybutyrate
Solvent Benzene
Methanol
Methoxybenzene
Nitrobenzene
Octane
Pyridine
Toluene
terf-Butyl methoxyperpropionate terr-Butyl perisobutyrate
Ethylbenzene Benzene
Bulk Chlorobenzene
Cumene
Decane
terf-Butyl percrotonate
Dodecane Hexadecane Iso-octane Nujol Octane Tetradecane Benzene
T( 0 C) 65.0 70.0 75.0 80.0 60.0 65.0 70.0 75.0 80.0 60.0 65.0 70.0 75.0 10.0 15.0 19.6 30.0 55.0 60.2 65.0 70.0 40.0 45.0 50.0 85.0 90.0 95.0 100.0 30.0 40.0 50.0 65.0 75.0 80.0 85.0 40.3 78 70 85 100 70 90.6 100.7 110.0 79 98 118 T(K) 90.6 100.7 110.0 70 85 100 100 100 100 103.4 103.4 100 100 100 115 130
^d(S"1) 1.56 x 10 " 5 3.09 x 10 ~5 5.27 XlO" 5 9.08 x l O " 5 9.5 x l O " 6 1.61 x 10~5 2.7OxIO- 5 5.23xl0-5 9.18 x l 0 ~ 5 9.6 XlO" 6 1.93 x l O - 5 3.57 XlO" 5 6.35 x l 0 ~ 5 7.19 x 10~5 9.37 x l 0 ~ 5 1.304 x l O - 4 2.604 x l O - 4 5.01 x 10 ~5 8.56 x l O " 5 1.378 x l O - 4 2.444 XlO" 4 3.26 x 10 ~5 6.36 x l O " 5 9.31 x 10 " 5 5.1 x 10 ~6 9.5 xlO~ 6 1.75 x l O - 5 3.41 x 10 " 5 2.74 x 10 " 5 7.66 x l O " 5 1.868 x l O " 4 1.88 x 10 " 5 4.66 XlO" 5 7.06 x l O " 5 1.203 x l O " 4 4.30xl0~ 3 3.77 x 10~5 6.69 x l O " 5 5.33 x l O - 5 3.5OxIO- 4 4.12 XlO" 5 8.13 x 10" 5 2.75 x l O " 4 8.92 x l O " 4 1.93 xlO~ 5 1.93 x l O - 4 1.93 x l O " 3 2.07 xlO 1 5 6.9 x l O " 5 2.35 x l O " 4 6.57 x l O " 4 4.7 x l O " 6 2.6 x l O - 5 1.55 x l O " 4 1.46 x l O " 4 1.56 x 10 " 4 1.47 x 10 " 4 2.16 xlO~ 4 2.23 x l O " 4 1.59 x 10 ~4 1.52 x 10 " 4 2.5xlO" 5 1.5OxIO- 4 7.39 x l O - 4
Ea (kj/mol)
Notes v 24 V24 V24 V24 V25 V25 V25 V25 V25 V26 V26 V26 V26
140.6
a a a a a h
exp[-135.16/,RrI 133.1
h
140.6
122
a a a
138
a a a
Refs. 370 370 370 370 370 370 370 370 370 370 370 370 370 369 369 369 369 370 370 370 370 370 370 370 370 370 370 370 370 370 370 369 369 369 369 328 37 126,337 126,337 126,337 37 136 136 136 344 344 344 344 136 136 136 337 337 337 270 270 270 251 251 270 270 337 337 337
TABLE 6. cont'd Number of C atoms 8 (cont'd)
Initiator
Solvent
tert-Butyl permaleic acid
Acetone
tert-Butyl permethacrylate
Benzene
tert-Butyl peroxyisopropyl carbonate
Benzene
Cyclohexyl peracetate
a-Methylstyrene
Diisopropyl peroxalate Diisopropyl peroxydicarbonate
Pentane Benzene Di-rc-butyl phthalate
Decane
Ethylbenzene Mineral spirits
2,2/-Oxydiethylenebis(allyl carbonate)
9
Ethyl tert-butyl peroxalate
Toluene Benzene
tert-Butyl 2-acetoxyperpropionate ter/-Butyl 5-bromo-2-perthenoate
Ethylbenzene Carbon tetrachloride
tert-Butyl 5-chloro-2-perthenoate
Carbon tetrachloride
tert-Butyl cyclobutanepercarboxylate
n-Hexadecane 2,2,4-Trimethylpentane
T( 0 C)
^d(S"1)
70 85 101 90 100 110 90 100 110 88.6 93.0 99.3 25 54.0 77 87 97 107 117 35 45 60 54.3 54.3 30 45 60 75 40 50 60 50 45 55 65 91.4 99.2 112.0 124.5 99.2 112.0 124.5
2.7xlO~ 6 1.6 x l O " 5 6.77 x l O " 5 1.92 x l O ' 5 7.66 XlO- 5 1.92 x l O " 4 6.64 x 10 " 6 2.21 x 10~5 6.87xl0-5 1.63 x l O " 5 2.30xl0"5 4.75 XlO" 5 6.0xl0~ 5 5.0xl0"5 1.39 x 10 ~3 4.09 x l O " 3 1.25 x l O " 2 3.54xl0-2 7.98 x l O " 2 6.3 x l O " 6 2.7xlO-5 1.85 x l O " 4 4.5 x 10 " 5 5.2x10-5 2xlO"6 1.8xl0-5 1.28 XlO" 4 7.55 x l O " 4 6.39 x 10~6 2.28 x 10 " 5 9.44xlO- 5 3.03 x 10 " 5 4.48 x 10~5 1.63 x l O " 4 5.93 x l O " 4 3.6OxIO" 4 2.24 x 10 " 6 1.18x10-5 4.30x10-5 2.29 x 10 " 6 9.56 XlO" 6 4.42x10-5
102.6 92.9 102.6 113.0
4.33 x 10~5 1.2IxIO- 5 4.84 x 10 " 5 1.668 XlO" 4
E2, (kj/mol)
Notes
113
a a a a a a a a a
137.0
109.4
113
113
117.6
112.5
143.5
143.5
ni2 yi 6 yi 6 y 16 yi6 y!6 a a a m2 a a a a a a a a c,h
a a a a a a
150.4
h
Refs. 337 337 337 211 211 211 9 9 9 253 253 253 203 60 236 236 236 236 236 337 337 337 60 60 337 337 337 337 90 90 90 90 31 31 31 328 176 176 176 176 176 176 255 255 255 255
ter/-Butyl 2,2-dimethyl3-bromoperpropionate
Cyclohexane
55 65 75
9.50xl0~ 6 3.58xl0-5 1.23 x l O " 4
118.2
h,t6 t6 t6
320 320 320
tert-Butyl 2,2-dimethyl3-chloroperpropionate
Cyclohexane
55 65 75
3.55 x 10" 6 1.48x10-5 5.65x10-5
128.6
h,t6 t6 t6
320 320 320
tert-Butyl 2,2-dimethyl3-iodoperpropionate
Cyclohexane Ethylbenzene
2.91 x 10" 5 3.76 x l O - 4 4.8 x 10~4 4.22 x l O - 4 1.39 x 10 " 3 2.68 x l O " 3
116.9
tert-Butyl isopropoxyperacetate
55 75 40.0 39.9 49.9 55.3
h,t6 t6 a,h h,m2
320 320 315 328 328 328
100.6 98.9
Notes page 11-69; References page 11-70
TABLE 6. cont'd Number of C atoms 9 (cont'd)
Initiator tert-Butyl 1-methylcyclopropylpercarboxylate Di-(tert-butylperoxy)-carbonate
terf-Butylperoxy isopropyl carbonate terf-Butyl perpivalate
Solvent 2,2,4-Trimethylpentane Chlorobenzene
1,2-Dichlorobenzene Cumene Isopropyl ether Benzene
Benzene
Chlorobenzene
Cumene
Cyclohexane
Decane
Dioxane/water (90/10) Dodecane Hexadecane Hexane
Heptane Isooctane Mineral spirits
tert-Buty\ perpivalate-d6
Octane Tetradecane Chlorobenzene
T(0C) 102.6 113.0 99.95 110.1 120.1 120.1 99.95 99.95 85 100 115 50 70 85 50 55 60 65 70 48.9 58.6 64.3 57 75 94 T(K) 74.8 60 60.6 74 45 55 60 65 64.6 75.6 84.6 70.3 55 65 75 50 70 80 60.6 80 80 55 60 65 70 80 60.6 73.9 55 60 65 70 75 T (K) 80 80 60.6 74.0
* d (s"1) 2.30 x 10 " 5 7.47 x l O " 5 6.72 x 10~5 2.13 xlO~ 4 6.05X10- 4 5.98 x 10 ~4 6.72 x 10 " 5 2.76 x 10 ~4 3.3xlO" 6 2.2xlO" 5 1.36xlO- 4 9.77 x 10 " 6 1.24X10- 4 7.64X10- 4 1.03 XlO" 5 1.94 XlO" 5 3.92 x l 0 ~ 5 7.31 x 10~5 1.30x10-4 8.4xlO" 6 3.35xlO- 5 7.0IxIO- 5 1.93 x l 0 ~ 5 1.93xlO- 4 1.93 x l O " 3 7.09 XlO 14 2.79xlO- 4 3.85 XlO" 5 4.0OxIO- 5 1.93X10- 4 3.53 x 10 ~6 1.73 x l O " 5 2.95 XlO" 5 4.53 x l O - 5 5.8IxIO- 5 2.1OxIO- 4 5.94 x l O " 4 1.11 x l O - 4 1.03 x 10 ~5 4.02 x l O - 5 1.45 x l O - 4 4.IxIO"6 5.52 XlO" 5 2.18 x l O - 4 6.26 x 10~5 2.38 x 10 ~4 2.39 x 10 " 4 8.42 x 10 '6 1.59 XlO" 5 3.39 x l O - 5 6.19 XlO" 5 2.33 x 10 ~4 1.97 x 10 ~5 8.82 x l O " 5 1.01 x 10 ~5 2.15 x l 0 ~ 5 4.14 x l O - 5 7.58 XlO" 5 1.47X10- 4 3.56 x 1014 2.34 x 10 ~4 2.27 x 10 ~A 3.24 x 10~5 1.57 xlO~ 4
£ a (kJ/mol)
Notes
Refs.
133.7
h
255 255 27 27 27 27 27 27 337 337 337 126,337 126,337 126,337 359 359 359 359 359 249 28 28 344 344 344 344 28 81 156 156 160 160 362 160 159 159 159 267 320 320 320 337 337 270 156 270 270 359 359 359 358 270 165 165 359 359 359 359 359 376 270 270 156 156
133.1
138
119.7
125.5
a a a a a a
k h
exp[- 123.59/RT] 128.0
106.7
a,h t9 t9 h
115.5
122.8
h
117
a a t9
t9 t9
exp[- 123/RT]
t9 t9
TABLE 6. cont'd Number of C atoms 9 (cont'd)
Initiator tert-Butyl
perpivalate-d6
tert-Butyl 2-perthenoate
tert-Butyl 1-pyrollidinepercarboxylate tert-Butyl Af-succinimidopercarboxylate
10
tert-Amyl
perpivalate
Solvent
(s"1) 5.05 x 10" 5 1.62 x 10~5 8.82 x l O - 5 3.3 x 10 " 6 1.66 x l 0 ~ 5 6.87 x l O - 5
Chlorobenzene
90
7.59 x 10 ~5
Acetonitrile Benzene Chlorobenzene
100 100 90 100 90 100 100 100 90 100 51 55 72 91 T (K) 50 60 70 80 35 45 60 47 63 82 T(K) 30 40 60 49 65 83 T (K) 74.7 80.7 90.8 40.3 99.8 116.6 129.9
9.9xlO~ 4 3.79 x 10~5 1.32 x 10 ~5 4.9IxIO-5 3.3xl0-6 1.10 x 10~5 9.OxIO- 6 6.00xl0"3 9.24 x 10 ~5 3.4IxIO-4 1.9XlO" 5 1.93 x 10 ~5 1.93 x l O - 4 1.93 x l O - 3 4.12 x 1015 1.05 x 10 ~5 3.5IxIO-5 1.309 XlO" 4 4.239 XlO" 4 6.9xlO~ 6 2.6xlO" 5 1.8OxIO- 4 1.93 x 10 ~5 1.93 XlO" 4 1.93 XlO" 3 3.19 xlO 1 5 2xlO"6 1.0 x l O - 5 1.34 x l O - 4 1.93 x 10 " 5 1.93 x l O - 4 1.93 XlO" 3 7.00 x 1015 1.98 xlO~ 4 4.37 x 10 " 4 1.25 x l O - 3 2.91 x 10 " 4 1.65 x 10 ~5 1.38 x 10~4 6.83 x l O - 4
113.0 92.9 102.6 113.0 75 93 113 T (K) 42.42 50.30 57.95 44.85 50.10 60.20
3.02 x 10 ~4 2.47 x 10 ~5 8.87 x 10 " 5 2.89 x l O - 4 1.93 x 10 " 5 1.93 x l O - 4 1.93 x l 0 ~ 3 2.45 x 1015 9.04 x 10 ~5 2.349 x l 0 ~ 5 5.66OxIO- 5 1.874 x 10 ~5 3.609 x l O - 5 1.306 x l O - 4
Carbon tetrachloride
Cumene Cyclohexane Cyclohexene Methanol Methylene chloride Nitrobenzene Benzene Chlorobenzene
Decane
Chlorobenzene
Mineral spirits
Di-w-butyl peroxydicarbonate
Chlorobenzene
tert-Butyl 2-acetoxy-2methyl perpropionate
Ethylbenzene
tert-Butyl tert-butoxyperacetate tert-Butyl 4-carbomethoxyperbutyrate
Ethylbenzene Cumene
tert-Butyl cyclopentylpercarboxylate
fcd
60.6 60.6 73.9 99.2 112.0 124.5
Dioxane/water (90/10) Isooctane
Cumene
Di-(sec-butyl)peroxydicarbonate
T( 0 C)
n-Hexadecane 2,2,4-Trimethylpentane
tert-Butyl peroxydiethyl acetate
Chlorobenzene
tert-Butyl 2,2-dimethylperbutenoate
Cumene
tert-Butyl 2,2-dimethylperbutyrate
Cumene
Ea (kj/mol)
147.3
Notes t9 t9 t9 m2 m2 m2
Refs. 156 165 165 176 176 176 141
113.4
h,m2 m2 t9
m2 a
exp[- 121J6/RT]
113
exp[-123.85//?7] 113
a a a
a a a
exp[- 126.65/RT] m2
151.3
h
140.8
h
exp[- 134.00/RT] 100.7
h
142 142 141 142 141 142 142 142 141 142 338 344 344 344 344 362 362 362 362 337 337 337 344 344 344 344 337 337 337 344 344 344 344 328 328 328 328 257 257 257 255 255 255 255 344 344 344 344 274 274 274 274 274 274
Notes page 11-69; References page II - 70
TABLE 6. cont'd Number of C atoms 10 (cont'd)
Initiator Di(tert-butylperoxy)-oxalate
Solvent Benzene
tert-Butanol Decane Dodecane Octane n-Pentane Tetradecane Styrene
11
tert-Butyl 5-methyl-7-perthenoate
Carbon tetrachloride
P-Methyl-P-phenyl-P-peroxypropiolactone
Carbon tetrachloride
Bis(2-nitro-2-methylpropyl)-peroxydicarbonate 1-Phenylethylperacetate tert-Butyl 4-chloroperbenzoate
tert-Butyl-JV-(2-chlorophenylperoxy)carbamate
Toluene Benzene Phenyl ether
Carbon tetrachloride Toluene
tert-Butyl-AK3-chlorophenylperoxy> carbamate
Toluene
tert-Butyl-AH4-chlorophenylperoxy)carbamate
Toluene
tert-Butyl cyclohexylperoxycarboxylate
«-Hexadecane 2,2,4-Trimethylpentane
tert-Butyl-iV-(2,5-dichlorophenylperoxy) carbamate
Toluene
tert-Butyl 2,2-dimethylperpentanoate
Cyclohexane
Cumene tert-Butyl 5-ethyl-2-perthenoate
Carbon tetrachloride
tert-Butyl 2-iodoperbenzoate
Chlorobenzene
tert-butyl 4-nitroperbenzoate
Phenyl ether
tert-Butyl 3,5-dinitroperbenzoate
Carbon tetrachloride Carbon tetrachloride
T( 0 C)
kd (s"1)
Ea (kj/mol)
Notes c,h c c
35.0 45.0 55.0 25.0 41 41 41 37.8 41 35 45 55 99.2 112.0 124.5 106.8 126 134 50
6.77 x 10" 5 2.6IxIO" 4 9.3 XlO" 4 1.83 x l O " 5 1.75 x 10 " 4 1.81 x 10" 4 1.79 x 10 " 4 1.01 x 10" 4 1.71 x 10~4 5.5xl0"5 1.71 x 10" 4 6.0IxIO" 4 4.6xlO~ 6 1.94 x l 0 ~ 5 7.95 XlO" 5 5.65 x 10 " 6 4.59 x 10 " 5 9.71 x 10" 5 2.22 x 10 ~5
106.7
100 100.0 110.1 120.2 130.9 80 87.0 95.5 103.3 78.0 87.0 96.6 102.7 73.0 78.5 87.0 92.5 92.9 102.6 82.2 92.9 102.6 113.0 88.0 95.0 103.3 114.5 55 65 75 45 55 99.2 112.0 124.5 85.0 102.4 118.8 110.1 120.2 130.9 141.5 80 80
1.14 x l O " 4 3.89 x 10 ~6 1.85 x l 0 ~ 5 6.39 XlO" 5 2.42 xlO~ 4 4.2xlO~ 7 3.5xl0"5 1.48 x 10 ~4 3.3 XlO" 4 2.6 x l O " 5 7.8xl0"5 2.03 xlO~ 4 4.62 XlO" 4 5.57 x 10 ~5 1.42 x 10 ~4 2.75 xlO~ 4 5.37 x l O " 4 6.70xl0~ 5 2.046 x 10 ~4 1.57 x l O " 5 6.13 x l 0 ~ 5 2.046 xlO~ 4 6.58 x l O " 4 2.75 x 10 ~5 5.58 x 10 ~5 1.48 xlO~ 4 4.82 xlO~ 4 1.66 x 10 ~5 6.31 x 10~5 2.23 xlO~ 4 6.2xlO~ 6 2.15 x l 0 ~ 5 5.39 x 10 ~6 2.12 x l 0 ~ 5 7.91 x 10~5 4.02 x 10 ~5 2.58 xlO~ 4 1.32 xlO~ 3 7.56 x 10 " 6 3.19 x l 0 ~ 5 1.11 xlO~ 4 3.92 xlO~ 4 2.9xlO~ 7 1.1 x 10 ~7
138.7 164.4
h a a a a
157.3
h
115.5
h
119.7
h
136.6
h
135.8
h
128.9
h
120.7
h
105.4
h
75.3
137.7
131.8
a,m2 a,m2 a,m2 h,v 9 c,v9 a
130.5
172.8
Refs. 30 30 30 197 270 270 270 197 270 215 215 215 176 176 176 195 195 195 90 259 53 53 53 53 354 36 36 36 36 36 36 36 36 36 36 36 255 255 255 255 255 255 36 36 36 36 320 320 320 160 160 176 176 176 134 134 134 53 53 53 53 354 354
TABLE 6. cont'd Number of C atoms W (cont'd)
Initiator
Solvent
/m-Butyl-AH3-nitrophenylperoxy)carbamate
Toluene
fm-Butyl-AK4-nitrophenylperoxy)carbamate
Toluene
terf-Butyl perbenzoate
Acetic acid Benzene
Bromobenzene rc-Butanol «-Butyl acetate
tert-Butylbenzene w-Butyl ether Carbon tetrachloride Chlorobenzene
4-Chlorotoluene
Cumene
Decane
Dodecane Ethylbenzene Heptane Hexadecane Methyl benzoate Octane Phenyl ether
Tetradecane Trimethylbenzene Xylene
T( 0 C) 78.0 88.7 98.0 106.0 73.0 87.0 98.0 106.0 100.0 110.0 100 115 130 110.0 119.4 130.0 119.4 90.0 100.0 110.0 119.4 110.0 1194 119.4 100.0 110.0 80 110.0 119.4 120 135 150 103 122 142 T(K) 110.0 119.4 130.0 60 79.6 85.0 99.3 115.0 130.2 100 115 130 115 115 119.4 115 115 119.4 115 100.0 110.1 120.2 130.9 115 T (K) 119.4 130.0
A:d (s"1) 8.4 x l O " 6 2.43 x 10 " 5 1.01 x 10- 4 2.36 x l O " 4 6.4xlO~ 6 3.11 x 10~5 8.75 x l O " 5 2.38 xlO~ 4 3.83 x 10 ~5 1.14 x 10~4 1.07 x KT 5 6.22 x l 0 ~ 5 3.5OxIO- 4 3.50xl0" 5 1.04 XlO" 4 3.30xl0~ 4 1.37 x 10 ~4 9.27 x 10 " 5 2.7OxIO- 4 1.06 x 10~4 2.67 x l O " 4 3.6IxIO- 5 1.10 xlO~ 4 1.03 x 10 ~4 7.8OxIO- 5 1.80 XlO" 4 8.8xl0"7 3.83 x 10~5 1.11 x l O " 4 1.3IxIO- 4 6.74 x l O - 4 3.12 x l O - 3 1.93 XlO" 5 1.93 x l O - 4 1.93 x l O " 3 2.23 xlO 1 6 3.25 x 10 " 5 9.80xl0"5 3.06 x l O - 4 3.85 XlO" 7 7.21 x 10 ~5 1.320xl0" 6 9.37 x l O - 6 5.8IxIO- 5 3.24 x l O " 4 1.4xlO- 5 8.05 XlO" 5 3.56 x l O - 4 6.77 XlO" 5 6.44 x KT 5 1.07 x 10~4 7.21 x 10~5 5.97 x 10 ~5 7.8OxIO" 5 7.06 x 10 " 5 6.94 x 10 ~6 2.28 x l O " 5 9.0OxIO- 5 2.92 x l O " 4 6.03 x 10 ~5 2.62 x 1016 1.09 x 10~4 3.42 x l O - 4
E2, (kj/mol)
Notes
133.1
h
113.8
h
130.1
a a a a a a a a a a a a a a,m2 a,m2 a a a
145.2
144.3
120.5 123.4 148.5
99.2
141.8
exp[- 151.59/RT\ 144.3
140.2
134
a a m2 m2 m2
c c c a,h
a a a
a
a 156.9
exp[-152.0/RT] 141.4
a a a a
a a
Refs. 36 36 36 36 36 36 36 36 56 56 126,337 126,337 126,337 56 56 56 56 56 56 56 56 56 56 56 56 56 354 56 56 22 22 22 344 344 344 344 55 55 55 81 272 345 345 345 345 337 337 337 270 270 56 270 270 56 270 53 53 53 53 270 376 56 56
Notes page 11-69; References page II - 70
TABLE 6. cont'd Number of C atoms 11 (cont'd)
Initiator
Solvent
terf-Butyl-AK4-bromophenylperoxy)carbamate
Toluene
tert-Butyl percarboxycyclohexane
Chlorobenzene
Cumene
12
tert-Butyl per-2-methylphenylacetate
Isooctane
tert-Butyl-N-(phenylperoxy) carbamate
Toluene
tert-Hexyl peroxypivalate
Chlorobenzene Cumene
1,1,2-Trimethylpropyl perpivalate
Cumene
Cumyl peracetate tert-Amyl peroxybenzoate
Carbon tetrachloride Toluene Chlorobenzene
4-Bromocumyl perpropionate
Benzene
oc-Methylstyrene
tert-Butyl bicyclo[2.2.1]lheptane2-percarboxylate
terf-Butyl endo-bicyclo[2.2.1]heptane percarboxylate
Cumene
Chlorobenzene
Cumene
terf-Butylexo-bicyclo[2.2.11]heptane-2-percarboxylate
Chlorobenzene
T( 0 C) 70.8 79.8 84.0 96.0 100.1 111.4 120.0 79.6 79.6 79.6 60.6 73.9 51.2 67.7 77.7 90.7 T(K) 40 50 60 70 80 40 50 60 70 100 100 99 118 139 T (K) 70 80 90 70 80 90 85 100 110 110 120 130 94.0 101.9 109.6 120.5 94.5 101.9 111.9 100.1 111.4 120.0 94.0 101.9 109.6 120.3 94.5 101.9 111.9 94.5 101.9 112.1
A^(S"1) 3.32 x 10 " 5 1.04 x 10 ~4 1.75 x l O - 4 7.70xl0~ 4 2.75 x 10 ~4 9.65 XlO- 4 2.39 XlO- 3 1.86 x l O " 5 1.42 x l 0 ~ 5 1.15xl0- 5 6.60 x 10 ~5 3.233 x l O - 4 3.4xlO-6 2.31 x 10 " 5 1.15 x l O - 4 6.41 x 10 ~4 1.51 x 1016 2.39 x 10 ~6 8.83 x l O - 6 3.37xl0-5 1.226 x l O - 4 4.166 x l O - 4 3.6xlO" 6 1.59x10-5 5.14x10-5 1.921 x 10- 4 4.68 x 10 " 5 3.43 x 10 ~5 1.93 x 10 ~5 1.93 x 10~4 1.93 x l O - 3 8.38 x 1015 1.48 x 10 " 6 5.73 x l O - 6 1.8IxIO- 5 1.99 x 10~6 4.93 x l O - 6 1.55x10-5 1.16 x 10~6 1.02 x 10 ~5 3.76xlO- 5 4.6x10-5 1.56 XlO" 4 4.99 x l O " 4 1.75XlO" 5 6.20xl0"5 1.7 x l O - 4 5.72 x l O - 4 9.69x10-5 1.96xlO- 5 6.53x10-5 4.6IxIO-5 1.96 xlO~ 4 5.4OxIO- 4 1.87 x l O " 5 5.3OxIO- 5 1.10 x l O " 4 4.3 x l O - 4 5.27xl0-5 1.12 x l O - 4 3.57 x l O - 4 8.86 x 10 ~5 2.28 x 10 ~4 8.85 x l O - 4
Ea (kj/mol)
Notes
177.6
h
131.0
h
139.7
z (1) z (2030) z (4050) ni2 m2 h
exp[- 136.0/RT]
c p
exp[- 147.02/RTl 129.7
121.3
a a a a a
155.2 160
h
150.2
h
137.2
h
149.0
h
154.0
h
130.1
h
Refs. 36 36 36 36 181 181 181 163 163 163 165 165 36 36 36 36 40 362 362 362 362 362 362 362 362 362 271 271 344 344 344 344 213 213 213 213 213 213 160 160 223 223 223 147 147 147 147 147 182 182 181 181 181 147 147 147 147 182 182 182 182 182 182
TABLE 6. Number of C atoms
cont'd
Initiator
Solvent
12 (cont'd)
Cumene
tert-Butyl endo-bicyclo[2.2.1]-hept5-ene-2-percarboxylate
Cumene
tert-Butyl exo-bicyclo[2.2.1]-hept5-ene-2-percarboxylate
Chlorobenzene
Cumene
tert-Butyl 4-bromophenoxyperacetate tert-Butyl 4-chlorophenoxyperacetate tert-Butyl 3-chlorophenylperacetate
Ethylbenzene Ethylbenzene Chlorobenzene
Cumene tert-Butyl 4-chlorophenyl peracetate
Chlorobenzene
Cumene tert-Butylcycloheptyl percarboxylate
rc-Hexadecane 2,2,4-Trimethylpentane
tert-Butyl 2,4-dichlorophenoxyperacetate tert-Butyl 2,2-diethyl perbutyrate
Ethylbenzene Cumene
tert-Butyl per-2-ethylhexanoate
Benzene Chlorobenzene
tert-Butyl 2-methoxy-2-methylperpropionate
Chlorobenzene
tert-Butyl 4-methoxyperbenzoate
Phenyl ether
tert-Butyl peroxy-2-methylbenzoate
Chlorobenzene
tert-Butyl 4-methoxyperbenzoate tert-Butyl 4-methylperbenzoate
Carbon tetrachloride Phenyl ether
T( 0 C)
£ d (s"1)
96.0 100.1 111.4 120.0 84.4 94.7 100.1 108.6 113.5 94.5 101.9 112.1 94.5 101.9 112.0 94.5 101.9 112.1 94.5 101.9 112.1 70.5 70.5 79.6 90.7 100.5 79.6 79.6 79.6 90.7 100.5 79.6 79.6 92.9 102.6 92.9 102.6 70.5
1.33 x 10"4 1.90xl0" 4 6.79 xlO" 4 1.64 xlO" 3 2.19 xlO" 5 7.29 x l 0 ~ 5 1.37 xlO~ 4 3.6 XlO" 4 6.19 XlO" 4 6.05 x l O " 5 1.53 x l O " 4 4.72 XlO" 4 3.11 x l O " 5 7.35 x 10 ~5 2.48 x l O " 4 5.59 x l O " 5 1 25 x 10" 4 5.0OxIO" 4 4.48 x l O " 5 1.18 x l O - 4 3.97 x l O " 4 2.6xlO~ 4 2.9xlO~ 4 4.05 x 10 ~5 1.44 x l O - 4 4.38 x l O " 4 2.98 x 10 " 5 1.99 x l O " 5 8.44 x 10 " 5 2.95 x l O - 4 8.19 x l O " 4 6.54 x 10 " 5 4.45 x 10 " 5 1.801 x 10 " 4 5.17 x l O " 4 1.703 x 10 " 4 5.07 x l O " 4 9.4xlO" 5
45 55 65 72 72 91 113 T(K) -14.0 -7.0 -1.0 15.0 100.0 110.1 120.2 130.9 96 115 136 T (K) 80 100.0 110.1 120.2
1.23 x 10 " 5 4.92 x l O " 5 1.46 x l O - 4 1.9xlO" 5 1.93 x 10 ~5 1.93 x l O " 4 1.93xl0- 3 1.54 xlO 1 4 2.05 x 10 " 5 6.73 x 10" 5 1.67 XlO" 4 1.28 XlO" 3 1.07 x 10 " 5 4.17 x l O " 5 1.28 x l O - 4 4.28 x l O " 4 1.93 x 10 " 5 1.93 x 10 " 4 1.93 x l O " 3 8.56 x 1015 l.OxlO" 6 9.42 x 10 " 6 3.19 XlO" 5 1.06 XlO" 4
Ea (kj/mol)
Notes
129.3
h
129.3
h
131.4
h
136.4
h
138.1
h
123.0
a a h
117.2
z (0.98) z (6090) h
121.5
z (0.98) z (6090) h
125.7
h a
100.3
h
a
exp[- 124.90/RT] 86.3
149.8
m2 m2 m2 m2 a a a a
expr[- 145.97/RT] 151.0
a a a
Refs. 147 181 181 181 147 147 147 147 147 182 182 182 182 182 182 182 182 182 182 182 182 315 315 178 178 178 207 207 178 178 178 207 207 255 255 255 255 315 160 160 160 338 344 344 344 344 275 275 275 275 53 53 53 53 344 344 344 344 354 53 53 53
Notes page 11-69; References page II - 70
TABLE 6. cont'd Number of C atoms 12 {cont'd)
Initiator terr-Butyl 4-methylperbenzoate rm-Butyl 2-methyl-2-terfbutylperoxyperpropionate
Solvent Phenyl ether Benzene
terf-Butyl 2-methylsulfonyl perbenzoate
Chlorobenzene
tert-Butyl 2-(methylthio)perbenzoate
Chlorobenzene
tert-Butyl 4-(methylthio)perbenzoate terf-Butyl 4-nitrophenoxyperacetate /m-Butyl 4-nitrophenylperacetate
Chlorobenzene Ethylbenzene Chlorobenzene
terf-Butyl 4-nitrophenylperacetate
Decane Dodecane Hexadecane Octane
Di-terf-butyl per-2-chlorosuccinoate
Tetradecane Unknown
T( 0 C) 130.9 9.0 19.0 30.0 42.0 105 120 135 150.6 60 39.4 50.1 50.2 69.8 120.4 70.5 79.6 90.7 100.5 80 77.5 77.5 100 77.5 77.5 100 77.5 105 115 125
tert-Butyl peroctoate
Benzene
Decane
Di-rm-butyl persuccinoate
Styrene
/m-Butyl phenoxyperacetate rm-Butyl phenylperacetate
Ethylbenzene Chlorobenzene
Cumene
Decane Dodecane Hexadecane Isooctane
70 85 100 70 85 100 105 115 125 70.5 60 77.0 88.6 79.6 90.7 100.5 79.6 79.6 79.6 79.6 85.0 79.6 79.6 79.6 79.6 79.61 77.5 77.5 77.5 85.0 95.2
^d(S"1) 3.25 x 10~A 6.66 xlO~ 5 1.99 x 10 ~4 6.94 xlO~ 4 2.43 x l 0 ~ 3 6.68 x 10 ~6 5.57 x 10~5 2.76 xlO~ 4 2.05 x l 0 ~ 3 8.08 x 10~A 2.59 x l O - 5 2.42 XlO- 4 1.88 x l O - 4 1.96 XlO" 3 1.75 x 10 ~4 6.7xlO" 5 2.5xlO" 5 8.9 XlO" 5 2.83 xlO~ 4 3.77 XlO" 5 6.3OxIO- 6 5.8IxIO" 6 1.3IxIO- 4 5.11 x 10" 6 6.42 x 10 " 6 1.6OxIO- 4 5.56 x 10 " 6 2.74 x 10 " 4 1.22 x l O - 5 5.9OxIO" 4 3.83 x l O - 5 1.52 XlO" 3 1.00 x l O - 4 1.4xlO" 5 8.55 x l O - 5 4.55 x l O - 4 6.9xlO~ 6 4.39 x l O - 5 2.64 x l O - 4 1.93 x 10 " 5 6.7 x l O - 5 2.53 XlO" 4 4.4xlO" 4 6.79 x 10~6 6.85 x l O - 5 2.45 x l O - 4 1.05 x l O - 4 3.53 XlO" 4 1.003 XlO" 3 1.07 x l O - 4 9.1 x 10 " 5 1.02 XlO" 4 9.0 x 10- 4 1.945 XlO" 4 6.6xlO- 5 5.6 xlO~ 5 6.78 x l O - 5 4.73 x l O - 5 1.1 x l 0 ~ 5 3.0OxIO- 5 2.75 x l 0 ~ 5 2.6OxIO- 5 1.08 x l O " 4 3.527 x l O - 4
E2, (kj/mol)
Notes
78.8
a m2
95.0
a,h b c m2
129.9 124.7
a,h h
102.9 143.5
X2 X2 X2 x2 X2 x2 a a a a a a Xi X1 X1 a,h a,h h m2 h
130
130
154.8
113.1 120.1 117.6 116.7
z (0.98) z (4050) z (0.98) z (4050) m2 z (0.98) z (4050) z (0.98) z (6090)
Refs. 53 275 275 275 275 22 22 22 22 97 134 134 134 134 134 315 178 178 178 169 168 168 168 168 168 168 168 214 214 214 214 214 214 337 337 337 337 337 337 215 215 215 315 81 28 28 178 178 178 157 157 163 163 165 157 157 163,207 163,207 274 168 168 168 165 165
TABLE 6. cont'd Number of C atoms 12 (cont'd)
Initiator tert-Butyl phenylperacetate
tert-Buty\ 2-propylperpenten-2-oate (cw)
(trans)
Solvent Octane Paraffin oil Tetradecane Cumene
Cumene
tert-Butyl 2,2,3,3-tetramethylperpropionate
Cumene
tert-Butyl thiophenylperacetate tert-Butyl per-o-toluate ferf-Butyl per-paratoluate
Ethylbenzene Benzene Cumene
tert-Butyl-AH3-tolylperoxy)carbamate
Toluene
tert-Butyl 2,4,5-trichlorophenoxyperacetate 4-Chlorocumyl perpropionate
Ethylbenzene Benzene
a-Methylstyrene
Cumyl perpropionate
Benzene
a-Methylstyrene
4-Iodocumyl perpropionate
Benzene
a-Methylstyrene
4-Nitrocumyl perpropionate
Benzene
a-Methylstyrene
13
1,1,3-Trimethylbutyl perpivalate
Cumene
tert-Amyl per-2-ethylhexanoate
Benzene Chlorobenzene
Benzyl(ter?-butylperoxy)oxalate
Benzene
T( 0 C) 77.5 85.0 77.3 94.9 100.1 100.1 100.1 110.1 94.9 100.1 100.1 100.1 110.1 42.2 54.9 70.3 70.5 97 84.0 99.3 115.0 64.0 70.7 78.0 88.5 70.5 70 80 90 70 80 90 70 80 90 70 80 90 70 80 90 70 80 90 70 80 90 70 80 90 40 50 60 70 70 73 91 111 T(K) 45 55 65
A^(S"1) 3.1IxIO"5 1.150 x 10~4 2.66 x 10 ~5 2.78 x 10 ~5 5.4 XlO" 5 4.26 x l 0 ~ 5 2.31 x 10~5 1.72 x l O - 4 2.47 x 10 ~5 4.7 x l O - 5 3.13 x l O - 5 1.42 x-K) - 5 1.64 x l O - 4 8.76 x l O " 6 5.84 x 10 ~5 3.36 x l O - 4 3.8 x 10 ~4 1.9xl0"5 1.660 x 10 ~6 1.139 x l O - 5 6.77 XlO" 5 4.58 x 10 " 5 9.17 x l O " 5 2.03 x l O - 4 5.78 x l O - 4 5.8 x l O " 5 1.46 x 10 " 6 5.68 x l O - 6 1.79 x l O " 5 1.50x 10" 6 4.54 x l O - 6 1.47 x l O - 5 2.6OxIO- 6 6.15 x l O - 6 1.90 x l O " 5 6.31 x 10 ~6 1.7IxIO- 5 4.94 x l O " 5 1.37 x 10~6 5.76 x l O - 6 1.79 x l O - 5 1.54 x 10~6 4.96 x l O - 6 1.62 x l O - 5 1.36 x 10 " 6 5.32 x l O " 6 1.78 x l O - 5 1.35 x 10~6 4.07 x l O - 6 1.43 x l O - 5 4.8OxIO- 6 1.77 x l O - 5 6.18 x l O " 5 2.344 x l O - 4 1.9xl0-5 1.93 x 10 ~5 1.93 x l O - 4 1.93 x l O - 3 1.77 x l O 1 5 3.65 x 10 " 5 1.33 x l O - 4 4.69 x l O - 4
Ea (kj/mol)
Notes
137.2
h z (0.98) z (1100) z (4000)
143.9
h z (0.98) z(llOO) z (3830)
114
h
a a
102.9
h
a 129.3
118.8
101.7
106.7
133.1
125.5
133.5
124.7
a a a a a a a a a a a a a a a a a a a a a a a a
a
exp[- 132.1 l/RT] 111.3
c,h c c
Refs. 168 165 168 172 172 172 172 172 172 172 172 172 172 267 267 267 315 338 345 345 345 36 36 36 36 315 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 213 362 362 362 362 338 344 344 344 344 31 31 31
Notes page 11-69; References page 11-70
TABLE 6. cont'd Number of C atoms 13 (cont'd)
Initiator
Solvent
tert-Butyl benzyloxyperacetate
Ethylbenzene
tert-Butyl benzylthioperacetate
Ethylbenzene
tert-Butyl bicyclo[2.2.2]octane1-percarboxylate
Cumene
ter/-Butyl endo-bicyclo[2.2.1j-2methylheptane-2-percarboxylate
Cumene
tert-Butyl exo-bicyclo[2.2.1]2-methylheptane-2-percarboxylate
Cumene
tert-Butyl 1,4-dimethylcyclohexane1-percarboxylate (cis)
Cumene
(trans)
Cumene
tert-Butyl 3-methoxyphenylperacetate
Chlorobenzene
terf-Butyl 4- methoxyphenylperacetate
Chlorobenzene
Cumene
tert-Butyl 4-methylphenyl peracetate
Decane Dodecane Ethylbenzene Isooctane Octane Paraffin oil Tetradecane Chlorobenzene
Cumene
Di-terr-butyl perglutarate
terf-Butylperoxy 2-ethylhexylcarbonate
Decane Dodecane Ethylbenzene Hexadecane Octane Tetradecane Styrene
Chlorobenzene
T( 0 C) 40.0 40.0 51.0 60.7 40.0 60.0 70.0 65 75 85 80 90 100 75 80 85 90 95 60 65 70 75 80 60.0 70.0 80.0 60.0 70.0 80.0 79.6 90.7 100.5 56.0 60.3 70.2 79.3 48.9 60 60 79.6 77.5 77.5 70.5 60.5 77.5 60.5 77.5 70.4 79.6 90.7 79.6 79.6 77.5 77.5 70.5 77.5 77.5 77.5 105 115 125 99 117 137
A:d (s"1) 1.3 x 10" 4 1.45 x l O - 4 5.03 XlO" 4 1.62 x l O - 3 2.60xl0~~5 3.31 x 10- 4 1.14 XlO" 3 7.5 x 10 ~6 2.82 x l O " 5 8.47 x l O " 5 5.IxIO"5 1.67 x l O - 4 4.86 XlO" 4 7.35 x 10 ~5 1.39 x 10 " 4 2.64 x l O - 4 4.81 x 10 " 4 8.41 x 10- 4 7.78 x 10 " 5 1.44 x 10 " 4 2.75 x l O " 4 4.89 XlO" 4 8.93 XlO" 4 7.52 x l O " 5 2.66 x 10 " 4 8.49 xlO~ 4 6.93 x 10 ~5 2.52 x l O " 4 7.79 x l 0 ~ 4 9.9xl0~5 3.45 x 10 ~4 1.051 x 10" 3 4.57 x 10 ~5 9.9xlO~ 5 3.06 x l O " 4 7.99 xlO~ 4 1.93 XlO" 5 6.85 x 10 ~5 5.31 x 10 ~5 5.942 x l O - 4 2.52 x 10 ~4 2.60xl0~ 4 1.4xlO~ 3 4.72 x 10 ~5 2.53 x 10 ~4 4.20 x l 0 ~ 5 2.68 x 10 ~4 8.67 x 10 ~5 2.37 xlO~ 4 7.95 xlO~ 4 1.649 x 10 ~4 1.180xl0~ 4 9.08 x 10 ~5 8.57 x l 0 ~ 5 7.2xlO~ 4 1.032 x 10 ~4 8.83 x 10 ~5 7.75 x 10 ~5 2.65 x 10 ~5 1.06 xlO~ 4 3.0OxIO- 4 1.93 x 10 ~5 1.93 x 10 ~4 1.93 x l 0 ~ 3
Ea (kj/mol)
Notes
100.6 101.8
a,h h,m2
108.1
h,m2
119.2
h
120.1
h
126.8
h
116.7
h
115.2
c h
116.3
c c,h c
122.2
h
105.4
h
k z (0.98) z (4050)
Refs. 315 328 328 328 328 328 328 160 160 160 223 223 223 206 206 206 206 206 206 206 206 206 206 206 206 206 206 206 206 178 178 178 178 178 178 178 249 207 207
207
104.8
a,h
110.9
h
z (0.98) z (6080)
a
Xi X1
168 168 315 169 168 169 168 178 178 178 207 207 168 168 315 168 168 168 215 215 215 344 344 344
TABLE 6.
cont'd
Number of C atoms 13 (cont'd)
14
Initiator terf-Butylperoxy 2-ethylhexylcarbonate terr-Butyl 2-phenylperpropionate
Solvent
T(K)
4.07 xlO 1 6
Cumene
40.7 60.1 80.1 40.8 54.7 70.7 40.0 95 114 135 T(K) 45 55 65 95 113 134 T (K) 54.7 70.2 85.4 70.8 85.4 101.0 40.0
7.88 x 10 " 6 8.44 x l O - 5 8.1OxIO- 4 6.15 x 10~6 3.82 x 10 ~5 2.73xlO- 4 2.62 x 10 " 5 1.93 x 10 " 5 1.93XlO" 4 1.93 x l O - 3 1.94 xlO 1 5 1.3OxIO" 5 4.89 x 10 " 5 1.89 x l O - 4 1.93 x 10 ~5 1.93 x l O " 4 1.93 x l O " 3 2.22 x 1016 4.38 x 1O -6 3.56 x l O - 5 2.44 x l O - 4 1.48 x 10 " 5 8.07 x 10" 5 4.38 x l O " 4 7.2xlO-4
50.0 50.0 50.0 60.0 67.0 50.0 60.0 67.0 50.0 60.0 67.0 99.6 109.8 99.6 109.8 34.1 39.7 47 46 64 84 T (K) 50.0 50.0 50.0 60.0 67.0 67.0 84.0 99.3 115.0 113.0 120.0 130.0 140.0
2.55 x 10 " 4 2.03 x 10 " 4 7.98 x 10~5 2.68 x l O - 4 6.36 x l O - 4 8.0OxIO- 5 2.56 x l O " 4 5.96 x l O - 4 8.1OxIO- 5 2.65 x l O - 4 5.95 x l O " 4 1.23 x 10 " 4 3.7OxIO- 4 3.5 x 10~5 1.03 x l O - 4 3.26 x 10 ~5 5.63 x 10" 5 1.9xlO- 5 1.93 x 10 " 5 1.93 x l O " 4 1.93 x l O " 3 1.52 x 1014 7.5OxIO- 5 6.4OxIO" 5 2.63 x 10- 5 9.27 x l O - 5 2.03 x l O " 4 1.98 x 10 - 4 1.464 x 10 " 5 9.94 XlO" 5 6.7 x l O - 5 8.67 x l O " 5 2.49 x 10 ~4 7.49 x l O " 4 2.22 x l O - 3
Cumene
terf-Butylthiobenzylperacetate tert-Butyl peroxy-3,5,5-trimethylhexanoate
Ethylbenzene Chlorobenzene
4-Nitrobenzyl(terf-butylperoxy)oxalate
Benzene
2-ethylhexyl-
Chlorobenzene
tert-Butyl di-terf-butylperacetate
Cumene
terf-Butyl 2-carbomethoxyphenylperacetate
Cumene
terf-Butyl 2-(4-chlorophenoxy)2-methylperpropionate tert-Butyl 2-(4-chlorophenyl)2-methylperpropionate
Ethylbenzene Acetonitrile Benzene Dodecane
Hexadecane
Octane
tert-Butyl a-methylpercinnamate (cis) (trans)
kd (s'1)
Chlorobenzene
tert-Butyl 2,2,4,4-tetramethylperbutyrate
terf-Amylperoxy carbonate
T(0C)
Cumene Cumene
tert-Butyl 2-methyl-2-phenylperpropionate tert-Butyl perneodecanoate
Chlorobenzene Cumene Benzene Chlorobenzene
tert-Butyl 2-(4-nitrophenyl)2-methylperpropionate
Acetonitrile Benzene Dodecane
tert-Butyl permesitoate
Octane Cumene
tert-Butyl 1-phenylcyclopropylpercarboxylate
rc-Dodecane Ethylbenzene
Ea (kj/mol)
Notes
exp[-151.72/RT]
344
111
h
100.6
a,h
exp[- 140.78/K7] 116.7
c,h c c
exp[- 148.41/#7] 125.3
h
116.9
h
a
108.1
h
128.0
f,h f f,h f
125.5
exp[- 115 A7/RT] 105.2
147.5
Refs.
h
h,t i ti ti
273 273 273 267 267 267 315 344 344 344 344 31 31 31 344 344 344 344 245 245 245 257 257 257 315 265 265 265 265 265 265 265 265 265 265 265 150 150 150 150 249 249 338 344 344 344 344 265 265 265 265 265 265 345 345 345 255 323 323 323
Notes page 11-69; References page 11-70
TABLE 6. cont'd Number of C atoms 14 (cont'd)
Initiator tert-Butyl 1-phenylcyclopropylpercarboxylate
Solvent 2,2,4-Trimethyl pentane
tert-Butyl phenyldimethylperacetate
Chlorobenzene Isooctane
tert-Butyl 2-phenyl-3-perbutenoate tert-Butyl 4-phenyl-3-perbutenoate tert-Butyl 2-phenyl-2-methylperpropionate
Chlorohenzene Chlorobenzene Acetonitrile Benzene Benzophenone Benzyl benzoate Butyl phthalate Chlorobenzene Cumene Dodecane
tert-Butyl 4-vinylphenylperacetate
Hexadecane Methyl benzoate Octyl phthalate Toluene Cumene
Dibenzyl peroxalate Di-tert-butyl adipate
Pentane Styrene
Dicyclohexyl peroxydicarbonate
Benzene Chlorobenzene
a-Methylstyrene Mineral spirits
15
4-Methoxybenzyl (tert-butylperoxy)oxalate
Benzene
1-Methyl-1-phenylethyl 2,2-dimethylperoxyporpionate
Cumene
tert-Amy\ perneodecanoate
Benzene Chlorobenzene
Dibenzoyl monopercarbonate tert-Butyl 1-adamantylpercarboxylate
Benzene Cumene
T( 0 C) 102.6 113.0 120.4 60 40.6 60.6 60.6 60 60 50.0 50.0 60 60 60 60 60 50.0 60.0 67.0 60 60 60 60 60 70.9 85.4 100.3 25 105 115 125 50 44 60 77 T (K) 50 45 50 60 45 55 65 40 50 60 70 45 43 61 81 T (K) 60.00 45 55 65 64.6 74.6 84.6 60 70 80
^d(S" 1 ) 2.53 x 10 ~5 8.96 x 10 ~5 2.04 xlO~ 4 9.6xlO~ 4 2.95 x 10 ~5 3.059 xlO~ 4 4.064 xlO~ 4 2.9xlO~ 3 1.15 x 10 ~4 3.08 x 10 " 4 2.18 xlO~ 4 7.73 x 10 ~A 7.92 x 10 ~4 6.5 x 10 ~4 7.00xl0~ 4 5.25 x 10 ~4 8.77 x 10 ~5 3.00xl0~ 4 7.13 xlO~ 4 2.88 xlO~ 4 3.53 x 10 ~4 7.55 x 10 ~4 5.70xl0~ 4 5.66 x 10 ~4 5.54 x 10 " 5 3.00xl0~ 4 1.48 x l 0 ~ 3 6.7 x 10 ~5 3.50xl0~ 5 1.23 xlO~ 4 3.05 xlO~ 4 5.4xlO~ 5 1.93 x 10 ~5 1.93 x l 0 ~ 4 1.93 x l 0 ~ 3 3.3 x 1016 5.9xlO~ 5 2.78 x 10 ~5 5.58 xlO~ 4 2.07 xlO~ 4 6.69 x 10 ~5 2.48 x 10 ~A 8.27 xlO~ 4 6.91 x 10 ~6 2.80 x 10 ~5 1.032 xlO~ 4 3.57 x l O - 4 1.9xl0~ 5 1.93 x 10 ~5 1.93 xlO~ 4 1.93 x l O - 3 1.47 x 1014 8.05 x 10 ~5 5.15 x 10 ~5 2.05 x 10 ~5 7.4OxIO- 5 6.87xl0-5 2.44 xlO~ 4 7.78 x l O - 4 5.4 x l O - 5 2.12 x l O - 4 7.20xl0~ 4
Ea (kj/mol)
Notes
141.2
h
109.2
96.2 98.3
c,h t9 t9 m2 c,h c,h,g
109.3
h
t 12
116.5
h,k k
151.0
X2 X1 X1 c
exp[- 129.0/RT] 117
109.6
a a a c,h c c
a
exp[- 114.38/K7] 116.5 115.5
h h
116.7
h
124.7
h
Refs. 255 255 255 81 165 165 165 81 81 265 265 334 334 334 334 334 265 265 265 334 334 334 334 334 254 254 254 203 215 215 215 201 344 344 344 344 201 337 337 337 31 31 31 368 368 368 368 338 344 344 344 344 280 160 160 160 159 159 159 223 223 223
TABLE 6. Number of C atoms 15 (cont'd)
cont'd
Initiator tert-Butyl 4-(carboethoxy)phenoxyperacetate tert-Butyl a,p-dimethylpercinnamate (cis)
Solvent Ethylbenzene
(trans)
tert-Butyl 1-pernaphthoate tert-Butyl 2,2-dimethyl3-phenylthio perpropionate
Chlorobenzene Cyclohexane
tert-Butyl 2-(4-methoxyphenyl)2-methylperpropionate
Acetonitrile Benzene Dodecane
tert-Butyl 1-phenylcyclo-n-Dodecane butylpercarboxylate
tert-Butyl 4-tert-butylperbenzoate
Chlorobenzene
Di-tert-butyl perpimelate
Styrene
tert-Butyl 2-(4-tolyl)2-methylperpropionate
Acetonitrile Benzene Dodecane
tert-Butyl triisopropylperacetate
16
Octane 52.3 Ethylbenzene n-Hexadecane 2,2,4-trimethyl pentane
Octane Cumene
l,l-Dimethyl-2-phenylethylperpivalate
Cumene
1-Phenylethyl 4-methoxyperacetate 1-Phenylethyl 3-nitroperbenzoate 1-Phenylethyl 4-nitroperbenzoate 1-Phenylethyl perbenzoate Dibenzyl peroxydicarbonate
Benzene Benzene Benzene Benzene Benzene
Di-tert-butyl2-iodoperisophthalate
Chlorobenzene
Di-tert-butyl perphthalate
Benzene
Di-n-butyl phthalate
Chlorobenzene
T( 0 C) 70.5 95.0 103.2 110.1 85.1 95.0 103.7 110.0 110.0 110.1 55 65 75 50 50 40 50 57 50 7.89 x 10 ~5 60.0 52.3 52.3 61.6 100.1 119.8 135.9 105 115 125 50.0 50.0 50.0 60.0 67.0 60.0 24.8 41.6 55.2 40 50 60 70 99.7 100 100 100 40 50 60 68.4 85.4 101.6 100 115 130 100 115 130 107 125 146 T(K)
A^(S"1)
Ea (kj/mol)
1.6xlO~ 4 1.02 xlO~ 4 2.29 x 10 ~4 5.15xlO- 4 3.9xl0~5 1.17xlO- 4 2.84xlO~4 6.05xl0-4 7.9OxIO- 4 8.69 x l 0 ~ 5 1.63 x 10 ~5 1.61 x 10 ~5 1.98xlO- 4 1.675 x 10 ~3 9.96 x 10 ~A 1.49 x l O " 4 4.21 x IO- 4 1.028 XlO" 3 4.18 xlO~ 4 3.62 x 10 " 4 8.80xl0~ 5 7.69 x 10 ~5 2.46x10-4 3.81 x 10 ~5 4.5OxIO- 4 2.38 x l 0 ~ 3 4.45 x 10 ~5 1.05x10-4 5.06x10-4 6.0OxIO" 4 3.85 x 10 " 4 1.9OxIO- 4 5.58 xlO~ 4 1.32OxlO" 3 5.43 x 10 " 4 5.32 x 10~6 6.84 x l O - 5 3.78 XlO" 4 4.56 x 10~6 1.833 x 10~5 6.1 x 10 ~5 2.5IxIO-4 3.50xl0"4 5.97 x 10 ~4 4.10xl0~4 4.03 x 10 ~4 2.0xl0"5 6.25 x l O - 5 2.67 x l O - 4 8.24 x 10~5 4.45 x l O - 4 1.68 x l O " 3 1.1 x 10 ~5 7.8IxIO-5 4.8IxIO"4 1.08 x 10 " 5 7.8 x l O " 5 4.8 XlO" 4 1.93 x 10 ~5 1.93 x l O - 4 1.93 x l O - 3 9.39 xlO 1 6
118.8
122.6
116.9
Notes a
315
a,h a a a,h a a a a,v6
151 151 151 151 151 151 151 151 154 320 320 320 265 265 265 265 265 265
h,t6 t6
93.0
h
255 ti 110.6
h
150.6
Xi X1 X1
100.6
h
111.5
h
134.1 136.2 146.2 123.6 117
h h h h a a a h
93.9
159
155.0
exp[-157.85/^7]
Refs.
a a a h
323 255 255 255 134 134 134 215 215 215 265 265 265 265 265 265 267 267 267 362 362 362 362 259 259 259 259 337 337 337 248 248 248 337 337 337 269 269 269 344 344 344 344
Notes page 11-69; References page 11-70
TABLE 6. cont'd Number of C atoms 16 (cont'd)
Initiator Di-tert-butyl perphthalate
Cumene
terr-Butyl 1-phenyl-l-cyclopentane percarboxylate terf-Butyl 2,3-dimethyl2-phenylperbutyrate Cumyl 7V-phenylperoxy carbamate Dibenzyl peroxydicarbonate Di-terr-butyl perphthalate
Di-tert-bxxty\ persuberate
17
Solvent
^d(S1) 6
Ethylbenzene
99.9 115.0 130.1 60.0
8.34 x 10" 4.68 XlO- 5 2.6OxIO- 4 1.52 x 10 ~3
Ethylbenzene
50
4.3OxIO- 5
T(K) 50 100 115 130 115 125 43.5 52.3 60 70 80 10 35 10 10 100
1.26 x l O 1 4 2.92 x 10 " 5 1.08 x 10 " 5 7.83 x l O - 5 4.8OxIO- 4 7.86 x 10 ~5 2.8IxIO-4 1.184 x l O " 4 3.51 x 10 ~4 1.9xlO~ 5 5.3OxIO- 5 1.38 x l O " 4 4.5 x 10~4 1.9 x l O - 3 6.4X10" 4 5.IxIO"4 2.16 x l O " 3
79.6 70.6 80.3 100.5 60.0 43.5 52.3 61.6 25 40 25 40 25 40 39.3 53.8 53.8 70.0 25 40 25 40 25 40 25 40 25 40 25 40 105 119.4 135.1 105 115 125 98 116 137 T (K)
2.38 x 10 " 5 9.44 x 10 ~6 2.8OxIO- 5 3.09 x l O - 4 1.9OxIO- 3 1.27 x 10 ~4 3.91 x 10 ~4 1.218 x l O - 3 1.89 x 10 ~5 1.22 x l O - 4 1.01 x 10 ~4 5.44 XlO" 4 5.26 x 10~5 3.24 x l O - 4 4.98 x 10 ~5 5.23 x l O ~ 4 4.58 x l O - 4 2.62 x l O " 3 1.76 XlO" 5 1.03 x l O - 4 9.8X10" 7 6.9 x l O - 6 1.11 x l O ~ 4 6.02 x 10 " 4 2.31 x 10~4 1.65 x l O " 3 1.33 x 10" 4 7.25 XlO" 4 8.21 x 10~4 4.75 x l O " 3 2.79 x 10 ~5 1.29 x 10 " 4 6.07 x l O - 4 5.13 x 10~5 1.2OxIO- 4 5.1OxIO- 4 1.93 x 10 ~5 1.93 x l O - 4 1.93 x l O - 3 1.35 x 10 16
Xylene Toluene Benzene
Styrene
tert-Butyl 1-phenylcyclopentylpercarboxylate 1,1,3,3-Tetramethylbutylper-2-ethylhexanoate
2,2,4-Trimethylpentane Benzene
2-Phenylazo-2-propylperbenzoate
Chlorobenzene
1-Phenylethyl 4-dimethylaminoperbenzoate Di-terf-butylperhomoterephthalate
J( 0 C)
/7-Chlorotoluene Chloroform-di Benzene Cumene Toluene
tert-Butyl 1-phenylcyclohexanepercarboxylate
Ethylbenzene 2,2,4-Trimethylpentane
tert-Butyl 2-(phenylthio)perbenzoate
Acetone Acetonitrile terf-Butanol Chlorobenzene
Cyclohexane DMSO Ethanol Isopropanol Methanol terf-Butyldibenzothiophene-4-percarboxylate
Chlorobenzene
Di-tert-butyl perazelate
Styrene
Chlorobenzene
E* (kj/mol)
Notes
140.8
h
ti
Refs. 269 269 269 323 324
exp[- U1.6/RT] 157.7
159.0 103.5
a a a a Xi Xi h
101
a a a
111.5
h
122.3
h
107.7
h
m2 ITi2 m2 m2 m2 m2 b m2
128.0
154.8
exp[- 141.95/RT]
m2 m2 m2 m2 m2 m2 m2 m2 m2 m2 m2 m2 h
40 90 126 126 126 215 215 255 255 337 337 337 260 260 260 260 259 272 272 272 272 323 255 255 255 22 22 22 22 22 22 134 134 134 134 22 22 22 22 22 22 22 22 22 22 22 22 22 22 22 215 215 215 344 344 344 344
TABLE 6. cont'd Number of C atoms 18
Initiator tert-Butyl 4-benzoylperbenzoate terf-Butyl diphenylperacetate
2,4,4-Trimethylpentyl2-perneodecanoate
a,co-Di-0,O-ter?-butyl-(bispersuccinyl)ethylene glycol
tert-Buty\ 1-phenyl-l-cycloheptanepercarboxylate Di-tert-buty\ /?-phenylenediperacetate
tert-Buty\ 2-(phenylthiomethyl)perbenzoate tert-Buty\ thioxanthone-4-percarboxylate Di-tert-butyl persebacate
Di-(2-ethylhexyl)peroxydicarbonate
Solvent Benzene Chlorobenzene Chlorobenzene Cumene
Decane Dodecane Hexadecane Octane tetradecane Chlorobenzene
Ethylbenzene
Ethylbenzene Cumene
Chlorobenzene Chlorobenzene Styrene
Benzene Chlorobenzene
Decane
Mineral spirits
19
Di-«-heptyl persuccinate
Styrene
tert-BxAy\ diphenylmethylperacetate terr-Butyl diphenylperglycidate (cis)
Chlorobenzene Cumene
(trans)
tert-Buty\ 2,2-diphenylperpropionate tert-Butyl 4-hydroxy-3,5-di(tert-butyl)perbenzoate tert-Butyl 4-(4-methylbenzoyl)perbenzoate
Cumene
Chlorobenzene Benzene Carbon tetrachloride Benzene Chlorobenzene
T( 0 C)
kd (s"1)
Ea (kj/mol)
25 110 60 40.3 49.6 59.9 70.4 77.5 77.5 77.5 77.5 77.5 40 57 76 T (K)
1.84 x 10 ~4 2.88 x 10 ~5 4.44 x 10 ~4 2.75 x 10 " 5 9.81xl0"5 3.10xl0"4 1.04 XlO- 3 1.66 x l O " 3 1.688 x l O " 3 1.632 x 10~3 1.651 x 10" 3 1.627 x 10 ~3 1.93 x 10 ~5 1.93 x 10 " 4 1.93 XlO" 3 3.97 x 1014
95 105 115
2.68 x 10 " 6 9.10xl0"6 2.97 XlO" 5
60.0
2.75 x 10 ~3
70.9 85.4 100.3 98.7 120.1 120 135 105 115 125
3.69 x 10 ~5 2.08 XlO" 4 8.83 x l O " 4 4.64 x 10 " 5 4.2OxIO" 4 1.89 x 10 " 4 1.15 x l O " 3 5.10xl0~ 5 1.2Ox 10" 4 5.0OxIO" 4
40 47 64 83 T (K) 30 45 60 40 50 60 60 73.5 85
1.9xlO~ 5 1.93 x 10 " 5 1.93 XlO" 4 1.93 XlO" 3 1.83 x 1015 5.3xl0"6 3.31xl0~ 5 2.32 XlO- 4 1.3xl0" 5 6.14 xlO" 5 2.3IxIO- 4 6.IxIO"" 6 3.85xl0- 5 1.70 XlO" 4
60 60.0 70.0 80.0 60.0 70.0 80.0 34.1 100 100 25 110
1.9xl0" 3 2.8xl0"5 5.5 x l 0 ~ 5 1.68 x l O " 4 1.6 x l O " 5 3.9 XlO" 5 1.20 XlO" 4 7.76 x 10 ~5 3.18 x 3.60 x 1.45 x 3.03 x
10 ~5 10 ~5 10 " 4 10 ~5
Notes p2
101.7 104.6
a,h h
exp[- 115.19/RT\ 147.5
Refs. 279 279 81 136 136 136 136 168 168 168 168 168 344 344 344 344 306 306 306 323
112.7
134.7 156.5 154.8
h,k k k h h,m2 m2 Xi Xi Xi a
exp[- 122.45//?7] 105
126
131.0
a a a a a a Xi X1 X1
103.3 112.1
a,h h
117.2
h
c,e c,e p2
254 254 254 154 154 22 22 215 215 215 338 344 344 344 344 337 337 337 337 337 337 215 215 215 81 204 204 204 204 204 204 249 246 246 279 279
Notes page 11-69; References page 11-70
TABLE 6. cont'd Number of C atoms 19 (cont'd)
20
21
22
23
Initiator ten-Butyl a-phenylpercinnamate (cw) (trans)
Cumene Cumene
Cumyl perneodecanoate
Benzene Chlorobenzene
Di-rc-heptyl peradipate
Styrene
tert-Butyl 2-carbobenzoxyphenylperacetate
Cumene
tert-Butyl 2-methyl-2-phenylperhexanoate oc,co-Di-0,O-tert-butyl-(bispersuccinyl)diethylene glycol
Ethylbenzene Ethylbenzene
tert-Butyl 8-(phenylthio)1-pernaphthoate
Chlorobenzene
tert-Butyl 4-(2,4,6-trimethylbenzoyl)perbenzoate tert-Butyl 2,2-diphenyl3,3-dimethylperbutanoate
Benzene Chlorobenzene Toluene (?)
Di-tert-butyl 2-thiophenylperisophthalate
Chlorobenzene
2,5-Dimethylhexyl 2,5-di(peroxybenzoate)
Benzene
Di-(4-tert-butylcyclohexyl)peroxydicarbonate
Chlorobenzene
tert-Butyl 2,6-di(phenylthio)perbenzoate tert-Butylperoxy stearyl carbonate
Chlorobenzene
tert-Butyl 2,4,6-tri-tert-butylperbenzoate
24
Solvent
tert-Butyl
triphenylperacetate
Chlorobenzene
Cumene
Chlorobenzene Cumene
Di-tert-butyl 2,3-diphenylpersuccinate
Cumene
Di-rc-heptyl persebacate
Styrene
2,5-Dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane
Benzene
Chlorobenzene
T( 0 C)
A:d (s"1)
Ea (kj/mol)
Notes
136.8
h
133.9
h
99.6 109.8 99.6 109.8 39 39 56 75 T(K) 60 73.5 85 71.0 85.4 102.4 50
1.52 x 10~4 4.4IxIO"4 8.2 x 10~5 2.59 x 10 ~4 1.9xl0~ 5 1.93 x 10 " 5 1.93 xlO~ 4 1.93 x l 0 ~ 3 3.12 xlO 1 4 1.02 x 10 ~5 6.57 x l O " 5 2.98 x l O - 4 8.84 x 10" 6 5.46 x 10 ~5 4.23 x l O - 4 5.01 x 10 " 5
95 105 115 50 70 70 80 25 110 30 39.7 50 12.1 25.0 40.0 100 115 130 48 64 82 T (K) 40.1
2.34 x 10 ~6 155.0 8.88 x 10 ~6 3.27 x l O - 5 3.83 x 10 ~5 99.2 3.44 x 10~4 3.12 x l O " 4 9.82 x l O - 4 1.34 x 10 ~4 1.8OxIO- 5 2.76 x 10 ~5 • 114.8 1.15 x 10 ~4 5.45 x l O - 4 1.68 x l O " 4 73.7 6.45 x 10 ~4 3.09 x l O - 3 1.87 x l 0 ~ 5 154.0 1.25 x 10 ~4 7.14 xlO~ 4 1.93 x 10 ~5 1.93 x 10 ~4 1.93 XlO" 3 7.44 x 1015 exp[- 12639/RT] 7.07 x l O " 5
98 117 137 T (K) 70.4 84.0 99.3 115.0 34.9 25.7 34.9 45.5 70.1 79.9 90.0 60 73.5 85 60 70 80 68 86
1.93XlO" 5 1.93 x l O - 4 1.93 XlO" 3 3.94 x 1016 5.84 x 10 " 6 3.54 x 10 " 5 2.67 x l O - 4 1.656 x l O " 3 7.8xlO" 4 1.7 x l O " 4 5.8 XlO" 4 2.3 XlO" 3 9.83 x 10 ~5 3.29 x 10 " 4 1.20 x l O " 3 1.17xlO" 5 7.13 x l O - 5 3.03 xlO~ 5 6.7xlO~ 6 2.92 x 10 " 5 1.14 XlO" 4 1.93 x 10 " 5 1.93 x l O " 4
a
exp[-114.59//?7] 133.1
129.5
Xi Xi X1 h
h
h,m2 m2 m2 p2 J2 J2 k h
a a a
exp[- 151.59/RT]
100.8
h
125.5
c,h c c xi Xi X1 a a a
131.0
142
Refs. 150 150 150 150 338 344 344 344 344 215 215 215 257 257 257 324 306 306 306 154 154 154 154 279 279 250 250 250 248 248 248 126,337 126,337 126,337 344 344 344 344 154 344 344 344 344 345 345 345 345 153 153 153 153 196 196 196 215 215 215 337 337 337 344 344
TABLE 6. cont'd Number of C atoms 24 (cont'd) 25
Initiator
Solvent
2,5-Dimethyl-2,5-bis(2-ethylhexanoylperoxy)hexane tert-Butyl 2-(2,2-diphenylvinyl)perbenzoate
Chlorobenzene Chlorobenzene
Cyclohexane Methanol tert-Butyl 2-percarboxybenzalfluorene 26
30
oc,co-Di-0,0-caprylyl-(bis succinyl)ethylene glycol
Chlorobenzene Methanol Ethylbenzene
oc,co-Di-0,O-caprylyl-(bispersuccinyl)triethylene glycol
Ethylbenzene
Dimyristyl peroxydicarbonate
Chlorobenzene
34
Dicetyl peroxydicarbonate
Chlorobenzene
36
oc,0)-Di-0,0-heptanoyl-(bisperphthaloyl)triethylene glycol
Ethylbenzene
42
oc,co-Di-0,0-caprylyl-(bispersuccinyl)nonaethylene glycol
Ethylbenzene
46
a,oo-Di-0,0-heptanoyl-(bisperphthaloyl)tridecaethylene glycol a,ca-Di-O,O-caprylyl-(bispersuccinyl)tridecaethylene glycol
Ethylbenzene
50
TABLE 7.
Ethylbenzene
T( 0 C) 106 T(K) 90.0 90.3 100.0 105.5 119.3 90.0 90.4
*d (s" 1 ) 1.93 2.19 1.32 7.45 3.27 4.64 1.54 3.5 2.3
x 10 ~3 x 1015 x 10~4 x 10~5 xlO"4 XlO" 4 xlO-3 x 10 ~5 x 10~3
90 90
3.75 x 10 ~4 2.47 x 10 ~3
65 75 85 95 65 75 85 95 48 65 84 T (K) 48 65 84 T (K) 65 75 85 95 65 75 85 95 75 85 95 65 75 85
1.48 x 10~5 4.10xl0"5 2.19 x l O - 4 6.92 x l O - 4 2.74 x 10 ~5 8.47 x 10 " 5 2.95 x l O - 4 8.92 x l O - 4 1.93 x 10 " 5 1.93 x l O - 4 1.93 x l O " 3 2.82 x 10 15 1.93 x 10 ~5 1.93 x l O - 4 1.93 x l O - 3 3.02 x 1015 5.02 x IO ~5 1.420 x 10 ~4 5.19 x l O - 4 1.410 x l O " 3 1.66 x 1O~5 6.57 x 10 " 5 1.78 XlO" 4 9.72 x l O - 4 1.13OxIO- 4 3.5OxIO" 4 8.80xl0~ 4 1.28 x l 0 ~ 5 4.46 x 10 ~5 1.91 x l O ~ 4
Ea (kj/mol)
Notes
Refs. 344 344 175 175 175 175 175 175 175
exp[- 130.SS/RT] t9 t9 t9 t9
175 175 120.7
h
306 306 306 306 306 306 306 306 344 344 344 344 344 344 344 344 306 306 306 306 306 306 306 306 306 306 306 306 306 306
116.9
exp[- 124.10/RT]
exp[- 124.30/RT] 124.4
116.9
122.3
128.2
MISCELLANEOUS INITIATORS
Initiator
Solvent
Acetyl cyclohexyl sulfonyl peroxide
Benzene
AH1-Cyanocyclohexyl)pentamethylene keteneimine
Chlorobenzene
Dibenzyl hyponitrite
Paraffin
T ( 0 C) 30 40 45 80.0 89.2 100.1 61.5 68.5 75.5 80.5 132
^d(S1) 1.4XlO" 5 9.42 x l 0 ~ 5 2.10xl0~4 3.25 x 10 ~6 1.007 x l 0 ~ 5 4.025 XlO" 5 6.5 x 10~4 3.7 x l 0 ~ 3 8.3 x l O - 3 1.45 x l O ~ 2 8.7XlO- 1
£ a (kj/mol)
Notes
147
a a a
Refs. 337 337 337 179 179 179 240 240 240 240 240
Notes page 11-69; References page 11-70
TABLE 7. cont'd Initiator Di-terf-butyl hyponitrite
Peroxybenzoylnitrate
Solvent tert-Butanol rc-Butyl ether Ethanol(95%) Isooctane
Nujol Vapor
Vapor + NO
Vapor + NO
2,3-Dimethyl-2,3-diphenylbutane
Chlorobenzene
3,4-Dimethyl-3,4-diphenylhexane
Chlorobenzene
l,4-Dimethyl-l,4-diphenyl-tetrazene-2
Benzophenone Cumene Paraffin
Siliconeoil Potassium persulfate
0.1 M NaOH
Water (pH 3) Water
1-Pentanesulfonylazide 1,4-Butanedisulfonyl azide 1,6-Hexanedisulfonyl azide 1,9-Nonanedisulfonyl azide
Diphenyl ether Diphenyl ether Diphenyl ether Diphenyl ether
1,10-Decanedisulfonyl azide l,4-Dimethylcyclohexane-a,a'-disulfonyl azide
Diphenyl ether Diphenyl ether
T( 0 C) 65 65 65 45 55 65 75 65 7.6 19.9 30.4 40.6 50.1 60.5 T(K) 18.1 30.4 40.6 T (K) 30.4 50.2 68.5 T(K) 237 259 284 T(K) 201 226 254 T(K) 121 149 120 130 140 164.2 174.3 186 194 126 139 50 60 70 80 90 50 80 80 40 50 60 50 60 70 50 166 163 163 150 160 170 163 163
kd (s" 1 )
Ea (kj/mol)
4.68 x 10 " 4 4.50 x 10 " 4 3.93 x 10 ~4 2.72 xlO~ 5 116.9 1.07 x l O - 4 4.0OxIO" 4 1.33OxIO-3 5.17 x 10~4 2.79 x 10 ~6 69.1 1.05 x l O - 5 2.02 XlO" 5 3.64 x l O - 5 1.21 x 10- 4 2.74 XlO" 4 1 x 107 exp[-69.1//?7] 8.18 xlO" 5 108.5 3.62 XlO" 4 1.42 x l O - 3 1.6 x 1015 exp[- 108.5/RT] 1.34 x l 0 ~ 5 79.2 7.22 x l O - 5 3.41 x 10" 4 6.3 x l O - 8 exp[-79.2/i?n 1.93 x 10 ~5 1.93 x l O " 4 1.93 x l O - 3 7.34 xlO 1 8 exp[-230.19//?n 1.93 x 10 ~5 1.93 x l O - 4 1.93 x l 0 ~ 3 1.45 xlO 1 5 exp[- IS032/RT] 3.3xl0"4 3.45 x l 0 ~ 3 2.3xlO" 4 6.5 x l O - 4 1.67 XlO" 3 2.6xlO- 2 5.6 x l O - 2 1.43XlO"1 2.5XlO- 1 3.7xlO" 4 1.92 x l O - 3 9.5 x 10 ~7 140.2 3.16 xlO~ 6 2.33 x l O - 5 9.16 XlO" 5 3.5 x l O - 4 1.66 x 10 ~6 6.89 x 10~5 5.78 x l O - 5 1.65 xlO" 2 83.4 4.02 x l O " 2 1.08XlO"1 3.78 XlO" 3 121.5 2.18 x l O - 2 5.01xl0~ 2 1.1 x 10- 6 4.46 x 10 " 4 5.02 x 10 " 4 5.02 x 10 ~4 8.84 x 10 " 5 2.25 xlO" 4 4.45 x l O - 4 4.45 x 10 ~4 4.82 x 10" 4
Notes
h
h
h
h
a a a a a a a,vn a,v u d 3 ,v 22 d 3 ,v 22 d 3 ,v 22 d 3 ,v 23 d 3 ,v 23 d 3 ,v 23
Refs. 317 317 317 317 317 317 317 317 261 261 261 261 261 261 261 261 261 261 261 261 261 261 261 344 344 344 344 344 344 344 344 240 240 240 240 240 240 240 240 240 240 240 242 242 242 242 242 242 115 115 262 262 262 262 262 262 262 166 166 166 166 166 166 166 166
ro-Xylene-a,a'-disulfonyl azide p-Xylene-o^oc'-disulfonyl azide Benzenesulfonyl azide
Diphenyl ether Diphenyl ether Naphthalene
/7-Bromobenzenesulfonyl azide p-Chlorobenzenesulfonyl azide p-Methoxybenzenesulfonylazide p-Nitrobenzenesulfonyl azide p-Toluenesulfonyl azide
Naphthalene Naphthalene Naphthalene Naphthalene 1,4-Dichlorobutane Dimethyl terephthalate Diphenyl ether
p-Toluenesulfonyl-p-tolylsulfone
Hexanoic acid Naphthalene Nitrobenzene 1-Octanol Tetradecane Acetonitrile
Dioxane
163 163 110 120 125 130 175 120 120 120 120 145 155 130 145 155 155 120 155 155 155 29.3 39.1 49.3 29.3 39.5 49.3
6.09 x 10 ~4 5.78 x 10 ~4 3.6xlO" 6 1.07 x l O - 5 1.97xlO- 5 3.41xl0"5 6.08 x l O - 5 1.36 x 10 ~5 1.15 x 10 " 5 1.31 x 10 ~5 1.6OxIO" 5 1.7OxIO- 4 3.23 x 10 ~4 3.30 x 10~5 1.44 XlO" 4 3.43 x l O " 4 2.97 x 10 ~4 1.12 x l O " 5 3.97 x 10 ~4 3.63 x 10" 4 3.80 x 10 ~4 3.9xl0-5 1.45 x l O - 4 5.4 XlO" 4 2.IxIO-5 1.01 x l O - 4 3.9 x 10 ~4
152.3
103.8
h
115.5
h
166 166 235 235 235 235 235 235 235 235 235 166 166 166 166 166 166 235 166 166 166 144 144 144 144 144 144
C. NOTES a /cd converted to s" 1 from author's units b kd values for several concentrations averaged t)2 analyzed from nonisothermal conditions c kd increases with increasing initiator concentration c 2 rate non-linear c3 hydroperoxide concentration 7.83 x 10~ 3 mol/1 C4 hydroperoxide concentration 2.50 x 10~ 3 mol/1 d kd decreases with increasing initiator concentration d2 after 1st half life; rate slower initially d3 rate is second order: units are 1/mol sec. e fcd listed is for lowest initiator concentration f &d is extrapolated value for zero initiator concentration g kd ^ has been corrected for induced decomposition g2 corrected for uncatalysed reaction (7 x 10 ~5 s" 1 ) h AH (not E2) i pressure (number gives mbar) j iodometric analysis j 2 manometer measurement k infrared analysis 1 kd is limiting value with respect to additive concentration mi 3,4-dichlorostyrene added to minimize induced decomposition m2 styrene added to minimize induced decomposition ni3 methyl methacrylate added to minimize induced decomposition ni4 isobutene added to minimize induced decomposition m5 acenaphthalene added to minimize induced decomposition m 6 1 mol/1 oc-methylstyrene added to minimize induced
decomposition mj butadiene added to minimize induced decomposition mg acrylonitrile added to minimize induced decomposition n trichloroacetic acid added n2 3.2wt.% or about 0.1 monolayer o addition of trichloroacetic acid did not affect kd p degassed p 2 photochemical benzophenone added: 6.56 x 10 17 quants/min @ 366 nm q addition of trichloroacetic acid increased kd several fold q 2 pH 2.90 q 3 pH 7.05 r not inhibited, but initiator concentration low enough (0.01-0.09 M) so that higher order decomposition is unimportant s solvent not degassed 11 2,6-di-terr-butylphenol added to inhibit induced decomposition t2 oc,a-diphenyl-P-picrylhydrazyl added to inhibit induced decomposition t3 phenyl-oc-naphthylamine added to inhibit induced decomposition t4 tetrachloroquinone added to inhibit induced decomposition t5 1,3,5-trinitrobenzene added to inhibit induced decomposition t6 12 added to inhibit induced decomposition tj O 2 added to inhibit induced decomposition t8 5-20% NO 2 added to inhibit decomposition References page II - 70
t9 tio
vi V2 V3 V4 V5 v6 v7 Vg v9
galvanoxyl added to inhibit induced decomposition a,y-bisdiphenylene-p-phenylallyl added to inhibit induced decomposition oc-naphthylamine added to minimize induced decomposition 2,3 / ,5 / ,6 / -tetra-te7t-butyl indophenoxy added benzoquinone added 2,6-di-teJt-butyl-4-methylphenol added in absence of oxygen from initiation data in multisurface reaction vessel rate reduced when nujol layer used to exclude Hg vapor rate increased when nujol layer used to exclude Hg vapor acetic acid added CuCl 2 added CuCl added 0.1 mol AgClO 4 /mol AIBN added 3.9 mol thiophenol added tert-bxxtyl mercaptan added 2.5 mol cyclohexane added ~ 4 x l O ~ 2 mol pyridine added 2 x 10~ 2 mol pyridine added
D.
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tn ti2 ti3 114 ui u2 u3 U4 U5
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2.5 mol cumene added buffered with sodium pyrophosphate saturated with ethyl acetate 3.11 mol CCl4 present peroxide in P(MMA) peroxide in P(sty.) 0.26 mol piperidine 0.24 mol triethylamine 0.21 mol AT,Af-diethylaniline 0.22 mol pyridine 0.9 mol Z n C l 2 in presence of 1 5 N O 0.12 mol 18 crown 6 added 0.24 mol diglyme added 0.02 M pyridine added 0.10 M pyridine added 0.10 M 2,6-lutidine added stereoisomers actual rate divided by 2 because of two identical peroxide groups each peroxide group has different k^ measured in differential scanning calorimeter: subscript is heating rate in deg/min pressure (in bar)
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P r o p a g a t i o n i n
F r e e
a n d
T e r m i n a t i o n
R a d i c a l
C o n s t a n t s
P o l y m e r i z a t i o n
M. Kamachi Department of Applied Physics and Chemistry, Fukui University of Technology, Gakuen, Fukui, Japan B. Y a m a d a Department of Applied Chemistry, Faculty of Technology Osaka City University, Sumiyoshi, Osaka, Japan A. Introduction B. Tables of Propagation and Termination Constants Table 1. Dienes Table 2. Olefins Table 3. Acrylic Derivatives Table 4. Methacrylic Derivatives Table 5. ltaconic Derivatives Table 6. Fumaric Derivatives Table 7. Vinyl Halides Table 8. Vinyl Esters Table 9. Vinyl Ethers Table 10. Styrene Derivatives Table 11. Vinyl Heteroaromatics Table 12. Aldehydes Table 13. Others C. References
11-77 11-79 II-79 II-79 II-80 II-82 II-85 U-87 II-87 II-87 II-88 II-88 II-90 II-90 II-90 11-91
The rate constants kv and kt have usually been assumed to be independent of chain length. In this chapter termination constants depending on the length of the polymer radicals are also reported. In American literature the right hand side of (A4) is written as 2£t[P#] . In this chapter the definition given in Eq. (A4) has been used. Simultaneous determination of absolute values of both kv and kt from a single experiment has not been reported. In practice, the ratio k^/kt is determined from measurements of molecular weight as a function of rate of polymerization for a low conversion polymerization or from measurements of initiation rate and polymerization rate in a low conversion. The ratio kp/kt is determined from nonsteady-state measurements of the average lifetime, r, of the growing polymer chain in a photochemically initiated polymerization. This lifetime may be defined by noting that the concentration of chains present must be related to their average lifetime and rate of disappearance by (A6)
A.
INTRODUCTION
In free radical polymerization the propagation and termination rate constants describe the reactions
which, from (A3) and (A4), yields (A7)
(Al) dead polymer
(A2)
where P^ is a propagating chain of any length n and M is the monomer. The rate constants are defined by the following equations:
By combining the separately determined ratios, k^/kt and kp/kt, the individual propagation and termination rate constants may be calculated. Alternatively, the rate of initiation, R[, may be measured as the rate of initiator disappearance and equated to R1. This gives (from (A6) and (A3))
(A3) (A4) where (A5)
(A8) There is a large degree of imprecision inherent in measuring r and in combining data from different experiments, which helps to explain the scatter in the data tabulated here.
/Ct(XiO"6)
kp
/C1(XiO-6)
Figure 1. Arrhenius plots of all bulk polymerization data for styrene for kp (•) and /ct (+). Solid lines are least squares obtained by assuming all points to be of equal value.
The two monomers styrene and methyl methacrylate have been so extensively studied that their data are presented as Arrhenius plots (Figs. 1 and 2). Because of the influence of solvents on the rates, only data of bulk polymerizations are shown. It remains a wide scatter, which should serve as a warning against casual acceptance of any single number. Solid lines are the least squares that have been calculated assuming all points to be of equal value. For the termination rate of methyl methacrylate the leastsquares line results in a positive slope and is not shown. In this case a temperature-independent kt could be a better representation of the experiments. The pulse laser polymerization (PLP) method has been developed as a new method of obtaining kp. In the PLP method, the value of kp can be estimated from the degree of polymerization of polymer formed, vp, a knowledge of the monomer concentration, [M], and tf the time between pulses: (A9) The reproducibility of the PLP method has been recognized by an IUPAC Working Party on Modeling of Kinetic and Process of Polymerization, which is establishing a critical review of the literature values of kp.
K9
1000 T Figure 2. Arrhenius plots of all bulk polymerization data for methyl methacrylate for /cp (•) and /ct(+). Solid lines are least squares obtained by assuming all points to be of equal value. The line for kx is not shown since a horizontal line for a temperature independent kt could be a better representation. Classification of the methods for the determination of rate constants The tabulated data refer to seven different methods. Method A uses the following four methods for the measurement of the lifetime r: Al -rotating sector or a "flashing" laser A2 - flow through a tube with spatially separated light and dark sections A3 - spacial intermittent polymerization (SIP) A4 - intermittent illumination method Method B effectively measures only a single decrease (increase), in the radical concentration by the following methods: B l - dilatometry B 2 - dielectric constant B 3 - interferomety B4 - temperature change B5 - viscosity B6 - light scattering B7 - monomer pressure
B 8 - cathetometer B9-inhibitor BlO-scavenger
Method F uses pulse laser photopolymerization (PLP) method
Method C uses electron spin resonance (ESR) for the determination of the radical concentration Method D refers to values obtained in emulsion polymerization by application of the Smith-Ewart theory
Fl - PLP F2 - PLP-GPC (MWD) F3 - PLP-MALDI TOF (-GPC) Method G refers to the method of measuring molecular weight (MW) and molecular weight distribution (MWD) by Gl - gel permeation chromatography (GPC) G2 - high performance liquid chromatography (HPLC)
Method E refers to recalculated values
B. TABLES OF PROPAGATION AND TERMINATION CONSTANTS TABLE 1. DIENES Monomer 1-Acetoxybutadiene Butadiene
k9 (1/mol/s)
M x I O " 6 ) (l/mol/s)
Temp. (0C)
Method
18.0 &p = 1 . 2 x l 0 8 x exp(- 39000/RT) 150 ± 4 0
281
25 10
Al D
152 23
kt = 1.13 x l O 4 xexp(-711/r)
5 45-60
C Gl
223 202
50
Fl
221
-
50
Fl F2
Solvent: chlorobenzene Solvent: chlorobenzene
-
40
D D
Quoted in Ref. 86
l n * p = l n (3.873 x 1010) - 53400/RT 111.6 kp = 8.05 x 107 xexp(-35710//?7) Chloroprene 220 fcp = 2 . 9 x l 0 9 x exp(-41000/^7) *p = 1.95 x l O 7 x exp(- 26630/RT) 2,3-Dimethyl-l,3-butadiene &p = 8 . 9 x l 0 7 x exp(- 38000//?7) Ethyl 4-ethoxy-2,4-pentadienoate 9.9 Ethyl 4-methyl-2,4-pentadienoate 29.7 Ethyl pentadienoate 30.9 1,3-Hexadiene 20 ± 1 0 2,4-Hexadiene 16 ± 1 2 Isoprene 2.8
2-Methyl-l,3-pentadiene
Remarks
Refs.
221 187 59 84
Fl
198
D
71 152 152 152 223 223 24
9.3 23 19 -
25 25 25 5 5 5
Al Al Al C C D
125 ± 3 0 35 ± 10
-
5 5
C C
k p (1/mol/s)
M x I O 6 ) (1/mol/s)
Temp. (° C)
Method
1050 ± 5 0 455 ± 5 0 200
83 -20.01 130
Al Al Al
3.9 (7.8) x 102 1.99 x 102 -
130 190 230
Al C Fl
3.2 x 103
190
Fl
Calalyst system: diisopropylbenzene, monohydroperoxidetetraethylenepentamine
223 223
TABLE 2. OLEFINS Monomer Ethylene
Propylene
470 ± 3 0 18.6 ± 2 5400 £ p = 4.8x 107 x exp[(- 4450 + 3.Ix 10~6p)/T] 1.2 x 104 1.09 x 104 3.08 x 104
&p = 2 x l 0 6 x exp(- 32000/RT)
50-150
Remarks Solvent: benzene Pressure 1.8 x 10 8 Pa Pressure (5-17.5) x 10 7 Pa, using results of Ref. 141 Pressure 1.9 x 108 Pa Initial pressure 2.27 x 108 Pa Pressure 2.55 x 108 Pa, at low or moderate conversion Pressure 2.50 x 108 Pa, at conversion 0 Radical telomerization
Refs. 53 66 139 142 135 151 167 167 129
References page 11-15
TABLE 3. ACRYLIC DERIVATIVES Monomer
kp (1/mol/s)
kt (xlO~ 6 ) (1/mol/s)
Acrylamide
6000 ± 1000 18000 ±1500 8200 220 (7.9 ±0.5) x 10 4 (4.3 ±0.2) x 104 (3.3 ±0.2) x 104 (2.3 ±0.1) x 10 4 fcp=7xl06 x exp[(- 21000 ± 2000)/RT]
3.3 ±0.6 14.5 ±2.0 5.5 1.0 660 ± 4 0 350 ± 2 0 230 ± 2 0 160 ± 1 0
650
2.6
3150
2.6
Temp. (0C)
25 19 26 30 30
Method Al, Bl Al A A Al Al Al Al Fl
Remarks Solvent: water, pH 5.5 Solvent: water Solvent: water Solvent: DMSO Solvent: water 0.38M H 2 O : DMSO (90:10) H 2 O:dioxane (90:10) H 2 O : THF (92:8)
Refs. 79 41 89 89 126 119 119 119 197
Acrylic acid
-,butyl ester
- , cyclohexyl ester -,ethyl ester
6600 2.7 13 0.018 2100 330 1977 3.84 679±66 6.4±0.6 log 10 fcp = 6.0123-748.4/7 ln[(*t[p]/(1.00 + OMp)] = l n * t [I]-0.6Op 1360 1.28 963 1.18 1320 1.07 360 0.36 2722 ±248 3.2 ±0.3 800 1.76 12.39 x 10 3 139.2
- , 2-ethylhexyl ester - , methyl ester
23
Al Al
30 25-80 30
Al Al B4 Al Al Fl B5
30
Al
30 50 50
Al Al Al
25 25
155 1300
0.233 75
50 15
Al Al
880
260
15
Al
25 25
Al Bl Al
1580 580 fcp = 1 . 0 x l 0 8 x exp(- 30000/RT) 1000 11680 21300 (1.5 ±0.2) x 10 4 (3.7 ±0.6) x 104 6.3 x 104 (1.4 ±0.2) x 104
55 6.5 fct = 2.8xl0n x exp(- 22000/RT) 3.5550 194 -
60
Al Al Al G2
-
60 60 60
G2 G2 G2
- , 2-(acetoacetoxy-methyl)-, ethyl ester - , 2-cyano-, ethyl ester
300 1622 1610 1613 1607
1.0 411 404 411 404
60 30 30 30 30
C Al Al Al Al
- , 2-chloro-, ethyl ester
1660 1408 1120 978 350
333 244 4.8 x 102 435 2.1
30 30 30 30 60
Al Al Al Al C
- , 2-fluoro-, ethyl ester - , 2-acetoxymethyl-, methyl ester
Solvent: Water, pH 7.9, (with 1.2MNaOH) Solvent: water, pH 7.9 (with 1.5NNaCl) Solvent: water, pH 11
Pressure 5.0 x 107 Pa Solvent: benzene 1.76M kt \p\; kt for pressure p (bar), kt [l] = 3.5x 106 Solvent: anisole 2.00M Solvent: benzene 2.00M Solvent: chlorobenzene 2.00M Solvent: benzonitrile 2.00 M Solvent: benzene 1.76M Solvent: toluene 1.84 M Solvent: benzene x\ molar fractions of monomer, x = 0.401, kp and kt also given by other [M] Solvent: toluene 1.94M From unpublished results of Ross and Melville From unpublished results of Matheson
99 99 99 10 57 107 137 201 122 138 138 138 138 137 108 171
108 22 22 19 48 21
Solvent: benzene 2.69 M Primary propagating step (jfcpl), Ph-MA* PhCO 2 -MA' tert-BuO-MAm Secondary propagating step (kp2), Ph-MA-MA*, PhCO 2 -MA-MA', tert-BuO-MA-MA* Solvent: benseme AcOH 7 wt.% 1,3-propanesulfone 0.5 wt.% Optimum value, solvent: AcOH Optimum value Solvent: propanesulfone AIBN 4.88 x 10" 2 M Optimum value Optimum value Solvent: benzene LOOM, MAIB 0.050 M
50 144 144 190 190 190
170 143 143 123 123 140 123 146 123 225
TABLE 3. cont'd Monomer
fep
(1/mol/s)
fct(x..l0-6)
(l/mol/s)
Temp. ( 0 C)
Method
- , 2-acetyloxy-, methyl ester
430
-
60
C
- , 2-benzoyloxy-, ethyl ester - , 2-(benzyloxymethyl)-, methyl ester
990 182
2.9 1.6
60 60
C C
- , 2-[2,2-bis(carbomethoxy) ethyl], methyl ester
4.0
0.038
60
C
- , 2-butoxy-, methyl ester
298 184
8 -
60 60
C C
- , 2-butyroxymethyl-, methyl ester
360
1.4
60
C
19
0.51
60
C
8.6 1.6 300
21 1.8 1.1
60 60 60
C C C
11
0.08
50
C
0.57
0.11
60
C
0.76
1.4
60
C
- , 3-methyl, dimethyladamantyl ester
0.41 0.71
0.081 1.1
60 60
C C
- , 3-methyl, terf-butyl ester
0.90 LO
2.3 4.7
60 60
C C
- , 2-naphthoyloxymethyl-, ethyl ester
320
0.37
60
C
- , 2-pivaroxymethyl-, methyl ester
230
0.59
60
C
- , trans-2-vinyl-, methyl ester
125
-
60
C
3000-5000 127 52 51 20000 24
12.2 5 1.8
OD 25 25 25 40 50
B4 B4 B4 D
1960 15400 28000 1910 382 ±230 3300 ± 300 3200 ±400 3000 ± 600 (6.5 ± 1.3) x 103 28.2
782 2700 3700 290 47.6 ± 2 2 1200 ± 170 300 ± 5 0 240 ± 70 4700± 1300 0.20
60 25 25 25 25 50 50 50 50 60
Al Al Al Al Al Al Al Al Al C
273 273 8267
17.9 11.9 2200
30 30 30
Al Al Al
- , 2-(2-carbomethoxy)- ethyl-, methyl ester - , 2-ethyl-, methyl ester - , 2-ethyl-, cyclohexyl ester - , 2-isobutyroxymethyl-, methyl ester -,-2-(methoxycarbonylmethyl)-, phenetyl ester - , 3-methyl, adamantyl ester
Acrylonitrile
Ar-Acryloyl-2,2-dimethyl5 (R)-phenyl-l,3-dioxazoline 7V-Acryloylpiperidine N-Acryloylpyrrolidine
23
Remarks Solvent: 1,1,2-trichloroethane 2.0M 2,2'-azobis (4-methoxy-2,4dimethylvaleronitrile) 0.030 M, kp also given by other temp. Solvent: benzene 1.56M Solvent: benzene 2.0M, AIBN 5 ^ x IQ^ 3 M Bulk AVN 0.05 M, Ic p and kt also given by other temp. Solvent: benzene 2 M Solvent: 1,1,2-trichloroethane 2.0M 2,2'-azobis (4-methoxy-2,4dimethylvaleronitrile) 0.030 M, kp also given by other temp. Solvent: benzene LOOM, MAIB 0.050 M Bulk MAIB 0.05 M, kp and kt also given by other temp. Bulk AIBN 0.10M Bulk AIBN 0.10M Solvent: benzene LOOM, MAIB 0.050 M Solvent: benzene 2.22 M, kp and kt also given by other temp. and [M] Bulk 4.8 M MAIB 0.05 M Solvent: benzene 2.4 M, MAIB 0.05 M, kp also given by other [M] Bulk 4.0 M, MAIB 0.05 M Solvent: benzene 2.0M, MAIB 0.05 M Bulk 5.9 M, MAIB 0.05 M Solvent: benzene 2.0M, MAIB 0.05 M Solvent: benzene LOOM, MAIB 0.01 M Solvent: benzene LOOM, MAIB 0.005 M Solvent: benzene LOM, AIBN 0.25 M
Solvent: DMF
Refs. 224
172 206 228
176 224
225 229 230 230 225 157
232 232
232 232 232 232 226 225 227 42 49 63 75 42 35
Primary radical termination in a precipitating medium Solvent: DMF 43 Solvent: water 54 Solvent: water 55 Solvent: DMSO 70 Solvent: DMF 68 Solvent: DMF 3.8 M 88 Solvent: DMSO 3.8 M 88 Solvent: Ethylene carbonate 3.8 M 88 Solvent: Mg (C1O4)2 • 12H2O 3.04M 88 Solvent: benzene 1.08 M, 231 MAIB 0.05 M, kp and kt also given by other temp. 145 Optimum value 123 Optimum value 123
References page 11-15
TABLE 3. cont'd Monomer
kp (1/mol/s)
ifetCxlO"6) (1/mol/s)
Temp. (0C)
Method
JVW'-Dimethylacrylamide
11000 27200 29198 15 x 10 3 2330 ±230
38 3540 4080 0.540 ±0.053
50 30 30 25 30
Al Al Al Fl A4
2760 ±342
0.452 ±0.056
30
9.9 x 10 3
-
25
Fl
kp (1/mol/s)
kt (x 10 ~6) (1/mol/s)
Temp. (0C)
Method
79.6 ±5.6 1.1 x 10 3 ~21 26
16.5 ± 1 . 4 ~27 21
25 25 30 25
Al Fl Al
670
2.1
23
Al
1950 1410 110 895 1250 510
2.25 41.9 80 40 41.9 2.87
30 32.5 32.5 30 20
Al Al C C Al Al
- , bornyl ester
580
3.3
60
C
- , n-butyl ester
369 573 360 lnfcp = 6 . 1 3 + 6.33 x 10 ~9 p lnfcp = 15.8-2751/7
10.2 18.0 10
30 30 30 30 12-93 70 30
Al Al Al F2 F2 B5 B5
10-90
Fl Fl A3 Al
3-Dimethyl-(acryloyloxyethyl)ammonium propane sulfonate
N-Methylacrylamide
Remarks
Optimum value Solvent: water, pH 1.4 Solvent: formamide: 1,4-dioxane (3:1 (v/v)) Solvent: formamide: 1,4-dioxane (3:1 (v/v)), NaCl 0.1 M Solvent: water, pH 1.9
Refs. 74 121 123 197 192 192 197
TABLE 4. METHACRYLIC DERIVATIVES Monomer Methacrylamide Methacrylonitrile £p
Remarks Solvent: water Solvent: water, pH 1
Refs. 69 197 26 39
106.43±0.26
=
xexp[(-29700±1500)//?n Methacrylic acid
- , benzyl ester
- , terf-butyl ester
2.6 In [(kt\p]/(\M + 0.0lp)] = InJt1[I] - 0.73/7 ln*p = (14.41 ±0.09) - (2472±29)/T jfcp = 3.44 x 10 6 exp(- 23300/RT) 1576 9.74 350 14 £p
=
1O7.4±o.4
30 25 9
_66
Solvent: water, pH 8.0 (with 0.22MNaOH) pH=13.6
kp and kt also given as a function of viscosity Solvent: benzene 1.0 M, AIBN 0.05 M Pressure: 5.0 x 10 7 Pa
Pressure 1.0 x 10 8 Pa 77=1.92cp kt \p]\ kt for pressure p (bar), kt[l] = 13.4 x 10 6
99 99 101 153 153 87 103 193 27 106 109 216 216 212 122 219 169 225 52 203
F 1
xexp[-(27.7±2.5)x IO3/RT] - , trans-4-tert-buty\cyclohexyl ester
- , cetyl ester - , p-Ip-(cetyloxy)benzoyloxy]phenyl ester - , 2-chloroethyl ester - , 2-cyclohexylethyl ester - , cyclohexyl ester - , 2-decahydronaphthyl ester
550
1.9
60
C
510 570 ± 1 0 300 ± 9 0 300
1.9 0.5-2.3 0.16 ±0.04 0.25
60 60 30 50
C C Al Al
170 254 1190
0.30 6.71 32.8
50 30 30
Al Al Al
510
5.4
60
C
570
3.1
60
C
Solvent: benzene LOM, AIBN 0.05 M, trans 100% trans 28.9% Solvent: benzene Solvent: dioxane 0.2 M
Solvent: toluene 0.2M
Solvent: benzene LOM, AIBN 0.05 M Solvent: benzene LOM, AIBN 0.05 M
194 194 210 109 97
97 87 87 193 193
TABLE 4. cont'd Monomer - , 2,6-dimethylphenyl ester - , dodecyl ester -,ethyl ester
- , hexadecyl ester - , isobornyl ester - , isobutyl ester - , isopropyl ester - , lauryl ester
- , 2-methoxyethyl ester - , methyl ester
kp (1/mol/s)
M x l O " 6 ) (1/mol/s)
Temp. (0C)
Method
68
2.1
30
Al
72 126
2.4 0.6 7.35 10
30 70 30 70
Al B5 Al B5 Fl
0.16 3.5
10-90 70 60
Fl B5 C
10-90 30 30
Fl Al Al Fl
219 87 109 169
30 23.6
Al Al Al
87 9 7
32.5 40 50 -30 20
C Bl E Bl Al
* p = 1.50 XlO 6 x exp(- 20460/RT) ln* p = (15.11±0.17)-(2753±55)/r 390
lnfcp = (14.72±0.13)-(2590±42)/7 121 4.52 460 ±140 0.6 ±0.2 kp = 2.93 x l O 5 x exp(- 16190/RT) 249 9.30 310 ± 2 0 66 ± 4 fcp = 5 . 1 3 x l 0 6 kt = 1.36 x l O 3 x exp(- 26400/RT) x exp(- 11900/flT) 187 72.1 404 17.6 410 24 13.2 0.488 390 517 527 28 260 270 280 285 310 330 340 240 335 270 330 250 240 280 320 390 ± 4 0 410 ± 40 410 ± 4 0 180±50
37 23 4.4 21 21 19.5 17.5 17 17 17 11.5 9 22 16 29 25 14 28 42 ± 4 29 ± 3 26 ± 3 20 ± 6
10 10 10 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 20
Bl Bl Bl Al Al Al Al Al Al B5 B5 B5 B5 B5 B5 B5 B5 B5 Al Al Al E
500 ±250 41.6 62 200 128 364
63 ± 3 2 2.69 8.44 41.8
20 0 5 20 22 22.5
B6 B5 D B6 Bl B4
512.6 410
46.6 42.7
25 25
Al Al
248 141 106 140
22.7 11.6 5.7 -
30 30 32 40
Al A B4 D
Remarks
Refs. 120
Optimum value r? = 3.96cp
123 212 87 212 169
7^ = 0.91 cp
rj = 7.52cp Solvent: benzene 1.0 M, AIBN 0.05 M
Solvent: ethyl acetate Using results of Ref. 7 Solvent: ethyl acetate kp also given as a function of temp. and of viscosity for other solvents Solvent: methanol Solvent: pyridine Solvent: DMF Solvent: benzene 4.69 M Solvent: fluorobenzene 4.69 M Solvent: chlorobenzene 4.69 M Solvent: anisole 4.69 M Solvent: bromobenzene 4.69M Solvent: benzonitrile 4.69 M Solvent: methyl benzoate 4.69 M Solvent: methylphenyl acetate 4.69 M Solvent: dimethyl phthalate 4.69 M Solvent: dimethyl carbonate 4.69 M Solvent: diethyl oxalate 4.69 M Solvent: methyl formate 4.69 M Solvent: methyl propionate 4.69 M Solvent: diethyl succinate 4.69 M Solvent: acetonitrile 4.69 M Solvent: methanol 50% by vol. Solvent: n-octane 5% by vol. Solvent: «-nonane 20% by vol. DP = (2-8) x 10 3 using results of Ref. 86 DP = ( 3 - 5 ) x l 0 4 Assuming biradical initiation Jfcp found as a linear function of Mw Rate of initiation; 1.20 x 10 " 8 (moles/1/s) kp and kt also given as a function of viscosity for other solvents
219 212 193
153 51 62 72 92 94 94 94 85 85 85 85 85 85 90 90 90 90 90 90 90 90 90 104 104 104 96 96 11 65 91 29 60 30 93 14 87 58 65
References page 11-15
TABLE 4. cont'd Monomer
A:p (1/mol/s)
M x l O ~ 6 ) (1/mol/s)
Temp. (0C)
Method
0.224 573
2.0
45 60
D E
573
11.9
60
E
995 ± 83 506 ±48 450 ± 3 3 456±29 448 ±47 498 ± 39 614±43 427 ±38 290 1020 530 550
43.6 ± 4.9 35.6 ±3.9 42.0 ±3.0 43.8±2.0 47.2 ±6.6 42.9 ± 4.7 39.9±3.3 30.9 ±3.7 21 292 55 68
80 30
kp= 4.92 XlO 5 x exp(- U210/RT) 315
kt = 9S x exp(- 2930/RT) 33.9
15-30
A2
25
A2
336 ± 9 0 441 fcp = 2 . 5 x l 0 6 x exp[(- 23000 ± 2500)/RT] kp=k® (0.33 < Wp < 0.84) = ££exp[-29.8(Wp-0.84)] (0.84 < w p < 0.99)
28 ± 12 19.7 720
25 30 25-60
Al Al C
50
C
w p (weight fraction of polymer)
150
At high conversions ( ~ 65%) Special evaluation from steady-state and Mn Solvent: toluene
148 134
30 60
Al Al Al Al Al Al Al Al Al Al Al
Remarks
Refs.
Termination by combinat. using results of Refs. 7 and 31 Termination by disprop. using results of Refs. 7 and 31 Solvent: benzene 4.7 M Solvent: anisole 2.0M Solvent: benzene 2.0M Solvent: C 6 D 6 2.0M Solvent: fluorobenzene 2.0M Solvent: chlorobenzene 2.0 M Solvent: benzonitrile 2.0M Solvent: benzene 1.0 M Addition of 1 x 10 " 3 mol pyridine Addition of 1 x 10" 3 mol acetone Addition of 1 x 10 " 3 mol triethanolamine P n = IO4 kp and kt also given as a function of P n Pressure 5.0 x 106 Pa Pressure 5.0 x 10 7 Pa
67 33 33 111 133 133 133 133 133 133 133 118 118 118 118 114 110 127 105 45
(*J= 790 ±300) 130 705.6
20.7 ±1.0 25
0 60
Al
170 306 292
-
0.2 25 25
F3 Fl Fl
60 20-90
C Fl
30
B5
670 ± 3 0 22 InATp = 14.69-2670/7+ 0.201/7x(1.0x 1 0 " 5 P - I ) \nkt[p] = InA:t[l] -0.57/7 26.6
1.4
5
BlO
5.8
0.017
5
BlO
kt(m,n) = 1.22 x W2(n x m)~ 0075
25
A3
21
70
B5
0.034
50
D
0.16
50
D
- 1 to - 70 60
Fl C
- 8 30
F3 Fl
fcp = 106 694 exp(- 23940/RT) lnJfcp (VmoVmin) = ln*p,<>-(3.86 [AIBME]0 + 0.8) x (l-(f>m)- 1.6 (l-cj)m)60
131 680- 820
-
690-810
-
Fl
222 196
Solvent: ethanol (50%) 4.67 M, kv also given by other [M] and solvents 175 207 kt\p\\ kt for pressure/? (bar), fct[l] = 15.4x 106 Scavenger DPPH, solvent: DMF, blank polymn. Scavenger DPPH, solvent: DMF, template polymn., template; it-MMA n: n-mer; m: m-mer, coupling with rt-mer and m-mer 77 = 0.53 cP No addition of chain-transfer agent, Time 7.5-20.5 min. Addition of 2% CBr4, Time 7.5-20.5 min. AIBME (dimethyl 2,2'azodiisobutyrate) 0.0434M, m; monomer volume fraction £pX) = 700(l/mol/min) Benzoin 7 x 10 " 4 M Solvent: toluene, pressure 1.0 x 108 Pa, k p also given by other pressures Solvent/2-butanone, pressure 1.OxIO 8 Pa
122 115 115
147 212 149 149 217 158
199 208
208
TABLE 4. cont'd Monomer
kp (1/mol/s)
M x l O " 6 ) (1/mol/s)
Temp. (0C)
Method
313±8.1 794.0 815.0 957.0
39±4 62.4 51.6 38.2 25(±3)
25 60
Fl B5
60
C
21 ± 2 45 50
60 25 40
C Al
191 160 160
-
25 50
Fl Fl C
198 220 184
510 ±100 299 431 )tp = 2.39 x 106 x exp(- 22000/#D 359 12
135 292 200 135 ± 5 0 170
-, octyl ester
35 2960 *p = 1.9068 x 106 xexp(-21181.07//?D kp = 1.2169 x 106 x exp(- 25203.59//?D kp = 3.0598 x 107 x exp(-28008.18/RT) 35 1710 240 ± 8 0
0 25 28 0 50
29.1
50 30
Al Fl Bl Al C
Values from Chem. Abstr.
159 164 83 165 155
30% MMA in benzyl alcohol
227
Fl
30% MMA in NMP
227
p.s. 500 nm Pressure 5.0 x 10 7 Pa
155 113 109 122
30 30 30 60
Al Al Al Al Al Al Al Al Al Al C
26 1470 ±170
0.301 0.499 ±0.058
32.5 30
C A4
2760 ±342
0.452 ±0.056
30
185
0.034
20
B8
230
0.053
20
B8
kp (1/mol/s)
£ t ( x l 0 ~ 6 ) (1/mol/s)
Temp. (0C)
Method
1.7 3.9
2.5 x 10" 3 3.4xl0~3
60 60
C C
Polyhydroxytetramethylene-a, co-methacrylate of MW = 700
particle size 260 nm, kp also given by other particle sizes kp; average value
Fl
411 230 ± 1 5 176±8 180±9 223 ±11 235 ± 8 273 ± 8 228 149 467 590
30 30
Emulsion polymn.,
161 204 204 204 166
A3 Fl
50 30 30
Solvent: benzene 3 M Solvent: chlorobenzene 3 M Solvent: benzonitrile 3 M
Refs.
Emulsion polymn., n-butyl aery late: MMA: methacrylic acid (8:91:1), particle size (p.s.) 50 nm, kp also given by other temp, and particle sizes p.s. 500 nm 155 225 227
62.6 2.6 ±0.9 ln[(fct[p]/(1.00- 0.19)] = \nkt[l]-l.01p 11.9 2.02 ±0.22 2.06±0.21 2.16±0.19 2.26 ± 0.22 1.72 ±0.11 1.96 ±0.12 1.88 0.813 45.1 2.6
-, phenyl ester
- , 2-phenylethyl ester - , 3-phenylpropyl ester - , rc-propyl ester - , 3-tetracyclo-[4.4.02'5.l7'10]dodecyl ester -, triphenylmethyl ester 3-Dimethyl-(methacryloyloxy-ethyl) ammonium propane sulfonate
25.6 -
Remarks
Al Al B5
kt[p]\ kt for pressure p (bar), ikt[l] =40.0 x 106 Solvent: Solvent: Solvent: Solvent: Solvent: Solvent:
anisole 2.00M benzene 2.00M fluorobenzene 2.00M chlorobenzene 2.00M bromobenzene 2.00M benzonitrile 2.00M
Solvent: benzene 1.0M, AIBN 0.05 M
87 116 116 116 116 116 116 87 87 28 193
153 Solvent: formamide: 192 1,4-dioxane (3 :1 (v/v)) Solvent: formamide: 192 1,4-dioxane (3 : 1 (v/v)), NaCl 0.1 M Calcd. from nonstationary 125 state kinetics Calcd. from stationary state kinetics 125
TABLE 5. ITACONIC DERIVATIVES Monomer Itaconic acid - , bis (4-terf-butyl-cyclohexyl) ester - , bis (cyclohexyl-methyl) ester
Remarks
Solvent: benzene 0.5M Solvent: benzene 1.5M, MAIB 0.02 M
Refs.
213 182
References page 11-15
TABLE 5. cont'd kp (1/mol/s)
M x l O " 6 ) (1/mol/s)
Temp. (0C)
Method
- , bis (3,5-dimethyl-l-adamantyl) ester - , bis (2-ethylhexyl) ester
0.92 6.8 3.4 2.0 2.1 2.2 2.1 2.1 1.4 3.0
0.32 x 10~3 0.001
60 50 50 50 50 50 50 50 50 50
C C C C C C C C C C
- , diadamantyl ester
0.56
0.30 x 10~3
60
C
- , di-n-butyl ester
3.5
1.59 x l O " 2
60
C
13
0.11
50
C
11 6.8 9.4 6.7 3.4 3.2
0.13 0.07 0.11 0.083 0.068 0.13 1.0 x l O " 3
50 50 50 50 50 50 50
C
5.3
8.5 x l O " 2
50
C
5.9
0.053
50
C
- , di-sec-butyl ester
0.6
4.0 x 10 ~3
60
C
- , di-terf-butyl ester
0.2
5.6 x 10~3
60
C
- , dicyclohexyl ester
2.3
1.4xlO" 3
60
C
- , diethyl ester
7.7
0.24
50
C
3.7
6.41 x l 0 ~ 2
60
C
- , diisobutyl ester
2.7
1.56 x 10~2
60
C
- , diisopropyl ester
1.1
5.0xl0~~ 3
60
C
- , dimethyl ester
5.2
0.36
60
C
10
0.59
50
C
- , a-ethyl-P-hexarluoropropyl ester
5.0
0.28
60
C
- , a-methyl-P-isopropyl ester - , a-methyl-P-tert-butyl ester - , a-isopropyl-P-methyl ester - , a-fm-butyl-P-methyl ester AT(2,6-dimethylphenyl)itaconimide
3.4 4.2 1.9 0.91 26
0.06 0.051 0.07 0.056 0.082
60 60 60 60 50
C C C C C
15
0.29
60
C
Monomer
Methyl N-phenyl-itaconamate
Remarks Solvent: benzene 1.5 M Solvent: hexane 1.03 M Solvent: cyclohexane 1.03 M Solvent: toluene 1.03 M Solvent: benzene 1.03 M Solvent: chlorobenzene 1.03 M Solvent: ethyl acetate 1.03 M Solvent: THF 1.03 M Solvent: acetone 1.03 M Solvent: benzene 2.0M, MAIB 0.05 M Solvent: benzene 1.5 M, kp and kt also given by other [M] Solvent: benzene 1.5M, MAIB 0.02 M Solvent: cyclohexane 1.33 M, MAIB 5.00 x 10~2 M, kp and kt also given by other temp. Solvent: n-hexane 1.33 M Solvent: chlorobenzene 1.33 M Solvent: methyl benzoate 1.33 M Solvent: benzene 1.33 M Solvent: acetone 1.33 M Solvent: acetonitrile 1.33 M Solvent: benzene 0.794M, AIBN 0.05 M kt also given by other [M] Solvent: benzene 0.794M, MAIB 0.05 M Solvent: benzene 2.0M, MAIB 0.05 M Solvent: benzene 1.5 M, MAIB 0.02 M Solvent: benzene 1.5M, MAIB 0.02 M Solvent: benzene 1.5 M, MAIB 0.02 M Solvent: benzene 2.0M, MAIB 0.05 M Solvent: benzene 1.5M, MAIB 0.02 M Solvent: benzene 1.5M, MAIB 0.02 M Solvent: benzene 1.5M, MAIB 0.02 M Solvent: benzene 1.5 M, MAIB 0.02 M Solvent: benzene 2.0M, MAIB 0.05 M Solvent: benzene 2.0M, MAIB 0.05 M, kp and kt also given by other [M] and temp.
Solvent: THF 0.44 M, AIBN 0.05 M, J^p andfct also given by other [M] Solvent: DMF 1.4 M, AIBN 0.05 M, jfcp andfct also given by other [M] and temp.
Refs. 213 185 185 185 185 185 185 185 185 177 213 182 162
162 162 162 162 162 162 154
154 177 182 182 182 177 182 182 182 195 177 233
195 195 195 195 234
235
TABLE 6. FUMARIC DERIVATIVES Monomer Fumaric acid - , bis (2-methoxy-ethyl) ester - , bis (2-chloro-ethyl) ester - , tert-butyl methyl ester - , tert-buty\ isopropyl ester
- , di-terf-butyl ester - , dicyclohexyl ester - , diethyl ester
- , diisopropyl ester
- , dimethyl ester - , dineopentyl ester Ethyl o-formylphenyl fumarate
TABLE 7.
M x l O " 6 ) (1/mol/s)
Temp. (0C)
Method
0.19 0.26 0.23 0.51 0.35 0.39 0.61 0.60 0.21 0.015
330 x 10~6 320 x 10~6 150xl0~6 26xlO"6
60 60 60 60 60
C C C C C
1.75 x l O - 5 30 x 10~6 40 x 10~6 (510-560) x 10" 6 1.64 x l O - 4
60 60 60 30
C C C Al
0.029 ±0.003
8 xlO-6
30
BlO
0.46 0.31 ±0.07
(80-100) x 10~6 0.84 x l O - 6
60 30
C BlO
0.058 0.028 4.0
430 x 10~6 44xlO~6 1.4
60 60 60
C C C
k p (1/mol/s)
M x I O " 6 ) (1/mol/s)
Temp. (0C)
Method
7400
7.4xlO"5
40
22.7 570 kp = 3.3 x 106 x exp(- 15000/RT) 11000 3130 8.6 kp = 10 9 x exp(- 4540/7)
92 385 kt = 1.3 x 106 x exp(- 4200/RT) 2100 2300 0.175 kt = 106 x exp(- 2670/7)
-30 20
kp (1/mol/s) 4600 795 556-586 670-770 700 559 1100 1000 895 kp = 2.43 x l O 8 x exp(- 30600/RT) 9500-19000 (15-26) x 102
Remarks
Solvent: benzene l.OM Solvent: benzene l.OM Solvent: benzene l.OM Solvent: benzene l.OM AIBN MAIB Solvent: benzene l.OM Solvent: benzene l.OM Solvent: benzene l.OM AVN (2,2'-azobis-2,4dimethylvaleronitrile), ACN (l.l'-azobiscyclo-hexane1 -carbonitrile) ACN, scavenger TPV (1,3,5-triphenylverdazyl), sovent: benzene Solvent: benzene l.OM ACN, scavenger TPV, solvent: benzene Solvent: benzene l.OM Solvent: benzene l.OM Solvent: benzene 1.16 M, MAIB 0.100 M, kp and ^ t also given by other [M]
Refs.
211 211 211 211 181 181 211 211 211 173
179
211 180 211 211 236
VINYL HALIDES
Monomer Tetrafluoroethylene
Vinyl bromide Vinyl chloride
Vinylidene chloride
TABLE 8.
kp (1/mol/s)
Remarks Large active chain end concentration measured by addition of inhibitor in aqueous solution polymn.
Al
Refs. 81
Al
80 44 32
25 25 25 22-75
Al Al Al Al
56 77 18 117
M x I O " 6 ) (1/mol/s)
Temp. (0C)
Method
220 46 2860-3040 2500-3100 2600 51.8 80 59 24 kt =4.16 x 105 x exp(- 21900/RT) 380-760 25
25 15 15.9 15.9 15.9 20 25 25 25
B5 Bl Al Al Al B4 Al Al B4 Al
60 50
E Al
Quoted in Ref. 80
Solvent: N-methylpyrrolidone 2.0M
VINYL ESTERS
Monomer Vinyl acetate
Remarks
Solvent: «-hexane
At 4% conversion
Using results of Refs. 8 and 15
Refs. 13 47 1 3 4 37 2 15 36 8 64 128
References page 11-15
TABLE 8. cont'd Monomer
Vinyl benzoate
TABLE 9.
kv (1/mol/s)
£ t (xIO~ 6 ) (1/mol/s)
Temp. (0C)
Method
Remarks
117zb 12 113±10 48 ± 5 97 ± 10 61 ± 9 37 ± 5 8± 1 637 ± 101 78 #
319±61 351±54 239 ± 4 5 311 d= 59 266 ± 7 5 412 ± 104 258 ± 76 94.2 ± 23.7 -
30
Al Al Al Al Al Al Al Al
32.5 32.5 32.5 32.5 30 15-60
Al C C C Al C
Solvent: benzene 2.00M Solvent: C 6 D 6 2.00M Solvent: anisole 2.00M Solvent: fluorobenzene 2.00M Solvent: chlorobenzene 2.00M Solvent: ethyl benzoate 2.00M Solvent: benzonitrile 2.00M Solvent: ethyl acetate 2.00M Solvent: ethyl acetate: ethyl benzoate (1:1 (v/v)) Solvent: benzene Solvent: benzene 5.41 M Solvent: ethyl acetate 5.43 M
120 310 530 630 1900 280 1400 4435 64.4 £ p = 2.0 XlO 6 27.5 x exp[(- 19000 ± 2900)/RT] Jcp = 2 . 1 x l O 8 x exp(- 27820//?7) ln[(*t|>]/(1.00-0.07/?)] = lnJfct[l]-0.50p 106 ± 1 4 253 ± 6 3 185 ± 8 402 ± 3 2 245 ± 13 522 ± 48 168 ± 18 383 ± 76 69 ± 13 257 ± 72 33 ± 3 299 ± 4 4 267±33 451 ± 6 5
Monovinyl ether of ethylene glycol Monovinyl ether of diethylene glycol
Monomer Styrene
Pressure 5.0 x 10 7 Pa
Fl 30
B5
30
Al Al Al Al Al Al Al
130 130 130 130 130 130 130 130 130 153 153 153 153 112 45 209
kt\p]; kt for pressure p (bar) £ t [l] = 52.0x 106 Solvent: anisole 1.01 M Solvent: benzene 1.01 M Solvent: fluorobenzene 1.01 M Solvent: chlorobenzene 1.01 M Solvent: ethyl benzoate 1.01 M Solvent: benzonitrile 1.01 M Solvent: ethyl acetate 1.01 M
122 116 116 116 116 116 116 116
VINYL ETHERS
Monomer
TABLE 10.
Refs.
k p (1/mol/s)
kt (x 10 6 ) (1/mol/s)
5.0 ±1.0 3.0 ± 0.8
1.5 ±0.3 1.4 ± 0.3
Temp. ( C )
Method
50 50
Al Al
Refs. 136 136
STYRENE DERIVATIVES k p (1/mol/s)
kt (x 10 ~6) (1/mol/s)
Temp. (0C)
Method
40 ± 20 24
80 ± 40 14
15 20
Al Al
51.9 108 106 102 390 209 18.7 39.5 £p = 2 . 1 6 x l 0 7 x exp(- 32500/RT) 22
10.5 32.5 108 -
30 30 30 40 50 50 25 25
Al Al Al D D E B5 Bl Al
5
D
40 50 50
D D D
139 223 206
115 2.79 5.96 2£t = 2 . 5 9 x l 0 3 x exp(- 9920/RT) -
Remarks Dimension of kp and kt: kg/mol/s From copolymn. data with sulfur dioxide
Quoted in Ref. 86 Using results of Ref. 20
Catalyst: cumene hydroperoxidetriethylenetetramine Catalyst: persulfate
Refs. 46 25 16 38 78 59 5 61 6 17 20 24 24 40 67
TABLE 10. cont'd Monomer
kp (1/mol/s)
M x l O " 6 ) (l/mol/s)
Temp. (0C)
* p = 2.24 XlO 14 xexp(-73510//?r) 50 80 64 370 915 25 ± 3 9 ± 1.5 35 ± 7 19 ± 4 35 ± 5 19 ± 3 29 ± 7 15 ± 4 23±8 11 ± 2 27 ± 4 31 ± 0.4 *p = 1.09 XlO 7 * t = 1.703 x l O 3 x exp(- 31380/K7) x exp(- 9489/RT) 66.6 22.4 66.5 £ p = 2.4 XlO 8 x exp(- 38000 ± 11OO)/RT 187.1 29.4
84
-,p-bromo-,/?-chloro-,/7-cyano-,p-fluoro-,/7-methoxy-
25 60
D Al
25 25 25 25 25 25 15-30
Al Al Al Al Al Al A2
65 118 Addition of 1 x 10 " 3 mol pyridine 118 Solvent: dodecane 40% by vol 104 100 Solvent: bromobenzene 20% by vol 100 Solvent: diethyl malonate 20% by vol 100 Solvent: diethyl phthalate 20% by vol 100 Solvent: dinonyl phthalate 60% by vol 100 DP = 2500 114
30 25 50-90
Al C
60 F2 Fl
25 25 40 70
Fl Fl Fl C
16.6-17.0
100
C
190 -
50 25
C Gl
kt (m,/i) = 1.97 x 102 (n x m) " ° 1 2
30
A3
5 30-90
C Fl F2
25 25 60
Fl Fl B5
91.2 25 30 25 25 28
Gl Al Fl Fl Fl Bl Fl
180 ± 1 0 £ p = 1.99xl0 7 exp(-30780//?D In kp = 17.14-1.873 x 10" 9 p - 3748/r + 2.02 x 10 " 6 p/T 77 ±4.1 79 ±5.1 187.0 201.0 167.0 641 ±48 89 107 92 78 23 In kp = 16.09-28950//?r (overall) = 16.47-3003/KT (chain length > 4) * p = 107-1±0-5 xexp[-(29±3)xlO3/*r] fcp = 1.8861 x 107 x exp(- 30737.52//?r) kp = 4.2060 x l O 8 x exp(- 37468.93/RT) kp = 4.2458 x 108 xexp(-39014.90//?7) 186 150 219 112 2.92 71
-
78 ± 1 2 96 ± 9 63.2 51.1 37.9 132 0.6
46 77 35 127 1.06 33
Refs. 73
-
256 107
Remarks
Bl
kp = 107-630 x exp(- 32510/RT) - 1 2 - 93 25
76 70 380 ±110 480 ± 1 0
Method
30 30 30 30 0 30
Pressure 5.0 x 10 7 Pa
102 98 98
Special evaluation from steady-state kinetics and Mn
134
215 kp also given by other [M] and 196 solvents Solvent/ethanol(25%)6.52M 196 Solvent: methanol (25%) 6.52 M 196 Pressure 2.0 x 108 Pa 186 Over a range of degree of polymn. 188 of the polymer radical from 40 to 410 Conversion 0-20% 174 TBP (terf-butyl peroxide) kp and kt also given by other temp. 189 Laser-flash-initiated polymn. by 156 benzoin n: n-mer, m: m-mer, 147 coupling with n-mer and m-mer 223 169 Pressure 1 x 10 5 -2.8 x 108 Pa 214
Solvent: Solvent: Solvent: Solvent: Solvent:
toluene 50% (v/v) benzene 3 M chlorobenzene 3 M benzonitrile 3 M toluene
kp also given by other temp.
Solvent: benzene 4.33 M
161 161 204 204 204 178 160 198 220 164 83 200
Bl
131
Fl
227
Fl
30% styrene in benzylalcohol
227
Fl
30% styrene in NMP
227
Al Al Al Al B5 Al
Solvent: dimethylacetamide
78 78 78 78 12 78
References page 11-15
TABLE 10. cont'd Monomer
kv (l/mol/s) kp = 1.67 x 1 0 n x exp(- 58240/RT) 84 kp = 2.27 XlO 7 x exp(- 32060/RT) kp = 10 5 7 7 x exp(- 23.0/RT) &p = 3 . 6 3 x l 0 7 x exp(- 31500/RT)
- , o-methyl- , p-methyl-
Styrene-d8
TABLE 11.
A: t (xl0~ 6 ) (l/mol/s)
66
Temp. (0C)
Method Bl
73
30
Al Bl
78 73
24-55
Fl
£t = 2 . 5 5 x l 0 4 x exp(- 14200/7?7)
Solvent: toluene 2M
Al
kp (l/mol/s)
Ict (x 10~ 6 ) (l/mol/s)
Temp. (0C)
Method
6.0 186 96.6 12 47 122
0.306 33 8.9 3 3.5 66
10 25 25 25 25 20
Al Al B4 B5 B4 Bl
209 17.3 953 22000 ± 4000
43 1.2 65 600 db 200
20 20 20 25
Bl Bl B4 Al
k p (l/mol/s)
M x 10 ~6) (l/mol/s)
Temp. (0C)
Method
-
(7-10) x 10 ~3
—190
B4
kp (l/mol/s)
kt(x 10~ 6 ) (l/mol/s)
Temp. (0C)
Method
Maleimide - , N-tert-amyl- , N-tert-butyl-
69 100
0.048a,0.017b 0.021 a ,0.023 b
60 60
C C
-, -, -, -,
120 23 120 49
0.20a 0.027 a ,0.015 b 0.15 a ,0.23 b 0.054
60 60 60 50
C C C C
55
0.069
W-Vinylcarbazole 2-Vinylpyridine 4-Vinylpyridine 5-Vinylpyridine - , 2-methyl-
Af-Vinylpyrrolidone
226 168
Remarks
Refs. 80 76 76 34 75 94
Solvent: methanol 1.95 M, kp also given as a function of [M] Solvent: 50% (molar) aqueous methanol 94 Solvent: acetic acid 94 82 Solvent: water 132
ALDEHYDES
Monomer Formaldehyde
TABLE 13.
Refs.
VINYLHETEROAROMATICS
Monomer
TABLE 12.
Remarks
Remarks Solid monomer, gamma irradiation
Refs. 95
OTHERS
Monomer
A^m-butyl-dimethylsilylN-tert-octylN-trimethylsilylN-cyclohexyl-
Remarks
Solvent: benzene 1M (a) Determined from steady-state equation kt = (2kdf[l])/[P']2, AIBN 0.005 M; (b) determined from second order plot of the decay curve of the radical concentration, ATMP (2,2 '-azobis-(2,4,4-trimethylpentane)) 0.02 M, for tert-BMl, ATMP 0.01 M
Solvent: benzene 0.559 M, AIBN 1.39 x 10" 2 M Solvent: benzene 0.698 M, AIBN 1.00 x 10~2 M, kp and kt also given by other [M] and [I]
Refs.
205 205
205 205 205 163 163
TABLE 13. cont'd A: p (1/mol/s)
Jt t (xl0" 6 ) (1/mol/s)
Temp. (0C)
- , AH2,6-diethylphenyl-
2.0
0.0078
60
C
- , Af-(2,6-dimethylphenyl)-
14
0.034
60
C
- , AH4-ethylphenyl)-
1200
3.9
60
C
- , #-(2-methylphenyl)-
190
0.59
60
C
- , Af-(2-carboethoxyphenyl)- , N-dodecyl-
96 54 104 175 80 128 149
0.10 0.12 0.45 1.0 0.40 0.064 0.17
60 50 50 50 50 50 50
C C C C C C C
386 250 235 196
0.55 -
50 50 50 50
C C C C
33
0.10
50
C
400
0.07
50
B9
Monomer
- , iV-octadecylOligotetramethylene glycol dimethacrylic ester (MW 600)
Method
Remarks Solvent: benzene 1M, AIBN 5 x 10- 3 M Solvent: benzene 1M, AIBN 5 x 10- 3 M Solvent: benzene 1M, AIBN 5 x 10- 3 M Solvent: benzene 1M, AIBN 5 x 10- 3 M Solvent: benzene MAIB 0.005 M Solvent: benzene MAIB 0.01 M Solvent: toluene MAIB 0.01 M Solvent: anisole MAIB 0.01 M Solvent: chlorobenzene MAIB 0.01 M Solvent: bromobenzene MAIB 0.01 M Solvent: methyl benzoate MAIB 0.01 M Solvent: THF, MAIB 0.01 M Solvent: dioxane, MAIB 0.01 M Solvent: ethyl acetate MAIB 0.01 M Solvent: methyl ethyl ketone MAIB 0.01 M Solvent: benzene AIBN 0.20M, kp and k[ also given by other [I]
Refs. 183 183 183 183 237 238 238 238 238 238 238 238 238 238 238 239 124
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T r a n s f e r
C o n s t a n t s
P o l y m e r s ,
C a t a l y s t s
S o l v e n t s S u l f u r
a n d
t o a n d
I n i t i a t o r s ,
A d d i t i v e s ,
C o m p o u n d s
R a d i c a l
M o n o m e r s ,
i n
a n d F r e e
P o l y m e r i z a t i o n
A. Ueda Osaka Municipal Technical Research Institute, Osaka, Japan S. Nagai Plastics Technical Association, Osaka, Japan
A. Introduction B. Tables Table 1. Transfer Constants Table 2. Transfer Constants Table 3. Transfer Constants Initiators Table 4. Transfer Constants Additives Table 5. Transfer Constants Compounds C. Remarks D. References A.
to Monomers to Polymers to Catalysts and
11-97 11-98 II-98 11-103 11-106
to Solvents and 11-110 to Sulfur 11-150 11-157 11-159
INTRODUCTION
The transfer reaction in radical polymerization describes a process in which the polymer radical reacts with another molecule (monomer, polymer, catalyst, solvent, modifier, etc.) forming a dead polymer and new radical. This new radical can continue the kinetic chain:
If it is assumed that (a) all new radicals X# react only by formation of growing polymer radicals; (b) all polymer radicals have equal reactivities independent of their size; (c) all rate constants are independent of solvent; (d) the consumption of monomer by initiation and transfer is negligible compared with propagation; (e) a steady-state concentration of polymer radicals is quickly established (d[P#]/dr = 0). The application of these assumptions to the common reaction scheme results in the following relationship of ideal kinetics (Ref. 145):
P n , p n 0 = number-average degree of polymerization obtained in the presence or absence, respectively, of transfer agent X. [M], [X] = concentration of monomer or transfer agent, respectively.
The dimensionless transfer constant is defined by the ratio
where kv is the rate constant of propagation. Based on the tables in the third edition, by K. C. Berger and G. Brandrup.
The left-hand side of this equation is obtained by measuring the number average molecular weight of polymer at different concentrations of the transfer agent X, all other variables being kept constant. In many cases the degree of polymerization was determined by measurement of viscosity (Remark R). It should be noted that the ratio of
viscosimetric to number average molecular weight shows a considerable dependence on the molecular weight distribution. The first term P n 0 of the right-hand side of this equation is the number average molecular weight measured in the absence of transfer agent X. This is limited to cases where the transfer agent is a modifier. In all other cases, Pno is calculated by combination of several kinetic expressions and used with its numerical value:
This decrease of the transfer agent concentration with increasing monomer conversion is important in practice because very reactive transfer agents are used up preferentially, giving a broad molecular weight distribution if they cannot be replenished. In analogy to quickly decomposing initiators with their criterion of "half-life", one can define, in addition to the transfer constant Cx, a "half-conversion" U\/2 as that monomer conversion where the transfer agent is half consumed:
Initiation Termination Propagation Number-average molecular weight where ku fct,d, and k^c are the rate constants of termination, termination by disproportionation, and termination by combination, respectively.
The second term of the right-hand side of the above equation is given by the following expression:
where Cp is the constant of chain transfer with added polymer before starting polymerization. The transfer constant of very reactive molecules can be determined from the rate of disappearance of both transfer agent and monomer:
The following table demonstrates (with some examples for a calibration curve) that the "half-conversion" IZ1^2 decreases with increasing transfer constant Cx: The "Half-Conversion" of Transfer Agents Cx
U1/2(%)
Cx
Ul/2(%)
0.1 0.2 0.5 1 2
99.9 96.8 75.0 50.0 29.3
5 10 20 50 100
13.0 6.7 3.4 1.4 0.7
The transfer agent must be replenished at this monomer conversion at the latest, if polymerization is to proceed, still yielding a narrow molecular weight distribution. Numerous examples are known of polymerization systems that possibly do not satisfy basic assumptions: retardation (Remark J), induced decomposition and primary radical termination by peroxide or hydroperoxide initiation (Remarks C and B), diffusion control of termination (Remark X), electron donor/acceptor complexes (Remarks JJ), etc. Corresponding data in this table have to be used with caution.
B. TABLES OF TRANSFER CONSTANTS TABLE 1. TRANSFER CONSTANTS TO MONOMERS Monomer
T( 0 C)
Acetic acid, allyl ester
80
Acrylamide
25
Acrylamide, AT,iV-dimethylAcrylic acid, benzyl ester
50 60 60 50 55 60 60 60
- , butyl ester
C M (xlO 4 ) 170 700 0.12 0.16 0.2 0.2 0.558 0.651 0.6 1.5 0.883 0.905 0.333 1.05
Remarks
D E C2, F13, LL C2, F13, LL E
Cl, H, KK Cl, H, KK
Refs. 29 27 92 74 75 103 560 560 103 272 291 291 561 561
TABLE 1. cont'd Monomer Acetic acid, butyl ester (cont'd) -,ethyl ester
T( 0 C) 60 65 50 60 65 70
- , - 2 ethylhexyl ester - , methyl ester
70 80 50 55 60 65
70
75 -, tetrahydrofurfuryl ester -, 2-chloro-, ethyl ester - , thio-, methyl ester Acrylonitrile
40 60 60 20 25 30 40 50 60
Allyl bromide Ammonium chloride, A^-diallyl-MJV-diethyl- , Ar,Ar-diallyl-AW-dimethylAnisole, p-\iny\ Anthranilic acid, vinyl ester Benzoic acid, vinyl ester
1,3-Butadiene, 2-chloro- , 1,1,2-trichloro1-Butene 2-Butene, cis- , trans3-Butene-2-one, 3-methyl-
60 60 60 60 60 60 0 60 70 60 80 95 50 25 40 50 60 40 50 60 40 50 60 80
C M (xlO 4 )
Remarks
1.25 0.955 0.193 0.90 0.41 0.579 0.332 0.351 0.789 6.28 3.79 0.80 0.275 0.036 0.325 0.10 0.11 0.11 0.37 0.01 0.072 0.16 0.18 0.405 0.224 0.25 0.25 4.0 3.0 560 0.18 0.105 1.5 0.17 0.050 0.27 8.2 0.26 0.3 0.333 0.57 1.02 30 18 7 0.198 0.74 80 6.0 7.0 2.0 4.0 2.32 16 3.1 5.1 7.3 3.2 4.9 11.2 3.0 5.2 10.8 4.00
Cl, H, KK
F7 C, F17, R C, F17, R C, F17, R C, F17, R C, F17, R F7 C,AA B, AA C, AA C,AA CFlO CAA C, AA CFlO B, AA CAA C AA C, AA CAA C, FlO C AA C, F2 E F8 F18 F17 F16 Cl, H, KK Cl, H, KK Cl, H, KK C, R, HH Cl, F30 Cl, F30
F2 E
C
Refs. 561 291 306 510 512 512 306 306 512 512 512 510 221 221 221 221 123 221 221 322 221 221 221 221 221 123 221 319 342 140 299 284 196 284 410 376 362 95 23 561 561 561 505 538 538 13 53 139 321,393 26 321 213 153 230 334 334 334 334 334 334 334 334 334 84
Remarks page 11-157; References page 11-159
TABLE 1. cont '6 Monomer Butyric acid, vinyl ester Carbamic acid, vinyl-, ethyl ester Carbazole, A^-vinyl-7H-benzo(2)Decanoic acid, vinyl ester Ethylene
T( 0 C) 50 80 60 70 50 60
70
26.7 22.3 0.25 11 45.5 0.4 1.4 4.2 5.0 5.32 1.1 3.5 9.0 0.0 1.6 4.7 11.2 5 3.2 3.2 7.0 6.25 19.4 50 6.4 7.8 8.5 11 13.5 10.8 12.3 12.8 23.8
60
42
83 110
130
- , chloro-
50-70 20 25 30 40 50
60
Glutaramic acid, MA^-diisobutyl-, vinyl ester - , AW-diisopentyl-, vinyl ester
Hexanoic acid, vinyl ester 5-Hexen-3-yn-2-ol, 2-methylIsobutyric acid, vinyl ester Laurie acid, vinyl ester Maleic anyhydride Maleic anhydride/methyl methacrylate Maleimide, A^-(3-dimethylamino-6-methyl-phenyl) Methacrylamide Methacrylic acid, bornyl ester - , butyl ester
-, -, -, -, -, -,
tert-butyl ester o-r-butylphenyl ester /?-?-butylphenyl ester n-dodecyl ester 2,3-epoxypropyl ester ethyl ester
-, -, -, -, -,
0-ethylphenyl ester p-ethylphenyl ester glycidyl ester hexadecyl ester isobornyl ester
C M (xlO 4 )
60 70 80 80 60 80 50 75 60 50 60 60 50 60 70 60 60 60 60 45 60 80 90 60 60 60 70 60
51 51 51 36 5.0 46 45.5 750 100 720 10 x 105 2.85 0.54 120 x 105 0.14 0.35 30.41 2.01 80xl05 0.59 0.248 0.259 0.456 0.442 3.63 1.36 45 x 105 0.14 1.85
Remarks
Refs.
F4 Y
71 200 117 522 71 102 102 102 204 205 102 102 102 259 102 102 102 218 94 315 425 58 463 246 379 379 379 392 58 379 379 379 58
C, FlO
106
C, FlO C, FlO CFlO
107 107 107 200 226 200 71 175 367 542 515 162 233 515 264 9 550 550 515 198 193 193 193 193 550 550 515 138 162
R, F2 W5 W4, W5 W4 D, W D, W W4, W5 W4, W5 W4 C, F21,W5 W4, W5 W4, W5 W4 W3
Y F5 F3 F4 C, F26 Y F3
C F2 JJl
JJl
C C JJl CC CC CC CC C C JJl
TABLE 1. cont'd Monomer Methacrylic acid, isobutyl ester
- , n-nonyl ester - , phenyl ester - , o-tolyl ester - , p-tolyl ester Methacrylonitrile
Methyl methacrylate
J( 0 C) 35 50 60 80 100 60 27 60 60 60 25 60 70 80 0 30
40 50
60
65 70
75
80
Naphthalene, 1-vinyl1,4-Pentadiene, 1,1,2,3,3,4,5,5-octafluoroPhernol, o-vinyl2-Picoline, 5-vinyl1-Propene, 2-chloro-, 2-methylPropionic acid, vinyl ester
90 100 120 50 60 70 110 70 70 80 40 50 60 50
C M (xlO 4 ) 0.189 0.179 0.14 0.165 0.224 0.301 0.382 105 x 105 400 0.61 1.13 1.06 2.08 5.81 8.00 10.05 0.128 0.148 0.117 0.260 0.15 30 x 105 242 x 105 0.10 0.15 0.477 241 x 105 0.85 0.07 0.10 0.103 0.18 240 x 105 0.20 0.17 0.20 0.23 0.265 0.29 0.30 0.45 0.807 1.37 240 x 105 0.27 0.33 0.60 0.70 0.25 0.40 0.10 0.38 0.58 290 310 300 500 130 6.7 1600 2.5 4.4 6.9 3.6 48.9
Remarks DD DD F2 DD DD DD JJl R C C C Z Z Z Z
D JJ2 JJl F2 D JJl
C JJO CFlO
C, F17 D JJl CFlO C CFIl C, F2
WlO
Refs. 193 193 264 264 193 193 193 515 534 550 550 550 125 125 125 125 69 18 69 224 508 525 528 147,327 145 224 528 69 274 34,290,317 316 145 556 123 123 267 145 440 123 123 104 224 459 528 123 123 123 123 145 123 147 145 145 216 216 216 68 186 11 27 334 334 334 158 71
Remarks page II-157; References page II-159
TABLE 1. cont'd Monomer Pyridine, 2-vinyl- , 4-vinyl2-Pyrrolidinone, 1-vinylStearic acid, vinyl ester Styrene
T( 0 C) 15-35 25 20 50 O 25 27 30 45 50
60
67.8 70
75
80 80.3 90
99 100
110 117 132
Styrene, p-boromo-, o-chloro-
50 30 50
C M (xlO 4 ) O 6.7 4.0 69.8 O
Remarks D
BB 0.108 0.279 0.358 0.31 0.2 0.32 0.3 0.35 0.40 0.50 0.6 0.62 0.65 0.78 0.07 0.6 0.6 0.6 0.75 0.79 0.85 0.92 1.1 1.37 20 x 10 5 1.0 O 0.6 0.6 0.8 0.96 1.16 1.35 2.0 O 1.6 5.0 5.00 0.7 0.75 1.00 4.0 0.85 1.25 1.47 1.79 1.5 1.72 1.8 1.83 2.80 1.40 2.45 3.0 3.4 5.33 23 0.25 0.25 0.28
A BB BB H F2 C, H C A, K B, C, H A C C BB A A, F
C JJl CFlO BB B, H A A C, F2 C,F10 C C, F2 CFIl BB BB CF A A A A, F A A A A, F A A
C C, H
Refs. 38 283 59 71 360 17,69 69,245 17 145 318,360 245 360 354,355 318,327 388 145 145 388 146 467 34,171,223 145,240 318,360 467 145 145 447 53 234 515 34 123 104 360 388 67 145 145 123 123 123 123 123 98 360 318 34 360 145 145 145 98 145 145 145 145 318 145 145 145 145 192 62 60 60
TABLE 1. cont'd Monomer Styrene, p-iodoSuccinimide, JV-vinylValeric acid, 4-methyl-, vinyl ester Vinyl acetate
T( 0 C) 50 55 80 -60 -40 -20 -20 O 20 25
40 45 50
60
65 70 Vinylidene chloride
50 60
C M (xlO 4 )
Remarks
Refs.
1.9 0.55 24.8 1.9 0.40 0.60 0.70 0.30 0.50 0.90 0.96 0.94 0.90 1.3 1.45 2.4 10.7 1.29 1.32 2.0 0.25 0.41 0.54 0.61 1.29 2 4.55 20 1.75 1.8 1.9 1.91 1.93 2.0 2.1 2.4 2.5 2.5 2.6 2.8 2.1 2.4 2.9 22 38
Fl C
113 R R
56 93 200 158 464 464 464 241 241 86 464 328 241 86 86 202 69 12 328 51 466 265 265 265 12 552 71 225 12 466 124 328 348 231 145 294 86 167 167 80 466 403 86 541 541
C P (xlO 4 )
Remarks
Refs.
D D D D D 14 D D 17 17 D
W14 W15 C
112 C
C C
TABLE 2. TRANSFER CONSTANTS TO POLYMERS Polymer Acrylamide, N,N-dimethylPoIy(N, Af-dimethylacrylamide) Acrylic acid, ethyl ester Poly(methyl methacrylate) - , methyl ester Poly(isoprene) - , chlorinated Poly (methyl acrylate) Poly (methyl methacrylate) Acrylonitrile Cellulose
T( 0 C) 50
0.61
272
60
12800
M6
120
75 60
12.6 0.5 1.0 18000
C, F2 L L M6
308 212 105 120
1.0 11 20
L, N L, M4 L, M5
361 361 361
60 60
Remarks page 11-157; References page 11-159
TABLE 2. cont'd Polymer Acrylonitrile, (cont'd) Poly(acrylonitrile) Poly(methyl methacrylate)
Poly(sarcosine) 1,3-Butadiene PoIy(1,3-butadiene) Ethylene
-, chloro Poly(vinyl chloride) Hexanoic acid, vinyl ester Poly(oxyethylene), dodecyl ether Methacrylic acid, butyl ester Poly(methyl methacrylate) -, dodecyl ester Poly (methyl methacrylate) -, ethyl ester Poly(isoprene), chlorinated Poly (vinyl chloride) Methyl methacrylate Poly(ethylene) Poly(isoprene), chlorinated Poly(methyl methacrylate)
T(0C)
50 60 60
60
Poly(vinyl chloride) Poly(vinyl urethane) Rubber, natural 2-Pyrrolidinone, 1-vinyl-dextran Dextran
376 135 25 25 25 25 23
C, C, C, C, C, C, C, C, C, C,
50
5
L
60
780
60
7700
M6
120
60
12800
M6
120
C, F2 C, F28
308 308
70 70
18.3 21.0
50 80 40
0.6 23.4 1.5 360 0.22 1.5 1.5 360 360 1000 0.1 1.5 2.1 360 2.48 0.22 1000 0.04 1.0 0.42 0.75 2.20 2.95 2.0 2.8 11 10.0 17 10.9 11.0
80 90
Poly(vinyl acetate)
F14 L N M2 M3 M
Refs.
11 108.40 150.70 194.81 214.46 337.31 256.85 195.81 199.89 155.78 348.46
60
Poly(styrene)
4.7 3.5 0.2 240 900 1270 400
Remarks
50 174.8 201.6 215.0 231.2 230.3 229.2 230.3 230.4 230.5 256.0
50
Poly(propylene)
C P (xlO 4 )
50 130 50 60 80 60 80 70 50 50 50
5 5.87
W20, F32 W20, F32 W20, F32 W20, F32 W22, F32 W21, F32 W20, F32 W19, F32 W18, F32 W20, F32
142 540 540 540 540 540 540 540 540 540 540 211 278
C, F17 N M N N M M N M N M N M C
C, F28 C, F8 C
209 307 326 326 147 326 327 326 327 147 105 326 262 326 262 147 147 292 209 292 148 262 262 263 263 250 308 157 258 258 333 203
TABLE 2. cont'd Polymer Styrene Poly(oxyadipoyloxy-2,2-dibromomethyl trimethylene) Poly(oxyethylene) - , dodecyl ether Poly(oxythexamethyleneoxy sebacoyl) Poly(methyl methacrylate)
T( 0 C)
60 70 70 60 80 50
60
Poly(propylene)
Poly(styrene)
80 100 60 66 130 50
55 60
73.5 85 90 100 110
Poly(vinyl acetate) Poly(vinyl chloride) Poly(2-vinylpyridine) Vinyl acetate Poly(oxyethylene) - , dodecyl ether Poly (methyl methacrylate) Poly(styrene) Poly(vinyl acetate)
130 154 100 130 50 60 60 60 75 40 60 75 -15 0 11 21 31 40 50
C P (xlO 4 ) 4.05 19 14 20 13 0.4 <0.3 1110 1140 16.4 17.5 5.7 x 104 32 x 104 3.74 6.04 0.025 26 0.3 0.30 1.9 4.5 14.0 16.6 15 0.8 1.9 3.1 15.4 15.8 16.6 1.0 1.4 5.8 2.0 9.2 10.8 1.8 1.5 6.6 9.2 160 8-10 17 40 10 40 750 21 26 12 15 19 0.36 0.5 1.7 2 4 16 11.2 30.9 32.0 0.06
Remarks
L MlO MlO C, N N M N M Ml Ml M7 M6 C
L
Ml Ml C C N
N M M8 M9
O O O
W15
Refs.
325 562 562 278 394 327 326 326 327 64 64 120 120 262 262 292 486 292 207 144,148 327 327 176 177 105 73 105 64 64 176 8 8 327 276 177 176 43 43 263 263 250 279 277 277 277 277 271 263 263 263 263 263 97 97 350 145 145 145 12 43 263 265
Remarks page 11-157; References page 11-159
TABLE 2. cont'd T( 0 C)
Polymer Vinyl acetate {cont'd) Poly (vinyl acetate) (cont 'd)
60
60-70 70 Poly(vinyl acetate-co-vinyl chloride)
TABLE 3.
60
C P (xlO 4 )
Remarks
0.11 0.15 3 10.2 1.2 1.4 1.8 1.9 2.5 3.0 4.0 6.8 8.0 47.0 3.5 2 4 0.21 3.0
W14
P O VCL-Part VOAC-Part
Refs.
265 265 43 12 124 168,169 348 328 329 165 105 12 105 263 350 403 403 166 166
TRANSFER CONSTANTS TO CATALYSTS AND INITIATORS
Catalyst/Initiator Acrylamide Bisulfite ion Hydrogen peroxide Potassium persulfate Acrylic acid, benzyl ester Isobutyronitrile, 2,2'-azobis-
- , ethyl ester Isobutyronitrile, 2,2'-azobis- , methyl ester Benzoyl peroxide
2-Butanone, peroxide
T(0C)
tert-Butyl peroxide
Chloroform/CuCl2 Acrylonitrile Isobutyronitrile, 2,2'-azobis-
Azodiphenylmethane, benzyl-
-, cyclohexyl-
Remarks
0.17 0.0005 0.0258 0.028
55 60 65
0 0 0
291 291 291
65
0
306
55 60 65 70 65
60 70 65 70 75 120
0.0143 0.0246 0.0375 0.01 0.05 0.05 0.05 0.077 0.113 0.113 0.01 0.0266 0.00047 0.00082 0.00111 600
F13 D F13, LL F13, LL
Refs.
75 25 50 60
70 75 tert-Butyl hydroperoxide
Ci
C, FlO FlO
FlO
Q(5-19), Fl
352 92 560 560
221 221 221 322 221 123 221 221 123 221 221 221 221 221 221 551
50 60
0 0
F16
362 95
50 60 80 50 60 80
0.07 0.07 0.07 0.02 0.04 0.05
R R R R R R
536 536 536 536 536 536
TABLE 3. cont'd Catalyst/Initiator Azodiphenylmethane (cont'd) - , 1-phenylethyl-
- , 2-propyl-
Benzoic acid, vinyl ester Benzoyl peroxide Isobutyronitrile, 2,2'-azobis3-Buten-2-one, 3-methylBenzoyl peroxide Ethylene Azoethane, 1,1 '-dimethylEthylene, chloroValeronitrile, 2,2'-azobis[2,4,4-trimethylMaleic anhydride Benzoyl peroxide Methacrylonitrile Isobutyronitrile, 2,2'-azobisMethyl methacrylate Acetophenone, 2-diazo-2-phenyl/7-Anisoyl peroxide Benzoyl peroxide
2-Butanone peroxide
T (0C)
Remarks
0.1 0.1 0.1 0.02 0.04 0.05
80 80
0.0527 0
26 26
80
0.0509
84
83
0.5 0.51
25
0.85
425
75
2.63
175
60
0
125
70 60 50 60
0.0 0.037 0.01 0 0.02 0.0025 0.00698
459 316 145 34 145 123 123
65
75
80 tert-Buty\ hydroperoxide terf-Butyl peroxide Butyronitrile, 2-ethyl-,2,2'-azobis- , 2-methyl-, 2,2'-azobis- , 2,3,3-trimethyl-, 2,2'-azobisCinnamoyl peroxide Cobalt, [bis-[ja-[(2,3-butane-dionedioximato)(2-)-O,O;]] tetrafluorodiborato(2-)-A^',vV",;V'']-
60 20 60 60 60 60
Cyclohexanecarbonitrile, l,l'-azodiCyclopropanecarboxylic acid, 1-methyl2-(9/-anthryl)-, methyl ester Hydrogen peroxide Hydroperoxide, a,oc-dimethylbenzyl Isobutyronitrile, 2,2'-azobis-
60
Methane, diazodiphenylPalmitoyl peroxide
70 60 60 50 60 70 60
Peroxide, bis(ra-chlorobenzoyl) - , bis(o-chlorobenzoyl)
60 60
60 60
0.0033 0.0033 0.0040 0.0092 0.00553 0.00667 0.0071 0.0089 0.0111 0.0128 1.27 x [cat] < 0.0001 0 0 0 0.009 36000 2500 0 0.002 0.046 0.33 0 0 0.0 0 0.16 0.003 0.019 0.35 0.8 0.009 0.012
R R R R R R
Refs.
50 60 80 50 60 80
70
- , bis(p-chlorobenzoyl) - , bis(m-nitrobenzoyl)
C1
D, W D, W
12 F2
F17 FlO FIl FIl F2 FlO F17
C, D
536 536 536 536 536 536
204 205
123 123 123 123 123 123 123 123 123 123 34 35 317 317
317 316 563 F17 317 440 FIl F2 FlO
111
FlO 110
563
290 34 327 34,290,317 267 316 145 316 316 290 145 316 316
Remarks page 11-157; References page 11-159
TABLE 3.
cont'd
Catalyst/Initiator Methyl methacrylate (cont'd) - , bis(p-nitrobenzoyl) - , bis(m-phenylazobenzoyl) 2-Tetrazene, 1,1,4,4-tetramethyl0-Toluoyl peroxide Valeronitrile, 2-methyl, 2,2'-azobisStyrene Acetyl peroxide p-Anisoyl peroxide Benzoyl peroxide
J(0C)
Ci
60 50 30 60
0.144 0.00001 0.038 0.046 0.06 0
60 70 70 22 50 60 70
80 Cobalt, [Bis-[^-[(2,3-butane-dionedioximato)(2-)-O,O/]] tetrafluorodiborato(2-)-N,iV/,A^//,N//]Di-3-phenylazo benzoyl peroxide 2-Butanone, peroxide
50 70 90 50 70 75
tert-Butyl hydroperoxide
Butyl peroxide sec-Butyl peroxide tert-Buty\ peroxide
60 70
80 60 80 60 80 60
70 80 Butyryl peroxide Cinnamoyl peroxide Crotonyl peroxide Cyclohexanone peroxide Ethyl peroxide Formamide, 2-cyano-2-propylazoFuroyl peroxide Hexanoyl peroxide Hydroperoxide, a,a-dimethylbenzyl
70 70 70 60 60 80 100 70 70 40
0 0.074 0.1 0.13 0.048 0.055 0.101 0 0.075 0.12 0.18 0.13 0.813 1500 6.7 5.5 4.8 0.46 0.0667 0.1250 0.1670 0.1250 0.1670 0.2000 0.243 0.035 0.051 0.060 0.063 0.064 0.066 0.003 0.00076 0.00092 0.0029 0.0004 0.0021 0.00023 0.0003 0.0006 0.00086 0.0013 0.039 0.0022 0.0033 0.018 1.10 0.146 0.062 0.00066 0.0024 0.17 0.23 0.166 0.052
Remarks
C D 111
D
C
F17 R R R H F2 FlO FIl F2 FlO FIl H F6 F2, F5 F9 F2 F9 F2 F2 F9 F2, F12 F2 F2
F2 F2
H
Refs.
316 282 483 316 145 317 87,217 87 65 58 171 240 234 217 87 67 58,65 58,65 530 563 527 527 527 388 123 123 123 123 123 123 123 171 388 399 400 400 400 385 302 302 302 301 301 303 303 303 300 304 400 303 385 87 87 87 33 301 301 47 87 87 388
TABLE 3. cont'd T( 0 C)
Catalyst/Initiator Styrene (cont'd) Hydroperoxide, a,a-dimethylbenzyl (cont'd)
-, a,a-dimethylbenzyl, /?-isopropylIsobutyronitrile,2,2'-azobis-
50 60 70 70 50 60
Isopropyl peroxide Lauroyl peroxide
60 80 70
p-Menth-8-yl hydroperoxide Myristoyl peroxide
84 50 70
2-Naphthoyl peroxide Nickel peroxide Octanoyl peroxide
70 60 70
Oleoyl peroxide Palmitoyl peroxide Peroxide, bis(p-acetoxybenzoyl) -, bis(ra-bromobenzoyl) -, bis(o-[bromobenzoyl)
70 70 70 70 50 70 70 70 70 22 70 70 70 60 70 50 70 70 70 50 70 70 70 70 70 90 70 50 70 70 70 80 90 80 90 80 90 80 90 70
-, bis(/?-bromobenzoyl) - , bis(p-ter£-butylbenzoyl) -, bis(m-chlorobenzoyl) Peroxide, bis(o-chlorobenzoyl) - , bis(p-chlorobenzoyl) - , bis(/7-cyanobenzoyl) - , bis(2,4-dichlorobenzoyl) -, -, -, -, -, -, -, -, -, -,
bis(oc,a-dimethylbenzyl) bis(m-fluorobenzoyl) bisO-fluorobenzoyl) bis(p-fluorobenzoyl) bis(hydroxyheptyl) bis(m-iodobenzoyl) bis(/?-methoxycarbonyloxy-benzoyl) bis(m-nitrobenzoyl) bis(/?-nitrobenzoyl) bis(m-phenylazobenzoyl)
- , bis(5-phenyl-2,4-pentadienoyl) - , bis(2-thiophenecarbonyl) -, -, -, butylidenebis[rm-butyl
tert-butoxymaleoyl tert-butoxyphthaloyl
-, sec-butylidenebis[terf-butyl -, isobutylidenebis[terr-butyl - , isopropylidenebis[tert-butyl Pinanyl hydroperoxide
Ci 0.069 0.063 0.082 0.10 0.033 0 0 0 0 0.012 0.16 0.0003 0.0015 0 0.024 0 0.048 0 0.116 0.178 0.00265 0 0.098 0.154 0.142 0.187 0.465 1.0 2.17 0.193 0 0.346 2.0 1.91 0.216 0.804 2.9 2.6 0.01 0.246 0.40 0.219 < 0.005 0.262 0.208 6.2 7.4 5.5 4.8 5.24 0.23 0.38 1.52 0.018 0.00077 0.00140 0.00072 0.00115 0.00083 0.00155 0.00040 0.00105 0.026
Remarks H H H F2 H
F2 F2
H
C, F2
D
H
H
C C
C C C C C C C C H
Refs. 388 171 388 399 388 327 388 171 318 468 447 301 301 217 87 217 388 217 87 87 266 217 87 87 87 87 87 58,65 87 87 87 87 65 87 217 87 217 217 388 87 87 87 388 87 87 87 87 281 281 87 65 65 87 87 411 411 411 411 411 411 411 411 388
Remarks page II-157; References page II-159
TABLE 3. cont'd Catalyst/Initiator Styrene (cont'd) Pivalonitrile Propylene, oxidized Propyl peroxide Sorboyl peroxide Stearoyl peroxide Succinonitrile, tetramethyl2-Tetrazene, 1,1,4,4-tetramethylo-Toluoyl peroxide /7-Toluoyl peroxide 9-Undecenoyl peroxide Valeronitrile, 2,2/-azobis[2,44-trimethylVinyl acetate Benzoyl peroxide
T( 0 C)
60 60 70 60 70 70 60 30 70 50 70 70 25 60
Lauroyl peroxide Palmitoyl peroxide
65 50 60 60 60
Peroxide, bis(m-bromobenzoyl)
60
- , bis(o-bromobenzoyl)
60
- , bis(/?-bromobenzoyl) - , bis(o-chlorobenzoyl)
60 60
Isobutyronitrile, 2,2/-azobis-
Ci
0.000038 1.01 1.14 0.00084 1.19 0.154 0.000037 0.038 0.175 0.17 0.003 0.19 0.065 0.59 0.032 0.09 0.15 0.040 0.025 0.055 0.10 0.10 0.17 0.24 0.6 0.25 3.5 0.17 0.17
Remarks
D
13 13 13 13
Refs.
468 396 396 305 87 87 468 483 87 65 87 65 87 426 465 231 80 466 466 466 80 80 145 80 145 80 145 80 145
TABLE 4. TRANSFER CONSTANTS TO SOLVENTS AND ADDITIVES Solvent/Additive Acetic acid, allyl ester Benzene /7-Benzoquinone -, 2,3,5,6-tetrachloro- , 2,3,5,6-tetramethyl- , 2,3,5-trichloroCarbon tetrachloride Phosphorus trichloride Acrylamide Acetonitrile tris(2-Carbamoylethyl)amine Iron(III) chloride Isopropyl alcohol Methanol Propionamide
Water Acrylic acid, butyl ester Aniline, MN-dimethylEthanol Methanol Propanol Iso-propanol
J( 0 C)
C s (xlO 4 )
Remarks
80 80 80 80 80 100 40
21.0 5.2 x 105 16 x 105 4.14 x l O 4 5.5 x 105 2.0 x 104 1.0 x 104
J J J J C C, D
25 50 80 30 25 60
5.5 85 4.26 x 104 19 7.2 0.13 220 64
25 40 50 80 80 80 80
0.204 5.8 380 4.28 0.47 3.78 14.12
F13 Fl 3
Refs.
273 27 27 27 27 210 214
F13 F13, S C, F13 E E
564 564 75 353 353 130 103 103
C, F13 F13
437 444
A, R F31, A, R A, R A, R
161 548 548 548 548
TABLE 4. cont'd Solvent/Additive Acrylic acid, ethyl ester Acetic acid Acetone
Acetonitrile
Aniline, A^-dimethylBenzene
-, bromo- , chloro- , ethyl-
2-Butanone
Butyl alcohol
sec-Butyl alcohol
terf-Butyl alcohol
Butyric acid Carbon tetrachloride
Chloroform
Cumene
Cyclohexane
T( 0 C)
50 80 100 40 60 80 100 50 60 80 100 50 50 60 80 100 60 80 100 40 80 100 40 60 80 100 50 60 80 90 40 60 80 100 45 63 80 100 40 60 80 100 80 40 60 70 80 100 40 60 70 80 100 50 60 80 90 50 60
C 8 (xlO 4 )
0.176 0.537 1.05 0.207 0.27 1.10 2.30 0.158 0.245 0.55 1.43 2300 0.016 0.22 0.27 0.45 0.525 2.2 0.163 0.685 3.34 0.054 0.37 1.68 0.668 11.6 16.80 28.7 1.44 0.151 1.92 3.29 4.45 1.28 2.91 5.85 12.6 10.6 18.5 22.20 31.5 0.068 0.17 0.712 1.64 0.855 0.332 0.90 3.2 1.13 1.55 2.80 0.195 0.89 1.57 1.49 4.74 11.7 13.8 22.2 26.0 28.9 0.48 0.61
Remarks
A A C A A A A F16 C C A A A A A A A A C A A A A A A A A A
C A A C C A A A A C
Refs.
472 471 472 472 134 471 472 472 472 471 472 228 472 472 133 134 471 472 472 471 472 472 471 472 472 472 471 472 472 134 472 471 472 472 472 471 472 472 472 471 472 472 472 471 472 471 472 472 416 134 471 472 472 134 134 471 472 472 472 471 472 472 472 134
Remarks page II-157; References page II-159
TABLE 4. cont'd Solvent/Additive Acrylic acid, ethyl ester (cont'd) cyclohexane (cont'd) Dimethylformamide Ethanol Ethyl acetate
T( 0 C)
C s (xlO 4 )
Remarks
80 100 50 80 50 60
1.22 3.08 0.1 4.38 0.298 0.448 0.69 0.89 1.82 0.046 0.524 0.593 0.97 1.46 2.1 3.31 4.65 8.06 21 28.70 0.32 1.70 0.36
A A F7 A, R
80 100 80 50 60 80 100 45 63 80 100
Formic acid Heaxane
Isobutyl alcohol
Isopropyl alcohol 80 60
Methanol
80
Propanol Toluene
80 40 50 60 70 80 100
- , 2-ethylhexylester Toluene - , methyl ester Acetone
70 80
28.70 2.13
60 80
0.23 0.622 1.1 <2.5 480 <1.0 60 42.1 26.7 72.7 1000 0.326 0.45 0.52 0.986 0.71 309 6.056 46.4 2040 107 <1.0 600 1890 1000 3.92 400 1200 33.1 1600
Acetophenone Aluminum, triethyl Aniline -,MTV-dimethyl- , m-nitro-,p-nitroAnisole, m-nitroAnthracene Benzene
50 60 50 50 50 50 50 50 80
- , chloro-
80
- , 0-dichloro-, -,ethyl- , nitro- , 1,3,5-trinitroBenzoic acid, /?-nitroBenzonitrile Copper(II) chloride Phosphine, tributylPhosphorus trichloride Propanol Silane, dimethyphenyl- , methyldichloro- , tetraethyl- , trichloro-
ra-dinitro-
4.73 0.88 0.611 0.929 1.37 1.84 2.60 6.80
80 50 80 50 50 50 50 120 60 40 80 60 60 60 60
C A A A
A A
A A C A, R C 4 A, R
A,R
Refs.
471 472 510 548 472 472 134 471 472 471 472 472 471 472 472 472 471 472 445 548 134 472 548
C, F17, R C, F17, R C, F17, R C A A
548 472 512 512 512 134 471 471
C, F17, R C, F17, R
512 512
C
470 332 111 15 156 15 228 15 15 15 15 332 111 111 332 111 15 332 15 15 15 15 565 156 214 548 539 539 156 539
C F2, S F16
C C C
F34 F2 C, D A, R A, R A, R F2 A, R
TABLE 4.
cont'd
Solvent/Additive Acrylic acid, methyl ester(cont'd) - , triethyl- , triphenylStearic acid, methyl ester Toluene - , m-nitro-,/7-nitroTriethylamine Tripropylamine - , tetrahydrofurfuryl ester Carbon tetrachloride Acrylonitrile Acetaldehyde Acetamide, AW-dimethylAcetic acid Acetone Acetonitrile Acrolein, bis(2-ethoxyethyl)acetal - , bis(2-butoxyethyl)acetal Aluminum, hydrodiisobutyl -,triethyl - , triisobutyl Aniline
- , N,N-diethy\-
T( 0 C)
Remarks
Refs.
A, R A, R
50 50 60 60
300 800 0.751 2.7 1.775 2.7 41.2 48.6 400 470
539 539 441 21,24 332 111 15 15 24 156
40
1.0
C, F2
60 60 60 60 80
50 50 50 50 60 50 60 60 60 60 60 100 100 40 50 60 40 50 60
Aniline, AW-dimethyl-
40 50
60 Anthracene Arabinose Benzene - , bromo- , tert-butyl- , chloro-,ethyl- , iodoBenzoic acid, vinyl ester /7-Benzoquinone Borane, tributyl 2-Butanone - , 3-methyll-Buten-3-yne Butyl alcohol sec-Butyl alcohol tert-Butyl alcohol
C s (xlO 4 )
50 60 60 60 60 60 60 60 65 50 60 60 60 50 60 60 60
14 47 4.945 5.05 0.81 1.7 1.13 0.7 2.0 120 90.5 3940 590 17.0 x 104 28.0 x 104 32.0 44.0 9600 1.22 xlO 4 215 5.8IxIO 4 359 9.38 x 104 547 14.3 x 104 605 1.19 xlO 4 708 1040 1.5 x 104 1.54 xlO 4 870 964 2.18 xlO 4 1.8 x 104 13.0 2.46 1.36 1.93 0.79 35.73 5.19 1400 1.3 x 104 6470 6.43 21.08 3800 15.42 97.55 0.44
C
F2
F F7 F14 F14 F F14 Fl 5 F7 F7 F7 F7 F7 F7 F2, G F2, J F16, G, J F16, G, J F2, J F16, G, J F2, J F16, G, J F2, J F16, G, J F2, J F16, G, J F2, J F16, J F16, G, J J F2, J F16, G, J F8 G G, S G G, S G G, S F7 G G F7 G G G
319 436 377 375 197 377 377 95 377 86 499 156 156 156 247 247 229 229 227,229 229 229 229 229 227,229 229 229 229 229 229 161 228 227,229 24 229 229 15 361 95 95 95 95 95 95 136 15 156 95 95 377 95 95 95
Remarks page 11-157; References page 11-159
TABLE 4. cont'd Solvent/Additive Acrylonitrile (cont'd) Butyric acid, 4-hydroxy-y-lactone Cadmium, dibutyl Carbonic acid, cyclic ethylene ester
Carbon tetrabromide Carbon tetrachloride
T( 0 C) 50 60 50
60 50 60
Copper(II) chloride
60 80 60 80 35
Copper(II) sulfate
60 35
Chloroform
Crotonaldehyde Crotononitrile, transCumene Cyclohexane -,methylDimethylamine m-Dioxane, 5,5-dimethyl-2-vinylm-Dioxane, 5,5-dimethyl-2-vinyl- , 4-methyl-2-vinyl- , 2-vinyl1,3,-Dioxolane, 2-vinyll,3-Dioxolane-4-methanol, 2-vinylDiphenylamine-T Erythritol Ethane, 1,2-dichloro- , 1,1,2,2-tetrachloro- , 1,1,1-trichloro- , 1,1,2-trichloroEthanol, 2,2MmInOdI- , 2,2',2"-nitrilotriEther, dodecyl vinyl Ethyl acetate Formamide, N,N-dimethyl-
50 50 60 60 60 50 60 60 60 60 60 60 60 60 60 60 60 30 30 50 60 20 25 40 50
60
C s (xlO 4 ) 0.658 0.74 5.5 x 104 0.073 0.33 0.39 0.474 0.5 0.511 1.0 0.128 400 500 1900 0.85 1.13 5.64 5.90 1.8 x 105 1.9 xlO 5 3.2 xlO 5 10 x 105 1900 2800 3000 1.07 x 104 1.35 xlO 4 3.93 x 104 13.6 x 104 21.OxIO 4 47 19 41.41 2.06 2.31 175 2.20 4.40 2.71 16.60 2.40 700 12.8 1.47 3.11 1.25 1.68 10.1 76.0 4.95 2.54 1.4 4.97 3.24 1.0 2.70 2.78 2.8 2.83 10 2.412 4.494 5.0
Remarks
F7
E
F7, J G C G C U(0.01) U(0.1) U(l.O) F7 F13, J J, V(0.0001) J, U(0.01) J, V(0.001) J, U(0.1) J, V(O.Ol) J, U(LO) J, V(0.1) F7 F7 G G G F7 F7 F7 F7 F7 F7 F7 F8 G G G G F13 F13 C G C, J, F7 D, J E
F7
F15
Refs. 375 374 156 293 197 374 375 404 458 356 293 493 20 24 96 336 95 336 402 402 402 37 402 402 402 402 402 402 402 402 377 377 95 95 95 377 498 498 498 498 498 61 361 95 95 95 95 476 476 4 95 248 91 458 347 374 197 377 375 356 347 22 86
TABLE 4. cont'd Solvent/Additive Acrylonitrile (cont'd) Formamide, A^N-dimethyl- (cont'd) -, Af-methylFormic acid Glucose ot,D-Glucoside, methyl- , -, 6-deoxy-6-iodo- , - , 6-deoxy-6-mercapto- , - , 6-deoxy-6-phthalimido- , -, 2,3-di-O-benzyl- , -, 2,3,4,6-tetra-O-acetyl- , -, 6,-O-(/?-toluenesulfonyl)- , - , 6-O-triphenylmethylP,D-Glucoside, methyl- , - , 6-deoxy-6-dipropylaminoGlutaronitrile, 2,4-dimethylGlyceraldehyde Glycerol 2,4,6-Heptanetricarbonitrile 1-Heptanol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluorol,5-Hexadien-3-yne Hydrocyanic acid
T( 0 C)
50 50 60 60 60 60 60 60 60 60 60 60 60 50 60 60 50 60 50 50
Indium, triethyl Iron(III) chloride Isobutyl alcohol Isobutylene Isobutyronitrile
60 60 60 60 50 60
Lactonitrile Lead, tetraethyl Magnesium perchlorate Mercury, diethyl Methane, dichloro- , nitroMethanol Methylamine 2,6-Octadiene, 2,6-dimethylOxime, acrolein -, crotonaldehyde-, ethylisopropenylketone-, methacrolein-, methylacrolein-, methylvinylketone-, methylisopropenylketone-, methylisobutenylketone1-Pentanol, 2,2,3,3,4,4,5,5-octa-fluoro1-Pentanol, 4-methylPiperidine, 1-ethyl- , 1-methyl1-Propanol, 2,2,3,3-tetrafluoroSilane, tetraethyl Sorbitol Stibine, tributyl Succinonitrile Sulfur dioxide Tin, tetrabutyl Toluene
50 60 50 60 60 60 50 50 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 50 60 50 60
o-Toluidine, MN-dimethyl-
40 50
C s (xlO 4 )
1.8 0.5 6.9 20 50 1300 60 90 30 10 80 20 1100 0.6 32.1 23.5 1.0 1.9 1.17 x 104 0.81 6.2 2220 3.33 x 104 24.06 70 1.3 1.8 3.5 4.0 1 243 < 0.05 72.2 3.06 6.0 0.5 175 450 6.26 x 105 2.05 x 104 1.03 x 104 9.41 x 104 5.35 x 104 1.2 x 104 1.71 x 104 2.65 x 104 1.9 11.79 3300 2300 1.5 21.0 6.1 11.1 x 104 0.6 0 80.8 1.153 2.632 3.2 5.83 272 334
Remarks
Refs.
F14 F14 F8 F7 F7 F7 F7 F7 F7 F7 F7 F7 F7 F14 F8 F8 F14 F2 F7 F14 F F7 F7 G
377 377 361 220 220 220 220 220 220 220 220 220 220 376 361 361 376 442 377 377 436 156 19 95 553 376 376 135 86 377 156 376 156 95 86 377 377 6 555 555 555 555 555 555 555 555 442 95 24 24 442 156 361 156 86 362 156 347 347 21 24,95 229 229
F14 16 F15 F14 F7 F7 G F15 F14 F7
F2 G J J F2 F7 F8 F7 F7 G G G F2, J F2, J
Remarks page 11-157; References page II-159
TABLE 4. cont'd Solvent/Additive
T( 0 C)
Acrylonitrile (cont'd) 0-Toluidine, ^//-dimethyl- (confd) Tributylamine Triethylamine
Trimethylamine Tripropylamine Zinc, diethyl Zinc chloride Acrylonitrile/styrene (38.5-61.5 mol%) Methanol Anisole, /?-vinylAnisole, /?-isopropylBenzonitrile,/7-isopropylCumene -,/7-bromo-,/7-tert-butyl-,/?-chloroBenzoic acid, vinyl ester Benzene Benzoic acid, isopropyl ester 2-Butanone Carbon tetrachloride Chloroform Cyclohexane 1,3-Butadiene, 2-chloro1-Butene, 3-chloro-3-methyl2-Butene, l-chloro-3-methyl2,6-Octadiene, 2,7-dichloro3-Buten-2-one, 3-methylBenzene -,ethylCyclohexane, methylToluene Butyraldehyde, divinyl acetal Aniline, N,TV-dimethylBenzene Butyl alcohol tert-Butyl alcohol 1,3-Dioxolane, 2-propylButyric acid, vinyl ester Benzene Carbamic acid, vinyl-, ethyl ester Acetone Benzene Chloroprene 3-Chloro-(methyl-14C)l-butene(4-14C) 3-Cfcloro-2-pentene-(2,4-14C) /?-Dioxin, 2,3-dihydro-/maleic anhydride Benzene Carbon tetrabromide Carbon tetrachloride Chloroform /7-Dioxane Toluene m-Xylene
60 60 60
50 60 60 60 50
C s (xlO 4 )
30200 463 6700 1700 1900 3800 5900 6600 175 790 4820 1.05 x l O 4 1.06 x l O 4 0.006
Remarks
Refs.
F16, G, J F2, J J T
227,229 229 24 20 20 22 24 24 377 24 156 24 156 410
F7, J J F7 J F7 J F7 F13
65
1.4
116
60 60 60 60 60 60
3.40 40.9 4.28 11.8 3.64 8.52
407 407 407 407 407 407
60 80 60 80 80 80 80
1.5 0.4 1.0 29.0 730 105 2.3
393 26 393 26 26 26 26
50 50 50
5.47 4.57 5.24
Fl F2 F2
80 80 80 80
2.489 6.934 0.500 3.282
C C C C
50 50 50 50 50
1060 27.7 3500 37.2 708
152 152 152 84 84 84 84 430 430 430 430 430
80
3.28
201
60 60
8.5 1.25
117 117
50 50
5.37 3.94
60 60 60 60 60 60 60
11500 100 x 105 1.7 x 105 3.6 x 104 1.07 x 104 6.OxIO 4 9.9 x 104
F2 F2
509 509
R R R R R R R
169 169 169 169 169 169 169
TABLE 4. cont'd Solvent/Additive Ethylene Acetamide, AW-diethyl- , AW-diisopropyl- , Ar,A7-dimethyl- , N-ethyl-,TV-methylAcetic acid, butyl ester - , tert-buty\ ester - , methyl ester Acetic acid, chloro- , - , methyl ester
T( 0 C)
C s (xlO 4 )
Remarks
130 130 130 130 130 130 130 130
125 57 182 115 61 89 40 40
C, W5 C, W5 C, W5 C, W5 C, W5 C, W5 C, W5 C, W5
454 454 454 454 454 454 454 454
90
130
610 1210 2170 2150 2580 630 1160 1880 1990 2090 1120
C, Ql C, Q2 C, Q3 C, Q4 C, Q5 CQl C, Q2 C, Q3 C, Q4 C, Q5 C, W5
434 434 434 434 434 434 434 434 434 434 454
130
6700
C, W5
454
55
1800 7900 11100 13000 1900 6900 9400 10500 2000 5900 8100 11100
C, Ql C, Q2 C, Q3 C CQl C, Q2 C, Q3 C C, Ql C, Q2 C Q3 C
435 435 435 435 435 435 435 435 435 435 435 435
700 16100 27500 38000 65700 1000 17000 27700 39000 65200 1200 15400 23600 33000 54100 130 160 165 168 282 100 1970 0.629 20 21 9.4 18
C, Ql C, Q2 C, Q3 C, Q4 C CQl C, Q2 C, Q3 C, Q4 C CQl C, Q2 C, Q3 C Q4 C C, W5 C, W17 C, F21, W5 C, W5 C,W5 C, F21, W5 C, W5 E, W D D, W C,W5 W3
484 484 484 484 484 484 484 484 484 484 484 484 484 484 484 454 456 259 456 455 159 457 143 204 205 260 218
120
Acetic acid, cyano- , - , methyl ester Acetic acid, dichloro- , -, methyl ester
90
120
Acetic acid, trichloro- , - , methyl ester
55
90
120
Acetic anhydride Acetone
130 130
Acetonitrile Benzaldehyde Benzene
200 130 130 20 83 130 50-70
Refs.
Remarks page 11-157; References page 11-159
TABLE 4. cont'd Solvent/Additive
T( 0 C)
Ethylene (cont'd) -,ethyl-
130
Benzene-D6 Benzoic acid, butyl ester -,ethyl ester - , methyl ester Butane
200 130 130 130 130 130
- , 1-iodo-
100
2-Butanone
130
- , 3-methyl1-Butene
200 130 130
- , 2-methyl-
189 200 130
-,3-methyl2-Butene
130 130
- , 1,4-dichloro-,2-methyl tert-Buty\ alcohol
130 130 30 130 130 130 130 130 20 50 70
Butylamine Butyraldehyde Butyric acid, methyl ester Butyronitrile Carbon tetrachloride
90
95
130
140
C s (xlO 4 )
Remarks
Refs.
430 480 520 560 500 5.6 140 55 53 40 45 9.45 x 104 11.3 xlO 4 12.6 x 104 550 600 750 840 330 470 560 900 570 210 530 1200 250 380 4100 470 0 2 220 3250 220 520 215 772 974 7000 32000 740 1210 20200 32500 34000 1250 ±200 22000 ± 1000 43000 ± 4000 1130 ±700 2000 ±1000 37000 ± 3000 9800
C, W17 C, W5 C, W5 C, W5 C, W5 C, W5 C, W5 C, W5 C, W5 C, F21, W5 C, W17 Ql, W14 Q2, W14 Q3, W14 C, W17 C, F21, W5 C, W5 C, F21, W5 C, W5 C, W5 C, F21, W5 B, W5 C, W5 C, F21, W5 C, F21, W5 C, F21, W5 C, F21, W5 C, W5 C, W5 C, F21, W5 E, W4 C, F21,W5 C-W5 C, W5 C, W5 C, F21, W5 E, W CQl, C, Ql C, W4 C Ql, W12 CQl Q2, W12 Q3, W12 W12 W23, Q(I) W23, Q(2) W23, Q(3) W20, Q(I) W20, Q(2) W20, Q(3) C,F21,W5
456 52 454 52 455 260 454 454 454 259 456 187 187 187 456 259 455 259 52 52 259 443 455 259 259 259 259 454 454 259 482 259 454 457 454 259 143 391 391 215 210 453 391 453 453 453 518 518 518 518 518 518 259
1600 1700 1800 2200 22000 23000 30000 36000 38000 39000 60000
CQl C, Ql, F19 C, Ql, W13 C, Ql, F20 C, Q2 C, Q2, F19 C, Ql, Wl C Q3 C Q2, F20 C Q3, F19 C,Q2, W13
170 170 170 170 170 170 170 170 170 170 170
TABLE 4. cont'd Solvent/Additive Ethylene (cont'd) Carbon tetrachloride (cont'd)
Chloroacetic acid, methyl ester Chloroform
Cumene Cyclohexane
-,methylCyclopentane Cyclopropane Decane 1-Decene Dibutylamine Dichloroacetic acid, methyl ester Dimethylamine p-Dioxane Ethane - , U-bis(dimethylamino)- , l-bromo-2-chloro- , chloro- , 1,2-dibromo- , 1,1-dichloro-
T( 0 C)
C s (xlO 4 )
60000 61000 70000 90000 100000 110000 130000 140000 180000 90 590, 550, 1200 1680, 2240, 2340 28 2100 13000 15000 70 8000 30000 80 2470 15500 24900 31200 43900 95 2000±120 10000 ±500 16000 ± 3000 1150±50 5000 ±300 8000 ±1000 101 1500 4500 5400 103 2890 15400 23800 29800 41100 130 2900 140 3210 15200 22200 28000 37600 130 500 130 80 90 91 200 190 130 110 130 109 127 200 22& 130 0 130 120 189 425 189 1090 130 1070 901900, 6900, 9400 130 1900 130 320 130 6 130 1070 130 390 70 120 130 1250 70 1500
Remarks C, Q3 C, Q3, F20 C, Q4, F20 C, Q4, F20 C, Q2, Wl C, Q3, Wl C, Q3, W13 C, Q4, Wl C C, Q(I), Q(2), Q(3) C, Q(4), Q(5), Q(6) E, Ql, W E, Q2, W E, Q3, W C, W4 C C, Ql, W12 C, Q2, W12 C, Q3, W12 C, Q4, W12 C, W12 W23, Q(I) W23, Q(2) W23, Q(3) W20, Q(I) W20, Q(3) W20, Q(3) E, Ql, W E, Q3, W E, Q2, W C, Q1,W12 C, Q2, W12 C, Q3, W12 C, Q4, W12 C, W12 C, F21,W5 C, Ql, W12 C, Q2, W12 C, Q3, W12 C, Q4, W12 C, W12 C, F21, W5 C, F21, W5 C, W17 C, F21, W5 C, W5 C, F21, W5 C, W17 C, F21, W5 C, W5 C, F21, W5 C, F21, W5 B, W5 B, W5 C, W5 C, Q(I), Q(2), Q(3) C, F21, W5 C, F21, W5 C, F21, W5 C, W5 C, W5 C, W4 C, W5 C, W4
Refs. 170 170 170 170 170 170 170 170 170 557 557 244 244 244 215 210 101 101 101 101 101 518 518 518 518 518 518 224 244 244 101 101 101 101 101 259 101 101 101 101 101 259 259 456 259 455 259 456 259 455 259 259 443 443 454 558 259 259 259 457 454 215 454 215
Remarks page 11-157; References page 11-159
TABLE 4. cont'd Solvent/Additive
T( 0 C)
Ethylene (cont'd) Ethane, 1,2-dichloro- , iodo-
130 65 100
- , 1,1,1-trichloroEthanol
Ethyl acetate Ethylene oxide Formaldehyde Fomamide, W,TV-dimethylFormic acid, methyl ester Furan, tetrahydroHeptaldehyde Heptane Hexane 1-Hexene - , 2-ethylHydrogen Isobutyronitrile Isocyanic acid, butyl ester Isopropanol
Isothiocyanic acid, butyl ester Methane - , bromochloro-
70 20 30 60 100 125 130 125-135 150 180 200 130 200 130 130 130 130 130 200 130 200 50-70 130 130 189 189 130 130 200 130 130 30 60 100 125 130 125-135 150 180 200 130 130 100
130 140
C s (xlO 4 )
110 1.51 x 105 1.59 x l O 5 1.65 x 105 1.1 x 105 1.36 x l O 5 1.43 x l O 5 1.48 x l O 5 1.49 x 105 500 5.71 110,210, 270 76,240, 280 89,270, 340 100,310, 320 68 69 75 190 92,260 73,350 135 45 121 7 560 260 42 288 289 401 2600 3900 4800 90 80 68 225 900 3300 159 160 400 1070 212 96,410, 520 65,310, 380 65,300, 350 75,380, 380 130 140 144 570 98,470, 460 86,440, 500 234 0 0 1600 4500 7500 8000 10000 16.OxIO 5
Remarks
C, F21, W5 Ql Q2 Q3 Ql Q1,W14 Q2, W14 Q3, W14 Q3 C, W4 E, W E, Q(I), Q(3), Q(5) E, Q(I), Q(3), Q(5) E, Q(I), Q(3), Q(5) E, Q(I), Q(3), Q(5) C, W17 C, F21, W5 C, W5 C, W2 E, Q(I), Q(3) E, Q(I), Q(3) C, W5 C, W5 C, W17 C, F21, W5 C, W5 C, F21, W5 C, W5 C, W5 C, F21, W5 C, W5 C, W17 C, W5 C, W5 W3 C, F21,W5 C, F21, W5 B, W5 B, W5 C, F21, W5 C, W5 C, F21, W5 C, W5 C, F21, W5 C, W5 E, Q(I), Q(3), Q(5) E, Q(I), Q(3), Q(5) E, Q(I), Q(3), Q(5) E, Q(I), Q(3), Q(5) C, W17 C, F21, W5 C, W5 C, Wl E, Q(I), Q(3), Q(5) E, Q(I), Q(3), Q(5) C, W5 C, W5 C, W5 C, Ql, WIl C, Q2, WIl C, Q3, WIl C, Q4, WIl C, W5 Ql, WIl, II
Refs.
259 189 189 189 452 188 188 188 452 215 143 523 523 523 523 456 259 454 381 523 523 455 454 455 259 457 259 454 454 259 455 457 457 457 218 259 259 443 443 259 454 259 455 259 454 523 523 523 523 456 259 454 381 523 523 455 454 259 2 2 2 2 454 1
TABLE 4. cont'd Solvent/additive Ethylene (cont'd) Methane, bromochloro- (cont'd) - , chloro- , dichloro- , dimethoxy- , iodo-
T( 0 C)
70 70 130 130 65 100
Methanol
Methylamine 1-Octene
30 60 100 125 130 150 180 130 130
Pentane, 2,2,4-trimethylPentene - , 4,4-dimethyl- , 4-methylPhosphine - , dibutyl - , tributyl - , triphenyl Phosphorous acid, dimethyl ester Propane
130 189 130 130 130 130 130 130 130 130
- , 2-chloroPropane, 2-chloro-2-methyl-, 2,2-dimethyl- , 2-iodo-
200 70 70 130 65 100
- , 2-methyl-
130
- , 1,1,1,2,2,3,3,3-octafluoro1-Propene
200 130 130
Propionaldehyde
200 130
Propionic acid, methyl ester
200 90
120
C 8 (xlO 4 ) 47.0 x 105 4 700 360 73 41000 45000 45000 41000 45000 45000 36, 84, 100 46, 100, 140 34, 90, 120 56, 100, 140 21 53, 120, 160 37, 120, 160 53 360 360 64 900 175 310 207000 36000 4500 50 5100 27 27.6 31 65.2 250 40 8 5.7 x 105 5.9 x 105 6.07 xlO 5 4.55 x 105 4.70 x 105 4.83 x 105 50 72 136 4 110 122 150 200 2300 3300 2830 63000 92000
1.08 xlO 5 630, 420, 780 890, 1030, 1230 78000 1.12 xlO 5 1.39 xlO 5 780, 430, 1060 1220, 1300, 1410
Remarks
Refs.
Q2, WIl, II C, W4 C, W4 C, F21,W5 C, W5 Ql Q2 Q3 Ql Q2 Q3 E, Q(I), Q(2), Q(3) E, Q(I), Q(2), Q(3) E, Q(I), Q(2), Q(3) E, Q(I), Q(2), Q(3) C, F21, W5 E, Q(I), Q(2), Q(3) E, Q(I), Q(2), Q(3) C, W5 C, W5 C, F21, W5 C, F21, W5 B, W5 C, W5 C, W5 C, W5 C, W5 C, W5 C, W5 C, F21, W5 C, F21, W5 C, W17 C, F21, W5 C, W5 C, W4 C, W4 C, F21, W5 Ql Q2 Q3 Ql Q2 Q3 C, F21, W5 C, W5 C, W5 C, F21, W5 C, W5 C, W5 C, W5 C, W5 C, W17 C, W5 C, W5 C, Ql C, Q3
1 215 215 259 454 189 189 189 189 189 189 523 523 523 523 259 523 523 454 52 259 259 443 454 454 457 454 454 454 259 259 456 259 455 215 215 259 189 189 189 189 189 189 259 454 455 259 52 454 52 455 457 457 457 485 485
C, Q5 C, Q(I), Q(2), Q(3) C, Q(4), Q(5), Q(6) CQl
485 516 516 485
C, Q3 C, Q5 C, Q(I), Q(2), Q(3) C, Q(4), Q(5), Q(6)
485 485 516 516
Remarks page II-157; References page II-159
TABLE 4. cont'd Solvent/Additive
T( 0 C)
Ethylene (cont'd) -, 3-cyano-, methyl ester Silane, tetramethyl Tetradecane 1-Tetradecene Toluene
130 130 189 189 130
Tributylamine Trichloroacetic acid, methyl ester Tridecane Trimethylamine
200 130 90 130 130
Water /?-Xylene
20 130 200
Ethylene, bromoCarbon tetrachloride Ethylene, chloroAcetaldehyde Aniline, A^-dimethylBenzene Butyraldehyde
Carbon tetrabromide
60 50 50 35 50
50 60
Cyclohexane, 1,2-epoxy-4- vinylEthane, 1,2-dichloroEther, dodecyl vinyl Furan, tetrahydroHeptane, 2,4,6-trichloroOxalic acid, diethyl ester Pentane, 2,4-dichloroEthylene, 1,1 -dichloroPhosphorus trichloride Ethylene, tetrafluoroEthanol
25 50 50 25 40 50 50 25 25 50
790 0 580 1760 130 154 180 220 820 1000, 1700, 2770 140 180 330 1.71 300 317 400 434
110 2700 1500 350 420 500 580 4.7 x 104 50.0 x 104 3300 1.85 xlO 4 7.45 x 104 12.15 xlO 4 264 4.0 4.5 156 16 30 24 5 1.4 9.0 5 14
100
800 820 860 880 1540 1660 1700 350 390
100
Methanol
100 80 140 125-135 30-35
Remarks
C, W5 C, F21, W5 B, W5 B, W5 C, W5 C, W5 C, W17 C, W5 C, W5 C, Q(I), Q(2), Q(3) C, F21, W5 C, F21, W5 C, W5 E, W C, F21, W5 C, W5 C, W17 C, W5
50
60
Isopropanol
Hexanoic acid, vinyl ester Benzene 1-Hexene Carbon tetrachloride Cyclohexanol Ethyl alcohol
C s (xlO 4 )
454 259 443 443 52 454 456 455 454 559 259 259 454 143 259 454 456 455 417
W8 W7 W15 F26 Ql Q2 Q3 Q4 C, F26
G D C, Q5, W2 C, Q6, W2 C, Q4, W2 C, Q3, W2 C, Q3, W2 C, Q4, W2 C, Q5, W2 C, Q3, W2 C, Q4, W2
4.9 4.1 x 104 390 170
Refs.
164 161 219 500 500 500 500 492 66 418 418 418 418 428 425 392 4 425 246 164 211 315 315 211 214 3 3 3 3 3 3 3 3 3 201
C, Ql, F19 C D
170 381 381
TABLE 4. cont'd Solvent/Additive
T( 0 C)
Isobutene Carbon tetrachloride
100
Isobutyric acid, vinyl ester Benzene Maleic acid, diethyl ester Stearamide, iV-allylMaleic anhydride/methyl methacrylate Acetone Maleic anhydride/styrene Aniline, A^-dimethylCarbon tetrachloride Methacrylic acid Bromotrichloromethane - , butyl ester Benzene -, 2-(diethylamino)ethyl ester/styrene Carbon tetrachloride Toluene -, ethyl ester Acetic acid Acetone Acetophenone Benzene -, chloro- , ethyl2-Butanone Butyl alcohol sec-Butyl alcohol tert-Butyl alcohol Carbon tetrachloride
80
Remarks
E, Q(I) E, Q(2)
4.49 22.4
60
Refs.
537 201
J
173
1.6
HH
367
60 70
930 1.04
HH
489 365
70
300
60 80 80 80 80 80 80 80 80 80 80 80 80 80
566
0.158
264
23.6 13.3
335 335
80 80 80 80 80 80 80 80
0.095 0.102 0.281 0.081 0.436 1.428 0.252 0.454 1.604 0.417 0.901 5.640 0.703 2.360 2.067 0.928 1.821 0.311 1.820 0.536 0.919 0.429 0.865 0.702 0.445 0.236 0.436
70 70
0.983 2.05
-
137 137
60 80 80 80 80
0.165 1.971 1.110 0.510 0.510
C C C C
264 183 183 183 183
100 120 60 60 60
900 1000 30800 0.001 0.996
80
Cumene Cyclohexane Ethane, 1,2-dichloroEthane, 1,1,2,2-tetrachloro-
80 80 80 80
Iron(III) chloride Isobutyraldehyde Toluene Methyl methacrylate Acetaldehyde Acetic acid
(7.1 ±0.2) x 104 (8.1 ±0.5) xlO 5
90
Chloroform
-, 1,1,1-trichloroEthyl acetate Ethyl alcohol Heptane 2-Heptanone Isobutyl alcohol 2,4-Pentanedione Toluene - , hexadecyl ester Carbon tetrachloride Cumene - , isobutyl ester Benzene Carbon tetrachloride Chloroform Ethane, 1,2-dichloro- , 1,1,2,2-tetrachloroMethacrylonitrile Carbon tetrabromide
C s (xlO 4 )
60 80
6.5 0.24
S
C C C C
A, F7 A, F7 F7
A
83 83 83 83 83 83 83 83 83 83 83 183 83 183 83 83 183 83 183 83 83 83 83 83 83 83 83
109 109 19 70 21 86 31
Remarks page II-157; References page 11-159
TABLE 4.
cont'd
Solvent/Additive
T (°)
Methyl methacrylate (cont'd) Acetic acid, monochloro- , dichloro- , l,l-dimethyl-2,2,2-trinitroethyl ester - , trichloroAcetone
60 60 45 60 60 80
Acetonitrile, (m-bromophenyl)- , (p-bromophenyl)- , (m-chlorophenyl)- , (p-chlorophenyl)- , (p-methoxyphenyl)- , phenyl- , m-tolyl-,/?-tolylAcetylene,/7-bromophenyl-,/?-chlorophenyl- , /MiitrophenylAluminum, hydrodiisobutyl - , triethyl
60 60 60 60 60 60 60 60 60 60 60 60 50 60 60 80 100 30 50
Aniline - , MN-dimethyl-
60 70 80 100 60 60 80 100 60 25 60 60 60 50 50 60
- , AW-divinyl- , Af-methylp-Anisaldehyde Anisole - , />-ethynyl-,/j-isopropyl-,p-methylAnthracene Azobenzene Benzaldehyde -,/j-bromo-, m-chloro-,p-chloro-,/?-cyanoBenzene
60 60 60 60 25 30 50 52 60 75 80
- , allyl- , bromo-,
tert-butyl-
90 60 25 80
C 8 (xlO 4 ) 0.64 0.80 520 1.10 0.195 0.225 0.275 3.89 2.78 4.28 3.21 19.0 5.18 5.75 7.83 41.3 38.9 127.5 3600 1550 1240 4.2 6.3 9.0 2.45 18 30.4 430 11.3 10.8 17.0 20.0 340 7.0 10.0 13.3 1.11 0 40.3 3.46 0.57 0 100 2.5 0.86 1.43 0.96 1.03 2.06 0 0.01 0.036 0.027 0.040 0.83 0.33 0.075 0.080 0.24 0.036 400 0 0.260
Remarks R R R A
K K K S R, F2 F2 F2 F2 F16 H A, F2 A, F2 A, F2 F2 F2 F2 D K
C
D
C C A Il D A
Refs. 529 529 110 529 81 31 81 462 461 462 461 461 461 462 461 151 151 151 156 547 156 424 424 424 508 228 409 161 424 270 424 424 82 424 424 424 495 16 151 406 496 15 282 86 495 495 495 495 495 16 508 147,327 81 81 181 123 31 81 145 147 502 16 31
TABLE 4. cont'd J( 0 C)
Solvent/Additive Methyl methacrylate (cont'd) -, chloro-
-,/7-diisopropyl-, - , ethyl-
25 60 80 ra-dinitro-
- , ethynyl-, Benzene sulfonylchloride -,/7-chloro-,/7-dimethylBenzonitrile -,p-hydroxy- , p-isopropylp-Benzoquinone - , 2,3,5,6-tetrachloroBenzothiazolethion, 3-allylBenzyl ether Bibenzyl Biphenyl, 2,2-methyleneBorane, tributylBromoform Butane, 1-chloro-, 1,1,1-trinitro1,4-Butanediol 2-Butanone
1-Butene - , 3,4-epoxy-2-methyl2-Butene, cis- , trans3-Buten-2-ol, l-chloro-3-methylButyl alcohol sec-Butyl alcohol tert-Butyl alcohol
60 50 52 60 80 60
fluoro-
25 60 60 60 25 60 50 60 44.1 50 60 44.1 60 25 60 50 60 60 60 77 80 45 60 80 60 70 75 80 40 50 80 40 50 40 50 80 60 80 60 80 60 80
Butylamine, N-nitroButyl ether 1-Butyne, 1-phenylButyraldehyde
45 60 60 50
Carbon tetrabromide
30
C s (xlO 4 )
0 0.074 0.200 0.207 5.72 52 0.501 0.766 1.311 1.350 2.1 21.9 22.3 0 5.16 8.56 4.06 0 0.162 6.0 4.99 5.5 x 104 5.7 x 104 4.5 x 104 2600 153 10.4 8.0 0.0 41.8 53.5 7.45 23 1.20 8300 0.61 1.07 0.45 0.56 0.83 0.70 3.1 5.1 29.6 3.2 4.9 3.0 5.2 18.8 0.394 0.25 0.259 0.85 0.085 0.100 0.152 0 0.8 10.8 1.47 2.25 3.40 2800 ±600 1000 ±100
Remarks
Refs.
D
16 81 31 81 406 15 81 81 81 31 145 151 150 16 543 543 543 16 150 479 406 194 15 42 194 502 368 368 354 567 567 156 506 31 110 421 421 290 123 123 31 287 287 269 287 287 287 287 269 479 31 479 31 81 31 81 110 86 150 500 500 500 521 521
A
A Il K J D R R R D
D F2
D, C, R A F24 F24 C C C A
A A A
W8 W7 D, R, JJ3a D, R, JJ3b
Remarks page 11-157; References page 11-159
TABLE 4. cont'd Solvent/Additive
T( 0 C)
Methyl methacrylate (cont'd) Carbon tetrabromide (cont'd)
Carbon tetrachloride
60 60 60 80 100 20 30 50 60
70 80
Chloroform
60 80
Copper(II) chloride Cumene
60 60 80
-,p-bromo-
60
-, p-tert-butyl-,/7-chloroCyclohexane
60 60 60 80 80 60 60 50 79.5 80 44.1 60 79.5 79.5 60 60 60 80 45 60 80
-,methyl- , trans-lA-, diacetate - , cis/trans-1,4-, dicarboxylic acid dimethylester Cyclotetrasiloxane, octamethylp-Dioxane Diphenylamine Diphenylamine-T Disiloxane, l,l-dimethoxy-3,3,3-trimethyl-l-phenyl- , hexamethylEpibromohydrin Epichlorohydrin Ethane, 1,2-dichloro- , nitro- , 1,1,2,2-tetrachloro- , 1,1,1-trichloro- , 1,1,1-trinitroEthyl acetate
80 45 60
C s (xlO 4 ) 1000 ±500 50Od= 200 2700 1500 1900 3300 4600 0.2 20 0.20 0.82 0.925 2.40 5 20.11 18.52 0.42 0.5 1.74 2.393 2.421 3.3 24.4 0.454 1.77 1.129 1.400 1.9 1.9 105 x 105 1.9 2.56 1.9 2.4
Remarks
Refs.
D, R, JJ3c D, R, JJ3d F2
521 521 109 568 568 109 109 35 451 514 514 81 181 86 529 529 568 568 514 31 81 145 427 81 181 81 31 145 427 36 7 406 31 145
F2 F2 C, D D, F2
C R R, H R R, H A Il D C A Il D F7 A Il
3.71
2.74 3.07 12 0.10 0.195 8.46 1.16 2.5 0.080 0.222 0 0.3 0.032 0.104 16.53 9.3 0.35 0.756 2.0 0.155 0.200 0.235 0.600 1400 0.100 0.13 0.132 0.134 0.155
406
A A C C C A F2 R R
A A C A C
406 406 86 31 31 569 569 450 474 31 194 46 474 474 529 529 81 81 110 81 31 81 31 110 316 290,316 216 290 290
TABLE 4. cont'd Solvent/Additive
T( 0 C)
Methyl methacrylate (cont'd) Ethyl acetate (cont'd)
Ethyl alcohol Ethylene glycol Germane, diethylchloro- , ethyldichloro- , triethyl- , triphenylGlycerol Heptane 1-Heptanol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoroHydrazyl, 2,2-diphenyl-l-picryl Hydroquinone Indium, triethylIsobutyl alcohol
70 75 80 60 80 100 60 80 60 60 60 60 60 50 60 44.1 45 131 60 60 80
Isobutyric acid - , methyl ester Isopropyl alcohol
80 60 60 80 100 130
Lead, tetraethyl Malononitrile, furfurylideneMercury, diethyl Methane, bromotrichloro- , bromotrinitroMethane, dichloro- , nitro- , trinitro- , triphenylMethanol 1-Naphthol 2,6-Octadiene, 2,6-dimethylOleic acid, methyl ester Oxime, acrolein- , crotonaldehyde-, ethylisopropenylketone- , methacrolein- , methylacrolein-, methylisobutenylketone-, methylisopropenylketone- , methylvinylketoneOxolane, c/s-3,4-diacetoxyPentane, 2,2,4-trimethyl1-Pentanol, 2,2,3,3,4,4,5,5-octa-fluoro2-Pentanone, 4,4-dimethyl-5,5,5-trinitro-
60 44.1 60 30 45 60 80 60 45 60 60 80 100 45 60 60 60 60 60 60 60 60 60 60 60 50 60 45
C s (xlO 4 )
0.156 0.46 0.55 0.83 0.240 0.40 0.625 0.80 0.28 0.60 22000 39300 5800 18500 0.152 1.8 2.8 20OxIO 5 7.0 100 332 0.10 0.505 0.229 0.250 0.900 0.26 0.583 1.907 3.00 8 43 45 3.14 1.2 x 104 0.898 830 1.2 xlO 4 4.5 xlO 4 1.0 x 104 0.100 0.217 2.0 5400 4.0 0.2 0.33 0.45 <5.0 6.7 1.68 8.0 25500 500 3000 17000 5200 4700 2900 1300 1.39 1.2 2.36 400
Remarks
C 110 C C A A, F2 A, F2 A F24 F24 A, R A, R A, R A, R F2 A
A A
A C C C S D, Q3 D D, Q4
A, F2 A, F2 A
C F2
Refs.
290 146 123 123 31 423 423 49 421 421 539 539 539 539 479 206 442 194 30 398 156 81 479 81 31 31 275 81 81 49 337 337 480 156 194 156 311 311 311 110 81 81 86 110 44 423 423 49 30 324 441 7 555 555 555 555 555 555 555 555 569 206 442 110
Remarks page II-157; References page II-159
TABLE 4. cont'd Solvent/Additive Methyl methacrylate (cont'd) - , 4-methyl3-Pentanone
Pentasiloxane, dodecamethylPhenol - , 0-bromo-,/7-bromo- , o-chloro- , o-ethyl-,/?-ethyl- , 0-isopropyl- , /?-isopropyl-,/7-methoxy- , 2,3,4,6-tetramethylPhenyl ether Phosphine, octyl-,phenyl- , tributylPhthalic acid, dimethylester Piperidine, 1-nitrosoPropane, 1,2-dichloro- , 1,1-dinitro- , 2,2-dinitro- , 1-nitro1,2-Propanediol 1-Propanol, 2,2,3,3-tetrafluoroPropene, 1,3-diphenyl1-Propene, 2-methylPropionic acid, 2,2,2-trinitroethyl ester Propionitrile, 3-phosphino- , 3,3/-phosphinylidenediPropyl alcohol
Pyridine Pyrocatechol - , p-tert-buty\Pyrogallol Silane, (oc-bromotolyl)trimethoxy- , bromomethylphenyltrimethoxy- , chlorotrimethyl- , dichlorodimethyl- , dichloromethyl- , diethylchloro- , dimethoxymethylphenyl- , dimethylphenyl- , hexamethoxy-^^'-thiodipropyDbis- , methyldichloro- , (3-mercaptopropyl)trimethoxy- , tetraethyl- , tetramethyl- , trichloro - , trichloromethyl-
J(0C)
80 60 80
79.5 50 50 50 50 50 50 50 50 45 45 25 60 60 60 60 30 45 80 45 45 45 60 80 60 60 40 50 45 60 60 60 80 100 70 45 45 45 79.5 79.5 30 50 30 50 79.5 60 79.5 60 79.5 79.5 60 79.5 60 30 50 60 30 50
C s (xlO 4 )
0.700 0.833 1.729 1.775 2.7 0.145 2.5 5.0 5.0 3.5 7.2 7.5 13.3 13.3 <5.0 11.0 6.42 9.13 2.3 x 104 16.IxIO4 30.6 0.2 8.2 0.675 68 15 5 0.48 0.86 1.86 15.6 2.5 4.4 3000 1.4 x l O 4 1.3 x 104 0.69 0.84 1.25 0.176 <5 9 26 29.8 29.8 144 2.2 175 2.45 15.2 1700 0.20 0.2 300 25.8 15.2 3100 6930 5.75 5.0 1.3 5000 185 2.7
Remarks
A
A Il
D
S
A
F24 F24 F2
A, F2 A, F2 A
R D, F2 D, F2
A, R R A, R R R A, R R D, F2 A, R D, F2
Refs.
31 81 81 31 145 474 479 479 479 479 479 479 479 479 30 30 368 368 295 295 156 508 110 31 110 110 110 421 421 442 567 287 287 110 295 295 423 423 49 514 30 30 30 474 554 451 249 451 249 474 539 474 554 539 554 554 539 554 156 451 249 539 451 249
TABLE 4. cont'd T( 0 C)
Solvent/Additive Methyl methacrylate (cont'd) - , triethyl - , triisopropoxymethyl-
60 79.5
- , trimethoxymethyl-
79.5
- , trimethoxyphenyl-
79.5
- , triphenylSilicon chloride
60 30 50 79.5 79.5 79.5 79.5 79.5 79.5 79.5 79.5 79.5 79.5
Siloxane, l,l-dimethoxy-trimethyl-l-phenyl-di-3,3,3- , dodecamethyl penta- , l,l,l,3,5,5,5-heptamethyl-3-phenyltri- , 1,1,1,3,5,5,5-heptamethyl-tri- , 1,1,1,3,5,5,5-heptamethyl-tri- , l,l,l,3,5,5,5-heptamethyl-3-(3,3,3,3-tri-fluoropropyl)-tri- , hexamethyl-di- , hexamethyl-phenyl-tri- , l,l,l,5,5,5-bexamethyl-3-(2-phenylpropyl)-tri- , 3-(3-mercaptopropyl)1,1,1,3,5,5,5-heptamethyl-tri- , octamethyl cyclotetra- , octamethyl triSorbit-2,5-diacetate, 1,4:3, 6-, dianhydroStearamide, JV-allylStearic acid, methyl ester Stibine, tributyl Tin, tetrabutyl Toluene
79.5 79.5 60 90 60 60 60 20 52 60
70 80
-, p-bromo-, -,p-chloro-, a-chloro - , p-ethynyl-,p-nitro-, 2,4,6-trinitrom-Tolunitrile, a-cyanop-Tolunitrile -, a-cyanoTributylamine Triethylamine
ra-chloro-
Tripropylamine Trisiloxane, 1,1,1,3,5,5,5-heptamethyl- , - , 3-(p-methylphenethyl)- , - , 3-phenyl- , - , 3-propyl- , - , 3-(3,3,3-trifluoropropyl)-
60 60 60 60 60 44.1 44.1 60 60 60 70 20 60 60 79.5 79.5 79.5 79.5 79.5
C s (xlO 4 )
200 0.697 0.697 0.331 0.331 0.053 0.053 1200 256 3.0 0.032 0.145 0.232 0.284 0.189 0.205 0.104 1.84 2.08 1284.5 0.08 0.0316 29 3.01 0.282 <1.0 1.32 0.04 0.084 0.170 0.190 0.202 0.250 0.26 0.400 0.45 0.567 0.292 0.303 0.52 0.525 0.91 0.58 0.48 0.49 4.17 64.4 0 500 4.55 0.73 1.74 25.7 1.5 8.3 1900 14.6 0.284 2.08 0.232 0.189 0.205
Remarks
A, R
Refs.
R R R R R R R R R R
539 474 554 474 554 474 554 539 451 249 554 554 554 554 554 554 554 554 554 554
R R C
554 554 569
R R R A, R D, F2
C, J
C, D C C C C C C Il A C
C K
C, D J
173 441 156 156 35 81 21,81 316 32,316,317 316 275 316 496 123 32 81 145 31 123 496 496 496 181 151 194 194 462 496 461 270 35 24 25 156 474 474 474 474 474
Remarks page 11-157; References page 11-159
TABLE 4. cont'd Solvent/Additive Methyl methacrylate {cont'd) - , l,l,l,5,5,5-hexamethyl-3-phenyl- , octamethylUrea, thioWater
m-Xylene p-Xylene 2,4-Xylenol Naphthalene, 1-vinylNaphthalene Nonanoic acid, vinyl ester Toluene 1-Octene Butyl alcohol sec-Butyl alcohol Ethyl alcohol Isopropyl alcohol Methanol Phthalimide, N-vinylChloroform Ethane, 1,2-dichloroMethane, dichloro2-Picoline, 5-vinylAllyl ether 1-Propene Carbon tetrachloride Chloroform 1-Propene, 3-chloroCarbon tetrachloride Hydrochloric acid 1-Propene, 2-methylCarbon tetrachloride - , 3,3,3-trifluoroCarbon tetrabromide Propionic acid, vinyl ester Toluene Propylene Bromoethane
J( 0 C) 79.5 79.5 42 60 80.5 60 60 50
30-50
50 60 70
11.1 13.9 15.2
117-118 117-118 115-118 30-35 120-125 116-120 55 55 55 70 100 100
Styrene Acetaldehyde
270 520 230 630 520 110
Remarks
A, R F7, F24
4800 1.8 x 104 5.4 xlO 4
100
17.0 x 104 640000
474 474 503 268 479 529 48 496 496 479
R R R
357 357 357
C C C D C C
381 381 381 381 381 381 313 313 313
21.4 (5-10) x 104 1.03 x 104
Refs.
216
3.4 0.35 0.97
100 80
11 C C
210 210
C Ql Q2
210 238 238
C
210
C, Q(I-3)
570
-
1.4
50 75
1200 1400 1500 1800 1700 1900 1800 2200 2100 2700 17200 ±1100 33000 ± 15000 17000 ±800 299000 ± 8000
Q(I-4) Q(I) Q(2) Q(3-4) Q(I) Q(2) Q(3-4) Q(l-2) Q(3-4) Q(l-4) W23, Q(I) W23, Q(2) W24, Q(I) W24, Q(2)
517 517 517 517 517 517 517 517 517 517 518 518 518 518
13800 ±800 266000 ± 10000
W20, Q(I) W20, Q(2)
518 518
125
Stearic acid, vinyl ester Toluene
1.84 0.032 1.21 0 0.002 0.03 0 0.43 0.50 6.5
60
100
Chloroform
C s (xlO 4 )
150 95
50 70
20.7 21.6
60
8.5
158
R R
357 357 86
TABLE 4. cont'd Solvent/Additive Styrene (cont'd) Acetamide, N,Af-dimethylAcetic acid - , methyl ester - , bromo- , chloro- , - , methyl ester - , dibromo-, ethyl ester - , monochloro- , dichloro-, -, -, -, -,
dichloro-, ethyl ester iodophenyl- , ethyl ester tribromo-
- , -, ethyl ester - , trichloro-
-, - , ethyl ester
T( 0 C)
50 60 40 100 60 68 68 60 100 90 60 60 60 68 60 100 90 90 60
Acetic anhydride Acetoacetic acid, ethyl ester - , 2-acetyl, ethyl ester Acetone
60 90 100 60 100 100 60
- , oxime Acetonitrile - , m-bromophenylAcetonitrile, p-bromophenyl-, m-chlorophenyl-,/7-chlorophenyl-,/?-methoxyphenyl-,phenyl-, m-tolyl-,/7-tolylAcetyl bromide Acetyl chloride, chloroAcetylene, p-bromophenyl- , p-chlorophenyl-,/7-nitrophenylAdipic acid, diallyl ester - , di-(3,3,5,5-tetramethyl-4-nitrosocyclohexyl) ester Allyl alcohol Aluminum, hydrodiisobutyl
60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 60 100
- , triethoxy- , triethyl
100 100
-, triisobutyoxy- , triisobutyl Aniline
100 110 50 60 50
- , MN-dimethyl- , AW-divinyl-
60
C s (xlO 4 )
0.743 4.6 2.22 0.33 430 300 200 0.3 0.75 2700 28.6 0.76 35.0 1.0 1.3 8000 6.0 8.8 3.0 x 104 2.4 xlO 4 10.5 x 104 270 66.0 100 3.75 65.0 90.0 145.0 0.7 1.3 3.0 4.1 <0.5 0.32 2.2 0.44 66.7 68.5 65.2 66.0 51.0 45.1 48.5 49.2 8600 3300 188.5 161 3130 6.0 1.1 x 104 1.5 26.9 x 104 28.OxIO 4 <0.1 8.05 x 104 17.OxIO4 <1.0 28.5 x 104 20 2.0 12 53 130
Remarks
C
A A C R R, H R R, H A A C C A R R, H A C A A C A A A A
S K K K F9, J A A A A A A F2 A F2
Refs.
375 113 385 72 112 149 149 128 128 64 529 529 529 529 128 149 128 72 178 64 64 178 128 529 529 128 64 128 128 72 72 182 128 501 128 128 462 461 462 461 461 461 462 461 112 112 151 151 151 446 314 128 156 155 155,156 156 155 155 155 154 128 154 161 82
Remarks page 11-157; References page 11-159
TABLE 4. cont'd Solvent/Additive
T (°)
C s (xlO 4 )
Styrene (cont'd) Aniline, N-methyl- , 2,4,6-trinitro/7-Anisaldehyde Anisole,/7-ethynyl- , m-isopropyl- , p-isopropyl- , p-methyl-,2,4,6-trinitroAnthracene - , dihydro2H-Azepin-2-one, hexahydroAzobenzene Benzaldehyde
50 50 60 60 60 60 60 50 44.1 50 130 70 60
13 11.8 x 104 2.86 60.0 5.23 3.23 0.78 20.3 x 104 2.OxIO 4 610 0.61 750 4.54 5.5 2.6 12.2 13.7 8.63 5.6 76.7 3.9 5.8 0.01 0.018 0.023 0.028 0.04 1.92 5.50 6.67 0.061 0.121 0.156 0.184 0.23 0.31 0.42 0.81 0.89 1.5 36 1.78 3 6.22 0.04 0.06 0.193 0.55 0.133 1.50 0.235 0.874 0.54 0.6 58.5 x 104 1950 7.02 10.70
-,/7-bromo-, m-chloro-,/7-chloro-,p-cyanoBenzene
100 60 60 60 100 60 35 40 50 60
70 75 80
100
132
-, allyl-, bromo- , sec-butyl- , tert-bx\ly\-
100 60 155 60 60
- , chloro-
80 100 60 80
- , - , 2,4,6-trinitro- , 1,2-dibromoethyl-,/?-dibutyl - , /?-di-seobutyl- , p-<\i-tert-bu\y\-
100 140 50 60 60 60 60
0.87
- , m-dichloro-
140
- , o-dichloro-,/7-dichloro-
60 60
0.2 1.4 3.4 2.6
Remarks F2
Refs.
H H
154 370,372 495 151 405 406 496 370,372 159 271 108 281 495 86 298 495 495 495 298 495 119 119 327 127 79 255 145 415 123 123 185 255 273 127 145 235 235 235 127 145 524 182 237 415 145 127 185 127 255 182 255 185 235 58 370,372 112 415 415
H
415
C C
58 67 182 182
K
J D C, I C A
A F2 F2 A C A, 15 H C C 15 C A A, 15 A A A A A, 15 A, R C A H A, 15 A 15 A C C C 15 A
TABLE 4. cont'd Solvent/Additive
T( 0 C)
C s (xlO 4 )
Remarks
Styrene (cont'd) Benzene, diethyl-, (mixture)
100
A A A
-, ethynyl-
60
-, -, -, -,
60 60 60 40 50 60 44.1
3.35 6.33 5.13 3.30 6.60 0.67 0.70 0.710 0.83 2.7 1.07 1.113 1.38 1.62 2.2 2.33 2.31 2.9 4.9 96.3 98.3 12.76 9.43 13.30 9.48 x 105 6.43 x 105 3.51 x 105 1.3 x 105
70 50 60 60 60 44.1 60 80 45 80 80 80 80 80 25 60 60 60 80 60 60 100 100 60 100 60 100 60 100 60 60 100 60 80 100
700 5.72 x 105 40 5.3 18.6 1.4 x 105 22.7 x 105 56.6 x l O 5 53.2 x 105 4.3 x 105 21.OxIO 5 95.0 x 105 6700 2.6 x 105 71.6 62.4 3020 1.12 x 104 1.2 x l O 4 142 97.9 <0.1 34.8 0.06 0.35 0.04 0.37 1.2 0.3 0.43 1.85 5.5 3.2 5.6 9.3
-,/?-diisopropyl-,ethyl-
132 60 60
80 100
132
sec-hexylsec-pentyltri-sec-butyl1,3,5-trinitro-
Benzo[B] chrysene Benzoic acid -, m-(phenylazo)-, methyl ester - , 2,4,6-trinitro-, ethyl ester Benzoin Benzonitrile -,/7-isopropyl Benzo[A]pyrene p-Benzoquinone /7-Benzoquinone, 2-anilino- , 2,5-dimethyl- , 2-methyl- , 2,3,5,6-tetrachloro- , 2,3,5,6-tetramethyl- , 2,3,5-trimethylBenzyl ether Bibenzyl, ococ'-dibromoBicyclohexyl, 3,3,3',3',5,5,5',5'-octamethyl-4,4'-dinitrosoBiphenyl, 2,2 '-methyleneBorane, tributoxy- , tributyl Butane, 1-bromo- , 1-chloro-, 2-chloro- , 2,2-dimethyl- , 1-iodo1,4-Butanediol
A C A, 15 C 15 C A A A, 15 A A A A, 15 K J H H H
J C A J J J J J J J J D F9, J F9, J
A A A A A, S A A A F24 F24 F24
Refs. 235 235 235 497 406 127 79 255 145 363 185 255 235 127 145 235 235 127 145 151 150 415 415 415 372 370,372,373 372 159 281 370,372 128 150 406 159 42 27 199 27 27 27 27 27 368 368 112 314 314 567 567 156 156 128 128 128 128 128 128 304 128 128 422 422 422
Remarks page II-157; References page 11-159
TABLE 4. cont'd Solvent/Additive Styrene (cont'd) 2-Butanone
T( 0 C)
1-Butene - , 3,3-dimethyl-2-phenyl- , 2,4-diphenyl- , 3,4-epoxy-2-methyl- , 2-methyl- , 3-methyl-
60 70 75 100 110 110 80 100 100
2-Butene - , 1,4-dichloro- , 2,3-dimethyl-
100 80 100
-,2-methyl3-Buten-2-ol, l-chloro-3-methylButyl alcohol
100 80 40 50 60
sec-Butyl alcohol terf-Butyl alcohol
Butylamine terf-Butyl ether tert-Buty\ isocyanide 1-Butyne, 1-phenylButyraldehyde
60 50 60 80 100 130 60 60 80 100 60 50
- , diallyl acetal Butyric acid, 4-hydroxy-, y-lactone Cadmium, dibutyl Carobonic acid, cyclic ethylene ester - , diallyl ester - , di-(3,3,5,5-tetramethyl-4-nitrosocyclohexyl) ester Carbon tetrabromide
60 100 60 50 100 50 60 60 80 40 60
60 60 70 80 90 100
C s (xlO 4 ) 4.98 8.60 12.00 2.6 10 70 17.4 3.1 6.9 6.1 2.0 51 5.4 5.1 2.9 8.2 11.2 6.5 0.06 1.6 0.562 6.6 0.22 6.65 0.345 0.55 1.0 0.5 2.6 1.0 33.0 34.3 2.7 14.3 2.7 3.7 4.0 4.7 8.0 8.0 11.7 14.3 5.7 11.0 20.2 0.409 1170 0.235 6.2 1.3 x 104 1.4 x l O 4 1.8 x 104 1.78 x l O 4
2.2 x 10 4 2.5 x 10 4 13.6 x 10 4 4.2 x 10 4 (5.09 ±0.18) xlO 5 88300 40600 1.8 x 10 4 2.3 xlO 4 2.51 x 10 4 2.35 x 10 4
Remarks C C C A A A A A A, R A C A A, R A F24 A A, C
A A A A C, F2 C, F2 W8 F29, W8 F29, W16 F2, W7 F29, W7 F2, W15 F29, W15 F2 F29 A A
E F27, J F9, J F2 C
F2 Fl A 112
F2 C A
Refs. 182 123 123 358 433 433 269 358 358 524 358 112 358 524 358 269 119 430 128 323,385 479 430 422 385 422 261 261 128 301 301 4,75 150 412 412 414 414 413 414 413 414 413 414 128 128 446 375 156 458 446 314 314 109 64
109 109 128 487 520 568 568 61 109 64 128
TABLE 4. cont'd Solvent/Additive
F( 0 C)
C s (xlO 4 )
Remarks
80 100 17 248 69 84 87 90 92 98 100 109 110 120 122 144.1 130.9 148 92 110 18 117 133 34.1 148 186 185 304 300 0.41 0.5 0.566 3.40 4.0 0.50 0.916 3.3 11 33 43 22.1 39 <5 0.8 0.82 1.04 3.88 1.31 2.00 2.90 8.29 7.57 3.46 6.90 0.024 0.031 0.04 0.063 8.5 0.066 0.083 0.156 0.16 0.23
W8
Refs.
Styrene (cont'd)
Carbon tetrachloride
50 60
60 60 76 80 85 95
Chloroform
100 132 140 60
68 80 Chloroform/acetone m-Cresol 0-Cresol p-Cresol - , a-phenylCumene
60 50 50 60 50 60 60 60
80 100 - , m-bromo-,/7-bromo- , p-tert-butyl-,p-chloroCyclohexane
60 60 60 60 60
80 100
Q36 C, W8 C C, W7 A C Q142 A, X R R, H X C A 15 Q38 Q142 A A A A C C 15 C
A A, 15 15 A A, 15
A A, 15 C F23 15 C A A, 15
412 412 513 513 63 401 113,183 401 128,129,210 401 366 63 223 416 114 529 529 115 568 568 236 236 185 163 63 63 128,129 129 58 501 128,210 255 182 149 185 255 501 247,248 247,248 121 247,248 121 121 7 127 145 406 185 127 145 405 406 406 406 127 79 145 255 119 185 255 273 127 145
Remarks page 11-157; References page 11-159
TABLE 4.
cont'd
Solvent/Additive
T( 0 C)
Styrene (cont'd) Cyclohexane (cont'd) 132 Cyclohexanone •-, trans-lA-, diacetate - , cis/trans-1,4-, dicarboxylic acid dimethylester Cyclopentanone 1-Cyclopentene- 1-carboxylic acid, 3,3,5,5-tetramethyl-4-nitroso-, diester with pyrocatechol Cyclotetrasiloxane, octamethyl1,2,3,4-Dibenzpyrene 1,2,7,8-Dibenztetracene 1,2,9,10-Dibenztetracene p-Dioxane
Diphenylamine-T Disiloxane, hexamethylEpibromohydrine Epichlorohydrine Ethane, 1,2-dibromo-,1,2-dichloro-
60 60 60 60 60 80 50 44.4 44.4 44.4 60 100 60 79.5 60 60 60 80 60 70 80
- , pentaphenyl- , 1,1,2,2-tetrachloro- , l,l,2,2-tetrachloro-l,2-difluoro- , l,l,2-trichloro-l,2,2-trifluoroEthanehexacarboxylic acid, hexaethyl ester 1,1,2-Ethanetricarboxyic acid Ether, benzyl methyl -, p-bromobenzyl methyl - , p-chlorobenzyl methyl -, /7-cyanobenzyl methyl - , dodecyl vinyl Ethyl acetate
Ethyl alcohol Ethylene, 1,1-diphenylEthylene glycol - , bis(m-phenylazobenzoate) Ethyl ether Fluorene Formamide, N,AT-dimethyl-
100 60 100 90 90 50 100 68 68 68 68 60 60 70 75 100 60 80 110 60 80 100 70 60 60 100 40 50 60 100
C 8 (xlO 4 )
Remarks
0.31 12.3 0.81 0.87 1.5 7.90 16.9 4.2 3.30
A A, R A A A, 15 C C C C
235 524 235 127 145 182 569 569 182
1.3 x 104 1.0 x l O 4 4.0 6.0 x 104 13.OxIO 4 13.OxIO 4 0 2.28 2.75 0.8 0.9 0.387 67.48 37.87 0.988 1.914 0.333 4.12 1.1 1.137 9.8 3.84 20000 10.8 1.13 0.84 <50 0.94 6.0 6.0 4.0 20.0 3.32 4.11 15.5 5.5 6.67 0.39 1.32 1.611 2.60 450 1.36 2.70 4.70 900 5.64 75.0 124.0 1.09 0.869 4.0 1.08
F27, J F9, J C J J J A, S C C
314 314 450 159 159 159 128 4 182 220 46 474 529 529 255 255 255 182 67 255 112 235 127 235 14 14 89 72 149 149 149 149 4 4 119 123 123 72 423 479 423 432 422 422 422 281 4 127 127 458 375 113 256
F2 R R C C C C C C A A A A A
C C FlO C C F2 F2 A F24 F24 F24 C C A A E
Refs.
TABLE 4. cont'd Solvent/Additive
T( 0 C)
C s (xlO 4 )
Remarks
Refs.
Styrene (cont'd)
Furan, tetrahydroa, D-Glucoside, methyl- , - , 6-deoxy-6-mercapto- , - , 2,3-di-O-benzyl- , - , 2,3,4,6-tetra-O-acejyl- , -,6-0-(p-toluenesulfbnyl)- , - , 2,3,4-tri-0-acetyl-6-deoxy-6-iodo- , - , 6-0-triphenylmethylP, D-Glucoside, methyl- , - , 6-deoxy-6-dipropylaminoGermane, ethyldichloro- , diethylchloro- , triethyl- , dimethylchloro- , triphenylHeptane
50
0.50
100 100 100 100 100 100
55000 62 2.0 2.0 50 21
1-Heptanol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluoro1-Heptene 2-Heptene Hexane 1-Hexene
100 60 60 60 60 60 60 100 60 100 100 100 100
2-Hexene Hydrochloric acid Hydroquinone Hydroxylamine, MW-dibenzyl- , N-benzyl-N-phenyl- , iV,AT-diethylene- , W-ethyl-W-phenylIndium triethyl Iron(III) chloride Isobutyl alcohol
100 100 60 60 60 60 60 100 60 60
Isobutyl alcohol-D
100 130
22 56900 31600 2400 33500 23000 0.42 0.95 13.33 2.7 3.2 0.9 2.5 2.5 3.6 0 3.6 5000 3.8 x 104 2.5 x 104 20.5 x 104 1.760OxIO4 536.0 x 104 0.17 0.497 2.9 7.8 8.2 21.0 2.5 4.6 2.7 3.5 3.5 3.05 4.00 1.7 6.0 2.7 1.6 0.78 1.24 5.2 0.47 0.46 0.42 1.2 700 1200 0.82 1.2 x 104 30.0 62.0 0.88 0.72
Isobutyraldehyde Isobutyric acid
60
Isobutyronitrile
100 130 60 60 80 100
Isophthalic acid, diallyl ester Isopropyl alcohol
Isopropyl alcohol-D Isopropyl-1-D alcohol-D Lead, tetraethyl Malonic acid, diallyl ester - , diethyl ester - , dimethyl ester - , acetyl-, diethyl ester - , bromo-, diethyl ester - , butyl-, diethyl ester - , dibromo-, diethyl ester - , dichloro-, diethyl ester - , diethyl-, diethyl ester - , ethyl-, diethyl ester
130 100 100 100 60 60 100 100 100 60 100 100 60 60 100 100 100
C
449 220 220 220 220 220 220
A, R A, R A, R A, R A, R A A F2 A A A A A, R A A R R R R A A A W8 C A A A F2 F2 A F2 A A A A
A A A A A
220 539 539 539 539 539 127 127 442 358 358 358 358 524 358 238 128 533 533 533 533 156 19 385 479 261 261 412 412 385 385 261 261 446 423 423 261 423 261 261 261 156 446 128 72 72 72 128 128 72 128 128 128 72 72
Remarks page 11-157; References page 11-159
TABLE 4. cont'd Solvent/Addition
J( 0 C)
Styrene (cont'd) Malonic acid, phenyl-, diethyl ester Mercury, diethyl Methane, bis(2-chloroethoxy)- , bromotrichloro-
100 100 80 80
60-80 - , dibromo- , dichloro- , diiodo- , diphenyl- , nitro- , triphenyl-
80 60 60 80 100 60 60 100
Methanetricarboxylic acid Methanol
60 60 80 100 100 60
- , (4-biphenylyl)phenyl(p-vinyl-phenyl)- , bis(4-biphenylyl)(/?-vinyl-phenyl)Naphthalene - , decahydro- , 2-isopropenyl-
80 100 50 50 60 60 80 99
- , 2-methoxy- , 1,2,3,9-tetahydro-l-phenyl1-Naphthol - , 2,4-dichloro1-Naphthol-D 2-Naphthol Naphtho[2,3-a]pyrene 2,6-Octadiene, 2,6-dimethyl2-Octene Oleic acid, methyl ester
60 60 60 60 60 60 44.4 60 100 60
Oxalic acid, diallyl ester - , diethyl ester Oxetane, 3,3-bis(chloromethyl)Oxime, acrolein - , crotonaldehyde- , ethylisopropenylketone- , methacrolein- , methylacrolein- , methylisobutylketone-,methylisopropenylketone-, methylvinylketoneOxolane, ds-3,4-diacetoxyPentane, 1-chloro- , 2,2,4-trimethyl2,4-Pentanedione
70 90 60 60 50 60 60 60 60 60 60 60 60 60 60 100 100
C s (xlO 4 )
3.5 0.335 6.0 7.6 x 104 7.7 x 104 2.4 xlO 6 2.78 x 106 6.5 x 105 (6.5 ±0.4) xlO 5 9450 110 0.15 9.5 11.8 710 2.3 4.2 35 10 3.5 6.0 8.0 0.91 0.296 0.74 1.10 1.22 3.5 3.5 11 0.4 56 70 69 86 <5.0 10000 480 490 75 77 24.0 x 105 2.0 2.8 3.15 3.52 455 420 6.64 4.2 13.5 8.0 10800 1500 4300 13000 400 2300 1100 2700 1.89 0.49 < 10 2.0
Remarks
C D, Q2 D, Q2 D, Q3 D, Q3 15 A C A A A A, R A A F2 F2 F2
A
C J J J C A C C A F22 C
C A A
Refs.
72 156 112 312 195 312 195 439 504 185 112 128 112 128 112 127 127 524 86 127 44 127 72 479 423 423 423 57 57 216 127 98 98 98 98 121 467 50,121 121 50,121 122 159 324 358 441 441 239 141 441 446 119 449 555 555 555 555 555 555 555 555 569 128 155 72
TABLE 4. cont'd Solvent/Additive Styrene (cont'd) 1-Pentanol, 2,2,3,3,4,4,5,5-octa-fluoro3-Pentanone Pentasiloxane, dodecamethyl1-Pentene - , 4,4-dimethyl-2-phenyl- , 2,4-diphenyl- , 4-methyl-2,4-diphenyl- , 4-methyl-2-phenyl- , 2,4,4-triphenyl2-Pentene - , 2-methyl- , 4-methylPhenol -,/7-benzyloxy - , p-tert-buty\- , 0-chloro-,p-chloro- , 2,6-di-terf-butyl- , 2,6-diisopropyl-,p-fluoro-, m-methoxy-, o-methoxy-,/7-methoxy- , 0-phenyl- , 2,3,4,6-tetramethyl- , 2,4,6-trinitroPhenol-D,/7-benzyloxy- , 2,3,4,6-tetramethylPhenyl ether Phosphine, dibutyl - , diethyl - , octyl Phosphine, phenyl - , tributyl Phosphoric acid, tributyl ester Phosphorus, white (P4) Phosphorus trichloride o-Phthalic acid - , bis(2-methylallyl) ester - , diallyl ester - , di-(3,3,5,5-tetramethyl-4-nitrosocyclohexyl) ester Piperidine Propane, l-chloro-2,3-epoxy- , l-chloro-2-methyl - , l,l,l,3-tetrabromo-3-phenyl- , 1,1,1-tribromo1,2-Propanediol 1,3-Propanediol, 2,2-bis(bromomethyl)-, diacetate 1,3-Propanedione, 1,3-diphenyl1-Propene, 3-chloro-2-methyl- , 2-methyl-, 1,3-diphenylPropionaldehyde, diallyl acetal Propionic acid
T( 0 C)
C s (xlO 4 )
60 60 79.5 100 110 110 110 110 110 100 100 100 50 60 60 60 60 60 60 60 60 60 60 60 60 60 50 60 60 25 60 100 100 60 60 100 100 25 57 75
11.36 2.6 0.285 2.3 10 170 2900 10 2600 4.2 6.3 6.9 8.1 14 290 26 6.0 -11 49 310 54 <5 43 260 <5 580 2.1IxIO 5 10 20 7.94 7.86 2.08 x 104 1.35 x 104 3.6 x 104 43.9 x 104 24.4 <0.1 400 250 800
60 60 80 60 50 60 100 90 90 60 80 100 60 60 60 100 60 60 60
6.3 6.3 1.2 x 104 1.32 xlO 4 1.0 7.5 1.4 3.0 3.65 x 104 2.41 x 104 2.08 3.90 6.80 4.05 7.0 24.0 1.7 87.3 12.3 0.05 4.3 4.5 4.65
Remarks F2 A A A A A A A A A A J
J
J J
D
A A, S E C, D
F9, J F27, J A C A A C C F24 F24 F24 A A A A C A
Refs. 442 385 474 358 433 433 433 433 433 358 358 358 247,248 122 50,121 121 122 121 121 121 121 121 122 121 121 50,121 371 50 50 368 368 296 296 295 295 156 156 99 214 494 446 446 314 314 128 449 128 128 64 64 422 422 422 325 128 128 358 567 446 128 385 323 385
Remarks page 11-157; References page 11-159
TABLE 4. cont'd Solvent/Additive Styrene (cont'd) Propionitrile, 3-phosphino- , 3,3'-phophinylidenediPropyl alcohol Propylene oxide 2-Propyn-l-ol Pyridine Pyrocatechol - , p-tert-buty\Pyrocatechol-D - , p-tert-butylPyrogallol Pyrogallol-D Sebacic acid, diallyl ester Silane, chlorotrimethyl- , dichlorodimethyl- , diethylchloro- , dimethylphenyl- , hexamethoxy-(3,3'-thiodipropyl) bis- , methyldichloro- , 3-mercaptopropyl-trimethoxy- , trichloro- , tetraethyl- , tetramethyl- , trichloromethyl- , triethyl- , trimethoxymethyl- , triphenyl-
T( 0 C)
60 60 60 80 100 50 60 60 60 60 60 60 60 60 60 50 50 60 60 79.5 60 79.5 60 100 50 50 60 70 80 79.5
Silicon chloride Siloxane, hexamethyl-di- , dodecamethyl-penta- , octamethyltriSorbit-2,5-diacetate, 1,4:3,6-, dianhydroStannane, triphenylStearamide, Af-allyl-
60 70 80 50 79.5 79.5 79.5 60 60 90
Stearic acid, methyl ester
60
Stibine, tributyl Stibene, dibromoStyrene, oe-bromo- , p-bromo-,dibromo- , a-ethyl- , a-methyl-
70 90 100 60 70 70 60 110 60 74 80 99
Succinic acid, diallyl ester Succinonitrile, tetraphenylSulfonyl chloride, benzene-,/7-chloro-benzene- , p-methyl-benzene-
110 60 50 60 60 60
C s (xlO 4 )
50000 50000 2.00 3.14 3.60 1.6 7.0 0.6 1340 3600 260 370 10400 1600 4.8 12.5 17.8 5700 2200 118 9800 5.9 x 104 1.4 x 104 8.12 3.1 19.2 1200 33.4 36.8 0.23 0.230 3700 2.44 1.3 20.0 0.387 0.285 0.069 77 3.3 x 104 5.82 8.30 1.06 526 15.6 0.676 58.0 3020 10000 2000 1950 10 0.86 95 3.2 4.9 5.6 8.5 1.67 5.4 28000 4330 7650 3180
Remarks
A A F2 F2 F2 C A A J J J
A, R A, R R A, R R A, R
A, R
R A, R
R R R C A, R A, J C, J C A A
R R R
Refs.
295 295 423 423 423 449 128 128 50,121 50,121 50 50 50,121 50 446 249 249 539 539 554 539 554 539 156 249 249 539 90 90 474 554 539 90 90 249 554 554 554 569 539 173 173 441 239 141 441 156 112 172 172 112 439 431 343 98 98 98 98 431 446 89 543 543 543
TABLE 4. cont'd Solvent/Additive Styrene (cont'd) Sulfonyl chloride,/?-methoxy-benzene-,methane- , phenylmethane- , a-phenyl-P-(methanesulfonyl)-ethaneTerephthalamide, NX-dimethyl-MAr'-dinitrosoTerephthalic acid, diallyl ester Tin, tetrabutyl Toluene
T (°) 60 60 60 60 40 60 60 100 60
80
100
-,p-bromo- , m-chloro-,p-chloro- , oc-chloro-, oc,a-dichloro-, p-ethynyl-,(X- 2 Hi, toluene -, PP- 2 H 2 , toluene - , app- 2 H 3 , toluene - , aaa-trichloro- , 2,4,6-trinitro/?-Toluidine - , AW-dimethyl- , Af-methylm-Tolunitrile, a-cyanop-Tolunitrile -,a-cyanos-Triazine, trimethylTriethylamine
Tripropylamine Trisiloxane, octamethylUrea, l,3-bis(3,3,5,5-tetramethyl-4-nitrosocyclohexyl)Water m-Xylene p-Xylene - , ot,a'-dibromo2,6-Xylenol
132 60 60 70 140 60 60 60 60 80 80 80 60 50 50 50 50 60 60 60 60 60
100 79.5 60 80 60 60 60 60 60
C s (xlO 4 ) 3110 1180 3190 27600 1400 2000 4.5 3.71 0.105 0.121 0.125 0.134 0.16 0.21 0.82 1.10 2.05 0.15 0.298 0.3 0.308 0.310 0.313 0.813 0.53 0.55 0.645 0.72 0.8 1.12 1.30 1.25 0.62 1.8 1.07 1.56 50.0 72.0 0.825 0.820 0.992 57.5 14.6 x 104 78 16 11 91.4 2.07 112 0.468 1.4 3.0 7.1 7.5 24.2 0.069 14500 15000 0.006 0.31 0.78 0.84 150 110
Remarks R R R R
C A A, 15 C C 15 C C C, F17 A C A A A, 15 A
A A K C, F17 C, F17 C, F17 A F2 F2 F2
W9 W6
F9, J F9, J A, R
Refs. 543 543 543 543 160 160 446 156 255 21,24,79 127 78 145 318 496 363 363 385 185 385 255 76,77 78,273 530 235 385 127 235 145 235 496 496 67 67 496 128 128 151 530 530 530 128 370,372 154 154 154 462 496 461 88 364 364 24 363,364 156 474 314 314 479 529 496 496 112 121
Remarks page 11-157; References page 11-159
TABLE 4. cont'd Solvent/Additive Styrene {confd) Zinc, diethyl - , p-chloroAnisole, p-isopropylBenzaldehyde -,p-chloroBenzene, p-diisopropyl-
T( 0 C) 100 60 100 100 60
Benzonitrile, p-isopropylCarbon tetrabromide Carbon tetrachloride Cumene -,p-bromo- , p-terf-butyl--, p-chloro- , p-iodoBenzene - , p-methyl Anisole, p-isopropylBenzene, p-diisopropyl-
60 60 60 60 60 60 60
Benzonitrile, p-isopropylCumene -,p-bromo- , p-terf-butyl-,p-chloro- , pentafluoroBenzene, bromo- , chloro-,ethyl- , fluoro2-Butanone, 3-methylCumene Furan, tetrahydro-
60 60 60 60 60
2-Pentanone, 4-methylToluene Styrene/Styrene, p-chloroCarbon tetrachloride
60 60
Succinimide, N-vinylAcetic acid Ethane, 1,2-dichloroValeric acid, 4-methyl-, vinyl ester Benzene Vinyl acetate Acetaldehyde
Acetamide, N-butylAcetic acid
C s (xlO 4 )
Remarks
3660 3.86 1.9 9.7 3.62 7.24 8.84 52000 45 3.44 5.71 3.52 4.97
Refs. 156
A A
F2
406 298 298 497 406 406 109 366 406 406 406 406
50
0.2
56
60 60
3.27 3.67 7.34 26.0 4.12 9.23 3.59 7.67
408 408 406 408 408 408 408 408
60 60 60 60 60 60 60
60
0 0 5.35 0.117 1.09 6.76 1.53 1.61 0.033 1.20 15 115
55 55
0.077 0.127
80
6.2
30 45 50 60
400 530 390 0.72 200 220 500 570 660 610 700 40 0.180 0.166 0.200 1.0 1.13 10 0.170
70 75 60 50 60
65
A
EF EE C, F25 C, F26
469 469 469 469 469 469 469 469 469 469 366 366 93 93 201
J 18 F2 J J C 19 F2 C
346 86 460 257 145 232 460 86 86 460 86 86 466 465 466 145 289 86 466
TABLE 4. cont'd Solvent/Additive Vinyl acetate (cont'd) Acetic acid, allyl ester - , benzyl ester - , butyl ester - , sec-butyl ester - , tert-butyl ester - , isobutyl ester - , isopropyl ester
- , methyl ester - , propyl ester - , 1,3,3,3-tetrachloropropyl ester - , bromo- , chloro- , cyano-, methyl ester - , dichloro-, ethyl ester - , phenyl- , trichloro- , ethyl ester - , trifluoro-, ethyl ester Acetic anhydride Acetoacetic acid, ethyl ester Acetone
Acetonitrile -,phenylAcetophenone - , 3'-hydroxy- , 3'-hydroxy-DAniline - , AW-dimethyl- , W-methyl-,p-nitrom-Anisaldehyde o-Anisaldehyde /7-Anisaldehyde Anisole Anthracene
- , 9-phenylBenzaldehyde
T( 0 C)
60 60 50 50 60 50 60 50 50 60 67.5 75 60 50 60 70 60 70 70 60 60 60 70 60 50 60 70 60 70 75 60 60 50 60 70 45 45 50 50 50 50 60 60 60 60 20 30 40 50 60 50 60 70 75
C s (xlO 4 )
85 94 80 13.2 4.4 8.0 1.5 6.2 9.1 3.5 3.1 8.0 9.0 10 1.56 1.6 2.5 6.2 3.4 423.2 489 4450 2550 5000 210 400 1445 4400 30 8.0 80.4 1.5 11.70 12.0 25.6 42 10 2100 91.5 100 62.0 1405 1290 149 210 260 360 48600 2500 420 370 10 6.68 x 105 6.03 x l O 5 4.55 x 105 2.057 x 105 3.64 x 105 2.78 x 105 2.73 x 105 230 460 540 421 600
Remarks
F2 J F2, J
J J
C C, J C C J J C C C
C C J J C J J F2 F2 F2 J J J F2, J J J J J J J J F2 J C,J J
Refs.
86 86 86 208 208 86 208 232 208 208 145,232 86 86 86 145,231 145,232 86 208 145,232 389 386 389 389 86 86 86 389 86 71 86 390 86 289 145 330 184 86 86 15 86 390 51 51 15 154 154 154 15 86 86 86 86 41 41 41 15 41 41 41 145,355 86 86 390 86
Remarks page 11-157; References page 11-159
TABLE 4. cont'd T( 0 C)
Solvent/Additive Vinyl acetate (cont'd) Benzaldehyde, m-chloro- , o-chloro-,p-chloro-, - , p-cyano-,/7-isopropylBenz[A]anthracene Benzene
ra-cyano-
60 60 60 60 60 60 50 60
70 75 - , bromo-
- , tert-butyl- , chloro-
Benzene, o-dichloro-,/7-dichloro- , m-dinitro- , 0-dinitro - , p-dinitro-,ethyl- , nitro- , 1,3,5-trinitroBenzo[B]chrysene Benzoic acid - , ethyl ester -,p-nitroBenzoic anhydride Benzoin Benzonitrile - , m-hydroxy- , m-hydroxy-DBenzo[GHI]perylene Benzophenone Benzo[A]pyrene Benzo[E]pyrene p-Benzoquinone, 2,3,5,6-tetramethylBenzoyl chloride Benzyl alcohol Biphenyl Borane, tributyl
50 60 70 75 60 60
70 75 75 70 45 50 45 45 50 60 50 45 50 50 60 60 50 60 60 50 45 45 50 50 50 50 45 50 70 70 50 60 10
C s (xlO 4 )
860 390 340 1070 610 540 1.17 xlO 5 1.07 1.2 1.2 2.4 2.96 20 5.27 1.4 1.40 3.6 18.9 8.0 9.2 10.0 134.2 25.2 3.61 5.6 6.8 8.0 8.35 80 2.61 12.7 42 11.8 1.05 x 106 645700 9.6 x 105 26.7 x 105 662800 55.15 100 110300 8.9 x 106 434280 2.83 x 105 50 26 245700 130 800 40.6 820 805 1.82 xlO 4 286 3.06 x 105 8400 9.5 x 105 366 300 556 263 6.4 9000
Remarks
J J J J J J J J C C J C W7 W15 C C W7 W15 J C C C C C, J C, J C, J J C, J J J J J J J J J J J J C C
Refs.
86 86 86 86 86 86 41 263 86 294 80 289 294 390 86 263 184 15 265 265 265 389 184 289 265 265 265 289 86 389 184 184 389 28 15 28 28 15 289 86 15 28 15 41 86 86 15 86 86 15 51 51 370 15 41 370 27 15 389 390 15 132 191
TABLE 4. cont'd Solvent/Additive Vinyl acetate (cont'd) Butane, 1-bromo- , 1-chloro- , 1-iodo2,3-Butanedione 2-Butanone -, 3-methyl1-Butene, 3-chloro-3-methyl2-Butene, l-chloro-3-methyll-Buten-3-yne Butyl alcohol sec-Butyl alcohol tert-Butyl alcohol
Butyl ether 3-Butyn-2-ol, 2-methylButyraldehyde
T( 0 C)
60 70 60 60 60 60 75 60 50 50 60 60 70 60 70 75 60 70 60 60 40
60 Butyric acid, ethyl ester - , methyl ester
70 50 60
Carbon tetrabromide
60 70
Carbon tetrachloride
0 20 45 60
Chloral
Chloral hydrate Chloroform
2-Chloro-3-(methyl-14C)-lbutene(4-14C) 3-Chloro-2-pentene-(2,4-14C)
70 75 60 70
70 30 60
70 50 50
C s (xlO 4 )
50 1100 10 800 670 73.80 165 118.16 28900 4300 0 20.0 20.39 29.1 31.74 6.21 95.0 0.46 0.5 1.3 12.1 76 400 440 510 590 670 650 1000 388 45 18 19 7.39 x 106 28740 1500 4700 7600 800 1300 4700 6700 7300 8000 9000 9600 10000 10500 10700 2023 10500 5000 4927
4312 100 140 125.18 130 150 160 170 554 3980 628
Remarks
C F2, J C F2 F2 J 19 C C C 19 C,J J W8 W7 W15
C C F2 C E J Ql Q2 Q3 Q4 F2 Q5 Q6 J Q7 Q8 C J C
C
19 J F2 C F2 F2
Refs.
86 389 86 86 86 289 184 289 152 152 232 145 289 390 289 390 184 289 145 86 390 86 86 500 500 500 500 232,355 86 390 71 145,232 86 109,145 389 346 309 86 10 10 10 10 86 10 10 86 210 10 10 389 86 86 389
389 345 346 289 145 86 210 86 389 509 509
Remarks page II-157; References page 11-159
TABLE 4. cont'd Solvent/Additive Vinyl acetate (cont'd) Chrysene w-Cresol m-Cresol-D p-Cresol p-Cresol-D Crotonaldehyde Cumene
Cyclohexane
T( 0 C)
50 45 45 45 45 60 60 70 75 60
-,methyl-
60
1,3-Cyclohexanedione, 5,5-dimethylCyclohexanol Cyclohexanone
70 70 60 75 60
Cyclohexene Dibenz[a,h]anthracene Dibenzo[def,mno]chrysene 1,2,3,4-Dibenzpyrene Diethylene glycol Diethylphosphonate
p-Dioxane Diphenylamine Diphenylamine-D Diphenylamine-T Ethane, 1,1-dibromo- , 1,2-dibromo- , 1,1-dichloro- , 1,2-dichloro-, -, -, -, -,
75 50 40 50 60 50 70 60 60 60 60 60 70 50 60 60 60 60 70 60 60
1,2-dichlorohexachloropentachloro1,1,2,2-tetrabromo1,1,2,2-tetrachloro-
70 70 70 60 60
- , 1,1,1-trichloro- , 1,1,2-trichloro1,1-Ethanediol, diacetate Ether, benzyl methyl - , bis(2-chloroethyl) - , dodecyl vinyl
70 60 60 60 60 70 60
-,ethyl Ethyl acetate
60 20 40 50 60
C s (xlO 4 )
3360 375 85 710 130 1800 89.9 100 139 356 6.59 7.0 100 11.75 24 5580 127 180 670 620 1600 770 8.7 x 104 156.5 x 104 129.2 xlO 4 105.4 xlO 4 73.6 x 104 85.3 350 910 830 730 20 49.1 138 240 170 230 1100 134 65 5 7 7.18 10.2 1210 1348 6000 107.03 160 67.72 71.11 35.98 40 280 245 57.2 73.5 45.3 1.52 2.11 2.9 12 1.07
Remarks
J J J J J J C C 19 F2 C C F2 C J F2 J J J J J J C Fl F2 F2 F2 F2 C
C 19 C C C
C
F2, J C C C C
C
Refs.
370 51 61 51 51 355 289 7,86 390 184 289 145 86 289 86 390 390 86 184 86 86 86 370 41 41 41 41 390 571 571 571 571 86 390 15 46 46 46 86 389 86 86 145 289 389 389 389 86 289 86 389 289 289 86 86 389 4 4 4 328 328 208 71 289
TABLE 4. cont'd Solvent/Additive
T( 0 C)
Vinyl acetate (cont'd) Ethyl acetate (cont'd)
Ethyl alcohol Ethylene, tetrabromo- , tetrachloro- , tribromo- , trichloroEthylene glycol Fluorene - , 9-phenylFormamide, N9N, -dimethylFormic acid, ethyl ester - , methyl ester 2-Furaldehyde Furfuryl alcohol Germane, diethylchloro- , dimethylchloro- , triethyl-,triphenylGlycolic acid, methyl ester Heptane 1-Heptanol, 2,2,3,3,4,4,5,5,6,6,7,7-dodecafluorol,5-Hexadien-3-yne Hexanoic acid, 2-ethyl-, ethyl ester Hydroquinone - , 2,5-di-terf-butyl- , 2,6-dimethyl- , tetramethylIsobutyl alcohol Isobutyric acid Isobutyric acid, ethyl ester -, methyl ester Isobutyronitrile Isopropyl alcohol Lactic acid, ethyl ester -, methyl ester Laurie acid, ethyl ester Malonic acid, dimethyl ester /?-Mentha-l,8-dene Mesitol Methane, bromotrichloro-
- , dichloro- , iodo- , nitro-,tribromo- , triphenylMethanol
C s (xlO 4 ) 1.25
70 60 70 70 70 70 70 70 60 70 70 60 50 60 60 70 60 60 60 60 60 50 60 60 50 50 50 50 50 60 70 60 50 60 60 70 60 60 50 60 60 50 25 60 70 60 70 60 75 70 60 10 60
2.6 2.96 3.3 3.4 7.8 25 26.3 2800 465 34720 3810 83.0 4700 3610 16240 50 22 3 15000 2520 7800 86600 4500 56000 300 17.0 33.3 0 65 7000 38000 29000 74000 21.75 32.4 5.02 160 58 71 86 100 44.6 700 640 105 17 1900 5000 > 104 6000 >4xlO5 6303 4 1230 2300 2600 34760 700 9.0 10.0 10.5 3.4 2.26
Remarks
C
C F2 C C C C C C, J J C,J C C J C, J A, R A, R A, R A, R F2 C J J J J C C
C C J J D, S C C C C F2, J J C
Refs.
80
145,232 328 86 420 390 86 390 389 389 389 389 390 86 390 390 86 71 86 86 390 539 539 539 539 86 208 442 232 71 338 338 338 338 289 390 289 71 145,232 420 86 86 390 86 86 71 86 86 338 39 39 39 389 86 389 86 86 389 45 5 5 5 190 145,231
Remarks page II-157; References page 11-159
TABLE 4. cont'd Solvent/Additive
T (0C)
Vinyl acetate (cont'd) Methanol (cont'd) Naphthacene Naphthalene
70 50 50
- , decahydroNaphtho[l,2,3,4-def]chrysene Nonanoic acid, ethyl ester 2,6-Octadiene, 2,7-dichloro- , 2,6-dimethyl-
70 60 50 50 50 60
Octanoic acid, ethyl ester Oleic acid, methyl ester
50 60
Oxalic acid, diethyl ester - , dimethyl ester
90 30 60 60
Paraldehyde Pentane, 2,2,4-trimethyl2,4-Pentanedione 1-Pentanol, n 2,2,3,3,4,4,5,5-octafluoro2-Pentanone, 4-methyl3-Pentanone
70 50 60 60 60 60
Pentyl acetate
70 75 75 50 50
Orthoformic acid, trimethyl ester
Pentyl alcohol Perylene Phenanthrene
Phenol
70 45 50 60
- , m-chloro-,p-chloro- , p-nitro- , 2,3,4,6-tetramethylPhenol-D -,m-chloro-,p-chloro-,2,3,4,6-tetramethylPhosphorus trichloride Propane, 2-bromo-2-methyl- , 2-chloro-2-methyl 1-Propanol, 2,2,3,3-tetrafluoro1-Propene, 3-chloro- , 3-chloro-2-methylPropionaldehyde
45 45 50 45 45 45 45 45 60 60 60 60 60 60 60
Propionic acid, ethyl ester - , methyl ester
70 50 60
Pyrene Pyrocatechol, 4-(l,l,3,3,-tetramethylbutyl)Pyrogallol Salicylic acid Silane, dimethylphenyl-
50 50 50 70 60
C s (xlO 4 )
4.3 6.0 5.5 8.62 x 106 1150 1457 1715 48 1.35 x 105 80 3200 430 700 70 217 1000 358 7.6 8.0 4.0 1.0 2.0 136 8.0 10 26.1 34.52 10.0 114.39 7.2 87.0 56 2.88 x 105 870 5600
3380 215 120 600 205 400 8.86 x 104 1.13 x 104 35 70 80 800 1.5 x 104 150 26 7.11 3100 400 950 1000 457 40 23 26 11500 11000 50000 296 2200
Remarks
J J C,J J C F2 C J
C F2 19 C C C J J
C,J J J J J J J J J J C, D F2 J J F2 C C J J J C A, R
Refs.
320 86 320 370 370 15 390 86 41 71 152 324 7 71 441 86 441 345 346 86 86 145,232 390 208 86 442 289 145 289 390 184 184 41 370 15
390 51 15 86 51 51 15 51 51 51 51 51 214 86 86 442 86 86 86 86 390 71 232 420 370 338 338 390 539
TABLE 4. cont'd Solvent/Additive Vinyl acetate (cont'd) Silane, methyldichloro- , trichloro- , triethyl- , triphenylStearamide, N-allylStearic acid, ehtyl ester - , methyl ester Succinic acid, diethyl ester - , dihexyl ester - , dimethyl ester m-Tolualdehyde p-Tolualdehyde Toluene
T( 0 C)
60 60 60 60 90 50 60 60 60 60 60 60
75 80 50 70 70 60 70 75 50 50 50 50 50 50 60 50 60 50 70 75 60 60 60
280 290 400000
Q(3) Q(3) Q(3)
511 511 511
50 60
20 20
R R
541 541
60 60 60 60 60
5400 8600 12000 2000 4000
A, R A, R A, R A, R A, R
539 539 539 539 539
C, Q(I-2)
572
60 70
Triphenylene Veratraldeyhyde Xylene Vinyl chloride Carbon tetrachloride Chloroform Bromotrichloromethane Vinylidene chloride Af-Methylpyrolidone 2-Vinylpyridine Silane, diethylchloro- , Methyldichloro-,trichloro-,triethyl-,triphenylVinyltrimethylsilane Bromoform
Refs.
A, R A, R A, R A, R C, J C
60
Toluene, p-nitrop-Toluidine -, N,Ar-dimethyl-, AT-methylToluonitrile Triethylamine
Remarks
5800 8800 1200 2700 620.1 140 38.2 41 40 31 570 440 3.3 12.0 14.9 100 123 17.8 20.75 20.89 21.6 34 35 49.0 69.0 21.1 21.8 29.2 66 91.6 20.6 92.86 195 450 584 118 106300 750 380 830 38.3 360 370 160 550 14.9 278 166
50
- , bromo- , o-chloro-,p-chloro- , a-chloro-
C s (xlO 4 )
1200000
J J R C R C J F2 W15 R C C C C J C C F2 F2 F2 F2 J J J C C
539 539 539 539 173 71 441 420 420 420 86 86 158 15 357 71 71 357 80 21,59,289 357 86 86 265 265 357 390 357 184 273 15 389 389 86 389 184 15 154 154 154 15 154 24,145 370 86 15 390 184
Remarks page 11-157; References page 11-159
TABLE 5. TRANSFER CONSTANTS TO SULFUR COMPOUNDS Modifier Acrylamide, A/-octadecyl-/acrylonitrile (1:1 mol ratio) 1-Dodecanethiol Acrylic acid 1-Dodecanethiol - , methyl ester 1-Butanethiol
J( 0 C)
Cx
Remarks
Refs.
60
0.539
C, F24
174
45
1.9
C, F31
549
Ethanethiol
30 60 50
2-Propanethiol
60
1.53 1.69 0.78 0.94 ±0.07 1.65 ±0.12 1.57 ±0.09 1.57 ±0.18 1.79 5.00 0.544 0.668 0.700 0.656
A A Ql Ql Q2 Q3 Q4 Q2 Q3 Ql Q2 Q3 Q4
Acrylonitrile 1-Dodecanethiol Hydrogen sulfide Methyl sulfoxide
Methyl tetrasulfide p-Toluenethiol Acrylonitrile/1,3-butadiene (10-90%) 1-Hexanethiol, - , 1,1,3,3,5,5-hexamethyl1-Pentanethiol, - , 1,1,3,3-tetramethylAcrylonitrile/1,3-butadiene (20-80%) 1-Hexanethiol - , 1,1,3,3,5,5-hexamethyl1-Pentanethiol - , 1,1,3,3-tetramethylAcrylonitrile/1,3-butadiene (30-70%) 1-Hexanethiol - , 1,1,3,3,5,5-hexamethyl1-Pentanethiol - , 1,1,3,3-tetramethylAcrylonitrile/styrene (38.5-61.5 mol%) 1-Pentanethiol - , 1,1,3,3,4-pentamethylButadiene Xanthogendisulfide, dibutyl- , diethyl- , di-2-ethylhexyl- , di-isopropyl1,3-Butadiene 1-Butanethiol, 1,1,3,3-tetramethyl1-Octanethiol - , 1,1,3,3,5,5,7,7-octamethyl1-Tetradecanethiol 1,3-Butadiene/styrene 1-Dodecanethiol Formic acid, thio-, dithiobis_, _, _, ao'-dibutyl ester
50 50 20 30 40 50 80 50 5
0.73 0.13 0.1 0.47 0.0000812 0.11 0.29 0.795 0.69 0.97
C, F8 E
J
397 69,397 330 478,507 478,507 508 330,509 330 330 477 477 477 477 378 378 248 196 458 404 197 375 85 378
1.5
C, H
380
53.3
C, H
380
5
1.2
C, H
380
5
2.1
C, H
380
5
1.1
C, H
380
5
1.8
C, H
380
50
1.02
C, H
380
60 60 60 60
6.9 8.1 7.5 8.3
J J J J
532 532 532 532
5 50 5 50
5.3 3.7 21.8 16.0 19.0 3.0 19.5
H H H H H H H
242 242 242 242 243 242 242
50 50 5
0.66
B, H, J
384
5
2.42
B, H, J
383
TABLE 5. cont'd Modifier
T( 0 C)
1,3-Butadiene/styrene {cont'd)
- , - , ao'-diisopentyl ester
-5 50 5 -5 5 50 5 -5 50 5 50 5 50 5 -5 50 5
- , - , - , 0,O'-diisopropyl ester
-5 50 5
- , - , - , O,O'-di-sec-butyl ester - , - , - 0,O'-dicyclohexyl ester _, _, _, 0,0'-diethyl ester - , - , - , 0,O'-diheptyl ester - , - , - , 0,6>'-dihexyl ester - , - , - , 0,O'-diisobutyl ester
- , - , - , 0,O'-dimethyl ester - , - , - , 0,O'-dineopentyl ester - , - , - , 0,0'-dioctyl ester - , - , - , 0,O'-dipentyl ester - , - , - , 0,0'-dipropyl ester 1-Heptanethiol - , 1,1,3,3,5,5,6-heptamethyl1-Hexanethiol - , 1,1,3,3,5,5-hexamethyl1-Octanethiol - , 1,1,3,5,5,7,7-octamethyl/7-Dioxin, 2,3-dihydro/maleic anhydride 1-Butanethil Ethylene 1-Butanethiol Ethyl sulflde Methyl sulfoxide 2-Propanethiol, 2-methylSulfur hexafluoride Methyl methacrylate Acetic acid, dithiodi-, diethyl ester - , mercapto-, methyl ester Acetophenone, 3'-mercapto- , 4'-mercapto-
-5 50 5 -5 50 5 50 5 50 5 -5 50 5 -5 50
Cx 1.75 5.34 1.65 1.565 1.78 3.71 8.43 4.23 16.04 0.41 1.12 0.74 1.78 1.87 1.573 6.43 1.21 7.0 1.85 4.38 2.83 3.4 12.5 0.40-1.31 0.80-3.01 1.40-3.70 1.80-3.50 1.80-6.0 9.78 1.185 9.78 16.43 15.86 27.04 1.01 3.40 0.23 0.64 1.45 1.70 3.20 4.42 1.815 9.20
Remarks H C, H, J B, H, J H B, H, J C, H, J B, H, J H C, H, J B, H, J C, H, J B, H, J C, H, J B, H, J H C, H, J B, H, J B, H, J H C, H, J B, H, J B, H, J B, H B, H, J, B, H, J, B, H, J, B, H, J, B, H, J,
Refs. 180 382
H C, H, J B, H, J H C, H, J B, H, J C, H, J B, H, J C, H, J B, H, J H C, H, J B, H, J H C, H, J
180 383 383 383 180 382 383 382 383 382 383 180 382 383 341 180 382 383 341 100 100 100 100 100 100 179 180 382 383 180 382 383 382 383 382 383 180 382 383 180 382
GG4 GG3 GG2 GGl GG5
5
0.64
B, H, J
384
5
1.22 4.1 2.7-4.7
B, H, J H H
384 54,55 54
5
0.34
B, H, J
384
R
169
C, W5 C, W5 C, F21, W5 C, W5 C, F21, W5
457 454 259 457 259
60 130 130 130 130 130 60 60 45 45
6300 5.8 0.027 12 15.0 0.0000 0.00065 0.63 4.2 2.6
86 274 30 30
Remarks page II-157; References page 11-159
TABLE 5. cont'd Modifier Methyl methacrylate {cont'd) Anisole, 4,4'-dithiodip-Anisoyl disulfide Benzenesulfonic acid - , compound with pyridine - , thio-, S-phenyl ester Benzenethiol - , m-bromo- , /7-bromo- , m-chloro-,p-chloroBenzoyl disulfide Benzyl disulfide Benzyl sulfide
J( 0 C) 50 60 60
0.0044 0.0052 14.6
60 60 45 60 70 45 45 45 45 60 25 50 60 25 50
0.00365 0.0196 4.7 2.7 15 3.8 5.6 3.5 4.6 10.0 0.134 0.016 0.00627 0.0183 0.0098 0.0098 0.00154 0.0040 0.0039 0.084 0.021 0.66 0.67 0.008 0.22 0.09 0.35 0.33 0.21 0.13 0.55 0.00007 0.00258 16.7 0.0046 0.0098 10.0 0.0072 0.0117 290 0.0115 694 0.0176 0.0508 0.0127 0.0193 0.7 0.55 0.42 0.33 0.17 0.15 0.43 0.62 0.40 0.00013
Benzyl sulfone Benzyl sulfoxide Benzyl tetrasulfide Benzyl trisulfide 1-Butanethiol
60 50 50 50 50 60
Carbanilide, thio-
50
_, _, 4,4/-bis(dimethylamino)- , - , 4,4'-dichloro- , - , 3,3/-dimethoxy-, -, 3,3'-dimethyl- , -, 4,4'-dimethyl- , - , 3,3'-dinitroCarbon disulfide 2,13-Dioxa-7,8-dithia-3,12-disila-tetradecane, 3,3,12,12-tetrameth oxyDisulfide, bis(p-bromobenzoyl)- , bis (p-bromophenyl)-
50 50 50 50 50 50 60 79.5 60 50 60 60 50 60 60 70 60 50 60 50 60 60 70 80 90 50 70 50 60 70 60
- , bis(p-chlorobenzoyl)- , bis(p-chlorophenyl)-, -, -, -,
bis(p-cyanobenzoyl)bis(dimethylthiocarbamoyl)bis(p-nitrobenzoyl)bis(onitrophenyl)-
- , bis(/?-nitrophenyl)1-Dodecanethiol
Ethanethiol, 2-amino-, hydrochloride Ethanol, 2-mercaptoEthyl disulfide Formamidine, A^Af'-diphenyl- , - , U'-dithiobisMethyl sufoxide
Cx
50 60
0.22 0.0000071
Remarks
Refs. 285 285 369
A
F2 D F2
F2, J F2, J A F2 C, F2 C, F2 C, F2 C, F2 C, F2 C, F2 C, F2 A
F7 F7 F2 F2 C, F2 A
490 491 30 274 566 30 30 30 30 369 368 354 368 368 252 354 368 252 252 354 354 274 69,397 251 251 251 251 251 251 251 251 288 474 369 285 285 369 285 285 369 104 369 285 285 285 285 573 573 573 573 473 473 473 274 473 310 251 438
TABLE 5. cont'd Modifier Methyl methacrylate (cont'd) 2-Naphthalenethiol 1-Penthanethiol Phenyl disulfide
Phenyl disufone Phenyl sulfide Phenyl sulfone Phenyl sulfoxide 1-Propanethiol, 3-[l,3,3,3-tetramethyl-l-(trimethylsiloxy)disiloxanyl]- , 3-(trimethoxy)2-Propanethiol - , 2-methylPropionic acid, 3-mercaptoSulfide, benzoyl dimethylthiocarbamoyl Sulfur Thiosulfuric acid, S-butyl ester - , - , sodium salt - , S-isopropyl ester - , - , sodium salt - , S-phenyl ester - , - , compound with pyridine - , - , potassium salt - , S-propyl ester - , - , sodium salt m-Toluenethiol p-Toluenethiol a-Toluenethiol p-Toluoyl disulfide p-Tolyl disulfide Styrene Acetic acid, dithiodi-, -, -, -, -, -,
-, -, -, -, -, -,
diethyl ester dimethyl ester mercaptobutyl ester ethyl ester methyl ester
- , phenyl- , - , /?,/?'-dithiodi- , thio Aniline, 2,2' dithiodi-
-, 4,4'-dithiodi- , N-dodecyl-, 4,4'-dithiodiAnisole, 2,2'-dithiodi- , 4,4'-dithiodi- , p-methyl-, a,a'-dithiobis-
T( 0 C) 45 60 50 25 50 60
Cx
Remarks
Refs.
60 25 50 60 50 50 79.5 79.5 60 60 50 70 20 60 44.1 50
1.3 3.1 0.8 0.0174 0.0038 0.0007 0.00176 0.0085 0.0110 0.0003 0.00554 0.0064 0.00132 0.0006 0.0013 0.128 0.693 0.38 0.18 0.39 0.38 5.5 0.08 1.3 0.075 0.106
60
0.00226
490
60
0.00167
490
60 60
0.374 0.00537
490 490
60 45 45 50 60 50 60
0.00190 4.7 7.4 0.027 11.0 0.0031 0.0044
490 30 30 354 369 285 285
50 99 60 99 99 50 60 60 99
< 0.005 0.2 0.015 0.1 >14.0 26.0 58.0 0.63 27.6
50 99 25 50
0.24 >14.7 3.8 3.0 3.4 3.0 0.24 0.21 3.0 0.18 0.021
75 50 50 50 50 99
H D
A A D
F2 F2 D A C F2, J
F2, J
J, R A A
J
30 274 344 368 285 310 368 285 491 491 368 252 368 252 252 474 474 274 274 473 473 280 280 118 194 354
297 96 86 96 96 146 126 323 96 89 96 297 297 297 297 89 89 89 89 96
Remarks page 11-157; References page 11-159
TABLE 5. cont'd Modifier Styrene {cont'd) /7-Anisoyl disulfide Anthranilic acid, 4,4'-dithiobisArylbenzene thiolsulfonate - , /?-chloro - , p-methoxy- , p-methylBenzenesulfonic acid - , compound with pyridine - , thio-, S-phenyl ester Benzenethiol - , o-ethoxy-,p-ethoxyBenzene thiosulfonate - , aryl-p-chloro- , aryl-p-methoxy- , aryl-p-methyl 2-Benzimidazolethiol Benzoic acid, 2,2/-dithiodi- , - , diethyl ester - , -,dimethyl ester -, 4,4'-dithiodi- , - , diethyl ester - , o-mercapto- , -, methyl ester -,thioBenzothiazole, 2,2/-dithiobis-
- , 2,2'-thiobis2-Benzothiazolethiol Benzo[B]thiophene, 4,5,6,7-tetrahydro-4(2-thienyl)Benzoyl disulfide
Benzyl alcohol, ^o'-dithiobis-,/vAdithiobisBenzyl diselenide Benzyl disulfide
T( 0 C) 60 50 60 60 60 60
96.0 3.0 0.95 2.22 1.872 1.237
60 50 60 99 99 99
0.00617 1.60 1.67 0.08 25.1 0.13
60 60 60 99 50 50 99 50
2.597 1.475 1.099 0.21 0.01 < 0.005 0.2 0.11 0.17 0.11 >14.7 17.0 6.23 2.3 2.1 2.3 2.4 2.73 < 0.005 0.03 0.26 0.011 < 0.005 0.010 0.0107 36.0 0.11 0.58 0.09 2.0 0.02 0.03 0.00878 0.01 0.011 0.548 0.069 0.00335 0.052 0.051 5.4 13.2 21.0 22.0 25 15.0 17.0 15.4
50 99 99 99 25 50 75 99 50 50 99 60 50 60 99 50 50 60 50 60
Benzyl sulfide Benzyl sulfone Benzyl sulfoxide 1-Butanethiol
Cx
99 25 50 60 50 50 25 60
70 80 99
Remarks
R, F2 R, F2 R, F2 R, F2 A A
R, F2 R, F2 R, F2
J
A
A D
D, Ql D A A A A
Refs. 369 89 544 544 544 544 490 491 491 96 96 96 544 544 544 96 89 89 96 297 89 89,297 96 96 96 297 297 297 297 96 297 297 96 419 89 545 304 369 96 89 297 128 89 297 368 128 96 368 252 368 252 252 340 340 395 69,397 131 395 395 96
TABLE 5. cont'd Modifier Styrene (cont'd) 1-Butanethiol, 1,1,3,3-tetramethyl-
1-Butanethiol-D
Butyl disulfide
sec-Butyl disulfide tert-Butyl disulfide Butyl sulfide tert-Butyl sulfide Carbanilic acid, /?,/?'-dithiodi-diethyl ester Carbon disulfide Carbonic acid, dithio- , - , S,S'-bis(carboxymethyl)ester - , trithio- , - , S,S'-bis(carboxymethyl) ester 1-Decanethiol 2,13-Dioxa-7,8-dithia-3,12-disilatetradecane, 3,3,12,12-tetramethoxyDiphenyldisulfide Disulfide, bis(/?-bromobenzoyl) - , bis(a-bromo-o-tolyl) - , bis(/?-chlorobenzoyl) - , bis(chlorobenzyl) - , bis(2-chloroethyl) - , bis(a-chloro-o-tolyl) - , bis(>-cyanobenzoyl) - , bis(diethylthiocarbamoyl) - , bis(dimethylthiocarbamoyl)
T( 0 C)
5 50 60 70 80 25 55 60 99 150 50 50 60 60 60 50 60 50 50 80 80 79.5 60 60 50 60 50 50 50 60 60 60 70 80 95 115 130
- , bis(2-ethylhexyl) - , bis(A^ethyl-A^phenylthio-carbamoyl) - , bis(l-methylheptyl) - , bis(morpholinothiocarbonyl) - , bis(l-naphthylmethyl) - , bis(/?-nitrobenzoyl - , bis(o-nitrophenyl) - , bis(l-phenylethyl) - , bis(P-(2-pyridyl)ethyl) - , bis(2,3,5,6-tetramethylphenyl) - , bis(2,4,6-triisopropylphenyl) 1-Dodecanethiol
50 60 99 60 99 60 50 50 50 50 50 60 70 70 90 100 110
Cx
5.5 6.4 4.3 5.2 4.0 7.0 0.00079 0.00154 0.0024 0.0068 0.022 < 0.005 < 0.005 0.00014 0.0022 0.025 0.24 0.00066
Remarks
H H H A A A
A
A
0.36 0.21 4.3 4.2 0.0118 0.147 745 1.0 196 < 0.005 0.01 1.3 3190 0.724 1.11 0.0136 0.568 0.620 0.780 0.860 0.939 1.035 0.984 1.150 < 0.005 1.75 0.0104 6.1 0.033 6650 <0.005 0.03 0.73 0.12 14.8 19.0 19 0.69 1.3 13.0 26.0
Refs.
242 222 242 395 395 395 448 448 304 96 359 89 89 304 304 304 89 288 297
C3, H C3, H
J
J J J
A
C3, H C3, H
297 574 574 474 546 369 297 369 297 297 297 369 286 286 104 40 481 481 40 40 481 40 481 297 286 96 286 96 369 89 89 297 297 89 69,126 59 562 574 574 156 156
Remarks page II-157; References page 11-159
TABLE 5. cont'd Modifier Styrene (cont'd) terf-Dodecanethiol Ethanethiol Ethanol, 2,2'-dithiodi- , - , di(chloroacetate) Ether, ethyl 3-mercaptopropyl Ethyl disulfide Formamidine, AW-diphenyl-, l,l'-dithiobisFormic acid, thio-, dithiobis, 0,0'-diisopropyl ester 1-Heptanethiol 1-Hexanethiol - , 1,1,3,3,5,5-hexamethylHexyl disulfide Hydrogen sulflde Isobutyl disulfide Isopropyl disulfide Lauryl disulfide Lepidine, 2,2-dithiodiMesityl disulfide Methyl disulfide Methyl sulfoxide
T( 0 C)
70 90 90 50 50 50 60 100 99 50 50 99 99 99 25 50 75 99 70 60 60 60 50 50 60 40 50
60 Morpholine, 4,4'-dithiodi1-Naphthalenemethanethiol
1-Naphthalenethiol 2-Naphthalenethiol 1-Naphthoyl disulfide 1-Naphthyl disulfide 2-Naphthyl disulfide
1-Octadecanethiol Octadecyl disulfide 1-Octanethiol - , 1,1,3,3,5,5,7,7-octamethyl2-Octanethiol 1,4,5-Oxadithiepane 1-Pentanethiol Phenetole, 2,2'-dithiodi- , 4,4'-dithiodiPhenyl disulfide
50 25 50 75 99 99 99 50 99 25 50 75 99 99 99 5 50 50 99 150 50 99 99 50 60
Phenyl disulfone Phenyl sulfide
50 60 25 50 60
Cx
1.5 1.5 1.6 17.1 < 0.005 <0.005 14.1 21.0 13.7 0.0045 6.72 5.3 7.5 15.1 15.3 3.2 2.9 2.4 0.0104 5.0 0.0020 0.00066 0.00023 0.04 0.69 0.0094 0.0000693 0.548
0.0000242 0.000048 < 0.005 12.7 18.3 15.7 24.6 0.15 0.18 0.34 1.57 0.17 0.19 0.29 0.36 14.7 0.024 19.3 23.0 19.0 4.7 3.2 0.057 20.0 0.075 0.33 0.06 0.102 0.0103 0.111 0.147 0.022 0.025 0.0325 0.056 0.00548
Remarks
C3, H C3, H C3, H
A
C, F2
A
E
A
H H H H A H
A A A A D
Refs.
574 574 574 331 297 297 126 69 69 96 251 297 96 96 96 297 297 297 96 145 304 304 128 89 89 304 458 375
429 438 297 297 297 297 96 96 96 89 96 297 297 297 96 96 96 339 242 242 242 96 359 344 96 96 297 491 368 491 285 491 491 368 252 368
Next Page
TABLE 5. cont'd Modifier Styrene (cont'd) Phenyl sulfone Phenyl sulfoxide 1-Propanethiol, 3-(trimethoxysilyl)2-Propanethiol, 2-methyl-
T( 0 C)
50 50 79.5 50 60 60 100
Propionic acid, 3,3-dithiodi- , - , dipropyl ester - , 2-mercapto- , 3-mercaptoPropyl disulfide Pyridine, 2,2'-dithiodiQuinoline, 2,2'-dithiodiSulfide, ethyl 2,4-diphenylbutyl - , ethyl phenethyl 1-Tetradecanethiol Thiosulfuric acid, S-butyl ester - , - , sodium salt - , S-isopropyl ester, sodium salt - , 5-phenyl ester - , - potassium salt - , 5-propyl ester, sodium salt p-Toluenethiol a-Toluenethiol -,/7-methoxy/7-Toluoyl disulfide o-Tolyl disulfide
p-Tolyl disulfide 2,6-Xylyl disulfide Vinyl acetate Acetic acid, dithiodi- , - , diethyl ester Acetic acid, ithio- , - , S-(2-hydroxyethyl)ester, acetate Acetyl disulfide 1-Butanethiol Butyl disulfide Butyl sulfide 1,4,5-Oxadithiepane Sulfur oc-Toluenethiol Thiol acetate
Cx
0.021 0.024 5.90 4.0 3.1 3.7 4.6 1.8 2.3
Remarks
Refs.
A A
252 252 474 344 261 69,126 59 261 69,126
H
297 178 178 297 304 89 89 331 331 242
H A A
50 50 60 50 50 50 50 50
< 0.005 7.7 9.4 6.0 0.00234 0.01 0.05 30.0 7.15 19.0
60 60
0.173 0.407
490 490
60 60 99 99 99 60 25 50
0.763 0.150 0.07 25.5 26.0 46.3 0.22 0.23 0.28 0.32 0.11 0.15 0.69
490 490 96 96 96 369 297 297 297 297 297 96 297
1.41 1.5
86 351
75 50 99 50
60
60 60 60 60 60 60 45 70 60
0.0132 0.29 48.0 1.0 0.026 0.25-2.5 470.0 0.885 0.186
J J J J J C F20
140 86 140,397 86, 351 351 351 28 390 575
C. REMARKS A. B. C.
D.
Thermal initiation Hydroperoxide initiation Peroxide initiation C1. Ammonium persulfate C2. Potassium persulf ate C3. Sodium persulf ate Photoinitiation
E. F.
y-Ray initiation Solution polymerization in: Fl. Acetonitrile F2. Benzene F3. Butyl acetate F4. Butyl chloride F5. Chlorobenzene References page 11-159
Previous Page
TABLE 5. cont'd Modifier Styrene (cont'd) Phenyl sulfone Phenyl sulfoxide 1-Propanethiol, 3-(trimethoxysilyl)2-Propanethiol, 2-methyl-
T( 0 C)
50 50 79.5 50 60 60 100
Propionic acid, 3,3-dithiodi- , - , dipropyl ester - , 2-mercapto- , 3-mercaptoPropyl disulfide Pyridine, 2,2'-dithiodiQuinoline, 2,2'-dithiodiSulfide, ethyl 2,4-diphenylbutyl - , ethyl phenethyl 1-Tetradecanethiol Thiosulfuric acid, S-butyl ester - , - , sodium salt - , S-isopropyl ester, sodium salt - , 5-phenyl ester - , - potassium salt - , 5-propyl ester, sodium salt p-Toluenethiol a-Toluenethiol -,/7-methoxy/7-Toluoyl disulfide o-Tolyl disulfide
p-Tolyl disulfide 2,6-Xylyl disulfide Vinyl acetate Acetic acid, dithiodi- , - , diethyl ester Acetic acid, ithio- , - , S-(2-hydroxyethyl)ester, acetate Acetyl disulfide 1-Butanethiol Butyl disulfide Butyl sulfide 1,4,5-Oxadithiepane Sulfur oc-Toluenethiol Thiol acetate
Cx
0.021 0.024 5.90 4.0 3.1 3.7 4.6 1.8 2.3
Remarks
Refs.
A A
252 252 474 344 261 69,126 59 261 69,126
H
297 178 178 297 304 89 89 331 331 242
H A A
50 50 60 50 50 50 50 50
< 0.005 7.7 9.4 6.0 0.00234 0.01 0.05 30.0 7.15 19.0
60 60
0.173 0.407
490 490
60 60 99 99 99 60 25 50
0.763 0.150 0.07 25.5 26.0 46.3 0.22 0.23 0.28 0.32 0.11 0.15 0.69
490 490 96 96 96 369 297 297 297 297 297 96 297
1.41 1.5
86 351
75 50 99 50
60
60 60 60 60 60 60 45 70 60
0.0132 0.29 48.0 1.0 0.026 0.25-2.5 470.0 0.885 0.186
J J J J J C F20
140 86 140,397 86, 351 351 351 28 390 575
C. REMARKS A. B. C.
D.
Thermal initiation Hydroperoxide initiation Peroxide initiation C1. Ammonium persulfate C2. Potassium persulf ate C3. Sodium persulf ate Photoinitiation
E. F.
y-Ray initiation Solution polymerization in: Fl. Acetonitrile F2. Benzene F3. Butyl acetate F4. Butyl chloride F5. Chlorobenzene References page 11-159
F6. o-Dichlorobenzene F7. Dimethylformamide F8. Dimethyl sulfoxide F9. /7-Dioxane FlO. Ethyl acetate FIl. Ethyl methyl ketone F12. Heptane F13. Water F14. Magnesium perchlorate F15. Succinonitrile F16. Sulfur dioxide F17. Toluene Fl 8. Zinc chloride F19. Octane F20. Methanol F21. Propane F22. Diethyl oxalate F23. Cyclohexane F24. Butyl alcohol F25. Acetic acid F26. 1,2-Dichloroethane F27. Ethylbenzene F28. Cylohexanone F29. Parabutyr aldehyde F30. Water-methanol mixture F31. tert-Butyl alcohol F32. Hexane F33. 1-Propanol F34. Carbon tetrachloride G. Heterogeneous polymerization H. Emulsion polymerization I. Recalculated from data of: 11. Basu, Sen, and Palit (1950) 12. Baysal and Tobolsky (1952) 13. Chadha and Misra (1958) 14. Dixon-Lewis (1949) 15. Gregg and Mayo (1953) 16. Ham (1956) 17. Kwart, Broadbent, and Bartlett (1950) 18. Matsumoto, et. al. (1959) 19. Palit and Das (1954) 110. Palit, Nandi, and Saha (1954) Il 1. Saha, Nandi, and Palit (1956) 112. Stein and Schulz (I960) 113. Wheeler, Lavin, and Crozier (1952) J. Apparent transfer constant; retardation occurred K. Average value L. Estimated from model compounds M. For end groups: M1. Tribromomethy 1 M2. Butylamino M3. Diethylamino M4. Hy droxy methyl M5. Aldehyde M6. Thioglycolate M7. -CH(OH)CH2-SH M8. Dodecyl M9. 2-Hydroxyethyl
N. O. P. Q. R. S. T. U. V. W.
X. Y. Z. AA. BB. CC. DD. EE. FF. GG.
HH.
II.
MlO. -(CH 2 )IiSH For middle groups For side chain For main chain Telomerization (number of monomer units in transferring chain) Calculated from viscosity average molecular weight Value uncertain In presence of 0.4 mol/1 lithium nitrate In presence of ( ) mol/1 sodium chloride In presence of ( ) mol/1 sodium bromide Under pressure of: Wl. 200psi (13.8bar) W2. 250psi(17.2bar) W3. 1470psi(101.4bar) W4. 5000 psi (344.8 bar) W5. 20000 psi (1379.0 bar) W6. 26600psi (1834.1 bar) W7. 28400 psi (1958.2bar) W8. 56000psi(3861.2bar) W9. 64600 psi (4454.2 bar) WlO. 168000psi (11583.6 bar) WIl. 600psi (41.4 bar) W12. 2500psi (172.4bar) W13. 18 psi (1.2bar) W14. 735 psi (50.7 bar) W15. 14200psi (979.1 bar) W16. 42600 psi (2937.3 bar) W17. 34500 psi (2378.8 bar) Wl8. 3000bar W19. 2700 bar W20. 2400 bar W21. 2000bar W22. 1800 bar W23. 150 bar W24. 600 bar Corrected for loss of low molecular weight polymer CM = 125 x exp(-7300//?r) CM = 3.0 x exp(-5673/#r) CM = 0.4 x exp(-6219//?r) CM = 0.2 x exp(-5400/#r) CM = 6.4 x exp(-4120/#r) CM = 4.77 x exp(-3540/#r) Radical is styrene Radical is p-chlorostyrene 1/C varies with polym. rate and emulsifier of: GGl. Kcaprate GG2. Klaurate GG3. K myristate GG4. Kpalmitate GG5. K rosinate C is combined constant for copolymerization, = (Csi X i J 1 X M i + CS2 XiJ 2 X M 2 )/ (Ri x Mi x Mi + 2 x Mi x M 2 +R2 x M 2 x M2) In presence of FeBr2
111. 112. JJO. JJl.
In presence of FE(CO)5 In presence of methacrylic acid methyl ester Catalyzed by Co(II)-tetramethylhematoporphyrine Catalyzed by Co(II)-hematoporphyrinetetramethyl ether JJ2. Catalyzed by Co(II)-tetra-4-tertbutylbenzoporphyrine
JJ3. In presence of ZnCl 2 ; [ZnCl 2 ]/[MMA] = (a)0 (b) 0.1 (c) 0.23 (d) 0.40 KK. Copolymerization of acrylonitrile and butyl acrylate LL. Controlled to pH 3 - 4 with acetic acid
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P h o t o p o l y m e r i z a t i o n
R e a c t i o n s
J. P. Fouassier Laboratoire de Photochimie Generale, Mulhouse, Cedex, France
A. Introduction 11-169 B. Tables 11-170 Table 1. Rate Constants of Cleavage, Electron Transfer and Monomer Quenching in Radical Photoinitiators 11-170 Annex to Table 1. Photoinitiator Compound Chemistries 11-173 Table 2. Bimolecular Rate Constants for the Reaction of Phosphonyl Radicals with Various Monomers in Cyclohexane at Room Temperature 11-176 Table 3. Bimolecular Rate Constants for the Reaction of Various Radicals with Various Olefinic Monomers at Room Temperature 11-176 Table 4. Bimolecular Rate Constants for the Reaction of Ph 2 P=O and Ph2P = S with Various Monomers 11-176 Table 5. Electron Transfer Reaction of Radicals with Diphenyliodonium Salts 11-176 Table 6. Electron Transfer Rate Constants (ke) Between Photosensitizers and Cationic Photoinitiators and Quenching Rate Constants (fcq) for Cyclohexene Oxide in Methanol (M) and Acetonitrile (AN) 11-177 Table 7. Excitation Transfer Rate Constants (kj) for Thioxanthones and Photoinitiators 11-178 Annex to Table 7. Compound Chemistries 11-178 Table 8. Triplet State Lifetimes (rT) of the Sensitizer (TXI) in Different Media, and Rate Constant (A:T) of the Interaction between TXI and TPMK 11-179 Table 9. Some Values of the Triplet State Energy Levels of Photoinitiators and Monomers 11-179 Table 10. Values of r f , rT, and k% in Solution 11-179 Table 11. Rate Constant of Interaction of Ketones and Light Stabilizers in Solution 11-179 Annex to Table 11 11-179 C. References 11-180
A.
INTRODUCTION
UV curing technologies use light beams to start photochemical and chemical reactions in organic materials (monomers, oligomers, prepolymers, polymers), mostly through a Photo-Induced Polymerization (PIP) reaction. This leads to the formation of a new polymeric material whose applications lie in various industrial sectors, such as coatings, graphic arts, imaging, microelectronics, etc. Specific advantages of these technologies over the usual thermal operations are rapid through-cure, solvent-free formulation, room temperature treatment and low energy requirements. This PIP process is concerned with the creation of a polymer P through a chain radical or cationic reaction initiated by light in the presence of a photoinitiator (PI) and a coupled Pl/photosensitizer (PS): light
light
light
add species :X
excited PS excited PI
R* or acid species
The reactivities of PI and PS govern, for a large part, the practical efficiency of the PIP reaction. The present chapter reports typical data obtained (through time-resolved laser spectroscopy experiments) on the excited state processes in PI and PS occurring after the absorption of the photon. Rate constants reported in the following tables correspond to the following processes: 1.
PI (ground singlet state)
light
1 PI* first excited singlet state
cleavage H abstraction monomer quenching electron transfer
3 Pi* triplet state
2. R' (or A# or S*...) + M — ^ 3. 3 P F + light stabilizer (LS) 3
(b) Energy and electron transfer can also occur in the first excited singlet state 1 PS*.
RM'
—-
k
4. PS* + PI —- excitation transfer 5. Tj'. Triplet state lifetime under the given conditions (equal to the reciprocal value of the sum of the first-order rate constants of the different processes) Tj: Triplet state lifetime in the presence of a given additive 6 3
- PS* + cationic photoinitiator C+ —- PS" + C* (a) Energy transfer can sometimes occur: 3 PS*+ C+ - PS+ C+*
Detailed data are available, especially in several chapters of two edited books (1) and in a recent monograph (2). Few data are known on the photopolymerization itself and largely depend on the practical formulation used as well as the experimental conditions. Typically, one photon absorbed can lead to ~10000 polymerized double bonds (3). Rate constants of propagation kp and termination fct for a polyurethane acrylate resin containing an acrylate monomer (weight ratio, 1:1) as reactive diluent are ~10 4 1/mol/s and 3 x 10 4 l/mol/s respectively (when half of the double bonds have been polymerized) (3).
B. TABLES TABLE 1. RATE CONSTANTS OF CLEAVAGE, ELECTRON TRANSFER AND MONOMER QUENCHING IN RADICAL PHOTOINITIATORS0 10~9A:e (1/mol/s)
10~6A:q (1/mol/s)
Monomers famines 7 solventsd
Ha Hb Hc lid lie Hf Hg Hh Hi Ha
1.3 2.0 1.2 1.2 0.2 0.07 1.5 0.6 0.27
Mi, AHi, Si
Ha
0.003e 0.001^ 7 2 1.9 2 0.56
66 150 2.5 2 1 13 180 8 0.05 3200 360 5.4 34
Compound
10 "8Jk0 (s"1)
Ha
Hj Ilk 111 Hm Hn Up Hq Hr Hs Ilr Hs Hr Hs Hr Ils Ilr Hs I2a I2b I2c I2d I2e I2f I2g I2h I2i
10 0.5 0.9 0.0064* 0.0025e 0.0056e 0.0043*
7.14 0.87 0.003 0.00025 0.83 0.003 0.67 1.18 0.80
0.26 < 0.001 0.08 0.20 0.08 0.17 0.15 0.05
1500 1550
56 110 5500 7400 5100 6500 49 140 9.4 50 250 20 4.5 8 22 10 29 20 21
M2, M5, M3, M4,
Refs. 4
S2 S2 S2 S2
21 21 21 21 22
S 2 , AH3 S 2 , AH4 S 2 , AH2 S 2 , AH5 S 2 , AH6 S3 M 7 , AH2, S 4
26
S2
26
S 6 , Mi
26
S6, M2
26
S6, M5
26
S6, M3
26
S6, M4
26
Mi, AHi, Si
23 25
5
TABLE 1. cont'd Compound Ba I3b 13c I3d I3e I3f I3g I3h I4a I4b I4c I4d I4e I4f I4g I4h I4i I4e I4f I4g I4h I4i I4f I4g I4h I4i I4f I4g I4h I4i I5a I6a I7a I7b I8a I9a HOa Ilia IHb IHc Hid I12a I12b I12c I12d I12e I12a I12b I12c I12d I12e I12b I12c I12d I12e I12b I12c I12d I12e I13a I14a I14b I14c I14d I15a I15b I15c
10 8A: c (s"1) 10 1 25 0.005 10 0.006 0.007 0.13 >100 >100 > 100 >100
W~9ke (1/mol/s)
10 6 A: q (I/moI/s) >200 2
0.7 6 XlO" 5 0.85 2.5
0.9 0.4
0.7 0.05 440 0.35 11
700 1200 480 800 1000 200 13 8100 4800 6500 1500 190 6 17 <10 5.7 1300 700 380 180
1.6 6.5 6.0 3.5
>5 4 >5
Mi5AHi5S1
6
Si
7
M2, S2
7
Mi, S 2
7
M3, S2
7
M4, S2
7
Mj5S1 Mi, AHi, Si
8 9 9
«10 ~4 <10~ 4 <10~ 4
> 10 7 xlO-3
1.4
Refs.
<10~ 4
8100 4800 6500 1500 190 480 800 1000 200 13 60 17 <1 5.7 1300 700 380 180
> 10 0.8 >1 0.12 0.01
Monomers famines 7 solvents^
11000 2900 15 1200
Mi7AHi9S1 Mi5AH19Si Mi, AHi, Si
9 9 10 10
M15S2
11
M25S2
11
M3, S2
11
M4, S2
11
AH 2 , S 2 M19AH15S1
12 13
S2
14
References page 11-180
TABLE 1. cont'd Compound I15d I16a I16b I17a I18a I19a I20a I21a I22a I22b I22c I22d I23a I23b I23c I23d I23e I23f I23a I23b I23c I23d I23a I23b I23c I23d I23a I23b I23c I23d I23a I23b I23c I23d I23a I23b I23c I23d I23a I23b I23c I23d I23a I23a I23b I23b I23g I23h 124 125 126 127 128 129 a
10*kc (s1)
10~9ke (1/mol/s)
10~6kq (1/mol/s)
Monomers famines 7 solvents^
Refs.
3.3 1.5 >3 0.05 0.16 0.3 29 60 -10 -5 0.02 0.014
0.7
6 5 4 4 0.01 0.017 2.5
180
AH 1 9 S 1
15
300
S1 S1 S1 S2 S2 S3
16 17 18 18 18 19
M 1 , AH3, S 2
20
AH2, S 5
24
M 2 , S 2 , AH2
20
M3, S2
20
M4, S2
20
M5, S2
20
M6, S2
20
S 2 , AH4
26
S1, M8 S19M9 S 2 , AH7 S 2 , AH8 M7, S 4
13 13 26 26 25
S 2 , Mi S2, M10 S2, M10 S2
37 37 37 39
S 7 , AH 9
41
100
93 2.3 2.0 15 2 3 3 3000 6000 6000 6000 0.2 0.02 0.03 0.04 4 0.4 1 1 40 30 5 6 1 1 0.3 0.3
8 6 6 6 26 23 8 0.85 <10~5 <10~5
4.4-f 0.3 0.015
65 37 0.016 0.006 0.007
Compound chemistries given in Annex to Table 1. 1} Monomers: Mi - methyl methacrylate; M2 - styrene; M3 - vinyl acetate; M4 - acrylonitrile; M5 - vinyl pyrrolidone; M6 - butylvinylether; M 7 - acrylamide; Mg PETA; M 9 - TMPTA; M10 - butylmethacrylate. c Amines: AHi - methyl diethanolamine; AH 2 - triethylamine; AH 3 - ethyl-4-(dimethylamino)-benzoate; AH 4 - bis-(2-hydroxy ethyl)-methylamine; AH 5 - methyl-4amino benzoate; AH 6 - 1,4-diazabicyclo [2.2.2] octane (DABCO); AH 7 - dimethylamine; AHg - 2-(dimethyl aminoethyl)-benzoate; AH 9 - diethylaniline. d Solvents: Si - toluene; S 2 - benzene; S 3 - acetonitrile; S 4 - water; S5 - 2-propanol; S 6 - acetone; S 7 - ethanol. e Rate constant of H abstraction by THF. ^Rate constant of H abstraction by isopropanol.
ANNEX TO TABLE 1. PHOTOINITIATOR COMPOUND CHEMISTRIES Compound
R
Ri
R2
R3
R4
Ha lib lie Hd He iif Hg Hh
in Hj
Ilk 111 Hm Hn Up Hq Hr
Hs
I2a I2b I2c I2d I2e I2f I2g I2h I2i Ba I3b 13c Dd I3e I3f Bg Dh I4a I4b I4c I4d I4e I4f I4g I4h I4i
References page 11-180
ANNEX TO TABLE 1. cont'd Compound
R
Ri
R2
I5a
I6a
I7a I7b Fluorenone
H CH 2 SOjNa
+
I8a I9a
I9b
HOa
C2H5
Ilia IHb IHc IHd I12a 112b I12c I12d
H H CH 3 CH 3 O OH OCOCH3 H CH 3
I12e I13a
CH 3
I14a I14b I14c I14d
H /-C 3 H 7 OC 2 H 5 J-C 4 H 9
I15a
I15b I15c
I15d
I16a
H CH 3
H CH3 H H
R3
R4
ANNEX TO TABLE 1. cont'd Compound
R
Ri
R2
R3
R4
I16b I17a I18a I19a I20a I21a
I22a I22b I22c I22d I23a I23b I23c I23d I23e I23f
H Cl CH 3 CH 3 (CH 3 ) 2 H H
I23g
-OCH 2 COOH
I23h
OCH 2 CH 2 CH 2 N(CH 3 ) 3 SO 3 Me-
124 Acridine Phenazine
125 126 127
128
129
References page 11-180
TABLE 2. BIMOLECULAR RATE CONSTANTS0 FOR THE REACTION OF PHOSPHONYL RADICALS WITH VARIOUS MONOMERS IN CYCLOHEXANE AT ROOM TEMPERATU RE *
Radical Monomer Methacrylonitrile
5.0
4.6
4.5
Styrene Methylmethacrylate Acrylonitrile Methyl acrylate n-Butyl vinyl ether Vinyl acetate
6.0 8.0 2.0 3.5 0.4 0.16
4.5 5.0 2.0 2.1 0.3 0.13
8.0 5.8 0.18 1.3 0.23 0.082
a
b
kRM in 10 7 l/mol/s. Ref. 26.
9.2
11
22 5.8 0.58 1.7 2.1 0.29
25 5.3 0.26 1.6 1.4 0.18
TABLE 3. BIMOLECULAR RATE C O N S T A N T S " FOR THE REACTION OF V A R I O U S RADICALS W I T H V A R I O U S OLEFINIC M O N O M E R S AT R O O M TEMPERATURE*
Radical
Monomer 3.5 x 10" 2
Styrene
Methylmethacrylate Acrylonitrile Methyl acrylate n-Butyl vinyl ether Vinyl acetate Af-Vinyrpyrrolidone a
4
9xlO~ 4 x 10 ~4
2
5.4xlO~ 1.6 x 10~2
7 x 10~ 4
4xlO"
5
< 10 " 6
6 x 10 ~4
4xlO~
5
1.2 x 10 ~2
6
0.9xl0~ 2 2 x 10 ~3
6 2 2 0.5 0.2
2 x 10 ~2
18C
10" 3t
IO"1*
7
kRU in 10 l/mol/s. Ref. 26. From Ref. 40. +From Ref. 16.
fo c
TABLE 4. BIMOLECULAR RATE C O N S T A N T S 0 FOR THE REACT I O N OF P h 2 R = O A N D Ph 2 P-=* W I T H V A R I O U S M O N O M E R S * 0
Radical Monomer Methacrylonitrile Styrene Methylmethacrylate Acrylonitrile Methyl acrylate rc-Butyl vinyl ether Vinyl acetate a
Ph2P = O 1.9 4.6 4.1 1.3 1.7 5.0 1.4
Ph2P = S 0.9 0.4 0.19 0.52 0.62 0.15 0.042
kRM in 10 7 l/mol/s *Ref. 27. c Experiments were carried out in CH 2 C^ solution at room temperature.
TABLE 5. ELECTRON TRANSFER REACTION O F RADICALS W I T H D I P H E N Y L I O D O N I U M SALTS
Radicals
Ph2PO Ph2COH (CHs)2COH
10"9Jt6 (1/mol/s)
Refs.
<10"3 0.03 0.06
42 43
TABLE 6. ELECTRON TRANSFER RATE CONSTANTS (ke) BETWEEN PHOTOSENSITIZERS AND CATIONIC PHOTOINITIATORS AND QUENCHING RATE CONSTANTS (kq) FOR CYCLOHEXENE OXIDE IN METHANOL (M) AND ACETONITRILE (AN) Photosensitizer Chlorothioxanthone
Chlorothioxanthone
Cationic photoinitiator
Anion
Solvent
(1/mol/s)
(1/mol/s) 0.3
AsF6" Cl" PF6BF4; AsF 6
M
AN
24 24 26 24 290
AsF 6
M
400
Refs. 28
36 Benzophenone
AsF 6 Cl" BF4"
M
15 1 47
0.33
Ketocoumarin
BF 4
M
6.4
0.04
M
14
Chlorothioxanthone
PF 6
35
PF 6
28
SbF 6
4
AsF 6
8
BF 4
570
BF 4
110
PF 6
14
AsF 6
100
BF 4
38
29
15
References page 11-180
TABLE 6. cont'd Photosensitizer
Cationic photoinitiator
Xanthone Michler's ketone Thioxanthone 10-Methylacridone Acridone Anthracene Chlorothioxanthone Pyrene Benzophenone Isopropylthioxanthone
Anion
Solvent
10-7Are (1/mol/s)
Cl"
M
140
10~7A:q (1/mol/s)
Refs. 30
0.7 200 350 740 M (NO2Cp)2I+
l
Cl"
31 28
400 130 500 250
TABLE 7. EXCITATION TRANSFER RATE CONSTANTS (kT) FOR THIOXANTHONES AND PHOTOINITIATORSa Thioxanthone
Initiator
Solvent
TXI
HMK
Toluene Methanol Toluene Methanol Toluene Methanol Toluene Methanol Toluene Methanol Toluene Methanol
OMK TPMK NMK ETX
TPMK
ITX
TPMK
10 " 6 ^ x (1/mol/s) 100 290 75 380 240 630 4700 7900 12 110 60 55
"Ref. 32.
ANNEX TO TABLE 7. COMPOUND CHEMISTRIES
TX's
R
Ri
R2
R3
R4
Abbrev.
Triplet state energy level (kcal/mol)
H H CH 3 H
Cl CH(CH 3 ) 2 H H H
H H COOET
H H H COOET
CTX ITX ETX TXI
62 61 58,5 63
Mok's H SCH 3 OCH 3 N(CH 3 ) 2
HMK TPMK OMK NMK
65 61 65 63
TABLE 8. TRIPLET STATE LIFETIMES (TT) OF THE SENSITIZER (TXI) IN DIFFERENT MEDIA*, AND RATE CONSTANT (kj) OF THE INTERACTION BETWEEN TXI AND TPMK* XT
tl
Hr6Jkx
Medium
(ns)
(cp at 28° C)
(I/moI/s)
TMPTAC (100%) Acrylate (66/33) Toluene-Ep. acrylate (50/50) Toluene-TMPTA (25/75) Toluene-TMPTA (50/50) Toluene-TMPTA (75/25) HDDA^ (100%) HDDA-Ep. acrylate (50/50) Toluene-HDDA (50/50) Toluene-HDDA-Ep. acrylate (25/50/25) Toluene-PETAe (50/50) Toluene-PETA-Ep. acrylate (43/43/14) Toluene Methanol
650 2200 1500
40 185 9.5
80 31 35
270 200 280 650 2500
5.8 1.7 0.9 5.2 58
135 <40 150 95 22
1000 850
1.2 5.8
140 68
220 360
3.1 6.9
40 69
50 140
0.53 0.52
240 630
TABLE 11. RATE CONSTANT OF INTERACTION OF KETONES AND LIGHT STABILIZERS IN SOLUTION Photoinitiator
Light stabilizer
l
Benzophenone
LSI LS2 LS3 LS4 LS5 SL6 LSI LS7
6500 8550 10300 15000 7050 5900 500 700
Acetone
Refs. 34
35 36
ANNEX TO TABLE 11. LSI:
a
Viscosity: 77. Ref. 33; for formula, see Annex to Table 7. Trimethylolpropane triacrylate. ^Hexanedioldiacrylate. Tentaerythritol triacrylate. &
LS2:
TABLE 9. SOME VALUES OF THE TRIPLET STATE ENERGY LEVELS OF PHOTOINITIATORS AND MONOMERS
Compound
Triplet state energy (AE) (kcal/mol)
Ila I4a I7a I8a I9b M2 I14a 124
69 73 53 53 59 61 75 57
Cited in Ref. 13
LS3:
Cited in Ref. 38 LS4:
TABLE 10. VALUES OF T°, T1, AND IrJt IN SOLUTION Photoinitiators
t j (ns)
Xj (ns)
4200
4000
10"6JkJ (1/mol/s)
LS5:
0.85 LS6:
3300
2000
14
470
470
<5
4000
1750
24
LS7:
determined in bulk epoxyacrylate-HDDA (60:4OwAv); a in solution b in the presence of LSI (2%).; Ref. 34.
References page 11-180
C. REFERENCES 1. (a) "Lasers in Polymer Science and Technology: Applications", J. R Fouassier, J. F. Rabek (Eds.), CRC Press, Boca Raton, 1990. (b) "Radiation Curing in Polymer Science and Technology", J. P. Fouassier, J. F. Rabek (Eds.), Chapman & Hall, London, (1993). 2. J. P. Fouassier, "Photoinitiation, Photopolymerization, Photocuring", Hanser, Munich, (1995). 3. (a) C. Decker, in: S. P Pappas, (Ed.), "Radiation Curing: Science and Technology", Plenum Press, New York, 1992. (b) C. Decker, B. Elzaouk in "Laser Curing of Photopolymers", Proc. Polymer Photochemistry Symposium, Genes, 112,(1993). (c) C. Decker, B. Elzaouk, Eur. Polym. J., 31 (12), 1155 (1995). 4. D. Ruhlmann, J. R Fouassier, Eur. Polym. J., 27 (9), 991 (1991). 5. D. Ruhlmann, J. R Fouassier, W. Schnabel, Eur. Polym. J., 28 (3), 287 (1992). 6. D. Ruhlmann, E Wieder, J. R Fouassier, Eur. Polym. J., 28 (6), 591 (1992). 7. R. Kuhlmann, W. Schnabel, Polymer, 18, 1163 (1977). 8. J. P. Fouassier, in: J. R Fouassier, J. F. Rabek (Eds.) "Lasers in Polymer Science and Technology: Applications", CRC Press, Boca Raton, 1990. 9. J. R Fouassier, D. J. Lougnot, Polymer Comm., 31, 418 (1990). 10. J. R Fouassier, D. J. Lougnot, J. Chem. Soc, Faraday Trans., 1, 83 (9), 2935 (1987). 11. G. Amirzadeh, R. Kuhlmann, W. Schnabel, J. Photochem., 10, 133 (1979). 12. J. R Fouassier, D. J. Lougnot, L. Avar, Polymer, 36 (26), 5005 (1995). 13. J. R Fouassier, in: J. R Fouassier, J. F. Rabek (Eds.) "Radiation Curing in Polymer Science and Technology", Chapman & Hall, London, vol. II, 1993. 14. T. Sumiyoshi, W. Schnabel, A. Henne, J. Photochem., 32, 191 (1986). 15. D. Ruhlmann, K. Zahouily, J. R Fouassier, Eur. Polym. J., 28 (9), 1063 (1992). 16. J. R Fouassier, D. Burr, Macromolecules, 23, 3615 (1990). 17. J. R Fouassier, D. J. Lougnot, J. C. Scaiano, Chem. Phys. Lett., 160, 335 (1989). 18. R J. Wagner, M. J. Lindstrom, Jacs, 109, 3062 (1987). 19. F. Morlet-Savary, J. R Fouassier, H. Tomioka, Polymer, 33, 4202 (1992). 20. G. Amirzadeh, W. Schnabel, Makromol. Chem., 182, 2821 (1981).
21. R. Kuhlmann, W. Schnabel, Angew. Makromol. Chem., 57, 195 (1977). 22. R. Kuhlmann, W. Schnabel, Polymer, 17, 419 (1976). 23. F. Morlet-Savary, J. R Fouassier, T. Matsumoto, K. Inomata, Polymers for Adv. Techn., 5, 56 (1994). 24. N. S. Allen, A. W. Timms, W. A. Green, F. Catalina, T. Corrales, S. Navaratnam, B. J. Parsons, J. Chem. Soc. Faraday, 90, 83 (1994). 25. D. J. Lougnot, C. Turck, J. R Fouassier, Macromolecules, 22, 108 (1989). 26. W. Schnabel, in: J. R Fouassier, J. F. Rabek (Eds.), "Lasers in Polymer Science and Technology: Applications", vol. II, CRC Press, Boca Raton, 1990. 27. T. Sumiyoshi, W. Weber, W Schnabel, Z. Naturforsch, 40a, 541 (1985). 28. J. R Fouassier, D. Burr, J. V. Crivello, J. Photochem. Photobiol., A: Chem., 49, 318 (1989). 29. G. Mannivannan, J. R Fouassier, J. V. Crivello, J. Polym. Sci. Part A: Polym. Chem., 30, 1999 (1992). 30. H. J. Timpe, K. R Kronfeld, U. Lammel, J. R Fouassier, D. J. Lougnot, J. Photochem., 52, 111 (1990). 31. M. R. V. Sahyun, R. J. DeVoe, R M. Olofson, in: J. R Fouassier, J. F. Rabek, (Eds.), "Radiation Curing in Polymer Science and Technology", vol. II, Chapman & Hall, London, 1993. 32. A. Bohrer, G. Rist, K. Dietliker, V. Desobry, J. R Fouassier, D. Ruhlmann, Macromolecules, 25, 4182 (1992). 33. J. R Fouassier, D. Ruhlmann, Eur. Polym. J., 29 (4), 505 (1993). 34. J. R Fouassier, D. Ruhlmann, A. Erddalane, Macromolecules, 26, 721 (1993). 35. J. R Guillory, C. F. Cook, Jacs, 95, 4885 (1973). 36. R Bortolus, in: J. R Fouassier, J. F. Rabek (Eds.), "Radiation Curing in Polymer Science and Technology", vol. II, Chapman & Hall, London, 1993. 37. H-J. Timpe, Topics in Current Chemistry, vol. 156, 167, (1990). 38. H-J. Timpe, K-R Kronfeld, J. Photochem. & Photobiol., A: Chem., 46, 253 (1989). 39. J. C. Netto-Ferreira, D. Weir, J. C. Scaiano, J. Photochem. & Photobiol., A: Chem., 48, 345 (1989). 40. J. C. Scaiano, L. C. Stewart, J. Am. Chem. Soc, 105 (11), 3609 (1983). 41. E. Klimtchuk, M. A. J. Rodgers, D. C. Neckers, J. Phys. Chem., 96 (24), 9817 (1992). 42. Y. Yagci, W. Schnabel, Makromol. Chem., Rapid Commun., 8, 209 (1987). 43. Y. Yagci, S. R Pappas, W. Schnabel, Z. Naturforsch, 42a, 1425 (1987).
F r e e
R a d i c a l
C o p o l y m e r i z a t i o n
R e a c t i v i t y
R a t i o s
Robert Z. Greenley* Monsanto Co., 544 Oak Valley Drive, St. Louis, MO 63131, USA A. Introduction B. Tables Table 1. Copolymer Reactivity Ratios Table 2. Listing of Quick Basic (Microsoft) Program for Calculating Reactivity Ratios C. References A.
11-181 11-182 11-182
II-288 II-290
INTRODUCTION
When a vinyl monomer is copolymerized with a second monomer, the relationship between the composition of the initially formed copolymer and the initial monomer mixture is given by
where m \ is the number of moles of monomer 1 entering the copolymer, ra2, the number of moles of monomer 2 entering the copolymer, Mi, the number of moles of monomer 1 in the monomeric mixture, M2, the number of the moles of monomer 2 in the monomer mixture, and r\ and r2 are the monomer reactivity ratios. The monomer reactivity ratios, r\ and r 2 , for any monomer pair are the ratios of the rate constants of the different propagation reactions:
with r\ = &11/&12, ri = ^22/^21- ~ M" represents a polymer chain ending in a radical derived from monomer M. The original compilations of reactivity ratios and their references were published by L. J. Young in the first two editions of this Handbook. In the third edition, the original listings and those through 1986 were re-evaluated. This fourth edition contains an additional 548 evaluated monomer pairs giving a total of 3,265 such pairs. Only free * Retired.
radical reactivity ratios are listed. When the original references were available, they were read. If the experimental data was published, the reactivity ratios were recalculated according to the methods of Kelen and Tudos (803,804). The 95% confidence limits for the reactivity ratios were also calculated (805). If the authors used this method for r-value evaluation, including adjustment of the monomer feeds for total conversion, then the reported values were utilized. There are a number of reported reactivity ratios that are not reported here. This is due to the absence of these values in the abstracts of papers which were published in journals unavailable to the author. All of the monomer pairs in Table 1 are cross-referenced. The full spelling of each monomer was included in its Monomer 1 citation. Sometimes truncated but distinguishable names have been used in the Monomer 2 lists. If only the reactivity ratios and reference are given, then, either no experimental data was given or the journal was not available and the Chemical Abstracts summary was the source of the data. If a Y or N (yes or no) appears in the conversion (Conv.) column then the reactivity ratios were recalculated. If a recalculation was performed but the 95% confidence columns (95%) are still left blank, it indicates that only two feed/polymer data pairs were available. In general, if there is a citation (Y or N) in the Conv. column but no reactivity ratios are shown in the reactivity ratio columns, the copolymerization did not follow the copolymerization equation (ionic or penultimate effects were prevalent). In a few cases, the data were too scattered to allow a reactivity ratio calculation. Recalculations yield negative reactivity ratios in several cases. We are aware that this is a physically unrealistic artifact. When the 95% confidence limits are applied to these negative numbers, a value of zero usually falls within these limits. It may be noted that a single reference sometimes contains a variety of reactivity ratios for one monomer pair. The reader may assume that these result from a change of polymerization conditions; e.g., different polymerization temperatures or polymerization media of varying polarity. For those who are interested in using the Kelen-Tudos calculations, a listing of a simplistic program written in QuickBasic (Microsoft) is also given (Table 2).
B. TABLES TABLE 1. COPOLYMER REACTIVITY RATIOS Monomer 1 Acenaphthalene Acenaphthalene Acenaphthalene Acenaphthalene Acenaphthalene Acenaphthalene Acenaphthalene Acenaphthalene Acenaphthalene Acenaphthalene Acenaphthalene Acenaphthalene Acenaphthalene Acenaphthalene Acenaphthalene Acenaphthalene Acetamide, A^-(4-methacryloyloxyphenyl)2-(4-methoxy) Acetamide, TV-vinylAcetamide, Af-vinylAcetamide, AT-vinylAcetamide, N-vinylAcetamide, N-vinylAcetamide, Af-vinylAcetanilide, 4-(2-methacryloyloxy)ethyloxy) Acetanilide, 4-(2-methacryloyloxy)hexyloxy) Acetanilide, 4-(methacryloyloxy)Acetate, 2-chloro-, vinyl Acetate, allyl Acetate, chloro-, allyl Acetate, dichloro-, allyl Acetate, isopropenyl Acetate, trichloro-, allyl Acetylene, phenylAcetylene, phenylAcetylene, phenylAcetylene, phenylAcetylene, phenylAcetylene, phenylAcetylene, phenylAcetylene, phenylAcetylene, phenylAcetylene, phenylAcetylene, phenylAcetylene, phenylAcetylene, phenylAconitate, trimethyl Aconitate, trimethyl Aconitate, trimethyl Aconitate, trimethyl Aconitate, trimethyl Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein
Monomer 2 Acrylate, (-)-menthyl Acrylonitrile Carbazole, N-vinylFumarate, diisopropyl Maleic anhydride Maleic anhydride Maleimide, N-cyclohexylMethacrylate, (-)-menthyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylonitrile Pyrrolidone, N-vinylPyrrolidone, N-vinylStilbene Styrene Methacrylate, 2-hydroxyethyl Acrylamide Methacrylate, Methacrylate, Methacrylate, Vinyl acetate Vinyl acetate Methacrylate,
rx
2.56 6.62 2.57 0.46 0.46 0.57 2.48 1.05 0.99 2.25 2.38 5.65 0.33 1.49
±95%
1.77 0.13 0.55 0.14 0.15
0.23
r2
0.02 -0.03 0.06 0.02 -0.04 0.11 0.316 0.36 0.38 0.44 0.15 -0.01 3.81 0.61
±95%
Conv.
Refs.
Y
645 575 331 1039 1039 26 1039 645 326 326 575 575 326 326 725 525 1051
0.12
N
0.05
N
0.085 0.04 0.04
Y N N
0.04
N N N
2-hydroxyethyl
0.3 0.19 0.71 0.01 5.5 21 0.67
1.4 2.65 1.18 2.1 0.6 0 1.39
984 984 984 984 984 984 1096
Methacrylate, 2-hydroxyethyl
0.87
1.19
1096
Methacrylate, 2-hydroxyethyl Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Fumarate, diisopropyl Vinyl acetate Acrylate, methyl Acrylate, methyl Acrylonitrile Isoprene Maleic anhydride Methacrylate, methyl Methacrylate, butyl Methacrylate, isobutyl Methacrylate, methyl Methacrylate, methyl Methacrylonitrile Pyridine, 2-vinylStyrene Acrylonitrile Butadiene Styrene Vinyl chloride Vinylidene chloride Acrylamide Acrylamide Acrylate, butyl Acrylate, butyl Acrylate, ethyl Acrylate, ethyl Acrylate, methyl Acrylate, methyl
1.94 1.18 0.43 0.69 0.54 0.011 0.28 0.272 0.093 0.325 0.1 0.08 0.2 0.21 0.27 1.69 0.07 0.04
0.78 0.8 1.8 0.77 0.57 0.67 0.41 0.622 0.664 0.266 3.01 0.06 1.5 1.7 1.9 -0.06 1.111 0.78
1096 892 1045 1045 1045 1038 1045 60 731 60 648 797 443 565 565 357 732 648 192 357 147 147 147 147 149 207 208 291 292 291 292 207 291
methyl methyl methyl
0.33 -0.48 0 -0.013 0.19 0.15 1.95 1.59 1.86 2.29 1.2 1.98 -0.07 1.41
0.072 0.01 0.083
26.56 0.016 0.12 0.11 0.22 0.009 0.94 0.58 0.1 0.19 0.58 0.44 0.03 0.4
0.324 4.24 0.4 1.026 0.04 64.6 0.8 0.18 0.638 1.12 0.6 1.09 7.86 0.83
0.062 0.045 0.044
Y Y Y
0.16 0.095
Y Y
23.74 0.23 0.02 0.032 0.41
Y Y Y Y Y Y N N N Y N
0.25 3.58 0.12
N N Y
0.02 0.92 0.4 0.091
TABLE 1. cont'd Monomer 1 Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein Acrolein diethylacetal Acrolein diethylacetal Acrolein, methylAcrolein, methylAcrolein, methylAcrolein, methylAcrolein, methylAcrolein, methylAcrolein, methylAcrolein, methylAcrolein, methylAcrolein, methylAcrolein, methylAcrolein, methylAcrolein, 2-chloroAcryl-2/-ethyl-4,5,7-trinitro9-flurenone-2-carboxylate Acryl-2/-ethyl-4,5,7-trinitro-9-flurenone2-carboxylate Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide
Monomer 2 Acrylate, methyl Acrylic acid Acrylic acid Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Methacrylate, methyl Methacrylate, methyl Methacrylonitrile Methacrylonitrile Pyridine, 2-vinylStyrene Styrene Styrene Styrenesulfonate, /?-, sodium Styrenesulfonate, /?-, sodium Styrenesulfonate, p-, sodium Vinyl acetate Vinyl chloride Acrylonitrile Maleic anhydride Acrylate, butyl Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Methacrylate, methyl Methacrylonitrile Methacrylonitrile Methacrylonitrile Styrene Styrene Vinyl acetate Styrene Acrylate, iV-(2-hydroxyethyl)carbazolyl Methacrylate, JV-(2-hydroxyethyl)carbazolyl Acetamide, Af-vinylAcrolein Acrolein Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid, cw-3-bromoAcrylic acid, ds-3-ethylAcrylic acid, trans-3-bromoAcrylic acid, frcms-3-ethylAcrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Cinnamic acid, cisCinnamic acid, transCrotonic acid Crotonic acid Crotonic acid Crotonic acid Crotonic acid, cisCrotonic acid, trans-
r\
±95%
r2
±95%
Conv.
Refs.
0.93 1.24
0.38 0.28
N Y
0.06 0.03 0.01
N N N
0.05 0.4 0.05
Y N N
0.03 0.017 0.02 0.006 0.033 0.071 0.009 0.12 0.11
N Y N Y Y Y Y N N
0.19
Y
0.01
N
0.017
N
0.05 0.079
Y
292 57 57 207 207 208 504 291 292 208 446 208 291 292 307 57 57 57 207 271 767 767 589 455 587 589 91 589 208 587 589 223 589 589 806 715
0.096
Y
703
0.58 0.1 0.029 0.069 0.012 0.14
N N Y Y Y N
0.11 0.1 0.16 0.11 0.033 0.1 0.75
Y Y Y Y Y Y N
0.28 0.15 0.14 0.19
Y Y Y Y
0.024
Y Y
2.54 2.48 0.5 1.16 1.07 1.52 1.28 0.76 0.59 0.68 0.72 2.64 0.216 0.02 0.32 0.395 0.26 0.113 3.04 5.22 0.02 0.18 2.5 1.7 3.8 3.8 1.72 0.4 1.78 1.25 1.25 0.833 0.3 0.98 0.15 0.585
0.07 0.028
1.08 0.08 1.15 0.88 0.71 0.48 0.6 1.136 1.33 1.17 1.2 -0.12 0.257 0.22 0.205 0.327 0.047 0.01 -0.02 0.03 11.19 0.07 0.02 0.15 0.15 0.15 0.03 0.1 0.41 0.45 0.45 0.173 0.41 0.15 0.02 0.912
0.102
0.022
0.773
1.4 0.8 0.18 1.08 0.445 1.346 0.598 0.58 1.06 7.64 6.32 4.13 8.19 0.81 1.08 0.5 1.36 1.3 3.84 3.4 3.76 4.23 4.72 5.32 12
0.13 0.08 0.07 0.12 0.3 0.12 0.14 0.036 0.01 0.002 0.092 0.16 0.018 0.43 0.13
0.42 0.07 0.092
0.23 0.02 0.17 0.075 0.044 0.047 1.67 0.68 0.76 1.09 0.11 0.51 0.26 0.68 0.24 0.89 1.37
0.33
0.3 1.95 1.59 0.288 1.644 0.341 1.38 3.8 0.29 -0.2 -0.16 -0.33 -0.21 0.863 0.97 1.8 0.88 0.8 -0.24 -0.18 -0.19 0.11 0.12 -0.085
984 207 208 221 278 278 37 869 869 298 298 298 298 228 228 330 421 461 298 298 298 298 569 569 341 341
References page II - 290
TABLE 1. cont'd Monomer 1
Monomer 2
r\
Dioxolane, l,3,4-methylene-2-trichloro- 8.6 Maleic anhydride 0.56 Methacrylate, 2-hydroxyethyl 0.05 Methacrylate, 2-hydroxyethyl 0.14 Methacrylate, 3-methoxy0.04 2-hydroxypropyl Acrylamide Methacrylate, dimethylaminoethyl 0.52 sulfate Acrylamide Methacrylate, methyl 2.29 Acrylamide Methacrylate, methyl 0.53 Acrylamide Methacrylate, methyl 0.82 Acrylamide Methacrylate, methyl 0.9 Acrylamide Methacrylic acid 0.57 Acrylamide Methacrylic acid 0.58 Acrylamide Methacrylic acid 0.56 Acrylamide Methylenebutyrolactone 0.3 Acrylamide Styrene 0.58 Acrylamide Styrene 1.32 Acrylamide Styrene 0.33 Acrylamide Styrene 0.59 Acrylamide Styrene 8.97 Acrylamide Styrene 0.2 Acrylamide Succinimide, N-vinyl1.86 Acrylamide Vinyl chloride Acrylamide Vinyl methyl ketone 3.99 Acrylamide Vinyl methyl ketone 1.02 Acrylamide Vinylene carbonate 13.8 Acrylamide Vinylmethylphenylsulfonium 3.4 tetrarluoro Acrylamide Vinylsulfonic acid 3.5 Acrylamide, 2-chloro-WV-dimethylMethacrylate, methyl -0.159 Acrylamide, 2-chloro-AW-dimethylStyrene -0.036 Acrylamide, JV,7V-dibutylStyrene 0.294 Acrylamide, WV-diethylAcrylic acid 0.35 Acrylamide, iV,iV-diethylButanoate, 3-acrylamido-3-methyl-, 0.987 sodium Acrylamide, A^TV-diethylMethacrylate, methyl 0.41 Acrylamide, MN-diethylStyrene 0.39 Acrylamide, WV-diethylStyrene 0.34 Acrylamide, A^-diethylStyrene 0.18 Acrylamide, WV-dimethylMethacrylate, methyl 0.57 Acrylamide, iV,N-dimethylMethacrylate, methyl 0.59 Acrylamide, A^Af-dimethylMethacrylate, methyl 0.21 Acrylamide, A^V-dimethylStyrene 0.12 Acrylamide, A^V-dimethylStyrene 0.49 Acrylamide, A^V-dimethylStyrene 0.47 Acrylamide, MiV-dimethylSulfonate, 2-acrylamido1.108 2-methylpropane Acrylamide, N,7V-dimethylVinyl methyl ketone 0.82 Acrylamide, A^-(2-(4-hydroxyphenyl)ethyl)- Methacrylamide, A^-(2-hydroxypropyl)0.95 Acrylamide, N-(2-(propionamide)Styrene 0.86 Acrylamide, Af-methylMethacrylate, methyl 0.05 Acrylamide, N-methylol Acrylate, butyl 0.61 Acrylamide, Af-methylol Acrylate, ethyl 1.4 Acrylamide, N-methylol Acrylate, methyl 1.9 Acrylamide, iV-methylol Acrylonitrile 1.2 Acrylamide, N-methylol Acrylonitrile 2.33 Acrylamide, N-methylol Acrylonitrile 2.56 Acrylamide, TV-methylol Methacrylate, methyl 0.7 Acrylamide, N-methylol Methacrylate, methyl 0.7 Acrylamide, JV-methylol Styrene 0.48 Acrylamide, Af-methylol Vinyl chloride Acrylamide, N-methylolStyrene 0.4 Acrylamide, N-octadecylAcrylonitrile 1.4 Acrylamide, N-octadecylMethacrylate, methyl 0.42
±95%
Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide
r2
±95%
Conv.
0.037 0 1.89 0.98 3.98
616 655 689 928 689
0.05
1.9
0.2
0.44 0.09
2.34 3 2.53 3 1.63 4.4 0.15 2.85 1.17 1.21 1.49 1.13 0.65 1.05 0.17
0.17 0.09
N N
0.45
N
0.06 0.04 0.16
N N N
0.03
N
0.7 0.13
0.47 0.75 0.05 0.1
0.44 0.23
Y Y Y
0.15 0.502 0.152 0.058 0.12 0.153
0.3 2.71 1.29 1.6 0.36 0.22
0.1 0.398 0.065 0.058 0.04 0.138
N Y
0.15
1.65 1.23 1.36 1.54 2.15 2.8 2.64 1.15 1.37 1.32 0.162
0.16
N
0.08 0.1 0.15 0.35 0.1 0.12 0.949
N N N N N N Y Y
1.07
0.12 0.13 0.14 0.43
0.08 0.09 0.21 0.3 0.15 0.2 0.59
Refs.
0.36 0.09 0.3 0.72
0.1 1.01 1.84 1.14 0.87 1.4 1.3 0.7 0.98 0.22 1.62 1.62 0.03
0.43 0.09 0.21 0.09
0.03 0.17 0.11
1.55 1.034 4.119
0.05 0.02 0.07
1052
Y Y
N N
Y Y Y
314 314 314 691 1028 852 852 746 295 314 314 314 343 555 600 156 609 609 387 793 1066 917 917 806 205 857 170 739 739 739 315 315 691 170 315 315 857 609 965 295 691 441 442 441 442 577 596 593 596 596 157 891 119 290
TABLE 1. cont'd Monomer 1 Acrylamide, N-octadecylAcrylamide, N-octadecylAcrylamide, Af-octadecylAcrylamide, Af-octylAcrylamide, N-propylAcrylamide, N-propylAcrylamide, N-tert-buty\Acrylamide, N-tert-buty\Acrylamide, a-fluoroAcrylamido, 1-,-1-deoxy-D-glucitol Acrylamido, 1-,-1-deoxy-D-glucitol Acrylamido, 1-,-1-deoxy-D-glucitol Acrylamido, 2-,2-methylpropanesulfonate, sodium Acrylamido, 2-,-2-methylpropanesulfonic acid Acrylamido, 2-,-2-methylpropanesulfonic acid Acrylamido-2-methylpropane sulfonate sodium salt Acrylamidomethylamino, /?-, azobenzene Acrylamidomethylamino, p-, azobenzene Acrylate, (-)-menthyl Acrylate, (-)-menthyl Acrylate, 1,1,5-trihydroperfluoroamyl Acrylate, 2,3-dibromopropyl Acrylate, 2,4,5-trichlorophenyl Acrylate, 2,4,5-trichlorophenyl Acrylate, 2,4,6-tribromophenyl Acrylate, 2,4-dinitrophenyl Acrylate, 2,4-dinitrophenyl Acrylate, 2(0-ethyl methylphosphonoxy)-, methyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethyi Acrylate, 2-chloroethyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethylglucitol Acrylate, 2-cyano-, methyl Acrylate, 2-cyano-, methyl Acrylate, 2-cyanoethyl Acrylate, 2-ethylhexyl Acrylate, 2-ethylhexyl Acrylate, 2-ethylhexyl Acrylate, 2-ethylhexyl Acrylate, 2-ethylhexyl Acrylate, 2-ethylhexyl Acrylate, 2-hydroxyethyl Acrylate, 2-hydroxyethyl Acrylate, 2-hydroxyethyl Acrylate, 2-nitrobutyl Acrylate, 2-nitrobutyl Acrylate, 2-nitrobutyl Acrylate, 3,4-epoxyhexahydrobenzyl
Monomer 2 Styrene Vinyl acetate Vinylidene chloride Styrene Acrylate, butyl Acrylate, methyl Acrylonitrile Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Styrene Vinyl acetate Vinyl acetate
r\ 0.54 8.25 1.4 0.258 0.4 0.26 1.14 2.83 0.148 0.05 0.03 0.98 11.6
±95% 0.14 1.46 0.11 0.119
0.081 0.09 0.02 0.87
r2 2.08 0.004 0.432 2.715 0.8 1.2 0.2 0.25 2.13 3.75 2.42 0.03 0.05
±95%
Conv.
0.12 0.011 0.008 0.244
Y Y Y
0.136 0.24 0.08 0.17
Y N N N
Refs. 290 119 119 806 730 730 709 709 823 258 258 258 700
Methacrylate, 2-hydroxyethyl
0.9
0.86
618
Methacrylate, 2-hydroxypropyl
1.03
0.89
618
iV-Vinylpyrrolidone
0.66
0.13
939
0.083 0.126
858 858 645 667 809 643 840 622 643 716 716
Styrene 8.5 Vinyl acetate 12.98 Acenaphthalene Pyridine, 4-vinyl0.291 Methacrylonitrile 0.14 Styrene 0.16 Pyrrolidone, N-vinyl0.163 Styrene 0.23 Styrene 0.1 Acrylate, N-(2-hydroxyethyl)-carbazolyl 0.158 Methacrylate, A^-(2-hydroxyethyl)0.186 carbazolyl Methacrylate, methyl 0.44 Acrylate, ethyl Acrylate, methyl Acrylonitrile Itaconate, bis(tri-rc-butyltin) Itaconic anhydride Itaconic anhydride Maleic anhydride Methacrylate, methyl Pyrrolidone, Af-vinylStyrene Styrene Styrene Vinyl butyl ether Vinyl isobutyl ether Styrene Styrene, a-methylVinyl acetate Styrene Acrylate, glycidyl Methacrylate, glycidyl Styrene Styrene Vinyl acetate Vinyl chloride Acrylate, butyl Acrylate, ethyl Acrylate, methyl Acrylonitrile Methacrylate, methyl Styrene Acrylonitrile
1.03 1.07 0.87 0.683 -0.016 0.251 7.15 0.37 0.52 0.1 0.139 0.12 2.01 2.24 0.14 0.001 0.5 0.128 1.12 0.09 0.31 0.26 7.5 4.15 0.9 0.97 0.9 1.76 0.27 0.12 0.388
0.45
Y Y
0.008 0.048
Y Y
0.015 0.009
2.32 1.03 0.42 0.012 0.277 0.2 0.109 0.243
0.026 0.034
Y
0.25
0.73
0.04
0.017 0.02 0.021
0.022 0.021 0.31 0.17 0.083
0.09 0.074 0.07 0.13 0.6
0.23 0.24 0.13 0.69 0.04 0.01 0.074
0.9 0.9 1.03 0.391 2.46 2.61 0.027 2.15 0.03 0.55 0.494 0.54 0 0 0.49 0.05 0.005 0.399 1.18 2.41 0.96 0.94 0.04 0.16 0.3 0.5 0.94 0.67 1.19 0.35 0.25
882
0.38 0.32 0.004
Y Y Y
0.47 0.097
Y Y
0.2 0.032 0.06 0.46 0.3
Y N Y N
0.06 0.03 0.04 0.25 0.12 0.03 0.13
N N N N N N Y
726 726 790 940 365 365 117 790 790 140 178 790 790 790 806 452 452 178 126 674 126 463 570 510 868 868 868 234 234 234 680
References page II - 290
TABLE 1. cont'd Monomer 1 Acrylate, 3,4-epoxyhexahydrobenzyl Acrylate, 4-acetylphenyl Acrylate, P-acetoxymethyl-, methyl Acrylate, P-acetoxymethyl-, methyl Acrylate, |3-chloro-2-hydroxypropyl Acrylate, p-ethoxy-, ethyl Acrylate, (3-ethoxy-, ethyl Acrylate, N-(2-hydroxyethyl)3,6-dichlorocarbazolyl Acrylate, 7V-(2-hydroxyethyl)carbazolyl Acrylate, AH2-hydroxyethyl)carbazolyl Acrylate, iV-(2-hydroxyethyl)carbazolyl
Monomer 2 Styrene Methacrylate, glycidyl Methacrylate, methyl Styrene Acrylonitrile Acrylonitrile Styrene Methacrylate, 2,4-dinitrophenyl
Acryl^'-ethyl-^J-trinitro^-fluorene Acrylate, 2,4-dinitrophenyl Acryloyl-(3-hydroxyethyl3,5 -dinitrobenzoate Acrylate, iV-(2-hydroxyethyl)carbazolyl Methacryloyl-p-hydroxyethyl3,5-dinitrobenzoate Acrylate, A^-(2-hydroxyethyl)carbazolyl Methacryloyl-p-hydroxyethyl3,5-dinitrobenzoate Acrylate, a-(4-chlorobenzyl)-, ethyl Styrene Acrylate, a-(4-cyanobenzyl)-, ethyl Styrene Acrylate, a-(4-methoxybenzyl)-, ethyl Styrene Acrylate, a-((9-ethyl methylphosphonoxy)- Methacrylate, methyl methyl Acrylate, a-(hydroxymethyl)-, methyl Styrene Acrylate, a-[2,2-bis(carbomethoxy)ethyl]-, Methacrylate, methyl methyl Acrylate, a-[2,2-bis(carbomethoxy)ethyl]-, Styrene methyl Acrylate, a-acetoxy-, ethyl Acrylate, a-chloro-, ethyl Acrylate, a-acetoxy-, ethyl Acrylate, ethyl Acrylate, a-acetoxy-, ethyl Methacrylate, methyl Acrylate, a-acetoxy-, ethyl Styrene Acrylate, a-acetoxy-, ethyl Vinyl acetate Acrylate, a-benzyl-, methyl Styrene Acrylate, a-benzyl-, ethyl Styrene Acrylate, a-benzyl-, methyl Methacrylate methyl Acrylate, a-benzyl-, methyl Methacrylate methyl Acrylate, a-bromo-, ethyl Styrene Acrylate, a-butyl-, methyl Styrene Acrylate, a-chloro-, methyl Methacrylate, methyl Acrylate, a-chloro-, ethyl Acrylate, a-methoxy-, methyl Acrylate, a-chloro-, ethyl Acrylate, a-acetoxy-, ethyl Acrylate, a-chloro-, ethyl Acrylate, a-fluoro-, ethyl Acrylate, a-chloro-, ethyl Acrylate, methyl Acrylate, a-chloro-, ethyl Acrylonitrile, a-methoxyAcrylate, a-chloro-, ethyl Methacrylonitrile Acrylate, a-chloro-, ethyl Styrene Acrylate, a-chloro-, ethyl Vinyl acetate Acrylate, a-chloro-, methyl Acrylonitrile Acrylate, a-chloro-, methyl Methacrylate, methyl Acrylate, a-chloro-, methyl Styrene Acrylate, a-chloro-, methyl Vinylidene cyanide Acrylate, a-chloro-, sodium Styrenesulfonate, /?-, sodium Acrylate, a-cyano-, methyl Acrylonitrile Acrylate, a-cyano-, methyl Acrylate, methyl Acrylate, a-cyano-, methyl Methacrylate, methyl Acrylate, a-cyano-, methyl Methacrylate, methyl Acrylate, a-cyano-, methyl Methacrylonitrile Acrylate, a-cyano-, methyl Styrene Acrylate, a-cyclohexyl-, methyl Styrene Acrylate, a-ethyl-, methyl Styrene Acrylate, a-ethyloxymethyl-, methyl Styrene Acrylate, a-fluoro-, ethyl Acrylate, a-chloro-, ethyl Acrylate, a-fluoro-, methyl Styrene Acrylate, a-hexafluoropropyloxymethyl-, Styrene methyl
rx
±95%
r2
±95%
Conv.
Refs.
0.3 0.13
N Y
1.8 27.03 0.032
N Y Y
680 1012 1091 1091 654 194 194 736
1.97 0.292 0.24 0.19 0.7 -0.26 -0.21 0.115
0.35 0.141
0.56 0.44 0.029
0.27 0.644 0.91 0.34 0.24 2.42 46.98 1.207
0.912 0.109 0.62
0.079 0.026 0.044
0.585 0.158 0.361
0.028 0.015 0.016
Y Y Y
715 716 702
1.04
0.14
0.08
0.026
Y
702
0.334
0.022
1.364
0.018
Y
719
1.03 0.65 0.71 0.44
0.13 0.09 0.24
0.04 0.06 0.33 0.73
0.09 0.05 0.3
806 806 806 851
0.34 0.04
0.36 3.7
932 1092
0.09
0.58
1092
0.3 0.968 0.608 0.173 5.621 0.175 0.9 0.173 0.09 0.44 0.205 1.13 0.58 1.71 2.9 3.22 0.9 2 0.32 30 1.76 1.92 0.3 0.313 0.27 0.68 0.34 0.03 0.135 0.15 0.61 -0.001 0.197 0.24 0.21 0.16 0.07
0.033 0.02 0.01 0.094 0.053 0.2 0.022 0.01 0.08 0.053 0.19
0.11 0.18 0.08 0.021 0.06 0.09 0.07 0.01 0.016 0.01 0.05 0.034 0.014 0.11
1.71 0.943 1.65 0.557 0.08 0.57 0.14 2.36 3.9 0.02 0.812 0.31 0.11 0.3 0.21 0.09 0.3 0.45 0.08 0.03 0.122 0.11 0.25 0.066 1.44 0.01 0.02 0.21 0.068 0.18 0.05 1.615 0.758 0.37 2.9 0.66 0.23
0.075 0.12 0.031 0.021 0.028 0.17 0.23 0.19 0.04 0.043 0.24
Y Y Y Y Y Y N Y Y
0.07 0.081 0.09
Y N
0.07 0.31 0.02 0.04 0.02 0.014 0.01 0.01 0.048 0.014
Y Y N N N Y N N Y Y
0.17
638 244 244 244 244 49 806 610 610 806 49 6 638 638 638 638 638 638 806 638 6 31 74 82 834 141 141 141 182 143 141 49 49 1047 638 806 1047
TABLE 1. cont'd Monomer 1 Acrylate, a-hydroxymethyl-, ethyl Acrylate, a-hydroxymethyl-, ethyl Acrylate, a-hydroxymethyl-, ethyl Acrylate, a-isobutyl-, methyl Acrylate, a-isopropyl-, methyl Acrylate, a-isopropyloxymethyl-, methyl Acrylate, a-methoxy, methyl Acrylate, a-methoxy-, methyl Acrylate, a-p-chlorobenzyl-, methyl Acrylate, a-/?-methoxybenzyl-, methyl Acrylate, a-phenoxymethyl-, methyl Acrylate, a- phenoxymethyl-, methyl Acrylate, a-phenyl-, methyl Acrylate, a-phenyl-, methyl Acrylate, a-phenyl-, methyl Acrylate, a-phenyl-, methyl Acrylate, a-phenyl-, methyl Acrylate, a-phenyl-, methyl Acrylate, a-phenyl-, methyl Acrylate, a-phenyl-, methyl Acrylate, a-phenyl-, methyl Acrylate, a-phenyl-, butyl Acrylate, a-phenyl-, chloroethyl Acrylate, a-phenyl-, propyl Acrylate, a-propyl-, methyl Acrylate, a-propyloxymethyl-, methyl Acrylate, a-seobutyl-, methyl Acrylate, a-tetrafluoropropyloxymethyl-, methyl Acrylate, a-tetrafluoropropyloxymethyl-, methyl Acrylate, a-trifluoroethyloxymethyl-, methyl Acrylate, a-trifluoromethyl-, methyl Acrylate, a-trifluoromethyl-, methyl Acrylate, a-trifluoromethyl-, methyl Acrylate, a-trifluoromethyl-, methyl Acrylate, a-trimethylsiloxy-, methyl Acrylate, benzyl Acrylate, benzyl Acrylate, benzyl Acrylate, benzyl Acrylate, benzyl Acrylate, benzyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, butyl
Monomer 2
rx
±95%
Conv.
Refs.
0.229 0.17 0.03 0.022 0.052
Y N Y Y Y
0.078 0.222 0.109 0.038 0.05
Y Y Y Y
0.015 0.022 0.015 0.015 0.029
Y Y Y Y Y
0.068
Y
1011 1027 982 49 49 1047 638 806 905 905 1048 1048 141 141 141 49 143 141 399 488 49 488 488 488 49 1047 49 1047
0.668 1.34 0.546 0.202 0.036 0.26 0.11 0.513 0.255 0.13 0.755 0.256 1 6.7 0 0 0.25 1 0.4 0.45 1.275 0.107 0.201 0.126 0.208 0.29 0.004 0.61
Styrene
0.17
0.37
1047
Styrene
0.2
0.26
1047
-0.17 0 0.1 0 1.42 0.72 0.63 9.9 0.19 0.2 0.248 0.24 0.638 1.12 0.02 0.8 0.87 0.3 1.08 0.91 0.19 1.06 0.894 0.82 0.9 1.2 10.2 5.83 0.041 0.074 13.94 0.118
0.058 0.034 0.008 0.061 0.102
0.008 0.055 0.09 0.063 0.07 0.024
0.18 0.1 0.1 0.03 0.16 0.2 0.12 0.041 0.01 0.032 0.41
0.06 0.18 0.13 0.15 0.019 0.13 42.2 0.043 0.03 0.38 0.019
0.389 1.26 0.468 0.974 1.872 0.41 0.58 1.131 1.87 1.71 1.13 0.176 0.06 0.08 0.21 0.3 0.19 0.06 0.03 0.06 1.176 0.04 0.025 0.03 0.821 0.47 2.29 1.43
±95%
Azlactone, 2-vinyl-4,4-dimethylMethacrylate, methyl Styrene Styrene Styrene Styrene Acrylate, a-chloro-, ethyl Styrene Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Styrene Acrylate, methyl Acrylonitrile Methacrylate, methyl Methacrylate, methyl Methacrylonitrile Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Methacrylate, methyl
Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Styrene, p-chloroStyrene Acrylonitrile Acrylonitrile Allyl chloride Methacrylate, methyl Styrene Styrene 2-Oxazoline, 2-isopropenylAcrolein Acrolein Acrolein, methylAcrylamide, N-propylAcrylamide, Af-methylolAcrylate, 2-hydroxyethyl Acrylic acid Acrylic acid Acrylic acid, a-bromoAcrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Allyl acetate Allyl chloride Benzofuran, 2-vinylButadiene Ethylene Furan, 2-vinyl-5-methyl
0.12 0.062 0.127 0.042 0.034
r2
1.8 3.2 2.3 0.24 0.46 0.28 1.49 0.06 2.23 0.494 0.534 1.4 1.86 2.29 2.5 0.4 0.61 0.9 0.59 1.31 0.09 1.679 0.781 1.08 1 1 0.039 0.1 7.8 1.04 0.01 0.392
0.23 0.5 0.2 0.02
Y N N N
0.19
N
0.14 0.05 0.028 0.08 0.19 0.58
Y Y Y Y N
0.23 0.27 0.3
N N N
0.058 0.083 0.08
Y Y N
0.066
N
1.36 0.11 0.003 0.051
N Y N Y
681 825 825 825 1101 23 385 438 277 178 277 894 291 292 589 730 441 868 187 252 733 118 162 233 513 513 1053 438 1020 257 42 1105
References page II - 290
TABLE 1. cont'd Monomer 1 Acrylate, Acrylate, Acrylate, Acrylate,
butyl butyl butyl butyl
Acrylate, butyl Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate,
butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl butyl cis-B-cyano-, methyl c/s-B-cyano-, methyl cresyl cyclododecyl cyclododecyl cyclododecyl cyclohexyl cyclohexyl cyclohexyl cyclohexyl cyclohexyl cyclohexyl di-, copper
Acrylate, di-, copper Acrylate, di-, copper
Monomer 2 Itaconate, bis(tri-w-butyltin) Itaconate, dimethyl Maleimide, iV-(2,4-dimethylphenyl)Methacrylate, 2-(Af,AT-dimethylcarbamoyloxy)ethyl Methacrylate, 2-chloro2,3,3,3-fluoropropyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, butyl Methacrylate, glycidyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylic acid Oxazoline, 2,2-isopropenylPyridine, 2-vinylPyridine, 2-vinylPyridine, 4-vinylStyrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene, o-chloroStyrene, p-l-(2-hydroxybutyl)Styrene, p-octylamine sulfonate Succinimide, iV-vinylThiophene, 3-vinyl Vinyl acetate Vinyl bromide Vinyl bromide Vinyl chloride Vinyl fluoride Vinyl fluoride Vinyl methyl ketone Vinyl,/?-, benzylethylcarbinol Vinylanthracene, 9Vinylidene chloride Vinylidene chloride Vinylidene chloride Acrylonitrile Styrene Acrylonitrile Styrene Styrene Styrene N-Vinylpyrrolidone Styrene Styrene Styrene Styrene Styrene Methacrylate, di-, dicyclopentadienyltitanium Styrene Styrene
/*i
±95%
0.91 0.4 o.62 0.47
r2
±95%
Conv.
0.422 0.94 0.2 1.89
Refs. 940 398 788 600
0.079
0.304
0.221
0.636
N
927
0.09 0.171 0.24 0.3 0.083 0.13 0.11 0.43 0.31 0.24 0.1 0.11 0.23 0.25 0.34 0.38 -0.106 0.29 0.18 0.19 0.21 0.15 0.164 0.164 0.2 0.17 0.3 1.54 0.386 3.48 4.07 3.7 4.4 19 19 0.8 0.17 3.717 0.873 0.46 0.58
0.11 0.041 0.16
4.75 5.35 3.3 2.2 2.16 0.92 2.86 1.88 1.25 1.4 2.51 2.59 4.3 0.79 0.79 0.75 1.23 0.44 0.84 0.66 0.82 0.8 0.698 0.698 2.25 0.4 2.3 0.15 0.499 0.018 0.18 0.19 0.07 0.01 0.01 1.81 0.4 0.126 0.934 0.84 0.87
4.2 0.32 6.82
Y Y Y
0.57 0.2 0.32 0.4 0.31
Y N Y N N
0.14 0.34 0.08 0.11 0.1 0.21 0.03 0.2
N N
0.072 0.16
Y N
0.24
N
0.054 0.006
Y Y
358 333 662 187 674 30 639 87 187 862 236 78 78 1032 1032 1032 19 20 38 38 463 549 612 632 558 548 817 789 1000 301 268 268 518 604 606 53 591 123 118 464 464 1034 1034 363 806 806 806 1061 1061 806 806 806 806 876
0.052 0.15 0.018 0.07 0.1 0.01 0.04 0.05 0.06 0.05 0.099 0.05 0.03
3.39 0.44
0.06 0.046 0.022
0.773 0.34 0.31 0.301 1.297 0.272 0.254 0.16 0.17 0.18 1.09
0.067 0.15 0.08 0.072 0.088 0.048 0.141 0.13 0.09 0.07
0.72 0.47 0.54 0.461 0.122 0.913 0.885 0.53 0.7 0.58 0.89
0.15 0.14 0.08 0.07 0.014 0.107 0.102 0.11 0.12 0.1
0.12 0.56
0.08 0.09
5.94 1.74
0.05 0.03
N N N
N N Y
N N
829 829
TABLE 1.
cont'd
Monomer 1 Acrylate, di-, nickel Acrylate, di-, nickel Acrylate, di-, zinc Acrylate, di-, zinc Acrylate, dibutylchlorotin Acrylate, diethylaluminum Acrylate, diethylaluminum Acrylate, dodecyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ferrocenylmethyl
Monomer 2 Methacrylate, di-, dicyclopentadienyltitanium Styrene Acrylonitrile Styrene Acrylate, methyl Styrene Styrene Acrylonitrile 2-Oxazoline, 2-isopropenylAcrolein Acrolein Acrylamide, Af-methylolAcrylate, 2-chloroethyl Acrylate, 2-hydroxyethyl Acrylate, oc-acetoxy-, ethyl Acrylate, hydroxyethyl Acrylic acid Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Allyl chloride Benzofuran, 2-vinylCarbazole, N-vinylEthylene, 1,1-diphenylImidazolid-2-one, 1,3-divinylImidazolid-2-one, l-ethyl-3-vinylIsopropenylisocyanate Maleimide, 2,3-dimethylAf-(2-methacryloyloxy)ethyl Methacrylate, 2-(sulfonic acid)ethyl Methacrylate, 2-bromoethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, butyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylic acid Norbornadiene Oxazoline, 2-, 2-isopropenylPropanesulfonate, 3-[diethyl2- (2-methacroy loxyethoxy)] ethyl Pyridine, 2-vinylPyridine, 2-vinylPyridine, 4-vinylPyrimid-2-one, 1,3-divinylhexahydroStyrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene 3-tri-rc-butylstannylTropone, 2-methacryloyloxyVinyl 2-chloroethyl ether Vinyl 2-chloroethyl ether Vinyl isobutyl sulfide Vinyl isobutyl sulfide Vinylanthracene, 9Vinylidene chloride Acrylate, methyl
r\
±95%
0.95 0.53 0.24 0.9 0.09 0.046 0.88 0.19 0.6 1.09 1.4 0.9 0.5 0.943 0.5 1.02 1.2 0.81 4 0.95 7.73 0.015 1.1 0.8 0.41 0.47 0.79 0.28 0.3 0.37 0.189 0.273 0.207 0.22 0.47 0.28 0.22
r2
±95%
Conv.
0.65 0.06 0.07 0.035 0.16 0.02 0.25 0.03 0.075 0.05 0.07 0.27
0.01 0.13 0.06 1.15
0.008 0.054 0.045 0.17 0.05
2.39 0.19 3.97
0.44
0.21 0.21 0.29 0.59 0.139 0.16 0.19 0.2 0.48 0.152 0.152 10.4 0.387 5 4.65 0.36 0.32 3.498 0.72 0.14
0.06
1.03
0.13 0.085
0.027 0.02 0.02 0.041 0.39
876
1.83 0.41 1.1 0.81 -0.002
0.02
N
0.02
N
0.016
2.37 1.39 1.2 1.98 1.4 1.03 0.97 0.968 0.88 0.91 0.92 1.16 0.66 0.44 0.08 5.76 0.27 0.5 -0.08 0.01 0.15 1.55
0.07 0.06
Y Y N
3.2 2.7 11.21 13.32 9.08 2.43 1.83 2 2.04
Refs.
0.44
N
0.24 0.033 0.09
N Y
0.08 0.78
N
0.334
N
0.03 0.01
N N
3.06
Y
0.43 1.05 3.95 0.39
Y Y Y Y
0.28
-0.01 1.39 0.19
0.03
N N N
0.02
Y
0.28 2.25 2.58 -0.05 0.699 1.01 0.79 0.8 0.8 0.787 0.787 0.01 3.13 0.15 0 0.05 0.05 0.295 0.58 4.46
0.1
N
0.03 0.072
N Y
0.528
Y
0.04 0.05 0.056 0.15
N N Y Y
829 646 829 659 652 652 233 894 291 292 442 726 868 244 890 711 1023 198 389 542 438 1020 757 65 800 800 434 619 564 657 358 333 662 690 30 469 87 1065 267 862 962 250 832 832 800 178 463 530 530 542 673 677 985 1104 439 726 285 336 123 65 293
References page II - 290
TABLE 1. cont'd Monomer 1 Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate, Acrylate,
ferrocenylmethyl ferrocenylmethyl ferrocenylmethyl ferrocenylmethyl ferrocenylmethyl ferrocenylmethyl furfuryl glycidyl glycidyl glycidyl glycidyl glycidyl heptafluorobutyl heptafluorobutyl heptafluorobutyl heptyl heptyl hydroxyethyl hydroxyethyl hydroxyethyl isobutyl isobutyl isobutyl isopropyl m-chlorophenyl m-nitrophenyl methyl methyl
Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl
Monomer 2 Maleic anhydride Methacrylate, methyl Methacrylate, methyl Styrene Styrene Styrene Methacrylate, 2-hydroxyethyl Acrylate, 2-ethylhexyl Acrylonitrile Styrene Styrene Vinyl acetate Butadiene Methacrylate, methyl Styrene Maleimide, AH2,4-dimethylphenyl)Methacrylate, methyl Acrylate, ethyl Acrylate, methyl Acrylate, methyl Methacrylate, methyl Methacrylate, glycidyl Methacrylate, methyl Styrene Acrylonitrile Methacrylate methyl 2-Oxazoline, 2-isopropenyl2-Oxazolinium BF4, 3-methyl2-isopropenyl2-Oxazolinium, 2-isopropenylAcetylene, phenylAcetylene, phenylAcrolein Acrolein Acrolein Acrylamide, Af-methylolAcrylamide, Af-propylAcrylate, 2-chloroethyl Acrylate, 2-hydroxyethyl Acrylate, a-chloro-, ethyl Acrylate, a-cyano-, methyl Acrylate, ot-phenyl-, methyl Acrylate, dibutylchlorotin Acrylate, ferrocenylmethyl Acrylate, hydroxyethyl Acrylate, hydroxyethyl Acrylate, tributyltin Acrylic acid, oe-bromoAcrylonitrile Acrylonitrile Acrylonitrile Acryloyl chloride Allyl acetate Allyl acrylate Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allylbenzene Benzophenone, p-vinylBenzophenone,/7-vinylButadiene Butadiene, 2-chloroCarbamate, WV-diethyl-, vinyl
rx
±95%
-0.3 0.024 0.08 -0.016 0.02 0.02 0.88 1.18 1 0.17 0.24 7.6 0.073 0.177 0.049 0.14 0.46 0.88 1 0.94 0.135 0.282 0.29 0.195 0.85 1.04 0.16 0.096
2.96 0.064
0.191 0.622 0.664 7.86 0.83 1.08 1.3 1.2 0.9 0.94 0.09 0.02 0.06 0.81 4.46 1 0.23 0.82 0.24 0.51 0.844 0.85 0.34 5 0.52
0.031 0.062 0.045 3.58 0.12 0.38
0.06 0.19 0.06
0.031 0.013 0.02 0.09 0.1 0.1 0.02 0.026 0.04 0.027 0.036 0.135 0.04 0.057
0.04 0.04
0.1 0.03 0.02 0.037 0.2
r2 0.09 2.8 2.9 1.87 2.3 2.5 1.35 1.12 1.01 0.6 0.73 0.003 0.359 0.084 0.31 0.2 2.51 0.5 1 0.23 4.1 1.24 1.04 0.755 1.3 0.928 1.9 0.251 2.08 0.272 0.093 - 0.07 1.41 2.54 1.9 0.26 1.07 0.9 3.22 0.34 1 0.09 0.14 1 0.94 0.03 0.1 0.56 1.54 1.31 2.3 0 0.33
±95%
Conv.
Refs.
0.14 0.19
Y Y
0.17
Y
0.08 0.07
N
0.34
N
0.039
Y Y Y
325 293 293 293 293 576 1063 126 114 114 126 553 206 206 206 788 980 890 890 890 639 674 30 178 363 1074 894 908
0.01 0.13 0.05 0.1 0.03 0.5 0.12 0.08 0.024 0.073 0.248 0.08 0.483
Y Y N Y Y Y Y
0.327 0.072 0.01 0.03 0.4 0.93
Y Y Y N Y N
0.13
N
0.07
N
0.1 0.1 0.03 0.044 0.08
Y N
Y 8.45 5.45 6.46 9.1 11.35 0.09 1.1 0.07 0.06 4.78
0.66 0.02 0.02 0.87 0.22
0.05 0.07 0.4 -0.02 -0.036 3.6 3.54 1.09 10.4 - 0.027
0.016 1.06 0.077 4.53 0.049
Y Y Y Y Y Y
908 60 731 207 291 292 441 730 726 868 638 141 141 659 293 890 890 659 733 1024 151 233 508 470 578 204 437 437 437 437 351 866 911 257 61 92
TABLE 1. cont'd Monomer 1 Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl
Monomer 2
rx
Carbazole, JV-vinyl0.53 Carbazole, N-vinyl0.43 Carbazole, N-vinyl0.51 Cinnamate, dibutylchlorotin 1.65 Diallyl phthalate 6.208 Diallyl phthalate 6.18 Diallylcyanamide 6.7 Diallylcyanamide 6.7 Ethylene Ethylene 19.4 Ethylene 1,1-diphenyl0.09 Ethylene, 1,1-diphenyl0.12 Ethylene tetrachloro830 Ethylene, trichloro33 Fumarate, diisopropyl 1.9 Hexatriene, tetrachloro0.262 Hexene-1 -0.13 Imidazole, l-vinyl-2-methyl1.28 Indene 0.63 Indene 0.62 Isoprene 0.12 Isoprene, 3-acetoxy0.27 Isopropenyl, 3-1-cyclohexenyl, acetate 0.37 Isopropenylisocyanate 0.6 Isopropenylisocyanate 0.799 Maleic anhydride 2.788 Maleic anhydride 2.5 Maleimide, A^-(4-bromophenyl)0.429 Maleimide, A^-(4-chlorophenyl)0.684 Maleimide, JV-(4-tolyl)0.64 Maleimide, N-phenyl0.554 Methacrylate, 2,3-epithiopropyl 0.34 Methacrylate, 2-(AyV-dimethyl 0.22 carbamoyloxy)ethyl Methacrylate, 2-chloroethyl 0.29 Methacrylate, 2-hydroxyethyl - 0.005 Methacrylate, 2-hydroxypropyl 0.013 Methacrylate, ferrocenylmethyl 1.4 Methacrylate, methyl 0.4 Methacrylate, f-butyl dimethylsilyl 0.288 Methacrylic anhydride 0.16 Oxazoline, 2-,2-isopropenyl0.16 Oxazoline, 2-,2-isopropenyl0.328 Oxazoline, 2-,2-isopropenyl0.46 4,4-dimethyl Oxazoline, 2-,4-acryloxy-methyl0.29 2,4-dimethyl Oxazoline, 2-,4-methacryl-oxy0.4 2,4-dimethyl Oxazolinium, 2-, tetrafluoro-borate, 0.552 3-methyl Phthalimide, 7V-(4-vinylphenyl)1.14 Phthalimide, N-(methacryloyloxy)0.193 Propenyl, 2-chloro-, acetate 0.7 Pyridine, 2-methyl-5-vinyl0.18 Pyridine, 2-vinyl0.37 Pyridine, 2-vinyl0.17 Pyridine, 2-vinyl0.2 Pyridine, 2-vinyl-5-ethyl0.18 Pyridine, 4-vinyl0.2 Pyridine, 4-vinyl0.15 Pyrrolidone, 1 -benzyl-3-methylene0.125 5-methyl Styrene 0.24 Styrene 0.8
±95%
r2
0.13
0.049 0.11 0.028 -0.2 0.028 0.038 0.05 0.05
0.073 0.069 0.16
±95%
Conv.
Refs.
0.029
Y
0.045
Y
0.005 0.008
Y Y
13 551 98 659 297 297 603 604 41 768 334 334 402 470 1038 5 60 465 606 606 424 770 770 434 99 260 470 628 628 644 644 787 600
N 0.01 0.01
0.087 0.6
0.049 0.051 0.099 0.052 0.16 0.048
0.036 0.007 0.35 0.12 0.057 0.032
0.043
0.02 -0.24 0.21 0 0 0.091 3.19 -0.67 0.05 0.1 0.12 0.75 5.71 0.57 0.11 0.079 0.012 0 0.39 0.155 0.14 0.103 2.81 1.32 2.19 8.67 7.335 0.042 2.15 1.07 4.75 1.9 2.07 1.3
1.36 0.03
Y Y
0.047 0.013
Y Y
0.17 0.052 0.16 0.052
Y Y Y Y
8.28 0.083 0.085 0.04 0.21
Y Y Y N Y
0.191
Y
726 358 333 293 324 1069 275 862 877 596 596
0.56
596
0.344
0.025 0.21
0.82 0.192
0.05 0.4 0.03 0.03 0.004 0.03
N N
0.11
1.56 1.23 0 1 2.13 1.72 2.12 1.32 1.78 2.14 1.58
0.028
0.15 0.05
0.105
Y
877
0.168
Y
0.3 0.54 0.26 0.1 0.03 0.32
N Y N N N N
0.24
Y
636 979 445 232 2 231 749 231 231 424 633
0.057
Y
139 14
References page II - 290
TABLE 1. cont'd Monomer 1 Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, mono-, ethylene glycol Acrylate, o-chlorophenyl Acrylate, o-chlorophenyl Acrylate, octadecyl Acrylate, octadecyl Acrylate, octadecyl Acrylate, octadecyl Acrylate, octadecyl Acrylate, octadecyl Acrylate, octadecyl Acrylate, octadecyl Acrylate, octadecyl Acrylate, octyl Acrylate, octyl
Monomer 2 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, a-methoxyStyrene, m-methylStyrene, p-l-(2-hydroxybutyl)Styrene, /?-Af,N-dimethylaminoStyrene, /?-dimethylaminoStyrene, p-methoxyStyrene, /?-methylSuccinimide, N-vinylVinyl 2-chloroethyl ether Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl butyl ether Vinyl butyl ether Vinyl butylsulfonate Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl cymantrene Vinyl ethyl ether Vinyl fluoride Vinyl fluoride Vinyl hendecanoate Vinyl isobutyl ether Vinyl isobutyl sulfide Vinyl isobutyl sulfide Vinyl methyl sulfide Vinyl phenyl sulfide Vinyl stearate Vinyl thiolacetate Vinyl, 2-bromo-, ethyl ether Vinyl, /?-, benzylethylcarbinol Vinylanthracene, 9Vinylhydroquinone dibenzoate Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylisocyanate Acrylonitrile Acrylonitrile Methacrylate, methyl Acrylonitrile Acrylonitrile Acrylonitrile Methacrylate, methyl Styrene Styrene Styrene Styrene Vinylidene chloride Acrylonitrile Styrene
r\ 0.168 0.18 0.18 0.14 0.07 0.3 0.16 0.148 0.142 0.288 0.17 0.14 0.18 0.06 0.192 0.07 0.17 0.357 3.27 7.28 6.38 2.58 6.7 6.3 3.65 3.6 4.14 4.4 7.66 5 4 0.46 3.3 43 43 3.615 3.63 0.3 0.29 0.209 0.57 5.8 0.8 16.83 0.18 2.998 0.46 0.95 0.8 1 1.38 1.2 1.171 0.4 1.04 1.35 0.32 0.464 0.37 0.18 0.31 0.18 1 0.84 0.01
±95% 0.067
0.026 0.054 0.069 0.02 0.01 0.01 0.063 0.37 0.3 0.07 0.58 0.22 0.5 0.14
0.012 0.04 0.01 0.01 0.034 0.1 2.34 0.067 0.21
0.023 0.38 0.4 0.35 0.07 0.12
0.14 0.74 0.53
r2 0.722 0.75 0.75 0.68 0.9 0.65 0.4 0.871 3.93 4.47 0.003 1.65 0.48 0.38 0.372 2 1.54 0.9 0 0.04 0.03 0.405 0.03 0.03 0.01 0 0 0.093 0.002 0 0.06 0.211 0 0.01 0.01 0.033 0 0.05 0.06 0.084 -0.02 0.03 0.23 -0.79 0.48 0.08 0.75 0.9 0.7 1 0.14 0.8 1.123 1.25 1.91 4.39 1.76 2.477 0.777 0.44 0.79 0.44 0.9 1.98 0.39
±95%
Conv.
Refs.
0.056
Y
0.022 1.38 0.15 0.01
Y Y Y N
0.16 0.055
Y Y
0.17
Y
151 393 397 463 495 496 496 865 136 2 142 558 548 866 911 558 558 80 726 1067 158 25 489 568 345 574 185 151 46 470 518 354 470 604 606 145 347 285 336 195 193 537 566 194 591 123 440 107 107 377 435 682 363 621 118 233 290 290 290 290 290 290 118 118 806
0.01 0.043
Y Y
0.01
N
0.4 0.002 0.01
Y Y Y
0.067
Y
0.008 0.002 0.02 0.02 0.086 0.22
Y N N N Y Y
0.32
Y
0.092
Y
0.11
Y
0.037
Y
0.1 0.64 0.2 0.024 0.018
Y N Y Y Y
0.037 0.3 0.11
Y Y
TABLE 1. cont'd Monomer 1 Acrylate, octyl Acrylate, octyl Acrylate, p-(cinnamoylamino)phenyl Acrylate,/7-bromophenyl Acrylate,/7-bromophenyl Acrylate,/7-chlorophenyl Acrylate,/7-chlorophenyl Acrylate,/?-chlorophenyl Acrylate, p-methylphenyl Acrylate, pentabromophenyl Acrylate, pentachlorophenyl Acrylate, pentachlorophenyl Acrylate, phenyl Acrylate, phenyl Acrylate, phenyl Acrylate, phenyl Acrylate, sodium Acrylate, tert-buty\ Acrylate, tetrahydrofurfuryl Acrylate, thio- butyl Acrylate, thio-, ethyl Acrylate, thio-, tert-butyl Acrylate, tributyltin Acrylate, trifluoro-, methyl Acrylate, trifluoro-, methyl Acrylate, trifluoro-, methyl Acrylate, trifluoro-, methyl Acrylate, trifluoro-, methyl Acrylate, trifluoro-, methyl Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid
Monomer 2 Vinyl chloride Vinylidene chloride Styrene Acrylonitrile Methacrylate, methyl Acrylonitrile Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Styrene Acrylic acid Styrene Acrylonitrile Fumarate, diisopropyl Methacrylate, methyl Methacrylate, methyl Vinyl acetate Methacrylate, glycidyl Styrene Styrene Styrene Styrene Acrylate, methyl Styrene Styrene Vinyl acetate Vinyl acetate Vinyl chloride Vinyl chloride Acrolein Acrolein Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide, A^-dimethylAcrylate, pentachlorophenyl Acrylate, butyl Acrylate, butyl Acrylate, ethyl Acrylic acid, 2-benzamidoAcrylic acid, N-acetyl-a-aminoCarbamate, AW-diethyl-, vinyl Carbamate, //-vinyl-, ethyl Imidazole, 1-vinylMethacrylate, isopropyl Methacrylate, methyl Methacrylate, butyl N-Vinylimidazole Phosphonic acid, oc-phenylvinylPropenyl, 2-chloro-, acetate Propylene Pyrrolidone, N-vinylStyrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Vinyl acetate Vinyl chloride
rx 4.8 0.679 0.35 1.026 0.191 0.951 0.235 0.3 0.223 0.1 1.12 0.9 0.327 3.4 0.45 0.416
±95%
0.057 0.062 0.014 0.063 0.023 0.036
0.045 0.041
0.463 0.489 0.421 0.291 0.368 0.03 0 0 0 0 0 0 0.08 1.15 0.288 1.644 0.341 1.38 3.8 0.29 0.36 0.82 0.59 1.31 0.91 0.48 1.41 5.58 4.69 0.0025 1.03 1.73 0.24 1.932 0.7 1
0.079 0.196 0.17 0.075 0.055
0.88 0.05 0.08 0.25 0.35 0.136 0.15 0.45 0.25 8.66 6.69
0.69
0.28 0.029 0.069 0.012 0.14 0.04 0.27 0.3
0.32
0.096 0.21 0.077 0.13
0.029
6.63 0.88
r2 0.12 0.851 1.08 0.8 0.926 0.32 1.01 1.09 1.45 0.16 0.82 2.11 0.43 0.07 1.56 1.54 2.096 0.475 0.439 0.18 0.157 0.82 1.4 1.4 0.24 0.24 1.5 1.5 2.48 0.5 1.08 0.445 1.346 0.598 0.58 1.06 0.35 1.12 1.08 0.91 1.02 2.08 0.49 -0.097 0.26 0.32 0.68 0.418 3.53 0.187 0.04 0 0.1 0.25 1.1 0.15 0.22 0.253 0.25 0.25 0.15 0.021 0.107
±95%
Conv.
0.018
Y
0.13 0.056 0.056 0.132
Y Y Y Y
0.275
Y
0.13
Y
0.14
Y Y Y
0.443 0.186 0.14 0.038 0.034
1.24
Y
0.17 0.075 0.044 0.047
Y Y Y Y
0.12
N
0.18 0.13
N N
0.068
Y Y
0.02 0.42 0.025 0.83
N N Y Y
0.21
Y N
0.069
Y
0.059 0.011
Y Y
Refs. 518 118 685 363 1074 63 1074 621 1074 643 900 900 363 1038 621 672 37 814 806 806 806 806 659 595 598 595 598 595 598 57 57 221 278 278 37 869 869 205 900 187 252 711 1019 661 92 81 955 847 964 187 879 132 445 183 250 312 312 397 414 47 490 542 561 37 135
References page II-290
TABLE 1. cont'd Monomer 1 Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid, 2-benzamidoAcrylic acid, 2-benzamidoAcrylic acid, 2-ethyl Acrylic acid, 2-ethyl Acrylic acid, 2-ethyl Acrylic acid, N-acetyl-a-amino Acrylic acid, N-acetyl-a-aminoAcrylic acid, oc-bromo Acrylic acid, a-bromo Acrylic acid, a-bromo Acrylic acid, a-bromo Acrylic acid, a-bromo Acrylic acid, ds-3-bromoAcrylic acid, c/s-3-ethyl Acrylic acid, trans-3-bxomoAcrylic acid, frarcs-3-ethylAcrylic anhydride Acrylic anhydride Acrylic anhydride Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile
Monomer 2 Vinyl chloride Vinyl chloride Vinyl chloride Vinylhydroquinone Vinylhydroquinone dibenzoate Vinylidene chloride Vinylidene cyanide Acrylic acid Styrene Methacrylic acid Methacrylic acid Methacrylic acid Acrylic acid Styrene Methacrylate, methyl Acrylate, butyl Acrylate, methyl Methacrylate, butyl Pyrrolidone, Af-vinyl Acrylamide Acrylamide Acrylamide Acrylamide Allyl chloride Methacrylonitrile Styrene 1,3-pentadiene, cis1,3-pentadiene, cis1,3-pentadiene, trans1,3-pentadiene, trans2-Oxazoline, 2-isopropenylAcenaphthalene Acetylene, phenylAconitate, trimethyl Acrolein Acrolein Acrolein Acrolein Acrolein diethylacetal Acrolein, methylAcrolein, methylAcrolein, methylAcrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide, Af-methylolAcrylamide, N-methylolAcrylamide, Af-methylolAcrylamide, JV-octadecylAcrylamide, N-tert-butylAcrylate, 2-chloroethyl Acrylate, 2-nitrobutyl Acrylate, 3,4-epoxyhexahydrobenzyl Acrylate, p-chloro-2-hydroxypropyl Acrylate, P-ethoxy-, ethyl Acrylate, a-chloro-, methyl Acrylate, a-cyano-, methyl Acrylate, a-phenyl-, methyl Acrylate, benzyl Acrylate, benzyl Acrylate, butyl Acrylate, butyl Acrylate, butyl
rx 9.28 7.04 6.8 0.29 0.44 1.246 0.212 2.08 0.78 0.194 0.069 0.23 0.49 0.44 0.11 0.09 0.1 0.13 0.07 -0.2 -0.16 -0.33 -0.21 11.66 1 0.1 0.026 0.06 0.069 0.068 0.13 0.02 0.266 4.24 0.88 0.71 0.48 0.6 11.19 0.15 0.15 0.03 0.863 0.97 1.8 0.88 0.8 0.7 0.98 0.22 1.034 0.2 1.03 0.67 0.25 0.24 2.42 0.122 0.01 0.08 0.28 1.49 1.679 0.781 1.08
±95% 0.51 0.33 0.11 0.042 0.016 0.027 0.04
0.11 0.1 0.16 0.11 0.56 0.13 0.004 0.173 0.242 0.104 0.096 0.04 0.044 0.92 0.06 0.03 0.01
0.19 0.033 0.1 0.75
0.02 0.25 0.13 1.8 0.081 0.02 0.19 0.058 0.083 0.08
r2 0.03 0.024 0.11 0.026 0.95 0.437 0.291 0.48 0.13 1.12 2.29 1.14 1.41 0.91 0.37 0.19 0.24 0.85 0.25 7.64 6.32 4.13 8.19 0.02 0.42 0.16 0.017 0.071 0.018 0.064 0.52 2.56 0.325 -0.48 1.16 1.07 1.52 1.28 0.02 1.7 3.8 1.72 0.81 1.08 0.5 1.36 1.3 1.2 2.33 2.56 1.4 1.14 0.87 1.76 0.388 0.7 -0.26 1.76 0.68 6.7 0.72 0.63 1.06 0.894 0.82
±95%
Conv.
Refs.
0.09 0.069
N Y
0.092
Y
0.065 0.042
Y Y
0.132 0.417
Y Y Y
1.67 0.68 0.76 1.09 0.02 0.04 0.01 0.012 0.029 0.01 0.02 0.06
Y Y Y Y N N N Y Y Y Y
0.083 0.11 0.13 0.08 0.07
Y Y N N N
0.42 0.11 0.51 0.26
Y Y Y N
0.17
Y
0.69 0.074
N Y
0.56 0.18 0.09
N Y N
0.16
N
0.15 0.019 0.13
Y Y N
229 288 379 337 444 288 82 1019 1019 1004 1004 961 661 661 733 733 733 733 694 298 298 298 298 219 219 219 912 912 912 912 894 575 60 147 207 207 208 504 767 455 587 91 228 228 330 421 461 442 577 596 119 709 790 234 680 654 194 6 141 141 23 385 118 162 233
TABLE 1. cont'd Monomer 1 Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile
Monomer 2 Acrylate, butyl Acrylate, butyl Acrylate, cis-(3-cyano-, methyl Acrylate, cresyl Acrylate, di-, zinc Acrylate, dodecyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, glycidyl Acrylate, m-chlorophenyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, mono-, ethylene glycol Acrylate, tf-chlorophenyl Acrylate, octadecyl Acrylate, octadecyl Acrylate, octadecyl Acrylate, octyl Acrylate, /?-bromophenyl Acrylate, /7-chlorophenyl Acrylate, phenyl Acryloyl chloride Acryloylpyrrolidone Allyl acetate Allyl alcohol Allyl alcohol Allyl alcohol Allyl alcohol Allyl chloride Allyl chloride Allylbenzene Allylbenzene Allylcyclohexane Allylstearamide, NBenzothiazole, vinylmercaptoButadiene Butadiene Butadiene Butadiene Butadiene Butadiene, 1,4-dicarboxylate, diethyl Butadiene, l-(diethylamino)Butadiene, l-(diethylamino)Butadiene, 1-acetoxyButadiene, 1-ethoxy Butadiene, 1-ethoxy Butadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-fluoroButadiene, 2-trimethylsilyloxyButadiene-1-carboxylate, ethyl Butadiene-1-carboxylic acid Butadiene-1-carboxylic acid Butene-1 Butene-1, 4-(/?-chlorophenyl)Butene-1, 4-(p-methoxy-phenyl)Butene-1, 4-cyclohexylButene-1, 4-phenylButene-2, cis Butene-2, trans Carbazole, N-vinyl-
rt
±95%
1 1 0.72 0.41 2.37 0.92 1.16 0.66 0.44 1.01 1.3 0.56 1.54 1.31 0.8 1.123 1.91 4.39 1.76 1.98 0.8 0.32 0.43 1.2 1.56 6.57 2.6 3.9 1.79 2.145 3.45 3.82 5.35 3.81 3.79 0.191 0.046 0.1 0.05 0.06 0.03 0.29 0.481 0.208 -0.012 0.02 0.01 0.04 0.05 0.056 0.077 0.036 0.3 0.2 0.03 13.46 4.68 2.56 5.03 4.51 22.32 62.99 0.39
r2
±95%
Conv.
0.9 1.2 0.15 0.07 0.08 0.78
0.073 0.03 0.044 0.08 0.037 0.1 0.64 0.2 0.3 0.13 0.056 0.13 2.11 1.06 0.11 0.049 0.65 1.7 0.3 11.42 0.28 0.014 0.006 0.059 0.02 0.12 0.049 0.049 0.043 0.008 0.008 0.023 0.021
3.61 0.63 1.11 0.76 0.86 10.67 0.04
0.773 0.24 0.88 1.2 0.81 4 0.95 1 0.85 0.51 0.844 0.85 1.2 1.171 1.04 1.35 0.32 0.84 1.026 0.951 0.327 1 0.43 -0.09 0.05 0.1 0.12 -0.152 0.08 -0.05 -0.026 -0.18 0.03 0.178 0.358 0.452 0.35 0.1 0.2 2.79 0.426 0.425 0.82 0.065 0.065 5.35 4.8 5.38 0.6 0.065 3.2 4 11 0.24 0.066 -0.085 0.014 0.024 0.11 0.84 0.09
0.067 0.16 0.07 0.27
N Y N N
0.036 0.02 0.037 0.2
Y N
0.023 0.38 0.4 0.35 0.74 0.062 0.063 0.045
Y Y N Y Y Y Y Y
0.12
Y N
0.16 0.37 0.008 0.03 0.15 0.022 1.01 0.27 0.081 0.046 0.023
N Y Y Y Y Y Y Y Y Y Y
0.01 0.9 0.208 0.48 0.68 0.009 0.02
N N Y Y Y Y Y
0.45 0.18
Y Y
0.81 0.044 0.088 0.055 0.069
Y Y Y Y Y Y Y N
0.6 0.04
Y
Refs. 513 513 1034 363 646 233 1023 198 389 542 114 363 1024 151 233 682 363 118 233 290 118 363 363 363 580 666 108 108 108 176 300 108 47 24 351 24 119 763 21 255 418 501 66 327 864 889 91 864 889 402 504 61 174 993 791 791 799 211 24 24 24 24 211 211 269
References page II - 290
TABLE 1. cont'd Monomer 1 Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile
Monomer 2 Cinnamate, a-cyano-, ethyl Cinnamonitrile Cinnamonitrile, a-cyanoCitraconimide, N-methylCrotonaldehyde Crotonaldehyde Crotonate, a-chloro-, ethyl Crotonate, a-cyano-, ethyl Crotonate, a-methoxy-, methyl Crotonate, a-methyl-, methyl Crotonate, a-acetyl-, methyl Crotonate, a-carboethoxy-, ethyl Crotonate, ethyl Crotonic acid Cyclopentene, 4-, -1,3-dione Cyclopropene, 3,3-dimethoxyDiallyl phthalate Diallyl phthalate Ethylene Ethylene, 1,1-diphenylEthylene, tetrachloroEthylene, tetrachloroEthylene, trichloroEthylene, trichloroFumarate, diisopropyl Fumarate, diethyl Fumarate, diethyl Hexatriene, tetrachloroHexene-1 Indene Indene Isobutylene Isobutylene Isobutylene Isoprene Isopropenyl methyl ketone Isopropenyl methyl ketone Isopropenylisocyanate Itaconic acid Itaconic anhydride Maleate, diethyl Maleate, diethyl Maleic anhydride Maleimide, 7V-(2-bromophenyl)Maleimide, A^-(2-chlorophenyl)Maleimide, iV-(4-chlorophenyl)Maleimide, N-2-bromophenylMaleimide, N-2-chlorophenylMaleimide, N-4-chlorophenylMaleimide, N-octadecylMaleimide, N-octadecylMethacrylamide, N-(/?-chlorophenyl)Methacrylamide, iV-(/?-methoxyphenyl)Methacrylamide, A^-methylphenyl)Methacrylamide, Af-(p-nitrophenyl)Methacrylamide, N-phenylMethacrylate, 2,2,6,6-tetramethyl4-piperidinyl Methacrylate, 2-(AUV-dimethylcarbamoyloxy)ethyl Methacrylate, 2-bromoethyl Methacrylate, 2-chloroethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl
r\ 12.6 8.46 0.53 8 25 9.53 11.4 1 2.97 8.68 18.7 25.2 21 3.02 1.424 4.23 2.78 7 0.05 456 470 67 62.1 16 8 10 0.234 2.07 0.281 0.29 1.295 0.98 1.02 0.03 0.3 0.36 0.24 0.59 0.034 12 20 6 2.029 0.956 0.972 2.02 0.955 0.972 2.482 2.46 0.399 0.337 0.336 0.37 0.381 0.02
±95% 2.3 0.37
0.71 0.038 0.15 0.52 0.01
0.05 0.05 0.12 0.008 0.25
0.34 0.014
0.214 0.095 0.112 0.205 0.095 0.112 0.119 0.115 0.019 0.019 0.026 0.14 0.085
r2 -0.18 0.36 0.6 0 0.01 0 0.06 0 0 0 0 0 0 0.04 0.245 0.04 0.037 0 -0.02 0 0 0 0 0.2 0 0.1 4.01 -1.08 0.09 0.07 0 0.02 0 0.45 1.2 0.7 0.1 0.86 4.83 0 0 0 0.338 1.078 0.743 0.348 1.08 0.743 0.389 0.39 0.627 0.559 0.549 2.34 0.71 14
±95%
Conv.
Refs.
0.15 0.1
Y Y Y
0.058 0.037 0.012 0.031
Y Y Y Y
0.01
N
1.25 0.25 0.24 0.002 0.38
Y Y Y Y Y Y
0.74 0.33
Y Y
0.045 0.048 0.048 0.044 0.048 0.048 0.023 0.023 0.051 0.048 0.06 1.07 0.19
Y Y Y Y Y Y Y Y Y Y Y Y Y
310 310 310 460 429 504 785 785 785 785 785 785 785 402 95 838 153 153 415 143 571 59 470 572 1038 470 640 4 60 360 360 21 211 484 417 490 542 434 164 365 470 640 470 863 863 863 915 915 915 863 915 352 352 352 352 352 664
0.38
1.89
600
0.31 0.14 0.2 0.15 0.094
2.38 1.3 1 1.17 1.02
657 382 689 611 611
0.2 0.099
0.2 0.19
Y Y
TABLE 1. cont'd Monomer 1 Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile
Monomer 2
rx
Methacrylate, 2-naphthyl 0.06 Methacrylate, 2-naphthyl -0.01 Methacrylate, 3,5-dimethyladamantyl 0.19 Methacrylate, benzyl 0.2 Methacrylate, butyl 0.291 Methacrylate, ferrocenylmethyl 0.15 Methacrylate, glycidyl 0.95 Methacrylate, glycidyl 0.14 Methacrylate, isobutyl 0.217 Methacrylate, methyl 0.138 Methacrylate, methyl -0.016 Methacrylate, mono-, ethylene glycol 0.19 Methacrylate, phenyl 0.36 Methacrylate, potassium 0.226 Methacrylate, potassium 18-crown0.07 6-ether Methacrylic acid 0.04 Methacrylic acid 0.092 Methacrylonitrile 0.43 Methacryloyl chloride 0.35 Methacryloyl acetone 0.01 Methylenebutyrolactone 0.09 WV-Divinylaniline 0.246 AA-Vinylimidazole 3.393 Naphthalene, 1-vinyl0.107 Norbornadiene 0.48 Norbornadiene 0.66 Oct-1-ene, 6,6-dimethyl-4,8-dioxaspiro 0.985 Oxazoline, 2-,2-isopropenyl0.13 Oxazoline, 2-,2-isopropenyl-, 0.24 4-dimethyl Oxazoline, 2-,4-methacryloxy0.11 2,4-dimethyl Pentadiene, trans-1,30.06 Pentadiene, as-1,30.026 Pentadiene, cis-1,30.056 Pentadiene, cis-1,30.033 Pentadiene, trans-1,30.07 Pentadiene, trans-1,30.085 Pentadiene, trans-1,30.079 Pentadiene, cis-1,30.06 Pentadienoate, trans-4-ethoxy-2,4-, ethyl 0.01 Pentene-1, 5-cyclohexyl4.22 Pentene-1, 5-phenyl3.84 Phosphate, diethyl isopropenyl 15.2 Phosphine oxide, diphenylvinyl3.8 Phosphonic acid, a-phenylvinyl0.34 Phosphonic acid, a-phenylvinyl2.36 Phthalide, 3-(4-vinylphenoxy)0.084 Phthalimide, N-vinyl0.43 Phthalimide, AHmethacryloyloxy)0.204 Pinene 0.07 Propene, 2-chloro1.164 Propene, 3,3,3-trichloro12.2 Propene, 1-chloro-, cis23.37 Propene, 1-chloro-, trans19.61 Pyridazinone, 3-(2-vinyl)-6-methyl0.32 Pyridazinone, 3-(2-vinyl)-6-methyl-4,50.74 Pyridine, 2-methyl-5-vinyl0.16 Pyridine, 2-vinyl0.05 Pyridine, 2-vinyl0.1 Pyridine, 2-vinyl-5-ethyl0.02 Pyridine, 2-vinyl-5-ethyl0.06 Pyridine, 4-vinyl0.11 Pyridine, 4-vinyl0.09
±95% 0.1 0.16 0.01 0.1 0.039 0.04 0.06 0.037 0.037 0.048
0.04 0.006 0.13 0.06 0.04 0.004 0.014 0.008 0.028 0.27 0.01 0.675
r2
±95%
Conv.
0.76 0.64 1.3 0.96 0.98 0.82 0.85 1.32 1.05 1.322 1.11 1.5 0.46 0.203 0.175
0.18 0.24 0.23 0.1 0.2 0.42 0.05
Y N N N Y Y N
0.22 0.05 0.12
Y Y Y
0.086 0.018
Y Y
0.2 2.38 1.67 2.8 3.74 1.1 -0.006 0.832 0.451 0.05 0.44 1.484 0.52 1.83
0.26 0.29 0.12
Y Y N
0.22
Y
0.07 0.044 0.088 0.23 0.05 1.078
Y Y N N Y
0.89 0.064 0.018 0.017 0.017 0.018 0.071 0.45 0.48
0.12 0.053 0.01 0.016 0.01 0.053 2.99 1.72 0.02 0.02 0.01 0.03 0.07 0.04
0.095 0.172 0.198 0.188 0.104 0.132 0.114 0.241 5.4 -0.043 -0.026 0.03 0.16 -0.45 0 0.43 0.24 1.45 13.5 -0.023 0.1 -0.12 0.01 0.19 0.02 0.31 21.9 0.44 0.43 0.43 0.41 0.34
Refs. 611 611 335 23 165 325 114 433 165 216 681 682 363 808 808 16 216 198 580 339 745 45 879 967 267 69 838 862 596 596
0.021 0.012
Y Y
0.011 0.01
N Y
0.009 0.029
N Y
0.044 0.046
N Y
0.41
Y
0.19 0.02 0.072 0.1 0.062
Y Y
0.19 0.17 0.04 0.02 0.02
Y Y N N N
0.08
N
0.18
N
0.13
N
Y
867 867 952 997 867 952 997 867 723 24 24 650 843 132 590 721 1046 979 936 181 402 181 181 340 340 232 456 50 115 50 115 50
References page 11-290
TABLE 1. cont'd Monomer 1 Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile
Monomer 2
r\
Pyrrolidone, N-vinylSilane, y-methacryloxypropyltrimethoxy- 0.094 Styrene 0 Styrene 0.02 Styrene 0.05 Styrene 0.03 Styrene 0.06 Styrene 0.05 Styrene 0.07 Styrene 0.04 Styrene 0.17 Styrene 0.17 Styrene 0.15 Styrene 0.17 Styrene 0.07 Styrene 0.06 Styrene 0.03 Styrene 0.06 Styrene 0.01 Styrene, 2,4,6-trimethyl0.874 Styrene, 2,5-dichloro0.22 Styrene, 2,5-dichloro0.25 Styrene, 2,5-dichloro0.26 Styrene, 3-tri-rc-butylstannyl4.88 Styrene, 4-methyl0.079 Styrene, a-(trimethylsilyloxy)0.05 Styrene, a-methoxy0.06 Styrene, a-methyl0.07 Styrene, a-methyl0.04 Styrene, a-methyl0.04 Styrene, a-methyl0.04 Styrene, a-methyl0.063 Styrene, a-methyl0.34 Styrene, a-methyl0.03 Styrene, a-methyl- 0.02 Styrene, m-methyl0.07 Styrene, /?-l-(2-hydroxy-butyl)0.04 Styrene, /?-l-(2-hydroxy-propyl)0.1 Styrene, /?-2-(2-hydroxy-propyl)0.05 Styrene, p-acetoxy0.07 Styrene, /?-chloro-0.09 Styrene, p-chloromethyl0.067 Styrene/7-methyl0.05 Succinimide, N-vinyl0.116 Tetrazole, 2-methyl-5-(4/-vinyl)phenyl0.42 Tetrazole, 5-phenyl-2-(4/-vinyl)phenyl0.32 Tetrazole, 1-vinyl0.54 Toluenesulfonamide, A^V-methyl-vinyl- 0.42 Triallyl citrate 1.76 Tricyclo[4.2.2.0{2,5}]dec-7-ene2.75 3,4,9,10-tetracarboxylic acid Vinyl 12-ketostearate 3.3 Vinyl 2-chloroethyl ether 1.09 Vinyl 2-ethylhexanoate 9.24 Vinyl 3,3-bis(ethoxycarbonyl)propyl 1.02 ether Vinyl acetate 4.05 Vinyl acetate Vinyl acetate 5.51 Vinyl acetate 5.29 Vinyl acetate 9.2 Vinyl benzoate 5.03 Vinyl bromide 2.79 Vinyl bromide 2.25 Vinyl butyl ether
±95% 0.034 0.06
0.051 0.01
0.005 0.01 0.04 0.005 0.041 0.15 0.27
0.01 0.06 0.024 0.032 0.12 0.082 0.5 1.96
r2 3.79 0.33 0.29 0.4 0.36 0.39 0.37 0.37 0.4 0.3 0.33 0.33 0.36 0.46 0.41 0.43 0.55 0.35 0.065 0.08 0.07 0.09 0.001 0.227 0 - 0.002 0.08 0.17 0.24 0.14 0.09 0.103 0.14 0.08 0.43 0.31 0.53 0.41 0.4 0.92 0.56 0.33 0.516 1.1 1.4 0.314 0.04 -0.08 0.25 -0.18 0 -0.047 0.06
±95%
Conv.
Refs.
0.594
Y Y
0.04
N
0.048 0.03
Y N
0.021
Y
0.01 0.03
N N
0.03 0.024 0.036
N Y Y
0.07
N
0.03 0.06
N N
213 977 140 198 269 396 403 417 543 60 727 727 727 727 727 727 727 727 812 58 84 84 84 985 929 970 142 171 265 265 65 75 75 835 94 378 548 380 547 47 825 1035 378 80 583 583 925 80 367 963
0.081 0.066 1.04 0.1
Y Y Y
0.36
Y
0.05
Y Y N Y Y Y Y N
0.82
0.04
0.067
0.91 1.13 6.39 1.08 0.2
0.06 -0.06 - 0.03 0.019 0.06 0.06
0.22 0.08 0.09 0.051 0.04
N
146 597 47 1015 158 235 6 75 75 47 268 268 345
TABLE 1. cont'd Monomer 1 Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile
Monomer 2 Vinyl butyl ether Vinyl butyl sulfide Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloroacetate Vinyl chloroacetate Vinyl chloroethyl ether Vinyl chloromethyl ketone Vinyl cymantrene Vinyl dichloroacetate Vinyl dichloroacetate Vinyl dodecyl ether Vinyl ether Vinyl ethyl ether Vinyl ethyl oxalate Vinyl ethyl sulfide Vinyl ethyl sulfide Vinyl ethyl sulfoxide Vinyl fluoride Vinyl fluoride Vinyl formate Vinyl hendecanoate Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl sulfide Vinyl isobutyl sulfide Vinyl isobutyl sulfide Vinyl isothiocyanate Vinyl laurate Vinyl methyl ketone Vinyl methyl ketone Vinyl octadecyl ether Vinyl octyl ether Vinyl phenyl ether Vinyl phenyl sulfide Vinyl phenyl sulfide Vinyl stearate Vinyl terf-butyl sulfide Vinyl trichloroacetate Vinyl, a-chloro-, triethoxysilane Vinyl,/?-, benzylethylcarbinol Vinyl, /?-, benzylmethylcarbinol Vinyl-tris(trimethoxysiloxy)-silane Vinyl-tris(trimethoxysiloxy)-silane Vinylbenzoate, p-, sodium Vinylbenzoic acid, pVinylene carbonate Vinylethynyl-4-piperidinol, 1,2,5-trimethyl Vinylferrocene Vinylferrocene Vinylhydroquinone Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride
r\ 0.98 0.086 3.26 2.55 2.62 3.62 3.65 4 4.18 0.34 1.04 0.064 0.446 7.45 0.25 0.82 0.94 0.69 1.34 0.09 0.06 1.63 44 24 2.54 1.88 - 0.24 - 0.05 0.98 1.26 0.08 0.062 0.08 0.36 4 0.59 0.63 0.85 0.81 2.5 0.11 0.11 4.639 0.09 7.34 0.04 0.11 3.9 3.85 0.174 0.06 14.9 0.08 0.186 0.16 0.56 0.92 1.04 0.44 0.58 0.65 0.57 0.5
±95% 0.13 0.01 0.34 0.12 0.25 0.21 0.22 0.33 0.05 0.019 0.048 0.32
0.12 0.45 0.01 0.01 0.16 1.79 0.44 0.26 0.07 0.15 0.19 0.005 0.004 0.004 0.13
0.01 0.01 0.015 0.024 0.9 0.17 0.04 0.009
0.025 0.36 0.11 0.2
r2 -0.03 0.041 -0.01 0.07 0.02 0.044 0.052 0.04 -0.007 0.09 -0.02 0.88 - 0.065 0.044 0.18 0 0.02 0.06 0.06 0.06 0.05 -0.08 0.005 1 -0.004 0.09 0.7 0.99 -0.04 -0.04 0.03 0.022 0.03 1.4 0.04 1.75 1.39 0 0 0.23 0.03 0.03 0.078 0 0.047 0.31 0.54 0.07 0.08 0.23 1.63 0.08 0.38 0.165 0.15 0.04 0.32 0.28 0.4 0.42 0.49 0.69 0.76
±95%
Conv.
0.01 0.028 0.037 0.03 0.08 0.002 0.01
N Y Y N N Y Y
0.016
Y
0.02 0.12 0.093 0.015
N Y Y N
0.12 0.03 0.03 0.03 0.14
N N N N Y
0.12 0.91 0.09 0.06 0.01 0.02 0.01 0.038 0.01
Y Y N N N N N Y N
0.11
Y
0.02 0.01 0.007 0.013 0.039
N N Y Y Y Y
0.2
N
0.34 0.42
Y Y
0.092
Y
0.03 0.14 0.034
N Y Y
Refs. 347 303 140 202 22 238 46 529 362 542 116 356 354 362 542 373 386 194 285 285 336 286 528 590 47 145 322 322 347 347 285 303 336 542 381 140 504 373 373 556 285 336 145 303 362 591 48 209 573 175 175 579 783 294 294 338 138 238 404 404 404 404 404
References page II - 290
TABLE 1. cont'd Monomer 1 Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile, 2-chloroAcrylonitrile, 2-fluoroAcrylonitrile, oc-chloroAcrylonitrile, oc-fluoroAcrylonitrile, a-hydroxymethylAcrylonitrile, a-methoxy Acrylonitrile, a-methoxy Acrylonitrile, a-perfluoropropylAcryloxymethylpentamethyldisiloxane Acryloyl chloride Acryloyl chloride Acryloyl chloride Acryloyl chloride Acryloyl chloride Acryloyl chloride Acryloyl chloride Acryloyl chloride Acryloyl chloride Acryloyl-P-hydroxyethyl-3,5dinitrobenzoate Acryloyl-P-hydroxyethyl-3,5dinitrobenzoate Acryloyloxy, 2-, benzoic acid Acryloyloxy, 2-, benzoic acid Acryloylpyrrolidone Adipate, divinyl Allyl acetate Allyl acetate Allyl acetate Allyl acetate Allyl acetate Allyl acetate Allyl acetate Allyl acetate Allyl acetate Allyl acetate Allyl acetate Allyl acetate Allyl acetate Allyl acetate Allyl acetate Allyl acetate Allyl acrylate Allyl acrylate Allyl acrylate Allyl alcohol Allyl alcohol Allyl alcohol Allyl alcohol
Monomer 2
ri
Vinylidene chloride 0.48 Vinylidene chloride 0.65 Vinylidene chloride 0.65 Vinylidene chloride 0.66 Vinylidene chloride 0.63 Vinylidene chloride 0.63 Vinylidene chloride 0.58 Vinylisocyanate 0.19 Vinylmethyldiacetoxysilane 2.246 Vinylmethylphenylsulfonium 2.2 tetrafluoroborate Vinyltriethoxysilane 6.59 Vinyltriethoxysilane 26.83 Vinyltrimethoxysilane 9.09 Vinyltrimethylsilane 4.08 Styrene 0.087 Styrene Styrene 0.03 Styrene 0.03 Styrene 0.528 Acrylate, a-chloro-, ethyl 0.3 Styrene 0.312 Methacrylate, methyl 0 Methacrylate, 2-hydroxyethyl 0.52 Acrylate, methyl 2.3 Acrylonitrile 1 Methacrylate, 2-hydroxypropyl 0.29 Methacrylate, methyl 1.51 Methacrylate, methyl 0.05 Pyrrolidone, N-vinyl 0.15 Styrene 0.02 Vinyl chloride 3.03 Vinylidene chloride 1.12 Acrylate, A^-(2-hydroxyethyl)-carbazolyl 0.361 Methacrylate, N-ethyl3-hydroxymethylcarbazolyl Methacrylate, N-methyl-N-phenyl2-amino Styrene Acrylonitrile Styrene Acrylate, butyl Acrylate, methyl Acrylonitrile Isobutylene, 3-chloroMaleic anhydride Methacrylate, ethyl Methacrylate, methyl Methacrylate, methyl Styrene Styrene Vinyl acetate Vinyl acetate Vinyl acetate Vinyl chloride Vinyl chloride Vinylidene chloride Acrylate, methyl Allyl chloride Vinyl acetate Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile
±95%
0.054 0.6 29.59 0.76 0.04 0.02
r2 0.95 0.95 1.3 1.74 1.43 1.8 0.39 0.16 -0.11 0.1 0.41 2.69 0.45 0.1 0.014
±95%
Conv.
0.23
Y
0.38 2.5
Y Y Y Y Y Y
Refs. 404 404 404 404 404 404 468 435 754 793
0.05 0.029
N Y
0.044
Y
209 237 237 209 884 884 806 850 981 638 806 926 822 508 580 649 508 776 599 220 288 288 702
0.27 0.004
0.016
0.13 0.44 0.205 0.9 0.534 1.9 0.86 0.34 1.2 1.79 0.48 0.42 0.04 0.1 0.02 0.5 0.62
0.103
0.015
1.425
0.09
Y
701
1.82
0.2
0.22
0.03
N
651
0.64 0.43 0.011 0.039 0 -0.09 0.15 -0.001 -0.57 -2.42 0 0.01 0 0.45 0.7 0.7 1.2 0 0 0.33 10.4 17.35
0.02
0.06 1.56 20.36 10.2 5 6.57 4.5 0.028 81.27 99.24 23 62.8 90 0.6 1 1
0.02
N
0.26 42.2
Y N
2.11
Y
0.019 1.93 24.6
Y N N
82.7
N
651 666 815 1053 470 108 412 27 210 210 470 1053 470 140 502 998 470 475 470 578 578 578 108 108 176 300
0.086 0.054 0.05
0.02 0.22
0.011 0.066 0.12 0.007 0.82 37.66 0.05
0.04 0.029
Y
0.069 0.3
1.16 6.6 0.52 0.08 0.11 N
0.05 0.1 0.12
0.16 0.37
2.6 3.9 1.79
1.06 0.11
N Y
TABLE 1. cont'd Monomer 1 Allyl alcohol AUyI alcohol Allyl butyrate Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloride Allyl chloroacetate Allyl chloroacetate Allyl glycidyl hexahydrophthalate Allyl glycidyl phthalate Allyl isobutyrate Allyl propionate Allyl trichloroacetate Allyl trimethylacetate Allyl valerate Allylbenzene Allylbenzene Allylbenzene Allylbenzene Allylbenzene Allylbenzene Allylcyclohexane Allylstearamide, NAllylstearamide, NAllylstearamide,//Allyltriethoxysilane Allylurea Azlactone, 2-vinyl-4,4-dimethylAzlactone, 2-vinyl-4,4-dimethylAzobenzene, 4-(acrylamidomethylamino)Azobenzene, 4-(acrylamidomethylamino)Benzenesulfamide,/?-methacrylamideBenzimidazole, vinylmercaptoBenzoate, p-(acryloylethoxy)-, /?-butoxy phenyl Benzoate, /?-(acryloylethoxy)-, phenyl Benzoate, /?-(acryloyloxy)-, p-butoxy phenyl Benzoate, /?-(acryloyloxy)-, p-butoxy phenyl Benzoate, /?-(acryloyloxy)-, p-methoxy phenyl
Monomer 2 Methacrylate, ethyl Methacrylate, methyl Vinyl acetate Acrylate, benzyl Acrylate, butyl Acrylate, ethyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylic anhydride Acrylonitrile Acrylonitrile Allyl acrylate Methacrylate, benzyl Methacrylate, methyl Styrene Styrene Styrene Vinyl acetate Vinyl acetate Vinyl acetate Vinyl benzoate Vinyl butyrate Vinyl formate Vinyl propionate Vinylidene chloride Methacrylic anhydride Styrene Styrene Styrene Vinyl acetate Vinyl acetate Styrene Vinyl acetate Vinyl acetate Acrylate, methyl Acrylonitrile Acrylonitrile Maleic anhydride Methacrylonitrile Triallyl citrate Acrylonitrile Acrylonitrile Vinyl acetate Vinylidene chloride Vinyl chloride Methacrylic anhydride Acrylate, a-hydroxymethyl-, ethyl Styrene Styrene Vinyl acetate Vinyl butyl ether Styrene Benzoate, /?-(acryloyloxy)-, p-butoxy phenyl Benzoate, p-(acryloyloxy)-, p-butoxy phenyl Benzoate, /?-(acryloyloxy)-, p-butoxy phenyl Benzoate, /?-(acryloyloxy)-, phenyl Benzoate, p-(acryloyloxy)-, phenyl p-butoxyphenyl
ri
±95%
r2
±95%
Conv.
Refs.
-0.02 -1.62 0.64 0.06 0.1 0.08
1.92 2.9
107.4 78.79 0.97 9.9 5.83 7.73
5.3 6.5
N N
210 210 998 438 438 438 204 437 437 437 437 219 108 47 578 438 204 10 204 438 204 3 438 438 438 438 438 3 106 782 782 782 998 998 913 998 998 351 24 351 351 351 367 24 119 119 119 237 106 1011 1011 880 880 1005 764 881
Y 0.05 0.07 0.4 -0.02 0.02 -0.152 0.08 0.08 0.02 0.05 0.03 -2.4 0.61 0.75 0.88 1.15 0.78 0.68 0.24 -0.01 0.06 0.06 0.14 0.51 0.42 0.81 0.34 0.58 -0.036 -0.05 -0.026 -0.061 0.339 -0.18 0.03 0.68 -0.24 -0.94 -0.06 0.389 0.237 8.5 12.98 3.4 0.56 0.36
0.02 0.008 0.03
0.16 3.21 0.15
0.24 0.13
0.02 0.016 0.15 0.022 0.03 0.039 1.01 0.27 0.26 0.19 0.48 0.17 0.229 0.129 0.1 0.41
8.45 5.45 6.46 9.1 11.66 2.145 3.45 10.4 58.7 35.55 36.8 1.355 0.66 0.34 0.46 0.31 0.57 0.62 3.49 29.76 34.3 34.3 34.8 1.04 1.29 2.32 1.15 1.07 11.35 3.82 5.35 16.24 2.01 3.81 3.79 0.923 5.22 1.68 29.01 0.668 0.175 0.083 0.126 0 6.51 0.91
0.56 0.049 0.65
15.82 0.089 0.15
1.4 13
N Y Y Y Y Y Y
Y Y
0.15 0.66 1.7 0.3 1.36 0.5 11.42 0.28 0.092 0.15 0.38 18.48 0.12 0.054
Y Y Y Y Y Y Y Y Y Y Y Y Y Y
0.51
Y
0.61
0.32
881
0.91
0.36
881
0.32
0.61
881
0.49
1.5
881
References page 11-290
TABLE 1. cont'd Monomer 1 Benzoate, /?-(acryloyloxy)-, phenyl p-butoxy phenyl Benzoate, /?-(acryloyloxy)-, phenyl p-butoxy phenyl Benzoate, /?-(acryloyloxy)-, /7-butoxy phenyl Benzoate, /?-(acryloyloxy)-, p-butoxy phenyl Benzoate, p-(acryloyloxy)-, phenyl Benzoate, p-(acryloyloxy)-, phenyl Benzoate, p-(acryloyloxy-ethoxy)-, p-butoxy phenyl Benzoate, p-(acryloyloxy-ethoxy)-, p-methoxy phenyl Benzoate, p-(acryloyloxy-ethoxy)-,phenyl Benzoate, p-(methacryloyloxy)-, p-octyloxy phenyl Benzoate, p-(methacryloyloxyethoxy)-, p-octyloxy phenyl Benzocyclobutane, a-methyleneBenzocyclobutane, a-methyleneBenzocyclobutene, 4-vinylBenzofuran, 2-vinylBenzofuran, 2-vinylBenzofuran, 2-vinylBenzophenone, 2-hydroxy4-(methacryloxy)Benzophenone, p-vinylBenzophenone, p-vinylBenzophenone, p-vinylBenzophenone, p-vinylBenzophenone, p-vinylBenzophenone, p-vinylBenzothiazole, vinylmercaptoBenzothiazole, vinylmercaptoBenzothiazole, vinylmercaptoBenzothiazole, vinylmercaptoBenzothiazole, vinylmercaptoBenzothiazole, vinylmercaptoBenzothiazole, vinylmercaptoBenzothiazole, vinylmercaptoBenzothiazolone, Aq(methacroyloxy)methyl] Benzoxazole, vinylmercaptoBicyclo[2,2,l]hept-2-ene-5,6-dicarboximide, Af-benzyl Bicyclo[2,2,l]hept-2-ene-5,6-dicarboximide, N-benzyl Bicyclo[2,2,l]hept-2-ene-5,6-dicarboximide, N-benzyl Bicyclo[2,2,l]hept-2-ene-5,6-dicarboximide, Af-benzyl Bicyclo[2,2,l]hept-2-ene-5,6-dicarboximide, Af-benzyl Bicyclo[2,2,l]hept-2-ene-5,6-dicarboximide, TV-benzyl Bicyclo[2,2,l]hept-2-ene-5,6-dicarboximide, Af-benzyl Borazine, p-vinyl Butadiene Butadiene Butadiene
Monomer 2 Benzoate,/?-(acryloyloxy)-, /7-methoxyphenyl Benzoate,/?-(methacryloyloxy)-, (p-octyloxy)phenyl Benzoate, /?-(acryloyloxy-ethoxy)-, /?-butoxy phenyl Benzoate, p-(acryloyloxy-ethoxy)-, phenyl Benzoate, /?-(acryloyloxy-ethoxy)-, p-methoxy phenyl Benzoate, p-(methacryloyloxyethoxy)-, p-methoxy phenyl Benzoate, p-(acryloyloxy)-, p-butoxy phenyl Benzoate, p-(acryloyloxy)-, phenyl
T1
±95%
r2
±95%
Conv.
Refs.
1.5
0.49
881
0.23
1.26
881
0.91
0.36
856
0.32
0.61
856
1.5
0.49
856
0.23
1.26
856
0.36
0.91
856
0.49
1.5
856
Benzoate, p-(acryloyloxy)-, p-butoxy phenyl Benzoate, p-(acryloyloxy)-, phenyl butoxy phenyl Benzoate, p-(acryloyloxy)-, phenyl
0.61
0.32
856
1.26
0.23
881
1.26
0.23
856
Maleic anhydride Methacrylate, methyl Methacrylate, methyl Acrylate, butyl Acrylate, ethyl Methacrylate, methyl Methacrylate, methyl
0.002 0.46 1.47 7.8 5.76 3.89 1.65
1.36 0.334 0.617 0.114
0.025 0.32 0.6 0.041 0.015 0.006 0.315
0.043 0.01 0.02 0.036
N N N Y
1083 1083 1085 1020 1020 1020 934
Acrylate, methyl Acrylate, methyl Styrene, /?-A^A^imethyl-aminomethylStyrene, p-WV-dimethylaminoStyrene, p-dimethylaminoStyrene, p-dimethylaminomethylAcrylonitrile Fumaronitrile Maleic anhydride Methacrylate, methyl Styrene Styrene Vinyl acetate Vinyl phenyl sulflde Styrene
3.6 3.54 2.54 0.84 0.842 2.54 0.178
1.06 0.077 0.136 0.18 0.072 0.259 0.081
0.09 1.1 0.26 0.07 0.176 0.135 0.191
0.02 0.02 0.017 0.05 0.046 0.017 0.014
0.43 0.349 0.5 2.53 0.95 3.1
0.14 0.087 0.095 0.47 0.61 0.01
1.25 2.171 3.02 0.013 0.24 0.35
0.083 0.07 0.14 0.037 0.12 0.02
Y Y Y Y Y Y Y Y Y Y Y Y Y Y
866 911 86 866 911 911 763 763 763 763 764 764 763 763 960
Styrene Methacrylate, methyl
0.24 0
0.12
Y
764 994
Methacrylate, methyl
0
Styrene
0
18.2
994
Styrene
0
89.2
994
Vinyl acetate
0.35
1.26
994
Vinyl acetate
0.15
1.46
994
Vinyl acetate
0.014
1.99
994
Styrene Aconitate, trimethyl Acrylate, butyl Acrylate, heptafluorobutyl
0.001 0.4 1.04 0.359
2.87 30.5
0.19
108
0.016 0.4 0.11 0.039
4.53 0 0.074 0.073
994
0.62 0.22 0.03 0.031
Y Y Y
1018 147 257 206
TABLE 1. cont'd Monomer 1 Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene monoxide Butadiene, 1,4-dicarboxy late-,diethyl Butadiene, 1,4-dicarboxy late-, diethyl Butadiene, l,4-dicarboxylate-,diethyl Butadiene, l-(2-hydroxyethylthio)Butadiene, l-(diethylamino)Butadiene, l-(diethylamino)Butadiene, 1-acetoxy-
Monomer 2 Acrylate, methyl Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Butadiene, 2,3-dimethylButadiene, 2,3-dimethylButadiene, 2-chloroButadiene, 2-phthalidomethyl Cyclobutane, 1,2-dimethyleneCyclobutane, 1,2-dimethyleneEthylene, trichloroFerrocene, ethyl-oc-cylopentadienylide Fumarate, diethyl Isoprene Isoprene Maleamic acid, N-3-dimethylamino6-methyl phenyl Maleate, diethyl Methacrylate, 2-(AW-dimethylcarbamoyloxy)ethyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylonitrile Methyleneglutaronitrile, 2Pentadiene, cis-1,3Pentadiene, trans-1,3Pyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylStyrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, p-chloromethyl Styrene, ot-methylStyrene, /7-chloroVinyl chloride Vinyl chloride Vinylhendecanoate Vinyl pelargonate Vinyl stearate Vinylferrocene Vinylidene chloride Maleic anhydride Acrylonitrile Pyridine, 2-vinylStyrene Styrene, /?-chloroAcrylonitrile Acrylonitrile Acrylonitrile
rx 1.09 0.358 0.452 0.35 0.1 0.2 1.26 0.3 0.06 1.014 0.1 0.1 9.64 0.02 2.13 0.94 0.14 0.37
±95% 4.53 0.046 0.23 0.01 0.92 0.049 0.05 0.21
0.37 0.04
8.08 1.06 0.75 0.504 0.7 0.39 0.63 1.22 0.61 1.32 1.29 1.44 1.55 1.37
r2 0.07 0.046 0.1 0.05 0.06 0.03 0.78 0.86 3.41 1.35 5.76 5.76 -0.03 1.51 0.25 1.06 0.608 - 0.08
±95%
Conv.
Refs.
0.87 0.006 0.059
Y Y Y
0.02
N
0.24
Y
0.45
Y
0.36 0.07
N
0.062 0.03
Y N
257 21 255 418 501 66 173 83 418 735 854 885 89 699 466 173 83 679
0.11 0.35 0.024 0.15
0.02 0.56 0.14
0.25 0.027 0.32 0.053 0.26 0.09 0.47 0.72 0.41 0.84 0.37 0.38
466 600 0.004
Y
0.016
Y N
0.02 0.4 0.25
N Y N Y
1.35 1.59 1.8 1.4 1.4 0.5 1.38 1.83 1.38 0.449 0.662 0.87 1.5 1.22 8.8 5.27 22.56 26.3 42.5 4.34 1.97 0.05 2.79 0.69 0.55 3.27 0.426 0.425 0.82
0.11 0.41 0.043 0.017 0.13 2.16 3.35 24.54 4.73 0.18 0.25 0.18 0.9 0.23 0.1 0.208 0.48 0.68
0.58 0.44 0.6 0.44 0.38 0.68 0.82 0.83 0.64 0.45 0.187 0.42 0.139 1.6 0.04 -0.11 -0.22 0.02 0.02 0.16 -0.044 0.64 0.29 0.41 0.09 0.24 0.481 0.208 -0.012
0.13 0.21
N Y
0.17 0.049
Y Y
0.087 5.7
Y Y
0.31 1.26
Y Y
0.27 0.15 0.038 0.06 0.12 0.07 0.014
Y Y Y N N Y
0.049 0.049 0.043
Y Y Y
140 257 467 257 196 743 743 462 520 56 140 159 173 21 418 428 473 486 486 491 56 83 83 255 8 1075 70 255 517 717 145 145 145 802 257 1064 327 327 327 810 864 889 91
References page II - 290
TABLE 1. cont'd Monomer 1 Butadiene, 1-chloroButadiene, 1-ethoxyButadiene, 1-ethoxyButadiene, 1-phthalimidoButadiene, 1-succinimidoButadiene, 2,3-bis(diethylphosphono)Butadiene, 2,3-bis(diethylphosphono)Butadiene, 2,3-bis(diethylphosphono)Butadiene, 2,3-bis(diethylphosphono)Butadiene, 2,3-bis(diethylphosphono)Butadiene, 2,3-bis(diethylphosphono)Butadiene, 2,3-dichloroButadiene, 2,3-dichloroButadiene, 2,3-dichloroButadiene, 2,3-dichloroButadiene, 2,3-dichloroButadiene, 2,3-dichloroButadiene, 2,3-dichloroButadiene, 2,3-dimethylButadiene, 2,3-dimethylButadiene, 2,3-dimethylButadiene, 2,3-dimethylButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-chloroButadiene, 2,3-dichloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-fluoroButadiene, 2-fluoroButadiene, 2-fluoroButadiene, 2-fluoroButadiene, 2-fluoroButadiene, 2-fluoroButadiene, 2-fluoroButadiene, 2-fluoroButadiene, 2-phthalidomethylButadiene, 2-trimethylsilyloxyButadiene, 2-trimethylsilyloxy-
Monomer 2 Styrene Acrylonitrile Acrylonitrile Styrene Styrene Maleimide Maleimide, Af-(2-hydroxyethyl)Maleimide, iV-(4-chlorophenyl)Maleimide, N-(4-methoxy-phenyl)Maleimide, N-chloromethylMaleimide, N-phenylButadiene, 2-chloroEthylene, 1,1-diphenylMethacrylate, methyl Phosphonic acid, a-phenylvinylPhosphonic acid, a-phenylvinylStyrene Styrene Butadiene Butadiene Isoprene Styrene Acrylate, methyl Acrylonitrile Acrylonitrile Acrylonitrile Butadiene Butadiene, l-(2-hydroxyethyl-thio)Butadiene, 2,3-dichloroButadiene, 2-fluoroButadiene, hexafluoroButadiene, hexafluoroEthylene, 1,1-diphenylFumarate, diethyl Hexatriene, tetrachloroIsoprene Isopropenyl methyl ketone Methacrylate, methyl Maleic anhydride Methacrylate, isobutyl Methacrylate, methyl Methacrylic acid Phosphonate, vinyl-,dimethyl Phosphonic acid, a-phenylvinylPhosphonic acid, a-phenylvinylQuinoline, 2-vinylStyrene Styrene Vinyl acetate Vinyl butyrate Vinyl formate Vinyl formate Vinyl propionate Vinylidene cyanide Acrylonitrile Butadiene, 2-chloroButadiene, hexafluoroIsoprene Methacrylate, methyl Styrene Styrene Styrene, a-methylButadiene Acrylonitrile Styrene
T1 1.44 0.065 0.065 1.56 1.68 0.14 0.12 0.03 0.04 0.05 0.05 1.98 3.58 11.04 7.75 7.75 8.65 10.6 0.78 0.86 0.84 1.048 5.19 10.4 5.35 4.8 5.38 3.41 1 0.31 3.7 5.47 5.52 3.4 6.51 3.6 2.82 4.035 11.04 0.026 1.8 6.33 2.52 7.5 7.5 7.5 2.1 7.84 5.98 33.52 15 11.91 0.6 0.22 2.93 2.63 1.23 2.1 1.24 2.22 1.35 0.065 1.2
±95% 3.1 0.009 0.02 0.63 0.16
r2
±95%
Conv.
Refs. 695 864 889 163 163 759 759 759 759 759 759 122 61 61 588 597 587 61 173 83 173 173 457 61 402 504 61 418 810 122 493 127 453 61 61 459 418 259 61 1068 1057 61 259 594 546 597 456 61 8 247 247 127 247 247 82 174 493 453 174 174 174 174 174 735 993 993
0.27 0.02 0.01 0.299 0.286 0.43 0.49 0.41 0.47 0.3 0.42 0.31 -0.08 0.08 0.07 0.07 0.25 0.05 1.26 0.3 1.18 0.534 0.06 0.06 0.04 0.05 0.056 0.06 0.2 1.98 0.22 0.1 0.1 0.03 0.02 0.2 0.06 0.14
0.27 0.008 0.008 0.049 0.018
Y Y Y Y Y
0.12
Y Y Y
0.107 0.088
0.5 8.98
0.329 0.9 0.08 - 0.035 0.1 0.1 0.1 0.38 0.05 0.025 - 0.02
3.89
-0.04 -0.05
0.25
0.24 0.066
0.45 0.12
0.087 0.08 0.03 0.06 0.2
0.18 0.96 1.77 0.12 0.61 0.7 0.45
0.077 3.7 0.24 0.25 0.76 0.214 0.22 0.72 1.014 0.036 0.64
Y 0.92
Y
0.035
Y Y
0.023
Y
0.25
Y
Y Y 0.01
0.058
0.047 0.09 0.01
Y Y N N Y Y
Y Y N N
0.021
N N Y Y
0.12 0.77 0.03 0.15 0.24 0.049
Y Y Y Y Y Y
TABLE 1. cont'd Monomer 1 Butadiene, hexafluoroButadiene, hexafluoroButadiene, hexafluoroButadiene, hexafluoroButadiene, l-(2-hydroxyethylthio)Butadiene-lcarboxylate, ethyl Butadiene-lcarboxylate, S-(-)oc-phenethylammonium Butadiene-1-carboxylate, ethyl Butadiene-1-carboxylate, ethyl Butadiene-1-carboxylic acid Butadiene-1-carboxylic acid Butadiene-1-carboxylic acid Butadiene-1-carboxylic acid Butanoate, 3-acrylamido-3-methyl-, sodium Butene, cis-2Butene-1 Butene-1 Butene-1 Butene-1 Butene-1 Butene-1, 2-ethylButene-1, 2-methylButene-1, 3,3-dimethylButene-1, 3,3-dimethylButene-1, 4-(p-chlorophenyl)Butene-1, 4-(/?-methoxyphenyl)Butene-1, 4-cyclohexylButene-1,4-phenylButene-2 Butene-2 Butene-2, 2-methylButene-2, cwButene-2, cwButene-2, cisButene-2, transButene-2, transButenoate, 3-phenyl-3-, methyl Butyrolactone, oc-methyleneCaprolactam, N-vinylCaprolactam, TV-vinylCaprolactam, N-vinylCaprolactam, N-vinylCaprolactam, N-vinylCaprolactam, N-vinylCaprolactam, N-vinylCaprolactam, N-vinylCaprolactam, N-vinylCaprolactam, N-vinylCaprolactam, N-vinylCaprolactam, N-vinylCaprolactam, JV-vinylCaprolactam, TV-vinylCaprolactam, N-vinylCaprolactam, TV-vinylCaprolactam, TV-vinylCarbamate, TV,TV-diethyl-, vinyl Carbamate, TV,TV-diethyl-, vinyl Carbamate, TV,TV-diethyl-, vinyl Carbamate, TV,TV-diethyl-, vinyl Carbamate, TV,TV-diethyl-, vinyl Carbamate, TV-phenyl-, vinyl Carbamate, TV-phenyl-, vinyl Carbamate, N-vinyl-, ethyl
Monomer 2 Butadiene, Butadiene, Butadiene, Isoprene Butadiene, Styrene Styrene
2-chloro2-chloro2-fluoro2-chloro-
Acrylonitrile Pyridine, 2-vinylAcrylonitrile Acrylonitrile Styrene Styrene Acrylamide, TV,TV-dimethylMaleimide, TV-cyclohexylAcrylonitrile Ethylene Ethylene Vinyl acetate Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Ethylene Vinyl chloride Vinyl chloride Acrylonitrile Vinyl acetate Vinyl chloride Acrylonitrile Vinyl acetate Styrene Styrene Crotonaldehyde Crotonaldehyde N-Vinyl pyrrolidone Pyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 4-vinylPyridine, 4-vinylPyrrolidone, N-vinylStyrene Vinyl acetate Vinyl acetate Vinyl acetate Vinyl butyl ether Vinyl isopropyl ether Vinyl phenyl ether Acrylate, methyl Acrylic acid Maleic anhydride Styrene Vinyl acetate Methacrylate, butyl Methacrylate, di-, triethylene-glycol Acrylic acid
rx 0.1 0.1 0.24 0.78 0.2 0.56 6.81 3.2 0.8 4 11 0.52 5.55 0.22 3 0.24 3.25 0.16 0.11 0.12 -1.05 -1.18 -0.44 -0.07 -0.066 -0.085 0.014 0.024 -1.79 0.3 0.11 0.03 0 0.84 -0.03 -0.532 0.85 0.31 0.31 1.7 0.04 0.04 0.12 0.12 0.1 0.1 1.7 1.02 0.31 2.5 2.5 3.1 0.22 1.3 - 0.027 -0.097 0.024 -0.08 0.13 0.329 0.034 0.26
±95%
r2
1.68
5.47 5.52 2.93 1.19 1 0.12 0.45
0.138
0.3 0.4 0.2 0.03 0.15 0.08 0.987
0.81
0.42 0.12 0.89 1.2 0.28 2.5 0.044 0.088 0.055 0.069 5.22 5.31 0.25 0.6 0.44 0.512 0.06 0.005 0.2
0.01
5.3 1.95 2.43 0.049 0.068 0.066 0.18 0.19
0 13.46 3.6 1.55 3.34 1.56 1.01 5.64 6.18 4.68 2.56 5.03 4.51 7.5 3.3 8.52 22.32 8.27 8.8 62.99 7.2 1.97 0.14 0 0 2.8 11.58 11.58 4.35 4.35 4.43 4.43 2.8 0.2 0.63 0.35 0.35 0.03 0.01 0.26 4.78 5.58 0.025 29.56 1.7 0.418 0.504 4.69
±95%
Conv.
Refs.
Y
127 453 453 453 810 791 748
0.153
Y
791 791 791 799 791 799 857
3.61
Y
0.24 0.58 0.26 0.31 0.2 13.57 0.63 1.11 0.76 0.86
Y Y N N N Y Y Y Y Y
2.18 10.54 1.05
N N Y Y
10.67 1.69 0.364 0.01
Y Y Y N
0.13
0.2
0.01
0.73 0.96 0.37 0.22 0.32 0.034 3.59 0.04
Y Y Y Y Y Y Y Y
Y
995 211 388 407 211 30 329 329 329 6 24 24 24 24 477 329 329 211 211 230 211 211 1008 663 875 907 883 589 592 589 592 589 592 859 916 557 859 883 215 215 214 92 92 92 197 197 833 833 81
References page II - 290
TABLE 1. cont'd Monomer 1 Carbamate, N-vinyl-, ethyl Carbamate, N-vinyl-, ethyl Carbamate, N-vinyl-, ethyl Carbamate, TV-vinyl-, ter/-butyl Carbamate, N-vinyl-, terf-butyl Carbamate, N-vinyl-, terf-butyl Carbazole, 2-butenylCarbazole, 9-propenylCarbazole, 9-vinylCarbazole, 9-vinylCarbazole, N-butenylCarbazole, N-methyl-3-vinyl Carbazole, N-propenylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbon monoxide Carbon monoxide Carbon monoxide Carbon monoxide Carbon monoxide Carbon monoxide Cinnamat, methyl Cinnamate, 2-chloroethyl Cinnamate, a-cyano-, 2-ethylhexyl Cinnamate, a-cyano-, benzyl Cinnamate, a-cyano-, butyl Cinnamate, a-cyano-, cyclohexyl Cinnamate, a-cyano-, ethyl Cinnamate, a-cyano-, ethyl Cinnamate, a-cyano-, hexyl Cinnamate, a-cyano-, methyl Cinnamate, a-cyano-, methyl Cinnamate, benzyl
Monomer 2 Pyrrolidone, N-vinylVinyl acetate Vinyl acetate Vinyl acetate Methacrylate, methyl N-Vinylpyrrolidone Carbazole, 9-vinylCarbazole, 9-vinylCarbazole, 2-butenylCarbazole, 9-propenylCarbazole, N-vinylStyrene Carbazole, N-vinylAcenaphthalene Acrylate, ethyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylonitrile Carbazole, N-butenylCarbazole, N-propenylFumarate, diisopropyl Maleate, diethyl Maleate, dimethyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Propene, 2,3-dichloroStyrene Styrene Styrene Styrene, /?-chloroSuccinimide, N-vinylVinyl acetate Vinyl acetate Vinyl acetate Vinyl butyrate Vinyl chloride Vinyl formate Vinyl propionate Vinyl thiolacetate Vinylidene chloride Vinylidene chloride Ethylene Ethylene Ethylene Ethylene Vinyl acetate Vinyl chloride Styrene Styrene Styrene Styrene Styrene Styrene Acrylonitrile Styrene Styrene Pyrrolidone, N-vinylStyrene Styrene
/*i
±95%
r2
±95%
Conv.
Refs.
0.371 2.09 0.4 0.46 0.17 2.4 0.02 0.02 2.6 2.8 0.02 1.404 0.02 -0.03 0.27 0.049 0.11 0.028 0.09 2.6 2.8 0 0.21 0.51 0.14 0.033 0.06 0.75 0.08 0.33 0.031 1 -0.02 0.026 0.032 0.02 0.04 2.67 3.02 3.9 1.33 4.77 4.142 1.69 0.44 3.6 3.65 0.32 0.004 -0.15 0 0.33 0.121 0.04 0.01 0.06 -0.16 - 0.09 - 0.24 -0.18
0.05
0.12
Y
0.063 0.07 0.2 0.06 0.5 0.5 0.003 0.003
Y N
0.011 0.13 0.11 0.01 0.17 0.08 0.22 0.15
1.77 0.39 0.418 1.12 1.87 0.4 2.6 2.8 0.02 0.02 2.6 0.735 2.8 6.62 1.1 0.53 0.43 0.51 0.39 0.02 0.02 0 0 0 1.55 2.12 1.8 0.57 1.84 0.44 2.123 0 6 5.93 5.72 7 0.11 0.126 0.15 0.13 0.07 0.17 0.192 0.081 0.45 -0.023 -0.008 0.068 0.025 0.04 0.5 0.24 13.52 1.799 1.394 0.58 0.4 0.47 0.37 12.6
0.26 0.001 0.35 0.13
0.39 0.044 0.4 1.33
81 629 81 827 991 991 904 904 904 904 871 806 871 331 757 13 551 98 269 871 871 1038 361 361 11 13 738 738 758 758 98 376 11 13 98 551 284 246 246 551 246 427 246 246 97 13 98 51 51 52 52 474 184 488 488 282 282 282 282 310 134 282 816 282 488
-0.17 -0.001 -0.21 0.14
0.26 0.03 0.1 0.5 0.003 0.003 0.5 0.5 0.146 0.12 0.029 0.045 0.04
0.05 0.11 0.03 0.015 0.05 0.18 0.022 0.06 0.034 0.057 0.09 0.13 0.34 0.011 0.21 0.28 0.12 0.3 0.65 0.012 0.07
0.067 1.77
N
0.13
Y
0.073 0.04
Y N
0.01 0.01 0.16 0.14
N N N Y
0.26 0.22 0.048
N N Y
1.34 1.05 0.4
N Y Y
0.83 0.023
Y Y
0.12
Y
0.001 0.073 0.15 0.068 0.018 0.012 0.006 0.01
Y Y N Y Y Y Y N
0.25 0.073 0.068 0.004 0.03 0.03 0.04 2.3
Y Y Y N N N N Y Y N Y N Y
0.04 0.008 0.06 0.12
TABLE 1.
coni'd
Monomer 1 Cinnamate, butyl Cinnamate, dibutylchlorotin Cinnamate, ethyl Cinnamate, ethyl Cinnamate, methyl Cinnamate, p-chloro-, methyl Cinnamate, /?-methyl-, methyl Cinnamate, phenyl Cinnamate, tert-butyl Cinnamic acid, cisCinnamic acid, transCinnamide, AW-diethylCinnamide, p-chloro-, AW-diethylCinnamide, p-methyl-, AW-diethylCinnamonitrile Cinnamonitrile Cinnamonitrile, a-cyanoCinnamonitrile, a-cyanoCitraconate, di-sec-buiy\ Citraconate, dibenzyl Citraconate, dibutyl Citraconate, dicyclohexyl Citraconate, diethyl Citraconate, diisobuty Citraconate, diisopropyl Citraconate, dimethyl Citraconate, dipropyl Citraconic acid Citraconic anhydride Citraconimide, p-iso-, N-(4-acetylphenyl)Citraconimide, p-iso-, AK4-acetylphenyl)Citraconimide, p-iso-, A^-(4-ethoxycarbonylphenyl)Citraconimide, p-iso-, 7V-(4-methoxyphenyl)Citraconimide, p-iso-, N-{p-to\y\)Citraconimide, p-iso-, N-phenylCitraconimde, TV-(I-menthylcarboxylatomethyl)Citraconimide, A^-(4-acetoxyphenyl)Citraconimide, A^-(4-acetoxyphenyl)Citraconimide, A^-(4-chlorophenyl)Citraconimide, Af-(4-chlorophenyl)Citraconimide, A^-(4-ethoxycarbonylphenyl)Citraconimide, A^-(4-ethoxycarbonylphenyl)Citraconimide, N-(4-methoxyphenyl)Citraconimide, A^-(4-methoxyphenyl)Citraconimide, N-aHyl Citraconimide, N-benzylCitraconimide, Af-benzyl Citraconimide, TV-butylCitraconimide, TV-butylCitraconimide, TV-ethylCitraconimide, TV-ethylCitraconimide, TV-hexylCitraconimide, TV-hexylCitraconimide, TV-isobutylCitraconimide, TV-isobutylCitraconimide, TV-isopropylCitraconimide, JV-isopropylCitraconimide, TV-methylCitraconimide, TV-methylCitraconimide, TV-methyl-
Monomer 2 Styrene Acrylate, methyl Styrene Styrene Styrene Styrene Styrene Styrene Styrene Acrylamide Acrylamide Styrene Styrene Styrene Acrylonitrile Styrene Acrylonitrile Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
r\
±95%
0.04 -0.2 -0.076 0.082 0.02 0.04 0 0.029 0.1 -0.48 -0.24 0.01 0.01 0.01 0.36 -0.008
0.15
0.13 0.047 0.054 0.03 0.029 0.03 0.076 0.049 0.027 0 0.021 0 0 0
0.054 0.045
0.055 0.12 0.28 0.15
0.1 0.021
0.058
r2 1.757 1.65 1.52 1.566 1.27 2.24 2.84 1.66 1.692 3.84 3.4 4.17 2.99 4.95 8.46 2.549 2 1.55 2.74 1.88 2.48 1.8 1.62 1.58 2.19 1.36 0.16 0.42 0.28 0.3
±95%
Conv.
Refs.
0.082
Y
0.31 0.035
Y Y
0.12 0.087 0.68 0.24
Y Y Y Y
0.37 0.092
Y Y Y Y
0.15
Y
488 659 200 488 653 653 653 488 488 298 298 737 737 737 310 134 310 134 841 841 841 841 841 841 841 841 841 1021 47 608 608 608
Styrene
0
0.27
608
Styrene Styrene Methacrylate, methyl
0 0 0.109
0.115
0.4 0.39 3.47
0.335
Y
608 608 950
Methacrylate, methyl Styrene Methacrylate, methyl Styrene Methacrylate, methyl
0.18 0.015 -0.01 0.075 -0.027
0.13 0.086 0.18 0.093 0.084
1.88 0.151 2.93 0.181 2.72
0.16 0.054 0.4 0.057 0.18
Y Y Y Y Y
728 728 728 728 728
0.004
0.033
0.148
0.018
Y
728
0.19 0.11
3.16 0.63 0.142 2.77 0.19 2.17 0.169 3.25 0.231 2.38 0.316 1.78 0.326 2.7 0.244 0.53 3.24 0.15
0.73 0.19
Y Y
0.28 0.087 0.56 0.028 0.79 0.044 0.45 0.086 0.85 0.094 0.51 0.055
Y Y Y Y Y Y Y Y Y Y Y Y
728 728 959 714 714 714 714 714 714 714 714 714 714 714 714 460 460 460
Styrene Methacrylate, Styrene Styrene Methacrylate, Styrene Methacrylate, Styrene Methacrylate, Styrene Methacrylate, Styrene Methacrylate, Styrene Methacrylate, Styrene Acrylonitrile Methacrylate, Styrene
methyl methyl methyl methyl methyl methyl methyl methyl
-0.1 0.04 0.004 0.02 -0.066 -0.12 0.03 -0.04 -0.002 -0.08 -0.03 -0.18 0.07 0.09 -0.014 0.6 0.15 0.24
0.14 0.082 0.36 0.045 0.33 0.05 0.28 0.11 0.42 0.14 0.27 0.063
References page II - 290
TABLE 1. cont'd Monomer 1 Citraconimide, Af-methylCitraconimide, AT-phenylCitraconimide, N-phenylCitraconimide, Af-propylCitraconimide, N-propylCitraconimide, N-tert-buty\Citraconimide, N-tert-butylCitraconimide, N-tolylCitraconimide, JV-tolylCitraconimide, a-iso-, 7V-(4-acetylphenyl)Citraconimide, a-iso-, A^-(4-chlorophenyl)Citraconimide, a-iso-, N-(4-ethoxycarbonylphenyl)Citraconimide, a-iso-, N-(4-methoxyphenyl)Citraconimide, a-iso-, TV-(p-tolyl)Citraconimide, a-iso-, TV-phenylCopper diacrylate Crotonaldehyde Crotonaldehyde Crotonaldehyde Crotonaldehyde Crotonaldehyde Crotonaldehyde Crotonaldehyde Crotonaldehyde Crotonaldehyde Crotonaldehyde Crotonate, hydrocortisone 21Crotonate, a-acetyl-, methyl Crotonate, a-acetyl-, methyl Crotonate, a-bromo-, ethyl Crotonate, a-carboethoxy-, ethyl Crotonate, a-carboethoxy-, ethyl Crotonate, a-chloro-, ethyl Crotonate, a-chloro-, ethyl Crotonate, a-cyano-, ethyl Crotonate, a-cyano-, ethyl Crotonate, a-methoxy-, methyl Crotonate, a-methoxy-, methyl Crotonate, a-methyl-, methyl Crotonate, a-methyl-, methyl Crotonate, ethyl Crotonate, ethyl Crotonate, methyl Crotonic acid Crotonic acid Crotonic acid Crotonic acid Crotonic acid' Crotonic acid Crotonic acid Crotonic acid Crotonic acid Crotonic acid Crotonic acid Crotonic acid, cisCrotonic acid, transCrotononitrile Crotononitrile Crotononitrile, a-phenylCyclobutane, 1,2-dimethyleneCyclobutane, 1,2-dimethyleneCyclobutane, 1,2-dimethylene-
Monomer 2 Styrene Methacrylate, Styrene Methacrylate, Styrene Methacrylate, Styrene Methacrylate, Styrene Styrene Styrene Styrene
methyl methyl methyl methyl
rx 0.24 0.001 -0.001 -0.03 -0.014 0.038 0.045 0.003 -0.02 0 0 0
±95%
0.033 0.023 0.43 0.087 0.072 0.05 0.088 0.18
r2 0.14 3.081 0.175 3.23 0.196 2.88 0.465 2.75 0.31 0.81 1.03 0.96
±95%
0.074 0.016 0.98 0.062 0.19 0.039 0.19 0.13
Conv.
Y Y Y Y Y Y Y Y
Refs. 506 728 728 714 714 714 714 728 728 608 608 608
Styrene
0
0.39
608
Styrene Styrene Titanium, dicylopentadienyl-, dimethacrylate Acrylonitrile Acrylonitrile Caprolactam, N-vinylCaprolactam, N-vinylPyrrolidone, N-vinylStyrene Styrene Styrene Vinyl chloride Vinylidene chloride N-Vinyl pyrrolidone Acrylonitrile Styrene Styrene Acrylonitrile Styrene Acrylonitrile Styrene Acrylonitrile Styrene Acrylonitrile Styrene Acrylonitrile Styrene Acrylonitrile Styrene Styrene Acrylamide Acrylamide Acrylamide Acrylamide Acrylonitrile Pyrrolidone, TV-vinylStyrene Vinyl acetate Vinyl acetate Vinyl acetate Vinylidene chloride Acrylamide Acrylamide Styrene Styrene Styrene Butadiene Butadiene Styrene
0 0 1.09
1.69 1.76 0.89
608 608 895
0 0.01 0 0 -0.15 0.03 0.07 0.12 -0.56 0 0.05 0 0 0 0 0 0 0 0.06 0.02 0 0.04 0 0.02 0 0 -0.27 -0.18 -0.19 0.11 0.12 0 0 0 0.04 0.01 0.001 -0.2
8 25 0.31 0.31 0.42 14.7 14.7 14.7 1.55
429 504 875 907 248 428 428 428 271 405 1022 785 785 785 785 785 785 785 785 785 785 785 785 785 785 785 112 298 298 569 569 402 245 402 47 526 94 47 341 341 112 785 785 854 885 854
-0.085 -0.012 0 0 5.76 5.76 3.6
0.01
0.25 0.05
0.22 0.14 0.19
0.03 0.14 0.1 1.03 0.024 0.06
0.36
0.75 8.68 2.7 4.42 18.7 8.24 9.53 5.13 11.4 0.26 1 18.4 2.97 30.7 25.2 27 9.68 3.76 4.23 4.72 5.32 21 0.84 20 0.317 0.3 0.31 18.1 7.2 23.29 23.8 0.43 0.1 0.1 0.26
0.005 0.02
N
0.26
N
0.02
1.86 0.89 1.37
Y Y Y
0.07
N
0.081
Y
0.07 43.7 0.33 1.7
0.05
N Y Y Y Y
TABLE 1. cont'd Monomer 1 Cyclobutane, 1,2-dimethyleneCyclopentene, 4-,-1,3-dione Cyclopentene, 4-,-1,3-dione Cyclopentene, 4-,-1,3-dione Cyclopentene, 4-,-1,3-dione Cyclopentene, 4-,-1,3-dione Cyclopropane, l,l-bis(ethoxycarbonyl)2-vinylCyclopropane, l,l-bis(ethoxycarbonyl)2-vinylCyclopropene, 3,3-dimethoxyDiallyl P-cyanoethylisocyanurate Diallyl melamine Diallyl melamine Diallyl melamine Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallyl, l,3-,5-(2-hydroxy3-phenoxypropyl)isocyanate Diallyl, l,3-,5-(2-hydroxy3-phenoxypropyl)isocyanate Diallylcyanamide Diallylcyanamide Diallylcyanamide Diallylcyanamide Diallylcyanamide Diallylcyanamide Diallylcyanamide Diallyldimethylammonium chloride Dicyclopentadiene Dihydroxydiphenylsulfone diallyl ether Dimethyleneheptanedioate, 2,6-,dimethyl Dioxolane,l,3-,4,4-dimethyl-5-methylene2-trichloroDioxolane,l,3-,4-methylene2-trichloromethylDioxolane,l,3-,4-methylene2-trichloromethylDiphenylsulfone,3,3'-bisitaconimido-m,m'Dithiane, 2-methylene-l,3Dithiane, 2-methylene-1,3Divinylbenzene, mDivinylbenzene, p-
Monomer 2
rx
±95%
r2
±95%
Conv.
Refs. 885 95 95 263 264 264 1076
Styrene Acrylonitrile Methacrylate, methyl Styrene Styrene, p-chloroVinylidene chloride Methacrylate, methyl
3.6 0.04 0.094
0.16 0.058 0.017
0.28 3.02 8.11
0.05 0.71 0.38
0.014 0.113 0.223
0.006 0.027 0.194
0.294 1.88 4.21
0.081 0.35 0.905
Y Y Y Y Y Y
Methacrylate, methyl
0.111
0.194
2.5
Y
1076
Acrylonitrile Vinyl acetate Methacrylate, methyl Styrene Vinyl acetate Acrylate, methyl Acrylate methyl Acrylonitrile Acrylonitrile Fumarate, dibutyl Fumarate, diethyl Fumarate, dioctyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Vinyl acetate Vinyl acetate Vinyl acetate Vinyl chloride Vinylidene chloride Vinyl acetate
0.245 4.6
0.037
1.424 0.06
0.038
Y
-0.32 0.318 0.028 0.038 0.04 0.037 0.02 0.01 0.02 -0.001 0.029 0.076 0.041 0.026 0.038 0.08 0.09 0.1 0.1 0.13 2.19 1.66 2 0.7 0.2 5.5
0.2 0.073 0.005 0.008 0.012 0.031
36.96 0.68 6.208 6.18 4.23 2.78 1.01 1.25 0.96 26.56 22.73 21.52 36.41 25.59 23.67 18.8 27.5 16.9 23.8 15.1 0.336 0.414 0.72 0.833 5 0.15
4.02 0.026 0.069 0.16 0.15 0.52
Y Y Y Y Y Y Y
1.98 1.48 0.39 1.23 2.19 1.2
Y Y Y Y Y Y
0.049 0.029
Y Y
0.012
Y
838 778 201 201 201 297 297 153 153 665 665 665 153 153 153 152 152 152 152 152 152 152 152 297 297 509 296 376 671
0.011 0.026 0.006 0.038 0.071 0.04
0.34 0.16 0.046
18.3
Vinyl acetate
3.65
0.16
676
Acrylate, methyl Acrylate, methyl Methacrylate, methyl Methacrylate, methyl Vinyl acetate Vinyl chloride Vinyl chloride Vinyl acetate Maleic anhydride Styrene Methacrylate, methyl Pyrrolidone, N-vinyl-
0.05 0.05 0.04 0.04 1.62 0.68 0.68 1.95 0.037 0.92 0.53 0.01
6.7 6.7 25 25 0.01 0.44 0.44 0.35 0.071 0.975 2.36 3.87
603 604 603 604 581 602 603 1029 914 1016 795 647
Acrylamide
0.037
8.6
616
Pyrrolidone, N-vinyl-
0.04
2.98
647
Methacrylic acid
0.015
Methacrylate, methyl Styrene Styrene Maleic anhydride
4.12 3.35 0.58 0.01
0.112 0.16 0.02
0.058
0.564
0.04 0.01
0.08 0.03 0.58 0.09
0.045 0.015 0.25
0.032
0.15 0.01
Y N
Y
N
1042 1031 1031 262 943
References page II - 290
TABLE 1. cont'd Monomer 1 Divinylbenzene, pEthene, 2-phenyl-l,l-dicyanoEthylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene, 1,1 -dichloro-2,2-difluoro Ethylene, 1,1-diphenylEthylene, 1,1-diphenylEthylene, 1,1-diphenylEthylene, 1,1-diphenylEthylene, 1,1-diphenylEthylene, 1,1-diphenylEthylene, 1,1-diphenylEthylene, 1,1-diphenylEthylene, 1,1-diphenylEthylene, 1,1-diphenylEthylene, 1,1-diphenyl-
Monomer 2 Styrene N-Vinylpyrrolidone Acrylate, butyl Acrylate, methyl Acrylate, methyl Acrylonitrile Butene-1 Butene-1 Butene-2 Carbon monoxide Carbon monoxide Carbon monoxide Carbon monoxide Ethylene, tetrafluoroEthylene, tetrafluoroEthylene, tetrafluoroEthylene, tetrafluoroFumarate, diethyl Maleate, diethyl Maleic anhydride Methacrylate, di-, zinc Methacrylate, methyl Phosphonate, vinyl-, diphenyl Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl- diisobutyl Propylene Propylene Styrene Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl butyrate Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl diethylphosphinate Vinyl diphenylphosphinate Vinyl ethyl ether Vinyl fluoride Vinyl fluoride Vinyl propionate Vinylidene chloride Vinyl acetate Acrylate, ethyl Acrylate, methyl Acrylate, methyl Acrylonitrile Butadiene, 2,3-dichloroButadiene, 2-chloroMethacrylate, methyl Methacrylate, methyl Methacrylonitrile Styrene Styrene
r\
±95%
r2
±95%
Conv.
Refs.
1.18
0.17
0.26
0.25
0.01
0.003
13.94
0.38
N Y N N
262 947 42 41 768 415 388 407 477 51 51 52 52 1093 1094 563 563 41 41 620 935 41 801 801 801 388 477 615 309 41 413 42 559 68 68 766 605 180 270 42 472 536 63 63 64 68 311 311 584 42 590 605 299 6 65 334 334 143 61 61 65 901 143 189 281
0.02 0 3.25 3.6 7.5 0.068 0.025 0.04 0.5 0.52 0.575 0.61 0.38 0.11 0.25 0.04 0.19 0.088 0.077 3.43 3.2 0.05 0.16 0.28 0.88 0.74 0.67 0.13 0.79 0.7 0.19 0.24 0.34 0.2 0.21 0.21 0.14 0.23 0.16 0.15 0.05 2.7 2.52 1.7 0.67 0.018 -0.13 0.5 -0.24 0.21 -0.02 -0.08 0.03 0.09 0 -0.45 0.01 -0.02
19.4 7 0.16 0.012 0.006 0.01 0.18 0.09 1.14
0.32 0.004 -0.15 0 0.067 0.065 0.02 0.1 1.91 10 0 40
0.65 0.012 0.07
Y Y N
0.12 0.027 3.4
N
N Y Y Y
0.01 0.003
1.66 7.73
2.22 2.19
0.03
0.62 14.88 0.72
1.2
N N
0.77
N
0.64 0.21
N N
0.42 0.58 0.44
N N N
0.1 0.22 0.22 0.18 80.64 34.66
N N N N Y Y
0.15
N
1.96 0.58
Y Y
0.01 0.01 0.01
N N N Y Y
0.1 0.02 0.01
N N N
0.52 0.03 0.01 0.17 0.13 0.13 0.01 0.12 0.01 0.01 0.16 0.01 0.32 0.005 0.36 0.15 0.05 0.01
0.11 0.02 0.01
1.14 1.03 1.52 3.74 1.23 1.4 1.5 1.99 1.74 4.38 2 3.21 1.85 0.96 1.63 1.55 -11.99 -62.84 0 0.01 0.3 1.5 15.71 0.33 0.8 0.09 0.12 0.05 3.58 3.4 2.1 8.7 0.48 0.33 0.34
Next Page
TABLE 1. cont'd Monomer 1 Ethylene, 1,1-diphenylEthylene, chlorotrifluoroEthylene, chlorotrifluoroEthylene, chlorotrifluoroEthylene, chlorotrifluoroEthylene, chlorotrifluoroEthylene, chlorotrifluoroEthylene, chlorotrifluoroEthylene, chlorotrifluoroEthylene, chlorotrifluoroEthylene, chlorotrifluoroEthylene, chlorotrifluoroEthylene, chlorotrifluoroEthylene, chlorotrifluoroEthylene, dichloro-, cis Ethylene, dichloro-, cis Ethylene, dichloro-, cis Ethylene, dichloro-, cis Ethylene, dichloro-, cis Ethylene, dichloro-, cis Ethylene, dichloro-, cis Ethylene, dichloro-, cis Ethylene, dichloro-, cis Ethylene, dichloro-, cis Ethylene, dichloro-, cis Ethylene, p-vinyl- 1,1-diphenylEthylene, tetrachloroEthylene, tetrachloroEthylene, tetrachloroEthylene, tetrachloroEthylene, tetrachloroEthylene, tetrachloroEthylene, tetrachloroEthylene, tetrachloroEthylene, tetrachloroEthylene, tetrachloroEthylene, tetrachloroEthylene, tetrachloroEthylene, tetrafluoroEthylene, tetrafluoroEthylene, tetrafluoroEthylene, tetrafluoroEthylene, trichloroEthylene, trichloroEthylene, trichloroEthylene, trichloroEthylene, trichloroEthylene, trichloroEthylene, trichloroEthylene, trichloroEthylene, trichloroEthylene, trichloroEthylene, trichloroEthylene, trichloroEthylene, trichloroFerrocene, ethyl-a-cyclopentadienylidene Ferrocene, ethyl-a-cyclopentadienylidene Formaldehyde-S-vinyl-O-ethylthioacetal Fumarate, allyl methyl Fumarate, bis(2-butyl) Fumarate, bis(3-[tris(trimethylsiloxy)silyl)propyl] Fumarate, bis(3-[tris(trimethylsiloxy)silyl)propyl] Fumarate, bis(3-chloro-2-butyl)
Monomer 2 Styrene Ethylene, tetrafluoroIsobutylene Methacrylate, methyl Propionate, vinyl Propylene Pyrrolidone, N-vinylStyrene Styrene Vinyl acetate Vinyl acetate Vinyl chloride Vinyl fluoride Vinylidene chloride Styrene Styrene Styrene Styrene Styrene Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinylidene cyanide Vinylidene cyanide Styrene Acrylate, methyl Acrylonitrile Acrylonitrile Methacrylate, methyl Styrene Styrene Styrene Styrene Styrene Vinyl acetate Vinyl acetate Ethylene Ethylene Ethylene Ethylene Ethylene, chlorotrifluoroAcrylate, methyl Acrylonitrile Acrylonitrile Butadiene Methacrylate, methyl Styrene Styrene Styrene Styrene Styrene Vinyl acetate Vinyl acetate Vinyl isobutyl ether Butadiene Isoprene Styrene Styrene Styrene Fumarate, di-te/t-butyl Fumarate, diisopropyl Styrene
r\ 1.15 1 0.01 -0.074 0.08 0.02 0.3 -0.1 0.01 0.04 - 0.02 0.01 1.2 0.02 -3.1 -2.2 -0.28 -0.02 0.067 0.055 0.01 0.058 0.1
±95%
0.02 0.062 0.01 0.08 0.21 0.02
0.12 0.062 0.053 0.024 0.03 0.14
1.31 0 0 0
r2 0.87 1 0.06 51.36 0.63 0.08 0.38 4.38 5.2 0.68 0.47 2.53 0.8 17.14 3.1 63.1 21.4 161.3 24.75 1.02 6.4 0.898 4.13
±95%
Conv.
0.03 3.31 0.04 0.07
N Y N
0.99
Y
0.11 Y
4.9 30.3 2.64 0.27 0.06 1.94
Y Y Y Y Y Y Y Y Y Y Y
0.46 830 456 470 Y Y
200 Y 0 0 -0.07 0.067 0.065 0.02 0.1 1 0 0 0 -0.03 0 0 0 0 0 -0.006 -0.06 -0.006 0.014 1.51 1.91 0.32 0.03 0 0.21
0.15 0.12 0.027
0.07
0.37 0.34 0.019 0.003 0.24 0.02 0.01
0.07 - 0.06
187 185 4.45 0.52 0.575 0.61 0.38 1 33 67 62.1 9.64 100 17.1 16.5 12.1 12.7 16 0.607 0.7 0.05 0.02 0.01 7.75 0.25 0.51 0.67
1.87
Y Y
0.18 0.09
0.21
N
11 0.076 0.1 0.009
Y Y Y Y
0.68 0.01 0.04
Y N N
0.87 0.03
0.26
Refs. 901 392 318 236 1097 318 830 236 567 1097 236 454 406 454 137 137 40 9 9 137 137 9 9 82 82 742 402 571 59 204 204 204 40 40 59 3 59 1093 1094 563 563 392 470 470 572 89 470 40 40 40 40 59 158 9 332 699 699 273 713 249 1040 1040
0.04
N
249
References page II - 290
Previous Page
TABLE 1. cont'd Monomer 1 Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate,
di-(2-chloroethyl) di-(2-cyanoethyl) di-(2-(methoxyethyl) di-(2-phenylethyl) di-^c-butyl di-terf-amyl di-tert-butyl
Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate,
di-terf-butyl di-tert-buty\ di-terf-butyl dibenzyl dibutyl dibutyl dibutyl dibutyl dicyclohexyl dicyclopentyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diethyl diisobutyl diisopropyl diisopropyl diisopropyl diisopropyl diisopropyl diisopropyl diisopropyl
Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate, Fumarate,
diisopropyl diisopropyl diisopropyl diisopropyl diisopropyl diisopropyl diisopropyl dimethyl dimethyl dimethyl dioctyl dioctyl dipropyl dipropyl isopropyl butyl isopropyl butyl
Monomer 2 Styrene Styrene Styrene Styrene Styrene Styrene Fumarate, bis(3-[tris(trimethylsiloxy) silyl)propyl Fumarate, dimethyl Maleate, dimethyl Styrene Styrene Diallyl phthalate Imidazole, 1-vinylStyrene Styrene, terf-butoxy Styrene Styrene Acrylonitrile Acrylonitrile Butadiene Butadiene, 2-chloroDiallyl phthalate Ethylene Methacrylate, methyl Methacrylate, methyl A^-Vinylimidazole Styrene Styrene Styrene Styrene Styrene Styrene Styrene Vinyl acetate Vinyl acetate Vinyl chloride Vinyl ethyl ether Vinyl isobutyl ether Vinylidene chloride Styrene Acenaphthalene Acetate, isopropenyl Acrylate, methyl Acrylate, phenyl Acrylonitrile Carbazole, iV-vinylFumarate, bis(3-[tris(trimethylsiloxy) silyl)propyl Isobutylene Methacrylate, methyl Methacrylonitrile Styrene Vinyl acetate Vinyl chloride Vinylidene chloride Fumarate, di-tert-buty\ JV-Vinylimidazole Styrene Diallyl phthalate Pyrrolidone, N-vinylImidazole, 1-vinylStyrene Styrene Styrene
r\
±95%
0 0.09 0.03 O 0.04 0.08 0.67 1.57 18.2 0.04 O 1.01 0.182 0.04 0.01 0.06 0.06 0 0.1 0.25 0.02 1.25 1.91 0.04 0.05 0.191 0.02 0.081 0.11 0.07 0 0.1 0.02 0.443 0.33 0.48 1.63 0.52 0.012 0.05 0.06 0.67 0.091 0.07 0.2 0 0.87 0.42 0.17 0 0.055 0.9 0.49 0.095 0.156 0.252 0.03 0.96 0.04 0.163 0.02 0.01 0.01
r2
±95%
Conv.
0.18 0.07 0.35 0.27 0.55 0.69 0.21 0.365 6.7
0.054
3.4 0.004 0.022 0.005 0.022 0.01 0.007 0.1 0.16 0.038
0.227 0.015 0.04 0.69
0.156 0.011 0.57 0.32 0.02 0.03 0.35 0.18 0.49 0.3 8 10 2.13 6.51 0.01 0.11 40.3 2.1 0.113 0.29 6.3 0.394 0.3 0.31 0.36 0.29 0.011 0.09 0.13 -0.124 0 12.19 0.37 2.57 0.011 1.9 3.4 16 0 0.07 0 23 85 0.4 0.012 0.29 48 1.57 0.133 0.39 0.02 0.02 0.009 0.32 0.42 0.3
Refs. 1038 1038 1038 1038 1038 1038 1040
0.227 0.037
Y Y
0.01
Y
Y 1.14 0.6
N N
0.019
Y
0.26 0.06
Y Y
0.02
N
0.004
Y
0.1 0.059
Y Y
1.58
Y
0.365 0.021
Y Y
0.01 0.012
N Y
1049 1049 1038 1038 665 614 1038 1077 1038 1038 470 640 466 61 665 41 28 394 879 1038 139 139 139 249 562 640 137 718 137 194 640 59 1038 1039 1038 1038 1038 1038 1038 1040 1038 1038 1038 1038 1038 1038 1038 1049 879 1038 665 121 614 1038 1056 1056
TABLE 1. cont'd Monomer 1 Fumarate, isopropyl isobutyl Fumarate, isopropyl methyl Fumarate, isopropyl sec-butyl Fumarate, methyl butyl Fumarate, methyl ethyl Fumarate, methyl isobutyl Fumarate, methyl isopropyl Fumarate, methyl propyl Fumarate, methyl 5ec-butyl Fumarate, methyl terf-amyl Fumarate, methyl tert-bvXy\ Fumarate, mono-2-butyl Fumarate, tert-buiyl 2-ethylhexyl Fumarate, terr-butyl 4-methyl-2-pentyl Fumarate, tert-b\xiy\ ethyl Fumarate, terf-Butyl isoamyl Fumarate, tert-buiy\ methyl Fumarate, tert-bxxtyX sec-butyl Fumaricacid Fumaronitrile Fumaronitrile Fumaronitrile Fumaronitrile Fumaronitrile Fumaronitrile Fumaronitrile Fumaryl chloride Fumaryl chloride Furan, 2,3-dihydroFuran, 2-vinyl-5-methyl Furan, 2-vinyl-5-methyl Furan, 2-vinyl-5-methyl Hex-3-yne-5-ene, 2-methyl-terf-butyl peroxide Hexatriene, tetrachloroHexatriene, tetrachloroHexatriene, tetrachloroHexatriene, tetrachloroHexatriene, tetrachloroHexatriene, tetrachloroHexatriene, tetrachloroHexene, 1-, 3,4-dioic anhydride Hexene, 2-, 3,4-dioic anhydride Hexene, 3-, 3,4-dioic anhydride Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene-1 Hexene-1 Hexene-1 Hexene-1, 2,5-dicarboxylate, dimethyl Imidazole, 1-vinyl Imidazole, 1-vinylImidazole, 1-vinylImidazole, 1-vinyl-
Monomer 2 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene N-vinylimidazole Benzothiazole, vinylmercaptoMethacrylate, methyl Styrene Styrene Styrene Styrene Styrene, a-methylStyrene Vinyl acetate Styrene Acrylate, butyl Methacrylate, isobutyl Methacrylate, methyl Maleic anhydride Acrylate, methyl Acrylonitrile Butadiene, 2-chloroIsoprene Methacrylate, methyl Styrene Vinyl acetate Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Acrylate, methyl Acrylonitrile Vinyl chloride Styrene Triazole, 1-N-vinyl-1,2,4Acrylic acid Fumarate, dibutyl Fumarate, dipropyl
rx 0.01 0.16 0.02 0.02 0.02 0.03 0.16 0.05 0.02 0.06 0.03 - 0.04 0.01 0.01 0.04 0.06 0.03 0.07 0.313
±95%
0.03
0.012
r2 0.46 0.3 0.54 0.36 0.32 0.32 0.3 0.28 0.45 0.53 0.45 0.33 0.54 0.57 0.25 0.45 0.45 0.55 0.121
±95%
Conv.
0.03
N
0.01
Y Y Y Y Y
-0.064 -0.016 0.006 0
0.096 0.021 0.031
6.74 0.202 0.294 0.3
0.79 0.058 0.044
-0.01
0.078
0.094
0.02
0.051 0.169 0.292
20 0.118 0.105 0.183 0.01
0.019 0.044 0.146
Y Y Y
0.087 0.05
Y Y
0.057 0.042
Y Y Y Y Y Y
0 0.392 0.716 0.867 0.36 3.19 4.01 0.2 1.58 1.76 0.85 -0.052 -0.08 -0.54 1.22 1.38 1.52 1.73 1.91 1.91 2.07 2.46 2.69 2.93 3.19 4.11 -0.67 -1.08 -1.72 0.196 0.32 0.03 0.009
1.36 1.25
0.28 0.22 1 1.17 5.83
0.262 0.234 3.6 0.58 0.504 0.123
9.23 0.043
8.57 3.63 17.17 0.031 0.049 0.066 0.07 0.171 0.179 0.173 0.121 0.24 0.014 0.044 0.028 -0.13 2.07 1.54 0.678
0.01 0.012
0.002 0.182 0.163
0.03
8.4 5.6 436
0.6 0.98 0.031
0.054 0.069
Y Y Y Y
Y Y N Y N Y Y
Refs. 1056 1056 1056 1056 1056 1056 1056 1056 1056 1056 1056 249 1056 1056 1056 1056 1056 1056 879 763 191 137 199 478 77 77 91 91 806 1105 1105 1105 637 5 4 459 459 5 4 4 933 933 933 931 931 931 931 931 931 931 931 931 931 931 931 60 60 329 828 972 955 614 614
References page II - 290
TABLE 1. cont'd Monomer 1 Imidazole, 1-vinylImidazole, 1-vinylImidazole, 1-vinylImidazole, 1-vinylImidazole, 1-vinylImidazole, 1-vinylImidazole, 1-vinylImidazole, 1-vinylImidazole, l-vinyl-2-methylImidazole, l-vinyl-2-methylImidazole, l-vinyl-2-methylImidazole, l-vinyl-2-methylImidazole, l-vinyl-2-methylImidazole, l-vinyl-2-methylImidazole, N-vinylImidazole, N-vinylImidazole, TV-vinylImidazolid-2-one, 1,3-divinylImidazolid-2-one, l-ethyl-3-vinylIndene Indene Indene Indene Indene Indene Indene Indene Indene Indene Indene Isobutene Isobutylene Isobutylene Isobutylene Isobutylene Isobutylene Isobutylene Isobutylene Isobutylene Isobutylene Isobutylene Isobutylene Isobutylene, 3-chloroIsobutylene, 3-chloroIsobutylene, 3-chloroIsobutylene, 3-chloroIsooctene Isoprene Isoprene Isoprene Isoprene Isoprene Isoprene Isoprene Isoprene Isoprene Isoprene Isoprene Isoprene Isoprene Isoprene Isoprene Isoprene Isoprene
Monomer 2 Maleate, dibutyl Maleate, dipropyl Maleate, monomethyl Maleic acid Methacrylate, methyl Pyrrolidone, N-vinylStyrene Vinyl acetate Acrylate, methyl Methacrylate, methyl Methacrylate, methyl Styrene Styrene Vinyl chloride Silane, methacryloxypropyldimethoxy methylSilane, methacryloxypropyltrimethoxyStyrene, /?-trimethyoxysilylAcrylate, ethyl Acrylate, ethyl Acrylate, methyl Acrylate, methyl Acrylonitrile Acrylonitrile Styrene, /?-chloroVinyl acetate Vinyl 1-menthyl ether Vinyl methyl ketone Vinyl methyl ketone Vinylidene chloride Vinylidene chloride Maleimide, Af-cyclohexylAcrylonitrile Acrylonitrile Acrylonitrile Ethylene, chlorotrifluoroFumarate, diisopropyl Maleic anhydride Vinyl acetate Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Allyl acetate Vinyl acetate Vinyl chloride Vinylidene chloride Maleimide, JV-cyclohexylAcetylene, phenylAcrylate, methyl Acrylonitrile Butadiene Butadiene Butadiene, 2,3-dimethylButadiene, 2-chloroButadiene, 2-fluoroButadiene, hexafluoroFerrocene, ethyl-oc-cyclo-pentadienylide Hexatriene, tetrachloroMethacrylate, methyl Methacrylate, methyl Methacrylate, methyl Pyridine, 2-vinylPyridine, 2-vinylPyridine, 4-vinyl-
T1 0.486 0.314 0.4 0.3 0.014 0.96 0.071 1.9 0.05 0.047 0.003 0.09 0.07 2.15 0.079 0.158 0.002 -0.08 0.01 0.1 0.12 0.09 0.07 -0.069 8.64 12.64 0.2 0.25 0.293 0.34 0.41 0 0.02 0 0.06 0 0.012 0.17 0.06 0.268 -0.54 0.08 4.5 0 0 0 0.72 3.01 0.75 0.45 1.06 0.608 1.18 0.06 0.25 1.19 0.01 0.58 0.65 0.64 0.64 0.59 0.58 0.32
±95% 0.057 0.028 0.03 0.19 0.029 6.99 0.088 0.064 0.26 0.04 0.03 0.01 0.25 0.24 0.066 2.8 12.59 0.095 0.85 0.002 0.38 0.03 0.19 0.8 0.043 5.8
0.062 0.12
0.23
r2
±95%
Conv.
Refs. 614 614 724 635 364 364 364 364 465 364 479 364 479 154 1095
0.093 0.053 0.6 0.6 4.36 0.16 9.94 -0.11 1.28 4 3.48 8.87 8.97 0.188 1.39
0.08 0.035
Y Y
1.86 0.074 0.24 1.17
Y Y Y Y
0.54
Y
0.62
Y
0.077
Y
2.27 6.9 0.41 0.47 0.63 0.62 0.281 0.29 2.86 0.39 0.67 2.63 2.9 0.49 -0.02 0 1.295 0.98 1.02 0.01 0.42 0.065 1.66 2.04 2.12 1.2 1.54 0.15 0.13 0.31 1.1 0 0.1 0.12 0.03 0.94 0.14 0.84 2.82 2.63 0.78 1.91 1.58 0.26 0.25 0.25 0.47 0.46 2.49
1.12
Y
0.13 0.06
N N
0.05 0.12 0.83 0.2 2.82
Y Y Y Y Y
0.15 1.15
Y Y
0.008 0.25
Y Y
0.02
N
0.18 1.82 0.2 2.05
Y Y Y N
0.37
Y
0.96
Y
0.21
Y
1088 1095 800 800 606 606 360 360 6 360 750 606 606 6 6 995 21 211 484 318 1038 988 211 140 155 329 560 412 475 475 470 995 648 424 417 173 83 173 418 174 453 699 459 302 698 704 456 458 424
TABLE 1.
cont'd
Monomer 1 Isoprene Isoprene Isoprene Isoprene Isoprene Isoprene Isoprene, 3-acetoxyIsoprene, 3-acetoxyIsoprene, 3-acetoxyIsopropenyl acetate Isopropenyl acetate Isopropenyl acetate Isopropenyl acetate Isopropenyl methyl ketone Isopropenyl methyl ketone Isopropenyl methyl ketone Isopropenyl methyl ketone Isopropenyl methyl ketone Isopropenyl methyl ketone Isopropenyl, 3-(l-cyclohexenyl), acetate Isopropenyl, 3-(l-cyclohexenyl), acetate Isopropenyl, 3-(l-cyclohexenyl), acetate Isopropenyl-, p-, phenol glycidyl ether Isopropenylacetophenone, pIsopropenylisocyanate Isopropenylisocyanate Isopropenylisocyanate Isopropenylisocyanate Isopropenylisocyanate Isopropenylisocyanate Isopropenylisocyanate Isopropenylisocyanate Isopropenylisocyanate Isopropenyltoluene Isopropenyltoluene Isopropylidene, 2,3:4,5-di-0-, -1 - vinylbenzyl- (3-D-fructose Itaconamate, N-(4-carboethoxyphenyl)-, butyl Itaconamate, Af-(4-carboethoxyphenyl)-, ethyl Itaconamate, N-(4-carboethoxyphenyl)-, ethyl Itaconamate, N-(4-carboethoxyphenyl)-, methyl Itaconamate, Af-(4-carboethoxyphenyl)-, propyl Itaconamate, A^-(4-carboethoxyphenyl)-, propyl Itaconamate, A^-(4-chlorophenyl)-, ethyl Itaconamate, N-(4-chlorophenyl)-, ethyl Itaconamate, A^-(4-chlorophenyl)-, methyl Itaconamate, Af-(4-chlorophenyl)-, propyl Itaconamate, A^-(4-chlorophenyl)-, propyl Itaconamate, Af-(4-methoxyphenyl)-, butyl Itaconamate, N-(4-methoxyphenyl)-, ethyl Itaconamate, A^-(4-methoxyphenyl)-, ethyl Itaconamate, N-(4-methoxyphenyl)-, methyl Itaconamate, Af-(4-methoxyphenyl)-, propyl Itaconamate, AH4-methoxyphenyl)-, propyl Itaconamate, Af-(4-methylphenyl)-, propyl Itaconamate, Af-(4-methylphenyl)-, propyl
Monomer 2 Quinoline, 2-vinylStyrene Styrene Styrene Styrene Styrene Acrylate, methyl Methacrylate, methyl Styrene Maleic anhydride Methacrylate, methyl Vinyl acetate Vinyl chloride Acrylonitrile Acrylonitirle Butadiene, 2-chloroStyrene Styrene Vinylidene chloride Acrylate, methyl Methacrylate, methyl Styrene Maleic anhydride Styrene Acrylate, ethyl Acrylate, methyl Acrylate, methyl Acrylonitrile Methacrylate, methyl Styrene Styrene Vinyl chloride Vinylidene chloride Methacrylate, methyl Methacrylate, methyl Styrene
r\ 1.88 1.922 1.957 1.98 2.02 1.3 5.71 2.81 4.47 0.034 -0.09 1.082 0.23 1.2 0.7 0.14 0.29 0.66 4.06 0.57 0.4 0.56 0.003 0.84 0.15 0.11 0.079 0.1 0.14 0.07 0.122 3 0.31 0.04 0.04 3.26
±95%
0.016 0.011
0.022 0.12 0.074 0.16 0.01 0.66
0.59 0.047
0.047
1.12
r2 0.53 0.513 0.476 0.44 0.42 0.48 0.27 0.16 0.34 0.002 17.36 1.171 2.26 0.3 0.36 4.035 0.44 0.32 0.134 0.37 0.81 1.59 0.002 0.3 0.79 0.6 0.799 0.24 3.1 8.12 6.84 0.39 0.85 0.68 0.68 0.14
±95%
Conv.
0.02 0.018
Y Y
0.011 1.95 0.038 0.13
Y Y Y Y
0.087
Y
0.099
Y
0.18
Y
0.049
Y
0.18
Y
0.055
Y
Refs. 456 366 366 544 544 83 770 770 770 260 100 100 100 490 542 259 542 542 47 770 770 770 937 266 434 434 99 434 434 434 99 777 434 688 722 772
Styrene
0.61
0.2
678
Methacrylate, methyl
0.48
1.21
678
Styrene
0.2
0.23
678
Styrene
0.58
0.15
678
Methacrylate, methyl
0.53
1
678
Styrene
0.4
0.26
678
Methacrylate, methyl Styrene Styrene Methacrylate, methyl Styrene Styrene Methacrylate, methyl Styrene Styrene
0.36 0.16 0.18 0.31 0.31 0.69 0.43 0.34 0.41
1.24 0.35 0.38 1.26 0.39 0.12 1.31 0.33 0.26
678 678 678 678 678 678 678 678 678
Methacrylate, methyl
0.4
1.03
678
Styrene
0.4
0.38
678
Methacrylate, methyl Styrene
0.28 0.19
1.11 0.54
678 678
References page II - 290
TABLE 1. cont'd Monomer 1 Itaconamate, N-(4-methylphenyl)-, butyl Itaconamate, Af-(4-methylphenyl)-, ethyl Itaconamate, A^-(4-methylphenyl)-, ethyl Itaconamate, Ar-(4-methylphenyl)-, methyl Itaconamate, N-phenyl-, butyl Itaconamate, N-phenyl-, ethyl Itaconamate, N-phenyl-, ethyl Itaconamate, N-phenyl-, methyl Itaconamate, N-phenyl-, methyl Itaconamate, Af-phenyl-, propyl Itaconamate, Af-phenyl-, propyl Itaconate, bis(2-ethylhexyl) Itaconate, bis(tri-w-butyltin) Itaconate, bis(tri-rc-butyltin) Itaconate, bis(tri-n-butyltin) Itaconate, bis(tri-rc-butyltin) Itaconate, di-2[-2(2-methoxyethoxy)ethoxy]ethyl Itaconate, di-^-butyl Itaconate, diamyl Itaconate, dibutyl Itaconate, dibutyl Itaconate, dibutyl Itaconate, dibutyl Itaconate, diethyl Itaconate, diethyl Itaconate, diethyl Itaconate, dimenthyl Itaconate, dimenthyl Itaconate, dimenthyl Itaconate, dimenthyl Itaconate, dimethyl Itaconate, dimethyl Itaconate, dimethyl Itaconate, dimethyl Itaconate, dimethyl Itaconate, dimethyl Itaconate, dimethyl Itaconate, dimethyl Itaconate, dimethyl Itaconate, dimethyl Itaconate, dioctyl Itaconate, dipropy Itaconate, ethyl hexafluoroisopropyl Itaconate, glycidyl methyl Itaconate, mono-methyl Itaconate, mono-methyl Itaconate, mono-methyl Itaconate, mono-methyl Itaconate, mono-methyl Itaconate, mono-methyl Itaconate, mono-methyl Itaconate, mono-methyl Itaconate, monomethyl Itaconic acid Itaconic acid Itaconic acid Itaconic acid Itaconic acid Itaconic acid mono(/?-sulfamidoanilide) Itaconic anhydride Itaconic anhydride Itaconic anhydride Itaconic anhydride Itaconic anhydride
Monomer 2 Styrene Methacrylate, methyl Styrene Styrene Styrene Methacrylate, methyl Styrene Styrene Styrene Methacrylate, methyl Styrene Maleimide, N-cyclohexylAcrylate, 2-chloroethyl Acrylate, butyl Methacrylate,allyl N-Vinylpyrrolidone Styrene Maleimide, N-cyclohexyl Styrene Itaconate, dimethyl Methacrylate, methyl Methacrylate, methyl Styrene Pyridine, 2-methyl-5-vinylStyrene Vinyl chloride Maleimide, 7V-cyclohexylMethacrylate, methyl Styrene Vinyl acetate Acrylate, butyl Itaconate, dibutyl Methacrylate, methyl Methacrylonitrile Pyridine, 2-methyl-5-vinylStyrene Styrene Styrene Styrene, /?-chloroVinyl chloride Styrene Styrene Styrene Styrene Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Styrene Styrene Styrene Styrene Methacrylate, methyl Acrylonitrile Methacrylate, methyl Methacrylate, methyl Styrene Styrene Methacrylate, propargyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethyl Acrylonitrile Methacrylate, methyl Styrene
rx 0.31 0.63 0.26 0.16 0.49 0.47 0.21 0.52 0.18 0.15 0.18 0.38 0.391 0.422 0.038 0.065 0.2 0.34 0.5 1.1 0.717 0.4 0.34 0.17 0.34 5.65 0.318 -0.156 0.483
±95%
0.04 0.015 0.04 0.09 0.11 0.05 0.12 0.213 0.02 0.364
r2 0.19 1.43 0.38 0.3 0.12 1.32 0.45 0.31 0.39 1.13 0.5 0.34 0.683 0.91 1.08 0.21 0.53 0.21 0.36 1.1 1.33 0.8 0.42 0.51 0.23 0.06 0.601 3.34 0.502
0.94 1.1 0.3 0.28 0.22
0.4 1.1 1.2 1.26 0.88
0.14 0.06 0.15 5 0.14 0.28 0.039 0.041 0.31 0.36 0.135 0.04 0.111 0.33 0.33 0.218 0.139 0.86 0 0 0 0.12 0.58 2.46 2.61 4.83 1.17 0.405
0.48 0.5 0.69 0.05 0.33 0.16 0.435 0.376 0.52 0.59 0.223 0.189 0.029 0.34 0.52 0.404 1.1 0.59 1.23 1.14 0.34 0.26 1.65 -0.016 0.251 0.034 0.155 0.004
±95%
0.013 0.022 0.04 0.05
Conv.
Y
N
0.09 0.06
N
0.11
N
0.193 0.557 0.188
Y Y Y Y
N
0.12 0.06 0.035 0.079 0.42 0.21 0.028 0.11 0.052 0.15 0.11 0.086 0.103 0.74
0.67 0.05 0.38 0.32 0.33 0.33 0.09
0.16 0.07 0.025 0.036 0.16 0.14 0.02 0.055 0.039 0.077 0.085 0.06 0.071 0.34
0.08 0.02 0.022 0.021 0.014 0.024 0.01
N N N Y Y Y Y Y Y Y Y Y Y
Y Y Y Y Y Y
Refs. 678 678 678 678 678 678 678 1059 678 678 678 1060 940 940 940 941 1098 1014 39 398 1073 398 39 545 39 480 975 975 975 975 398 398 398 398 545 39 398 586 398 479 39 39 1103 806 613 613 613 613 656 656 656 656 1010 164 260 408 420 76 957 365 365 365 1010 365
TABLE 1. cont'd Monomer 1 Itaconic anhydride Itaconic anhydride Itaconic anhydride Itaconic anhydride Itaconimide, AH2-chloroethyl)Itaconimide, AK2-chloroethyl)Itaconimide, AH4-acetoxyphenyl)Itaconimide, Af-(4-chlorophenyl)Itaconimide, N-(4-ethoxycarbonylphenyl)Itaconimide, N-(p-chlorophenyl)Itaconimide, N-(p-lo\y\)Itaconimide, Af-benzylItaconimide, Af-benzylItaconimide, Af-butylItaconimide, iV-ethylItaconimide, JV-ethylItaconimide, N-isobutylItaconimide, AMsopropylItaconimide, N-methylItaconimide, N-methylItaconimide, N-naphthylItaconimide, W-phenylItaconimide, Af-phenylItaconimide, N-phenylItaconimide, N-propylItaconimide, N-XxAyV Malemic acid, A^-3-dimethylamino6-methylphenylMalemic acid, A^-3-dimethylamino6-methylphenylMaleate, chloro-, diethyl Maleate, dibutyl Maleate, allyl methyl Maleate, butyl stannylallyl Maleate, di-tert-butyl Maleate, dibutyl tin Maleate, dibutyl tin Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, diethyl Maleate, dimethyl Maleate, dimethyl Maleate, dimethyl Maleate, dimethyl Maleate, dimethyl Maleate, dimethyl Maleate, dimethyl Maleate, dioctyl
Monomer 2 Styrene Styrene Vinyl acetate Vinyl acetate Methacrylate, Styrene Styrene Styrene Styrene Styrene Styrene Methacrylate, Styrene Styrene Methacrylate, Styrene Styrene Styrene Methacrylate, Styrene Styrene Styrene Styrene Styrene Styrene Styrene Butadiene
rx 0.456 0.785 1.57 2.87 0.54 0.162 0.21 0.2 0.112 0.14 0.24 1.06 0.2 -0.019 0.42 0.172 -0.03 0.045 1.12 0.12 0.35 0.109 0.08 0.998 0.04 0.219 - 0.08
Styrene Styrene Imidazole, 1-vinylStyrene Styrene Vinyl acetate Methacrylate, methyl Styrene Acrylonitrile Acrylonitrile Butadiene Carbazole, N-vinylEthylene Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl iV-Vinylimidazole Styrene Styrene Styrene Styrene Styrene Vinyl acetate Vinyl chloride Vinyl chloride Vinyl chloride Vinyl isobutyl ether Vinylidene chloride Carbzole, Af-vinylFumarate, di-tert-butyl N-Vinylimidazole Styrene Styrene Succinimide, Af-vinylVinyl acetate Vinyl chloride
methyl
methyl methyl
methyl
±95%
±95%
Conv.
Refs.
0.015 0.005 0.045 0.024 0.11 0.045 0.12 0.084 0.032
Y Y Y Y Y Y Y Y Y
0.18 0.048 0.03 0.066 0.029 0.11 0.043 0.22 0.069
Y Y Y Y Y Y Y Y Y
0.043
Y
0.123 0.18 0.079 0.03
0.086 0.003 -0.019 - 0.04 0 0.069 0.35 0.159 0.232 0.15 0.16 0.46 0.056 0.22 0.486 0.232 0.44 0.308 0.38 0.153 0.08 0.116 0.05 0.05 0.28 0.134 0.37
0.248 0.12 0.031 0.04
N Y Y N
62 62 365 365 642 642 729 729 729 740 740 642 642 642 642 642 642 642 642 642 740 729 740 978 642 729 679
-0.19
0.03
0.55
0.03
N
679
-0.043 0.093 0.02 0.06 0.199 -0.095 0.194 0 0 0.11 0 10 -0.1 0 -0.02 0.106
0.021 0.08 0.01 0.03 0.02 0.199 0.121
2.07 0.486 8.29 0.1 0.005 72.7 2.08 12 20 8.08 0.21 0.25 341 20 285.8 0.057
0.14 0.057 0.14 0.02 0.024 5.93 0.118
Y Y N N Y Y Y
0.05
N
14 614 713 811 1049 987 987 470 640 466 361 41 28 470 873 879 14 139 640 874 888 137 137 449 6 640 3 361 1049 879 137 317 284 1049 3
-0.013 0.07 0.01 0.001 0.04 -0.003 0 0.046 0.17 12.5 0 0.011 0.046 0.15 0.105 -0.012 0.257 0.608
0.09 0.05 0.3 0.32 0.39 0.092 0.21 0.18 0.054
r2
0.75 0.11 0.04 0.13 0.06 0.11 0.064 0.73 0.12 0.082
0.01 0.05 0.015 0.147 0.022 0.01 0.012 0.044 0.07 0.01 0.037 0.438 0.12 0.058 0.021 0.086 0.099
6.59 8 6.07 6.592 0.171 0.768 0.8 0.9 0 0.51 18.2 0.046 10.65 0.083 1.25 -0.006 0.05
46
N
35.9 0.028 0.46
Y Y Y Y
0.07
N
0.025 0.078
Y Y
0.11
Y
0.11 6.7 0.046 2.81 0.015 0.16 0.084 0.14
N Y Y Y Y Y Y Y
References page II - 290
TABLE 1. cont'd Monomer 1 Maleate, dipropyl Maleate, monoallyl Maleate, monoallyl Maleate, monomethyl Maleate, tributylstannyl allyl Maleic Anhydride Maleic acid Maleic acid Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic Maleic
anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride anhydride
Monomer 2 Imidazole, 1-vinylMaleic anhydride Styrene Imidazole, 1-vinylMaleic anhydride Isopropenyl-, /?-, phenol glycidyl ether Imidazole, 1-vinylN-Vinylimidazole Acenaphthalene Acenaphthalene Acetylene, phenylAcrolein diethylacetal Acrylamide Acrylate, 2-chloroethyl Acrylate, ferrocenylmethyl Acrylate, methyl Acrylate, methyl Acrylonitrile Allyl acetate Allylbenzene Benzocyclobutane, oc-methyleneBenzothiazole, vinylmercaptoButadiene monoxide Butadiene, 2-chloroCarbamate, AUV-diethyl-, vinyl Dicyclopentadiene Divinylbenzene, p Ethylene Hex-3-yne-5-ene, 2-methyl-terf-butylperoxide Isobutylene Isopropenyl acetate Maleate, monoallyl Maleate, tributylstannyl allyl Maleimide, N-phenylMaleimide, N-phenylMethacrylate, ferrocenylmethyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, di-, di-rc-butylstannyl Methacrylate, benzyl Methacrylate, benzyl Phthalimide, N-vinylPropene, 1-chloro-, cisPropene, 1-chloro-, transStyrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene, a-methyl-
rx
±95%
0.053 0.027 0.07 0.6 0.095 0.002 0.6 0.094 0.02 -0.04 0.06 0.07 0 0.027
0.035 0.014 0.02
0.012 0 0 0.028
0.013
0.104 0.027 0.05
0.004
0.019
0.025
r2 0.314 0.051 0.14 0.4 0.032 0.003 0.3 0.018 0.46 0.46 0.08 0.18 0.56 7.15 2.788 2.5 6 -0.001
±95%
Conv.
Refs.
0.028 0.054 0.01
Y N N
0.017
N
0.007
Y
0.13
N
0.31 2.96 0.051
Y Y Y Y
614 906 811 724 906 937 635 879 1039 326 797 767 655 117 325 260 470 470 27 351 1083 763 1064 1068 92 914 943 620 637
0.007
Y Y
0.002 Y
0.64 0.329 0.025 0.071 0.09 0 0.01 0.065 0.002 0.051 0.032 -0.095 0.02 0.24 -0.163 -0.019 0.08 0.02 0.01 0.01 0.01 0.02 0.024 0.372 0.008 0.347 0.28 0.001 0 0.003 0.02 0 0 0.02 0.01 0.001 0.005 0.01 0.02 0.05
0.06 0.107 0.034 0.045 0.01
0.011 0.054 0.017 0.106 0.65 0.28 0.027 0.026 1.77 0.004
0.008 0.093 0.012 0.082 0.012 0.008 0.13 0.03 0.01
0.05 0.026 0.024 0.037 0.01 0.04 0.36 0.012 0.034 0.027 0.095 1.08 1.92 0.33 4.18 6.36 0.46 5.2 3.1 3.85 3.4 3.85 0.012 - 0.075 0.344 -0.022 0.05 0.097 0.04 0.02 0 0.02 0.02 0.04 0.04 0.04 0.05 0.02 0.04 0.04
0.18 0.03 0.066 0.112 0.01
N Y Y
0.022 0.014 0.104 0.13 11.83 0.65 0.31 0.64 0.69 0.47
Y N N Y Y Y Y Y N N
0.016
Y Y Y Y Y Y N Y N N
0.088 0.061 0.08 0.015 0.002 0.12 0.003 0.01
N 0.08
0.04
988 260 906 906 990 341 325 169 260 320 33 524 524 524 524 954 720 720 284 181 181 105 12 17 241 384 397 483 506 522 522 522 522 522 923 492
TABLE 1. cont'd Monomer 1 Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride Maleic anhydride, a-chloroMaleimide Maleimide Maleimide Maleimide Maleimide Maleimide Maleimide, N-hydroxymethyl Maleimide, 2,3-dimethylAf-(2-methacryloxyethyl)Maleimide, 2,3-dimethylAf-(2-methacryloxyethyl)Maleimide, 2,3-dimethylAf-(2-methacryloxyethyl)Maleimide, A^-(2,4-dimethylphenyl)Maleimide, N-(2,4-dimethylphenyl)Maleimide, N-(2,6-diethylphenyl)Maleimide, A^-(2,6-diethylphenyl)Maleimide, A^-(2,6-diisopropylphenyl)Maleimide, Af(2,6-dimethylphenyl)Maleimide, J/V-(2,6-dimethylphenyl)Maleimide, A^-(2-bromophenyl)Maleimide, AH2-chlorophenyl)Maleimide, N-(2-chlorophenyl)Maleimide, iV-(2-chlorophenyl)Maleimide, iV-(2-chlorophenyl)Maleimide, N-(2-chlorophenyl)Maleimide, A^-(2-chlorophenyl)Maleimide, N-(2-hydroxyethyl)Maleimide, 7V-(2-hydroxyethyl)Maleimide, iV-(2-hydroxyethyl)Maleimide, A^-(2-hydroxyethyl)Maleimide, A^-(2-hydroxyethyl)Maleimide, A^-(2-hydroxyethyl)Maleimide, TV-(2-methylphenyl)Maleimide, iV-(3,5-dimethylphenyl)Maleimide, AK3-dimethylaminophenyl)Maleimide, N-(3-methylphenyl)Maleimide, A^-(3-trifluoromethylphenyl)Maleimide, A^-(4-bromophenyl)Maleimide, A^-(4-bromophenyl)Maleimide, A^-(4-carboxyethylphenyl)Maleimide, JV-(4-carboxyethylphenyl)a-chloroMaleimide, A^-(4-carboxyethylphenyl)a-chloroMaleimide, A^-(4-chlorophenyl)Maleimide, A^-(4-chlorophenyl)Maleimide, 7V-(4-chlorophenyl)Maleimide, A^-(4-chlorophenyl)Maleimide, N-(4-chlorophenyI)-a-chloroMaleimide, A^-(4-chlorophenyl)-a-chloroMaleimide, iV-(4-hydroxyphenyl)Maleimide, A^-(4-hydroxyphenyl)Maleimide, AT-(4-hydroxyphenyl)Maleimide, Af-(4-hydroxyphenyl)-
Monomer 2
rx
Succinimide, N-vinyl0.021 Vinyl 2-chlorocyclohexyl ketone 0.83 Vinyl 4-chlorocyclohexyl ketone 0.08 Vinyl acetate -0.058 Vinyl chloride -0.22 Vinyl chloride 0.4 Vinyl chloride 0.67 Vinylidene cyanide Styrene 0 Butadiene, 2,3-bis(diethyl-phosphono)0.43 Methacrylate, methyl 0.166 Methacrylate, methyl 0.17 Piperidinol, 4-, TV-methyl0.49 4-(vinylethynyl)Styrene 0.088 Vinylidene chloride 0.464 Methacrylate, methyl 0.263 Acrylate, ethyl 1.55
±95% 0.027
0.074 0.38
r2 0.148 1.7 0.12 0.019 0.098 0.04 0.1
±95%
Conv.
0.073
Y
0.008 0.042
Y Y
Y
Refs. 284 836 836 260 260 521 521 82 845 759 251 992 948
0.061
0.01
0.07 0.14 2.576 2.5 2.05
0.036 0.083 0.026 3.06
0.057 0.666 1.745 0.28
0.012 0.056 0.03 1.15
Y Y Y Y
251 251 323 619
0.047
Y
0.03
Methacrylate, methyl
1.1
3.58
0.51
1.66
Y
619
Methacrylic acid
1.33
0.1
0.746
0.059
Y
619
Acrylate, butyl Acrylate, heptyl Methacrylate, methyl Styrene Methacrylate, methyl Methacrylate, methyl Styrene Acrylonitrile Acrylonitrile Methacrylate, methyl Styrene Styrene Styrene Styrene Butadiene, 2,3-bis(diethyl-phosphono)Methacrylate, methyl Pyrrolidone, TV-vinylStyrene Vinyl acetate Vinyl acetate Methacrylate, methyl Methacrylate, methyl Styrene Methacrylate, methyl Methacrylate, methyl Acrylate, methyl Styrene Vinyl chloride Methacrylate, methyl
0.2 0.2 0.05 0.02 0.02 0.07 0.08 0.338 1.078 0.1 0.013 0.028 0.01 0.006 0.49 0.201 0.038 0.011 0.61 0.88 0.09 0.28 0.19 0.22 0.1 0.39 0.018 3.29 -0.004
0.17 0.007 0.18 0.168
0.62 0.14 4.78 0.19 10.9 3.62 0.14 2.029 0.956 2.1 0.011 0.038 0.013 0.038 0.12 1.396 0.002 0.046 -0.014 0.01 2.22 1.63 0.03 1.18 1.57 0.429 0.02 0.04 0.472
0.045 0.048 0.002 0.003 0.005 0.003 0.083 0.01 0.027 0.12 0.17
0.214 0.095
Y Y
0.004 0.006 0.012 0.28
Y Y Y Y
0.089 0.002 0.017 0.037 0.041
Y Y Y Y Y
0.099 0.006 0.03 0.114
Y N Y
788 788 992 992 992 992 992 863 863 992 853 853 910 910 759 323 323 323 323 323 992 992 747 992 992 628 1030 306 973
Styrene
0.022
0.041
0.059
0.021
Y
973
Acrylate, methyl Acrylonitrile Butadiene, 2,3-bis(diethyl-phosphono)Vinyl chloride Methacrylate, methyl Styrene Methacrylate, methyl Styrene Vinyl acetate Butadiene, 2,3-bis(diethyl-phosphono)-
0.155 0.743 0.41 3.65 0.02 0.019 0.345 0.13 1.75 0.47
0.052 0.048
0.684 0.972 0.03 0.026 0.562 0.149 1.392 -0.059 -0.011 0.04
0.052 0.112
Y Y
0.044 0.025 0.048 0.001 0.041 0.027
Y Y Y Y Y Y
628 863 759 306 973 973 323 323 323 75
0.39 0.03 0.038 0.001 0.1 0.17
References page II - 290
TABLE 1. cont'd Monomer 1 Maleimide, A^-(4-methoxyphenyl)-a-chloroMaleimide, AH4-methoxyphenyl)-a-chloroMaleimide, TV-(4-methylphenyl)Maleimide, TV-(4-methylphenyl)Maleimide, AK4-methylphenyl)-a-chloroMaleimide, iV-(4-methylphneyl)-a-chloroMaleimide, TV-(4-tolyl)Maleimide, TV-(P-chloroethyl)-a-chloroMaleimide, AHP-chloroethyl)-oc-chloroMaleimide, TV-(p-chloroethyl)-a-chloroMaleimide, TV-(L-menthoxycarbonylmethyl)Maleimide, TV-(L-menthoxycarbonylmethyl)Maleimide, TV-2-bromophenylMaleimide, TV-2-chlorophenylMaleimide, TV-4-chlorophenylMaleimide, TV-[TV'-a-methylbenzyl) aminocarbonylpentyl]Maleimide, TV-[TV'-a-methylbenzyl) aminocarbonylpenty 1] Maleimide, TV-[TV'-a-methylbenzyl) aminocarbonylpenty I]Maleimide, TV-a-methylbenzylMaleimide, TV-a-methylbenzylMaleimide, TV-allylMaleimide, TV-benzylMaleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide, Maleimide,
TV-benzylTV-benzylTV-benzyl-a-chloroTV-butylTV-butylTV-butylTV-butylTV-chloromethylTV-cyclohexyliV-cyclohexylTV-cyclohexylTV-cyclohexylTV-cyclohexylTV-cyclohexylTV-cyclohexylTV-cyclohexylTV-cyclohexylTV-cyclohexylTV-cyclohexylTV-cyclohexylTV-cyclohexylTV-ethyl-a-chloroTV-ethyl-a-chloroTV-hexylTV-hexyliV-hydroxymethylTV-hydroxymethylTV-methyl-a-chloroTV-methyl-a-chloroTV-octadecylTV-octadecylTV-phenylTV-phenylTV-phenylTV-phenylTV-phenyl-
Maleimide, TV-phenyl-
Monomer 2
T1
±95%
Methacrylate, methyl Styrene Methacrylate, methyl Vinyl chloride Methacrylate, methyl Styrene Acrylate, methyl Methacrylate, methyl Methacrylate, methyl Styrene Maleimide, TV-benzyl Maleimide, TV-phenyl-
0.064 0.049 0.34 4.49 0.029 0.019 0.14 0.05 0.11 0 0.848 0.79
0.189 0.061
Acrylonitrile Acrylonitrile Acrylonitrile Methacrylate, methyl Styrene
r2
±95%
Conv.
Refs.
0.145 0.031
Y Y
0.34 0.158 0.078 0.16 0.04 0.05 0.06 0.221 0.261
0.556 0.112 0.83 0.022 0.564 0.107 0.64 0.94 0.59 0.29 0.474 0.798
0.048 0.117 0.048 0.16 0.06 0.06 0.05 0.087 0.141
Y Y Y Y
Y Y
973 973 992 306 973 973 644 974 974 974 1089 1089
0.348 1.08 0.743 0.582
0.044 0.048 0.048 0.359
2.02 0.955 0.972 1.37
0.205 0.095 0.112 0.291
Y Y Y Y
915 915 915 1099
0.258
0.25
0.198
0.143
Y
1099
Y
1099 1055 1055 1003 1089
Styrene Maleimide, TV-cyclohexyl1.07 Maleimide, TV-phenyl0.683 Styrene 0.035 Maleimide, TV-(L-menthoxycarbonyl0.474 methyl)Methacrylate, methyl 0.03 Styrene 0.013 Styrene 0 Methacrylate, methyl -0.1 Styrene Styrene 60 Vinyl chloride -12.7 Butadiene, 2,3-bis(diethyl-phosphono)0.3 Methacrylate, methyl 0.24 Acenaphthalene 0.11 Butene, cis-20 Isobutene 0 Itaconate, bis(2-ethylhexyl) 0.34 Itaconate, di-n-butyl 0.21 Itaconate, dimenthyl 0.601 Maleimide, TV-a-methylbenzyl0.392 Methacrylate, methyl 0.19 Methacrylate, methyl 0.106 Styrene 0.1 Styrene 0.162 Isooctene 0 Methacrylate, methyl 0.13 Styrene 0 Methacrylate, methyl 0.1 Styrene 0.09 Styrene 0.06 Vinyl acetate 1.45 Methacrylate, methyl 0.11 Styrene 0 Acrylonitrile 0.389 Acrylonitrile 0.39 Acrylate, methyl 0.103 Butadiene, 2,3-bis(diethyl-phosphono)0.42 Maleic anhydride 1.92 Maleic anhydride 1.08 Maleimide, TV-(L-menthoxycarbonyl0.798 methyl)Maleimide, TV-a-methylbenzyl0.788
0.177 0.177
0.214 0.5
Y Y
0.087
0.392 0.788 0.056 0.848
0.221
Y
0.23 0.031 0.06 0.16
1.28 0.058 0.42 1.41
0.23 0.021 0.06 0.19
Y Y
1.13
Y
0.04 0.213 0.177
Y Y
0.066
Y
0.017
Y
106.2
0.04 0.193 0.214 0.048 0.054 0.03 0.04 0.15 0.16 0.11 0.21 0.03 0.03 0.023 0.023 0.052 11.83 0.13 0.141 0.5
0.02 0.24 0.05 1.35 0.57 3 0.41 0.38 0.34 0.318 1.07 1.31 2.26 0.102 -0.01 0.72 0.53 0.9 1.9 -0.041 -0.035 0.017 0.63 0.63 2.482 2.46 0.554 0.05 0.02 -0.095 0.79
0.04 0.05 0.2 0.069 0.053 0.037 0.34 0.04 0.119 0.115 0.048
Y Y Y
0.65 0.106 0.261
Y Y Y
348 348 974 115 115 50 305 759 992 1039 995 995 1060 1014 975 1055 1100 348 1100 348 995 974 974 348 348 323 323 974 974 863 915 644 759 341 990 1089
0.683
0.177
Y
1055
Y Y
Y Y Y Y
TABLE 1. cont'd Monomer 1 Maleirnide, W-phenylMaleimide, N-phenylMaleimide, N-phenylMaleimide, N-phenylMaleimide, 7V-phenylMaleimide, N-phenylMaleimide, iV-phenylMaleimide, JV-phenylMaleimide, N-phenyl-a-chloroMaleimide, N-phenyl-a-chloroMaleimide, N-propylMaleimido-A^V-dimethylaniline, 4-(2-chlorophenyl)azo Mesaconate, dibenzyl Mesaconate, di-seobutyldithiol Mesaconate, diamyl Mesaconate, dibenzyldithiol Mesaconate, dibutyl Mesaconate, dibutyldithiol Mesaconate, dicyclohexyl Mesaconate, diethyl Mesaconate, diethyldithiol Mesaconate, dihexyl Mesaconate, diisoamyl Mesaconate, diisobutyl Mesaconate, diisobutyldithiol Mesaconate, diisopropyl Mesaconate, diisopropyldithiol Mesaconate, dimethyl Mesaconate, dimethyldithiol Mesaconate, dioctyl Mesaconate, diphenyl Mesaconate, diphenyldithiol Mesaconate, dipropyl Mesaconate, dipropyldithiol Mesaconic acid Methacryl-2'-ethyl-4,5J-trinitro9-fluorenone-2-carboxylate Methacrylamide Methacrylamide Methacrylamide Methacrylamide Methacrylamide Methacrylamide Methacrylamide Methacrylamide Methacrylamide Methacrylamide Methacrylamide, 1-deoxy-D-glucitol Methacrylamide, AK2-hydroxypropyl)Methacrylamide, A^-(4/-nitro-4-stilbenyl)Methacrylamide, iV-(4-stilbenyl)Methacrylamide, N-(p-chloroprienyl)Methacrylamide, N-(/?-methoxyphenyl)Methacrylamide, Af-(/?-methyrphenyl)Methacrylamide, 7V-(/?-nitrophenyl)Methacrylamide, A^-[4-(4-methoxyphenylacetyloxy)phenyl]Methacrylamide, iV-methoxymethylMethacrylamide, Af-/?-bromophenylMethacrylamide, N-p-tolylMethacrylamide, N-phenyl Methacrylamide, N-phenylMethacrylamide, N-phenyl-
Monomer 2 Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Styrene Styrene Styrene Vinyl acetate Vinyl chloride Methacrylate, methyl Styrene Vinyl chloride Styrene
rx 0.3 0.164 0.3 0.044 0.01 1.284 4.01 0.077 - 0.002 2.38 0.04
0.065 0.017 0.046 0.18 0.098 0.073 0.16
r2 0.98 1.014 0.91 0.016 0.07 -0.003 0.023 0.657 0.087 0.06 0.05
Conv.
0.06
Y
0.004
N Y
0.006 0.026 0.083 0.04 0.05
Y Y Y Y N
Refs. 323 328 992 1026 328 992 328 306 973 973 305 747
0.593 0.7 0.627 0.559 0.549 2.34 0.29
0.047 0.23 0.051 0.048 0.06 1.07
1.474 1.842 0.399 0.337 0.336 0.37 1.47
0.05 0.062 0.019 0.019 0.026 0.14
Y Y Y Y Y Y
342 342 352 352 352 352 1051
Methacrylate, Methacrylate, Methacrylate, Methacrylate, Acrylonitrile Methacrylate,
0.265 0.38 0.78 0.28 0.71 0.56
0.009 0.2 0.2 0.2 0.19 0.12
1.678 3.48 1.43 1.95 0.381 1.42
0.048 0.2 0.2 0.2 0.085 0.096
Y
227 968 968 968 352 352
methyl
1.27 0.425 0.49 0.33 1.28 0.2 0.48 1.24 3 1.72 0.56 1.01
0.014 0.24 0.085 0.25 0.014 0.2 0.38 0.18 0.26 0.09
0.73 0.45 1.27 0.28 1.28 0.41 1.25 1.24 0.4 1.51 1.34 1.29 0.41 1.31 0.44 0.98 0.35 1.23 0.45 0.16 1.22 0.39 1.6 0.63
±95%
Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Methacrylate, AT-(2-hydroxyethyl)carbazolyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylic acid Methacrylic acid Methacrylic acid Styrene Styrene Vinyl methyl ketone Vinyl methyl ketone Vinyl acetate Acrylamide, AH2-(4-hydroxyphenyl)ethyl)Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Methacrylate, 2-hydroxyethyl methyl methyl methyl methyl
0.08 0.02 0.02 0.06 0.05 0.05 0.1 0.06 0.03 0.1 0.07 0.1 0.03 0.04 0.05 0.04 0.07 0.01 0.07 0.15 0.05 0.06 0 0.382
±95%
1.57 1.39 1.65 2.73 1.55 2.006 1.4 1.42 0.25 0.28 0.16 0.95
0.041
Y
0.11 0.074
N Y
0.28
Y
0.09 0.13 0.17 0.12 0.24
Y N N Y Y
0.09
Y Y
658 624 658 624 658 624 658 658 624 658 658 658 624 658 624 658 624 658 658 624 658 624 1021 703 316 54 55 190 527 55 316 316 609 609 258 965
References page II - 290
TABLE 1. cont'd Monomer 1 Methacrylamide, N-phenylMethacrylamide, 1-deoxy-D-glucitol Methacrylamide, 1-deoxy-D-glucitol Methacrylamide, Af-/?-nitrophenylMethacrylate, 2-ethylhexyl Methacrylate, ferrocenylmethyl Methacrylate, ferrocenylmethyl Methacrylate, octyl Methacrylate, potassium 18-crown6-ether Methacrylate, tert-butyl Methacrylate, (-)-menthyl Methacrylate, (2,2-dimethyl1,3-dioxolane-4-yl)methyl Methacrylate, 1,1-diphenylethyl Methacrylate, 1-naphthyl Methacrylate, 1-naphthyl Methacrylate, 1-naphthyl Methacrylate, 1-naphthyl Methacrylate, 2,2,6,6-tetramethyl4-piperidinyl Methacrylate, 2,2,6,6-tetramethyl4-piperidinyl Methacrylate, 2,2,6,6-tetramethyl4-piperidinyl Methacrylate, 2,2,6,6-tetramethyl4-piperidinyl Methacrylate, 2,2-dimethylaminoethyl Methacrylate, 2,3-epithiopropyl Methacrylate, 2,3-epithiopropyl Methacrylate, 2,3-epithiopropyl Methacrylate, 2,3-epithiopropyl Methacrylate, 2,4,6-trinitrophenyl Methacrylate, 2,4-dinitrophenyl ethyl Methacrylate, 2,4-dinitrophenyl Methacrylate, 2,6-(diphenyl)phenyl Methacrylate, 2-(2-carboxybenzoyloxy)ethyl Methacrylate, 2-(2-carboxybenzoyloxy)ethyl Methacrylate, 2-(N,Ar-dimethylcarbamoyloxy)ethyl Methacrylate, 2-(AW-dimethylcarbamoyloxy)ethyl Methacrylate, 2-(N,N-dimethylcarbamoyloxy)ethyl Methacrylate, 2-(AW-dimethyl carbamoyloxy)ethyl Methacrylate, 2-(N,AT-dimethylcarbamoyloxy)ethyl Methacrylate, 2-acetoxyethyl Methacrylate, 2-acetoxyethyl Methacrylate, 2-acetoxyethyl Methacrylate, 2-acetylsalicylicoyloxy3-hydroxypropyl Methacrylate, 2-bromoethyl Methacrylate, 2-bromoethyl Methacrylate, 2-bromoethyl Methacrylate, 2-bromoethyl Methacrylate, 2-bromoethyl Methacrylate, 2-bromoethyl Methacrylate, 2-chloro-2,3,3,3-fluoropropyl
Monomer 2
rx
±95%
Styrene Methacrylate, methyl Styrene Methacrylate, methyl Methacrylate, 2-hydroxypropyl Maleic anhydride Pyrrolidone, Af-vinylMethacrylonitrile Acrylonitrile
0.88 0.04 0.005 0.29 0.083 0.33 2.57 0.61 0.175
0.17
Methacrylate, 2-chloroethyl Acenaphthalene Methacrylate, methyl
0.98 0.316 1.1
0.22 0.085
Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Acrylonitrile
methyl methyl methyl methyl methyl
Styrene Vinyl acetate
0.77 1.8 1.68 2.62 1.52 14
0.2 0.006 0.65 2.77 0.05 0.018
0.73 0.38 0.47
r2
±95%
Conv.
1.24 4.2 2.09 5.05 4.56 0.24 0.073 0.75 0.07
0.06
N
0.2 0.18 0.28 0.096 0.04 0.006
Y Y Y N Y
1.18 2.48 0.9
0.11 0.55
Y Y
0.14 0.078 0.084
Y Y Y
0.72 0.77 0.809 0.851 0.61 0.02
Refs. 352 258 258 968 708 325 325 44 808 179 645 807 761 752 752 752 761 664
0.3
0.63
664
13.7
0.2
664
0.41
664
Vinyl methyl ketone
0.53
Methacrylate, methyl Acrylate, methyl Methacrylate glycidyl Methacrylate, methyl Styrene Methacrylate, 2-naphthyl Acrylate, AK2-hydroxyethyl)-oxy) 3,6-dichloro Methyacrylate, A^-(2-hydroxyethyl)3,6-dichloro Methacrylate, methyl Methacrylate, butyl
1.01 2.81 0.78 0.97 0.28
0.54
0.42 0.34 0.81 0.83 0.41
0.02
N
1.207
0.032
0.115
0.029
Y Y
1.112
0.026
0.126
0.026
Y
0.071 0.85
0.004
1.42 0.75
0.06
Methacrylate, butyl
0.85
0.75
1041
Acrylate, butyl
1.89
0.47
600
Acrylate, methyl
1.32
0.22
600
Acrylonitrile
1.89
0.38
600
Butadiene
0.35
1.06
600
Methacrylate, methyl
0.42
0.59
600
Methacrylate, 2-hydroxyethyl Methacrylate, methyl Styrene Af-Vinylpyrrolidone
0.99 1.12 0.58 0.85
Acrylate, ethyl Acrylonitrile Methacrylate, methyl Pyrrolidone, N-vinylStyrene Vinyl butyl ether Acrylate, butyl
2.7 2.38 1.18 2.44 0.41 13.7 0.221
0.02 0.06 0.04
0.636
1.02 0.94 0.44 0.34 0.37 0.31 0.79 0.02 0.32 0 0.079
0.01 0.02 0.02
0.304
691 787 787 787 787 744 736
1079 1009
N N N
N
346 346 346 1080 657 657 657 657 657 657 927
TABLE 1. cont'd Monomer 1 Methacrylate, propyl Methacrylate, propyl Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
Monomer 2
r2
±95%
Conv.
Refs.
Methacrylate, methyl
0.583
1.17
0.984
0.395
N
927
2-chloro-2,3,3,3-fluoro-
Styrene
0.243
0.15
0.121
0.068
N
927
2-chloroethyl 2-chloroethyl 2-chloroethyl 2-chloroethyl 2-chloroethyl 2-chloroethyl 2-chloroethyl 2-chloroethyl 2-chloroethyl 2-chloroethyl 2-chloroethyl 2-chloroethyl 2-chloroethyl 2-ethylhexyl 2-hydroxyethyl
Acrylate, methyl Acrylonitrile Methacrylate, benzyl Methacrylate, butyl Methacrylate, isobutyl Methacrylate, methyl Methacrylate, methyl Methacrylate, phenyl Methacrylate, tert-buiy\ Styrene Styrene Styrene Methacrylate, tributyltin Methacrylate, 2-hydroxypropyl Acetamide, 7V-(4-methacryloyloxyphenyl)-2-(4-methoxy) Acetanilide, 4-(2-(methacryloyloxy) ethyloxy) Acetanilide, 4-(2-(methacryloyloxy) hexyloxy) Acetanilide, 4-(methacryloyloxy)Acrylamide Acrylamide Acrylamido, 2-,2-methylpropanesulfonic Acrylate, butyl Acrylate, ethyl Acrylate, furfuryl Acrylate, methyl Acrylonitrile Acryloxymethylpentamethyl disiloxane Methacrylate, 2-hydroxypropyl Methacrylamide, AK4'-nitro-4-stilbenyl)Methacrylamide, J/V-(4-stilbenyl)Methacrylamide, Af-[4-(4-methoxyphenylacetyloxy )phenyl] Methacrylate, 2-acetoxyethyl Methacrylate, dodecyl Methacrylate, dodecyl Methacrylate, dodecyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacryloxymethylpentamethyl disiloxane Pyridine, 2-vinylPyridine, 3-vinylPyridine, 4-vinylPyrrolidone, N-vinylStyrene Styrene Styrene Styrene Styrene Styrene Styrene Acrylamido, 2-, 2-methylpropanesulfonic Acrylate, butyl Acrylate, butyl Acrylate, ethyl Acrylate, ethyl
2.19 1.3 0.989 0.82 0.85 0.97 0.48 1.02 1.18 0.341 0.34 0.23 0.53 0.083 0.61
Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl 2-hydroxyethyl 2-hydroxyethyl 2-hydroxyethyl 2-hydroxyethyl 2-hydroxyethyl 2-hydroxyethyl 2-hydroxyethyl 2-hydroxyethyl
Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxypropyl Methacrylate, Methacrylate, Methacrylate, Methacrylate,
±95%
2-chloro-2,3,3,3-fluoro-
Methacrylate, 2-hydroxyethyl
Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
T1
2-hydroxypropyl 2-hydroxypropyl 2-hydroxypropyl 2-hydroxypropyl
0.098 0.041 0.14 0.18 0.21 0.11 0.075 0.08 0.16 0.006
0.29 0.14 1.068 1.086 1.014 1.156 0.55 0.785 0.98 0.35 0.345 0.42 0.2 4.56 1.49
0.042 0.02 0.064 0.082
Y Y Y Y
0.083 0.22 0.046 0.048
Y Y Y Y
0.444 0.18
N Y
726 382 179 179 179 179 382 179 179 179 179 382 945 692 1051
1.39
0.67
1096
1.19
0.87
1096
0.78 1.89 0.98 0.86 4.75 11.21 1.35 8.67 1 0.86 0.55 1.474 1.842 1.47
1.94 0.05 0.14 0.9 0.09 0.189 0.88 - 0.005 0.2 0.52 1.82 0.593 0.7 0.29
1096 689 928 618 358 358 1063 358 689 822 686 342 342 1051
1.02 11.2 1.6 0.8 0.63 0.81 1.5 0.97 0.56 0.69 0.62 4.841 0.54 0.856 0.65 1.65 0.53 0.59 1.65 0.89 5.35 3.3 13.32 9.08
4.2 0.43 0.08 8.28
0.05 0.062 0.01
0.076 1.02
0.04 0.01 0.04 0.133 0.03 0.018
0.32 6.82 1.05 3.95
0.11 0.008 0.19 0.036
Y
0.047 0.23
Y Y
0.02
N
0.01 0.09
Y Y
0.64 0.73 0.9 -0.019 0.44 0.332 0.57 0.5 0.59 0.53 0.5 1.03
0.16 0.04 0.09 0.046 0.02 0.006
N N N Y N Y
342 342 342 840 346 350 463 878 878 903 903 618
0.171 0.24 0.273 0.207
0.041 0.16 0.054 0.045
Y Y Y Y
333 662 333 662
0.99 0.7 0.5 0.8 0.824 0.192 0.75 0.33
Y Y
346 837 837 837 350 358 710 822
References page II - 290
TABLE 1. cont'd Monomer 1 Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacryiate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl-, methyl Methacrylate, 2-naphthyl-, methyl Methacrylate, 2-naphthyl-, methyl Methacrylate, 2-naphthyl-, methyl Methacrylate, 2-sulfonic acid)ethyl Methacrylate, 2-sulfonic acid)ethyl Methacrylate, 2-sulfonic acid)ethyl Methacrylate, 2-sulfonic acid)ethyl Methacrylate, 2-methoxyethyl Methacrylate, 3,5-dimethyladamantyl Methacrylate, 3,5-dimethyladamantyl Methacrylate, 3,5-dimethyladamantyl Methacrylate, 3,5-dimethyladamantyl Methacrylate, 3-methoxy-2-hydroxypropyl Methacrylate, 5-oxo-pyrrolidinylmethyl Methacrylate, 5-oxo-pyrrolidinylmethyl Methacrylate, p-(2-benzothiazolylthio) ethyl Methacrylate, A^-(2-hydroxyethyl)3,6-dichlorocarbazolyl Methacrylate, N-(2-hydroxyethyl)carbazolyl Methacrylate, JV-(2-hydroxyethyl)carbazolyl Methacrylate, A^-(2-hydroxyethyl)carbazolyl Methacrylate, iV-ot-benzothiazolonylmethyl Methacrylate, iV-ethyl3-hydroxymethylcarbazolyl Methacrylate, N-ethyl-3hydroxymethylcarbazolyl Methacrylate, Af-methyl-N-phenyl2-aminoethyl Methacrylate, A^-methyl-A^-phenyl2-aminoethyl Methacrylate, N-methyl-N-phenyl2-aminoethyl
Monomer 2
T1
±95%
Acrylate, methyl Acryloyl chloride Methacrylate, 2-ethylhexyl Methacrylate, 2-ethylhexyl Methacrylate, 2-hydroxyethyl Methacrylate, butyl Methacrylate, butyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, methyl Methacrylate, tributyltin Methacrylic acid Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Itaconate, mono-methyl Itaconate, mono-methyl Itaconate, mono-methyl Itaconate, mono-methyl Methacrylate, 2,4,6-trinitrophenyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Styrene Styrene Styrene Styrene Styrene Acrylate, ethyl Methacrylate, ethyl Styrene Vinylidene chloride Styrene Acrylonitrile Methacrylate, methyl Styrene Vinyl chloride Acrylamide Methacrylate, methyl Styrene Vinyl chloride
7.335 1.79 4.56 4.56 1.82 2.35 2.35 1.878 1.844 1.055 1.81 0.31 1.17 1.02 0.76 0.64 0.52 0.59 0.223 0.189
0.083
0.85 2.57 2.53 1.91 4.41 3.83 0.534 0.113 0.321 0.576 0.216 3.2 2 0.6 3.6 0.48 1.3 0.45 0.63 1.85 3.98 0.694 0.411 0.26
0.34 0.48 0.27 0.6 0.76 0.57 0.099 0.126 0.098 0.477 0.422
Methacrylate, 2,4-dinitrophenyl
0.126
Acryl-2/-ethyl-4,5,7-trinitroflourenone
r2
±95%
Conv.
Refs.
0.013 0.29 0.083 0.083 0.55 0.158 0.158 0.245 0.267 0.402 0.728 0.99 0.15 0.094 0.06 -0.01 0.31 0.36 0.135 0.04
0.007
Y
0.006 0.006
Y Y
0.007 0.007 0.007 0.005 0.017 0.517
Y Y Y Y Y N
0.2 0.099 0.1 0.16 0.42 0.21 0.028 0.11
0.75 0.602 0.581 0.532 0.614 0.623 0.56 0.786 0.486 0.61 0.384 0.3 1 0.37 0.22 0.46 0.19 0.68 0.89 0.21 0.04 0.421 0.342 0.64
0.16 0.059 0.023 0.055 0.051 0.048 0.025 0.16 0.117 0.195 0.225
Y Y Y N Y Y Y Y Y Y Y Y Y Y Y Y Y Y Y Y
0.01 0.04 0.14 0.04
N N N N
0.033 0.013
Y Y
0.026
1.112
0.026
Y
736
0.773
0.096
0.102
0.022
Y
703
Acrylate, 2,4-dinitrophenyl
0.243
0.034
0.186
0.009
Y
716
Methacryl-2/-ethyl-4,5,7-trinitro9-fluorenone Methacrylate, methyl Acryloyl-p-hydroxyethyl3,5-dinitrobenzoate Methacryloyl-P-hydroxyethyl3,5-dinitrobenzoate Acryloyloxy, 2-, benzoic acid
0.63
0.041
0.382
0.014
Y
703
0.6 1.425
0.02 0.09
0.5 0.103
0.01 0.015
Y
887 701
0.729
0.051
0.554
0.019
Y
701
0.22
0.03
1.82
0.2
N
651
Methacrylic acid
0.2
0.01
2.16
0.18
N
651
Methacryloyloxy, 2-,benzoate, methyl
0.55
0.04
1.11
0.18
N
651
0.18 0.18 0.13 0.13 0.056 0.039 0.04 0.275 0.2 0.19 0.18 0.24 0.16 0.14 0.02 0.055
0.23 0.16 0.21 8.87 0.087 0.033
333 649 692 708 686 692 708 692 708 333 945 886 611 611 611 611 613 613 613 613 744 540 760 760 760 760 760 540 924 924 924 924 564 564 564 564 918 335 335 335 335 689 633 633 741
TABLE 1. cont'd Monomer 1
Monomer 2
Methacrylate, N-methyl-Ar-phenyl2-aminoethyl Methacrylate, A^-methyl-A^-phenyl2-aminoethyl Methacrylate, a,a-dimethylbenzyl Methacrylate, oc-naphthoyloxy-, ethyl Methacrylate, acetonyl Methacrylate, allyl Methacrylate, amyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzylmethylaminoethyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, Methacrylate, Methacrylate, Methacrylate,
butyl butyl butyl butyl
Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, butyl Methacrylate, chloromethyl Methacrylate, chloromethyl
rx
±95%
r2
±95%
Conv.
Methacryloyloxy, 2-,benzoic acid
0.2
0.01
2.6
0.08
N
651
Styrene
0.58
0.02
0.44
0.04
N
651
Methacrylate, methyl Styrene Styrene Itaconate, bis(tri-w-butyltin) Styrene Acrylonitrile Allyl chloride Maleic anhydride Maleic anhydride Methacrylate, 2-chloroethyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, phenyl Styrene Styrene Styrene Styrene Styrene Styrene Vinylidene chloride Methacrylate, methyl Acetylene, phenylAcrylate, butyl Acrylate, ethyl Acrylic acid Acrylic acid, a-bromoAcrylonitrile Carbamate, Af-phenyl-, allyl Methacrylate, 2-(2-carboxybenzoyloxy)ethyl Methacrylate, 2-(2-carboxybenzoyloxy)ethyl Methacrylate, 2-chloroethyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, ethyleneglycolAf-phenylcarbamate Methacrylate, glycidyl Methacrylate, methyl Methacrylate, methyl Methacrylic acid Methacrylic acid Methacrylonitrile Styrene Styrene Styrene Styrene Styrene Styrene Styrene, o-chloroStyrene, p-chloroStyrene p-chloroStyrene chloromethylStyrene/?-octylamine sulfonate Thioindigoid Vinyl acetate Vinyl chloride Vinylidene chloride Methacrylate, methyl Styrene
0.92 0.242 0.505 1.08 0.46 0.96 58.7 - 0.075 1.068 1.112 1.05 1.38 0.67 0.658 0.467 0.51 0.42 0.3 0.5 3.3 0.296 1.7 2.2 2.43 3.53 0.85 0.98 0.418 0.75
0.018 0.115 0.2 0.1 0.088 0.042 0.093 0.06 0.084 0.048
0.38 0.123 0.39 0.42 0.2
0.75
0.372 0.989 0.808 0.93 0.78 1.42 0.463 0.435 0.45 0.48 0.8 0.45 0.34 0.523 0.21 0.3 0.22 0.24 0.13 0.291 0.329 0.85
0.043 0.041
Y
0.11 0.1
Y N
0.093 0.098 0.03
Y Y Y Y
0.09 0.041 0.026
N Y Y
0.32 0.134
Y
0.17 0.21
Y N
0.039
Y
0.85
1.086 0.158 0.158 0.395
0.02 0.007 0.007
0.85 2.11 1.2 1.26 1.15 0.75 0.31 2.52 0.47 0.64 0.64 0.59 0.32
0.03 0.08
0.564 0.38 0.7 11.5 30.18 13.5 2.07 1.02 0.298
0.81 0.216 0.285 0.038 0.52 0.2 0.02
0.12 0.12 0.07 0.2 1.1
0.1 0.131
14.47 0.18 0.16 0.03
0.82 2.35 2.35 0.299 0.94 0.52 1.27 0.8 0.73 0.56 0.56 -0.05 0.52 0.63 0.54 0.74 1.24 1.025 1.46 1.5 0.5 -0.003 0.05 0.35 0.477 0.208
Refs.
761 1102 958 940 179 23 438 720 720 179 111 32 540 32 111 179 487 540 602 806 432 1081 565 187 690 187 733 165 833 1009 1041
0.041 0.13 0.13
Y Y Y
179 692 708 833
0.06 0.07
N N
0.16 0.2 0.15 0.12 1.09
N N N Y N
0.1 0.124
N
0.15
Y
0.03 0.029 0.006
Y Y Y
224 30 844 187 224 44 179 43 463 530 530 835 558 872 966 1035 817 1007 165 519 3 712 712
References page II - 290
TABLE 1. cont'd Monomer 1 Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, titanate Methacrylate, titanate Methacrylate, Methacrylate, Methacrylate,
Monomer 2
T1
cyanomethyl cyanomethyl cyclohexyl cyclohexyl decyl di-, di-n-butylstannyl di-, di-rc-butylstannyl di-, zinc di-, dicyclopentadienyl-
Methacrylate, methyl Styrene Methacrylate, tributyltin Styrene Oxazolidone, TV-vinylMaleic anhydride Vinyl acetate Ethylene Acrylate, di-, copper
0.73 0.28 0.891 0.57 12.19 0.012 0.013 40 0.89
di-, dicyclopentadienyl-
Acrylate, di-, nickel
0.65
di-, ethylene glycol di-, triethyleneglycol di-, triethyleneglycol
Styrene Carbamate, N-phenyl-, allyl Methacrylate, ethylene-glycol Af-phenylcarbamate Methacrylate, methyl Methacrylic acid Methacrylate, methyl Acrylamide Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, dodecyl Methacrylate, methyl Styrene Allyl acetate Allyl alcohol Methacrylate, 2-(sulfonic acid)ethyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-hydroxypropyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, tributyltin Methacrylic acid Methacrylonitrile Styrene Styrene Styrene Styrene Styrene, o-chloroStyrene, p-chloromethylVinyl acetate Vinylidene chloride Methacrylate, butyl
0.67 0.504 0.59
Methacrylate, diethylaminoethyl Methacrylate, diethylaminoethyl Methacrylate, dimethylaminoethyl Methacrylate, dimethylaminoethyl sulfate Methacrylate, diphenylmethyl Methacrylate, diphenylmethyl Methacrylate, diphenylmethyl Methacrylate, diphenylmethyl Methacrylate, diphenylmethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyleneglycolAf-phenylcarbamate Methacrylate, ethyleneglycolAf-phenylcarbamate Methacrylate, ferrocenylmethyl Methacrylate, ferrocenylmethyl Methacrylate, ferrocenylmethyl Methacrylate, ferrocenylmethyl Methacrylate, ferrocenylmethyl Methacrylate, furfuryl Methacrylate, glycidyl Methacrylate, glycidyl Methacrylate, glycidyl Methacrylate, glycidyl Methacrylate, glycidyl Methacrylate, glycidyl Methacrylate, glycidyl Methacrylate, glycidyl Methacrylate, glycidyl Methacrylate, glycidyl Methacrylate, glycidyl
Methacrylate, di-, triethyleneglycol Acrylate, methyl Acrylonitrile Styrene Styrene Vinyl acetate N-Vinylpyrrolidone Acrylate, 2-ethylhexyl Acrylate, 4-acetylphenyl Acrylate, butyl Acrylate, isobutyl Acrylate, tert-butyl Acrylonitrile Acrylonitrile Methacrylate, 2,3-epithiopropyl Methacrylate, butyl Methacrylate, methyl Methacrylate, methyl
1.44 2.34 1.2 1.9 0.5 0.8 0.7 1.07 0.3 81.27 107.4 1 0.245 0.267 1.08 1 0.601 0.71 0.83 0.36 0.26 0.29 0.33 0.45 0.36 131.8 2.18 0.299
±95% 0.11 0.041 0.136 0.28 1.35 0.016 0.036
0.399 0.144 0.395 0.586 -0.052 0.024 0.013 0.19 1.09
±95% 0.019 0.011 0.428 0.088 0.049 0.008 0.018
Conv. Y Y N Y Y Y Y
0.95 0.08
0.085 1.59 0.154 0.2
0.1 1.93 5.3 0.007 0.005 0.09 0.123 0.05 0.12
29.8 0.1
0.24 0.042 0.82 -0.01 0.01 1.52 5.16 2.41 0.644 2.16 1.24 2.096 0.85 1.32 0.81 0.94 0.52 0.934
r2
0.39 0.034 0.24 0.843 0.63 0.699 0.52 1.6 0.8 11.2 0.81 0.528 -0.57 -0.02 2 1.878 1.844 1.08 1.16 0.299 0.57 0.46 0.55 0.67 0.65 0.55 1.34 1.29 -0.77 0.353 0.395
1.13 0.46 0.13 0.57 0.12 0.443 0.05 0.06 0.06 0.085
1.4 0.15 3.6 0.2 0.0036 0.09 0.292 0.083 0.282 0.463 0.95 0.14 0.78 0.85 0.71 0.726
625 625 945 179 36 954 949 935 876 876
0.15
N
262 833 833
0.128 1.47 0.051 0.05
Y Y Y
0.05 0.82 1.92
Y N N
0.056 0.039
Y Y N
0.19 0.607
N N
0.04 0.062
N Y
5.29 0.02
N Y
1081 16 1081 1052 837 837 837 761 179 210 210 564 692 708 32 844 87 945 820 44 179 530 530 570 558 1035 210 3 833
0.59 0.085 0.42 0.14
Refs.
833 0.35 0.04 3.63
Y Y Y
0.02 0.13 0.141 0.052 0.026 0.079 0.06
Y Y Y Y Y Y N
0.03 0.08 0.042
N Y Y
293 325 293 576 293 1050 674 1012 674 674 814 114 433 787 224 113 226
TABLE 1. cont'd Monomer 1 Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
Monomer 2 glycidyl glycidyl glycidyl glycidyl glycidyl glycidyl glycidyl glycidyl glycidyl glycidyl glycidyl glycidyl glycidyl glycidyl hexyl hydroxyethyl
Methacrylate, hydroxyethyl Methacrylate, iso-butyl Methacrylte, isobornyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, m-chlorophenyl Methacrylate, m-nitrophenyl Methacrylate, methoxymethyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl
rx
Methacrylate, methyl 1.05 Methacrylate, methyl 0.501 Methacrylic acid 1.2 Af-Vinylpyrrolidone 4.29 Styrene 0.16 Styrene 0.539 Styrene 0.46 Styrene 0.54 Styrene 0.55 Styrene 0.74 Styrene 0.73 Styrene 0.514 Vinyl phenyl ketone 0.719 Vinyl, mono-, ethylene glycol ether 4.41 Styrene 0.44 Methacrylate, tetra(2-hydroxypropyl) 0.606 ethylenediamine Methacrylate, tributyltin 2.33 Butadiene, 2-chloro0.9 Styrene 0.24 Acetylene, phenyl1.9 Acrylic acid 0.68 Acrylonitrile 1.05 Furan, 2-vinyl-5-methyl 0.105 Methacrylate, 2-chloroethyl 1.014 Methacrylate, methyl 1.88 Methacrylate, methyl 1.2 Methacrylate, methyl 0.488 Methacrylic acid 0.47 Methacrylonitrile 0.68 Methacrylonitrile 0.94 Styrene 0.271 Styrene 0.58 Styrene 0.42 Styrene 0.4 Styrene 0.74 Vinyl acetate 29.7 Styrene 0.209 Styrene 0.185 Styrene 0.586 2-Oxazoline, 2-isopropenyl0.69 3-Pyridazone, 2-vinyl 0.63 3-Pyridazone, 2-vinyl-6-methyl0.16 3-Pyridazone, 2-vinyl-6-methyl1.65 4,5-benz-33-Pyridazone, 2-vinyl-6-phenyl0.58 4H-1,3-Oxazinium F 3 CSO 3 , 3-methyl0.37 2-vinyl-5,6-dihydroAcenaphthalene 0.36 Acenaphthalene 0.38 Acenaphthalene 0.44 Acetamide, N-vinyl2.65 Acetamide, N-vinyl1.18 Acetamide, N-vinyl2.1 Acetylene, phenyl-0.06 Acetylene, phenyl1.5 Acetylene, phenyl1.111 Acrolein 1.136 Acrolein 1.33 Acrolein, methyl0.1 Acrylamide 2.34 Acrylamide 3 Acrylamide 2.53 Acrylamide 3 Acrylamide, 2-chloro-AyV-dimethyl2.71
±95%
0.027 0.1 0.498 0.03 0.04 0.08 0.1 0.284 0.098 0.13 0.416 0.185 0.088 0.3 0.22 0.044 0.064 0.07 0.029 0.05 0.12 0.036
24.16 0.013 0.054 0.069 0.02
r2 0.8 0.688 0.98 0.003 0.54 0.278 0.47 0.44 0.45 0.31 0.11 0.435 0.697 0 0.58 1.44 0.282 1.8 0.61 0.27 1.03 0.217 0.716 0.85 0.62 0.89 0.92 2.01 0.74 0.43 0.509 0.56 0.5 0.55 0.47 -0.06 0.375 0.44 0.395 0.99 1.56 0.3 0.27
±95%
Conv.
0.076 0.16 0.018 0.07 0.086 0.02
Y N
0.04 0.045 0.033
N N Y
0.07 1
Y Y
0.424 0.06 0.45
N N
0.037 0.169 0.14 0.08
Y Y Y N
0.15
Y
0.07 0.08 0.014
N N Y
0.22 0.05 0.16 0.014 0.07
Y Y Y Y
N Y N
0.49 0.31 0.04 0.04
0.16 0.095 0.05 0.4 0.17 0.09 0.45 0.398
1.05 0.99 2.25 0.19 0.71 0.01 1.69 0.2 0.07 0.76 0.59 0.4 2.29 0.53 0.82 0.9 -0.159
Refs. 463 639 224 1017 114 217 225 225 463 849 893 999 946 780 179 996 945 1057 806 565 847 165 1105 179 30 541 639 847 44 44 179 463 463 487 541 165 177 177 821 894 897 897 897 897 909
0.14 0.15
N N
26.56
Y
0.016 0.12 0.3
Y Y N
0.44 0.09
N N
1.07 0.502
N Y
326 326 575 984 984 984 357 443 732 291 292 589 314 314 314 691 917
References page II - 290
TABLE 1. cont'd Monomer 1
Monomer 2
Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
Methacrylate, Methacrylate, Methacrylate, Methacrylate,
methyl methyl methyl methyl
Methacrylate, methyl Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
Acrylamide, N,N-dimethylAcrylamide, AA,A^-dimethylAcrylamide, WV-dimethylAcrylamide, WV-dimethylAcrylamide, N-methylAcrylamide, N-methylolAcrylamide, N-methylol Acrylamide, N-octadecylAcrylamide, N-tert-butylAcrylamide, a-fluoroAcrylamido, 1-,-1-deoxy-D-glucitol Acrylate, a-benzyl-, methyl Acrylate, a-chloro-methyl Acrylate, ferrocenylmethyl Acrylate, 2-(0-ethyl methylphosphonoxy)-, methyl Acrylate, 2-chloroethyl Acrylate, 2-nitrobutyl Acrylate, p-acetoxymethyl-, methyl Acrylate, a-(0-ethyl methylphosphenoxy) Acrylate, a-[2,2-bis(carbomethoxy)ethyl]-, methyl Acrylate, oc-acetoxy-, ethyl Acrylate, a-benzyl-, methyl Acrylate, a-chloro-, methyl Acrylate, oc-cyano-, methyl Acrylate, a-cyano-, methyl Acrylate, a-hydroxymethyl-, ethyl Acrylate, a-phenoxymethyl-, methyl Acrylate, a-phenyl-, methyl Acrylate, a-phenyl-, methyl Acrylate, oc-tetrafluoropropyloxymethyl-, methyl Acrylate, a-trifluoromethyl-, methyl Acrylate, a-trifluoromethyl-, methyl Acrylate, a-trifluoromethyl-, methyl Acrylate, benzyl Acrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, ethyl Acrylate, ethyl Acrylate, ethyl Acrylate, ferrocenylmethyl Acrylate, heptafluorobutyl Acrylate, heptyl Acrylate, isobutyl Acrylate, isobutyl Acrylate, m-nitrophenyl Acrylate, methyl Acrylate, o-chlorophenyl Acrylate, octadecyl Acrylate, p-bromophenyl Acrylate, p-chlorophenyl Acrylate,/?-chlorophenyl Acrylate, methylphenyl Acrylate, phenyl Acrylate, phenyl Acrylate, a-p-chlorobenzyl-, methyl Acrylate, a-p-methoxybenzyl-, methyl Acrylic acid Acrylic acid, a-bromoAcrylonitrile Acrylonitrile, a-trifluoromethyl-
rx 1.65 2.15 2.8 2.64 1.14 1.62 1.62 4.119 0.25 2.13 3.75 3.9 0.11 2.9 0.73 2.15 1.19 0.91 0.73
±95% 0.16 0.08 0.1 0.15 0.09 0.07 0.136 0.24 0.19 0.09 0.04 0.12
3.7
r2 0.41 0.57 0.59 0.21 0.05 0.7 0.7 0.42 2.83 0.148 0.05 0.09 1.92 0.08 0.44 0.37 0.27 0.24 0.44
±95%
Conv.
0.15 0.08 0.09 0.21 0.72
N N N N N
0.11
Y
0.081 0.09 0.01 0.08
Y N N N
0.25 0.04
N
0.04
1.65 2.36 0.31 0.21 0.068 1.26 1.13 0.21 0.3 1.43
0.12 0.23 0.24 0.02 0.014 0.17 0.038
1.8 3.2 2.3 2.23 0.92 2.86 1.88 1.83 2 2.04 2.8 1.387 2.51 1.04 4.1 0.928 2.15 1.25 2.477 0.926 1.01 1.09 1.45 1.56 1.54 1.87 1.71 0.418 0.37 1.322 1.11
0.23 0.5 0.2 0.14 0.2 0.32 0.4 0.28 0.19 0.072 0.13 0.08 0.5 0.248 0.04 0.024 0.056 0.132 0.275 0.14 0.222 0.109 0.02 0.05 0.12
Refs. 170 315 315 691 691 593 596 290 709 823 258 610 31 293 882 790 234 1091 851 1092
0.608 0.173 1.13 0.03 0.135 1.34 0.755 0 0 0.61
0.02 0.022 0.19 0.01 0.016 0.062 0.061
Y Y Y N Y N Y
244 610 6 141 182 1027 1048 141 49 1047
-0.17 0 0.1 0.19 0.13 0.11 0.43 0.47 0.28 0.22 0.024 0.177 0.46 0.29 0.135 1.04 0.4 0.4 0.464 0.191 0.235 0.3 0.223 0.45 0.416 0.255 0.13 1.73 0.11 0.138 -0.016
0.18 0.1 0.1 0.2 0.15 0.018 0.07
Y N N Y N Y N
0.05 0.064 0.084 0.02 0.04 0.02 0.135 0.12
N Y Y N Y Y N
0.07 0.014 0.023
Y Y Y
0.036
Y
0.041 0.034 0.008 0.096
Y Y Y N
0.037 0.048
Y Y
681 825 825 277 30 639 87 30 469 87 293 206 980 30 639 1074 324 621 290 1074 1074 621 1074 621 672 905 905 964 733 216 681
TABLE 1. cont'd Monomer 1 Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
Monomer 2 methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
Methacrylate, methyl Methacrylate, methyl Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
Methacrylate, methyl Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
methyl methyl methyl methyl methyl methyl methyl
Methacrylate, methyl Methacrylate, methyl
Acrylonitrile, a-perfluoropropylAcryloyl chloride Acryloyl chloride Allyl acetate Allyl acetate Allyl alcohol Allyl chloride Benzocyclobutane, a-methyleneBenzocyclobutene, 4-vinylBenzofuran, 2-vinylBenzophenone, 2-hydroxy4-(methacryloxy)Benzothiazole, vinylmercaptoBicyclo[2,2,l]hept-2-ene5,6-dicarboximide, TV-benzyl Bicyclo[2,2,l]hept-2-ene5,6-dicarboximide, TV-benzyl Butadiene Butadiene Butadiene Butadiene, 2,3-dichloroButadiene, 2-chloroButadiene, 2-fluoroCarbamate, TV-vinyl-f-butylCarbazole, TV-vinylCarbazole, TV-vinylCarbazole, TV-vinylCarbazole, TV-vinylCarbazole, TV-vinylCarbazole, TV-vinylCarbazole, TV-vinylCitraconimide, TV-(4-acetoxyphenyl)Citraconimide, TV-(4-chlorophenyl)Citraconimide, TV-(4-ethoxycarbonylphenyl)Citraconimide, TV-(4-methoxyphenyl)Citraconimide, TV-( 1 -menthylcarboxylatomethyl)Citraconimide, TV-benzylCitraconimide, TV-butylCitraconimide, TV-ethylCitraconimide, TV-hexylCitraconimide, TV-isobutylCitraconimide, TV-isopropylCitraconimide, TV-methyl Citraconimide, TV-phenyl Citraconimide, Af-propyl Citraconimide, N-tert-butylCitraconimide, TV-tolylCyclopentene, 4-,-1,3-dione Cyclopropane, l,l-bis(ethoxycarbonyl)-2-vinylCyclopropane, 1,1-bis(ethoxycarbonyl)-2-vinylDiallyl melamine Diallyl phthalate Diallyl phthalate Diallyl phthalate Diallylcyanamide Diallylcyanamide Dimethyleneheptanedioate, 2,6-dimethyl Ditiane, 2-methylene-l,3Ethylene
rx
±95%
r2
1.9 0.48 0.42 99.24 23 78.79
0.3
0 1.51 0.05 -2.42 0 -1.62
0.32 0.6 0.006 0.315 1.25 30.5
24.6 6.5
0.02 0.036 0.083
108 0.25 0.027 0.32 0.08 0.08 0.76 1.87 1.55 2.12 1.8 0.57 1.84 0.44 2.123 1.88 2.93 2.72
0.46 1.47 3.89 1.65 0.43 0
±95%
Conv.
0.05
37.66
N
2.9
N Y
0.617 0.114
N Y
0.14
Y
0
Refs. 926 508 776 210 470 210 204 1083 1085 1020 934 763 994 994
0.26 0.22 0.048 0.16 0.4 0.18
0.75 0.504 0.7 11.04 6.33 1.23 0.17 0.14 0.033 0.06 0.75 0.08 0.33 0.031 0.18 -0.01 -0.027
3.16 3.47
0.73 0.335
-0.1 0.109
0.19 0.115
Y Y
728 950
2.77 2.17 3.25 2.38 1.78 2.7 3.24 3.081 3.23 2.88 2.75 8.11 4.21
0.28 0.56 0.79 0.45 0.85 0.51
0.02 -0.12 -0.04 -0.18 -0.18 0.09 0.15 0.001 -0.03 0.038 0.003 0.094 0.223
0.14 0.36 0.33 0.28 0.42 0.27
Y Y Y Y Y Y
0.033 0.43 0.072 0.088 0.017 0.194
Y Y Y Y Y Y
714 714 714 714 714 714 460 728 714 714 728 95 1076
0.111
0.194
Y
1076
-0.001 0.029 0.076 0.04 0.04 0.53
0.011 0.026 0.006
Y Y Y Y
0.02
N
201 153 153 153 603 604 795
N
1031 41
0.004
0.77 0.2 0.16 0.14
0.074 0.98 0.19 0.19 0.38 0.905
18.3
2.5
26.56 22.73 21.52 25 25 2.36
1.98 1.48 0.39
0.08
0.25
1.77 0.1 0.03 0.015
N Y
0.05 0.18 0.022 0.13 0.18 0.084
N N Y Y Y Y
140 257 467 61 61 174 991 11 13 738 738 758 758 98 728 728 728
0.024
Y Y Y Y
4.12
References page II - 290
TABLE 1. cont'd Monomer 1 Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
Monomer 2 methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
rt
Ethylene, 1,1-diphenyl2.1 Ethylene, 1,1-diphenyl8.7 Ethylene, chlorotrifluoro51.36 Ethylene, tetrachloroEthylene, trichloro100 Fumarate, diethyl 40.3 Fumarate, diethyl 2.1 Fumarate, diisopropyl 23 Fumaronitrile 6.74 Furan, 2-vinyl-5-methyl 0.183 Hexatriene, tetrachloro0.504 Imidazole, 1-vinyl4.36 Imidazole, l-vinyl-2-methyl4 Imidazole, l-vinyl-2-methyl3.48 Isoprene 0.26 Isoprene 0.25 Isoprene 0.25 Isoprene, 3-acetoxy0.16 Isopropenyl acetate 17.36 Isopropenyl, 3-(l-cyclohexenyl), acetate 0.81 Isopropenylisocyanate 3.1 Isopropenyltoluene 0.68 Isopropenyltoluene 0.68 Itaconamate, Af-(4-chlorophenyl)-, ethyl 1.24 Itaconamate, Ar-(4-chlorophenyl)-, 1.26 propyl Itaconamate, N-(4-methoxyphenyl)-, 1.31 ethyl Itaconamate, A^-(4-carboethoxyphenyl)1.21 ethyl Itaconamate, Ar-(4-methylphenyl)-, ethyl 1.43 Itaconamate, iV-(4-methoxyphenyl)-, 1.03 propyl Itaconamate, A^-(4-methylphenyl)-, 1.11 propyl Itaconamate, Af-phenyl-, ethyl 1.32 Itaconamate, N-phenyl-, propyl 1.13 Itaconamate, Af-(4-carboethoxyphenyl)1 propyl Itaconate, dibutyl 1.33 Itaconate, dibutyl 0.8 Itaconate, dimethyl 3.34 Itaconate, dimethyl 1.2 Itaconate, monomethyl 1.1 Itaconic acid 1.23 Itaconic acid 1.14 Itaconic anhydride 0.155 Itaconimide, N-(2-chloroethyl)0 Itaconimide, N-benzyl0.46 Itaconimide, JV-ethyl0.486 Itaconimide, N-methyl0.38 Maleate, dibutyl tin 72.7 Maleate, diethyl 341 Maleate, diethyl 20 Maleate, diethyl 285.8 Maleic anhydride 4.18 Maleic anhydride 6.36 Maleic anhydride 0.46 Maleic anhydride 5.2 Maleic anhydride 3.1 Maleic anhydride 3.85 Maleic anhydride 3.4 Maleic anhydride 3.85 Maleimide 2.576 Maleimide 2.5
±95%
3.31 0.6 0.79 0.146 0.057 1.86 0.54 0.21
1.95
0.09 0.557 0.071 0.024 0.11 0.18 0.066 0.22 5.93 46 35.9 0.31 0.64 0.69 0.47
0.061
r2 0.09 O -0.074 0 0.04 0.05 0.17 -0.064 0.867 1.76 0.014 0.047 0.003 0.65 0.64 0.64 2.81 -0.09 0.4 0.14 0.04 0.04 0.36 0.31
±95%
Conv.
0.062
Y Y
0.004
N
0.096 0.292 0.28 0.03 0.088
Y Y Y Y Y
0.23
Y
0.12
Y
Refs. 65 901 236 204 470 28 394 1038 191 1105 5 364 364 479 302 698 704 770 100 770 434 688 722 678 678
0.43
678
0.48
678
0.63 0.4
678 678
0.28
678
0.47 0.15 0.53
678 678 678
0.717 0.4 -0.156 0.3 0.139 0 0 1.17 0.54 1.06 0.42 1.12 -0.095 -0.1 0 -0.02 -0.163 -0.019 0.08 0.02 0.01 0.01 0.01 0.02 0.166 0.17
0.11 0.02
Y
0.103
Y
0.33 0.39 0.75 0.13 0.73 0.199 0.05
Y Y Y Y Y Y N
0.015 0.027 0.026 1.77 0.004
Y Y Y N N
0.047
Y
1073 398 975 398 1010 260 408 1010 642 642 642 642 987 28 470 873 169 260 320 33 524 524 524 524 251 992
TABLE 1. cont'd Monomer 1
Monomer 2
Methacrylate, methyl Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
methyl methyl methyl methyl methyl methyl methyl methyl methyl
Maleimide, 2,3-dimethylA^-(2-methacryloyloxyethyl) Maleimide, A^-(4-hydroxyphenyl)Maleimide, 7V-(2-hydroxyethyl)Maleimide, Af-(2,6-diethylphenyl)Maleimide, 7V-(2,6-diisopropylphenyl)Maleimide, AT-(2,6-dimethylphenyl)Maleimide, A^-(2-chlorophenyl)Maleimide, 7V-(2-methylphenyl)Maleimide, Af-(3,5-dimethylphenyl)Maleimide, 7V-(3-methylphenyl)Maleimide, AK3-trifluoromethylphenyl)Maleimide, 7V-(4-carboxyethylphenyl)a-chloroMaleimide, 7V-(4-chlorophenyl)-a-chloroMaleimide, Af-4-methoxyphenyl)a-chloroMaleimide, AK4-methylphenyl)Maleimide, A^-(4-methylphenyl)a-chloroMaleimide, AK|3-chloroethyl)-a-chloroMaleimide, AH (3-chloroethyl)-a-chloroMaleimide, N-[JV'-(a-methylbenzyl) aminocarbonylpenty 1] Maleimide, TV-benzyl Maleimide, TV-butyl Maleimide, 7V-cyclohexyl Maleimide, N-cyclohexyl Maleimide, Af-cyclohexyl Maleimide, AT-ethyl-a-chloroMaleimide, TV-hexylMaleimide, 7V-hydroxymethylMaleimide, 7V-methyl-a-chloroMaleimide, 7V-phenylMaleimide, 7V-phenylMaleimide, Af-phenyl-a-chloroMaleimide, N-phenylMethacrylate, 2-acetoxyethyl Methacrylate, cyanomethyl Methacrylate, diphenylmethyl Methacrylamide Methacrylamide Methacrylamide Methacrylamide Methacrylamide, Af-methoxymethylMethacrylamide, iV-p-bromophenyl~ Methacrylamide, N-p-tolylMethacrylamide, N-phenyl Methacrylamide, N-phenylMethacrylamide, 1-deoxy-D-glucitol Methacrylamide, N-/?-nitrophenylMethacrylate, tert-butyl Methacrylate, a,a-dimethylbenzyl Methacrylate, (2,2-dimethyl1,3-dioxolane) Methacrylate, 1,1-diphenylethyl Methacrylate, 1-naphthyl Methacrylate, 1-naphthyl Methacrylate, 1-naphthyl Methacrylate, 1-naphthyl Methacrylate, 2,2-dimethylaminoethyl Methacrylate, 2,3-epithiopropyl Methacrylate, 2,6-(diphenyl)phenyl Methacrylate, 2-(Ar,N-dimethylcarbamoyloxy)ethyl
/*i
±95%
r2
±95%
Conv.
0.51
1.66
1.1
3.58
Y
619
1.392 1.396 4.78 10.9 3.62 2.1 2.22 1.63 1.18 1.57 0.472
0.001 0.089
0.001 0.083
Y Y
0.114
0.345 0.201 0.05 0.02 0.07 0.1 0.09 0.28 0.22 0.1 -0.004
0.168
Y
323 323 992 992 992 992 992 992 992 992 973
0.562 0.556
0.025 0.145
0.02 0.064
0.03 0.189
Y Y
973 973
0.83 0.564
0.117
0.34 0.029
0.158
Y
992 973
0.94 0.59 1-37
0.06 0.06 0.291
0.05 0.11 0.582
0.04 0.05 0.359
Y
974 974 1009
1.28 1.41 1.35 1.31 2.26 0.53 1.9 1.745 0.63 0.98 0.91 0.657 1.014 0.94 0.399 0.81 1.57 1.7 1.39 1.65 1.678 3.48 1.43 1.95 1.42 4.2 5.05 0.96 0.81 0.9
0.23 0.19
0.23 0.16
Y Y
0.048 0.03 0.15 0.026 0.03
Y
0.72 0.77 0.809 0.851 0.61 0.42 0.83 1.42 0.59
0.066 0.04 0.2 0.03 0.34 0.083 0.06 0.02 0.019 0.11 0.04 0.074 0.048 0.2 0.2 0.2 0.096 0.2
0.14 0.078 0.084 0.02 0.06
0.03 -0.1 0.24 0.19 0.106 0.13 0.1 0.263 0.11 0.3 0.3 0.077 0.164 1.12 0.73 1.07 1.27 0.44 0.425 0.49 0.265 0.38 0.78 0.28 0.56 0.04 0.29 1.35 0.92 1.1 0.77 1.8 1.68 2.62 1.52 1.01 0.97 0.071 0.42
Y Y
0.098 0.065 0.06 0.11
Y Y N Y
0.24 0.06 0.085
N N Y
0.009 0.2 0.2 0.2 0.12
Y
Y
0.2
0.73 0.38 0.47
Y Y Y
0.54
N
0.004
Refs.
348 115 992 1100 348 974 348 323 974 323 992 973 328 346 625 761 316 316 54 55 227 968 968 968 352 258 968 761 761 807 761 752 752 752 761 691 787 1079 600
References page II - 290
TABLE 1. cont'd Monomer 1
Monomer 2
Methacrylate, methyl Methacrylate, methyl Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
Methacrylate, 2-bromoethyl Methacrylate, 2-chloro2,3,3,3-fluoropropyl Methacrylate, 2-chloroethyl Methacrylate, 2-chloroethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxypropyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-naphthyl Methacrylate, 2-phenylethyl Methacrylate, 3,5-dimethyladamantyl Methacrylate, 5-oxo-pyrrolidinylmethyl Methacrylate, N-a-benzothiazolonylmethyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzyl Methacrylate, benzylmethylaminoethyl Methacrylate, butyl Methacrylate, butyl Methacrylate, chloromethyl Methacrylate, diethylaminoethyl Methacrylate, dimethylaminoethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, ethyl Methacrylate, glycidyl Methacrylate, glycidyl Methacrylate, glycidyl Methacrylate, glycidyl Methacrylate, isobutyl Methacrylate, isobutyl Methacrylate, isopropyl Methacrylate, methyl diphenylsilyl Methacrylate, methylthiomethyl Methacrylate, /?-acetylphenyl Methacrylate, /?-chlorophenyl Methacrylate, /?-methoxyphenyl Methacrylate, /7-tolyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, propyl Methacrylate, sulfolanyl Methacrylate, f-butyl dimethylsilyl Methacrylate, f-butyl diphenylsilyl Methacrylate, tributyltin Methacrylate, tributyltin Methacrylate, trimethyltin Methacrylate, trimethyltin Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid
/*i 0.79 0.984 1.156 0.55 0.824 0.192 0.75 0.402 0.602 0.581 0.532 0.614 0.623 0.75 0.68 0.421 0.5 0.808 0.93 0.78 0.523 0.52 1.27 0.477 0.843 0.699 0.81 1.08 1.16 0.71 0.726 0.8 0.688 0.62 0.92 0.89 0.438 0.639 0.47 0.54 0.72 0.59 0.53 0.58 0.56 0.66 0.55 1.21 1.07 0.897 0.636 0.58 0.62 0.63 0.6 0.63 0.1 0.78 0.31 0.27 0.1 0.78 0.32
±95%
0.395 0.082 0.01 0.09 0.017 0.059 0.023 0.055 0.051 0.048 0.16 0.04 0.033 0.01 0.03 0.134 0.07 0.029 0.128 0.051 0.22 0.19 0.08 0.042 0.076 0.08 0.15 0.075 0.057
2.48 0.05 0.014
0.03 0.01 0.03 0.02 0.03 0.01 0.03 0.02
r2
±95%
Conv.
Refs.
1.17
N
657 927
0.97 0.48 0.63 0.81 1.5 1.055 2.57 2.53 1.91 4.41 3.83 0.85 0.45 0.694 0.6
0.18
Y
0.076 1.02
Y Y
0.04 0.48 0.27 0.6 0.76 0.57 0.34 0.16 0.087 0.02
Y Y Y Y Y Y Y N Y
1.112 1.05 1.38 0.296 2.11 1.2 1.02 1.44 1.2 0.86 1.08 1 0.52 0.934 1.05 0.501 1.88 0.488 1.2 0.38 1.1 0.67 1.08 1.19 1.28 1.67 1.69 1.72 1.55 0.99 1.24 7.16 0.725 0.396 0.62 0.87 1.07 0.68 0.25 1.06 0.33 0.63 0.46 1.06 0.33 0.63
0.093
Y
0.123 0.08
Y N
0.16 0.085 0.154 0.12
Y Y Y N
0.09 0.06 0.085
N Y Y
0.027 0.07 0.029
Y N Y
0.178 0.356
Y Y
23.7 0.455 0.257
N Y Y
1.18 0.583
0.05 0.02 0.02 0.02 0.03 0.02 0.02 0.02
179 382 350 358 710 333 760 760 760 760 760 540 335 633 887 111 32 540 1081 30 844 712 1081 1081 32 844 87 113 226 463 639 30 639 541 1069 920 769 769 769 769 32 32 32 761 769 844 359 1069 1069 1082 1082 1082 1082 1071 1072 1072 1072 1072 1087 1087 1087
TABLE 1.
cont'd
Monomer 1 Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
Monomer 2 methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl
Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic anhydride Methacrylophenone, aMethacrylophenone, aMethacryloyl chloride Methacryloyl chloride Methacryloyl fluoride Methacryloyl fluoride Methacryloyl isocyanate Methacryloyloxy-, o-, benzoic acid Methylenebutyrolactone Methyleneglutaronitrile, 2Methyleneglutaronitrile, 2Myrcene AW-divinylaniline W-Vinylimidazole N-Vinylpyrrolidone N-Vinylpyrrolidone iV-Vinylpyrrolidone Af-Vinylpyrrolidone Naphthalene, 1-vinylNorbornadiene Oxazolidone, N-vinylOxazolidone, Af-vinylOxazoline, 2-,2-isopropenyl 4,4-dimethyl Oxazoline, 2-,2-isopropenyl Oxazoline, 2-,4-acryloxymethyl 2,4-dimethyl Oxazoline, 2-,4-methacryloxy2,4-dimethyl Pentadiene, trans-1,3Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl
/*i
±95%
r2
±95%
Conv.
Refs.
0.87 1.81 0.56 0.29 1.28 0.77 0.36 1.18 0.55 0.209 1.25 0.48 0.22 1.79 1.74 0.45 0.45 0.405 0.53 0.75 0.908 0.6 1.36 1.27 0.256 1.06 4.306 4.78 5.93 2.07 4.04 0.321 14.68 6.75 9.46 0.53
0.05 0.16 0.23 0.04 0.1 0.05 0.08
2.16 1.63 0.99 1.18 0.48 1.84 1.38 0.63 1.55 1.26 0.78 0.68 1.58 0.11 0.119 0.2 0.2 0.43 0.9 0.35 1.37 1.67 0.12 0.12 0.448 0.005 0.663 0.006 0.014 0.027 0.066 0.574 - 0.5 0.04 0.027 0.82
0.28 6.25 0.55 0.19 0.1 0.24 0.27
N N Y N N N N
0.2
Y
0.06 0.02 0.009
N N Y
0.12 0.16
Y N
0.64
Y
0.74
N
0.06 0.018 0.104 2.29 0.899 0.062 3.96 0.073 0.52 0.13 0.008
Y Y Y
203 210 216 276 276 312 313 313 424 54 630 819 275 798 798 591 593 617 660 944 938 746 196 196 1062 45 879 1084 1084 1084 1084 967 267 102 36 596
0.05 0.02 0.07 0.22 0.037 0.06 0.252 0.28 0.013 0.18 0.185 0.236 0.198 0.247 0.956 0.096 16.78 0.37 0.39
N Y Y
0.69 0.41
0.99 0.11
862 596
1.17
0.19
596
0.404 0.555 0.424 0.591 0.443 0.34 0.57 0.606 0.269 0.715 0.528 0.597 0.38 0.513 0.43 0.474 0.581 0.616 0.663 0.528 2.37 2.23 1.87
0.038 0.032 0.022 0.046 0.032 0.031 0.023 0.045 0.027 0.048 0.02 0.03 0.034 0.022 0.034 0.023 0.025 0.024 0.023 0.02 0.046 0.047 0.086
0.379 3.39 2.02 3.06 1.67 1.24 1.72 1.69 0.72 1.55 1.09 2.56 0.748 1.14 0.952 1.67 1.04 1.05 0.725 1.09 0.486 0.521 0.946
0.013 0.263 0.141 0.349 0.183 0.168 0.123 0.236 0.12 0.224 0.09 0.218 0.155 0.109 0.164 0.143 0.111 0.108 0.08 0.09 0.088 0.138 0.436
Y N N N N N N N N N N N N N N N N N N N N N N
1058 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 971 971 971
References page II - 290
TABLE 1. cont'd Monomer 1 Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
Monomer 2 methyl methyl methyl methyl methyl methyl
Methacrylate, methyl Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphonate, a-bromovinyl-,diethyl Phosphonate, a-carboethoxyvinyl-, diethyl Phosphonate, a-carbomethoxyvinyl-, diethyl Phosphonate, isopropenyl-, dimethyl Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, diethyl Phosphonic acid, a-phenylvinylPhthalimide,-N-)methacryloyloxy)Pinene, aPropene, 2,3-dichloroPropene, 2-chloro-3-hydroxyPropenyl, 2-chloro-, acetate Propenyl, 2-methyl, acetate Pyridazinone, 3-(2-vinyl)-6-methyl-4,5Pyridazinone 3-(2-vinyl)-6-methylPyridine, 2-methyl-5-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinyl-5-ethylPyridine, 4-vinylPyridine, 4-vinylPyrrolidone, l-benzyl-3-methylene5-methyl Pyrrolidone, N-vinylPyrrolidone, N-vinylPyrrolidone, A^-vinylPyrrolidone, N-vinylPyrrolidone, Af-vinylPyrrolidone, a-methylene-AT-methylSilane, y-methacryloxypropyltrimethoxyStyrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
rx 1.97 2.1 2.56 2.04 1.25 1
±95%
0.01
684
30 29.9 11.1 1.362 0.69 10 6.02 4.4 1 10 1.19 0.86 0.42 0.42 0.4 0.35 0.31 0.27 0.39 0.57 0.54 0.387
0.2 0.26
684 410 684 131 979 48 11 445 445 470 340 340 232 231 532 6 623 749 231 231 691 33
0.04 0.02 0.09 0.02 0.19 0.04 0.02 0.02 0.01 0.07
0.3 0.34 0.61 0.61 0.058 0.082
0.13 0.085 0.029 0.011 0.01
N N N N
Refs.
4.7
1.66
0.248 0.097 0.226 0.052
Conv.
0.05
0.04 0.084 0.048
1.16 0.42 0.258 0.0701
±95%
971 971 971 971 684 684
5.62 4.63 4.36 4.04 0.577 0.788 0.5 0.46 0.46 0.42 0.45 0.46 0.47 0.48 0.5 0.22 0.32 0.418 0.54 0.478 0.45 0.45 0.49 0.47 0.48 0.46 0.42 0.5 0.46 0.44 0.49 0.49
0.029 0.045 0.094 0.012 0.04
r2
-0.063 1.45 0.08 0.18 0 0 0 0.08 0.56 0.54 0.73 0.86 0.76 0.64 1.1 0.68 0.77 0.99 2.28
0.077 0.151
Y Y
0.1
N
0.03 0.04 0.19 0.06
N N N N
0.12
Y
0.08 0.06 0.07 0.18 0.47
N N N N Y
- 0.05 -0.032 -0.052 0.01 0.24 2.06 0.5 0.52 0.52 0.48 0.52 0.49 0.45 0.58 0.44 0.396 0.42 0.49 0.564 0.585 0.44 0.47 0.54 0.52 0.38 0.52 0.54 0.44 0.52 0.5 0.56 0.53
0.08 0.068 0.028 0.15 0.14 0.309
Y N Y Y N Y Y
0.048
Y
0.14 0.047 0.007 0.08
Y Y Y N
213 320 321 36 691 641 977 138 139 179 20 21 21 21 21 21 241 241 254 254 287 324 324 403 416 451 463 492 492 505 531 531 534
TABLE 1. cont'd Monomer 1 Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate, Methacrylate,
Monomer 2 methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl methyl
Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl
Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene, 2,4,6-trimethylStyrene, 2,4,6-trimethylStyrene, 2,5-dichloroStyrene, 2,6-dichloroStyrene, 3-methyl Styrene, 3-methyl Styrene, 3-methyl Styrene, 3-tri-rc-butylstannylStyrene, 4-methylStyrene, a-methoxyStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, m-bromoStyrene, m-chloroStyrene, m-methylStyrene, m-nitroStyrene, /?-chloroStyrene, o-chloroStyrene, /?-l-(2-hydroxypropyl)Styrene, p-JVyV-dimethylaminoStyrene, p-bromoStyrene, /?-chloroStyrene, p-chloroStyrene, /7-chloroStyrene, /?-chloromethylStyrene,/?-cyanoStyrene, /?-methoxyStyrene, p-methylStyrene,/7-octylamine sulfonate Styrene, p-tert-buty\Styrene, pentachloroSuccinamete, potassium N-vinylSuccinimide, TV-vinylSuccinimide, N-vinylTetrazole, 1-VinylTetrazole, 2-methyl-5-vinylTetrazole, 2-phenyl-5(4/-vinyl) phenylThiophene, 3-vinyl Thioxanthone, 2-(acryloyloxy)Toluenesulfonamide, Af,N-methylvinylTriallyl cyanurate Triallyl isocyanurate Triazole, 1,2,3-, 1-p-bromophenyl4-vinyl Triazole, 1,2,3-, 4(5)-vinylUrea, TV-vinyl-AT'-ethyl-
r\ 0.409 0.504 0.611 0.59 0.6 0.63 0.58 0.64 0.41 0.454 0.464 0.422 0.41 0.314 1.511 1.45 0.44 1.98 0.48 0.38 0.41 0.69 0.345 2.5 0.48 0.55 0.55 0.5 0.42 0.47 0.48 0.512 0.35 0.5 0.46 0.26 0.204 0.4 0.334 0.42 0.43 0.408 0.22 0.29 0.4 0.6 0.44 3.65 1.1 9.94 0.01 7.13 1.026 0.7 0.563 1.36 1.87
±95% 0.02 0.026 0.028
0.072 0.16 0.13 0.16 0.04 0.03 0.04 0.008 0.39 0.02
0.036 0.11
r2 0.485 0.48 0.371 0.62 0.52 0.5 0.55 0.55 0.41 0.472 0.497 0.432 0.57 0.275 0.083 -0.01 2.66 -0.15 0.53 0.36 0.51 0.03 0.46 - 0.02 0.27 0.51 0.6 0.14 0.22 0.48 1.17
±95%
Conv.
Refs.
0.052 0.059 0.055
Y Y Y
0.045 0.11 0.38 0.27 0.04 0.06 0.05
Y Y Y N
0.022 0.04 0.07
Y N N
0.02 0.32
Y Y Y
0.016
Y
0.12
Y
0.15
Y
0.05 0.12 0.026 0.096 0.026 0.075
N Y Y Y Y Y
0.26
Y
751 751 751 753 753 753 753 753 753 824 824 824 835 860 58 58 3 324 1087 1087 1087 985 929 142 265 265 265 532 835 899 256 150 256 222 532 558 380 256 256 150 256 476 756 256 35 256 817 634 7 771 104 693 925 670 583 1000 986 80
0.19
0.486 0.8 1.37 1.34 1 0.101 1.1 0.77 0.89 0.47 0.91 1.41 0.32 0.44 2.6 0.5 0.3 -0.02 0.048 -0.059 0.262 0.486 0.4 0.25 0.5 -1.83
16.12 16.88 0.832
0.56 6.64 0.022
-0.005 -0.49 0.266
0.05 0.94 0.058
Y Y Y
201 201 670
0.839 1.85
0.055 0.23
0.27 -0.008
0.13 0.029
Y Y
670 101
0.022 0.016
0.038
0.85 0.17 0.27 0.031 0.093 0.029
References page II - 290
TABLE 1. cont'd Monomer 1 Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl
Monomer 2 Vinyl 2-chloroethyl ether Vinyl 4-chlorocyclohexyl ketone Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl benzoate Vinyl bromide Vinyl bromide Vinyl bromide Vinyl bromide Vinyl butyl ether Vinyl butyrate Vinyl chloride Vinyl chloromethyl ketone Vinyl ether Vinyl ethyl ether Vinyl ethyl ketone Vinyl ethyl oxalate Vinyl ethyl sulfide Vinyl ethyl sulfide Vinyl ethyl sulfoxide Vinyl isobutyl sulfide Vinyl isobutyl sulfide Vinyl isobutyl sulfide Vinyl isopropyl ketone Vinyl isopropyl ketone Vinyl isopropyl sulfide Vinyl isothiocyanate Vinyl m-cresyl ether Vinyl methyl sulfide Vinyl o-cresyl ether Vinyl /7-cresyl ether Vinyl phenyl ether Vinyl phenyl ether Vinyl phenyl ketone Vinyl phenyl sulfide Vinyl phenyl sulfide Vinyl propionate Vinyl sulfone Vinyl tert-butyl ketone Vinyl, 4-, dithiobenzoate, methyl Vinyl, /?-,benzylmethylcarbinol Vinyl-tris(trimethoxysiloxy)silane Vinylacetophenone, p Vinylanthracene, 9Vinylbenzoic acid, p Vinylbenzyl chloride Vinylene carbonate Vinylferrocene Vinylhydroquinone Vinylhydroquinone dibenzoate Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene cyanide Vinylisocyanate
T1 18.8 0.77 2.71 137.5 26 28.6 22.21 20.3 14.11 17.1 25.1 19.84 25 8.99 0.121 4.9 37 0.42 4.74 1.03 2.7 11.17 0.89 0.985 0.88 0.81 0.54 0.822 0.85 3.3 1 1.8 2.6 11.34 2.8 0.71 0.79 0.85 24 4.5 1.21 0.151 0.24 34 0.33 4.068 0.398 0.46 126 1.22 0.49 0.34 2.6 2.38 2.16 2.5 2.5 2.1 1.8 2.83 1.23 2.77 3.3
±95%
0.25 5.9
0.67 0.88 2.58 2.97 0.021 0.99 0.17 2.95 0.11 0.48 0.01 0.077 0.02 0.22 0.064
5.76 0.6 0.06 0.49 0.11 0.092 0.26 0.36 0.04 0.097 298 0.21 0.02 0.06
0.95 0.06 0.012
r2 0 0.51 -0.2 -0.81 0.03 0.04 0.07 0.07 0.12 0.33 0.052 0.05 0.03 0.07 0.593 -0.15 0.01 0.65 -0.05 0.036 0.3 0.37 0.05 0.021 0.03 1.44 0.6 0.046 0.6 0.2 0.03 0.1 0 0.01 0 0.59 0.06 0.08 0.03 0.1 0.65 0.3 0.98 0.02 1.65 0.117 1.16 1.02 -0.04 0.52 0.02 0.41 0.3 0.36 0.18 0.5 0.34 0.09 0.094 0.19 0.02 0.27 0.01
±95%
Conv.
0.01 1.17
N
0.06
N
0.026 0.074
Y Y N
0.047 0.092 0.16
Y Y Y
0.42 0.44 0.017
Y Y Y
0.06 0.03 0.034 0.02
Y N Y N
0.47 0.025
Y Y
0.32
Y
1.9 0.09
Y N
0.16 0.15 0.29 0.28
Y Y Y Y
3.81 0.043 0.3
Y Y Y
0.85
Y
0.13
Y
0.03 0.18
Y N N
0.032
Y
0.01 0.013
N Y
Refs. 597 668 158 210 272 383 471 272 268 268 34 34 127 272 3 356 45 106 794 124 303 507 286 285 303 336 601 794 303 422 605 106 605 605 172 605 794 239 239 272 45 794 697 48 482 266 123 266 792 103 294 337 440 138 324 324 426 432 538 65 762 762 786 82 422
TABLE 1. cont'd Monomer 1 Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl diphenylsilyl Methacrylate, methylthiomethyl Methacrylate, methylthiomethyl Methacrylate, mono-,ethylene glycol Methacrylate, octyl Methacrylate, octyl Methacrylate, octyl Methacrylate, /?-(cinnamoylamino)phenyl Methacrylate, /?-acetylphenyl Methacrylate,/?-carbomethoxyphenyl Methacrylate, p-chlorophenyl Methacrylate, p-chlorophenyl Methacrylate, /?-methoxyphenyl Methacrylate, p-methoxyphenyl Methacrylate, p-methylphenyl Methacrylate, p-methylphenyl Methacrylate, p-tolyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, potassium Methacrylate, propargyl Methacrylate, propyl Methacrylate, propyl Methacrylate, sodium (2-sulphoxyethyl)Methacrylate, sulfolanyl Methacrylate, sulfolanyl Methacrylate, sufolanyl Methacrylate, f-butyl dimethylsilyl Methacrylate, f-butyl dimethylsilyl Methacrylate, f-butyl diphenylsilyl Methacrylate, terf-butyl Methacrylate, terf-butyl Methacrylate, tetra(2-hydroxypropyl)ethylenediamine Methacrylate, tetra(2-hydroxypropyl)ethylenediamine Methacrylate, tributyltin Methacrylate, tributyltin Methacrylate, tributyltin Methacrylate, tributyltin Methacrylate, tributyltin Methacrylate, tributyltin Methacrylate, triethyltin Methacrylate, trimethyltin Methacrylate, triphenyltin Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid
Monomer 2
rx
Vinylphenyldimethylsilane 29.79 Vinyltrimethylsilane 35.66 Xanthate, 5-methacryloyl O-ethyl 0.76 Methacrylate, methyl 0.38 Methacrylate, methyl 1.1 Styrene 0.512 Acrylonitrile 1.5 Styrene 0.56 Styrene 0.68 Vinyl chloride 14 Styrene 0.31 Methacrylate, methyl 0.67 Styrene 0.178 Methacrylate, methyl 1.08 Styrene 0.243 Methacrylate, methyl 1.19 Styrene 0.244 Styrene 0.225 Styrene 0.185 Methacrylate, methyl 1.28 Acrylonitrile 0.46 Methacrylate, 2-chloroethyl 0.785 Methacrylate, benzyl 1.42 Methacrylate, methyl 1.67 Methacrylate, methyl 1.69 Methacrylate, methyl 1.72 Methacrylate, methyl 1.55 Methacrylate, methyl 0.99 Methacrylic, acid 1.89 Methacrylic, acid 0.589 N-Vinylpyrrolidone 4.17 Styrene 0.48 Styrene 0.55 Styrene 0.51 Acrylonitrile 0.203 Itaconic acid mono(/?-sulfamidoanilide) 1.65 Methacrylate, methyl 1.24 Styrene 0.38 Methacrylic, acid 1.2 Methacrylate methyl 7.16 Methacrylic, acid 0.81 Styrene -0.2 Acrylate, methyl 1.07 Methacrylate, methyl 0.725 Methacrylate, methyl 0.396 Methacrylate, methyl 1.35 Styrene 0.61 Methacrylate, hydroxyethyl 1.44
±95% 1.89 0.85 0.04 0.178 0.356 0.05
r2
0.51 1
-0.009 0.028 0.6 0.438 0.639 0.338 0.19 0.65 0.56 0.04 0.62 0.47 0.482 0.54 0.34 0.72 0.499 0.49 0.223 0.59 0.36 1.02 0.67 0.53 0.58 0.56 0.66 0.55 0.211 0.398 -0.026 0.246 0.247 0.26 0.226 0.58 1.21 0.565 0.78 1.07 0.81 0.2 0.288 0.897 0.636 0.96 0.545 0.606
0.16
0.027 0.022 0.026 0.04 0.039
0.083 0.09
0.17 0.081 0.756 0.23 0.33 0.086 0.02 0.11 0.19 23.7 0.24 2.46 0.21 0.455 0.257
±95%
Conv.
Refs.
Y Y
0.034 0.016 0.08 0.075 0.057 0.01
Y Y Y
0.1
Y
0.084
Y
0.11
Y
0.089 0.25 0.09
Y Y Y
0.21 0.06
Y N
0.018 0.019 0.032 0.049 0.064
Y Y Y Y Y
0.04 0.05
Y
0.081 0.08 2.48 0.03 0.1 0.057 0.05 0.014
Y N N N N Y Y Y
0.054 0.416
Y Y
482 482 1086 1069 920 920 682 179 463 511 685 769 177 769 177 769 177 177 177 769 363 179 32 32 32 32 761 769 88 88 1013 177 179 463 808 957 844 179 745 359 359 359 1069 1069 1069 761 179 996
Methacrylic acid
0.328
0.181
1.56
0.237
Y
996
Methacrylate, 2-ethoxyethyl Methacrylate, 2-hydroxypropyl Methacrylate, cyclohexyl Methacrylate, ethyl Methacrylate, hydroxyethyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Acrylamide Acrylamide Acrylamide Acrylate, butyl
0.2 0.728 0.395 0.299 0.282 0.62 0.87 1.07 0.68 1.63 4.4 0.15 1.25
0.444 0.517 0.428 0.607 0.424
0.53 1.81 0.891 0.601 2.33 0.58 0.62 0.63 0.6 0.57 0.58 0.56 0.31
0.16 0.275 0.136 0.123 0.185
N N N N N
0.1
N
945 945 945 945 945 1082 1082 1082 1082 1028 852 852 187
0.31
References page II - 290
TABLE 1. cont'd Monomer 1 Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic
Monomer 2 acid acid acid acid acid acid acid acid
Methacrylic acid Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic
acid acid acid acid acid
Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic
acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid
Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic
acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid acid
rx
Acrylate, ethyl Acrylic acid, 2-ethyl 1.12 Acrylic acid, 2-ethyl 2.29 Acrylic acid, 2-ethyl 1.14 Acrylonitrile 0.2 Acrylonitrile 2.38 Butadiene, 2-chloro-0.035 Diphenyl sulfone, 0.564 3,3 '-bisitaconimido-m,ra 'Maleimide, 2,3-dimethyl0.746 AH2-methacryl) Methacrylamide 2.73 Methacrylamide 1.55 Methacrylamide 2.006 Methacrylate, 2-hydroxypropyl 0.99 Methacrylate, N-methyl-N-phenyl2.16 2-amino Methacrylate, butyl 0.8 Methacrylate, butyl 0.73 Methacrylate, diethylaminoethyl 0.63 Methacrylate, ethyl 0.57 Methacrylate, glycidyl 0.98 Methacrylate, isopropyl 2.01 Methacrylate, methyl 0.25 Methacrylate, methyl 1.06 Methacrylate, methyl 0.33 Methacrylate, methyl 0.63 Methacrylate, methyl 0.46 Methacrylate, methyl 1.06 Methacrylate, methyl 0.33 Methacrylate, methyl 0.63 Methacrylate, methyl 2.16 Methacrylate, methyl 1.63 Methacrylate, methyl 0.99 Methacrylate, methyl 1.18 Methacrylate, methyl 0.48 Methacrylate, methyl 1.84 Methacrylate, methyl 1.38 Methacrylate, methyl 0.63 Methacrylate, methyl 1.55 Methacrylate, methyl 1.26 Methacrylate, methyl 0.78 Methacrylate, methyl 0.68 Methacrylate, phenyl 0.211 Methacrylate, phenyl 0.398 Methacrylate, sodium (2-sulphoxyethyl)- 0.78 Methacrylate, sulfolanyl 0.81 Methacrylate, tetra(21.56 hydroxypropyl)ethylenediamine Methacrylonitrile 1.74 Methacrylonitrile 0.54 7V-Vinylimidazole 1.384 Phosphonate, vinyl-, diethyl 1.9 Phosphonic acid, a-phenylvinyl1.49 Piperylene, cis0.4 Piperylene, trans0.38 Propene, 2,3-dichloro4 Propene, 2-chloro-3-hydroxy4.5 Pyridine, 2-methy 1-5-vinyl0.43 Pyridine, 2-vinyl0.58 Pyridine, 2-vinyl0.44 Styrene 0.55 Styrene 0.64 Styrene 0.66 Styrene 0.49
±95%
r2
±95%
Conv.
Refs. 1065 1004 1004 961 16 216 259 1042
0.027 0.04
0.26 0.29 0.058 0.032
0.194 0.069 0.23 0.04 0.092 2.52 0.015
0.13 0.06 0.2 0.058
N Y Y Y Y Y Y Y
0.059
1.33
0.1
Y
619
0.28
0.33 1.28 0.2 0.31 0.2
0.25
Y
0.014
Y
0.01
N
190 527 55 886 651
0.12 0.12 1.59
N N Y
0.1
N
0.03 0.01 0.03 0.02 0.03 0.01 0.03 0.02 0.05 0.16 0.23 0.04 0.1 0.05 0.08
N N Y N N N N
0.05
Y
0.17 0.081 0.19 0.24 0.181
Y Y N N Y
0.07 0.32 0.022
N N Y
0.3
Y
0.71
Y
0.02
N
0.04
N
0.132 0.417
0.09 0.18 0.16 0.2 1.47 0.16 0.05 0.02 0.02 0.02 0.03 0.02 0.02 0.02 0.28 6.25 0.55 0.19 0.1 0.24 0.27 0.2 0.018 0.019 0.08 0.03 0.237 0.1 3.71 0.034 0.16
0.21 0.66 0.08
1.26 1.15 2.34 0.71 1.2 0.47 0.63 0.1 0.78 0.31 0.27 0.1 0.78 0.32 0.87 1.81 0.56 0.29 1.28 0.77 0.36 1.18 0.55 0.209 1.25 0.48 1.89 0.589 1.2 0.81 0.328 0.64 0.52 0.145 0.15 0.17 0.38 0.33 0 0 0.85 1.69 1.38 0.21 0.22 0.2 0.15
187 224 16 820 224 847 1071 1072 1072 1072 1072 1087 1087 1087 203 210 216 276 276 312 313 313 424 54 630 819 88 88 745 359 996 44 85 879 431 130 773 773 445 445 552 15 498 166 166 203 312
TABLE 1. cont'd Monomer 1 Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic
Monomer 2 acid acid acid acid acid acid acid acid acid acid acid acid acid acid
Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic Methacrylic
acid acid acid acid acid acid
Methacrylic acid Methacrylic anhydride Methacrylic anhydride Methacrylic anhydride Methacrylic anhydride Methacrylic anhydride Methacrylic anhydride Methacrylic anhydride Methacrylic anhydride Methacrylic anhydride Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile
Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene, 3-methyl Styrene, 3-methyl Styrene, 3-methyl Styrene, o-chloroSulfonic acid, o-methacryloylaminobenzeneSulfonic acid, o-methacryloylaminobenzeneSulfonic acid,/7-methacryloylaminobenzeneSulfonic acid, p-methacryloylaminobenzeneVinyl acetate Vinyl chloride Vinyl chloride Vinyl chloride Vinyl, mono-, diethyleneglycol ether Vinylethynyl-4-piperidinol, 1,2,5-trimethyl Vinylidene chloride Acrylate, methyl Allyl chloroacetate Allylurea Methacrylate, methyl Methacrylonitrile Styrene Styrene Vinyl benzyl sulfide Vinyl chloroethyl ether Acenaphthalene Acetylene, phenylAcrolein Acrolein Acrolein, methylAcrolein, methylAcrolein, methylAcrylate, 1,1,5-trihydroperfluoroamyl Acrylate, a-chloro-, ethyl Acrylate, oc-cyano-, methyl Acrylate, oc-phenyl-, methyl Acrylic anhydride Acrylonitrile Allylbenzene Butadiene Ethylene 1,1-diphenylFumarate, diisopropyl Itaconate, dimethyl Methacrylate, butyl Methacrylate, ethyl Methacrylate, isobutyl Methacrylate, isopropyl Methacrylate, octyl Methacrylic acid Methacrylic acid Methacrylic anhydride Phosphonic acid, a-phenylvinyl-
rx 0.56 0.28 0.602 0.85 0.631 0.6 0.44 0.39 0.12 0.35 0.18 0.51 0.622 0.203
±95%
±95%
Conv.
Refs.
0.04
N
0.092
Y
0.146 0.249 0.089 0.199 0.118 0.08 0.02 0.01 0.058 0.067
0.2 0.38 0.124 0.17 0.041 0.067 0.627 0.55 0.221 0.06 0.33 0.42 0.101 0.217
0.03 0.046 0.031 0.06 0.048 0.03 0.02 0.01 0.034 0.122
Y Y Y Y Y
Y Y
313 313 47 812 842 842 842 842 842 1087 1087 1087 6 1006
0.188
0.076
0.523
0.195
Y
1006
0.156
0.081
1.08
0.338
Y
1006
0.155
0.052
1.65
0.27
Y
1006
0.008 0.02
Y Y
0.047
Y
0.13 0.17 0.02 0.06 0.01
Y Y N N N
0.033
Y Y
0.12
N
0.07
N
0.01
N
0.13 0.04 0.03 0.15 0.11
N N Y Y N
0.07 0.05 0.05 0.12 0.05 0.1 3.71 0.18
N N N N N N N N
0.2 23.52 23.26 9.05 0 0.4 3.368 4.75 29.76 29.01 1.58 1.45 0.27 0.33 0.97 0.15 0.78 1.17 1.2 0.41 0.45 0.45 1.03 0.45 0.18 0.19 0.42 1.67 16.24 0.053 0.48 85 1.26 0.56 0.46 0.74 0.43 0.75 0.64 0.52 0.26 2.24
0.19
r2
0.088
0.98 0.96
0.098 13 18.48 0.06 0.18 0.02 0.27
0.05 0.01
0.01 0.04 0.12 1.36 0.016 0.1 0.15 0.04 0.07 0.08 0.04 0.07 0.32 0.06
0.01 0.064 -0.022 0.07 2.2 0.05 0.154 0.16 -0.01 -0.06 0.22 0.26 0.13 0.1 - 0.048 2.38 0.04 0.68 0.72 1.78 1.25 1.25 0.14 2 0.15 0.25 1 0.43 -0.061 0.39 -0.45 0 0.28 0.75 0.83 0.68 0.94 0.61 1.74 0.54 1.45 0
377 135 229 46 831 734 6 275 106 106 275 219 219 275 106 106 575 648 208 446 208 587 589 809 638 143 143 219 198 351 257 143 1038 398 44 44 44 44 44 44 85 219 590
References page II - 290
Next Page TABLE 1.
cont'd
Monomer 1 Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylophenone, aMethacrylophenone, aMethacryloxymethylpentamethyldisiloxane Methacryloxypropyltrimethoxysilane Methacryloyl chloride Methacryloyl chloride Methacryloyl chloride Methacryloyl chloride Methacryloyl chloride Methacryloyl fluoride Methacryloyl fluoride Methacryloyl fluoride Methacryloyl fluoride, perfluoroMethacryloyl isocyanate Methacryloyl-P-hydroxyethyl3,5-dinitrobenzoate Methacryloyl-P-hydroxyethyl3,5-dinitrobenzoate Methacryloyl-P-hydroxyethyl3,5-dinitrobenzoate Methacryloylacetone Methacryloylacetone Methacryloylacetone Methacryloyloxy, 2-benzoate methyl Methacryloyloxy, 2-benzoate methyl Methacryloyloxy, 2-benzoic acid methyl Methacryloyloxy, 2-benzoic acid Methacryloyloxy, 4-,2,2,6,6-tetramethylpiperidine Methacryloyloxy-, o-, benzoic acid Methacryloyloxy-, o-, benzoic acid Methylenebutyrolactone Methylenebutyrolactone Methylenebutyrolactone Methylenebutyrolactone Methyleneglutaronitrile, 2Methyleneglutaronitrile, 2Methyleneglutaronitrile, 2Methyleneglutaronitrile, 2Methyleneglutaronitrile, 2Methyleneglutaronitrile, 2Methyleneglutaronitrile, 2Myrcene Myrcene Myrcene N-N-Divinylaniline N-TV-Divinylaniline JV-JV-Divinylaniline N-N-Divinylaniline TV-N-Divinylaniline
Monomer 2
rx
Styrene Styrene Styrene Styrene Styrene Styrene Styrene, oc-methoxyStyrene, a-methylStyrene, ochloroVinyl acetate Vinyl cinnamate Vinylidene chloride Vinylidene chloride Methacrylate, methyl Methacrylate, methyl Methacrylate, 2-hydroxyethyl Styrene Acrylonitrile Methacrylate, methyl Methacrylate, methyl Pyrrolidone, N-vinylVinyl chloride Methacrylate, methyl Methacrylate, methyl Styrene Vinylidene fluoride Methacrylate, methyl Acrylate, Af-(2-hydroxyethyl)carbazolyl
0.41 0.42 0.28 0.21 0.25 0.21 0.83 0.21 0.86 12 4.6 2.43 2.38 0.11 0.119 0.33 0.58 2.8 0.2 0.2 0.58 2 0.43 0.9 0.164 0.02 0.35 0.08
Acrylate, N-(2-hydroxyethyl)carbazolyl Methacrylate, N-ethyl-3-hydroxymethylcarbazolyl Acrylonitrile Pyrrolidone, TV-vinylStyrene Methacrylate, N-methyl-JV-phenyl2-amino ethyl Styrene Methacrylate, Af-methyl-7V-phenyl2-amino ethyl Styrene Styrene Methacrylate, methyl Vinylchloride Acrylamide Acrylonitrile Methacrylate, methyl Styrene Butadiene Methacrylate, methyl Methacrylate, methyl Styrene Styrene Styrene Vinyl methyl ketone Methacrylate, methyl Styrene Styrene/7-fluoroAcrylonitrile Methacrylate, methyl Styrene Styrene, p-methylVinyl acetate
±95%
r2
±95%
Conv.
Refs.
0.026
0.37 0.38 0.43 0.34 0.25 0.34 - 0.02 0.15 0.78 0.01 0.15 0.3 0.36 1.79 1.74 0.97 0.36 0.35 0.45 0.45 0.05 0.3 0.405 0.53 0.069 7.6 0.75 1.04
1.364
0.018
0.334
0.022
Y
719
0.554
0.019
0.729
0.051
Y
701
3.74 5.66 1.66 1.11
0.22 0.4 0.16 0.18
0.01 0.008 0.067 0.55
0.004 0.004 0.007 0.04
Y Y Y N
339 339 339 651
0.48 2.6
0.02 0.08
0.27 0.2
0.04 0.01
N N
651 651
1.17 0.32
0.03
0.15 0.6
0.04
N
651 687
1.37 11.26 2.85 1.1 1.67 0.7
0.64 3.5
0.908 0.004 0.3 0.09 0.6 0.09
0.252 0.052
Y Y
0.12 0.12 -0.02 0.02 0.25 1.24 0.448 1.38 0.87 -0.006 0.005 0.033 0.06 3.99
0.74
1.36 1.27 0.42 0.5 0.85 5.05 0.256 0.891 0.362 0.246 1.06 5.38 6.15 0.058
0.28
N N
0.52
N
0.013 0.015 0.022 0.014 0.18 0.36 0.16 0.009
Y Y Y Y Y Y Y Y
938 938 746 745 746 746 196 196 196 196 196 512 512 1062 1062 1062 45 45 45 45 45
0.04
0.1 0.05 0.02 0.009
0.12 0.16 0.045
1.3
0.06 0.081 0.143 0.07 0.018 0.067 0.03 0.12
0.005
N
0.1 0.05 0.07 0.22
N N N Y
0.037 0.06 0.014
Y N Y
0.14
Y
311 311 542 707 75 835 143 542 44 75 200 781 781 798 798 822 951 580 591 593 599 432 617 660 660 669 944 702
Previous Page
TABLE 1. cont'd Monomer 1 JV-Vinylimidazole N-Vinylimidazole Af-Vinylimidazole N-Vinylimidazole N-Vinylimidazole N-Vinylimidazole N-Vinylimidazole N-Vinylimidazole Af-Vinylimidazole Af-Vinylimidazole W-Vinylimidazole N-Vinylpyrolidone AT-Vinylpyrolidone Af-Vinylpyrrolidone Af-Vinylpyrrolidone N-Vinylpyrrolidone N-Vinylpyrrolidone Af-Vinylpyrrolidone AT-Vinylpyrrolidone N-Vinylpyrrolidone N-Vinylpyrrolidone N-Vinylpyrrolidone Af-Vinylpyrrolidone N-Vinylpyrrolidone JV-Vinylpyrrolidone N-Vinylpyrrolidone N-Vinylpyrrolidone N-Vinylpyrrolidone N-Vinylpyrrolidone N-Vinylpyrrolidone Af-Vinylpyrrolidone Af-Vinylpyrrolidone Af-Vinylpyrrolidone Naphthalene, 1-vinylNaphthalene, 1-vinylNaphthalene, 1-vinylNaphthalene, l-vinyl-4-chloroNaphthalene, 2-vinylNaphthalene, 2-vinyl-6-chloroNaphthalene, 6-vinyl-2-tert-butyl Nickel diacrylate Norbornadiene Norbornadiene Norbornadiene Norbornadiene Norbornadiene Norbornadiene Norbornadiene Norbornadiene OcM-ene, 4,8-dioxaspiro(2.5)Oct-1-ene, 6,6-dimethyl4,8-dioxaspiro(2.5)Oct-1-ene, 6,6-dimethyl4,8-dioxaspiro(2.5)Oct-1-ene, 6,6-dimethyl4,8-dioxaspiro(2.5)Oct-1-ene, 6,6-dimethyl4,8-dioxaspiro(2.5)Octene-1 Oxazinium F3CSO3, 3-methyl-2-vinyl5,6-dihydro-4H-l,3-
Monomer 2
rx
±95%
r2
±95%
Acrylic acid 0.187 Acrylonitrile 0.832 Fumarate, diethyl 0.113 Fumarate, dimethyl 0.133 Fumaric acid 0.121 Maleate, diethyl 0.057 Maleate, dimethyl 0.046 Maleic acid 0.018 Methacrylate, methyl 0.663 Methacrylic acid 0.145 Styrene 0.68 Caprolactam, N-vinyl2.8 Crotonate, hydrocortisone 210.75 2-Oxazoline, 2-isopropenyl0.01 Acrylamido-2-methylpropane sulfonate 0.13 sodium salt Acrylate, cyclohexyl 0.122 Carbamate, N-vinyl-f-butyl0.4 Ethene, 2-phenyl-l,l-dicyanoItaconate, bis(tri-rc-butyltin) 0.21 Methacrylate, 2-acetylsalicylicoyloxy0.34 3-hydroxypropyl Methacrylate, furfuryl 0.0036 Methacrylate, glycidyl 0.003 Methacrylate, methyl 0.006 Methacrylate, methyl 0.014 Methacrylate, methyl 0.027 Methacrylate, methyl 0.066 Methacrylate, phenyl -0.026 Pyridine, 2-methyl-5-vinyl0.039 Pyridine, 2-vinyl0.014 Pyridine, 4-vinyl0.01 Quinine 2.2 Styrene sulfonate, sodium salt 0.084 Vinyl trimethylammonioethyl ether 11.6 iodide Acrylonitrile 0.451 Methacrylate, methyl 0.574 Styrene 2.02 Styrene 0.75 Styrene 1.345 Styrene 2.44 Styrene 1.014 Titanium, dicylopentadienyl-, 0.95 dimethacrylate Acrylate, ethyl -0.01 Acrylonitrile 0.05 Acrylonitrile 0.44 Methacrylate, methyl -0.5 Styrene, p-chloro0 Vinyl acetate 1.354 Vinyl chloride 0.41 Vinylidene chloride 0.09 Styrene 0.246 Acrylonitrile 1.484
0.025 0.044 0.019 0.021 0.01 0.028 0.046 0.007 0.104 0.022 0.02 0.2 0.02 0.02
1.932 3.393 0.191 0.252 0.313 0.106 0.046 0.094 4.306 1.384 8.377 1.7 0.05 3.5 0.66
0.077 0.008 0.022 0.015 0.012 0.147 0.438 0.027 0.185 0.034 0.149 0.2 0.05 1.2
0.014 0.06
1.297 2.4
0.088 0.5
0.013
0.065 0.85
0.04
Pyridine, 2-vinyl-
0.02 0.018 2.29 0.899 0.062 3.96 0.032 0.006 0.002 0.002 0.03
5.16 4.29 4.78 5.93 2.07 4.04 4.17 13 12.4 9.8 0.37 7.19 0
1.13 0.498 0.236 0.198 0.247 0.956 0.756 2 2.3 1.5
Conv.
Refs.
Y Y Y Y Y Y Y Y Y Y Y
879 879 879 879 879 879 879 879 879 879 879 883 1022 894 939
Y Y Y
Y
0.02
1061 991 947 941 1080 1050 1017 1084 1084 1084 1084 1013 1070 1070 1070 922 939 1037
0.088 0.073 0.401 0.45 0.093 1.38 0.244
0.107 0.321 0.699 0.76 0.395 0.39 0.616 0.65
0.028 0.096 0.233 0.68 0.049 0.6 0.069
0.03 0.23 0.05 0.52 0.12 0.07 0.01 0.17 0.024 1.078
2.39 0.48 0.66 14.68 69.93 0.818 0.67 1.36 1.831 0.985
0.44 0.27 0.01 16.78 24.19 0.019 0.02 0.63 0.027 0.675
N N N N Y Y N N Y Y
267 267 69 267 188 188 267 267 838 838
0.073
0.04
2.216
0.062
Y
838
Pyrrolidone, Af-vinyl-
0.552
0.075
-0.009
0.018
Y
838
Styrene
0.271
0.109
1.93
0.098
Y
838
0.85
3.26 0.37
0.45
N
329 909
Vinyl chloride Methacrylate, methyl
-0.57 0.31
967 967 967 806 806 806 806 895
ReferencespageII-290
TABLE 1. cont'd Monomer 1 Oxazolidone, N-vinylOxazolidone, N-vinylOxazolidone, N-vinylOxazolidone, N-vinylOxazolidone, TV-vinylOxazolidone, N-vinylOxazolidone, JV-vinylOxazolidone, N-vinylOxazoline, 2-, 2-isopropenylOxazoline, 2-, 2-isopropenylOxazoline, 2-, 2-isopropenylOxazoline, 2-, 2-isopropenylOxazoline, 2-, 2-isopropenylOxazoline, 2-, 2-isopropenylOxazoline, 2-, 2-isopropenylOxazoline, 2-, 2-isopropenylOxazoline, 2-, 2-isopropenylOxazoline, 2-, 2-isopropenyl4,4-dimethylOxazoline, 2-, 2-isopropenyl4,4-dimethylOxazoline, 2-, 2-isopropenyl4,4-dimethylOxazoline, 2-, 2-isopropenyl4,4-dimethylOxazoline, 2-, 4-acryloxymethyl2,4-dimethylOxazoline, 2-, 4-acryloxymethyl2,4-dimethylOxazoline, 2-, 4-acryloxymethyl2,4-dimethylOxazoline, 2-, 4-acryloxymethyl2,4-dimethylOxazoline, 2-, 4-methacryloxy2,4-dimethylOxazoline, 2-, 4-methacryloxy2,4-dimethylOxazoline, 2-, 4-methacryloxy2,4-dimethylOxazoline, 2-, 4-methacryloxy2,4-dimethylOxazoline, 2-isopropenyl-2Oxazoline, 2-isopropenyl-2Oxazoline, 2-isopropenyl-2Oxazoline, 2-isopropenyl-2Oxazoline, 2-isopropenyl-2Oxazoline, 2-isopropenyl-2Oxazoline, 2-isopropenyl-2Oxazoline, 2-isopropenyl-2Oxazolinium BF4, 3-methyl2-isopropenyl-2Oxazolinium BF4, 3-methyl2-isopropenyl-2Oxazolinium, 2-, tetrafluoroborate 3-methyl-2-isopropenylOxazolinium, 2-, tetrafluoroborate 3-methyl-2-isopropenylOxazolinium, 2-isopropenyl-2Oxirane, 4-vinylphenylPentadiene, cis-1,3Pentadiene, cis-1,3Pentadiene, cis-1,3Pentadiene, cis-1,3Pentadiene, cis-1,3Pentadiene, cis-1,3-
Monomer 2 Methacrylate, decyl Methacrylate, methyl Methacrylate, methyl Styrene Vinyl acetate Vinyl acetate Vinyl chloride Vinylidene chloride Acrylate, butyl Acrylate, ethyl Acrylate, methyl Acrylate, methyl Acrylonitrile Methacrylate, methyl Pyrrolidone, N-vinylStyrene Vinyl acetate Acrylate, methyl
T1 -0.052 0.04 0.027 -0.029 1.55 2.04 0.822 0.091 1.4 1.39 1.9 2.07 0.52 0.99 3.5 0.64 7.1 1.3
±95% 0.049 0.13 0.008 0.014 0.28 0.13 0.048 0.077
0.191
r2 12.19 6.75 9.46 29.42 0.602 0.55 0.313 1.42 0.24 0.19 0.16 0.328 0.13 0.69 0.01 0.67 0.25 0.46
±95%
Conv.
Refs.
1.35 0.37 0.39 2.19 0.038 0.18 0.095 0.11
Y Y Y Y Y Y Y Y
0.032
Y
36 102 36 36 102 36 36 102 862 862 862 877 862 862 862 862 862 596
Acrylonitrile
1.83
0.24
596
Methacrylate, methyl
0.82
0.53
596
Styrene
0.68
0.55
596
Acrylate, methyl
0.11
0.29
596
Methacrylate, methyl
0.11
0.41
596
Styrene
0.14
0.56
596
Vinyl acetate
1.41
0.03
596
Acrylate, methyl
0.56
0.4
596
Acrylonitrile
0.89
0.11
596
Methacrylate, methyl
0.19
1.17
596
Vinyl acetate
6.2
0.05
596
Acrylate, butyl Acrylate, ethyl Acrylate, methyl Acrylonitrile Methacrylate, methyl 7V-Vinylpyrrolidone Styrene Vinyl acetate Acrylate, methyl
1.4 1.39 1.9 0.52 0.99 3.5 0.64 7.1 0.251
0.08 0.06 0.08 0.06 0.07 1.2 0.03 2 0.483
0.24 0.19 0.16 0.13 0.69 0.01 0.67 0.25 0.096
0.01 0.02 0.04 0.04 0.02 0.02 0.02 0.04 0.057
Y
894 894 894 894 894 894 894 894 908
Vinyl acetate
0.413
0.005
0.114
0.021
Y
908
Acrylate, methyl
0.344
0.105
0.552
0.043
Y
877
Vinyl acetate
0.366
0.151
0.43
0.057
Y
877
Acrylate methyl Styrene Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile
2.08 1.06 0.172 0.241 0.017 0.071 0.198 0.188
0.327
0.191 0.78 0.026 0.06 0.026 0.06 0.056 0.033
0.031
Y
0.018 0.071 0.173 0.242
Y Y Y Y
0.017
N
908 1001 867 867 912 912 952 997
0.012 0.029 0.012 0.029 0.011
TABLE 1. cont'd Monomer 1 Pentadiene, cis-1,3Pentadiene, cis-1,3Pentadiene, trans-1,3Pentadiene, trans-1,3Pentadiene, trans-1,3Pentadiene, trans-1,3Pentadiene, trans-1,3Pentadiene, trans-1,3Pentadiene, trans-1,3Pentadiene, trans-1,3Pentadiene, trans-1,3Pentadienoate, frarcs-4-ethoxy-2,4-,ethyl Pentadienoate, frarcs-4-ethoxy-2,4-,ethyl Pentadienoate, trans-4-ethoxy-2,4Penten-2,4-one Pentene-1 Pentene-1 Pentene-1, 2-methylPentene-1, 5-cyclohexylPentene-1, 5-phenylPentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-OXO-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-OXO-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Pentenoate, 4-methyl-3-oxo-4-, ethyl Phenol, 3-(methacryloylamino)Phenol, 4-(methacryloylamino)Phosphate diethyl isopropenyl Phosphate diethyl isopropenyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl
Monomer 2 Butadiene Pentadiene, trans-1,3Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Butadiene Methacrylate, methyl Pentadiene, cis-1,3Styrene Acrylonitrile Styrene Styrene Vinyl chloride Vinyl chloride Vinyl chloride Acrylonitrile Acrylonitrile Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Styrene Styrene Acrylonitrile Vinyl acetate Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Styrene Styrene Styrene Styrene Styrene Styrene
T1 0.26 0.86 0.104 0.095 0.018 0.064 0.132 0.114 0.09 0.379 0.37 12.2 5.4 11.8 -0.033 0.001 0.81 -1.16 -0.043 -0.026 3.29 1.57 1.29 1.4 0.923 0.747 0.635 1.12 0.568 3.39 2.02 3.06 1.67 1.24 1.72 1.69 0.72 1.55 1.09 2.56 0.748 1.14 0.952 1.67 1.04 1.05 0.725 1.09 0.99 0.86 0.03 0.44 0.486 0.521 0.946 1.16 0.42 0.258 0.0701 0.171 0.15 0.146 0.168 0.094 0.23
±95%
0.01 0.021 0.01 0.02 0.009 0.013
0.055 5.2 2.31 0.044 0.046 0.712 0.193 0.309 0.322 0.075 0.073 0.068 0.112 0.035 0.263 0.141 0.349 0.183 0.168 0.123 0.236 0.12 0.224 0.09 0.218 0.155 0.109 0.164 0.143 0.111 0.108 0.08 0.09 0.04 0.03 0.088 0.138 0.436 0.248 0.097 0.226 0.052 0.01 0.05 0.073 0.355 0.02 0.187
r2 0.63 0.37 0.07 0.06 0.069 0.068 0.085 0.079 1.22 0.404 0.86 0.04 0.01 0.08 13.84 4 2.08 1.59 4.22 3.84 0.233 0.161 0.215 0.189 0.179 0.164 0.162 0.178 0.217 0.555 0.424 0.591 0.443 0.34 0.57 0.606 0.269 0.715 0.528 0.597 0.38 0.513 0.43 0.474 0.581 0.616 0.663 0.528 0.5 0.71 15.2 1.56 2.37 2.23 1.87 1.97 2.1 2.56 2.04 0.629 0.612 0.595 0.597 0.633 0.61
±95%
Conv.
0.017 0.064 0.104 0.096
Y Y Y Y
0.018
N
0.038
Y
0.57
Y
1.78 0.68 0.45 0.48 0.069 0.028 0.051 0.05 0.014 0.015 0.015 0.02 0.009 0.032 0.022 0.046 0.032 0.031 0.023 0.045 0.027 0.048 0.02 0.03 0.034 0.022 0.034 0.023 0.025 0.024 0.023 0.02 0.06 0.04
N N N Y N N N N N N N N N N N N N N N N N N N N N N N N N N N N
0.046 0.047 0.086 0.029 0.045 0.094 0.012 0.003 0.004 0.005 0.044 0.002 0.018
N N N N N N N N N N N N N
Refs. 743 743 867 867 912 912 952 997 743 1058 743 723 723 723 112 3 329 329 24 24 930 930 930 930 930 930 930 930 930 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 1033 896 896 650 650 971 971 971 971 971 971 971 971 971 971 971 971 971
References page II - 290
TABLE 1. cont'd Monomer 1 Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, vinyl bis(chloroethyl) Phosphate, vinyl diethyl Phosphate, vinyl diethyl Phosphate, vinyl diphenyl Phosphate, vinyl diphenyl Phosphazene, isopropenylpentafluoroPhosphazene, isopropenylpentafluoroPhosphine oxide, diphenylvinylPhosphine oxide, diphenylvinylPhosphonate, 2-(4-vinylphenyl)ethyl, diethyl Phosphonate, 4-vinylphenyl, diethyl Phosphonate, a-bromovinyl-, diethyl Phosphonate, a-carboethoxyvinyl-, diethyl Phosphonate, a-carboethoxy vinyl-, diethyl Phosphonate, a-carboethoxy vinyl-, diethyl Phosphonate, isopropenyl-, dimethyl Phosphonate, isopropenyl-, dimethyl Phosphonate, isopropenyl-, dimethyl Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, dibutyl Phosphonate, vinyl-, diethyl Phosphonate, vinyl-, diethyl Phosphonate, vinyl-, diethyl Phosphonate, vinyl-, diethyl Phosphonate, vinyl-, diethyl Phosphonate, vinyl-, diethyl Phosphonate, vinyl-, diethyl Phosphonate, vinyl-, diethyl Phosphonate, vinyl-, diethyl Phosphonate, vinyl-, diisobutyl Phosphonate, vinyl-, diisobutyl Phosphonate, vinyl-, diisopropyl Phosphonate, vinyl-, dimethyl Phosphonate, vinyl-, dimethyl Phosphonate, vinyl-, dimethyl Phosphonate, vinyl-, dimethyl Phosphonate, vinyl-, dimethyl Phosphonate, vinyl-, dimethyl Phosphonate, vinyl-, dimethyl Phosphonate, vinyl-, diphenyl Phosphonate, vinyl-, diphenyl Phosphonate, vinyl-, dipropyl Phosphonic acid, a-phenylvinyl Phosphonic acid, a-phenylvinylPhosphonic acid, a-phenylvinylPhosphonic acid, a-phenylvinylPhosphonic acid, a-phenylvinylPhosphonic acid, a-phenylvinylPhosphonic acid, a-phenylvinylPhosphonic acid, a-phenylvinylPhosphonic acid, a-phenylvinylPhosphonic acid, a-phenylvinylPhosphonic acid, a-phenylvinyl-
Monomer 2
r\
Styrene Styrene Vinyl chloride Vinyl chloroacetate Vinyl chloride Vinyl chloroacetate Styrene Styrene, p-chloromethylAcrylonitrile Vinyl acetate Styrene
0.108 0.03 0.15 0.374 0.327 0.53 -0.121 —0.048 0.16 1.7 1.36
Styrene Methacrylate, methyl Methacrylate, methyl Phosphonate, vinyl-, diethyl Methacrylate, methyl Methacrylate, methyl Styrene Vinyl acetate Ethylene Methacrylate, methyl Styrene Styrene Styrene Styrene Styrene Vinyl acetate Vinyl acetate Vinyl acetate Styrene Methacrylate, methyl Methacrylic acid Phosphonate, a-carbomethoxyvinyl-, diethyl Styrene Styrene Styrene Styrene Vinyl acetate Vinyl acetate Ethylene Styrene Styrene Butadiene, 2-chloroStyrene Styrene Styrene Styrene Vinyl acetate Vinyl acetate Ethylene Styrene Styrene Vinylidene cyanide Acrylic acid Acrylonitrile Acrylonitrile Butadiene, 2,3-dichloroButadiene, 2,3-dichloroButadiene, 2-chloroButadiene, 2-chloroMethacrylate, methyl Methacrylic acid Methacrylonitrile
1.4 0.04 0.05 0.55 0.01 0.2 0.23 0.99 7.73 0.26 0.02 0.16 0.2 0.18 0.18 0.85 0.85 0.47 -0.12 0.04 0.15 0.62
±95% 0.034 0.23 0.047 0.046 0.023 0.12 0.088 0.067
2.19 0.39
2.33
r2 0.599 2.47 3.4 2.01 3.009 1.42 1.6 1.64 3.8 0.38 0.55 0.7 1.25 1 0.62 4.7 30 8.6 0.14 0.077 29.9 2.46 2.3 2.2 6.32 6.32 0.09 0.09 0.33 4.97 11.1 1.9 0.55
±95% 0.002 0.78 0.21 0.2 0.077 0.15 0.27 0.58
Conv.
Refs.
N Y Y Y Y Y Y Y
971 133 779 779 779 779 765 765 843 843 796
0.003
Y
0.43
Y
3.44
Y
-0.15 -0.52 0.02 0 0.74 0.6
2.18 0.22
4.36 1.59 2.45 3.88 0.04 0.09
4.27 0.24
Y Y
-0.32 -0.52 0.1
1.46 2.52
3.87 2.57 7.5
1.59 2.13
Y Y Y Y
0.4 0.15 0.02 0.74 0.74 1.66 -0.38 -0.41 0.1 0.04 -0.45 0 0.07 0.07 0.1 0.1 -0.063 0.17 0
2.22 0.29 0.72 0.83 0.41
0.077 0.3
4.61 2.45 2.45 0.04 0.04 0.088 1.74 3.81 4.58 0.7 0.34 2.36 7.75 7.75 7.5 7.5 1.362 1.49 2.24
0.01 0.16 0.68
Y Y Y
0.13 0.12
Y Y
0.084 0.16
Y Y
796 684 684 684 684 684 684 684 801 410 133 410 485 592 594 592 594 595 129 684 431 684 129 18 592 684 592 684 801 129 129 594 129 129 592 594 592 594 801 129 129 921 132 132 590 588 597 546 597 131 130 590
TABLE 1. cont'd Monomer 1 Phthalide, 3-(4-vinylphenyl)Phthalimide, N-(4-vinylphenyl)Phthalimide, Af-(methacryloyloxy)Phthalimide, AKmethacryloyloxy)Phthalimide, AA-(methacryloyloxy)Phthalimide, N-vinylPhthalimide, TV-vinylPhthalimide, N-vinylPinene Pinene, aPiperidinol, 4-, A/-methyl-4-(vinylethynyl)Piperylene, cisPiperylene, transPropanesulfonate, 3-[diethyl[2-(2-methacroyloxyethoxy)ethyl Propene, 3,3,3-trichloroPropene, 3,3,3-trichloroPropene, 3,3,3-trichloroPropene, 1-chloro-cwPropene, 1-chloro-cwPropene, 1-chloro-cwPropene, 1-chloro-cwPropene, \-ch\oxo-transPropene, \-ch\oxo-transPropene, \-c\\\oxo-transPropene, \-c\\\oxo-transPropene, 2,3-dichloroPropene, 2,3-dichloroPropene, 2,3-dichloroPropene, 2,3-dichloroPropene, 2,3-dichloroPropene, 2-chloroPropene, 2-chloroPropene, 2-chloroPropene, 2-chloroPropene, 2-chloroPropene, 2-chloro-3-hydroxyPropene, 2-chloro-3-hydroxyPropene, 2~chloro-3-hydroxyPropene, 3-chloro-2-chloromethylPropenyl methyl ketone Propenyl, 2-, acetate Propenyl, 2-chloro-, acetate Propenyl, 2-chloro-, acetate Propenyl, 2-chloro-, acetate Propenyl, 2-chloro-, acetate Propenyl, 2-chloro-, acetate Propenyl, 2-methyl-, acetate Propenyl, 2-chloro-, acetate Propenyl, 2-methyl-, acetate Propenyltriethoxysilane Propiolactam, A^-phenyl-a-methylenePropionate, vinyl Propylene Propylene Propylene Propylene Propylene Propylene Propylene Propylene Propylene Pyrazole, 3-methyl-l-vinylPyrazole, 5-methyl-l-vinylPyrazole, N-vinyl-3,5-dimethyl-
Monomer 2 Acrylonitrile Acrylate, methyl Acrylate, methyl Acrylonitrile Methacrylate, methyl Acrylonitrile Maleic anhydride Styrene Acrylonitrile Methacrylate, methyl Maleimide Methacrylic acid Methacrylic acid Acrylate, ethyl Acrylonitrile Styrene Vinyl acetate Acrylonitrile Maleic anhydride Vinyl acetate Vinyl chloride Acrylonitrile Maleic anhydride Vinyl acetate Vinyl chloride Carbazole, TV-vinylMethacrylate, methyl Methacrylic acid Styrene Styrene Acrylonitrile Vinyl acetate Vinyl chloride Vinyl chloride Vinylidene cyanide Methacrylate, methyl Methacrylic acid Styrene Styrene Styrene Vinyl chloride Acrylate, methyl Acrylic acid Methacrylate, methyl Styrene Vinyl chloride Methacrylate, methyl Styrene Vinylidene chloride Vinyl chloride Styrene Ethylene, chlorotrifluoroAcrylic acid Ethylene Ethylene Ethylene, chlorotrifluoroVinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Pyrazole, 5-methyl-l-vinylPyrazole, 3-methyl-l-vinylStyrene
rx 0.43 1.56 1.23 1.45 1.45 0.24 0.344 0.07 13.5 0.08 2.05 0.38 0.33 0.19 0.1 0 0.19 -0.12 -0.022 -0.012 0.1 0.01 0.05 0.011 0.33 0 0.18 0 0.05 0.036 -0.023 1.65 4.75 0.58 0.001 0 0 0 0.01 0.08 0.25 0 0 0 0 0 0 0 0 0.406 0.63
±95% 0.19 0.168 0.072 0.151 0.02 0.061 0.11 0.1 0.03
0.02
0.19 0.08 0.061 0.63 0.17 0.015 0.074 0.4 0.1 0.01 0.062 0.36 5.12 0.003
0.1 0.3
0.106 0.04
r2 0.084 1.14 0.193 0.204 0.69 0.43 0.008 6.27 0.07 10 0.49 0.4 0.38 3.97 12.2 6.9 0.19 23.37 0.347 7.08 11.52 19.61 0.28 3.13 4.45 1 6.02 4 3.51 3 1.164 0.186 0.095 0.75 0.204 4.4 4.5 12.5 3.37 18.12 2.2 0.7 1 1 4.1 0.7 10 71 2.4 0.626 0.08
±95%
Conv.
Refs.
0.053
Y
0.028 0.016 0.048 0.01 0.012 0.66 0.01
Y Y Y
721 636 979 979 979 1046 284 163 936 848 948 773 773 962
Y Y
0.01
1.03
Y
2.99 0.082 0.35 2.14 1.72 0.012 0.15 0.81
Y Y Y Y Y Y Y Y
1.66
N
0.18
N
0.053 0.091 0.085
Y Y Y
0.079
Y
0.73 6.09
0.025 0.01
Y Y Y
0.62 0.08 0.196 3.1 -0.02 0.09 0.42 1.35 0.049
0.07 0.023 0.21 0.04
0.011
3.43 3.2 0.02 2.35 -0.05 5.16 2.45 2.9 1.35 0.42 8.663
0.08 0.14 0.1 0.06
0.196
N Y N N
402 402 402 181 181 181 181 181 181 181 181 376 11 445 11 983 181 181 181 517 82 445 445 445 806 806 189 445 445 445 445 445 470 470 470 237 1002 1097 183 388 477 318 155 329 355 560 588 898 898 806
References page II - 290
TABLE 1. cont'd Monomer 1 Pyridazinone, 3-(2-vinyl)-6-methylPyridazinone, 3-(2-vinyl)-6-methylPyridazinone, 3-(2-vinyl)-6-methylPyridazinone, 3-(2-vinyl)-6-methyl4,5-dihydroPyridazinone, 3-(2-vinyl)-6-methyl4,5-dihydroPyridazinone, 3-(2-vinyl)-6-methyl4,5-dihydroPyridazone, 2-vinyl-3Pyridazone, 2-vinyl-3Pyridazone, 2-vinyl-6-methyl-3Pyridazone, 2-vinyl-6-methyl-3Pyridazone, 2-vinyl-6-methyl-4,5-benz-3Pyridazone, 2-vinyl-6-methyl-4,5-benz-3Pyridazone, 2-vinyl-6-phenyl-3Pyridazone, 2-vinyl-6-phenyl-3Pyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methy 1-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinyl-
Monomer 2
T1
±95%
r2
±95%
Conv.
Refs.
Acrylonitrile Methacrylate, methyl Styrene Acrylonitrile
0.19 0.56 0.85 0.02
0.04 0.04 0.05 0.02
0.32 0.86 0.9 0.74
0.02 0.02 0.03 0.02
N N N N
340 340 340 340
Methacrylate, methyl
0.08
0.03
1.19
0.04
N
340
Styrene
0.13
0.03
5.92
0.1
N
340
Methacrylate, methyl Styrene Methacrylate, methyl Styrene Methacrylate, methyl Styrene Methacrylate, methyl Styrene Acrylate, methyl Acrylonitrile Butadiene Butadiene Butadiene Caprolactam, N-vinylCaprolactam, Af-vinylItaconate, diethyl Itaconate, dimethyl Methacrylate, methyl Methacrylic acid N-Vinylpyrrolidone Styrene Styrene Styrene Styrene Sulfonic acid, o-methacryloylaminobenzeneSulfonic acid, p-methacryloylaminobenzeneVinyl acetate Acetylene, phenylAcrolein Acrylate, butyl Acrylate, butyl Acrylate, ethyl Acrylate, ethyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylonitrile Acrylonitrile Butadiene, 1,4-dicarboxylate-, diethyl Butadiene, 1-carboxylate, ethyl Butadiene, 2-chloroCaprolactam, N-vinylCaprolactam, N-vinylIsoprene Isoprene Methacrylate, 2-hydroxyethyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylic acid Methacrylic acid N-Vinylpyrrolidone
1.56 0.43 0.3 1.2 0.27 0.24 0.49 1.45 1 0.31 0.47 0.72 0.41 11.58 11.58 0.51 0.88 0.54 0.85 13 0.75 0.68 1.2 0.78 -0.002 -0.054
0.03 0.031
0.63 0.53 0.16 0.9 1.65 0.7 0.58 0.51 0.18 0.16 0.61 1.32 1.29 0.04 0.04 0.17 0.22 0.42 0.43 0.039 0.74 0.6 0.72 0.73 1.83
0.048
2.72
0.3 0.02 0.02
0.19 2 0.08
9 -0.12 2.51 2.59 0.28 2.25 2.13 1.72 2.12 21.9 0.44 0.41 0.4 0.06 4.35 4.35 0.47 0.46 0.64 0.73 0.86 0.76 0.64 1.1 1.69 1.38 12.4
0.05 0.01
N N
0.02
N
0.09
N
0.006 0.03
N
0.03 0.218
N Y
897 897 897 897 897 897 897 897 232 232 462 520 56 589 592 545 545 232 552 1070 232 500 514 56 1006
0.525
Y
1006
0.14
Y N
0.01 0.06
N N
0.4 0.03 0.03
Y N N
0.03 0.23
N
0.04 0.02
N N
0.19
Y
0.04 0.21
N Y
0.11 0.03 0.14 0.1 0.54 0.26 0.1 0.08 0.07
0.16 0.06 0.12 0.08 0.71 2.3
2.64 0.1 0.11 0.21 0.21 0.37 0.17 0.2 0.05 0.1 0.69 0.8 5.19 0.12 0.12 0.59 0.58 0.56 0.42 0.4 0.35 0.31 0.27 0.58 0.44 0.014
0.002
812 192 208 236 78 250 832 2 231 749 456 50 327 791 457 589 592 456 458 342 231 532 6 623 749 15 498 1070
TABLE 1. cont'd Monomer 1 Pyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinyl-5-ethylPyridine, 2-vinyl-5-ethylPyridine, 2-vinyl-5-ethylPyridine, 2-vinyl-5-ethylPyridine, 2-vinyl-5-ethylPyridine, 3-ethynyl-6-methylPyridine, 3-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, 4-vinylPyridine, TV-oxide-, 2-vinyl-5-ethylPyrimidine-2-one, 1,3-divinylhexahydroPyrimidine, 2-TV-TV-dimethylamino-4-vinylPyrimidine, 4-vinylPyrrolidone, l-benzyl-3-methylene5-methylPyrrolidone, l-benzyl-3-methylene5-methylPyrrolidone, l-benzyl-3-methylene5-methylPyrrolidone, TV-vinylPyrrolidone, N-vinylPyrrolidone, TV-vinylPyrrolidone, N-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, AT-vinylPyrrolidone, N-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, N-vinylPyrrolidone, N-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinyl-
Monomer 2
rx
±95%
r2
±95%
Conv.
Refs.
0.04 0.15
Y N
0.18 0.17
N Y
0.004
N
0.07 0.02 0.05
N N N
0.01 0.017 0.04
N Y N
0.03
N
0.04
N
0.09 0.07 0.18 1.5 0.16 0.22
0.073 0.46 0.5 0.55 0.57 0.55 0.14 -0.11 O 0.18 0.02 0.06 0.39 0.74 2.3 0.69 0.291 0.23 0.29 0.2 0.15 0.11 0.09 0.1 0.1 0.32 0.62 0.57 0.54 0.01 0.52 -0.73
0.04 0.02 0.01 0.002 0.07 1.09
N N N
0.4 0.88 0.03 0.071 1.06 0.24
0.03 - 0.23 0.06 0.59 0.338 0.219 0.125
0.36 0.11 0.13 0.017 0.095 0.025
Y N Y Y Y
838 231 41 456 499 532 2 6 6 231 115 50 231 231 784 342 667 78 832 231 424 115 50 589 592 424 342 231 691 1070 231 79 154 395 337 806 800 243 243 633
Oct-1-ene, 6,6-dimethyl-4,8-dioxaspiro 2.216 Styrene 0.75 Styrene 1.27 Styrene 1.81 Styrene 1.33 Styrene 1.14 Styrene, 2,5-dichloro0.62 Vinyl acetate 13.65 Vinyl acetate 30 Acrylate, methyl 1.32 Acrylonitrile 0.43 Acrylonitrile 0.43 Methacrylate, methyl 0.68 Styrene 1.09 Styrene 0.15 Methacrylate, 2-hydroxyethyl 0.73 Acrylate, (-)-menthyl 2.32 Acrylate, butyl 4.3 Acrylate, ethyl 2.58 Acrylate, methyl 1.78 Acrylate, methyl 2.14 Acrylonitrile 0.41 Acrylonitrile 0.34 Caprolactam, TV-vinyl4.43 Caprolactam, TV-vinyl4.43 Isoprene 2.49 Methacrylate, 2-hydroxyethyl 0.9 Methacrylate, methyl 0.77 Methacrylate, methyl 0.99 TV-Vinylpyrrolidone 9.8 Styrene 0.69 Styrene 1.04 Vinyl chloride Vinyl ether 32 Vinylhydroquinone 0.53 Styrene 2.27 Acrylate, ethyl -0.05 Styrene 1.404 Styrene 2.38 Acrylate, methyl 1.58
0.062 0.32
Methacrylate, methyl
2.28
0.47
0.387
0.07
Y
633
Styrene
0.71
0.17
0.555
0.053
Y
633
0.008
0.163 0.52 0.88 0.07
0.02
N Y
0.69
N
326 840 790 250 694 213 599 859 81 816 248 245 647 647 830 121 364 323 657 840
Acenaphthalene Acrylate, 2,4,5-trichlorophenyl 0.012 Acrylate, 2-chloroethyl 0.03 Acrylic acid 0.1 Acrylic acid, oc-bromo0.25 Acrylonitrile Acryloyl chloride 0.04 Caprolactam, N-vinyl2.8 Carbamate, N-vinyl-, ethyl 1.77 Cinnamate, a-cyano-, methyl 0.044 Crotonaldehyde 0.42 Crotonic acid 0.84 Dioxolane, l,3,4-methylene-2-trichlor 2.98 Dioxolane, 1,3-, 4,4-dimethyl-5-methyl 3.87 Ethylene, chlorotrirluoro0.38 Fumarate, dioctyl 0.02 Imidazole, 1-vinyl0.16 Maleimide, TV-(2-hydroxyethyl)0.002 Methacrylate, 2-bromoethyl 0.02 Methacrylate, 2-hydroxyethyl -0.019
0.12 3.64 0.03 0.18 0.06 0.12 0.04 0.45 0.34 0.32 0.13
0.21
N Y Y
Y 0.12 0.008 0.02 0.07
0.01 0.074 0.002 0.046
0.15 1.7 0.371 -0.001 -0.15 0 0.04 0.01 0.3 0.04 0.96 0.038 2.44 4.841
0.05 0.001 0.01 0.03
Y Y N N
0.04 0.19 0.01
N Y Y
0.133
Y
References page II-290
TABLE 1. cont'd Monomer 1 Pyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, TV-vinylPyrrolidone, a-methylene-TV-methylQuinine Quinoline, 2-vinylQuinoline, 2-vinylQuinoline, 2-vinylQuinoline, 2-vinyl5-Ethyl TV-vinyl-TV-methylthiolcarbamate S-Ethyl TV-vinyl-TV-methylthiolcarbamate S-Vinyl TV, TV-diethylthiolcarbamate 5-Vinyl ,V, TV-diethylthiolcarbamate Silane, 7-methacryloxypropyltrimethoxySilane, 7-methacryloxypropyltrimethoxySilane, 7-methacryloxypropyltrimethoxySilane, methacryloxypropyldimethoxymethylSilane, methacryloxypropyltrimethoxyStilbene Stilbene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2 Methacrylate, ferrocenylmethyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacryloyl chloride Methacryloylacetone Oct-1-ene, 6,6-dimethyl-4,8-dioxaspiro Oxazoline, 2-, 2-isopropenylStyrene Succinimide, TV-vinylTriazine, 2-allyloxy-4,6-dichloroVinyl acetate Vinyl acetate Vinyl acetate Vinyl benzoate Vinyl butyl ether Vinyl chloride Vinyl chloride Vinyl chloride Vinyl cinnamate Vinyl cyclohexyl ether Vinyl cymantrene Vinyl ethylene glycol glycidyl ether Vinyl ethyleneglycol glycidyl ether Vinyl isopropyl ether Vinyl phenyl ether Vinylene carbonate Vinylferrocene Methacrylate, methyl TV-Vinylpyrrolidone Butadiene, 2-chloroIsoprene Styrene Styrene Styrene Vinyl acetate Styrene Vinyl acetate Acrylonitrile Methacrylate, methyl Styrene Imidazole, TV-VinylImidazole, TV-VinylAcenaphthalene Styrene 2-Oxazoline, 2-isopropenyl3-Pyridazone, 2-vinyl3-Pyridazone, 2-vinyl-6-methyl3-Pyridazone, 2-vinyl-6-methyl4,5-benz-33-Pyridazone, 2-vinyl-6-phenyl4-Pentenoate, 3-oxo-, ethyl 4-Pentenoate, 3-oxo-, ethyl 4-Pentenoate, 3-oxo-, ethyl 4-Pentenoate, 3-oxo-, ethyl 4-Pentenoate, 3-oxo-, ethyl 4-Pentenoate, 3-oxo-, ethyl 4-Pentenoate, 3-oxo-, ethyl 4-Pentenoate, 3-oxo-, ethyl 4-Pentenoate, 3-oxo-, ethyl Acenaphthalene Acetylene, phenyl-
rx
±95%
r2
±95%
Conv.
Refs. 325 213 320 321 36 691 599 339 838 862 36 96 826 103 121 36 253 215 40 582 582 200 214 308 369 818 215 214 103 308 641 922 456 456 456 458 197 197 197 197 977 977 977 1095
0.073
0.096
2.57
2.77
- 0.05 -0.032 -0.052 0.01 0.05 0.008 -0.009 0.01 0.057 0.97 0.98 1.06 1.75 3.4 2.507 1.49 0.38 0.34 0.73 0.01 1.91 0.037 1.4 1.4 0.87 4.48 1.08 0.364 0.24 0.37 0.38 0.53 2.09 2.69 -0.11 1.22 0.1 1.89 3.79 2.06 0.868 1.39
0.08 0.068 0.028 0.15
5.62 4.63 4.36 4.04 0.58 5.66 0.552 3.5 17.2 3.67 0.5 0.26 0.19 0.195 0.408 -0.027 0.53 0.55 0.74 1.2 -0.11 0.093 0.06 0.06 0.03 0.253 0.056 0.71 0.577 2.2 2.1 1.88 0.49 0.49 10 0.67 4.45 0.133 0.094 0.788 0.425 0.079
0.3 0.34 0.61 0.61
Y Y N Y Y N
0.4 0.075
Y Y
1.55 0.89
Y N
0.25 1.77 0.057 0.03 0.063
Y N Y Y Y
0.59 0.053
Y Y
2.09 0.007 0.059 0.16 0.058
Y Y Y Y Y
1.72 0.1 0.48 0.025 0.034 0.082 0.048
Y Y Y Y Y Y Y
0.04 0.23 0.17 0.03
Y N N
0.712 0.193 0.309 0.322 0.075 0.073 0.068 0.112 0.035
N N N N N N N N N
0.12
Y
2.27 -0.01 0 0.67 0.53 0.9 0.7 0.51 0.233 0.161 0.215 0.189 0.179 0.164 0.162 0.178 0.217 3.81 0.324
0.004 0.018 0.028 0.42 0.25 2.79 0.21 0.039 0.95
9.39 0.03 9.3 0.1 0.11 0.068 0.14
0.26 1.17 0.34 0.77 0.594 0.309 0.096 1.12 0.04 0.09 0.02
0.069 0.028 0.051 0.05 0.014 0.015 0.015 0.02 0.009 0.02
0.158 5.65 3.92 0.64 0.43 1.2 0.24 1.45 3.29 1.57 1.29 1.4 0.923 0.747 0.635 1.12 0.568 0.33 0.33
1088 725 725 894 897 897 897 897 930 930 930 930 930 930 930 930 930 525 357
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2 Aconitate, trimethyl Acrolein Acrolein Acrolein Acrolein, 2-chloroAcrolein, methylAcrolein, methylAcrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide Acrylamide, 2-chloro-AyV-dimethylAcrylamide, AT,iV-dibutylAcrylamide, N,N-diethy\Acrylamide, JV,N-diethylAcrylamide, AW-diethyl Acrylamide, AW-dimethylAcrylamide, iV,iV-dimethylAcrylamide, MW-dimethylAcrylamide, N-(2-propionamido)Acrylamide, N-methylolAcrylamide, N-methylolAcrylamide, N-octadecylAcrylamide, Af-octylAcrylamido, 1- , -1-deoxy-D-glucitol Acrylamidomethylamino, p-, azobenzene Acrylate, 2,3-dibromopropyl Acrylate, 2,4,5-trichlorophenyl Acrylate, 2,4,6-tribromophenyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethyl Acrylate, 2-chloroethylglucitol Acrylate, 2-cyanoethyl Acrylate, 2-ethylhexyl Acrylate, 2-ethylhexyl Acrylate, 2-nitrobutyl Acrylate, 3,4-epoxyhexahydrobenzyl Acrylate, P-acetoxymethyl-, methyl Acrylate, p-ethoxy-, ethyl Acrylate, a-(4-chlorobenzyl)-, ethyl Acrylate, a-(4-cyanobenzyl)-, ethyl Acrylate, a-(4-methoxybenzyl)-, ethyl Acrylate, a-(hydroxymethyl)-, methyl Acrylate, a-[2,2-bis(carbomethoxy)ethyl]-, methyl Acrylate, a-acetoxy-, ethyl Acrylate, a-benzyl-, ethyl Acrylate, a-benzyl-, methyl Acrylate, oc-bromo-, ethyl Acrylate, oc-butyl-, methyl Acrylate, a-chloro-, ethyl Acrylate, a-chloro-, methyl Acrylate, a-cyano-, methyl Acrylate, a-cyclohexyl-, methyl Acrylate, a-ethyl-, methyl Acrylate, a-ethyloxymethyl-, methyl Acrylate, a-fluoro-, methyl Acrylate, a-hexafluoropropyloxymethyl-, methyl Acrylate, a-hydroxymethyl-, ethyl Acrylate, a-isobutyl-, methyl
rx 1.026 0.257 0.22 0.205 0.02 0.173 0.41 1.17 1.21 1.49 1.13 0.65 1.05 1.29 1.6 1.23 1.36 1.54 1.15 1.37 1.32 1.84 0.03 1.55 2.08 2.715 2.42 0.083 0.42 0.277 0.2 0.55 0.494 0.54 0.49 0.399 0.96 0.94 0.35 0.27 0.34 46.98 0.04 0.06 0.33 0.36 0.58
±95% 0.091 0.017 0.02 0.006 0.05 0.017 0.06 0.04 0.16 0.03 0.065 0.058
0.35 0.1 0.12 0.21 0.05 0.12 0.244 0.08 0.048 0.47 0.097 0.2 0.032 0.3 0.03 0.3 27.03 0.09 0.05 0.3
0.557 0.14 0.57 0.02 0.812 0.08 0.25 0.05 1.615 0.758 0.37 0.66 0.23
0.031 0.17 0.028 0.04 0.043 0.07
0.468 0.974
0.03 0.022
0.01 0.048 0.014 0.17
r2
±95%
Conv.
Refs. 147 291 292 307 806 223 589 295 314 314 314 343 555 917 806 739 739 739 170 315 315 295 596 891 290 806 258 858 643 622 643 140 178 790 806 178 126 463 234 680 1091 194 806 806 806 932 1092
-0.013 0.216 0.02 0.32 0.15 0.833 0.3 0.58 1.32 0.33 0.59 8.97 0.2 -0.036 0.294 0.39 0.34 0.18 0.12 0.49 0.47 0.86 0.48 0.4 0.54 0.258 0.03 8.5 0.16 0.23 0.1 0.1 0.139 0.12 0.14 0.128 0.31 0.26 0.12 1.97 0.19 -0.21 1.03 0.65 0.71 0.34 0.09
0.009 0.036 0.01 0.002 0.07 0.092
Y Y N Y
0.12 0.13 0.14
N N N
0.43
N
0.152 0.058
Y
0.3 0.15 0.2 0.3
N N N N
Y
0.03 0.14 0.119 0.02
N
0.021
Y
0.17 0.083
Y Y
0.09 0.074 0.6
Y N
0.01 0.35
N N
0.44 0.13 0.09 0.24
Y
0.173 0.9 0.175 0.44 0.205 0.32 0.3 0.61 -0.001 0.197 0.24 0.16 0.07
0.01 0.2 0.053 0.08 0.053 0.11
Y
0.546 0.202
0.127 0.042
0.05 0.034 0.014
Y
Y Y N Y Y
0.11 Y Y
244 806 49 806 49 806 74 141 49 49 1047 806 1047 982 49
References page II-290
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2
#*i
Acrylate, a-isopropyl-, methyl 1.872 Acrylate, a-isopropyloxymethyl-, 0.41 methyl Acrylate, a-methoxy-, methyl 1.131 Acrylate, a-phenoxymethyl-, methyl 0.176 Acrylate, a-phenyl-, chloroethyl 0.025 Acrylate, a-phenyl-, methyl 0.06 Acrylate, a-phenyl-, methyl 0.03 Acrylate, a-phenyl-, methyl 0.06 Acrylate, a-phenyl-, methyl 1.176 Acrylate, a-phenyl-, propyl 0.03 Acrylate, a-phenyl-, butyl 0.04 Acrylate, a-propyl-, methyl 0.821 Acrylate, a-propyloxymethyl-, methyl 0.47 Acrylate, a-sec-butyl-, methyl 2.29 Acrylate, a-tetrafluoropropyloxymethyl-, 0.37 methyl Acrylate, a-trifluoroethyloxymethyl-, 0.26 methyl Acrylate, a-trimethylsiloxy-, methyl 0.46 Acrylate, benzyl 0.494 Acrylate, benzyl 0.534 Acrylate, butyl 0.79 Acrylate, butyl 0.79 Acrylate, butyl 0.75 Acrylate, butyl 1.23 Acrylate, butyl 0.44 Acrylate, butyl 0.84 Acrylate, butyl 0.66 Acrylate, butyl 0.82 Acrylate, butyl 0.8 Acrylate, butyl 0.698 Acrylate, butyl 0.698 Acrylate, c/s-(3-cyano-, methyl Acrylate, cyclododecyl 0.47 Acrylate, cyclododecyl 0.54 Acrylate, cyclododecyl 0.461 Acrylate, cyclohexyl 0.913 Acrylate, cyclohexyl 0.885 Actylate, cyclohexyl 0.53 Acrylate, cyclohexyl 0.7 Acrylate, cyclohexyl 0.58 Acrylate, di-, copper 1.74 Acrylate, di-, copper 5.94 Acrylate, di-, nickel 1.83 Acrylate, di-, zinc 1.1 Acrylate, diethylaluminum -0.002 Acrylate, diethylaluminum Acrylate, ethyl 0.699 Acrylate, ethyl 1.01 Acrylate, ethyl 0.79 Acrylate, ethyl 0.8 Acrylate, ethyl 0.8 Acrylate, ethyl 0.787 Acrylate, ethyl 0.787 Acrylate, ferrocenylmethyl 1.87 Acrylate, ferrocenylmethyl 2.3 Acrylate, ferrocenylmethyl 2.5 Acrylate, glycidyl 0.6 Acrylate, glycidyl 0.73 Acrylate, heptafluorobutyl 0.31 Acrylate, isopropyl 0.755 Acrylate, methyl 0.82 Acrylate, methyl 0.192 Acrylate, methyl 0.722
±95%
r2
±95%
Conv.
Refs. 49 1047
0.052
0.036 0.26
0.034
Y
0.078 0.05 0.015
0.513 0.256 0.201 1 0.4 0.45 1.275 0.126 0.107 0.208 0.29 0.004 0.17
0.058 0.102 0.09
Y Y
0.008 0.063 0.055 0.07
Y Y Y Y
0.024
Y
0.015 0.015 0.022 0.029 0.068
0.2 0.05 0.028 0.08 0.11 0.1 0.21 0.03 0.2
1.42 0.2 0.248 0.25 0.34 0.38 -0.106 0.29 0.18 0.19 0.21 0.15 0.164 0.164
1047 0.12 0.041 0.05 0.06 0.05 0.099 0.05 0.03
Y Y
N N N
N 0.14 0.08 0.07 0.107 0.102 0.11 0.12 0.1 0.03 0.05 0.02 0.02 0.016
0.34 0.31 0.301 0.272 0.254 0.16 0.17 0.18 0.56 0.12 0.53 0.9 0.046
0.15 0.08 0.072 0.048 0.141 0.13 0.09 0.07 0.09 0.08 0.06 0.07 0.035
0.072
0.139 0.16 0.19 0.2 0.48 0.152 0.152 -0.016 0.02 0.02 0.17 0.24 0.049 0.195 0.24 0.8 0.168
0.085
N N N N Y Y Y
0.06
Y
0.58 0.013 0.027
N Y Y
0.21 0.067
Y Y
0.17
0.34 0.01 0.024 0.057 0.056
806 1048 488 141 399 488 49 488 488 49 1047 49 1047
1101 178 277 1032 1032 1032 19 20 38 38 463 549 612 632 1034 806 806 806 1061 806 806 806 806 829 829 829 829 652 652 178 463 530 530 542 673 677 293 293 576 114 126 206 178 139 14 151
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2 Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, octadecyl Acrylate, octadecyl Acrylate, octadecyl Acrylate, octadecyl Acrylate, octyl Acrylate, p-(cinnamoylamino)phenyl Acrylate, pentabromophenyl Acrylate, pentachlorophenyl Acrylate, tetrahydrofurfuryl Acrylate, thio-, butyl Acrylate, thio-, ethyl Acrylate, thio-, tert-butyl Acrylate, trifluoro-, methyl Acrylate, trifluoro-, methyl Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylic acid, 2-benzamidoAcrylic acid, Af-acetyl-oc-aminoAcrylic anhydride Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile- 2-chloroAcrylonitrile, 2-fluoroAcrylonitrile, a-chloroAcrylonitrile, a-fluoroAcrylonitrile, oc-hydroxymethylAcrylonitrile, a-methoxyAcryloyl chloride Acryloyloxy, 2-, benzoic acid Adipate, divinyl Allyl acetate Allyl acetate Allyl chloride Allyl chloride Allyl chloride Allyl glycidyl hexahydrophthalate Allyl glycidyl phthalate
rx 0.75 0.75 0.68 0.9 0.65 0.4 0.871 0.777 0.44 0.79 0.44 0.39 1.08 0.16 2.11 0.475 0.439 0.18 0.157 1.4 1.4 0.25 1.1 0.15 0.22 0.253 0.25 0.25 0.15 0.13 0.91 0.16 0.33 0.29 0.4 0.36 0.39 0.37 0.37 0.4 0.3 0.33 0.33 0.36 0.46 0.41 0.43 0.55 0.35 0.014 0.13 0.44 0.205 0.534 0.1 0.06 20.36 62.8 90 35.55 36.8 34.3 34.8
±95%
0.022 0.018
0.11
0.186 0.14 0.038 0.034
0.069
0.01 0.04
0.004 0.04 0.029 0.069 0.05 0.02 0.26 82.7 15.82
r2 0.18 0.18 0.14 0.07 0.3 0.16 0.148 0.37 0.18 0.31 0.18 0.01 0.35 0.1 0.9 0.489 0.421 0.291 0.368 0 0 0.05 0.08 0.25 0.35 0.136 0.15 0.45 0.25 0.78 0.44 0.1 0 0.02 0.05 0.03 0.06 0.05 0.07 0.04 0.17 0.17 0.15 0.17 0.07 0.06 0.03 0.06 0.01 0.087 0.03 0.03 0.528 0.312 0.02 0.64 0.011 0.01 0 0.05 0.03 0.06 0.14
±95%
0.026 0.12
Conv.
Y Y
0.53
0.196 0.17 0.075 0.055
0.029
Y
0.004
N
0.06
N
0.04
Y Y
0.02 0.086 0.054 0.02 0.02 0.011 0.05 0.16
Y N N Y N Y Y
Refs. 393 397 463 495 496 496 865 290 290 290 290 806 685 643 900 806 806 806 806 595 598 312 312 397 414 47 490 542 561 1019 661 219 140 198 269 396 403 417 543 60 727 727 727 727 727 727 727 727 812 884 884 806 850 981 806 220 651 815 1053 470 10 204 438 782 782
References page II - 290
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2 Allyl trichloroacetate Azlactone, 2-vinyl-4,4-dimethylAzobenzene, 4-(acrylamidomethylamino)Benzimidazole, vinylmercaptoBenzothiazole, vinylmercaptoBenzothiazole, vinylmercaptoBenzothiazolone, N- [(methacroyloxy )methyl] Benzoxazole, vinylmercaptoBicyclo[2,2,l]hept-2-ene5,6-dicarboximide, iV-benzyl Bicyclo[2,2,l]hept-2-ene5,6-dicarboximide, N-benzyl Borazine, (3-vinyl Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene Butadiene, 1,4-dicarboxylate-, diethyl Butadiene, 1-chloroButadiene, 1-phthalimidoButadiene, 1-succimmidoButadiene, 2,3-dichloroButadiene, 2,3-dichloroButadiene, 2,3-dimethylButadiene, 2-chloroButadiene, 2-chloroButadiene, 2-fluoroButadiene, 2-fluoroButadiene, 2-trimethylsilyloxyButadiene-1-carboxylate, 5(-)-a-phenethyl Butadiene-1-carboxylate, ethyl Butadiene- 1-carboxylic acid Butadiene-1-carboxylic acid Butenoate, 3-phenyl-3-, methyl Bntyrolactone, a-methyleneCaprolactam, N-vinylCarbamate, N, N-diethyl-, vinyl Carbazole, N-methyl-3-vinylCarbazole, JV-vinylCarbazole, Af-vinylCarbazole, N-vinylCinnamate, 2-chloroethyl Cinnamate, a-cyano-, 2-ethylhexyl Cinnamate, oc-cyano-, benzyl Cinnamate, a-cyano-, butyl Cinnamate, a-cyano-, cyclohexyl Cinnamate, a-cyano-, ethyl Cinnamate, a-cyano-, hexyl Cinnamate, a-cyano-, methyl Cinnamate, benzyl Cinnamate, butyl Cinnamate, ethyl Cinnamate, ethyl
r\
±95%
r2
±95%
Conv.
Refs.
Y
913 1011 880
2.32 0.175 0.083
0.15 0.054 8.5
0.81 0.237
0.02 0.129
6.51 2.171 3.02 0.35
0.51 0.07 0.14 0.02
0.56 0.349 0.5 3.1
0.41 0.087 0.095 0.01
Y Y Y
764 764 764 960
0.19
0.24 0
0.12
Y
764 994
2.87 18.2 89.2 4.53 0.84 0.37 0.38
0 0.62 0.4 0.25
0.001 1.44 1.55 1.37
994 0.016 0.56 0.14
Y N Y
0.58 0.44 0.6 0.44 0.38 0.68 0.82 0.83 0.64 0.09 0.27 0.299 0.286 0.25 0.05 0.534 0.05 0.025 0.214 0.22 0.64 0.45
0.13
1.35 1.59 1.8 1.4 1.4 0.5 1.38 1.83 1.38 0.55 1.44 1.56 1.68 8.65 10.6 1.048 7.84 5.98 2.1 1.24 1.2 6.81
0.12 0.15 0.08 1.97 0.14 0.2 29.56 0.735 6 5.93 5.72 1.394 0.58 0.4 0.47 0.37
0.364 0.01 0.01 3.59 0.067 1.34 1.05 0.4 0.068 0.004 0.03 0.03 0.04
0.56 0.52 5.55 -0.532 0.85 1.02 -0.08 1.404 -0.02 0.026 0.032 0.01 -0.06 -0.16 - 0.09 - 0.24
0.512 0.06 0.01 0.18 0.146 0.06 0.034 0.057 0.11 0.01 0.17 0.08 0.22
0.39 0.4 1.33 1.757 1.52 1.566
0.04 0.06 0.12 0.082 0.31 0.035
-0.17 -0.21 0.14 0.04 -0.076 0.082
0.26 0.35 0.13 0.15 0.054 0.045
0.13 0.21 0.014 0.27 0.049 0.018 0.035 0.047 0.03 0.15
0.11 0.41
N Y
0.1 3.1 0.63 0.16
Y Y Y Y
0.5 0.12 0.61
Y Y Y Y Y Y
1.68
Y
0.066
Y N Y N Y Y Y N N N N Y N N Y Y Y Y
1018 140 159 173 21 418 428 473 486 486 491 56 83 83 327 695 163 163 587 61 173 61 8 174 174 993 748 791 791 799 1008 663 916 197 806 11 13 98 488 282 282 282 282 134 282 282 488 488 200 488
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2 Cinnamate, methyl Cinnamate, methyl Cinnamate, p-chloro-, methyl Cinnamate, /?-methyl-, methyl Cinnamate, phenyl Cinnamate, tert-buty\ Cinnamide, AW-diethylCinnamide, p-chloro-, N, N-diethylCinnamide, /?-methyl-, 7V,N-diethylCinnamonitrile Cinnamonitrile, a-cyanoCitraconate, di-^c-butyl Citraconate, dibenzyl Citraconate, dibutyl Citraconate, dicyclohexyl Citraconate, diethyl Citraconate, diisobutyl Citraconate, diisopropyl Citraconate, dimethyl Citraconate, dipropyl Citraconic acid Citraconic anhydride Citraconimide, P-iso-, A^-(4-acetylphenyl)Citraconimide, p-iso-, N-(4-chlorophenyl)Citraconimide, p-iso-, Ar-(4-ethoxycarbonylphenyl)Citraconimide, p-iso-, Af(4-methoxyphenyl)Citraconimide, P-iso-, N-(p-to\y\)Citraconimide, P-iso-, N-phenylCitraconimide, N-(4-acetoxyphenyl)Citraconimide, JV-(4-chlorophenyl)Citraconimide, Af-(4-ethoxycarbonylphenyl)Citraconimide, AH4-methoxyphenyl)Citraconimide, N-allyl Citraconimide, N-benzylCitraconimide, N-butylCitraconimide, Af-ethylCitraconimide, N-hexylCitraconimide, N-isobutylCitraconimide, N-isopropylCitraconimide, N-methylCitraconimide, N-methylCitraconimide, N-phenylCitraconimide, N-propylCitraconimide, N-tert-buty\Citraconimide, 7V-tolylCitraconimide, a-iso-, A^-(4-acetylphenyl)Citraconimide, a-iso-, Af-(4-chlorophenyl)Citraconimide, a-iso-, Af-(4-ethoxycarbonylphenyl)Citraconimide, a-iso-, N-(4-methoxyphenyl)Citraconimide, a-iso-, N-(p-toly\)Citraconimide, a-iso-, Af-phenylCrotonaldehyde Crotonaldehyde Crotonaldehyde Crotonate, a-acetyl-, methyl Crotonate, a-bromo-, ethyl
rx 1.799 1.27 2.24 2.84 1.66 1.692 4.17 2.99 4.95 2.549 2 1.55 2.74 1.88 2.48 1.8 1.62 1.58 2.19 1.36 0.16 0.42
±95% 0.073
0.12 0.087
0.092
0.15
r2 0.04 0.02 0.04 0 0.029 0.1 0.01 0.01 0.01 -0.008 0.13 0.047 0.054 0.03 0.029 0.03 0.076 0.049 0.027 0 0.021 0
±95%
Conv.
Refs.
0.13
Y
0.055 0.12
Y Y
0.021
Y Y
0.058
Y
488 653 653 653 488 488 737 737 737 134 134 841 841 841 841 841 841 841 841 841 1021 47 608
0.28
0
608
0.3
0
608
0.27
0
608
0.4 0.39 0.151 0.181 0.148
0 0 0.015 0.075 0.004
608 608 728 728 728
0.63 0.142 0.19 0.169 0.231 0.316 0.326 0.244 0.15 0.14 0.175 0.196 0.465 0.31 0.81
0.054 0.057 0.018 0.19 0.087 0.028 0.044 0.086 0.094 0.055
0.016 0.062 0.039 0.13
0.04 0.004 -0.066 0.03 -0.002 -0.03 0.07 -0.014 0.24 0.24 -0.001 -0.014 0.045 -0.02 0
0.086 0.093 0.033
Y Y Y
0.11
Y
0.082 0.045 0.05 0.11 0.14 0.063
Y Y Y Y Y Y
0.023 0.087 0.05 0.18
Y Y Y Y
728 959 714 714 714 714 714 714 460 506 728 714 714 728 608
1.03
0
608
0.96
0
608
0.39
0
608
0 0 0.03 0.07 0.12 0 0
608 608 428 428 428 785 785
1.69 1.76 14.7 14.7 14.7 2.7 4.42
References page II - 290
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2
ri
Crotonate, oc-carboethoxy-, ethyl 8.24 Crotonate, oc-chloro-, ethyl 5.13 Crotonate, a-cyano-, ethyl 0.26 Crotonate, oc-methoxy-, methyl 18.4 Crotonate, a-methyl-, methyl 30.7 Crotonate, ethyl 27 Crotonate, methyl 9.68 Crotonic acid 20 Crotononitrile 23.29 Crotononitrile 23.8 Crotononitrile, a-phenyl0.43 Cyclobutane, 1,2-dimethylene0.26 Cyclobutane, 1,2-dimethylene0.28 Cyclopentene, 4-, -1,3-dione Diallyl melamine 36.96 Diallyl phthalate 36.41 Diallyl phthalate 25.59 Diallyl phthalate 23.67 Diallyl phthalate 18.8 Diallyl phthalate 27.5 Diallyl phthalate 16.9 Diallyl phthalate 23.8 Diallyl phthalate 15.1 Dihydroxydiphenylsulfone diallyl ether 0.975 Dithiane, 2-methylene-l,30.03 Divinylbenzene, m0.58 Divinylbenzene, p 0.26 Ethylene 14.88 Ethylene, 1,1 -diphenyl0.34 Ethylene, 1,1-diphenyl0.87 Ethylene, 1-diphenyl0.33 Ethylene, chlorotrifluoro4.38 Ethylene, dichloro-, cis3.1 Ethylene, dichloro-, cis63.1 Ethylene, dichloro-, cis21.4 Ethylene, dichloro-, cis161.3 Ethylene, dichloro-, cis24.75 Ethylene, p-vinyl-1,1 -diphenyl0.46 Ethylene, tetrachloroEthylene, tetrachloro200 Ethylene, tetrachloroEthylene, tetrachloro187 Ethylene, tetrachloro185 Ethylene, tetrafluoro5.2 Ethylene, trichloro17.1 Ethylene, trichloro16.5 Ethylene, trichloro12.1 Ethylene, trichloro12.7 Ethylene, trichloro16 Formaldehyde,-S-vinyl-O7.75 ethylthioacetal Fumarate, allyl methyl 0.25 Fumarate, bis(2-butyl) 0.51 Fumarate, bis(3-chloro-2-butyl) 0.26 Fumarate, di-(2-chloroethyl) 0.18 Fumarate, di-(2-cyanoethyl) 0.07 Fumarate, di-(2-methoxyethyl) 0.35 Fumarate, di-(2-phenylethyl) 0.27 Fumarate, di-^obutyl 0.55 Fumarate, di-tert-amyl 0.69 Fumarate, di-terf-butyl 0.57 Fumarate, dibenzyl 0.32 Fumarate, dibutyl 0.35 Fumarate, dicyclohexyl 0.49 Fumarate, dicyclopentyl 0.3
±95%
1.86 1.7
0.05 4.02 1.23 2.19 1.2
0.015 0.15 0.25 0.01 0.02 0.99 4.9 30.3 2.64
r2 0 0 0.02 0.04 0.02 0 -0.27 0 -0.012 0 0 3.6 3.6 -0.32 0.041 0.026 0.038 0.08 0.09 0.1 0.1 0.13 0.92 3.35 0.58 1.18 0.05 -0.02 1.15 0.01 -0.1 -3.1 -2.2 -0.28 -0.02 0.067 1.31
±95%
Conv.
0.22
Y
0.06
Y
0.16 0.2 0.038 0.071 0.04
Y Y Y Y Y
0.16 0.04 0.17
N N
0.01
N
0.02 0.21
N Y Y Y Y Y Y
0.12 0.062 0.053
Y Y
11 0.68 0.01 0.04 0.04
0 0 0.01 0 0 0 0 -0.006 0.32 0.03 0 - 0.06 0 0.09 0.03 0 0.04 0.08 0.04 0 0.04 0.06 0.06
0.37 0.24
Y Y
0.02 0.01 0.03
N N N
Refs. 785 785 785 785 785 785 112 402 112 785 785 854 885 263 201 152 152 152 152 152 152 152 152 1016 1031 262 262 615 281 901 189 236 137 137 40 9 9 742 204 204 40 40 59 567 40 40 40 40 59 273 713 249 249 1038 1038 1038 1038 1038 1038 1038 1038 1038 1038 1038
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2 Fumarate, diethyl Fumarate, diethyl Fumarate, diethyl Fumarate, diethyl Fumarate, diethyl Fumarate, diethyl Fumarate, diethyl Fumarate, diisobutyl Fumarate, diisopropyl Fumarate, dimethyl Fumarate, dipropyl Fumarate, isopropyl butyl Fumarate, isopropyl ethyl Fumarate, isopropyl isobutyl Fumarate, isopropyl methyl Fumarate, isopropyl sec-butyl Fumarate, methyl butyl Fumarate, methyl ethyl Fumarate, methyl isobutyl Fumarate, methyl isopropyl Fumarate, methyl propyl Fumarate, methyl sec-butyl Fumarate, methyl tert-amyl Fumarate, methyl tert-butyl Fumarate, mono-2-butyl Fumarate, tert-butyl 2-ethylhexyl Fumarate, tert-butyl 4-methyl-2-pentyl Fumarate, tert-butyl ethyl Fumarate, tert-butyl isoamyl Fumarate, tert-butyl methyl Fumarate, tert-butyl sec-butyl Fumaronitrile Fumaronitrile Fumaronitrile Fumaronitrile Fumaronitrile Fumaryl chloride Furan, 2,3-dihydroHexatriene, tetrachloroHexene, 1-, 3,4-dioic anhydride Hexene, 2-, 3,4-dioic anhydride Hexene, 3-, 3,4-dioic anhydride Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene, 5-, 2,4-dione Hexene-1,5-dicarboxylate, dimethyl Imidazole, 1-vinylImidazole, l-vinyl-2-methylImidazole, l-vinyl-2-methylIsoprene Isoprene Isoprene Isoprene Isoprene Isoprene, 3-acetoxyIsopropenyl methyl ketone
rt 0.29 6.3 0.394 0.3 0.31 0.36 0.29 0.37 0.4 0.39 0.32 0.42 0.3 0.46 0.3 0.54 0.36 0.32 0.32 0.3 0.28 0.45 0.53 0.45 0.33 0.54 0.57 0.25 0.45 0.45 0.55 0.202 0.294 0.3
±95%
0.26 0.06 0.02
0.03
0.058 0.044
r2 0.02 0.081 0.11 0.07 O 0.1 0.02 0.05 0.055 0.03 0.02 0.01 0.01 0.01 0.16 0.02 0.02 0.02 0.03 0.16 0.05 0.02 0.06 0.03 - 0.04 0.01 0.01 0.04 0.06 0.03 0.07 -0.016 0.006 0
±95%
Conv.
0.005 0.022
Y Y
0.01
N
0.03
N
0.021
Y Y Y
0.031
Y Y 20 0.123 8.57 3.63 17.17 0.031 0.049 0.066 0.07 0.171 0.179 0.173 0.121 0.24 0.014 0.044 0.028 0.678 9.94 8.87 8.97 0.513 0.476 0.44 0.42 0.48 0.34 0.44
0.0428 8.4 5.6 436
0.031 0.24 0.62 0.02 0.018
0 0.85 -0.052 -0.08 -0.54 1.22 1.38 1.52 1.73 1.91 1.91 2.07 2.46 2.69 2.93 3.19 4.11 0.196 0.071 0.09 0.07 1.922 1.957 1.98 2.02 1.3 4.47 0.29
0.22 1 1,17 5.83
Y Y Y Y
0.043 0.029 0.064
Y Y Y
0.016 0.011
Y Y
Refs. 1038 139 139 139 249 562 640 1038 1038 1038 1038 1056 1056 1056 1056 1056 1056 1056 1056 1056 1056 1056 1056 1056 249 1056 1056 1056 1056 1056 1056 137 191 199 478 77 91 806 4 933 933 933 931 931 931 931 931 931 931 931 931 931 931 931 828 364 364 479 366 366 544 544 83 770 542
References page II - 290
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2 Isopropenyl methyl ketone Isopropenyl, 3-(l-cyclohexenyl), acetate Isopropenylacetophenone, pIsopropenylisocyanate Isopropenylisocyanate Isopropylidene, 2,3:4,5-di-O-, -1-vinylbenzylItaconamate, A^-(4-carboethoxyphenyl)-, butyl Itaconamate, 7V-(4-carboethoxyphenyl)-, ethyl Itaconamate, N-(4-carboethoxyphenyl)-, methyl Itaconamate, Af-(4-carboethoxyphenyl)-, propyl Itaconamate, N-(4-chlorophenyl)-, ethyl Itaconamate, A^-(4-chlorophenyl)-, methyl Itaconamate, Af-(-chlorophenyl)-, propyl Itaconamate, N-(4-methoxyphenyl-, butyl Itaconamate, N-(4-methoxyphenyl)-, ethyl Itaconamate, A^-(4-methoxyphenyl)-, methyl Itaconamate, Af-(4-methoxyphenyl)-, propyl Itaconamate, N-(4-methylphenyl)-, butyl Itaconamate, A^-(4-methlyphenyl)-, ethyl Itaconamate, N-(4-methylphenyl)-, methyl Itaconamate, A^-(4-methylphenyl)-, propyl Itaconamate, N-phenyl, methyl Itaconamate, N-phenyl-, butyl Itaconamate, N-phenyl, ethyl Itaconamate, N-phenyl-, methyl Itaconamate, A^-phenyl-, propyl Itaconate, di-2[-2(2-methoxyethoxy)ethoxy]ethyl Itaconate, diamyl Itaconate, dibutyl Itaconate, diethyl Itaconate, dimenthyl Itaconate, dimethyl Itaconate, dimethyl Itaconate, dimethyl Itaconate, dioctyl Itaconate, dipropyl Itaconate, ethyl hexafluoroisopropyl Itaconate, glycidyl methyl Itaconate, mono-methyl Itaconate, mono-methyl Itaconate, mono-methyl Itaconate, mono-methyl Itaconic acid Itaconic acid Itaconic anhydride Itaconic anhydride Itaconic anhydride Itaconimide, A^-(2-chloroethyl)Itaconimide, N-(4-acetoxyphenyl)Itaconimide, N-(4-chlorophenyl)-
rY 0.32 1.59 0.3 8.12 6.84 0.14
±95%
0.18 0.18 0.055
r2 0.66 0.56 0.84 0.07 0.122 3.26
±95%
Conv.
Refs.
0.59
Y
0.047 1.12
Y Y
542 770 266 434 99 772
0.2
0.61
678
0.23
0.2
678
0.15
0.58
678
0.26
0.4
678
0.35 0.38
0.16 0.18
678 678
0.39 0.12
0.31 0.69
678 678
0.33
0.34
678
0.26
0.41
678
0.38
0.4
678
0.19
0.31
678
0.38
0.26
678
0.3
0.16
678
0.54
0.19
678
0.39 0.12 0.45 0.31 0.5 0.53
0.022
0.18 0.49 0.21 0.52 0.18 0.2
0.015
678 678 678 1059 678 1098
0.36 0.42 0.23 0.502
0.05 0.06 0.11 0.188
0.5 0.34 0.34 0.483
0.09 0.05 0.12 0.364
N N N Y N
0.12 0.06 0.035 0.079 0.052 0.15 0.11 0.086
N N N
0.67 0.09 0.09 0.05 0.092 0.21 0.18
Y Y Y Y Y Y Y
0.48 0.5 0.33 0.16 0.435 0.376 0.029 0.34 0.52 0.404 0.34 0.26 0.004 0.086 0.003 0.069 0.35 0.159
0.16 0.07 0.025 0.036 0.039 0.077 0.085 0.06 0.08 0.01 0.015 0.005 0.045 0.12 0.084
0.14 0.06 0.14 0.28 0.039 0.041 0.111 0.33 0.33 0.218 0 0.12 0.405 0.456 0.785 0.162 0.21 0.2
Y Y Y Y
39 39 39 975 39 398 586 39 39 1103 806 656 656 656 656 420 76 365 62 62 642 729 729
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2
rx
Itaconimide, 0.232 iV-(4-ethoxycarbonylphenyl) Itaconimide, Af-(/?-chlorophenyl)0.15 Itaconimide, N-(p-tolyl)0.16 Itaconimide, N-benzyl0.056 Itaconimide, Af-butyl0.22 Itaconimide, AT-ethyl 0.232 Itaconimide, AMsobutyl0.44 Itaconimide, Af-Isopropyl0.308 Itaconimide, Af-methyl0.153 Itaconimide, Af-naphthyl0.08 Itaconimide, Af-phenyl0.116 Itaconimide, N-phenyl0.05 Itaconimide, AT-phenyl0.05 Itaconimide, JV-propyl0.28 Itaconimide, N-tolyl0.134 Maleamic acid, 0.55 A^3-dimethylamino-6-methyl Maleate, allyl methyl 8.29 Maleate, butyl stannyl, allyl 0.1 Maleate, chloro-, diethyl 2.07 Maleate, dibutyl tin 2.08 Maleate, diethyl 6.59 Maleate, diethyl Maleate, diethyl 8 Maleate, diethyl 6.07 Maleate, diethyl 6.592 Maleate, dimethyl 10.65 Maleate, dimethyl 0.083 Maleate, monoallyl 0.14 Maleic anhydride 0.097 Maleic anhydride 0.04 Maleic anhydride 0.02 Maleic anhydride 0 Maleic anhydride 0.02 Maleic anhydride 0.02 Maleic anhydride 0.04 Maleic anhydride 0.04 Maleic anhydride 0.04 Maleic anhydride 0.05 Maleic anhydride 0.02 Maleic anhydride 0.04 Maleic anhydride 0.04 Maleic anhydride Maleic anhydride, a-chloro0.07 Maleimide 0.057 Maleimide, A^-(2,6-diethylphenyl)0.19 Maleimide, A^-(2,6-dimethylphenyl)0.14 Maleimide, N-(2-chlorophenyl)0.011 Maleimide, 7V-(2-chlorophenyl)0.038 Maleimide, A^-(2-chlorophenyl)0.013 Maleimide, AH2-chlorophenyl)0.038 Maleimide, N-(2-hydroxyethyl)0.046 Maleimide, A^-(3-dimethylaminophenyl)- 0.03 Maleimide, AK4-bromophenyl)0.02 Maleimide, A^-(4-carboxyethylphenyl)0.059 a-chloroMaleimide, A^-(4-chlorophenyl)0.149 oc-chloroMaleimide, N-(4-hydroxyphenyl)-0.059 Maleimide, A^-(4-methoxyphenyl)0.112 a-chloroMaleimide, 7V-(4-methylphenyl)0.107 oc-chloroMaleimide, 7V-(p-chloroethyl)-a-chloro- 0.29
±95% 0.032
r2 0.112
0.248 0.12 0.031 0.03
0.14 0.24 0.2 -0.019 0.172 -0.03 0.045 0.12 0.35 0.109 0.08 0.998 0.04 0.219 -0.19
0.14 0.02 0.14 0.118 0.46
0.02 0.06 -0.043 0.194 -0.013
0.048 0.03 0.029 0.11 0.043 0.069 0.043
±95% 0.054
Conv. Y
0.11 0.04 0.06 0.11 0.064 0.12
Y Y Y Y Y Y
0.082
Y
0.123 0.18 0.079 0.03
N Y Y N
0.01 0.03 0.021 0.121 0.022
N N Y Y Y Y
0.01
N
0.12 0.058 0.02 0.008 0.13 0.03 0.01
Y Y N N Y N N
Refs. 729 740 740 642 642 642 642 642 642 740 729 740 978 642 729 679
0.036
Y
0.002 0.003 0.005 0.003 0.027
Y Y Y Y Y
0.007 0.041
Y Y
713 811 14 987 139 14 640 874 888 137 317 811 105 12 17 241 384 397 483 506 522 522 522 522 522 923 845 251 992 992 853 853 910 910 323 747 1030 973
0.019
0.038
Y
973
0.041 0.031
0.13 0.049
0.1 0.061
Y Y
323 973
0.048
0.019
0.078
Y
973
0.05
0
0.06
0.07 2.81 0.015 0.01 0.002 0.12 0.003 0.01
0.07 0.01 0.001 0.15 0.105 0.07 0.001 0 0.003 0.02 0 0 0.02 0.01 0.001 0.005 0.01 0.02 0.05
N
0.006 0.021
0 0.088 0.02 0.08 0.013 0.028 0.01 0.006 0.011 0.19 0.018 0.022
0.048
0.012 0.004 0.006 0.012 0.028 0.017
974
References page II - 290
TABLE 1. Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
cont'd Monomer 2 Maleimide, TV-[TV'-(a-methylbenzyl)aminocarbonylpentyl] Maleimide, AKN'-(a-methylbenzyl)aminocarbonylundecy 1] Maleimide, TV-allyl Maleimide, iV-benzylMaleimide, TV-benzyl-a-chloroMaleimide, TV-butylMaleimide, TV-butylMaleimide, TV-cyclohexylMaleimide, TV-cyclohexylMaleimide, TV-ethyl-a-chloroMaleimide, TV-hexylMaleimide, iV-hydroxymethylMaleimide, TV-methyl-a-chloroMaleimide, TV-phenylMaleimide, TV-phenylMaleimide, TV-phenylMaleimide, TV-phenyl-a-chloroMaleimide-TV,TV-dimethylaniline, 4-(2-chlorophenyl)Mesaconate, di-sec-butyldithiol Mesaconate, diamyl Mesaconate, dibenzyl Mesaconate, dibenzyldithiol Mesaconate, dibutyl Mesaconate, dibutyldithiol Mesaconate, dicyclohexyl Mesaconate, diethyl Mesaconate, diethyldithiol Mesaconate, dihexyl Mesaconate, diisoamyl Mesaconate, diisobutyl Mesaconate, diisobutyldithiol Mesaconate, diisopropyl Mesaconate, diisopropyldithiol Mesaconate, dimethyl Mesaconate, dimethyldithiol Mesaconate, dioctyl Mesaconate, diphenyl Mesaconate, diphenyldithiol Mesaconate, dipropyl Mesaconate, dipropyldithiol Mesaconic acid Methacrylamide Methacrylamide Methacrylamide, 1-deoxy-D-glucitol Methacrylamide, TV-phenylMethacrylate, 2,2,6,6,-tetramethyl4-piperidinyl Methacrylate, 2,3-epithiopropyl Methacrylate, 2-(sulfonic acid)ethyl Methacrylate, 2-acetoxyethyl Methacrylate, 2-bromoethyl Methacrylate, 2-chloro2,3,3,3-fluoropropyl Methacrylate, 2-chloroethyl Methacrylate, 2-chloroethyl Methacrylate, 2-chloroethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxyethyl
rx 0.198
0.056 0.058 0.42
±95% 0.143
r2 0.258
0.021 0.06
0.035 0.013 0
0.017 0.05 0.069 0.053 0.04
0.06 0.1 0.162 0 0.09 0.06 0
±95% 0.25
0.031 0.06
Conv.
Refs.
Y
1099
Y
1099
Y Y
0.02 0.102 -0.01 0.9 -0.041 -0.035 0.63 0.016 0.07 0.087 0.05 0.45 1.27 0.73 0.28 1.28 0.41 1.25 1.24 0.4 1.51 1.34 1.29 0.41 1.31 0.44 0.98 0.35 1.23 0.45 0.16 1.22 0.39 1.6 1.4 1.42 2.09 1.24 0.63 0.41 0.37 0.44 0.32 0.121 0.35 0.345 0.42 0.44 0.332 0.57 0.5 0.59 0.53
0.004 0.04
0.13 0.17 0.06
0.02 0.068 0.046 0.048 0.02 0.006
0.044 0.01 - 0.002 0.04 0.02 0.02 0.08 0.06 0.05 0.05 0.1 0.06 0.03 0.1 0.07 0.1 0.03 0.04 0.05 0.04 0.07 0.01 0.07 0.15 0.05 0.06 0 0.48 1.24 0.005 0.88 0.3 0.28 0.6 0.58 0.41 0.243 0.341 0.34 0.23 0.54 0.856 0.65 1.65 0.53 0.59
0.054 0.04 0.16 0.11 0.03
Y Y Y
0.017
N Y
0.073
Y
0.2 0.38
N N
0.17
N
0.04
N
0.15
N
0.075 0.08
Y Y
0.03 0.018
N Y
1003 348 974 115 50 1100 348 974 348 323 974 1026 328 992 973 747 624 658 658 624 658 624 658 658 624 658 658 658 624 658 624 658 624 658 658 624 658 624 1021 316 316 258 352 664 787 564 346 657 927 179 179 382 346 350 463 878 878 903
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2
rx
Methacrylate, 2-hydroxyethyl 0.5 Methacrylate, 2-methoxyethyl 0.46 Methacrylate, 2-naphthyl-, methyl 0.786 Methacrylate, 2-naphthyl-, methyl 0.486 Methacrylate, 2-naphthyl-, methyl 0.61 Methacrylate, 2-naphthyl-, methyl 0.384 Methacrylate, 2-phenethyl 0.56 Methacrylate, 3,5-dimethyladamantyl 0.89 Methacrylate, 5-oxo-pyrrolidinylmethyl 0.342 Methacrylate, A^-methyl-7V-phenyl0.44 2-aminoethyl Methacrylate, a-naphthoyloxy-, ethyl 0.216 Methacrylate, acetonyl 0.285 Methacrylate, amyl 0.52 Methacrylate, benzyl 0.463 Methacrylate, benzyl 0.435 Methacrylate, benzyl 0.45 Methacrylate, benzyl 0.48 Methacrylate, benzyl 0.8 Methacrylate, bornyl 0.45 Methacrylate, butyl 0.56 Methacrylate, butyl -0.05 Methacrylate, butyl 0.52 Methacrylate, butyl 0.63 Methacrylate, butyl 0.54 Methacrylate, butyl 0.74 Methacrylate, chloromethyl 0.208 Methacrylate, cyanomethyl 0.144 Methacrylate, cyclohexyl 0.586 Methacrylate, di-ethylene glycol 0.39 Methacrylate, dodecyl 0.528 Methacrylate, ethyl 0.55 Methacrylate, ethyl 0.67 Methacrylate, ethyl 0.65 Methacrylate, ethyl 0.55 Methacrylate, ferrocenylmethyl 3.63 Methacrylate, ferrocenylmethyl 3.6 Methacrylate, glycidyl 0.54 Methacrylate, glycidyl 0.278 Methacrylate, glycidyl 0.47 Methacrylate, glycidyl 0.44 Methacrylate, glycidyl 0.45 Methacrylate, glycidyl 0.31 Methacrylate, glycidyl 0.11 Methacrylate, glycidyl 0.435 Methacrylate, hexyl 0.58 Methacrylate, isobornyl 0.61 Methacrylate, isobutyl 0.509 Methacrylate, isobutyl 0.56 Methacrylate, isobutyl 0.55 Methacrylate, isopropyl 0.5 Methacrylate, isopropyl 0.47 Methacrylate, m-chlorophenyl 0.375 Methacrylate, ra-nitrophenyl 0.44 Methacrylate, methoxymethyl 0.395 Methacrylate, methyl 0.5 Methacrylate, methyl 0.52 Methacrylate, methyl 0.52 Methacrylate, methyl 0.48 Methacrylate, methyl 0.52 Methacrylate, methyl 0.49 Methacrylate, methyl 0.45 Methacrylate, methyl 0.58 Methacrylate, methyl 0.44 Methacrylate, methyl 0.396
±95%
0.16 0.117 0.195 0.225 0.025 0.14 0.013 0.04 0.043 0.041 0.11 0.041 0.026
0.32 0.12 1.09
0.006 0.011 0.088 0.15 0.05 0.062
0.14 0.07 0.086 0.02 0.04 0.045 0.033 0.07 0.45 0.014
0.05 0.16 0.014
0.048
r2 1.65 0.48 0.113 0.321 0.576 0.216 0.534 0.63 0.411 0.58 0.242 0.505 0.46 0.658 0.467 0.51 0.42 0.3 0.5 0.31 2.52 0.47 0.64 0.64 0.59 0.298 0.28 0.57 0.67 0.3 0.36 0.26 0.29 0.33 -0.019 0.01 0.16 0.539 0.46 0.54 0.55 0.74 0.73 0.514 0.44 0.24 0.271 0.58 0.4 0.42 0.74 0.209 0.185 0.586 0.5 0.46 0.46 0.42 0.45 0.46 0.47 0.48 0.5 0.22
±95%
Conv.
0.126 0.098 0.477 0.422 0.099 0.21 0.033 0.02
Y Y Y Y Y N Y N
0.018 0.115 0.2 0.084 0.048
Y Y Y Y
0.38 0.2 1.1
Y N
0.03 0.041 0.28 0.08 0.1 0.12
Y Y Y N Y Y
0.022
Y
0.03 0.04 0.08
N Y N
0.1 0.284 0.098 0.13 0.3 0.036
N N Y Y
0.013 0.054 0.069
Y Y Y
0.13
Y
Y
Refs. 903 918 924 924 924 924 540 335 633 651 1102 958 179 111 179 487 540 602 806 179 43 463 530 530 835 712 625 179 262 179 179 530 530 570 293 576 114 217 225 225 463 849 893 999 179 806 179 463 487 463 541 177 177 821 138 139 179 20 21 21 21 21 21 241
References page II - 290
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2 Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methylthiomethyl Methacrylate, octyl Methacrylate, octyl Methacrylate, /?-(cinnamoylamino)phenyl Methacrylate,/7-carbomethoxyphenyl Methacrylate, /?-chlorophenyl Methacrylate,/7-methoxyphenyl Methacrylate, p-methylphenyl Methacrylate, p-nitrophenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, phenyl Methacrylate, propyl Methacrylate, sulfolanyl Methacrylate, tert-buty\ Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic acid Methacrylic anhydride Methacrylic anhydride Methacrylonitrile Methacrylonitrile Methacrylonitrile Methacrylonitrile
T1 0.42 0.49 0.564 0.585 0.44 0.47 0.54 0.52 0.38 0.52 0.54 0.44 0.52 0.5 0.56 0.53 0.485 0.48 0.371 0.62 0.52 0.5 0.55 0.55 0.41 0.472 0.497 0.432 0.57 0.275 0.338 0.65 0.56 0.62 0.482 0.34 0.499 0.49 0.223 0.246 0.247 0.26 0.565 0.2 0.545 0.21 0.22 0.2 0.15 0.2 0.38 0.124 0.17 0.041 0.067 0.627 0.55 0.221 0.13 0.1 0.37 0.38 0.43 0.34
±95%
0.14 0.047 0.007 0.08
0.052 0.059 0.055
0.1
0.084 0.11 0.089 0.25 0.09 0.049 0.064 0.081 0.1 0.054 0.02 0.04 0.04 0.092 0.03 0.046 0.031 0.06 0.048 0.01
r2 0.32 0.418 0.54 0.478 0.45 0.45 0.49 0.47 0.48 0.46 0.42 0.5 0.46 0.44 0.49 0.49 0.409 0.504 0.611 0.59 0.6 0.63 0.58 0.64 0.41 0.454 0.464 0.422 0.41 0.314 0.512 0.56 0.68 0.31 0.178 0.243 0.244 0.225 0.185 0.48 0.55 0.51 0.38 -0.2 0.61 0.55 0.64 0.66 0.49 0.56 0.28 0.602 0.85 0.631 0.6 0.44 0.39 0.12 0.27 0.33 0.41 0.42 0.28 0.21
±95%
Conv.
0.085 0.029 0.011 0.01
Y Y Y N
0.02 0.026 0.028
Y Y Y
0.05 0.16
Y Y
0.027 0.022 0.026 0.04 0.039 0.23 0.33
Y Y Y Y Y Y Y
0.11 2.46 0.51 0.66
Y N Y N
0.08 0.19
N N
0.088
Y
0.146 0.249 0.089 0.199 0.118 0.02
Y Y Y Y Y N
Refs. 241 254 254 287 324 324 403 416 451 463 492 492 505 531 531 534 751 751 751 753 753 753 753 753 753 824 824 824 835 860 920 179 463 685 177 177 177 177 177 177 179 463 179 359 179 166 166 203 312 313 313 47 812 842 842 842 842 842 219 275 311 311 542 707
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2 Methacrylonitrile Methacrylonitrile Methacryloxypropyltrimethoxysilane Methacryloyl fluoride Methacryloylacetone Methacryloyloxy, 2-, benzoate, methyl Methacryloyloxy, 2-, benzoic acid Methacryloyloxy, 4-, 2,2,6,6-tetramethyl Methylenebutyrolactone Methyleneglutaronitrile, 2Methyleneglutaronitrile, 2Methyleneglutaronitrile, 2Myrcene AW-Divinylaniline N-Vinylimidazole Naphthalene, 1-vinylNaphthalene, l-vinyl-4-chloroNaphthalene, 2-vinylNaphthalene, 2-vinyl-6-chloroNaphthalene, 6-vinyl-2-tert-butyl Oct-1-ene, 4,8-dioxaspiro(2,5)Oct-1-ene, 6,6-dimethyl-4,8-dioxaspiro Oxazolidone, N-vinylOxazoline, 2-, 2-isopropenyl4,4-dimethyl Oxazoline, 2-, 4-acryloxymethyl2,4-dimethyl Oxazoline, 2-isopropenylOxirane, 4-vinylphenylPentadienoate, trans-4-ethoxy-2,4-, ethyl Pentadienonitrile, trans-4-ethoxy-2,4Penten, 2-,-4-one Phenol, 3-(methacryloylamino)Phenol, 4-(methacryloylamino)Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, 2-(acryloyloxy)ethyl diethyl Phosphate, vinyl bis(chloroethyl) Phosphazene, isopropenylpentafluoroPhosphonate, 2-(4-vinylphenyl)ethyl, diethyl Phosphonate, 4-vinylphenyl, diethyl Phosphonate, oc-carbomethoxyvinyl-, diethyl Phosphonate, isopropenyl-, dimethyl Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, dibutyl Phosphonate, vinyl-, diethyl Phosphonate, vinyl-, diethyl Phosphonate, vinyl-, diethyl Phosphonate, vinyl-, diisobutyl Phosphonate, vinyl-, diispropyl Phosphonate, vinyl-, dimethyl Phosphonate, vinyl-, dimethyl Phosphonate, vinyl-, dimethyl Phosphonate, vinyl-, dimethyl
rx 0.25 0.34 0.36 0.069 0.067 0.27 0.15 0.6 0.09 0.42 0.5 0.85 0.891 5.38 8.377 0.699 0.76 0.395 0.39 0.616 1.831 1.93 29.42 0.55
±95%
0.014 0.007 0.04 0.04
0.52
0.015 0.36 0.149 0.233 0.68 0.049 0.6 0.069 0.027 0.098 2.19
r2 0.25 0.21 0.58 0.164 1.66 0.48 1.17 0.32 0.7 -0.02 0.02 0.25 1.38 0.033 0.68 2.02 0.75 1.345 2.44 1.014 0.246 0.271 -0.029 0.68
±95%
Conv.
0.045 0.16 0.02 0.03
Y Y N N
1.3
N
0.081 0.067 0.02 0.401 0.45 0.093 1.38 0.244 0.024 0.109 0.014
Y Y Y
Y Y Y
Refs. 75 835 951 660 339 651 651 687 746 196 196 512 1062 45 879 967 806 806 806 806 838 838 36 596
0.56
0.14
596
0.67 0.78 0.04 0.08 13.84 0.5 0.71 0.629 0.612 0.595 0.597 0.633 0.61 0.599 2.47 1.6 0.55
0.64 1.06 12.2 11.8 -0.033 0.99 0.86 0.171 0.15 0.146 0.168 0.094 0.23 0.108 0.03 -0.121 1.36
862 1001 723 723 112 896 896 971 971 971 971 971 971 971 133 765 796
0.57 0.06 0.04 0.003 0.004 0.005 0.044 0.002 0.018 0.002 0.78 0.27
0.7 3.88 8.6 2.46 2.3 2.2 6.32 6.32 4.97 4.36 1.59 2.45 3.87 2.57 4.61 2.45 2.45
0.055 0.04 0.03 0.01 0.05 0.073 0.355 0.02 0.187 0.034 0.23 0.088
Y
N N N N N N N Y Y
1.4 0
0.43
3.44 4.27 0.24 1.59 2.13
0.23 0.02 0.16 0.2 0.18 0.18 -0.12 -0.15 -0.52 0.02 -0.32 -0.52 0.4 0.15 0.02
796 684
0.39
Y
2.33 2.18 0.22
Y Y Y
1.46 2.52
Y Y Y
684 133 410 485 592 594 129 129 18 592 129 129 129 129 592 594
References page II - 290
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2 Phosphonate, vinyl-, diphenyl Phosphonate, vinyl-, dipropyl Phthalimide, N-vinylPropene, 2,3-dichloroPropene, 2,3-dichloroPropene, 2-chloro-3-hydroxyPropene 3,3,3-trichloroPropene, 3-chloro-2-chloromethylPropneyl methyl ketone Propenyl, 2-chloro-, acetate Propenyl, 2-methyl, acetate Propiolactam, Af-phenyl-a-methylenePyrazole, N-vinyl-3,5-dimethylPyridazinone, 3-(2-vinyl)-6-methylPyridazinone, 3-(2-vinyl)-6-methyl4,5-dihydro Pyridine, 2-methyl-5-vinylPyridine, 2-methy 1-5-vinylPyridine, 2-methy 1-5-vinylPyridine, 2-methyl-5-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinylPyridine, 2-vinyl-5-ethylPyridine, 3-ethynyl-6-methylPyridine, 4-vinylPyridine, 4-vinylPyridine, AT-oxide-, 2-vinyl-5-ethylPyrimidine, 2-WV-dimethylamino4-vinyl Pyrimidine, 4-vinylPyrrolidone, l-benzyl-3-methylene5-methyl Pyrrolidone, Af-vinylQuinoline, 2-vinylQuinoline, 2-vinyl5-Ethyl Ar-vinyl-N-methylthiolcarbamate 5-Vinyl AW-diethylthiolcarbamate Silane, y-methacryloxypropyltrimethoxyStilbene Styrene, 2,4-dibromoStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,4,5-tribromoStyrene, 3-m-n-butylstannylStyrene, 4-(f-butyldimethylsilyloxy)Styrene, 4-(trimethylsilyl)Styrene, 4-phenoxyStyrene, a-(trimethylsilyloxy)Styrene, a-methoxyStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, m-aminoStyrene, m-aminoStyrene, m-bromoStyrene, m-bromo-
r\
±95%
r2
±95%
Conv.
Refs.
1.74 3.81 6.27 3.51 3 12.5 6.9 3.37 18.12 4.1 71 0.626 8.663 0.9 5.92
0.16 0.68 0.66 0.18
-0.38 -0.41 0.07 0.05 0.036 0 0 0.01 0.08 0 0 0.406 0.049 0.85 0.13
0.29 0.72 0.11 0.01
Y Y Y N
0.106 0.011 0.05 0.03
N N
129 129 163 11 983 445 402 806 806 445 470 1002 806 340 340
0.74 0.6 0.72 0.73 0.46 0.5 0.55 0.57 0.55 0.74 2.3 0.52 -0.73 0.06 0.338
0.03
0.08
N
0.23 0.32
N N
0.12
N
0.07 1.09 0.11 0.017
0.75 0.68 1.2 0.78 0.75 1.27 1.81 1.33 1.14 1.09 0.15 0.69 1.04 2.27 1.404
0.16 0.22 0.88 0.071
N Y Y
232 500 514 56 231 41 456 499 532 231 784 231 79 806 243
0.095 0.053
2.38 0.71
1.06 0.17
Y Y
243 633
1.55
0.057 2.09 2.69 -0.11
0.028
Y
0.26
Y
36 456 458 197
0.219 0.555 17.2 0.49 0.49 10
0.73 6.09 0.025 0.196 0.03 0.1
0.03 0.15
0.05
1.72
0.1 0.3 Y
4.45 0.425
0.48 0.048
0.1 0.868
0.34 0.096
Y Y
197 977
3.92 0.14 0.268 0.18 0.23 0.26 0.23 18.5 0.877 0.48 1.38 1.48 2.51 1.21 0.96 1.09 1.13 1.08 1.12 1.04 0.786 0.5 0.55
0.17 1.61 0.08
0 0.91 0.81 0.25 2.2 0.14 2.78 0.03 0.863 0.28 0.94 0 0.07 0.14 0.05 0.3 0.4 0.521 0.63 1.16 1.18 1.6 1.05
0.09 2.88 0.14
N
0.04
N
0.193
Y
0.05 0.06 0.13
N N N
0.084
Y
0.007
Y
725 806 14 411 419 84 1054 985 976 1036 602 970 142 171 281 281 281 289 289 775 989 168 256
0.17 0.351
0.34 0.41 0.03 0.11 0.01
Y
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2 Styrene, ra-chloroStyrene, m-chloroStyrene, m-cyanoStyrene, m-diethylaminoethylStyrene, m-dimethylaminoStyrene, m-hydroxyStyrene, m-methoxyStyrene, m-nitroStyrene, m-sulfonic acid fluoride Styrene, p-2-methoxyphenyl ketone Styrene, p-4-methoxyphenyl ketone Styrene, p-phenyl ketone Styrene, p-phenyl ketone Styrene, p-l-(2-hydroxypropyl)Styrene, p-2-(2-hydroxypropyl)Styrene, p-2-(2-hydroxypropyl)Styrene, p-acetoxyStyrene, p-acetoxyStyrene,/7-aminoStyrene, p-aminoStyrene, p-bromoStyrene, p-bromoStyrene, p-bromoStyrene, p-bromoStyrene, p-bormoStyrene, p-chloroStyrene, p-chloroStyrene, p-chloroStyrene, p-chloroStyrene, p-chloroStyrene, p-chloroStyrene, p-chloroStyrene, p-chloromethylStyrene, p-chloromethylStyrene, p-chloromethylStyrene, p-cyanoStyrene, p-cyanoStyrene, p-decylStyrene, p-diethylaminoethylStyrene, p-ethoxy Styrene, p-fluoromethylStyrene, p-formylStyrene, p-formylStyrene, p-iodoStyrene, p-iodoStyrene, p-mercaptoStyrene, p-methoxyStyrene, p-methoxyStyrene, p-methoxyStyrene, p-methoxyStyrene, p-methylStyrene, p-nitroStyrene, p-octylamine sulfonate Styrene, p-sulfonic acid fluoride Styrene, p-trimethoxysilylStyrene, p-trimethylsilylStyrene, pentachloroSuccinimide, N-vinylSuccinimide, N-vinylSuccinimide, N-vinylSuccinimide, N-vinylTerpyridinyl, 4/-vinyl-2,2/:6/,2//Tetrazole, 1-vinylTetrazole, 2-methyl-5-(4/-vinyl)phenylTetrazole, 2-methy 1-5-vinyl-
r\ 0.57 0.64 0.851 1.2 1.027 0.78 1.742 0.279 0.788 0.23 0.423 0.11 0.13 0.97 0.5 0.79 0.835 0.887 0.41 0.876 0.7 0.67 0.71 0.71 0.69 0.62 0.744 0.816 0.74 0.39 0.76 0.74 0.622 0.62 0.6 0.24 0.28 0.88 1.12 0.98 0.474 0.2 0.16 0.485 0.629 0.607 0.85 1.14 1.16 1.05 0.891 0.193 0.7 0.171 0.774 1.26 1.33 10.74 10.09 2.31 0.052 0.53 3.85 0.65 1.124
±95%
0.534 0.28 0.248 0.07 0.456 0.055 0.183 0.07 0.071 0.15 0.02
0.029 0.034 0.007 0.03 0.09 0.14 0.1 0.08 0.029 0.043 0.047 0.15 0.3 0.07 0.22 0.19 0.19 0.151 0.093 0.039 0.188 0.19 0.6 0.086 0.092 0.045 0.126 0.47 0.19 0.49 0.46 0.98 0.032 0.384 0.045 0.081
r2 2.3 1.09 0.363 1.21 0.617 1.33 0.661 0.5 1.268 1.52 1.85 2.58 0.55 0.91 0.56 1.25 1.305 1.218 0.22 1.07 1.05 1.1 0.99 1.05 1 1.08 1.029 1.062 1.03 0.76 1.76 1.02 1.12 1.12 1.66 1.22 1.16 0.26 0.59 0.71 1.399 3 1.43 1.044 0.965 0.907 0.69 1.01 0.82 0.79 0.993 1.13 2.7 1.372 1.581 1.15 0.07 0.045 0.045 0.01 7 1.26 0.184 1.3 0.62
±95%
0.08 0.26 0.264 0.06 0.232 0.14 0.236 0.58 0.93 0.83 9.44
Conv.
N Y
0.05 0.069 0.004 0.07 0.05 0.11
Y N N Y
0.07 0.056 0.014
N Y Y
0.12
Y
0.17 0.2 0.46 0.11
Y N
1.32 0.19 0.14 0.236 0.159 0.124 0.223 0.1 1.27
N N
0.028 0.13
Y Y
0.188 0.342 0.72 0.1 0.036 0.072 0.23 1.6 0.33 0.031
N Y Y Y Y N Y
0.21
Y
Y
Refs. 168 256 806 806 806 35 806 222 806 806 806 806 806 380 390 547 806 806 775 989 125 128 256 447 554 128 139 139 140 150 523 554 756 806 806 128 256 806 806 806 806 1025 956 806 839 806 128 160 256 535 261 256 817 806 806 806 7 104 163 693 80 953 925 583 670
References page II - 290
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2
rx
Tetrazole, 2-phenyl-5-(4/-vinyl)phenyl0.95 Tetrazole, 5-phenyl-2-(4/vinyl)phenyl0.48 Tetrazole, 5-vinyl0.78 Tetrazole, 5-vinyl0.78 Toluenesulfonamide, 7V,N-methyl-vinyl5.6 Triallyl citrate 20.02 Triallyl cyanurate 32.45 Triallyl isocyanurate 28.6 Triazine, 1,3,5-, 2-amino-4-(N-methyl0.306 /7-aminoanilino)Triazine, 1,3,5-, 2-amino-4-(7V-methyl0.169 p-nitroanilino)Triazine, 1,3,5-, 2-amino-4-(/?-nitroanil)- 0.257 Triazine, 4,6-diamino-2-vinyl1.104 Triazole, 1,2,3-, l-/?-bromophenyl-4-vi 1.32 Triazole, 1,2,3-, 4(5)-vinyl1.48 Urea, l,3-divinyl-l,3-diphenyl3.62 Urea, N-acryloyl-W-benzoyl0.404 Urea, TV-vinyl-iV'-ethyl10.78 Valerolactone, a-methylen0.097 Valerolactone, a-methylene0.096 Vinyl 2-, 1,1-dichlorocyclopropane 17.98 Vinyl 2-, 2-methyl-4,4,6-6-tetraphenyl 0.11 cyclotrisiloxane Vinyl 2-chloroethyl ether 160 Vinyl 4, dithiobenzoate methyl 0.111 Vinyl 4-chlorocyclohexyl ketone 0.53 Vinyl acetate 42.48 Vinyl acetate 18.8 Vinyl acetate 56 Vinyl acetate 48 Vinyl acetate 60 Vinyl acetate 57.8 Vinyl acetoxymethyl ketone 0.103 Vinyl benzoate 34.8 Vinyl benzoate 31.56 Vinyl benzyl sulfide 2.32 Vinyl bromide 16.88 Vinyl bromide 18 Vinyl bromide 15 Vinyl butyl ether 21.25 Vinyl butyl sulfide 2.69 Vinyl butylsulfonate 1.74 Vinyl chloride 27.54 Vinyl chloride 17.24 Vinyl chloride 23.92 Vinyl chloride 25 Vinyl chloride 12.4 Vinyl chloride 14.7 Vinyl chloroacetate 14.57 Vinyl chloroacetate 45 Vinyl chloromethyl ketone 0.127 Vinyl cymantrene 2.324 Vinyl dichloroacetate 20 Vinyl dodecyl ether 27 Vinyl dodecyl ether 56 Vinyl ether 152 Vinyl ethyl ether 90 Vinyl ethyl ether 111 Vinyl ethyl ketone 13.83 Vinyl ethyl ketone 0.2 Vinyl ethyl ketone 0.29 Vinyl ethyl ketone 0.665 Vinyl ethyl oxalate 5.62 Vinyl ethyl sulfide 4.76
±95%
r2
±95%
Conv.
Refs.
0.3 1.13 0.81 1.27 1.39 0.054
1 2.2 0.31 0.31 -0.58 0.076 0.22 -0.05 0.44
0.02 0.44 0.041 0.12 0.11 0.12
Y Y Y Y Y
583 583 870 902 80 367 201 201 364
0.013
1.676
0.065
Y
364
0.062 0.157 0.15 0.12 0.98
0.91 0.538 0.73 0.52 -1.76 0.053 -0.33 1.42 1.44 0 0.8
0.18 0.141 0.4 0.26 1.36
Y Y Y Y
0.33
Y
364 806 670 670 800 1090 101 919 855 806 626
2.07
0.59
0.009 26.85 2.87
0.011 29.3 4.33 0.25 0.94 8.26 16.53 0.25 0.27 7.35 1.12 3.6 5 29.2 62.41 0.047 0.06
185 15.5 1.44 0.08 0.16 0.021 1.06 0.2
0.07 2.08 0.58 -0.04 0.02 0.01 0.05 0.16 0.08 0.368 -0.02 0.06 0.04 0.012 0.06 0.09 -0.08 -0.06 0 -0.06 0.058 0.16 0.005 0.04 0.01 -0.04 0.03 0.507 0.096 0.28 0 0 1.2 0 -0.122 -0.033 0.43 0.332 0.122 -0.12 0.113
0.034
0.81
Y
0.072 0.12
Y Y
0.018 1.62 0.15 0.17 0.049
Y N Y Y
0.2 0.78 0.18 0.16 0.08 0.003 0.08 0.031
N Y Y Y Y Y N Y
0.87 0.24
Y Y
0.039 0.014
Y Y
5.3
Y
0.066 0.023 0.06 0.043 0.017 0.19 0.032
Y Y N Y Y Y Y
597 697 668 158 241 481 481 481 812 806 26 696 303 34 34 368 241 303 185 109 238 242 46 516 59 212 542 353 354 542 374 374 45 140 194 112 344 353 550 124 303
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene
Monomer 2 Vinyl ethyl sulfide Vinyl ethyl sulfioxde Vinyl ethyl sulfoxide Vinyl hendecanoate Vinyl iodide Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl sulfide Vinyl isopropyl ketone Vinyl isopropyl ketone Vinyl isopropyl ketone Vinyl isopropyl sulfide Vinyl isothiocyanate Vinyl isothiocyanate Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl sulfide Vinyl methyl sulfide Vinyl methyl sulfide Vinyl methyl sulfone Vinyl methyl sulfoxide Vinyl octyl ether Vinyl pelargonate Vinyl phenyl ether Vinyl phenyl ketone Vinyl phenyl ketone Vinyl phenyl sulfide Vinyl phenyl sulfide Vinyl phenyl sulfone Vinyl stearate Vinyl sulfone Vinyl tert-butyl ketone Vinyl tert-butyl ketone Vinyl tert-butyl sulfide Vinyl thiolacetate Vinyl, 1-cyano, acetate Vinyl, 2-bromo-, ethyl ether Vinyl, p-benzylmethylcarbinol Vinyl-frts(trimethoxysiloxy)silane Vinyl-fns(trimethoxysiloxy)silane Vinylacetophenone, pVinylanthracene, 9Vinylanthracene, 9Vinylbenzoic acid, /?Vinylene carbonate Vinylene carbonate Vinylferrocene Vinylferrocene Vinylhydroquinone dibenzoate Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene cyanide Vinylidene cyanide Vinylisocyanate Vinylisocyanate Vinylmethyldiacetoxysilane Vinylmethyldiethoxysilane Vinylmethyldiethoxysilane Vinylphenyldimethylsilane
rx 6 9.64 6 24.89 7.401 11.58 11.96 50 2.38 0.46 0.36 0.4 4.61 0.65 0.8 0.288 0.237 0.35 4.5 4.46 5 1.146 3.57 65 49.5 1.7 0.24 0.21 3.63 3.96 1.562 15.96 0.731 0.3 0.36 4.36 4 0.181 0.98 26 24 0.246 2.12 2.12 0.282 411 21.03 4.37 2.76 0.22 1.81 1.79 1.8 1.839 1.81 1.7 0.015 0.003 8.13 6.9 4.08 5.68 11.29 32.53
±95%
0.54 1.22 0.315 1.91 2.32 0.41 0.05 0.1 0.18 0.092 0.023 0.11 0.24 0.087
0.04 0.042 0.12 0.27 0.091 13.32 0.058 0.31 0.11 0.76 0.409 0.32 0.072 0.011 23.45 1.44 0.22 0.35 0.14 0.024 0.12 0.007 0.001 0.14 0.1 0.43 0.49
r2 0.25 0.101 0.1 -0.17 0.126 0.65 0.29 0.01 -0.11 0.26 0.272 0.3 0.16 0.37 0.5 0.349 0.348 0.27 0.15 0.066 0.046 -0.22 0.01 0 0.01 0.01 0.3 0.465 0.019 0.26 -0.31 -0.39 -0.027 3.2 0.248 0.158 0.25 0.147 0.94 0 0.01 1.12 0.25 0.3 1.029 3.16 -0.73 0.2 0.14 0.43 0.134 0.098 1.5 0.87 0.15 0.11 0.72 0.001 0.08 0.1 0 0.08 -0.08 0.024
±95%
Conv.
0.044
Y
0.18 0.035 0.39 0.33
Y N N
0.2 0.07 0.046
Y N Y
0.068
Y
0.068 0.009
Y Y
0.056 0.084 0.17
Y Y Y
0.02 0.03 0.054 0.18 0.16 0.71 0.047 0.46 0.05 0.073
N Y Y N Y Y Y N Y Y
0.033 0.15
Y Y
0.42
Y
0.06 0.98 0.1 0.14
Y Y Y Y Y
0.48 0.01
Y Y
0.007
Y
0.005 0.16 0.001
N Y Y
0.15 0.14 0.2 0.016
Y Y Y Y
Refs. 507 286 286 145 806 349 349 490 303 344 353 599 303 422 542 140 353 550 193 195 303 195 737 374 145 423 344 353 193 239 193 145 45 344 353 303 566 806 194 48 209 482 266 123 48 266 103 120 274 294 440 138 238 393 59 812 93 134 82 435 533 754 754 754 482
References page II-290
TABLE 1. cont'd Monomer 1 Styrene Styrene Styrene Styrene Styrene Styrene Styrene sulfonate, sodium salt Styrene, 2,4,6-trimethylStyrene, 2,4,6-trimethylStyrene, 2,4,6-trimethylStyrene, 2,4,6-trimethylStyrene, 2,4-dibromoStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dichloroStyrene, 2,5-dimethylStyrene, 2,6-dichloroStyrene, 2,4,5-tribromoStyrene, 3-tri-rc-butylstannylStyrene, 3-tri-/2-butylstannylStyrene, 3-tri-n-butylstannylStyrene, 3-tri-rc-butylstannylStyrene, 3-tri-rc-butylstannylStyrene, 4-(te?t-butyldiinethylsilyloxy)Styrene, 4-(trimethylsilyl)Styrene, 4-methylStyrene, 4-methylStyrene, 4-phenoxyStyrene, a-(trimethylsiryloxy)Styrene, a-(trimethylsilyloxy)Styrene, a-methoxyStyrene, a-methoxyStyrene, a-methoxyStyrene, a-methoxyStyrene, a-methoxyStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methyl-
Monomer 2 Vinylphenylpropanol, 2-pVinyltriethoxysilane Vinyltrimethylsilane Vinyltrimethylsilane Vinyltrimethylsilane Xanathate, 5-methacryloyl O-ethyl N-Vinylpyrrolidone Acrylonitrile Methacrylate, methyl Methacrylate, methyl Styrene, /7-chloroStyrene Acrylate, methyl Acrylate, methyl Acrylonitrile Acrylonitrile Acrylonitrile Butadiene Butadiene Methacrylate, methyl Pyridine, 2-vinylStyrene Styrene Styrene Styrene Styrene, 2,5-dimethylStyrene, a-methylVinyl methyl ketone Vinylidene cyanide Styrene, 2,5-dichloroMethacrylate, methyl Styrene Acrylate, ethyl Acrylonitrile Methacrylate, methyl Styrene Vinyl acetate Styrene Styrene Acrylonitrile Methacrylate, methyl Styrene Acrylonitrile Styrene Acrylate, methyl Acrylonitrile Methacrylate, methyl Methacrylonitrile Styrene Acrylate, 2-cyano-, methyl Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Butadiene Butadiene, 2-fluoroFumaronitrile Maleic anhydride Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl
rx
±95%
r2
±95%
Conv.
Refs.
Y Y Y Y Y
72 209 209 482 73 1086 939 58 58 58 58 806 136 2 84 84 84 255 8 3 2 14 411 419 84 91 377 375 82 91 324 1054 985 985 985 985 985 976 1036 929 929 602 970 970 142 142 142 143 142 452 171 265 265 265 75 75 835 94 70 174 77 492 265 265 265
0.48 20.86 14.66
0.3 1.99 5.15
0.41 -0.09 -0.19
0.4 0.14 0.36
5.98 0.44 7.19 0.065 0.083 -0.01 0.34 0.91 3.93 4.47 0.08 0.07 0.09 0.45 0.187 2.66 0.14 0.81 0.25 2.2 0.14 1.543 3 2 0.026 0.263 -0.15 2.78 0.01 0.001 0.03 0.03 0.38 0.863 0.28 0.227 0.46 0.94 0 0 0.003 -0.002 -0.02 -0.02 0.07 0.05 0.08 0.14 0.17 0.24 0.09 0.103 0.14 0.08 0.139 0.72 0.094 0.04 0.27 0.51 0.6
0.18 0.06
0.049 0.36 0.084 0.874 1.511 1.45 17.83 0.14 0.142 0.288 0.22 0.25 0.26 0.449 0.662 0.44 0.62 0.268 0.18 0.23 0.26 0.263 0.14 0.5 0.005 1.543 1.98 0.23 10.4 4.88 0.69 18.5 5.33 0.877 0.48 0.079 0.345 1.38 0.05 1.48 0.17 0.06 2.5 0.83 2.51 0.001 0.07 0.04 0.04 0.04 0.063 0.34 0.03 - 0.02 1.5 2.22 -0.01 0.08 0.48 0.55 0.55
0.025 0.08
0.048 0.045 0.11 1.05 2.88 1.38 0.15 0.03 0.17 0.049 0.38 0.18 0.14 0.04 0.068 0.006 0.022 0.27
0.193 0.021 0.022
0.01 0.01 0.04 0.005 0.05 0.03 0.03 0.024 0.036 0.07 0.087 0.24 0.02 0.07
0.051 0.072 0.16 5.24 1.61 0.054 0.069 0.01
Y Y Y Y
0.043 0.017 0.13 0.12 0.08
Y Y Y N Y
0.17 0.022
N Y
0.009 0.068 0.16
Y Y N
0.351
Y
0.005 0.008
Y Y
0.02 0.01 0.39 0.04 0.34
N N N N N
0.04 0.005
N N
0.041 0.15
Y Y
0.27 0.13 0.7 0.078
N Y Y Y
0.02
N
Y Y N
Next Page
TABLE 1. cont'd Monomer 1 Styrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, a-methylStyrene, ra-aminoStyrene, ra-aminoStyrene, m-aminoStyrene, ra-bromoStyrene, ra-bromoStyrene, ra-bromoStyrene, ra-bromoStyrene, ra-bromoStyrene, ra-chloroStyrene, ra-chloroStyrene, ra-chloroStyrene, ra-cyanoStyrene, ra-diethylaminoethylStyrene, ra-dimethylaminoStyrene, ra-hydroxyStyrene, ra-methoxyStyrene, ra-methyl Styrene, ra-methyl Styrene, ra-methyl Styrene, ra-methyl Styrene, ra-methyl Styrene, ra-methyl Styrene, ra-methyl Styrene, ra-methylStyrene, m-methylStyrene, ra-nitroStyrene, ra-nitroStyrene, ra-nitroStyrene, ra-sulfonic acid fluoride Styrene, o-chloroStyrene, o-chloroStyrene, ochloroStyrene, o-chloroStyrene, o-chloroStyrene, ochloroStyrene, o-chloroStyrene, o-chloroStyrene, p-2-methoxyphenyl ketone Styrene, p-phenyl ketone Styrene, p-phenyl ketone Styrene, p-1 -(2-hydroxybutyl)Styrene,/7-1-(2-hydroxybutyl)Styrene, p-1-(2-hydroxybutyl)Styrene, p-1-(2-hydroxypropyl)Styrene, p-1-(2-hydroxypropyl)Styrene, p-1-(2-hydroxypropyl)Styrene, p-1-(2-hydroxypropyl)Styrene, p-2-(2-hydroxypropyl)Styrene, p-2-(2-hydroxypropyl)Styrene, p-2-(2-hydroxypropyl)Styrene, p-2-(2-hydroxypropyl)-
Monomer 2 Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylonitrile Styrene Styrene Styrene Styrene Styrene Styrene Styrene, 2,5-dichloroStyrene, p-chloroVinyl chloromethyl ketone Vinylhydroquinone dibenzoate Styrene Styrene Styrene, p-aminoMethacrylate, methyl Styrene Styrene Styrene, p-methoxyMethacrylate, methyl Styrene Styrene Styrene, p-methoxyStyrene Styrene Styrene Styrene Styrene Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylic acid Methacrylic acid Methacrylic acid Acrylate, methyl Acrylonitrile Methacrylate, methyl Methacrylate, methyl Styrene Styrene, p-chloroStyrene Acrylate, butyl Indene Methacrylate, butyl Methacrylate, ethyl Methacrylate, methyl Methacrylate, methyl Methacrylic acid Methacrylonitrile Styrene Styrene Styrene Acrylate, butyl Acrylate, methyl Acrylonitrile Acrylonitrile Methacrylate, methyl Styrene Styrene, p-chloroAcrylonitrile Styrene Styrene Styrene, p-chloro-
rx 0.14 0.22 0.48 0.15 0.14 0.05 0.3 0.4 0.521 0.63 0.14 0.21 0.009 0.11 1.16 1.18 0.63 1.17 1.6 1.05 1.4
±95%
0.06 0.13 0.084 0.2 0.01 0.007
r2 0.5 0.42 0.47 0.21 1.21 0.96 1.09 1.13 1.08 1.12 3 1.56 0.386 0.3 1.04 0.786 0.49 0.48 0.5 0.55 0.25
±95%
Conv.
0.41 0.03
N N
0.11
Y
0.42 0.034
Y Y
0.01
Y
Y 2.3 1.09 1.9 0.363 1.21 0.617 1.33 0.661 0.53 0.36 0.51 0.06 0.33 0.42 1.65 0.43 0.486 0.8 0.5 1.73 1.268 2.25 2.86 1.24 1.34 1.37 1.34 0.101 0.78 1.52 2.58 0.55 0.4 0.48 0.31 0.53 1 0.91 0.63 0.41 0.56 1.25 0.53
0.08 0.26 0.264 0.06 0.232 0.04 0.06 0.05 0.03 0.02 0.01 0.02 0.32 0.14 0.47 0.236 0.83
0.034 0.58 0.83 9.44
0.57 0.64 0.2 0.851 1.2 1.027 0.78 1.742 0.48 0.38 0.41 0.35 0.18 0.51 0.14 0.07 0.512 0.35 0.279 0.3 0.788 0.2 - 0.069 0.32 0.45 0.5 0.46 0.622 0.86 0.23 0.11 0.13 0.17 0.18 0.04 0.1 0.26 0.97 0.91 0.05 0.5 0.79 1.24
0.534 0.28 0.248 0.07 0.456 0.04 0.03 0.04 0.08 0.02 0.01
N
0.036 0.11 0.055 0.14 0.183
Y Y Y Y
0.066
Y
0.058
Y
0.07 0.15 0.02
Refs. 532 835 899 542 171 281 281 281 289 289 377 218 356 440 775 989 774 256 168 256 168 150 168 256 168 806 806 806 35 806 1087 1087 1087 1087 1087 1087 558 378 256 222 222 222 806 558 6 558 558 532 558 6 44 806 806 806 548 548 548 380 380 380 380 547 390 547 547
References page II - 290
Previous Page
TABLE 1. cont'd Monomer 1 Styrene, p-4-methoxyphenyl ketone Styrene, p-WV-dimethylaminoStyrene, p-WV-dimethylaminoStyrene, p-WV-dimethylaminoStyrene, p-AW-dimethylaminomethylStyrene, p-acetoxyStyrene,/7-acetoxyStyrene, p-acetoxyStyrene, p-aminoStyrene, p-aminoStyrene, p-aminoStyrene, p-bromoStyrene, p-bromoStyrene, p-bromoStyrene, p-bromoStyrene, p-bromoStyrene, p-bromoStyrene, p-bromoStyrene, /?-chloroStyrene, p-chloroStyrene, p-chloroStyrene,/7-chloroStyrene, p-chloroStyrene, p-chloroStyrene,/7-chloroStyrene,/7-chloroStyrene,/7-chloroStyrene,/?-chloroStyrene, /7-chloroStyrene, /7-chloroStyrene,/7-chloroStyrene, p-chloroStyrene,/7-chloroStyrene,/7-chloroStyrene,/?-chloroStyrene,/7-chloroStyrene,/7-chloroStyrene,/7-chloroStyrene,/7-chloroStyrene,/7-chloroStyrene, p-chloroStyrene, p-chloroStyrene, p-chloroStyrene, p-chloroStyrene, p-chloroStyrene, p-chloroStyrene, p-chloroStyrene, p-chloroStyrene, p-chloroStyrene, p-chloromethylStyrene, p-chloromethylStyrene, p-chloromethylStyrene, p-chloromethylStyrene, p-chloromethylStyrene, p-chloromethylStyrene, p-chloromethylStyrene, p-chloromethylStyrene, p-chloromethylStyrene, p-cyanoStyrene, p-cyanoStyrene, p-cyanoStyrene, p-cyanoStyrene, p-cyanoStyrene, p-decylStyrene, p-diethylaminoethyl-
Monomer 2 Styrene Acrylate, methyl Benzophenone, p-vinylMethacrylate, methyl Benzophenone, p-vinyl Acrylonitrile Styrene Styrene Styrene Styrene Styrene, m-aminoMethacrylate, methyl Styrene Styrene Styrene Styrene Styrene Styrene, p-methoxyAcrylate, a-trifluoromethyl-, methyl Acrylonitrile, a-trifluoromethylButadiene Butadiene, l-(2-hydroxyethylthio)Carbazole, Af-vinylCyclopentene, 4-,-1,3-dione Itaconate, dimethyl Methacrylate, butyl Methacrylate, butyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Norbornadiene Styrene Styrene Styrene Styrene Styrene Styrene Styrene Styrene, 2,4,6-trimethylStyrene, a-methylStyrene, m-nitroStyrene, p-l-(2-hydroxypropyl)Styrene, p-2-(2-hydroxypropyl)Styrene, p-cyanoStyrene, p-methoxyStyrene, p-methoxyStyrene, p-methylVinyl methyl sulfoxide Vinyl, p-, benzylmethylcarbinol Acrylonitrile Butadiene Methacrylate, butyl Methacrylate, ethyl Methacrylate, methyl Phosphazene, isopropenylpentafluoroStyrene Styrene Styrene Methacrylate, methyl Styrene Styrene Styrene, p-chloro Styrene, p-methoxyStyrene Styrene
r\ 1.85 0.38 0.07 0.101 0.26 0.4 1.305 1.218 0.22 1.07 0.49 1.1 1.05 1.1 0.99 1.05 1 1.15 0.24 0.92 1.6 0.24 7 0.294 0.69 1.036 1.025 0.77 0.89 0.47 69.93 1.08 1.029 1.062 1.03 0.76 1.76 1.02 17.83 1.56 0.3 0.91 1.24 0.26 0.47 0.86 1.15 6.46 1 0.56 0.42 1.46 1.29 0.91 1.64 1.12 1.12 1.66 1.41 1.22 1.16 1.28 0.89 0.26 0.59
±95% 0.93 0.16 0.05 0.016 0.017 0.03 0.05 0.069 0.004 0.07 0.05 0.11 0.08 0.02 0.06 5.7 0.081 0.1 0.124 0.12 24.19 0.07 0.056 0.014 0.12 5.24 0.42 0.14 0.08 0.16
0.15 0.58 0.17 0.2 0.46 0.11 0.13 0.03 1.32 0.19
r2 0.423 0.06 0.84 0.204 2.54 0.07 0.835 0.887 0.41 0.876 0.63 0.4 0.7 0.67 0.71 0.71 0.69 0.44 0 - 0.09 1.22 3.27 0.02 0.014 0.15 0.517 0.564 0.334 0.42 0.43 0 0.62 0.744 0.816 0.74 0.39 0.76 0.74 0.34 0.21 1.73 0.63 0.53 1.28 0.41 0.56 0.61 0.01 1 0.067 0.87 0.38 0.36 0.408 -0.048 0.622 0.62 0.6 0.22 0.24 0.28 0.26 0.14 0.88 1.12
±95%
Conv.
0.071 0.01 0.18 0.022 0.136 0.01 0.029 0.034
Y Y Y Y N
0.007
Y
0.03 0.09 0.14
N N Y
0.02 0.03 0.06 2.16
N N N Y
0.006
Y
0.1 0.131 0.016
N
0.12 0.1 0.08 0.029
Y N Y Y
0.043
Y
1.05 0.2 0.47
Y Y Y
0.13 0.08
N N
Y
Y
0.038 0.067 0.047 0.15 0.3
Y Y Y
0.07
N
0.08 0.05 0.22 0.19
N N
Refs. 806 866 866 256 86 47 806 806 775 989 774 256 125 128 256 447 554 128 825 825 255 810 551 264 398 872 966 150 256 476 188 128 139 139 140 150 523 554 58 218 222 380 547 128 128 256 256 737 48 1035 1075 1035 1035 756 765 756 806 806 256 128 256 128 128 806 806
TABLE 1. cont'd Monomer 1 Styrene,/7-dimethylaminoStyrene, /7-dimethylaminoStyrene,/7-dimethylaminomethylStyrene,/7-ethoxyStyrene, p-fluoroStyrene, /7-fluoromethylStyrene,/7-formylStyrene,/7-formylStyrene, /7-iodoStyrene,/7-iodoStyrene,/7-mercaptoStyrene, /7-methoxyStyrene, /7-methoxy Styrene,/7-methoxy Styrene,/7-methoxy Styrene,/?-methoxy Styrene, p-methoxy Styrene, /7-methoxy Styrene,/7-methoxy Styrene,/7-methoxy Styrene,/7-methoxy Styrene, /7-methoxy Styrene,/7-methoxy Styrene,/7-methyl Styrene,/7-methyl Styrene, /7-methyl Styrene,/7-methyl Styrene,/7-methyl Styrene,/?-methyl Styrene, p-methyl Styrene, p-nitro Styrene,/7-octylamine sulfonate Styrene,/7-octylamine sulfonate Styrene,/?-octylamine sulfonate Styrene,/7-octylamine sulfonate Styrene, p-sulfonic acid fluoride Styrene, p-tert-buty\Styrene, p-tert-buty\Styrene, p-trimethoxysilylStyrene,/7-trimethylsilylStyrene, pentachloroStyrene, pentachloroStyrene, pentachloroStyrene, tert-butoxyStyrenesulfonate,/7-, sodium Styrenesulfonate, p-, sodium Styrenesulfonate,/?-, sodium Styrenesulfonate,/?-, sodium Succinamate, potassium TV-vinylSuccinimide, TV-vinylSuccinimide, TV-vinylSuccinimide, TV-vinylSuccinimide, TV-vinylSuccinimide, TV-vinylSuccinimide, TV-vinylSuccinimide, TV-vinylSuccinimide, TV-vinylSuccinimide, N-vinylSuccinimide, TV-vinylSuccinimide, TV-vinylSuccinimide, TV-vinylSuccinimide, TV-vinylSuccinimide, N-vinylSuccinimide, N-vinylSuccinimide, TV-vinyl-
Monomer 2 Acrylate, methyl Benzophenone, p-vinylBenzophenone,/?-vinylStyrene Myrcene Styrene Styrene Styrene Styrene Styrene Styrene Acrylate, methyl Methacrylate, methyl Styrene Styrene Styrene Styrene Styrene; m-bromoStyrene, m-chloroStyrene, /7-bromoStyrene,/?-chloroStyrene, /7-chloroStyrene,/?-cyanoAcrylate, methyl Acrylonitrile Methacrylate, methyl TV,TV-Divinylaniline Styrene Styrene,/?-chloroVinyl methyl sulfoxide Styrene Acrylate, butyl Methacrylate, butyl Methacrylate, methyl Styrene Styrene Methacrylate, methyl Styrene Imidazole, TV-vinylStyrene Methacrylate, methyl Styrene Vinyl chloride Fumarate, dibutyl Acrolein Acrolein Acrolein Acrylate, oc-chloro-, sodium Methacrylate, methyl Acrylamide Acrylate, butyl Acrylate, methyl Acrylonitrile Carbazole, N-vinylMaleate, dimethyl Maleic anhydride Methacrylate, methyl Methacrylate, methyl Pyrrolidone, TV-vinylStyrene Styrene Styrene Styrene Vinyl acetate Vinyl acetate
rx 0.372 0.176 0.135 0.71 0.362 1.399 3 1.43 1.044 0.965 0.907 2 0.32 0.69 1.01 0.82 0.79 0.25 0.2 0.44 0.41 0.56 0.14 1.54 0.33 0.44 6.15 0.993 0.61 2.73 1.13 2.3 1.5 2.6 2.7 1.372 0.5 1.581 6.9 1.15 0.3 0.07 5.3 0.18 0.047 0.327 0.01 1.44 -0.02 0.17 0.15 0.9 0.516 0.11 1.25 0.148 0.048 -0.059 3.67 0.045 0.045 0.01 7 5.68 4.49
±95% 0.055 0.046 0.017 0.14 0.022 0.236
0.159 0.124 0.223
0.1 1.27
0.02 0.08 0.05
0.16 0.028
0.13
0.188 0.342 0.72 0.05 0.1
0.071 0.033 0.009 0.31 0.12
0.17 0.081 0.83 0.16 0.073 0.026 0.096 0.89 0.036 0.072 0.23 1.6 0.12 9.49
r2 0.192 0.842 2.54 0.98 0.87 0.474 0.2 0.16 0.485 0.629 0.607 0.07 0.29 0.85 1.14 1.16 1.05 1.4 1.9 1.15 0.47 0.86 0.89 0.17 0.05 0.4 0.06 0.891 1.15 0.01 0.193 0.3 0.7 0.6 0.7 0.171 0.44 0.774 0.002 1.26 3.65 1.33 0.43 0.01 0.26 0.395 0.113 0.27 1.1 1.86 1.54 0.357 0.116 0.04 -0.012 0.021 9.94 0.01 0.97 10.74 10.09 2.31 0.052 0.072 0.18
±95% 0.01 0.072 0.259 0.19 0.143 0.151
Conv.
Refs.
Y Y Y
911 911 911 806 1062 806 1025 956 806 839 806 558 35 128 160 256 535 168 168 128 128 256 128 558 378 256 45 261 256 737 256 817 817 817 817 806 634 806 1095 806 7 7 516 1077 57 57 57 834 771 600 789 80 80 284 284 284 104 693 96 104 163 693 80 104 167
Y
0.093 0.039 0.188
Y
0.19 0.6
N N
0.08 0.16
N N
0.03
N
0.03 0.086
Y Y
0.092
Y
0.045 0.126 0.47 0.85 0.19
N N
0.16 0.092 0.018 0.06 0.17
Y Y Y Y Y
0.063 0.024 0.09 0.021 0.027 0.27 0.031 0.42 0.49 0.46 0.98 0.32 0.009 0.54
Y Y Y Y Y Y Y N Y Y Y Y Y Y
References page II - 290
TABLE 1. cont'd Monomer 1 Succinimide, N-vinylSuccinimide, N-vinylSuccinimide, N-vinylSulfonate, 2-acrylamido2-methylpropane-, sodium Sulfonic acid, o-methacryloylaminobenzeneSulfonic acid, o-methacryloylaminobenzeneSulfonic acid, o-methacryloylaminobenzeneSulfonic acid,/?-methacryloylaminobenzeneSulfonic acid,/7-methacryloylamino benzeneSulfonic acid, /?-methacryloylamino benzeneTerpyridinyM'-vinyl^'tf'^''Tetrazole, 1-vinylTetrazole, 1-vinylTetrazole, 1-vinylTetrazole, 2-methyl-5-(4/-vinyl)phenylTetrazole, 2-methyl-5-(4/-vinyl)phenylTetrazole, 2-methyl-5-(4/-vinyl)phenylTetrazole, 2-methyl-5-vinylTetrazole, 2-methyl-5-vinylTetrazole, 2-methyl-5-vinylTetrazole, 2-phenyl-5-(4/-vinyl)phenylTetrazole, 2-phenyl-5-(4/-vinyl)phenylTetrazole, 2-phenyl-5-(4'-vinyl)phenylTetrazole, 2-phenyl-5-(4/-vinyl)phenylTetrazole, 2-phenyl-5-(4 '-vinyl)phenylTetrazole, 2-phenyl-5-(4/-vinyl)phenylTetrazole, 5-vinylTetrazole, 5-vinylThioindigoid Thiophene, 3-vinyl Thiophene, 3-vinyl Thioxanthone, 2-(acryloyloxy)Titanium, dicylopentadienyl-, dimethacrylate Titanium, dicylopentadienyl-, dimethacrylate Toluenesulfonamide, A^V-methyl-vinylToluenesulfonamide, AW-methyl-vinylToluenesulfonamide, WV-methyl-vinylToluenesulfonamide, AW-methyl-vinylTriallyl citrate Triallyl citrate Triallyl citrate Triallyl citrate Triallyl citrate Triallyl cyanurate Triallyl cyanurate Triallyl cyanurate Triallyl isocyanurate Triallyl isocyanurate Triallyl isocyanurate Triazine, 4,6-diamino-2-vinylTriazine, l,3,5-2-amino-4-(A^-methylp-aminoanilino)-6-isopropenylTriazine, l,3,5-2-amino-4-(N-methyl/?-aminoanilino)-6-isopropenylTriazine, 1,3,5-2-amino4-(p-nitroanilino)-6-isopropenyl-
Monomer 2
r\
±95%
r2
±95%
Conv.
Refs.
Vinyl acetate Vinyl thiolacetate Vinylidene chloride Acrylamide, AW-dimethyl-
1.99 0.17 0.311 0.162
0.43 0.15 0.058 0.949
0.229 2.47 1.441 1.108
0.06 0.37 0.061 0.59
Y N Y Y
80 97 104 857
Methacrylic acid
0.217
0.122
0.203
0.067
Y
1006
Methacrylic acid
0.523
0.195
0.188
0.076
Y
1006
Pyridine, 2-methyl-5-vinyl-
1.83
0.218
-0.002
0.031
Y
1006
Methacrylic acid
1.08
0.338
0.156
0.081
Y
1006
Methacrylic acid
1.65
0.27
0.155
0.052
Y
1006
Pyridine, 2-methyl-5-vinyl-
2.72
0.525
- 0.054
0.048
Y
1006
1.26 0.314 0.262 0.184 1.1 1.3 1.9 0.486 0.62 28.51 0.4 1 1.8 1.4 2.2 1.9 0.31 0.31 0.5 0.499 0.25 0.5 0.89
0.33 0.066 0.026 0.031
0.53 0.54 7.13 3.85 0.42 0.65 0.13 1.026 1.124 0.04 0.7 0.95 0.25 0.32 0.48 0.11 0.78 0.78 11.5 0.386 0.563 1.36 1.09
0.384 0.032 0.093 0.045
N Y Y Y
0.029 0.081 0.16
Y Y Y
953 925 925 925 583 583 583 670 670 670 583 583 583 583 583 583 870 902 1007 1000 1000 986 895
Styrene Acrylonitrile Methacrylate, methyl Styrene Acrylonitrile Styrene Vinylidene chloride Methacrylate, methyl Styrene Vinyl acetate Methacrylate, methyl Styrene Vinylidene chloride Acrylonitrile Styrene Vinylidene chloride Styrene Styrene Methacrylate, butyl Acrylate, butyl Methacrylate, methyl Methacrylate, methyl Copper diacrylate Nickel diacrylate Acrylonitrile Methacrylate methyl Styrene Vinyl butyl ether Acrylonitrile Allylbenzene Styrene Vinyl acetate Vinyl chloride Methacrylate, methyl Styrene Vinyl acetate Methacrylate, methyl Styrene Vinyl acetate Styrene Styrene
0.075 0.21 31.34
0.02
0.65
0.3
0.95
895
0.04 -1.83 -0.58 -0.31 -0.08 2.01 0.076 2.97 1.03 -0.005 0.22 1.29 - 0.49 -0.05 1.95 0.538 0.44
1.04 0.26 0.44 0.29 0.1 0.5 0.041 0.38 0.17 0.05 0.12 0.42 0.94 0.11 0.42 0.141 0.12
0.42 1.87 5.6 3.37 1.76 0.339 20.02 0.222 0.605 16.12 32.45 0.197 16.88 28.6 0.278 1.104 0.306
0.12 0.19 1.13 1.65 0.082 0.039 0.81 0.025 0.033 0.56 1.27 0.053 6.64 1.39 0.043 0.157 0.054
Y Y Y Y Y Y Y Y Y Y Y Y Y Y Y Y
80 80 80 80 367 367 367 367 367 201 201 201 201 201 201 806 364
Styrene
1.676
0.065
0.169
0.013
Y
364
Styrene
0.91
0.18
0.257
0.062
Y
364
TABLE 1. cont'd Monomer 1 Triazine, 2-allyloxy-4,6-dichloroTriazine, 4,6-diamino-2-vinylTriazole, 1,2,3-, l-/?-bromophenyl-4-vinylTriazole, 1,2,3-, l-p-bromophenyl-4-vinylTriazole, 1,2,3-, l-p-bromophenyl-4-vinylTriazole, 1,2,3-, 4(5)-vinylTriazole, 1,2,3-, 4(5)-vinylTriazole, 1 -N- vinyl-1,2,4Tricyclo[4,2,2,0{2,5}]dec-7-ene3,4,9,10-tetracarboxylicacid Tropone, 2-methacryloyloxyUrea, l,3-divinyl-l,3-diphenylUrea, JV-acryloyl-N'-benzoylUrea, N-vinyl-iV'-ethylUrea, N-vinyl-N'-ethylUrea, N-vinyl-W-ethylUrea, N-vinyl-N'-ethylUrea, JV-vinyl-iV'-ethylValerolactone, a-methyleneValerolactone, a-methyleneVinyl 1-cyano- acetate Vinyl 12-ketostearate Vinyl 12-ketostearate Vinyl 12-ketostearate Vinyl 12-ketostearate Vinyl 2-, 1,1-dichlorocyclopropane Vinyl 2-bromo-ethyl ether Vinyl 2-bromo-ethyl ether Vinyl 2-chlorocyclohexyl ketone Vinyl 2-chloroethyl ether Vinyl 2-chloroethyl ether Vinyl 2-chloroethyl ether Vinyl 2-chloroethyl ether Vinyl 2-chloroethyl ether Vinyl 2-chloroethyl ether Vinyl 2-chloroethyl ether Vinyl 2-chloroethyl ether Vinyl 2-ethylhexanoate Vinyl 3,3-bis(ethoxycarbonyl)propyl ether Vinyl 4-dithiobenzoate methyl Vinyl 4-dithiobenzoate methyl Vinyl 4-chlorocyclohexyl ketone Vinyl 4-chlorocyclohexyl ketone Vinyl 4-chlorocyclohexyl ketone Vinyl 4-chlorocyclohexyl ketone Vinyl 4-chlorocyclohexyl ketone Vinyl N,N-methylacetamide Vinyl oc-chloro-, triethoxysilane Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate
Monomer 2
r\
Pyrrolidone, N-vinylVinyl methyl ketone Methacrylate, methyl Styrene Vinyl acetate Methacrylate, methyl Styrene Imidazole, 1-Af-vinyl Acrylonitrile
0.5 1.35 0.266 0.73 42.47 0.27 0.52
Acrylate, ethyl Styrene Styrene Methacrylate, methyl Styrene Vinyl acetate Vinyl acetate Vinyl acetate Styrene Styrene Styrene Acrylonitrile Vinyl acetate Vinyl chloride Vinylidene chloride Styrene Acrylate, methyl Styrene Maleic anhydride Acrylate, ethyl Acrylate, ethyl Acrylate, methyl Acrylonitrile Methacrylate, methyl Styrene Vinyl acetate Vinyl chloride Acrylonitrile Acrylonitrile
3.13 -1.76 0.053 -0.008 -0.33 0.621 3.61 1.45 1.42 1.44 0.147 -0.18 -0.28 -0.01 0.26 0 -0.79
Methacrylate, methyl Styrene Maleic anhydride Methacrylate, methyl Styrene Vinyl acetate Vinyl cyclohexyl ketone Vinyl acetate Acrylonitrile 2-Oxazoline, 2-isopropenyl2-Oxazolinium BF4, 3-methyl2-isopropenylAcetamide, N-vinylAcetamide, N-vinylAcetate, 2-chloro-, vinyl Acetate, allyl Acetate, chloro-, allyl Acetate, dichloro-, allyl Acetate, trichloro-, allyl Acrolein Acrolein, methyl Acrylamide, N-octadecylAcrylamido, 1-, -1-deoxy-D-glucitol Acrylamido, 2-, -2-methylpropanesulfonate
±95%
0.68 0.058 0.4 9.84 0.13 0.26
0.25
1.7 0.15 0 0 0 0 0.07 0.16 -0.07 -0.047 0.06
r2 0.98 0.17 0.832 1.32 -0.011 0.839 1.48
±95%
Conv.
0.11 0.022 0.15 0.008 0.055 0.12
Y Y Y Y Y Y N
0.027 0.98
Y Y
0.23 2.07 0.029
Y Y Y
2.75 0.528 1.36 0.029 0.33 0.081
0.033 0.36 2.61 0.034 0.32
0.11 0.05
0.387 3.62 0.404 1.85 10.78 0.463 0.16 0.38 0.097 0.096 0.181 3.3 0.18 0.03 4.4 17.98 16.83 0.83 5 4.65 3.27 1.09 18.8 160 2.36 2.46 9.24 1.02
0.409 0.5 4.8 0.59 2.34
Y Y Y Y Y Y
0.52 1.96
Y Y Y Y
0.3 2.08 0.12 0.51 0.58 0.15 0.5 0.93
0.29 0.81
0.151 0.111 0.08 0.77 0.53 0.1 1.6 0.49
0.092 0.009
0.25 0.114
0.04 0.021
7.1 0.413
2 0.005
Y
0.6 0 0.8 1.8 0.77 0.57 0.41 -0.02 0.15 0.004 0.03 0.05
0.12 0.011 0.17
5.5 21 1.18 0.43 0.69 0.54 0.28 3.04 0.98 8.25 0.98 11.6
Y
0.43
N
1.46 0.87
Y N
Refs. 826 243 670 670 670 670 670 972 963 1104 800 1090 101 101 101 683 683 919 855 806 146 146 146 146 806 194 194 836 439 726 726 597 597 597 597 304 47 1015 697 697 836 668 668 668 668 631 237 894 908 984 984 892 1045 1045 1045 1045 207 589 119 258 700
References page II - 290
TABLE 1. cont'd Monomer 1 Vinyl acetate Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl
acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate
Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl
acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate acetate
Monomer 2 Acrylamidomethylamino, p-, azobenzene Acrylate, 2-cyano-, methyl Acrylate, 2-ethylhexyl Acrylate, a-acetoxy-, ethyl Acrylate, a-chloro-, ethyl Acrylate, butyl Acrylate, glycidyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, sodium Acrylate, trifluoro-, methyl Actylate, trifluoro-, methyl Acrylic acid Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Allyl acetate Allyl acetate Allyl acetate Allyl acrylate Allyl butyrate Allyl chloride Allyl chloride Allyl chloride Allyl isobutyrate Allyl propionate Allyl trimethylacetate Allyl valerate Allystearamide, NAzobenzene, 4-(acrylamidomethylamino)Benzothiazole, vinylmercaptoBicyclo[2,2,l]hept-2-ene5,6-dicarboximide, N-benzyl Bicyclo[2,2,l]hept-2-ene5,6-dicarboximide, N-benzyl Bicyclo[2,2,l]hept-2-ene5,6-dicarboximide, Af-benzyl Butadiene, 2-chloroButene-1 Butene-2, cisButene-2, transCaprolactam, Af-vinylCaprolactam, N-vinylCaprolactam, Af-vinylCarbamate, N,N-diethyl-, vinyl Carbamate, N-vinyl-, ethyl Carbamate, N-vinyl-, ethyl Carbamate, N-vinyl-, tert-buty\ Carbazole, N-vinylCarbazole, N-vinylCarbazole, N-vinylCarbon monoxide Crotonic acid Crotonic acid Crotonic acid Diallyl P-cyanoethylisocyanurate Diallyl melamine Diallyl phthalate
rx
±95%
r2
±95%
Conv.
Refs.
0.126
12.98
858
0.005 0.04 0.08 0.03 0.018 0.003 0.04 0.03 0.405 0.03 0.03
0.05 7.5 5.621 30 3.48 7.6 7.28 6.38 2.58 6.7 6.3
452 570 244 638 301 553 1067 158 25 489 568 37 595 598 37 158 235 6 75 75 140 502 998 578 998 204 3 438 998 998 998 998 119 880
0.021 0.072 0.01 0.043
0.094
Y
3.39
Y
0.37 0.3
Y Y
Y 0.24 0.24 0.021 0.04 0.06 -0.06 -0.03 0.6 1 1 0.11 0.97 1.355 0.66 0.34 1.04 1.29 1.15 1.07 0.923 0.126 0.013 1.26
0.059 0.067 0.22 0.08 0.09
0.089 0.15
0.092
0.037
0 0 8.66 4.05
Y Y N Y Y Y
5.51 5.29 9.2 0.45 0.7 0.7 17.35 0.64 -2.4 0.61 0.75 0.51 0.42 0.34 0.58 0.68 12.98
0.91 1.13 6.39
0.26
Y
2.53 0.35
0.47
Y
1.46
3.21
Y Y
0.15
0.15
1.99 - 0.02 1.55 %21 12 0.63 0.35 0.35 1.7 0.39 0.418 0.07 0.126 0.15 0.13 0.24 0.317 0.3 0.31 0.06 0.68 0.336
6.63 0.82
994
0.014 0.09 0.24 1.05 1.69
0.04 0.063 1.12 0.023
0.081 0.07 0.026 0.049
33.52 0.11 0.03 -0.03 0.31 2.5 2.5 0.13 2.09 0.4 0.46 2.67 3.02 3.9 0.33 0.04 0.01 0.001 4.6 0.318 2.19
763 994
994 8.98 0.42 0.25 0.44
N Y Y Y
0.19
Y
0.26 0.03 0.13
Y N Y
0.14
Y
0.1
N
0.073 0.34
Y Y
247 211 211 211 557 859 883 197 629 81 827 246 246 551 474 47 526 94 778 201 297
TABLE 1. cont'd Monomer 1 Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate
Monomer 2 Diallyl phthalate Diallyl phthalate Diallyl, 1,3-, 5-(2-hydroxy3-phenoxypropyl) Diallyl, 1,3-, 5-(2-hydroxy3-phenoxypropyl) Diallylcyanamide Diallyldimethylammonium chloride Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene, chlorotrifluoroEthylene, chlorotrifluoroEthylene, dichloro-, cisEthylene, dichloro-, cisEthylene, dichloro-, cisEthylene, dichloro-, cisEthylene, tetrachloroEthylene, tetrachloroEthylene, trichloroEthylene, trichloroFumarate, diethyl Fumarate, diethyl Fumarate, diisopropyl Fumaryl chloride Hexatriene, tetrachloroImidazole, 1-vinylIndene Isobutylene Isobutylene, 3-chloroIsopropenyl acetate Itaconate, dimenthyl Itaconic anhydride Itaconic anhydride Maleate, di-terf-butyl Maleate, diethyl Maleate, dimethyl Maleic anhydride Maleimide, A^-(2-hydroxyethyl)Maleimide, N-(2-hydroxyethyl)Maleimide, A^-(2-hydroxyphenyl)Maleimide, N-hydroxymethylMaleimide, W-phenylMethacrylamide, 1-deoxy-D-glucitol Methacrylate, 2,2,6,6-tetramethyl4-piperidinyl Methacrylate, butyl Methacrylate, di-, di-n-butylstannyl Methacrylate, ethyl Methacrylate, ferrocenylmethyl Methacrylate, isobutyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate acid Methacrylonitrile tyAr-Divinylaniline
rx 0.414 0.72 0.15
±95% 0.029
r2
±95%
Conv.
Refs.
1.66 2 5.5
0.16
Y
297 509 671
0.16
3.65
676
0.01 0.35 0.72
1.62 1.95 0.16
581 1029 309 41 413 42 559 68 68 766 6 1097 236 137 137 9 9 3 59 158 9 137 718 1038 91 4 364 360 211 475 100 975 365 365 1049 137 1049 260 323 323 323 323 328 258 664
1.14 1.03 1.52 3.74 1.23 1.4 0.33 0.68 0.47 1.02 6.4 0.898 4.13 4.45 0.607 0.7 0.011 0.09 0.012
1.2 0.77 0.64 0.21 0.58 0.11 0.27 0.06 1.94 1.87 0.076 0.1 0.004
0.28 0.88 0.74 0.67 0.13 0.79 -0.13 0.04 - .0.02 0.055 0.01 0.058 0.1 -0.07 -0.06 -0.006 0.443 0.33 0.9
N N
0.52
N
0.03 0.01
N N
0.36 0.02
Y
0.34 0.019 0.007
Y Y Y Y Y Y Y Y Y Y
6.99 2.8 0.19
Y Y Y Y Y
0.024 0.03 0.14 0.015
-0.11 0.39 1.66 0.13 1.171
1.17 0.2 0.18
-0.019 - 0.04 0.005 0.171 -0.006 0.019 -0.014 0.01 -0.011 0.017 -0.003 0.16 0.2
0.045 0.024 0.024 0.025 0.084 0.008 0.037 0.041 0.027 0.037 0.006
1.57 2.87 0.199 0.04 0.257 -0.058 0.61 0.88 1.75 1.45 1.284 0.56 13.7
0.36 0.32 0.02 0.012 0.086 0.074 0.12 0.17 0.17 0.21 0.046
Y Y Y Y Y Y Y Y Y Y Y Y Y
-0.003 0.013 -0.77 0.2 -0.06 -0.2 -0.81 0.03 0.04 0.07 0.01 0.01 0.058
0.15 0.018 5.29
30.18 0.013 131.8 1.52 29.7 2.71 137.5 26 28.6 22.21 0.2 12 3.99
14.47 0.036 29.8
Y Y N
24.16 0.25 5.9
Y Y N
0.12
Y
0.038
0.22 0.01 1.17
0.009
1.9 8.64 0.17 0 1.082
0.03
0.074
165 949 210 293 165 158 210 272 383 471 377 75 45
References page II - 290
TABLE 1. cont'd Monomer 1 Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate
Monomer 2
rx
Norbornadiene 0.818 Oxazolidone, N-vinyl0.602 Oxazolidone, Af-vinyl0.55 Oxazoline, 2-, 2-isopropenyl0.25 Oxazoline, 2-, 4-acryloxymethyl0.03 dimethyl-2,4-dimethyl Oxazoline, 2-, 4-methacryloxy0.05 2,4-dimethyl Oxazolinium, 2- tetrafluoroborate, 0.43 3-methyl Phosphate, diethyl isopropenyl 1.56 Phosphine oxide, diphenylvinyl0.38 Phosphonate, oc-carbomethoxyvinyl-, 0.09 diethyl Phosphonate, isopropenyl-, dimethyl 0.14 Phosphonate, vinyl-, bis(2-chloroethyl) 0.09 Phosphonate, vinyl-, bis(2-chloroethyl) 0.09 Phosphonate, vinyl-, bis(2-chloroethyl) 0.33 Phosphonate, vinyl-, diethyl 0.04 Phosphonate, vinyl-, dimethyl 0.04 Phosphonate, vinyl-, dimethyl 0.04 Propene, 1-chloro-, cis7.08 Propene, 1-chloro-, trans3.13 Propene, 2-chloro0.186 Propene, 3,3,3-trichloro0.19 Pyridine, 2-methyl-5-vinyl0.11 Pyridine, 2-vinyl-0.11 Pyridine, 2-vinyl0 Pyrrolidone, N-vinyl0.26 Pyrrolidone, Af-vinyl0.19 Pyrrolidone, N-vinyl0.195 5-Ethyl AT-vinyl-iV-methylthiolcarbamate 0.67 5-Vinyl AW-diethylthiolcarbamate 0.133 Styrene -0.04 Styrene 0.02 Styrene 0.01 Styrene 0.05 Styrene 0.16 Styrene 0.08 Styrene, 3-fn-rc-butylstannyl5.33 Succinimide, N-vinyl0.072 Succinimide, N-vinyl0.18 Succinimide, N-vinyl0.229 Tetrazole, 2-methyl-5-vinyl0.04 Triallyl citrate 0.222 Triallyl cyanurate 0.197 Triallyl isocyanurate 0.278 Triazole, 1,2,3-, l-/?-bromophenyl-0.011 4-vinylUrea, W-vinyl-AA'-ethyl0.463 Urea, N-vinyl-7V'-ethyl0.16 Urea, N-vinyl-Ar'-ethyl0.38 Vinyl 12-ketostearate 0.18 Vinyl 2-chloroethyl ether 2.36 Vinyl 4-chlorocyclohexyl ketone 0.1 Vinyl benzenesulfonate 0.628 Vinyl benzoate 0.455 Vinyl benzoate 0.35 Vinyl benzoate 0.78 Vinyl benzoate 0.7 Vinyl benzoate 0.66 Vinyl benzoate 0.24 Vinyl bromide 0.41 Vinyl bromide 0.6 Vinyl bromide 0.38
±95% 0.019 0.038 0.18
r2 1.354 1.55 2.04 7.1 1.41
±95%
Conv.
0.07 0.28 0.13
Y Y Y
6.2 0.057
0.35 0.15 0.091 0.17 0.25 1.77 0.057 0.1 0.025 0.072 0.12
0.009 0.54 0.06 0.16 0.025 0.053 0.043 0.008 0.029
0.036 0.069 0.52 0.2 0.13 0.09
0.366
Refs. 188 102 36 862 596 596
0.151
Y
877
0.44 1.7 0.6
650 843 684
0.99 0.85 0.85 0.47 0.74 0.74 0.74 -0.012 0.011 1.65 0.19 9 13.65 30 1.06 1.75 3.4 1.22 1.89 42.48 18.8 56 48 60 57.8 0.38 5.68 4.49 1.99 28.51 2.97 1.29 1.95 42.47
684 592 594 595 592 592 594 181 181 181 402 812 6 6 103 121 36 197 197 158 241 481 481 481 812 985 104 167 80 670 367 201 201 670
0.621 3.61 1.45 -0.28 0.16 0.15 -1.34 1.07 0.99 1.64 1.13 1.74 1.98 5.26 1.92 3
0.061 0.074 0.36
Y Y Y
3.64
Y
0.25 2.79 0.21 1.17 0.77 26.85 2.87
Y N Y Y Y Y Y
0.12 9.49 0.43 31.34 0.38 0.42 0.42 9.84
Y Y Y Y Y Y Y Y
0.081
Y Y
1.7 0.27
Y Y
1.93
Y
0.98 1.23 0.35
N Y N
101 683 683 146 597 668 942 253 253 26 272 430 696 158 268 268
TABLEI. cont'd Monomer 1 Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetoxymethyl ketone Vinyl benzenesulfonate Vinyl benzoate
Monomer 2 Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butylsulfonate Vinyl butyrate Vinyl butyrate Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloroacetate Vinyl chloroacetate Vinyl chloroacetate Vinyl chloroformate Vinyl chloroformate Vinyl chloromethyl ketone Vinyl cinnamate Vinyl cyclohexyl ketone Vinyl cymantrene Vinyl dodecyl ether Vinyl ethyl ether Vinyl ethyl ketone Vinyl ethyl oxalate Vinyl fluoride Vinyl formate Vinyl formate Vinyl isopropyl ketone Vinyl isopropyl ketone Vinyl laurate Vinyl methanesulfonate Vinyl methyl ketone Vinyl methyl sulfone Vinyl octadecyl ether Vinyl octyl ether Vinyl phenyl carbonate Vinyl phenyl carbonate Vinyl phenyl ketone Vinyl phenyl sulfone Vinyl propionate Vinyl propionate Vinyl stearate Vinyl stearate Vinyl tert-butyl sulfide Vinyl tert-butyl sulfide Vinyl thiolacetate Vinyl, N-, N-methylacetamide Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene cyanide Vinylidene fluoride Styrene Vinyl acetate Acrylonitrile
rx
±95%
3.72 0.71 2.5 0.025 1 1.35 0.43 0.981 0.24 0.263 0.25 0.65 0.26 0.83 0.803 0.8 0.67 0.66 0.044 0.04 0.08 0.072 3.67 3.42 -0.13 1.35 3.5 0.94 1.41 0.3 -0.154 1.4 0.639
0.09
0 4.5 3.47 0.85 0.85 -0.06 0.171 0.98 0.9 0.953 0.9 13 13 0.05 0.49 3.2 3 7.16 7.3 3.83 3.92 0.03 0.05 0.05 -0.002 0.12 0.003 6 0.368 -1.34 0.019
0.02
0.006 0.14 0.036 0.15 0.028 0.15 0.14 0.12 0.089 0.16 0.12 0.054 0.003 0.18 0.84 0.14 0.073 0.014
0.23 0.23 0.057 0.064 0.015
0.62 0.64 0.18 0.32 0.1 0.026 0.002 0.018 1.7 0.051
r2
±95%
Conv.
0.01 0.2 0.16 0.13 0.97 1.25 1.63 1.032 1.84 2.13 1.64 1.35 2.3 1.39 0.88 1.18 0.579 0.586 49.52 1.2 13.76 7.21 0 0.26 10.18 9.89 0.25 0.98 0.68 7.87 6.47 0.7 0.206
0.02
N
0.33
Y
0.32 0.097 0.68 0.2 0.12
Y Y Y Y Y
0.64 0.3 0.19
N N Y Y Y Y
0.355 0 0 0.384 0.384 5.81 -0.35 0.98 1 0.96 0.73 0.07 0.07 5.5 0.93 0.3 0.27 0.05 0.13 0.044 0.08 4.66 6.7 5 3.49 4.7 0.1 0.08 0.103 0.628 5.03
0.076 0.052 15.79 1.01
Y
6.62 8.44
Y Y Y
0.06
N
2.18
Y
0.427 0.21
Y Y Y
0.083 0.083 0.96 0.37
Y Y Y Y
0.17
Y
0.3
Y
0.16
Y
0.039 0.11 0.26
Y Y Y
0.17
Y
0.11
Y
0.011 0.036 1.08
Y Y
Refs. 345 448 553 185 272 515 109 148 158 283 3 450 86 71 779 861 675 706 356 200 846 354 372 158 794 124 755 272 401 601 794 503 942 91 195 372 372 675 705 794 193 272 425 1 537 598 601 566 631 103 103 120 120 144 90 3 432 436 59 812 82 627 806 942 47
References page II - 290
TABLE 1. cont'd Monomer 1 Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl benzyl sulfide Vinyl benzyl sulfide Vinyl bromide Vinyl bromide Vinyl bromide Vinyl bromide Vinyl bromide Vinyl bromide Vinyl bromide Vinyl bromide Vinyl bromide Vinyl bromide Vinyl bromide Vinyl bromide Vinyl bromide Vinyl bromide Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl ether Vinyl butyl sulfide Vinyl butyl sulfide Vinyl butylsulfonate Vinyl butylsulfonate Vinyl butylsulfonate Vinyl butylsulfonate Vinyl butylsulfonate Vinyl butyrate Vinyl butyrate Vinyl butyrate Vinyl butyrate Vinyl butyrate
Monomer 2 Allyl chloride Methacrylate, methyl Pyrrolidone, N-vinylStyrene Styrene Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl chloride Vinyl chloride Vinyl chloride Vinyl p-bromobenzoate Vinyl p-chlorobenzoate Vinyl p-cyanobenzoate Vinylidene chloride Vinylidene cyanide Methacrylic anhydride Styrene Acrylate, butyl Acrylate, butyl Acrylonitrile Acrylonitrile Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Styrene Styrene Styrene Vinyl acetate Vinyl acetate Vinyl acetate Acrylate, 2-chloroethyl Acrylate, methyl Acrylate, methyl Acrylonitrile Acrylonitrile Benzenesulfamide, /?-methacrylamideCaprolactam, TV-vinylMethacrylate, 2-bromoethyl Methacrylate, methyl Pyrrolidone, N-vinyl Styrene Toluenesulfonamide, AW-methyl-vinylVinyl acetate Vinyl acetate Vinyl acetate Vinyl chloride Vinyl chloroacetate Vinylidene chloride Acrylonitrile Styrene Acrylate, methyl Styrene Vinyl acetate Vinyl chloride Vinyl chloride Allyl chloride Butadiene, 2-chloroCarbazole, N-vinylEthylene Methacrylate, methyl
T1 0.46 0.07 0.408 -0.02 0.06 1.07 0.99 1.64 1.13 1.74 1.98 0.343 0.5 0.28 0.716 0.832 0.659 0.065 0 - 0.048 0.04 0.18 0.19 0.06 0.06 0.12 0.33 0.052 0.05 0.012 0.06 0.09 5.26 1.92 3 0 0.01 0 -0.03 0 0.03 0 -0.027 -0.08 3.37 0.01 0.2 0.16 0.023 0.12 0.004 0.041 -0.06 0 0 0.13 0.267 0.083 0.31 0.07 1.5 0.03
±95%
0.03 1.62 0.15 0.27 1.93 0.98 0.036 0.031 0.028 0.033 0.093 0.017 0.033 0.17 0.16 0.04 0.06 0.026 0.074 0.049 0.2 1.23 0.35 0.01 0.01 0.73 0.063 0.78 1.65 0.02 0.001 4.39 0.001 0.028 0.18 0.14 0.16 0.33 0.046 0.096 0.12
r2 0.88 20.3 2.507 34.8 31.56 0.455 0.35 0.78 0.7 0.66 0.24 1.66 1.7 0.72 1.17 0.81 0.878 5.58 0.061 0.97 2.32 4.07 3.7 2.25 2.79 14.11 17.1 25.1 19.84 16.88 18 15 0.41 0.6 0.38 2.01 3.65 3.6
±95%
Conv.
0.039 29.3 4.33 0.069
Y Y N Y
0.52
Y
0.2 0.16
N Y
0.13 0.072 0.094 1.76 0.047 0.27 0.25 0.44
Y Y Y Y Y Y Y N
0.2 0.67
N N
0.88 2.58 0.94
Y Y Y
8.26 0.13 0.09
N Y N
0.07
N N N
0.98 3.4 3.1 13.7
0.13 0.1 5.3
1.49 21.25 -0.31 3.72 0.71 2.5 2.084 1.49 1.75 0.086 2.69 4.14 1.74 0.025 0.325 8.47 1.15
0.95 16.53 0.29 0.09
N Y Y Y N
0.016 34.5 0.11 0.01 0.25 0.58 0.27 0.006 0.013 0.86
Y Y Y Y Y Y Y Y Y Y
0.34
N Y
1.33 0.7 25
Y
Refs. 438 272 253 26 696 253 253 26 272 430 696 283 450 519 110 110 110 47 82 106 303 268 268 268 286 268 268 34 34 34 34 368 158 268 268 790 345 574 345 347 1005 215 657 127 215 241 80 345 448 553 279 212 279 303 303 185 185 185 185 185 438 247 246 605 272
TABLE 1.
cont'd
Monomer 1 Vinyl butyrate Vinyl butyrate Vinyl butyrate Vinyl butyrate Vinyl butyrate Vinyl caproate Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride
Monomer 2 Vinyl acetate Vinyl acetate Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Aconitate, trimethyl Acrolein Acrylamide Acrylamide, Af-methylolAcrylate, 2-ethylhexyl Acrylate, butyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, methyl Acrylate, octyl Acrylate, trifluoro-, methyl Acrylate, trifluoro-, methyl Acrylic acid Acrylic acid Acrylic acid Acrylic acid Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acryloyl chloride Allyl acetate Allyl acetate Allyltriethoxysilane Butadiene Butadiene Butene-1 Butene-1, 2-ethylButene-1, 2-methylButene-1,3, 3-dimethylButene-1,3, 3-dimethylButene-2 Butene-2, 2-methylButene-2, cisCarbazole, N-vinylCarbon monoxide Crotonaldehyde Diallyl phthalate Diallylcyanamide Diallylcyanamide Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene Ethylene, chlorotrifluoroFumarate, diethyl Fumarate, diisopropyl Hexene-1 Imidazole, l-vinyl-2-methylIsobutylene
rx 0.97 1.25 0.302 0.55 0.65 0.348 0.04 0.03
0.16 0.07 0.093 0.002 0 0.06 0.12 1.5 1.5 0.107 0.03 0.024 0.11 -0.01 0.07 0.02 0.044 0.052 0.04 0.02 1.2 1.16 1.68 0.04 -0.11 3.34 1.56 1.01 5.64 6.18 3.3 8.52 8.8 0.17 13.52 1.55 0.833 0.44 0.44 3.82 1.99 1.74 4.38 2 3.21 1.85 0.96 1.63 1.55 2.53 0.13 0.29 1.54 0.188 2.04
±95%
0.013
0.05 0.11
0.002 0.01
0.011 0.09 0.069 0.037 0.03 0.08 0.002 0.01 0.029
0.38 0.31 0.58 0.26 0.31 0.2 13.57 2.18 10.54
0.25 0.26 0.012
0.59 0.42 0.58 0.44
0.1 0.22 0.22 0.18 0.1 0.98 0.077 1.82
r2 1 1.35 2.092 1.75 1.35 2.26 0.19 5.22
4.15 4.4 4.4 7.66 5 4 4.8 0 0 6.69 9.28 7.04 6.8 3.26 2.55 2.62 3.62 3.65 4 3.03 0 -0.94 8.8 5.27 0.12 -1.05 -1.18 -0.44 -0.07 -1.79 0.3 0 4.77 0.121 -0.56 0.7 0.68 0.68 0.02 0.19 0.24 0.34 0.2 0.21 0.21 0.14 0.23 0.16 0.01 0.48 0.49 -1.72 2.15 0.06
±95%
Conv.
0.074
Y
0.22 0.13
Y Y N Y Y
0.22 0.5
Y Y
0.88 0.51 0.33
Y N Y
0.34 0.12 0.25 0.21 0.22
Y N N Y Y
0.22
Y
0.48
Y
3.35 0.12 0.89 1.2 0.28 2.5 5.22 5.31
Y Y N N N Y N N
0.011 0.25 0.046
Y N Y
0.06 0.17 0.13 0.13
N N N N
0.01 0.12 0.01 0.01
N N N N
0.1
Y
9.23 0.26 0.8
N Y Y
Refs. 272 515 283 400 494 283 147 271 156 157 510 518 151 46 470 518 518 595 598 135 229 288 379 140 202 22 238 46 529 288 470 475 237 517 717 230 329 329 329 6 329 329 230 427 184 271 296 602 603 161 180 270 42 472 536 63 63 64 68 454 137 1038 329 154 140
References page II - 290
TABLE 1. cont'd Monomer 1 Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl
chloride chloride chloride chloride chloride chloride chloride chloride chloride chloride chloride chloride chloride chloride chloride chloride chloride chloride chloride chloride chloride chloride chloride
Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride
Monomer 2
rx
Isobutylene 2.12 Isobutylene 1.2 Isobutylene 1.54 Isobutylene, 3-chloro0.31 Isopropenyl acetate 2.26 Isopropenylisocyanate 0.39 Itaconate, diethyl 0.06 Itaconate, dimethyl 0.05 Maleate, diethyl 0.768 Maleate, diethyl 0.8 Maleate, diethyl 0.9 Maleate, dioctyl 0.05 Maleic anhydride 0.098 Maleic anhydride 0.04 Maleic anhydride 0.1 Maleimide, N-(4-carboxyethylphenyl)0.04 Maleimide, N-(4-chlorophenyl)0.026 Maleimide, AH4-methylphenyl)0.022 Maleimide, N-butyl0.24 Maleimide, N-phenyl0.023 Maleimide, Af-propyl0.06 Methacrylate, 3,5-dimethyladamantyl 0.21 Methacrylate, p-(2-benzothiazolylthio)- 0.64 ethyl Methacrylate, butyl 0.05 Methacrylate, methyl 0.07 Methacrylate, octyl 0.04 Methacrylic acid 0.064 Methacrylic acid -0.022 Methacrylic acid 0.07 Methacryloyl chloride 0.3 Methacryloyloxy-, 0-, benzoic acid 0.004 Norbornadiene 0.67 Octene-1 3.26 Oxazolidone, Af-vinyl0.313 Pentene-1 4 Pentene-1 2.08 Pentene-1, 2-methyl1.59 Phosphate, vinyl diethyl 3.4 Phosphate, vinyl diphenyl 3.009 Propene, 1-chloro-, ds11.52 Propene, 1-chloro-, trans4.45 Propene, 2-chloro0.095 Propene, 2-chloro0.75 Propenyl, 2-, acetate 2.2 Propenyl, 2-chloro-, acetate 0.7 Propenyltriethoxysilane Propylene 2.35 Propylene -0.05 Propylene 5.16 Propylene 2.45 Propylene 2.9 Pyridine, 4-vinylPyrrolidone, N-vinyl0.53 Pyrrolidone, N-vinyl0.55 Pyrrolidone, Af-vinyl0.74 Styrene -0.06 Styrene 0.058 Styrene 0.16 Styrene 0.005 Styrene 0.04 Styrene 0.01 Styrene, pentachloro0.43 Triallyl citrate 0.605 Vinyl 12-ketostearate 0.03
±95% 0.2 2.05 0.13
0.078 0.11 0.14 0.042 0.03 0.044 0.048 1.13 0.026 0.05 0.04
0.047 0.008 0.02 0.052 0.02 0.45 0.095 1.78 0.68 0.21 0.077 2.14 0.81 0.085
0.14 0.1 0.06
r2 0.268 -0.54 0.08 0 0.23 3 5.65 5 -0.003 0 0.046 0.608 -0.22 0.4 0.67 3.29 3.65 4.49 -12.7 4.01 2.38 1.85 0.26 13.5 8.99 14 23.52 23.26 9.05 2 11.26 0.41 -0.57 0.822 0.001 0.81 -1.16 0.15 0.327 0.1 0.33 4.75 0.58 0.25 0 0.196 3.1 -0.02 0.09
±95%
Conv.
Refs.
0.043 5.8
Y N
0.16
Y
0.044
Y
0.07 0.099 0.38
Y Y Y
155 329 560 475 100 777 480 479 137 449 6 3 260 521 521 306 306 306 305 306 305 335 741
0.18 0.39 0.34 106.2 0.18 0.16 8.87
N Y Y Y Y N N
2.97
Y
0.98 0.96
Y Y
3.5 0.01 0.85 0.048 5.2 2.31 0.047 0.023 0.63 0.4 5.12
Y N N Y Y N N Y Y Y Y Y
0.023 0.21 0.04
Y Y N N Y
0.08 0.003 0.08 0.031 0.87 0.033
0.38 0.34 0.73 27.54 17.24 23.92 25 12.4 14.7 5.3 1.03 - 0.01
7.35 1.12 3.6 5 29.2 0.17
Y Y N Y Y Y Y
519 3 511 135 229 46 432 938 267 329 36 3 329 329 779 779 181 181 181 517 189 445 237 155 329 355 560 588 154 40 582 582 109 238 242 46 516 59 516 367 146
TABLE 1. cont'd Monomer 1 Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloroacetate Vinyl chloroacetate
Monomer 2 Vinyl 2-chloroethyl ether Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl benzoate Vinyl benzoate Vinyl benzoate Vinyl butyl ether Vinyl butylsulfonate Vinyl butylsulfonate Vinyl butyrate Vinyl butyrate Vinyl butyrate Vinyl caproate Vinyl chloroacetate Vinyl dichloroacetate Vinyl dodecyl ether Vinyl fluoride Vinyl fluoride Vinyl hendecanoate Vinyl isobutyl ether Vinyl laurate Vinyl m-cresyl ether Vinyl methyl ketone Vinyl o-cresyl ether Vinyl octadecyl ether Vinyl octyl ether Vinyl p-chlorophenyl ether Vinyl /?-cresyl ether Vinyl p-terf-butylphenyl ether Vinyl p-vinyloxybenzoate Vinyl pelargonate Vinyl phenyl ether Vinyl phenyl ether Vinyl phenyl ether Vinyl propionate Vinyl propionate Vinyl stearate Vinyl tert-buty\ sulfide Vinyl terf-butyl sulfide Vinyl valerate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylethyldiethoxysilane Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene cyanide Vinylidene cyanide Vinylisocyanate Vinylphenylisocyanate, p Vinyltriethoxysilane Vinyltrimethoxysilane Acrylonitrile Acrylonitrile
rx 2.46 1.63 1.032 1.84 2.13 1.64 1.35 2.3 1.66 1.7 0.72 2.084 0.325 8.47 2.092 1.75 1.35 2.26 1.64 1.3 1.93 11 11.6 1.081 2.19 7.4 1.23 0.1 1.33 2.1 1.9 1 1.17 1.08 0.58 1.16 1.28 1.06 1.21 1.6 1.35 0.71 3 3 2.006 4.82 15.38 17.81 0.94 0.071 0.14 0.25 0.3 0.2 0.2 0.16 0.205 0.01 0.016 0.46 0.01 0.82 0.93 -0.007 0.09
±95% 0.52 0.32 0.097 0.68 0.2 0.12 0.64 0.16 0.016 0.013 0.86 0.074 0.22 0.34 0.55
0.016 1.43 0.04 0.02 0.04 0.02 0.06 0.06 0.14 0.03 0.097 0.071 0.49 1.44 7.84 1.53 0.025 0.32
0.003 0.002 0.16 0.016
r2 -0.07 0.43 0.981 0.24 0.263 0.25 0.65 0.26 0.343 0.5 0.28 0.023 0.267 0.083 0.302 0.55 0.65 0.348 0.421 0.91 0.15 0.05 0.11 0.38 0.04 0.2 0.13 8.3 0.14 -0.1 0.1 0.63 0.13 0.14 0.78 0.28 0.01 0.16 0.17 0.6 0.65 0.24 0.15 0.15 0.277 0.03 0.069 0 -0.44 2.06 3.39 8.92 3.2 4.5 1.8 4.5 3.068 0.72 0.6 3.7 11.9 -0.04 0.09 4.18 0.34
±95%
Conv.
0.11 0.14 0.036 0.15 0.028 0.15
Y Y Y Y Y Y
0.14 0.036
N Y
0.001 0.046 0.096 0.013
Y Y Y Y
0.05 0.055 0.49
Y Y Y
0.022 0.37
Y Y
0.02
Y
0.01
Y
0.05 0.01 0.02 0.07
Y Y Y N
0.59
Y
0.03
N
0.64
Y
0.014 0.12 0.068 0.22 2.97 0.32 1.16
Y Y Y Y Y Y N Y
0.076
Y
0.068
Y
0.44
Y Y Y
0.33
Refs. 304 109 148 158 283 3 450 86 283 450 519 279 185 185 283 400 494 283 283 283 370 590 755 145 47 450 279 375 279 370 370 279 279 279 497 145 172 279 280 400 450 145 598 601 283 103 319 319 237 238 29 3 470 517 539 585 67 409 82 777 777 237 237 362 542
References page II-290
TABLE 1. cont'd Monomer 1 Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl Vinyl
chloroacetate chloroacetate chloroacetate chloroacetate chloroacetate chloroacetate chloroacetate chloroacetate chloroacetate chloroacetate chloroacetate chloroacetate chloroethyl ether chloroethyl ether chloroformate chloroformate chloromethyl ketone chloromethyl ketone chloromethyl ketone chloromethyl ketone chloromethyl ketone chloromethyl ketone cinnamate cinnamate cinnamate cyclohexyl ether cyclohexyl ketone cyclohexyl ketone cymantrene cymantrene cymantrene cymantrene cymantrene dichloroacetate dichloroacetate dichloroacetate dichloroacetate diethylphosphinate diethylphosphinate dodecyl ether dodecyl ether dodecyl ether dodecyl ether dodecyl ether dodecyl ether ether ether ether ether ethyl ether ethyl ether ethyl ether ethyl ether ethyl ether ethyl ether ethyl ether ethyl ether ethyl ether ethyl ether ethyl ketone ethyl ketone ethyl ketone ethyl ketone ethyl ketone ethyl ketone
Monomer 2 Phosphate, vinyl diethyl Phosphate, vinyl diphenyl Styrene Styrene Vinyl acetate Vinyl acetate Vinyl acetate Vinyl butyl ether Vinyl chloride Vinyl ethyl ether Vinyl phenyl ether Vinylidene cyanide Acrylonitrile Methacrylic anhydride Vinyl acetate Vinyl acetate Acrylonitrile Methacrylate, methyl Styrene Styrene, a-methylVinyl acetate Vinylidene chloride Methacrylonitrile Pyrrolidone, N-vinylVinyl acetate Pyrrolidone, A^-vinylVinyl 4-chlorocyclohexyl ketone Vinyl acetate Acrylate, methyl Acrylonitrile Pyrrolidone, N-vinylStyrene Vinyl acetate Acrylonitrile Acrylonitrile Styrene Vinyl chloride Ethylene Ethylene Acrylonitrile Styrene Styrene Vinyl acetate Vinyl chloride Vinylidene chloride Acrylonitrile Methacrylate, methyl Pyridine, 4-vinylStyrene Acrylate, methyl Acrylonitrile Ethylene Fumarate, diethyl Methacrylate methyl Styrene Styrene Vinyl acetate Vinyl chloroacetate Vinylidene chloride Methacrylate, methyl Styrene Styrene Styrene Styrene Vinyl acetate
rt 2.01 1.42 -0.04 0.03 1.39 0.88 1.18 1.49 0.421 1.92 0.84 0 -0.02 0.579 0.586 0.88 0.593 0.507 0.386 49.52 6.8 0.15 1.2 1.2 -0.11 1.6 13.76 0.211 - 0.065 0.093 0.096 7.21 0.044 0.18 0.28 0.91 -11.99 -62.84 0 0 0 0 0.15 0 0.02 -0.15 0.03 1.2 0 0.06 0 -0.124 0.01 0 -0.122 0.26 0.43 0 0.65 -0.033 0.43 0.332 0.122 10.18
±95% 0.2 0.15 0.24 0.3 0.19 34.5 0.055 17.19 1.67 0.006 0.02 0.076 0.052 0.12 0.092 0.039 0.034 15.79 0.3
0.59
0.067 0.093 0.053 0.014 1.01 0.015
0.49 80.64 34.66
0.16 5.3 0.12 0.059
0.066 3.9 0.42 0.023 0.06 0.043 0.017 6.62
r2
±95%
Conv.
0.374 0.53 14.57 45 0.83 0.803 0.8 0.12 1.64 0.43 0.55 0.137 1.04
0.046 0.12 62.41
Y Y Y
0.12 0.089
N Y
4.39 0.34 3.9 0.61 0.037 0.05
0.67 0.66 0.064 0.121 0.127 0.009 0.044 0.018 4.6 0.01 0.04 1.91 0.5 0.08 0.46 0.446 0.037 2.324 0.072 7.45 0.25 20 1.3 0.15 0.05 0.82 27 56 3.67 1.93 1.3 0.94 4.9 32 152 3.3 0.69 2.7 1.63 37 90 111 3.42 1.92 3.2 0.42 13.83 0.2 0.29 0.665 -0.13
0.16 0.12 0.019 0.021 0.047 0.01 0.054 0.009
Y Y Y Y Y N Y Y Y Y Y Y Y Y Y
9.39
Y
0.14 0.048 0.03 0.06 0.003 0.32
Y Y Y Y Y Y
0.55 0.16 0.01
Y Y Y
0.99
Y
185
Y
0.12
N
0.16
Y
15.5 17.19 0.17 1.44 0.08 0.16 0.021 0.18
Y Y Y Y Y N Y Y Y
Refs. 779 779 212 542 71 779 861 212 283 212 212 82 116 106 675 706 356 356 353 356 356 356 200 200 200 214 668 846 354 354 308 354 354 362 542 542 283 311 311 373 374 374 372 370 371 386 45 395 45 470 194 584 194 106 140 194 158 212 470 794 112 344 353 550 794
TABLE 1. cont'd Monomer 1 Vinyl ethyl oxalate Vinyl ethyl oxalate Vinyl ethyl oxalate Vinyl ethyl oxalate Vinyl ethyl sulfide Vinyl ethyl sulfide Vinyl ethyl sulfide Vinyl ethyl sulfide Vinyl ethyl sulfide Vinyl ethyl sulfide Vinyl ethyl sulfoxide Vinyl ethyl sulfoxide Vinyl ethyl sulfoxide Vinyl ethyl sulfoxide Vinyl ethylene glycol glycidyl ether Vinyl ethylene glycol glycidyl ether Vinyl fluoride Vinyl fluoride Vinyl fluoride Vinyl fluoride Vinyl fluoride Vinyl fluoride Vinyl fluoride Vinyl fluoride Vinyl fluoride Vinyl fluoride Vinyl fluoride Vinyl fluoride Vinyl fluoride Vinyl formate Vinyl formate Vinyl formate Vinyl formate Vinyl formate Vinyl formate Vinyl formate Vinyl hendecanoate Vinyl hendecanoate Vinyl hendecanoate Vinyl hendecanoate Vinyl hendecanoate Vinyl hendecanoate Vinyl iodide Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl ether Vinyl isobutyl sulfide Vinyl isobutyl sulfide Vinyl isobutyl sulfide Vinyl isobutyl sulfide Vinyl isobutyl sulfide Vinyl isobutyl sulfide Vinyl isobutyl sulfide Vinyl isobutyl sulfide
Monomer 2
r\
Acrylonitrile Methacrylate, methyl Styrene Vinyl acetate Acrylonitrile Acrylonitrile Methacrylate, methyl Methacrylate, methyl Styrene Styrene Acrylonitrile Methacrylate, methyl Styrene Styrene Pyrrolidone, AT-vinylPyrrolidone, N-vinylAcrylate, butyl Acrylate, butyl Acrylate, methyl Acrylate, methyl Acrylonitrile Acrylonitrile Ethylene Ethylene Ethylene, chlorotrifluoroVinyl acetate Vinyl chloride Vinyl chloride Vinylidene chloride Acrylonitrile Allyl chloride Butadiene, 2-chloroButadiene, 2-chloroCarbazole, iV-vinylVinyl acetate Vinyl acetate Acrylate, methyl Acrylonitrile Butadiene Styrene Vinyl chloride Vinylidene chloride Styrene Acrylate, 2-chloroethyl Acrylate, methyl Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Ethylene, trichloroFumarate, diethyl Maleate, diethyl Styrene Styrene Styrene Vinyl chloride Vinylene carbonate Acrylate, ethyl Acrylate, ethyl Acrylate, methyl Acrylate, methyl Acrylonitrile Acrylonitrile Acrylonitrile Methacrylate, methyl
0 -0.05 -0.12 9.89 0.06 0.05 0.036 0.3 0.113 0.25 -0.08 -0.037 0.101 0.1 0.06 0.06 0.01 0.01 0.01 0.01 0.005 1 0.01 0.3 0.8 0.25 0.05 0.11 0.16 -0.004 0.57 -0.04 -0.05 0.192 0.98 0.68 0.033 0.09 -0.22 -0.17 0.38 0.04 0.126 0 0 0.7 0.99 -0.04 -0.04 0.05 0 0 0.65 0.29 0.01 0.04 0.18 0.05 0.05 0.05 0.06 0.03 0.022 0.03 0.05
±95% 0.28 0.44 0.19 8.44 0.03 0.03 0.017 0.032 0.14 0.06 0.044
0.15
0.12 0.01 0.001 0.06 0.008 0.91 1.26 0.18 0.022 0.16 0.035 0.002 0.09 0.06 0.01 0.02 0.009 0.39 0.33 0.37 0.04 0.05 0.02 0.02 0.01 0.038 0.01 0.03
r2
±95%
Conv.
1.34 4.74 5.62 1.35 0.09 0.06 1.03 2.7 4.76 6 1.63 11.17 9.64 6 1.4 1.4 19 19 43 43 44 24 2.52 1.7 1.2 3.5 11 11.6 6 2.54 0.78 15 11.91 4.142 0.94 1.41 3.615 1.88 22.56 24.89 1.081 2.72 7.401 2.24 3.63 - 0.24 - 0.05 0.98 1.26 0.014 0.52 0.17 11.58 11.96 50 2.19 0.16 0.36 0.32 0.3 0.29 0.08 0.062 0.08 0.89
0.45 2.95 1.06 0.84 0.01 0.01 0.11
Y Y Y Y N N Y
0.2
Y
0.16 0.48 0.54
Y Y Y
0.32
N
1.79
Y
3.89 0.011 0.14
N Y N
0.012 0.44 24.54 1.22 0.016 0.37 0.315
Y Y Y Y Y Y
0.04 0.26 0.07 0.15 0.19 0.003
N N N N N Y
1.91 2.32
N N
1.43
Y
0.02 0.02 0.01 0.01 0.005 0.004 0.004 0.01
N N N N N Y N N
Refs. 124 124 124 124 285 336 303 507 303 507 286 286 286 286 369 818 604 606 604 606 528 590 42 590 406 755 590 755 607 47 438 127 247 246 272 401 145 145 145 145 145 145 806 790 347 322 322 347 347 332 640 640 349 349 490 47 322 285 336 285 336 285 303 336 285
References page II-290
TABLE 1. cont'd Monomer 1 Vinyl isobutyl sulfide Vinyl isobutyl sulfide Vinyl isobutyl sulfide Vinyl isopropyl ether Vinyl isopropyl ether Vinyl isopropyl ketone Vinyl isopropyl ketone Vinyl isopropyl ketone Vinyl isopropyl ketone Vinyl isopropyl ketone Vinyl isopropyl ketone Vinyl isopropyl ketone Vinyl isopropyl sulfide Vinyl isopropyl sulfide Vinyl isothiocyanate Vinyl isothiocyanate Vinyl isothiocyanate Vinyl isothiocyanate Vinyl 1-methyl ether Vinyl laurate Vinyl laurate Vinyl laurate Vinyl m-cresyl ether Vinyl m-cresyl ether Vinyl m-cresyl ether Vinyl methanesulfonate Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl ketone Vinyl methyl sulfide Vinyl methyl sulfide Vinyl methyl sulfide Vinyl methyl sulfide Vinyl methyl sulfide Vinyl methyl sulfide Vinyl methyl sulfone Vinyl methyl sulfone Vinyl methyl sulfoxide Vinyl methyl sulfoxide Vinyl methyl sulfoxide Vinyl mono-diethyleneglycol ether Vinyl mono-ethyleneglycol ether Vinyl o-cresyl ether Vinyl o-cresyl ether Vinyl o-cresyl ether
Monomer 2 Methacrylate, methyl Methacrylate, methyl Styrene Caprolactam, N-vinylPyrrolidone, TV-vinylMethacrylate, methyl Methacrylate, methyl Styrene Styrene Styrene Vinyl acetate Vinyl acetate Methacrylate, methyl Styrene Acrylonitrile Methacrylate, methyl Styrene Styrene Indene Acrylonitrile Vinyl acetate Vinyl chloride Methacrylate, methyl Vinyl chloride Vinylidene chloride Vinyl acetate Acrylamide Acrylamide Acrylamide, AyV-dimethyl Acrylate, butyl Acrylonitrile Acrylonitrile Indene Indene Methacrylamide Methacrylamide Methacrylate, 2,2,6,6-tetramethyl4-piperidinyl Methyleneglutaronitrile, 2Styrene Styrene Styrene Styrene, 2,5-dichloroTriazine, 4,6-diamino-2-vinylVinyl acetate Vinyl chloride Vinyl phenyl ether Vinyl phenyl ketone Vinylidene chloride Acrylate, methyl Methacrylate, methyl Styrene Styrene Styrene Vinylene carbonate Styrene Vinyl acetate Styrene Styrene, /?-chloroStyrene, /7-methylMethacrylic acid Methacrylate, glycidyl Methacrylate, methyl Vinyl chloride Vinylidene chloride
rx 0.021 0.03 -0.11 0.01 0.03 1.44 0.6 0.26 0.272 0.3 7.87 6.47 0.046 0.16 1.4 0.6 0.37 0.5 0.67 0.04 0.7 0.2 0.2 0.13 0.04 0.206 0.47 0.75 0.1 1.81 1.75 1.39 2.63 2.9 0.25 0.28 0.41 5.05 0.349 0.348 0.27 0.5 0.17 8.3 4.4 0.74 1.8 0.084 0.03 0.15 0.066 0.046 7.72 -0.22 0.55 0.01 0.01 0.01 2.2 0 0.1 0.14 0.04
±95% 0.034 0.02 0.2 0.96 2.09 0.47 0.07 0.046 2.18 0.025 0.068
2.82
0.02 0.004 0.427 0.44 0.23 0.43 0.24 0.11
0.12 0.24
0.068 0.009 0.11
0.086 0.056 0.084 1.68 0.17 0.21
0.01 0.01
r2 0.985 0.88 2.38 0.22 0.87 0.81 0.54 0.46 0.36 0.4 0.3 -0.154 0.822 4.61 0.36 0.85 0.65 0.8 12.64 4 1.4 7.4 3.3 1.23 1.95 0.639 3.99 1.02 0.82 0.8 0.59 0.63 0.2 0.25 3 1.72 0.53 1.24 0.288 0.237 0.35 2 1.35 0.1 0.01 0.671 0.55 0.209 1 4.5 4.46 5 -0.08 1.146 0 3.57 6.46 2.73 0 4.41 1.8 1.33 2.1
±95%
Conv.
0.077 0.02 0.41 1.95 9.3
Y N Y Y Y
0.22 0.05 0.1
Y N Y
0.073 0.064 0.18
Y Y Y
12.59
Y
0.04 0.07 0.014 0.7 0.13 0.36 0.06 0.13
Y Y Y Y Y Y N Y
0.18 0.26
Y Y
0.092 0.023
Y Y
0.68
Y Y
0.034
Y
0.11 0.24 0.17 0.087 0.02
Y Y Y Y Y
0.02 0.1
Y Y
Refs. 303 336 303 215 215 601 794 344 353 599 601 794 303 303 542 422 422 542 750 381 503 450 605 279 279 942 609 609 609 53 140 504 606 606 609 609 664 512 140 353 550 375 243 91 375 423 946 375 195 106 193 195 303 120 195 195 737 737 737 831 780 605 279 279
TABLE 1. cont'd Monomer 1 Vinyl octadecyl ether Vinyl octadecyl ether Vinyl octadecyl ether Vinyl octadecyl ether Vinyl octyl ether Vinyl octyl ether Vinyl octyl ether Vinyl octyl ether Vinyl p-benzylethylcarbinol Vinyl p-benzylethylcarbinol Vinyl p-benzylethylcarbinol Vinyl p-benzylmethylcarbinol Vinyl p-benzylmethylcarbinol Vinyl p-benzylmethylcarbinol Vinyl p-benzylmethylcarbinol Vinyl p-bromobenzoate Vinyl p-bromobenzoate Vinyl p-bromobenzoate Vinyl p-bromobenzoate Vinyl p-chlorobenzoate Vinyl p-chlorobenzoate Vinyl p-chlorobenzoate Vinyl p-chlorobenzoate Vinyl p-chlorophenyl ether Vinyl p-chlorophenyl ether Vinyl p-cresyl ether Vinyl p-cresyl ether Vinyl p-cresyl ether Vinyl p-cyanobenzoate Vinyl p-cyanobenzoate Vinyl p-cyanobenzoate Vinyl p-cyanobenzoate Vinyl/?-cyanobenzoate Vinyl p-methoxybenzoate Vinyl p-methoxybenzoate Vinyl p-methoxybenzoate Vinyl p-methylbenzoate Vinyl p-methylbenzoate Vinyl p-methylbenzoate Vinyl p-tert-butylphenyl ether Vinyl p-terf-butylphenyl ether Vinyl p-vinyloxybenzoate Vinyl pelargonate Vinyl pelargonate Vinyl pelargonate Vinyl pelargonate Vinyl phenyl carbonate Vinyl phenyl carbonate Vinyl phenyl ether Vinyl phenyl ether Vinyl phenyl ether Vinyl phenyl ether Vinyl phenyl ether Vinyl phenyl ether Vinyl phenyl ether Vinyl phenyl ether Vinyl phenyl ether Vinyl phenyl ether Vinyl phenyl ether Vinyl phenyl ether Vinyl phenyl ether Vinyl phenyl ketone Vinyl phenyl ketone Vinyl phenyl ketone Vinyl phenyl ketone
Monomer 2
rx
Acrylonitrile Vinyl acetate Vinyl chloride Vinylidene chloride Acrylonitrile Styrene Vinyl acetate Vinyl chloride Acrylate, butyl Acrylate, methyl Acrylonitrile Acrylonitrile Methacrylate, methyl Styrene Styrene, p-chloroVinyl benzoate Vinyl p-cyanobenzoate Vinyl p-methoxybenzoate Vinyl p-methylbenzoate Vinyl benzoate Vinyl p-cyanobenzoate Vinyl p-methoxybenzoate Vinyl p-methylbenzoate Vinyl chloride Vinylidene chloride Methacrylate, methyl Vinyl chloride Vinylidene chloride Vinyl benzoate Vinyl p-bromobenzoate Vinyl/7-chlorobenzoate Vinyl p-methoxybenzoate Vinyl/7-methylbenzoate Vinyl/7-bromobenzoate Vinyl p-chlorobenzoate Vinyl p-cyanobenzoate Vinyl p-bromobenzoate Vinyl p-chlorobenzoate Vinyl p-cyanobenzoate Vinyl chloride Vinylidene chloride Vinyl chloride Butadiene Styrene Vinyl chloride Vinylidene chloride Vinyl acetate Vinyl acetate Acrylonitrile Caprolactam, N-vinylMethacrylate, methyl Methacrylate, methyl Pyrrolidone, N-vinylStyrene Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloroacetate Vinyl methyl ketone Vinylidene chloride Vinylidene chloride Methacrylate, glycidyl Methacrylate, methyl Styrene Styrene
0 0 -0.1 0 0 0 0 0.1 0.4 0.48 0.31 0.54 0.98 0.94 1 1.17 0.83 1.08 1.05 0.81 0.813 1 0.853 0.63 0.14 0 0.13 0.03 0.878 0.901 1.031 0.63 0.81 0.72 0.699 0.685 0.594 0.682 0.624 0.14 0.05 0.78 0.02 0.01 0.28 0 0.384 0.384 0.23 0.26 0.01 0 0.253 0.01 0.01 0.16 0.17 0.55 0.01 0.433 0.04 0.697 0.59 0.3 0.465
±95%
0.2 0.28 0.15 0.13 0.021 0.29 0.17 0.072 0.014 0.14 0.054 0.05 0.01 0.01 0.004 0.094 0.034 0.028 0.22 0.1 0.1 0.057 0.075 0.045 0.021 0.04 0.02 0.004 0.07
0.083 0.083 0.37 0.32 0.007 0.59 0.03 0.61 0.051 0.03 1.9 0.02 0.03
r2 0.85 4.5 2.1 1.5 0.81 65 3.47 1.9 0.17 0.18 0.04 0.11 0.24 0.98 1 0.716 0.901 0.72 0.594 0.832 1.031 0.699 0.682 1 2.44 2.6 1.17 1.97 0.659 0.83 0.813 0.685 0.624 1.08 1 0.63 1.05 0.853 0.81 1.08 2.04 0.58 26.3 49.5 1.16 4.08 0.85 0.85 2.5 1.3 11.34 2.8 4.48 1.7 1.28 1.06 1.21 0.84 4.4 2.45 2.11 0.719 0.71 0.24 0.21
±95%
0.17 0.26 0.32
Conv.
0.031 0.034 0.1 0.045 0.028 0.028 0.057 0.021 0.04 0.04
N Y Y Y Y Y Y Y Y Y Y Y Y Y
0.02 0.06 0.033 0.021 0.014 0.075 0.04 0.29 0.14 0.22 0.17 0.054 0.1 0.06 0.06 0.06
Y Y Y Y Y Y Y Y Y Y Y Y Y Y Y N
0.23 0.23
Y Y
2.43 5.76
Y Y
0.1
Y
0.14
Y
0.03 1.67
N Y
0.34 0.11
Y N
0.6 0.04 0.042
Y N Y
Refs. 373 372 370 371 373 374 372 370 591 591 591 48 48 48 48 110 110 110 110 110 110 110 110 279 279 605 279 279 110 110 110 110 110 110 110 110 110 110 110 279 279 497 145 145 145 145 675 705 556 214 172 605 214 423 172 279 280 212 423 240 280 946 794 344 353
References page II - 290
Next Page
TABLE 1. cont'd Monomer 1 Vinyl phenyl ketone Vinyl phenyl ketone Vinyl phenyl sulfide Vinyl phenyl sulfide Vinyl phenyl sulfide Vinyl phenyl sulfide Vinyl phenyl sulfide Vinyl phenyl sulfide Vinyl phenyl sulfide Vinyl phenyl sulfide Vinyl phenyl sulfone Vinyl phenyl sulfone Vinyl propionate Vinyl propionate Vinyl propionate Vinyl propionate Vinyl propionate Vinyl propionate Vinyl propionate Vinyl propionate Vinyl propionate Vinyl stearate Vinyl stearate Vinyl stearate Vinyl stearate Vinyl stearate Vinyl stearate Vinyl stearate Vinyl stearate Vinyl sulfone Vinyl sulfone Vinyl tert-butyl ketone Vinyl tert-butyl ketone Vinyl tert-butyl sulfide Vinyl tert-buty\ sulfide Vinyl tert-butyl sulfide Vinyl tert-butyl sulfide Vinyl tert-butyl sulfide Vinyl tert-butyl sulfide Vinyl tert-butyl sulfide Vinyl thiolacetate Vinyl thiolacetate Vinyl thiolacetate Vinyl thiolacetate Vinyl thiolacetate Vinyl thiolacetate Vinyl trichloroacetate Vinyl trimethylammonioethyl ether iodide Vinyl valerate Vinyl, 2-, 2-methyl-4,4,6,6-tetraphenylcyclotrisiloxane Vinyl-tris(trimethoxysiloxy)silane Vinyl-tris(trimethoxysiloxy)silane Vinyl-tris(trimethoxysiloxy)silane Vinyl-tris(trimethoxysiloxy)silane Vinyl-tris(trimethoxysiloxy)silane Vinylacetophenone Vinylacetophenone Vinylanthracene, 9Vinylanthracene, 9Vinylanthracene, 9Vinylanthracene, 9Vinylanthracene, 9Vinylanthracene, 9Vinylbenzoate, /?-, sodium
Monomer 2 Vinyl acetate Vinyl methyl ketone Acrylate, methyl Acrylonitrile Acrylonitrile Benzothiazole, vinylmercaptoMethacrylate, methyl Methacrylate, methyl Styrene Styrene Styrene Vinyl acetate Allyl chloride Butadiene, 2-chloroCarbazole, JV-vinylEthylene Methacrylate, methyl Vinyl acetate Vinyl acetate Vinyl chloride Vinyl chloride Acrylate, methyl Acrylonitrile Butadiene Styrene Vinyl acetate Vinyl acetate Vinyl chloride Vinylidene chloride Methacrylate, methyl Styrene Methacrylate, methyl Styrene Styrene Acrylonitrile Styrene Vinyl acetate Vinyl acetate Vinyl chloride Vinyl chloride Acrylate, methyl Carbazole, Af-vinylStyrene Succinimide, N-vinylVinyl acetate Vinylene carbonate Acrylonitrile Af-Vinylpyrrolidone Vinyl chloride Styrene Acrylonitrile Acrylonitrile Methacrylate, methyl Styrene Styrene Methacrylate, methyl Styrene Acrylate, butyl Acrylate, ethyl Acrylate, methyl Methacrylate, methyl Styrene Styrene Acrylonitrile
T1
±95%
r2
5.81 0.671 -0.02 0.03 0.03 0.24 0.06 0.08 0.019 0.26 -0.31 -0.35 0.62
0.96
-0.06 0.74 0.57 0.11 0.1.1 0.95 0.79 0.85 3.63 3.96 1.562 0.171 0.68
0.081 1.5 0.03 0.98 1 0.6 0.65 0.03 0.078 0.02 -0.39 0.96 0.73 0.24 0.08 0.1 -0.027 0.65 3.2 0.248 0 0.158 0.07 0.07 0.15 0.15 0.23 0.45 0.25 2.47 5.5 13.57 0.047 0 0.277 0.8 0.07 0.08 0.02 0 0.01 1.65 1.12 0.126 0.295 0.08 0.117 0.25 0.3 0.23
0.22 0.02 0.01 0.12 0.09 0.054 0.18 0.16 0.37 0.073
0.007 0.27 0.71 0.17 0.64 0.17 0.16 0.047 0.15 0.46 0.05 0.013 0.073
0.15 0.37 1.04 0.039 0.02 0.014
3.81 0.42 0.054 0.056 0.092 0.043 0.34
1.69 0.67 24 0.98 0.9 1.6 1.35 5.8 4.639 42.5 15.96 0.953 0.9 0.71 3.92 4.5 0.731 1.21 0.3 0.36 0.09 4.36 13 13 3 3 0.8 0.44 4 0.17 0.05 0.041 7.34 11.6 2.006 0.11 3.9 3.85 34 26 24 0.33 0.246 3.717 3.498 2.998 4.068 2.12 2.12 0.174
±95%
Conv.
Refs.
0.057
Y
0.1 0.01 0.01 0.61 0.06
Y N N Y N
0.12 0.27 0.091 0.064
Y N Y Y
0.21
N Y
0.015 4.73 13.32 0.015
Y Y Y Y
0.097 0.14 0.49 0.058 0.11 0.31 0.11 0.024 0.76
Y Y Y Y Y N Y Y Y
0.28
N
0.15
N
0.01 0.9 0.03 0.071
Y Y
794 946 193 285 336 763 239 239 193 239 193 193 438 247 246 605 272 272 425 400 450 537 145 145 145 1 537 145 145 45 45 794 344 353 303 303 598 601 598 601 566 97 566 97 566 186 362 1037 283 626
Y
0.36 0.072 0.046 0.041 0.067 0.04
Y Y Y Y Y Y
0.04
Y
209 573 482 209 482 266 266 123 123 123 123 123 48 175
Previous Page
TABLE 1. cont'd Monomer 1 Vinylbenzoic acid, pVinylbenzoic acid, pVinylbenzoic acid, pVinylbenzyl chloride Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylene carbonate Vinylethyldiethoxysilane Vinylethynyl-4-piperidinol, l,2,5-trimethyl-4Vinylethynyl-4-piperidinol, l,2,5-trimethyl-4Vinylferrocene Vinylferrocene Vinylferrocene Vinylferrocene Vinylferrocene Vinylferrocene Vinylferrocene Vinylhydroquinone Vinylhydroquinone Vinylhydroquinone Vinylhydroquinone Vinylhydroquinone dibenzoate Vinylhydroquinone dibenzoate Vinylhydroquinone dibenzoate Vinylhydroquinone dibenzoate Vinylhydroquinone dibenzoate Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride
Monomer 2 Acrylonitrile Methacrylate, methyl Styrene Methacrylate, methyl Acrylamide Acrylonitrile Methacrylate, methyl Pyrrolidone,//-vinylStyrene Styrene Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl chloride Vinyl chloride Vinyl chloride Vinyl isobutyl ether Vinyl 1-menthyl ether Vinyl methyl sulfide Vinyl thiolacetate Vinyl chloride Acrylonitrile Methacrylic acid Acrylonitrile Acrylonitrile Butadiene Methacrylate, methyl Pyrrolidone, N-vinylStyrene Styrene Acrylic acid Acrylonitrile Methacrylate, methyl Pyridine, 4-vinylAcrylate, methyl Acrylic acid Methacrylate, methyl Styrene Styrene, a-methylAconitate, trimethyl Acrylamide, N-octadecylAcrylate, butyl Acrylate, butyl Acrylate, butyl Acrylate, ethyl Acrylate, methyl Acrylate, methyl Acrylate, methyl' Acrylate, octadecyl Acrylate, octyl Acrylic acid Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile
rx 1.63 1.16 1.029 1.02 0.05 0.08 - 0.04 0.056 3.16 -0.73 0.3 0.27 0.05 0.13 0.044 0.08 0.03 0.069 0 0.16 0.14 -0.08 0.041 -0.44 0.38
±95% 0.42 0.3 0.06
0.85 0.059 0.98 0.3 0.16 0.039 0.11 0.12 0.068 0.22 1.91 0.17 0.01 2.97
0.05 0.165 0.15 0.16 0.52 0.71 0.2 0.14 0.026 0.04 0.02 - 0.23 0.75 0.95 0.41 0.43 0.3 64.6 0.432 0.934 0.84 0.87 0.58 0.9 0.7 1 0.9 0.851 0.437 0.32 0.28 0.4 0.42 0.49 0.69 0.76 0.95 0.95
r2 0.06 0.398 0.282 0.46 13.8 14.9 126 1.08 411 21.03 3.2 3 7.16 7.3 3.83 3.92 4.82 15.38 17.81 0.18 0.25 7.72 13.57 0.94 0.08
±95% 0.009 0.097 0.011
298 0.11
Conv. Y Y Y
23.45 0.62
Y Y Y Y Y
0.64
Y
0.18 0.32 0.49 1.44 7.84
Y Y Y Y Y
3.32 1.68 1.04 1.53
Y Y Y Y
0.4 0.092 0.15 0.16 0.1 0.14 0.092 0.03 0.13 0.36
23.74 0.008 0.006
0.15 0.11
0.037 0.018 0.065 0.14 0.034
0.186 0.16 4.34 1.22 0.364 4.37 2.76 0.29 0.56 0.49 0.53 0.46 0.44 0.34 0.22 0.11 0.15 1.4 0.873 0.46 0.58 0.72 0.95 0.8 1 1 0.679 1.246 0.92 1.04 0.44 0.58 0.65 0.57 0.5 0.48 0.65
Refs. 175 266 266 792 387 579 103 103 103 120 103 103 120 120 144 90 103 319 319 322 750 120 186 237 783 734
0.025
Y
0.18
Y
0.068 1.44 0.22 0.11 0.36 0.21 0.4
Y Y Y Y N Y Y
0.94 0.11 0.022
N Y Y
0.39 0.21
Y Y
0.14 0.057 0.042 0.11 0.2
Y Y Y Y Y
294 294 802 294 308 274 294 337 338 337 337 440 444 440 440 440 149 119 118 464 464 65 107 107 377 118 118 288 138 238 404 404 404 404 404 404 404
References page II - 290
TABLE 1. cont'd Monomer 1 Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride
Monomer 2 Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acrylonitrile Acryloyl chloride AHyI acetate Allyl chloride Allylstearamide, NButadiene Carbazole, N-vinylCarbazole, TV-vinylCrotonaldehyde Crotonic acid Cyclopentene, 4-, 1,3-dione Diallyl phthalate Ethylene Ethylene chlorotrifluoroFumarate, diethyl Fumarate, diisopropyl Indene Indene Isobutylene, 3-chloroIsopropenyl methyl ketone Isopropenylisocyanate Maleate, diethyl Maleimide Methacrylate, 2-(sulfonic acid)ethyl Methacrylate, benzyl Methacrylate, butyl Methacrylate, ethyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylate, methyl Methacrylic acid Methacrylonitrile Methacrylonitrile Norbornadiene Oxazolidone, AT-vinylPropenyl 2-methyl, acetate Styrene Styrene Styrene Styrene Styrene Styrene Succinimide, Af-vinylTetrazole, 2-methyl-5-(4/-vinyl)phenylTetrazole, 2-phenyl-5-(4'-vinyl)phenylTetrazole, 5-phenyl-2-(4'-vinyl)phenylVinyl 12-ketostearate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl acetate Vinyl benzoate Vinyl butyl ether
rx 1.3 1.74 1.43 1.8 0.39 0.5 6.6 3.49 5.22 -0.044 -0.023 -0.008 18.1 1.88 5 15.71 17.14 12.19 48 0.49 -0.02 1.1 0.134 0.85 12.5 0.666 0.22 0.34 0.35 0.353 0.3 0.36 0.18 0.5 0.34 0.09 0.094 0.19 0.02 0.27 0.154 0.3 0.036 1.36 1.42 2.4 0.134 0.098 1.5 0.087 0.15 0.11 1.441 0.13 0.25 0.11 4.4 4.66 6.7 5 3.49 4.7 5.58 1.75
±95%
1.4 0.15 0.038 0.068 0.018 43.7 0.35 1.96 1.58 0.15 1.15 0.099 0.056 0.03 0.02 0.03 0.18
0.032 0.01 0.047 0.1 0.05 0.63 0.11 0.048 0.01 0.007 0.005 0.061
4.8 0.26 0.17 1.76 0.11
r2 0.65 0.66 0.63 0.63 0.58 1.12 0 0.24 -0.24 1.97 3.6 3.65 0 -0.2 0.113 0.2 0.018 0.02 0.012 0.095 0.293 0.34 0 4.06 0.31 0.464 3.6 3.3 2.07 2.18 2.6 2.38 2.16 2.5 2.5 2.1 1.8 2.83 1.23 2.77 3.368 2.43 2.38 0.09 0.091 0 1.81 1.79 1.8 1.839 1.81 1.7 0.311 1.9 1.8 1.9 0.26 0.03 0.05 0.05 -0.002 0.12 0.065 0.004
±95%
Conv.
0.24 0.19 0.25 0.12 0.3
Y Y Y Y Y
1.03 0.027
Y Y
0.005
Y
0.038
Y
0.095 0.85
Y Y
0.66
Y
0.083
Y
0.18 0.1 0.02 0.06
Y Y Y N N
0.95
Y
0.06 0.098 0.1 0.05 0.17 0.077
N Y N N N Y
0.35 0.14
Y Y
0.024
Y
0.12 0.058
N Y
2.61 0.1
Y Y
0.026
Y
0.093 0.001
Y Y
Refs. 404 404 404 404 468 288 470 3 119 257 13 98 405 47 264 376 299 454 59 1038 6 6 470 47 434 3 251 564 432 3 3 138 324 324 426 432 538 65 762 762 786 6 781 781 267 102 470 138 238 393 59 812 93 104 583 583 583 146 3 432 436 59 812 47 279
TABLE 1. cont'd Monomer 1 Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene chloride Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene cyanide Vinylidene fluoride Vinylidene fluoride Vinylisocyanate Vinylisocyanate Vinylisocyanate Vinylisocyanate Vinylisocyanate Vinylisocyanate Vinylisocyanate Vinylmethyldiacetoxysilane Vinylmethyldiacetoxysilane Vinylmethyldiethoxysilane Vinylmethyldiethoxysilane Vinylmethylphenylsulfonium tetrafluoroborate Vinylmethylphenylsulfonium tetrafluoroborate Vinylphenyldimethylsilane Vinylphenyldimethylsilane Vinylphenylisocyanate, pVinylphenylpropanol, 2-p-
Monomer 2 Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloride Vinyl chloromethyl ketone Vinyl dodecyl ether Vinyl ethyl ether Vinyl fluoride Vinyl hendecanoate Vinyl m-cresyl ether Vinyl methyl ketone Vinyl o-cresyl ether Vinyl octadecyl ether Vinyl p-chlorophenyl ether Vinyl /?-cresyl ether Vinyl p-tert-buty\ phenyl ether Vinyl pelargonate Vinyl phenyl ether Vinyl phenyl ether Vinyl stearate Vinylidene cyanide Vinylisocyanate Acrylate, a-chloro-, methyl Acrylic acid Butadiene, 2-chloroEthylene, dichloro-, cisEthylene, dichloro-, cisMaleic anhydride Methacrylate, methyl Phosphonic acid, 1-phenylvinyl Propene, 2-chloroStyrene Styrene Styrene, 2,5-dichloroVinyl acetate Vinyl benzoate Vinyl chloride Vinyl chloride Vinyl chloroacetate Vinyl chloride Methacryloyl fluoride, perfluoroVinyl acetate Acrylate, methyl Acrylonitrile Methacrylate, methyl Styrene Styrene Vinyl chloride Vinylidene chloride Acrylonitrile Styrene Styrene Styrene Acrylamide Acrylonitrile Methacrylate, methyl Styrene Vinyl chloride Styrene
rx 2.06 3.39 8.92 3.2 4.5 1.8 4.5 3.068 0.018 1.3 3.2 6 2.72 1.95 0.55 2.1 1.5 2.44 1.97 2.04 4.08 2.45 2.11 3.92 0.009 1.46 0.066 0.291
0.028 4.58 0.204 0.72 0.001 0.005 0.1 0.061 0.72 0.6 0.137 0.049 7.6 0.08 0.14 0.16 0.01 0.08 0.1 3.7 0.33 -0.11 0 0.08 -0.08 0.1
±95% 0.32 1.16
0.076 0.009
0.37 0.07 0.1 0.04 0.06 0.06 0.34 0.11 0.14 0.001 0.07 0.042
0.013 0.079 0.16 0.001 0.009 0.11 0.047 0.068 0.037 0.02
0.23 0.15 0.14 0.2
0.1 -0.009 0.024 11.9 0.41
r2 0.071 0.14 0.25 0.3 0.2 0.2 0.16 0.205 6.8 0 0 0.16 0.04 0.04 1.8 0.04 0 0.14 0.03 0.05 0 0.433 0.04 0.08 0.049 0.33 0.313 0.212
0.057 0.1 0.001 0.015 0.003 0.026 0.003 0 0.01 0.016 0 0.009 0.02 6 1.38 0.19 3.3 8.13 6.9 0.46 1.46 2.246 4.08 5.68 11.29 3.4
±95%
Conv.
Refs.
0.025 0.32
Y N Y
0.003 0.3
Y Y
0.16 0.004
Y Y
0.01
Y
0.01 0.004 0.004
Y Y Y
0.051 0.03 0.17 0.02
Y N Y Y
0.021 0.016
0.012
Y Y Y Y Y Y Y
0.03 0.007 0.001 0.006 0.002 0.017
Y Y Y Y Y Y
0.002 0.006 0.001
Y Y Y
0.054 0.14 0.1 0.43
Y Y Y Y
238 29 3 470 517 539 585 67 356 371 470 607 145 279 375 279 371 279 279 279 145 240 280 145 82 435 82 82 82 82 82 82 82 921 82 134 82 82 82 82 409 82 82 82 669 627 435 435 422 435 533 777 435 754 754 754 754 793
2.2 0.034 0.016 0.4
29.79 32.53 0.1 0.48
793 1.89 0.49
Y Y
0.3
Y
482 482 777 72
References page II - 290
TABLE 1. cont'd Monomer 1 Vinylsulfonic acid Vinyltriethoxysilane Vinyltriethoxysilane Vinyltriethoxysilane Vinyltriethoxysilane Vinyltrimethoxysilane Vinyltrimethoxysilane Vinyltrimethylsilane Vinyltrimethylsilane Vinyltrimethylsilane Vinyltrimethylsilane Vinyltrimethylsilane Xanthate, S-methacryloyl O-ethyl Xanthate, S-methacryloyl O-ethyl
Monomer 2 Acrylamide Acrylonitrile Acrylonitrile Styrene Vinyl chloride Acrylonitrile Vinyl chloride Acrylonitrile Methacrylate, methyl Styrene Styrene Styrene Methacrylate, methyl Styrene
T1
±95%
r2
±95%
0.3 0.41 2.69 -0.09 -0.04 0.45 0.09 0.1 0.028 -0.19
0.1 0.38 2.5 0.14 0.44
0.15 0.6 29.59 1.99 0.16
0.27 0.016 0.36
3.5 6.59 26.83 20.86 0.82 9.09 0.93 4.08 35.66 14.66
0.025 0.08 0.08
5.98 0.76 0.44
0.18 0.04 0.06
0.049 0.6 0.36
TABLE 2. LISTING OF QUICK BASIC (MICROSOFT) PROGRAM FOR CALCULATING REACTIVITY RATIOS* 100 OPTION BASE 1 110 DIM eta (20) 120 DIM ksi (20) 130 DIM gee (20) 140 DIM ef (20) 150 DIM t (20) 151 F O R b = I TO 20 152 READ t(b) 153 NEXT b 170 DATA 12.71,4.3,3.18,2.78,2.57,2.45,2.37,2.31,2.26,2.23,2.2,2.18,2.16,2.14,2.13,2.12,2.11,2.1,2.09,2.09 180 DEF FNLog 10(X) = LOG(X)/LOG( 10#) 190 PRINT "Calculation of reactivity ratios by the method of Kelen and Tudos" 210 PRINT "Enter 0 for monomer 1 in the feed to start the calculation" 220 REM initialize all of the summing addresses 230 n = 0 231 m = 0 232 var = 0 233 sumasi = 0 234 sumi = 0 235 suma = 0 236 sumsqi = 0 237 sumnegi = 0 238 sum2i = 0 250 INPUT "Do you wish to stop (Y/N)?";f$ 260 IF f$ = "y" THEN GO TO 1510 270 REM enter the names and molecular weights of the monomers 280 INPUT "Monomer 1 is:"; mone$ 290 INPUT "Monomer 2 is:"; mtwo$ 340 REM enter the feed, polymer and conversion values 350 PRINT "Are the feed and polymer values in mol fractions (mol), mol ratios (ratio) or weight fractions (wt) ?" 370 INPUT type$ 380 IF type$ = "ratio" THEN GOTO 1210 390 IF type$ = "wt" THEN GOTO 1360 400 PRINT "Mol fraction of"; mone$; "in the feed = " 410 INPUTmIO 420 IF mlO = 0 THEN GOTO 800 430 n = n + 1 440 m20=l-ml0 450 PRINT "Mol fraction of"; mone$; "in the polymer= " 460 INPUTpI 470 p 2 = l - p l 480 PRINT "Conversion, weight fraction = ? (If none given enter 0)" 490 INPUT w 500 IF w = 0 THEN GOTO 680 * Method of Kelen and Tudos (803,804).
0.76 0.85 5.15
Conv.
Refs.
Y Y Y Y Y Y Y Y Y Y Y
1066 209 237 209 237 2.37 237 209 482 209 482 73 1086 1086
510 520 530 540 550 560 570 580 590 600 610 620 630 640 650 660 670 680 690 700 710 720 730 740 750 760 770 780 790 800 810 820 830 840 850 860 870 880 890 900 910 920 930 940 950 960 970 980 990 1000 1010 1020 1030 1040 1050 1060 1070 1080 1090 1100 1110 1120 1130 1140 1150 1160 1170 1180 1190
REM calculate G and F X = ml0/m20 y = pl/p2 mu = mw2/mw 1 zeta2 - w * (mu + X)/(mu -f y) zetal=(y/X)*zeta2 z = (FNLoglO(l-zetal))/(FNLoglO(l-zeta2)) g = (y-l)/z f=y/(zA2) I F n = I THEN fmin = f IF n = 1 THEN fmax = f IF fmin>f THEN fmin = f IF fmaxf THEN fmin = f IF fmax
References page 11-290
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C.
REM calculation of Ml and M2 from mol ratios PRINT "MoI ratio of"; mone$; "in the feed = " ; INPUT qf IF qf = 0 THEN GOTO 800 n= n+l ml0 = q£/(qf+l) m20=l-ml0 PRINT "Mole ratio of"; mone$ "in the polymer= " INPUT qp pl=qp/(qp+l) p2=l-pl PRINT '' Weight fraction conversion = '' INPUTw IF w - 0 THEN GOTO 680 GOTO 510 REM calculation of Ml and M2 from weight fractions PRINT "The molecular weight of"; mone$; "is" INPUT mwl PRINT "The molecular weight of"; mtwo$; "is" INPUT mw2 PRINT "Weight fraction of"; mone$ "in the feed = " INPUT rfl If rfl = 0 THEN GOTO 800 n= n+l rf2 = 1-rfl mlO = (if l/mwl)/((rf 1/mwl) + (rf2/mw2)) m20=l-ml0 PRINT "Weight fraction of"; mone$; "in the polymer= " INPUT rpl rp2 = l-rpl pi = (rpl/mwl)/((rpl/mwl) + (rp2/mw2)) PRINT "Weight fraction conversion= " INPUTw IF w = 0 THEN GOTO 680 GOTO 510 PRINT "FINI" END
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Q
a n d
e
V a l u e s
f o r
F r e e
C o p o l y m e r i z a t i o n s M o n o m e r s
a n d
o f
R a d i c a l V i n y l
T e l o g e n s
Robert Z. Greenley* Monsanto Co., 544 Oak Valley Drive, St. Louis, MO 63131, USA
A. Introduction B. Q and e Values for Free Radical Copolymerizations Table 1. Monomers Table 2. Telogens Table 3. Monomers Arranged by Q Values Table 4. Monomers Arranged by e Values C. References A.
11-309 11-310 11-310 11-314 11-314 11-317 11-319
INTRODUCTION
The Alfrey and Price Q and e equation (Al) is well known: (Al) Q and e are measures of the reactivity and polarity, respectively, of a vinyl monomer and r\ = kn/kn, a reactivity ratio. This equation may be arranged to a logarithmic form (A2) which provides a more convenient linear solution: (A2) When monomer 2 is the one to be characterized, its Q and e values may be determined from the slope (—^2) and intercept (InQ 2 ) of the equation. The first requirement for the use of Eq. (A2) is the selection of a small group of common monomers for which Q and e could be independently established. Since, by definition the Q and e scheme is based on styrene (Q=LO and e = — 0.8), the average Q and e values of these primary monomers were calculated using Eqs. (Al) and (A3) (Ref. 1). (A3) utilizing only their reactivity ratios with styrene. The six primary monomers (Group I) - acrylic acid, acrylonitrile, *Retired.
butadiene, methyl acrylate, methacrylonitrile and methyl methacrylate - were chosen because their reactivity ratios had been narrowly defined by several investigators. These primary reactivity ratios were taken from the compilation in the second edition of this Handbook. The Q and e values of a secondary group (Group II) of ten common vinyl monomers were determined using Eq. (A2), with the primary monomer group supplying the Qx and e\ values. The Q and e values were then calculated for a tertiary set (Group III) of reactivity ratios for which a set of reactivity ratios with four or more of the primary and secondary monomers was available. For all groups except Group I, recalculated reactivity ratios (see the preceding chapter) were used when available. Otherwise, reported values were included. The Q and e values developed for the three groups during the first pass through the data were subsequently used to recalculate the Q and e values for Groups II and III. Group I was not redetermined so that the styrene bias of the system could be better maintained. After four iterations, no significant changes were observed. During the iterative process, a number of reactivity ratio citations were dropped due to a lack of fit with the majority of data points. The final Q and e values for these three groups were then used to determine the Q and e values of other monomers with four or more reactivity ratio citations with at least three comonomers (Group IV), and monomers with three citations with three different comonomers (Group V). By replacing r\ in Eq. (A2) with the reciprocal of the chain transfer constant, \/Cs (3), Q and e values of telogens may also be estimated (4) from their coreactivity with vinyl monomers. The Monomer Table lists the monomer group designation, the Q and e values, and the correlation coefficient (r) for the regression. The Number column (n) represents the number of r\ values actually used in the regression. If the monomer is in Group V, the number is understood to be 3. The data are listed alphabetically as well as in increasing values of Q and e.
Recent work by Jenkins (5) has uncovered another approach to characterizing the copolymerization character of vinyl monomers. By deriving data from r\ and T2 values,
he was able to calculate three coefficients which appear to allow a more precise prediction of the actual reactivity ratios.
B. Q AND e VALUES FOR FREE RADICAL COPOLYMERIZATIONS TABLE 1. MONOMERS Monomer
Group
Q
e
n
r
5 6 5 16 5 17 6 4 5
0.98 0.75 0.63 0.97 0.98 0.64 0.91 0.93 0.56 0.68 0.99 0.87 0.38 0.99 0.90 0.92 0.94 0.91 0.65 0.87 0.81
Acenaphthalene Acetylene, phenylAconitate, trimethyl Acrolein Acrolein, methylAcrylamide Acrylamide, Af-methylolAcrylamide, Af-octadecylAcrylamide, N,iV-diethyl Acrylamide, WV-dimethyl-glucitol Acrylate, a-acetoxy-, ethyl Acrylate, a-chloro, ethyl Acrylate, a-chloro-, methyl Acrylate, a-cyano-, methyl Acrylate, oc-phenyl-, methyl Acrylate, benzyl Acrylate, butyl Acrylate, ethyl Acrylate, ferrocenylmethyl Acrylate, glycidyl Acrylate, heptafluorobutyl Acrylate, methyl Acrylate, octadecyl Acrylate, octyl Acrylate, trifluoro-, methyl Acrylate, 2-chloroethyl Acrylate, 2-ethylhexyl Acrylate, 2-nitrobutyl Acrylic acid Acrylic acid, oc-bromoAcrylic anhydride Acrylonitrile Acryloyl chloride AUyI acetate Allyl acrylate AUyI alcohol Allyl chloride Allylbenzene TV-Allylstearamide
IV IV III IV IV IV IV IV IV V V V IV IV IV IV II III IV IV V I IV V V V IV V I V V I IV III V IV III IV V
0.72 0.45 0.25 0.80 1.83 0.23 0.52 0.66 0.48 0.22 0.52 1.00 2.43 4.91 5.19 0.33 0.38 0.41 0.15 0.48 0.96 0.45 0.33 0.63 0.048 0.49 0.37 0.69 0.83 3.07 1.46 0.48 1.82 0.24 0.32 0.005 0.026 0.038 0.024
-1.88 0.10 2.27 1.31 0.71 0.54 1.15 1.64 -0.31 0.61 0.77 -1.03 0.35 0.91 0.96 1.13 0.85 0.55 0.51 1.28 1.34 0.64 1.26 2.01 1.20 1.03 0.24 1.09 0.88 1.37 0.31 1.23 1.92 -1.07 -0.99 -1.48 - 0.60 0.40 -0.41
Benzothiazole, vinylmercaptoBicyclo[2.2.1]hept-2-ene-5,6-dicarboxamine, TV-benzylButadiene Butadiene-1-carboxylate, ethyl Butadiene, 1,4-dicarboxylate, diethyl Butadiene, 2,3-dichloroButadiene, 2,3-dimethylButadiene, hexafluoroButadiene, 2-chloroButadiene, 2-fluoroButene-1 Butene-2 Carbamate, TV-vinyl-, ethyl Carbamate, TV,TV-diethyl-, vinyl Carbazole, TV-vinylCarbon monoxide
IV IV I V V V V IV II III IV IV V IV III V
0.36 0.01 1.70 1.67 1.94 9.08 1.42 0.82 10.52 1.88 0.007 0.002 0.037 0.028 0.26 0.013
- 0.44 -0.36 -0.50 1.26 1.39 0.14 -0.43 0.58 1.20 0.63 -0.06 -0.29 -1.12 -1.11 -1.29 1.68
4 4 8 5 20 12 4 4 7 5 4
0.97 0.99 0.55 0.95 0.37 0.98 0.99 0.37
6 8 5 12 4 4 6 24
4 10 6 5 6 4 12
0.90 0.85 0.96 0.98 0.93 0.60 0.62 0.95 0.47 0.82 0.99 0.99 0.93 0.58 0.93 0.98 0.77 0.08 0.44 0.91 0.95 0.99 0.70
TABLE 1. cont'd Monomer
Group
Q
e
n
r
Citraconimide, N-methylCrotonaldehyde Crotonicacid 4-Cyclopentene-l,3-dione
IV IV III IV
0.87 0.023 0.017 0.42
1.58 0.84 0.89 2.43
4 5 6 4
0.94 0.82 0.98 0.96
Diallyl melamine Diallyl phthalate Diallycyanamide AW-Divinylaniline
V IV IV II
0.059 0.031 0.14 0.26
-1.57 -0.26 2.41 -0.68
20 4 5
0.99 0.50 0.96 0.78
Ethylene Ethylene, 1,1-diphenylEthylene, chlorotrifluoroEthylene, tetrachloroEthylene, tetrafluoroEthylene, trichloro-
III IV III III IV III
0.016 0.17 0.026 0.001 0.032 0.010
0.05 -1.71 1.56 1.24 1.63 1.29
6 5 5 7 4 11
0.52 0.84 0.99 0.99 0.99 0.94
Fumarate, diethyl Fumarate, diisopropyl Fumaronitrile
IV IV IV
0.25 0.11 0.29
2.26 2.58 2.73
10 8 5
0.91 0.84 0.96
Hexatriene, tetrachloroHexene-1
IV V
1.83 0.035
0.94 0.92
6
0.98 0.69
Imidazole, 1-vinylImidazole, l-vinyl-2-methylIndene Isobutylene Isobutylene, 3-chloroIsoprene Isoprene, 3-acetoxyIsopropenyl acetate Isopropenyl methyl ketone Isopropenyl, 3-(l-cyclohexenyl), acetate Isopropenylisocyanate Itaconate, dibutyl Itaconate, diethyl Itaconate, dimethyl Itaconicacid
V IV IV III IV II V IV III V III V V III IV
0.11 0.14 0.13 0.023 0.17 1.99 1.91 0.023 1.03 0.57 0.18 0.82 1.04 0.73 0.78
-0.68 -0.98 -0.71 -1.20 -0.86 -0.55 -0.11 - 0.94 0.64 -0.66 -1.05 0.57 0.88 0.57 1.07
Maleate, diethyl Maleic anhydride Maleimide Maleimide, 2,3-dimethyl-iV-(2-methacryloxyethyl)Maleimide, 7V-(2-hydroxyethyl)Maleimide, AK2-chlorophenyl)Maleimide, A^-(4-chlorophenyl)Maleimide, Af-butylMaleimide, N-phenylMethacrylamide Methacrylamide, Af-phenylMethacrylamide, 1-deoxy-D-glucital Methacrylate, 2-chloro-2,3,3,3-tetrafluoropropyl Methacrylate, 2,2,6,6-tetra-methyl-4-piperidinyl Methacrylate, 2,3-epithio-propyl Methacrylate, benzyl Methacrylate, butyl Methacrylate, ethyl Methacrylate, ferrocenylmethyl Methacrylate, glycidyl Methacrylate, isobutyl Methacrylate, isopropyl Methacrylate, methyl Methacrylate, phenyl Methacrylate, sulfolanyl
IV IV V V V IV V V IV IV V V V IV IV IV III III IV III III IV I IV V
0.053 0.86 0.94 2.54 1.26 2.29 2.98 0.88 2.81 0.40 0.40 0.15 2.09 0.52 1.04 0.88 0.82 0.76 0.22 0.96 0.82 0.97 0.78 1.25 1.18
1.08 3.69 2.86 1.64 1.07 2.87 2.75 3.70 3.24 -0.05 0.19 -0.16 0.62 -1.09 0.29 0.35 0.28 0.17 0.65 0.20 0.27 0.10 0.40 0.79 0.95
6 8 7 4 11 4 6 8 8 5 12 25
5 4 8
4 4 10 10 7 7 9 5 4 7
0.98 0.93 0.45 0.99 0.98 0.86 0.10 0.98 0.78 0.98 0.94 0.88 0.98 0.90 0.99 0.87 0.98 0.99 0.98 0.68 0.96 0.99 0.92 0.99 0.29 0.70 0.19 0.56 0.68 0.84 0.97 0.68 0.62 0.85 0.92 0.76 0.46 0.91 0.95
References page 11-319
TABLE 1. cont'd Monomer
Group
Q
e
n
r
8 5 4
Methacrylate, 2-naphthyl Methacrylate, 2-(N,Ar-dimethyl-carbamoyloxy)ethyl Methacrylate, 2-(sulfonic acid)ethyl Methacrylate, 2-acetoxyethyl Methacrylate, 2-bromoethyl Methacrylate, 2-chloroethyl Methacrylate, 2-hydroxyethyl Methacrylate, 2-hydroxypropyl Methacrylic acid Methacrylic anhydride Methacrylonitrile Methacryloyl chloride Methacryloylacetone Methylenebutyrolactone 2-Methyleneglutaronitrile
IV IV IV V IV IV IV IV III IV I V V V IV
1.04 1.14 1.09 0.60 1.18 1.04 1.78 4.38 0.98 3.00 0.86 2.04 5.47 2.48 0.41
-0.09 0.84 0.25 0.51 0.74 0.31 -0.39 1.86 0.62 0.56 0.68 1.54 -0.76 0.83 1.25
4 7 7 7 23 5
0.46 0.74 0.52 0.80 0.96 0.79 0.67 0.81 0.73 0.93
6
0.94 0.79 0.90 0.83
Norbornadiene
III
0.051
-1.48
7
0.90
Oct-1-ene, 6,6-dimethyl-4,8-dioxaspiro(2.5)Oxazolidone, N-vinylOxazoline, 2,-2-isopropenyl-4,4-dimethylOxazoline, 2-isopropenyl-2Oxazoline, 2-,4-acryloxymethyl-2,4-dimethylOxazoline, 2-,4-methacryloxymethyl-2,4-dimethyl-
V III IV IV IV IV
0.25 0.087 0.87 0.59 0.97 0.44
0.61 -1.70 0.34 - 0.64 -0.51 - 0.70
6 4 7 4 4
0.82 0.95 0.65 0.54 0.71 0.99
Pentadiene, trans-1,3Phosphonate, a-carbomethoxyvinyl-, diethyl Phosphonate, isopropenyl-, dimethyl Phosphonate, vinyl-, bis(2-chloroethyl) Phosphonate, vinyl-, diethyl Phosphonate, vinyl-, dimethyl Phosphonic acid, a-phenyl-vinylPhthalimide, iV-Cmethacryloyloxy)Propene, 3,3,3-trichloroPropene, 1-chloro-, cisPropene, 1-chloro-, transPropene, 2-chloroPropene, 2-chloro-3-hydroxyPropene, 2,3-dichloroPropenyl, 2-chloro-, acetate Propenyl, 2-methyl-, acetate Propylene Pyridazinone, 3-(2-vinyl)-6-methylPyridazinone, 3-(2-vmyl)-6-methyl-4,5-dihydroPyridine, 2-methyl-5-vinylPyridine, 2-vinylPyridine, 2-vinyl-5-ethylPyridine, 4-vinylPyrrolidone, l-benzyl-3-methylene-5-methyl-
IV V V V V V IV V V V V V V IV IV V V V V III II IV III V
1.28 0.14 0.032 0.044 0.27 0.24 0.65 1.89 0.030 0.003 0.006 0.073 0.091 0.12 0.20 0.040 0.009 0.57 0.18 1.32 1.41 1.29 2.47 1.50
-0.13 —0.04 0.96 1.64 - 0.40 - 0.25 0.52 0.96 1.00 -0.46 -0.16 -0.16 -0.95 -0.40 -0.85 - 2.08 -1.69 0.24 -0.32 -0.66 -0.42 -0.91 0.84 -0.59
Quinoline, 2-vinyl-
IV
1.04
-0.09
Silane, 7-methacryloxypropyl-trimethoxy Styrene Styrene, 2,4,6-trimethylStyrene, 2,5-dichloroStyrene, 3-tri-«-butylstannylStyrene, a-methoxyStyrene, a-methylStyrene, m-bromoStyrene, m-chloroStyrene, m-methylStyrene, m-nitroStyrene,/7-bromoStyrene,/7-chloro-
V I IV II IV IV III IV IV V IV IV III
1.08 1.00 0.15 1.50 0.014 0.39 0.97 1.25 2.46 1.57 2.66 1.30 1.33
0.07 -0.80 -0.58 0.94 -0.61 -1.02 -0.81 -0.27 - 0.90 -0.03 1.57 -0.68 -0.64
8
5
4 5 7
9 12 4 7
4
0.54 0.96 0.98 0.89 0.54 0.53 0.76 0.74 0.99 0.84 0.28 0.99 0.99 0.67 0.61 0.97 0.84 0.58 0.35 0.95 0.97 0.94 0.86 0.98 0.46 0.35
4 12 4 5 15 4 4 7 7 12
0.41 0.96 0.51 0.77 0.98 0.98 0.87 0.06 0.85 0.99 0.92
TABLE 1. cont'd Monomer
Group
Q
e
n
r
7 5 6 5
0.74 0.75 0.99 0.98 0.65 0.51 0.91 0.87 0.96
Styrene, p-chloromethylStyrene, p-cyanoStyrene, p-methoxyStyrene,/?-methylStyrene, p-\-(2-hydroxybutyl)Styrene,/7-l-(2-hydroxypropyl)Styrene,/?-2-(2-hydroxypropyl)Styrene, pentachloroSuccinimide, iV-vinyl-
IV IV III III V IV IV V III
1.39 2.93 1.53 1.10 0.70 1.08 1.15 0.20 0.19
-0.38 -0.38 -1.40 -0.63 -0.97 -0.35 -0.49 0.79 -1.42
Tetrazole, 1-vinylTetrazole, 2-methyl-5-(4/-vinyl)phenylTetrazole, 2-methyl-5-vinylTetrazole, 2-phenyl-5-(4/-vinyl)phenylTetrazole, 5-phenyl-2-(4/-vinyl)phenylToluenesulfonamide, A^methyl-vinylTriallyl citrate Triallyl cyanurate Triallyl isocyanurate
V V V V V V IV V V
0.13 0.86 0.55 0.84 1.11 0.18 0.054 0.14 0.035
-0.14 0.51 - 0.46 -0.52 0.53 -0.53 0.26 2.41 -0.23
Urea, N-vinyl-iV'-ethyl-
V
0.17
-1.88
Vinyl acetate Vinyl benzoate Vinyl bromide Vinyl butyl ether Vinyl butylsulfonate Vinyl butyrate Vinyl chloride Vinyl chloroacetate Vinyl chloromethyl ketone Vinyl cinnamate Vinyl cymantrene Vinyl dichloroacetate Vinyl dodecyl ether Vinyl ether Vinyl ethyl ether Vinyl ethyl oxalate Vinyl ethyl sulfide Vinyl ethyl sulfoxide Vinyl fluoride Vinyl formate Vinyl hendecanoate Vinyl isobutyl ether Vinyl isobutyl sulfide Vinyl isopropyl ketone Vinyl isothiocyanate Vinyl laurate Vinyl-m-cresyl ether Vinyl methyl ketone Vinyl methyl sulfide Vinyl methyl sulfoxide Vinyl
II III IV IV IV IV II IV IV IV IV V IV IV III IV IV IV IV III III IV IV V IV V V II IV V V IV IV V IV IV IV IV IV III IV IV
0.026 0.030 0.038 0.038 0.16 0.024 0.056 0.039 16.00 0.18 0.39 0.059 0.041 0.029 0.018 0.056 0.27 0.065 0.008 0.043 0.056 0.030 0.49 0.58 0.59 0.011 0.016 0.66 0.42 0.60 0.010 0.024 0.020 0.015 0.046 0.046 1.16 0.33 0.027 0.043 0.046 0.27
-0.88 -0.89 -0.23 -1.50 1.06 -0.89 0.16 -1.61 1.78 0.76 -0.57 -1.38 -1.69 -1.16 -1.80 - 0.65 -1.31 0.05 0.72 -1.19 -0.84 -1.27 - 0.95 -1.16 0.37 -0.54 - 6.33 1.05 -1.66 -1.79 -8.53 -1.93 -1.57 -6.86 -1.22 -2.16 1.02 -0.99 -0.68 -0.97 - 2.20 -0.52
4 4 8
4
0.39 0.49 0.85 0.97 0.53 0.78 0.50 0.17 0.35 0.98
49 9 10 10 4 8 38 5 4 4 4 6 4 8 4 6 4 8 5 5 7 7 4 8 5 4 4 4 9 5 5 7 7 4 5
0.87 0.95 0.94 0.87 0.97 0.91 0.37 0.98 0.97 0.99 0.88 0.95 0.83 0.80 0.90 0.53 0.96 0.21 0.71 0.99 0.82 0.98 0.99 0.44 0.77 0.81 0.99 0.98 0.99 0.46 0.97 0.87 0.98 0.99 0.79 0.95 0.95 0.96 0.82 0.85 0.72 0.85
References page II - 319
TABLE 1. cont'd Monomer
Group
Vinyl 4-chlorocyclohexyl ketone Vinyl 2-chloroethyl ether Vinyl-tris(trimethoxysiloxy)silane /?-Vinylbenzylethylcarbinol /?-Vinylbenzylmethylcarbinol 9-Vinylanthracene Vinyl AW-diethylcarbamate p-Vinylbenzoic acid Af-Vinylcaprolactam Vinylene carbonate Vinylferrocene Vinylhydroquinone Vinylhydroquinone dibenzoate Vinylidene chloride Vinylidene cyanide Vinylisocyanate JV-Vinylpyrrolidone Vinyltriethoxysilane Vinyltrimethylsilane
IV IV IV V V IV IV V IV III IV V IV II IV III II V V
Q 0.66 0.019 0.022 0.69 1.70 0.14 0.028 5.17 0.14 0.004 0.31 4.30 1.73 0.31 14.22 0.14 0.088 0.021 0.027
e - 0.82 -1.64 -0.12 -0.98 -1.27 0.82 -1.10 1.08 -1.18 - 0.49 -1.34 2.26 0.84 0.34 1.92 -0.95 -1.62 0.82 0.19
n
9 5 5 4 4 9 6 5 40 9 6 12
r 0.50 0.96 0.75 0.67 0.98 0.90 0.95 0.95 0.72 0.73 0.91 0.87 0.87 0.68 0.82 0.98 0.95 0.61 0.58
TABLE 2. TELOGENS Telogen
Temp. (0C)
Acetone
60 80 60 80 60 80 60 80 60 80 60 60 60 80 60 80 60 80 60 60 60 60 60 60 60 80 60 80 60 60
Benzene -, chloro-,ethyl-,methylBenzoyl peroxide Butanol Butanone Cyclohexane 1,2-Dichloroethane Ethyl acetate Mercaptan, alkylMercaptoacetate, alkylMethane, dichloro-, nitro-, tetrabromoMethane, tetrachloro-, trichloroMethanol Triethylamine
Q ( x 104) 0.11 0.32 0.05 0.07 0.07 0.13 0.95 0.91 0.16 0.34 36 0.53 0.82 1.40 0.11 0.14 0.62 1.1 0.07 14500 15100 0.10 3.26 7300 3.64 5.15 1.18 1.24 0.18 28.8
e
No.
r
0.35 0.45 -1.21 -0.61 0.08 -0.06 -1.02 -0.61 -0.95 -0.87 -1.89 -0.57 0.53 1.00 -0.64 -1.41 1.34 2.07 -0.87 2.44 3.27 -0.68 -1.50 2.90 3.21 3.41 0.47 0.70 -0.93 -2.39
5 5 16 9 7 5 8 7 12 11 4 6 4 7 6 7 3 6 11 11 4 4 4 8 13 9 8 10 5 7
0.80 0.68 0.94 0.72 0.30 0.30 0.84 0.86 0.93 0.94 0.93 0.63 0.60 0.80 0.86 0.77 0.96 0.96 0.97 0.99 0.99 0.82 0.92 0.99 0.99 0.99 0.95 0.82 0.76 0.99
TABLE 3. MONOMERS ARRANGED BY Q VALUES Monomer Ethylene, tetrachloroButene-2 Propene, 1-chloro-, cis-
Q
e
0.001 0.002 0.003
1.24 - 0.29 - 0.46
Monomer Vinylene carbonate Allyl alcohol Propene, 1-chloro-, trans-
Q
e
0.004 0.005 0.006
- 0.49 - 1.48 -0.16
TABLE 3.
cont'd
Monomer Butene-1 Vinyl fluoride Propylene Bicyclo[2.2.1]hept-2-ene5,6 dicarboxamine, N-benzylEthylene, trichloroVinyl o-cresyl ether Vinyl laurate Carbon monoxide Styrene, 3-tri-rc-butylstannylVinyl p-cresyl ether Ethylene Vinyl m-cresyl ether Crotonic acid Vinyl ethyl ether Vinyl 2-chloroethyl ether Vinyl octyl ether Vinyltriethoxysilane Vinyl-tris(trimethoxysiloxy)silane Crotonaldehyde Isobutylene Isopropenyl acetate N-Allylstearamide Vinyl butyrate Vinyl octadecyl ether AUyI chloride Ethylene, chlorotrifluoroVinyl acetate Vinyl propionate Vinyltrimethylsilane Carbamate, MN-diethyl-, vinyl Vinyl WV-diethylcarbamate Vinyl ether Propene, 3,3,3-trichloroVinyl benzoate Vinyl isobutyl ether Diallyl phthalate Ethylene, tetrafluoroPhosphonate, isopropenyl-, dimethyl Hexene-1 Triallyl isocyanurate Carbamate, AT-vinyl-, ethyl Allylbenzene Vinyl bromide Vinyl butyl ether Vinyl chloroacetate Propenyl, 2-methyl-, acetate Vinyl dodecyl ether Vinyl formate Vinyl stearate Phosphonate, vinyl-, bis(2-chloroethyl) Vinyl pelargonate Vinyl phenyl ether Vinyl tert-butyl sulfide Acrylate, trifluoro-, methyl Norbornadiene Maleate, diethyl Triallyl citrate Vinyl chloride Vinyl ethyl oxalate Vinyl hendecanoate Diallyl melamine Vinyl dichloroacetate Vinyl ethyl sulfoxide Propene, 2-chloro-
Q
e
0.007 0.008 0.009
-0.06 0.72 -1.69
0.010 0.010 0.010 0.011 0.013 0.014 0.015 0.016 0.016 0.017 0.018 0.019 0.020 0.021 0.022 0.023 0.023 0.023 0.024 0.024 0.024 0.026 0.026 0.026 0.027 0.027 0.028 0.028 0.029 0.030 0.030 0.030 0.031 0.032 0.032 0.035 0.035 0.037 0.038 0.038 0.038 0.039 0.040 0.041 0.043 0.043 0.044 0.046 0.046 0.046 0.048 0.051 0.053 0.054 0.056 0.056 0.056 0.059 0.059 0.065 0.073
- 0.36 1.29 - 8.53 - 0.54 1.68 -0.61 - 6.86 0.05 - 6.33 0.89 -1.80 -1.64 -1.57 0.82 - 0.12 0.84 -1.20 - 0.94 -0.41 - 0.89 -1.93 - 0.60 1.56 - 0.88 - 0.68 0.19 -1.11 -1.10 -1.16 1.00 - 0.89 -1.27 -0.26 1.63 0.96 0.92 - 0.23 -1.12 0.40 - 0.23 -1.50 -1.61 - 2.08 -1.69 -1.19 - 0.97 1.64 - 1.22 - 2.16 - 2.20 1.20 -1.48 1.08 - 0.26 0.16 - 0.65 - 0.84 -1.57 -1.38 0.05 -0.16
Monomer Oxazolidone, N-vinylN-Vinylpyrrolidone Propene, 2-chloro-3-hydroxyFumarate, diisopropyl Imidazole, 1-vinylPropene, 2,3-dichloroIndene Tetrazole, 1-vinylN-Vinylcaprolactam Diallylcyanamide Imidazole, l-vinyl-2-methylPhosphonate, a-carbomethoxyvinyl-diethyl Triallyl cyanurate 9-Vinylanthracene Vinylisocyanate Acrylate, ferrocenylmethyl Methacrylamide, 1-deoxy-D-glucitol Styrene, 2,4,6-trimethylVinyl butylsulfonate Ethylene, 1,1 -diphenylIsobutylene, 3-chloroUrea, TV-vinyl-TV'ethylIsopropenylisocyanate Pyridazinone, 3-(2-vinyl)-6-methyl4,5-dihydroToluenesulfonamide, iVyV-methyl-vinylVinyl cinnamate Succinimide, N-vinylPropenyl, 2-chloro-, acetate Styrene, pentachloro1-Acrylamido-1-deoxy-D-glucitol Methacrylate, ferrocenylmethyl Acrylamide AHyI acetate Phosphonate, vinyl-, dimethyl Aconitate, trimethyl Fumarate, diethyl Oct-1-ene, 6,6-dimethyl-4,8-dioxaspiro(2,5)Carbazole, N-vinylAW-Divinylaniline Phosphonate, vinyl-, diethyl Vinyl ethyl sulfide Vinyl thiolacetate Fumaronitrile Vinylferrocene Vinylidene chloride Allyl acrylate Acrylate, benzyl Acrylate, octadecyl Vinyl phenyl sulfide Benzothiazole, vinylmercaptoAcrylate, 2-ethylhexyl Acrylate, butyl Styrene, a-methoxyVinyl cymantrene Methacrylamide Methacrylamide, N-phenylAcrylamide, A^Af-dimethylAcrylate, ethyl 2-Methyleneglutaronitrile 4-Cyclopentene-l,3-dione Vinyl methyl sulfide Oxazoline, 2-,4-methacryloxymethyl2,4-dimethylAcetylene, phenyl-
Q
e
0.087 0.088 0.091 0.11 0.11 0.12 0.13 0.13 0.14 0.14 0.14 0.14 0.14 0.14 0.14 0.15 0.15 0.15 0.16 0.17 0.17 0.17 0.18 0.18
-1.70 -1.62 -0.95 2.58 -0.68 -0.40 -0.71 -0.14 -1.18 2.41 -0.98 —0.04 2.41 0.82 —0.95 0.51 —0.16 -0.58 1.06 -1.71 -0.86 -1.88 —1.05 -0.32
0.18 0.18 0.19 0.20 0.20 0.22 0.22 0.23 0.24 0.24 0.25 0.25 0.25 0.26 0.26 0.27 0.27 0.27 0.29 0.31 0.31 0.32 0.33 0.33 0.33 0.36 0.37 0.38 0.39 0.39 0.40 0.40 0.41 0.41 0.41 0.42 0.42 0.44
—0.53 0.76 -1.42 - 0.85 0.79 0.61 - 0.65 0.54 -1.07 - 0.25 2.27 2.26 0.61 -1.29 - 0.68 - 0.40 -1.31 - 0.52 2.73 -1.34 0.34 - 0.99 1.13 1.26 - 0.99 — 0.44 0.24 0.85 - 1.02 - 0.57 - 0.05 0.19 -0.26 0.55 1.25 2.43 -1.66 — 0.70
0.45
0.10
References page 11-319
TABLE 3.
cont'd
Monomer Acrylate, methyl Acrylamide, N,N-diethy\ Acrylate, glycidyl Acrylonitrile Acrylate, 2-chloroethyl Vinyl isobutyl sulfide Acrylamide, Af-methylolAcrylate, a-acetoxy-, ethyl Methacrylate, 2,2,6,6-tetramethyl4-piperidinyl Tetrazole, 2-methyl-5-vinylIsopropenyl, 3-(l-cyclohexenyl)acetate Pyridazinone, 3-(2-vinyl)-6-methylVinyl isopropyl ketone Oxazoline, 2-isopropenyl-2Vinyl isothiocyanate Methacrylate, 2-acetoxyethyl Vinyl methyl sulfoxide Acrylate, octyl Phosphonic acid, a-phenylAcrylamide, Af-octadecylVinyl methyl ketone Vinyl 4-chlorocyclohexyl ketone Acrylate, 2-nitrobutyl p-Vinylbenzylethylcarbinol Styrene, p-1 -(2-hydroxybutyl)Acenaphthalene Itaconate, dimethyl Methacrylate, ethyl Itaconic acid Methacrylate, methyl Acrolein Butadiene, hexafluoroItaconate, dibutyl Methacrylate, butyl Methacrylate, isobutyl Acrylic acid Tetrazole, 2-phenyl-5-(4'-vinyl)-phenylMaleic anhydride Methacrylonitrile Tetrazole, 2-methyl-5-(4/-vinyl)-phenylCitraconimide, TV-methylOxazoline, 2-, 2-isopropenyl-4,4-dimethylMaleimide, A^-butylMethacrylate, benzyl Maleimide Acrylate, heptafluorobutyl Methacrylate, isopropyl Oxazoline, 2-,4-acryloxymethyl-2,4-dimethylStyrene, a-methylMethacrylic acid Acrylate, a-chloro-, ethyl Styrene Isopropenyl methyl ketone Itaconate, diethyl Methacrylate, 2-naphthyl Methacrylate, 2,3-epithiopropyl Methacrylate, 2-chloroethyl Quinoline, 2-vinylSilane, y-methacryloxypropyl-trimethoxy Styrene, /?-l-(2-hydroxypropyl)Methacrylate, 2-(sulfonic acid)ethyl Styrene, p-methyl-
Q
e
0.45 0.48 0.48 0.48 0.49 0.49 0.52 0.52 0.52
0.64 - 0.31 1.28 1.23 1.03 - 0.95 1.15 0.77 -1.09
0.55 0.57 0.57 0.58 0.59 0.59 0.60 0.60 0.63 0.65 0.66 0.66 0.66 0.69 0.69 0.70 0.72 0.73 0.76 0.78 0.78 0.80 0.82 0.82 0.82 0.82 0.83 0.84 0.86 0.86 0.86 0.87 0.87 0.88 0.88 0.94 0.96 0.97 0.97 0.97 0.98 1.00 1.00 1.03 1.04 1.04 1.04 1.04 1.04 1.08 1.08 1.09 1.10
- 0.46 —0.66 0.24 —1.16 - 0.64 0.37 0.51 -1.79 2.01 0.52 1.64 1.05 - 0.82 1.09 - 0.98 - 0.97 -1.88 0.57 0.17 1.07 0.40 1.31 0.58 0.57 0.28 0.27 0.88 -0.52 3.69 0.68 0.51 1.58 0.34 3.70 0.35 2.86 0.20 0.10 -0.51 -0.81 0.62 -1.03 -0.80 0.64 0.88 -0.09 0.29 0.31 -0.09 0.07 - 0.35 0.25 - 0.63
Monomer Tetrazole, 5-phenyl-2-(4'-vinyl)-phenylMethacrylate, 2-(N,N-dimethylcarbamoyloxy)ethyl Styrene, /?-2-(2-hydroxypropyl)Vinyl phenyl ketone Methacrylate, sulfolanyl Methacrylate, 2-bromoethyl Methacrylate, phenyl Styrene, m-bromoMaleimide, A^-(2-hydroxyethyl)Pentadiene, trans-1,3Pyridine, 2-vinyl-5-ethylStyrene, p-bromoPyridine, 2-methyl-5-vinylStyrene, /?-chloroStyrene, /?-chloromethylPyridine, 2-vinylButadiene, 2,3-dimethylAcrylic anhydride Pyrrolidone, l-benzyl-3-methylene-5-methylStyrene, 2,5-dichloroStyrene, p-methoxyStyrene, m-methylButadiene-1-carboxylate, ethyl Butadiene p-Vinylbenzylmethylcarbinol Vinylhydroquinone dibenzoate Methacrylate, 2-hydroxyethyl Acryloyl chloride Acrolein, methylHexatriene, tetrachloroButadiene, 2-fluoroPhthalimide, AHmethacryloyloxy)Isoprene, 3-acetoxyButadiene, 1,4-dicarboxylate, diethyl Isoprene Methacryloyl chloride Methacrylate, 2-chloro2,3,3,3-tetrafluoropropyl Styrene, m-nitroMaleimide, Ar-(2-chlorophenyl)Acrylate, a-chloro-, methyl Styrene, ra-chloroPyridine, 4-vinylMethylenebutyrolactone Maleimide, 2,3-dimethylAf-(2-methacryloxyethyl)Styrene, o-chloroMaleimide, JV-phenylStyrene, /?-cyanoMaleimide, A^-(4-chlorophenyl)Methacrylic anhydride Acrylic acid, a-bromoVinylhydroquinone Methacrylate, 2-hydroxypropyl Acrylate, a-cyano-, methyl /7-Vinylbenzoic acid Acrylate, a-phenyl-, methyl Methacryloylacetone Butadiene, 2,3-dichloroButadiene, 2-chloroVinylidene cyanide Vinyl chloromethyl ketone
Q
e
1.11 1.14
0.53 0.84
1.15 1.16 1.18 1.18 1.25 1.25 1.26 1.28 1.29 1.30 1.32 1.33 1.39 1.41 1.42 1.46 1.50 1.50 1.53 1.57 1.67 1.70 1.70 1.73 1.78 1.82 1.83 1.83 1.88 1.89 1.91 1.94 1.99 2.04
- 0.49 1.02 0.95 0.74 0.79 -0.27 1.07 -0.13 - 0.91 - 0.68 -0.66 — 0.64 - 0.38 -0.42 -0.43 0.31 -0.59 0.94 —1.40 -0.03 1.26 -0.50 —1.27 0.84 -0.39 1.92 0.71 0.94 0.63 0.96 —0.11 1.39 -0.55 1.54
2.09 2.19 2.29 2.43 2.46 2.47 2.48 2.54
0.62 0.20 2.87 0.35 - 0.90 0.84 0.83 1.64
2.66 2.81 2.93 2.98 3.00 3.07 4.30 4.38 4.91 5.17 5.19 5.47 9.08 10.52 14.22 16.00
1.57 3.24 - 0.38 2.75 0.56 1.37 2.26 1.86 0.91 1.08 0.96 - 0.76 0.14 1.20 1.92 1.78
TABLE 4. MONOMERS ARRANGED BY e VALUES Monomer Vinyl ethyl sulfoxide Ethylene Silane, y-methacryloxypropyl-trimethoxy Acetylene, phenylMethacrylate, isopropyl Butadiene, 2,3-dichloroVinyl chloride Methacrylate, ethyl Vinyltrimethylsilane Methacrylamide, N-phenylMethacrylate, glycidyl Styrene, ra-nitroAcrylate, 2-ethylhexyl Pyridazinone, 3-(2-vinyl)-6-methylMethacrylate, 2-(sulfonic acid)ethyl Methacrylate, isobutyl Methacrylate, butyl Methacrylate, 2,3-epithiopropyl Methacrylate, 2-chloroethyl Acrylic anhydride Vinylidene chloride Oxazoline, 2-,2-isopropenyl-4,4-dimethylMethacrylate, benzyl Acrylate, a-chloro-, methyl Vinyl isothiocyanate Allylbenzene Methacrylate, methyl Acrylate, ferrocenylmethyl Methacrylate, 2-acetoxyethyl Tetrazole, 2-methyl-5-(4'-vinyl)-phenylPhosphonic acid, oc-phenylvinylTetrazole, 5-phenyl-2-(4'-vinyl)-phenylAcrylamide Acrylate, ethyl Methacrylic anhydride Itaconate, dimethyl Itaconate, dibutyl Butadiene, hexafluoro1-Acrylamideo-l-deoxy-D-glucitol Oct-1-ene, 6,6-dimethyl-4,8-dioxaspiro(2.5)Methacrylic acid Butadiene, 2-fluoroAcrylate, methyl Isopropenyl methyl ketone Methacrylonitrile Acrolein, methylVinyl fluoride Methacrylate, 2-bromoethyl Vinyl cinnamate Acrylate, oc-acetoxy-, ethyl Styrene, pentachloroMethacrylate, phenyl Vinyltriethoxysilane 9-Vinylanthracene Methylenebutyrolactone Vinylhydroquinone dibenzoate Crotonaldehyde Methacrylate, 2-(ATv/V-dimethylcarbamoyloxy)ethyl Pyridine, 4-vinylAcrylate, butyl Acrylic acid Itaconate, diethyl Crotonic acid Acrylate, a-cyano-, methyl
Q
e
Monomer
0.065 0.016 1.08 0.45 0.97 9.08 0.056 0.76 0.027 0.40 0.96 2.19 0.37 0.57 1.09 0.82 0.82 1.04 1.04 1.46 0.31 0.87 0.88 2.43 0.59 0.038 0.78 0.15 0.60 0.86 0.65 1.11 0.23 0.41 3.00 0.73 0.82 0.82 0.22 0.25 0.98 1.88 0.45 1.03 0.86 1.83 0.008 1.18 0.18 0.52 0.20 1.25 0.021 0.14 2.48 1.73 0.023 1.14
0.05 0.05 0.07 0.10 0.10 0.14 0.16 0.17 0.19 0.19 0.20 0.20 0.24 0.24 0.25 0.27 0.28 0.29 0.31 0.31 0.34 0.34 0.35 0.35 0.37 0.40 0.40 0.51 0.51 0.51 0.52 0.53 0.54 0.55 0.56 0.57 0.57 0.58 0.61 0.61 0.62 0.63 0.64 0.64 0.68 0.71 0.72 0.74 0.76 0.77 0.79 0.79 0.82 0.82 0.83 0.84 0.84 0.84
2.47 0.38 0.83 1.04 0.017 4.91
0.84 0.85 0.88 0.88 0.89 0.91
Hexene-1 Styrene, 2,5-dichloroHexatriene, tetrachloroMethacrylate, sulfolanyl Phosphonate, isopropenyl-, dimethyl Phthalimide, AHmethacryloyloxy)Acrylate, a-phenyl-, methyl Propene, 3,3,3-trichloroVinyl phenyl ketone Acrylate, 2-chloroethyl Vinyl methyl ketone Vinyl butylsulfonate Itaconic acid Maleimide, A^-(2-hydroxyethyl)/?-Vinylbenzoic acid Maleate, diethyl Acrylate, 2-nitrobutyl Acrylate, benzyl Acrylamide, Af-methylolAcrylate, trifluoro-, methyl Butadiene, 2-chloroAcrylonitrile Ethylene, tetrachloro2-Methyleneglutaronitrile Acrylate, octadecyl Butadiene-1-carboxylate, ethyl Acrylate, glycidyl Ethylene, trichloroAcrolein Acrylate, heptafluorobutyl Acrylic acid, a-bromoButadiene, 1,4-dicarboxylate, diethyl Methacryloyl chloride Ethylene, chlorotrifluoroStyrene, ochloroCitraconimide, N-methylEthylene, tetrafluoroPhosphonate, vinyl-, bis(2-chloro-ethyl) Acrylamide, N-octadecylMaleimide, 2,3-dimethyl-Af(2-methacryloxyethyl)Carbon monoxide Vinyl chloromethyl ketone Methacrylate, 2-hydroxypropyl Vinylidene cyanide Acryloyl chloride Acrylate, octyl Methacrylate, 2-chloro2,3,3,3-tetrafluoropropyl Vinylhydroquinone Fumarate, diethyl Aconitate, trimethyl Fumarate, diisopropyl Triallyl cyanurate Diallylcyanamide 4-Cyclopentene-l,3-dione Fumaronitrile Maleimide, AT-(4-chlorophenyl)Maleimide Maleimide, N-(2-chlorophenyl)Maleimide, Af-phenylMaleic anhydride Maleimide, N-butylStyrene, m-methylPhosphonate, a-carbomethoxyvinyl-, diethyl
Q
e
0.035 1.50 1.83 1.18 0.032 1.89 5.19 0.030 1.16 0.49 0.66 0.16 0.78 1.26 5.17 0.053 0.69 0.33 0.52 0.048 10.52 0.48 0.001 0.41 0.33 1.67 0.48 0.010 0.80 0.96 3.07 1.94 2.04 0.026 2.66 0.87 0.032 0.044 0.66
0.92 0.94 0.94 0.95 0.96 0.96 0.96 1.00 1.02 1.03 1.05 1.06 1.07 1.07 1.08 1.08 1.09 1.13 1.15 1.20 1.20 1.23 1.24 1.25 1.26 1.26 1.28 1.29 1.31 1.34 1.37 1.39 1.54 1.56 1.57 1.58 1.63 1.64 1.64
2.54 0.013 16.00 4.38 14.22 1.82 0.63 0.62
1.64 1.68 1.78 1.86 1.92 1.92 2.01 2.09
4.30 0.25 0.25 0.11 0.14 0.14 0.42 0.29 2.98 0.94 2.29 2.81 0.86 0.88 1.57 0.14
2.26 2.26 2.27 2.58 2.41 2.41 2.43 2.73 2.75 2.86 2.87 3.24 3.69 3.70 -0.03 —0.04
References page 11-319
TABLE 4. cont'd Monomer Methacrylamide Butene-1 Methacrylate, 2-naphthyl Quinoline, 2-vinylIsoprene, 3-acetoxyVinyl-tris(trimethoxysiloxy )silane Pentadiene, trans-1,3Tetrazole, 1-vinylPropene, 1-chloro-, transPropene, 2-chloroMethacrylamide, 1-deoxy-D-glucitol Triallyl isocyanurate Vinyl bromide Phosphonate, vinyl-, dimethyl Triallyl citrate Diallyl phthalate Acrylamide, WV-dimethylStyrene, m-bromoButene-2 Acrylamide, MA^-diethyl Pyridazinone, 3-(2-vinyl)-6-methylStyrene, /?-l-(2-hydroxypropyl)Bicyclo[2.2.1]hept-2-ene5,6 dicarboxamine, Af-benzylStyrene, /?-chloromethylStyrene, /?-cyanoMethacrylate, 2-hydroxyethyl Propene, 2,3-dichloroPhosphonate, vinyl-, diethyl N-Allylstearamide Pyridine, 2-vinylButadiene, 2,3-dimethylBenzothiazole, vinylmercaptoTetrazole, 2-methyl-5-vinylPropene, 1-chloro-, cisVinylene carbonate Styrene, p-2-(2-hydroxypropyl)Butadiene Oxazoline, 2,4-acryloxymethyl-2,4-dimethylVinyl thiolacetate Tetrazole, 2-phenyl-5-(4/-vinyl)-phenylToluenesulfonamide, iVVV-methyl-vinylVinyl laurate Isoprene Vinyl cymantrene Styrene, 2,4,6-trimethylPyrrolidone, l-benzyl-3-methylene-5-methylAUyI chloride Styrene, 3-tri-n-butylstannylStyrene, /?-methylOxazoline, 2-isopropenyl-2Styrene, /?-chloroVinyl ethyl oxalate Methacrylate, ferrocenylmethyl Isopropenyl, 3-(l-cyclohexenyl)-acetate Pyridine, 2-methyl-5-vinylVinyl propionate Imidazole, 1-vinylMN-Divinylaniline Styrene, p-bromoOxazoline, 2-,4-methacryloxymethyl2,4-dimethylIndene Methacryloylacetone Styrene Styrene, a-methyl-
Q
e
0.40 0.007 1.04 1.04 1.91 0.022 1.28 0.13 0.006 0.073 0.15 0.035 0.038 0.24 0.054 0.031 0.41 1.25 0.002 0.48 0.18 1.08
- 0.05 -0.06 -0.09 -0.09 —0.11 -0.12 -0.13 -0.14 -0.16 - 0.16 —0.16 - 0.23 - 0.23 - 0.25 - 0.26 -0.26 -0.26 -0.27 - 0.29 -0.31 -0.32 - 0.35
0.01 1.39 2.93 1.78 0.12 0.27 0.024 1.41 1.42 0.36 0.55 0.003 0.004 1.15 1.70 0.97 0.27 0.84 0.18 0.011 1.99 0.39 0.15 1.50 0.026 0.014 1.10 0.59 1.33 0.056 0.22 0.57 1.32 0.027 0.11 0.26 1.30 0.44
— 0.36 - 0.38 - 0.38 -0.39 -0.40 - 0.40 -0.41 - 0.42 -0.43 — 0.44 - 0.46 - 0.46 - 0.49 - 0.49 -0.50 -0.51 - 0.52 -0.52 - 0.53 -0.54 -0.55 - 0.57 -0.58 —0.59 -0.60 -0.61 - 0.63 —0.64 - 0.64 - 0.65 - 0.65 —0.66 -0.66 - 0.68 -0.68 - 0.68 - 0.68 - 0.70
0.13 5.47 1.00 0.97
-0.71 - 0.76 -0.80 -0.81
Monomer Vinyl 4-chlorocyclohexyl ketone Vinyl hendecanoate Propenyl, 2-chloro-, acetate Isobutylene, 3-chloroVinyl acetate Vinyl butyrate Vinyl benzoate Styrene, m-chloroPyridine, 2-vinyl-5-ethylIsopropenyl acetate Vinylisocyanate Vinyl isobutyl sulfide Propene, 2-chloro-3-hydroxyVinyl stearate Styrene, p-1 (2-hydroxybutyl)/7-Vinylbenzylethylcarbinol Imidazole, l-vinyl-2-methylVinyl phenyl sulfide AHyI acrylate Styrene, oe-methoxyAcrylate, a-chloro-, ethyl Isopropenylisocyanate Allyl acetate Methacrylate, 2,2,6,6-tetramethyl-piperidinyl Vinyl AW-diethylcarbamate Carbamate, AW-diethyl-, vinyl Carbamate, N-vinyl-, ethyl Vinyl ether Vinyl isopropyl ketone N- Vinylcaprolactam Vinyl formate Isobutylene Vinyl pelargonate Vinyl isobutyl ether /7-Vinylbenzylmethylcarbinol Carbazole, N-vinylVinyl ethyl sulfide Vinylferrocene Vinyl dichloroacetate Styrene, p-methoxySuccinimide, N-vinylAllyl alcohol Norbornadiene Vinyl butyl ether Vinyl octyl ether Diallyl melamine Vinyl chloroacetate N-Vinylpyrrolidone Vinyl 2-chloroethyl ether Vinyl methyl sulfide Vinyl dodecyl ether Propylene Oxazolidone, TV-vinylEthylene, 1,1-diphenylVinyl methyl sulfoxide Vinyl ethyl ether Urea, Af-vinyl-Af'ethylAcenaphthalene Vinyl octadecyl ether Propenyl, 2-methyl-, acetate Vinyl phenyl ether Vinyl terf-butyl sulfide Vinyl m-cresyl ether Vinyl /?-cresyl ether Vinyl o-cresyl ether
Q
e
0.66 0.056 0.20 0.17 0.026 0.024 0.030 2.46 1.29 0.023 0.14 0.49 0.091 0.043 0.70 0.69 0.14 0.33 0.32 0.39 1.00 0.18 0.24 0.52 0.028 0.028 0.037 0.029 0.58 0.14 0.043 0.023 0.046 0.030 1.70 0.26 0.27 0.31 0.059 1.53 0.19 0.005 0.051 0.038 0.020 0.059 0.039 0.088 0.019 0.42 0.041 0.009 0.087 0.17 0.60 0.018 0.17 0.72 0.024 0.040 0.046 0.046 0.016 0.015 0.010
- 0.82 - 0.84 - 0.85 -0.86 - 0.88 - 0.89 - 0.89 - 0.90 - 0.91 - 0.94 —0.95 - 0.95 -0.95 - 0.97 - 0.97 - 0.98 -0.98 - 0.99 - 0.99 -1.02 -1.03 —1.05 -1.07 -1.09 -1.10 -1.11 -1.12 -1.16 —1.16 -1.18 -1.19 -1.20 -1.22 -1.27 —1.27 -1.29 -1.31 —1.34 -1.38 -1.40 —1.42 -1.48 -1.48 -1.50 -1.57 -1.57 -1.61 -1.62 -1.64 -1.66 -1.69 -1.69 -1.70 -1.71 -1.79 -1.80 -1.88 -1.88 -1.93 - 2.08 -2.16 - 2.20 - 6.33 - 6.86 - 8.53
C. REFERENCES 1. T. Alfrey, C. C. Price, J. Polym. ScL, 2, 101 (1947). 2. R. Z. Greenley, J. Macromol. Sci. A: Chem., 9, 505 (1975). 3. L. J. Young, in: J. Brandrup, E. H. Immergut (Eds.), "Polymer Handbook", 2nd ed., Wiley, New York, 1975.
4. R. Z. Greenley, J. Macromol. Sci. A: Chem., 11, 933 (1977). 5. A. D. Jenkins, J. Polym. Sci.: Part A: Polym. Chem., 34, 3495 (1996).
P a t t e r n s f o r
t h e
o f
R e a c t i v i t y
P r e d i c t i o n
R a t i o s i n
a n d
o f
( U , V )
M o n o m e r
T r a n s f e r
R a d i c a l
P a r a m e t e r s R e a c t i v i t y
C o n s t a n t s
P o l y m e r i z a t i o n
A u b r e y D . Jenkins, Jitka Jenkins School of Chemistry, Physics and Environmental Science, University of Sussex, Brighton, Sussex, BN1 9QJ, UK
A. B. C. D.
Introduction Example Transfer Constants Tables of Parameters Table 1. Monomers Table 2. Transfer Agents E. References
A.
11-321 II-322 II-322 II-323 II-323 II-326 II-327
INTRODUCTION
The relation between monomer reactivity ratios and the Alfrey-Price Q-e parameters is explained in the introduction to the tables of monomer reactivity ratios and Q-e values, compiled by Robert Z. Greenley and published in the present volume (1,2). Although very widely used, the Q-e scheme is well known to have serious limitations (3), which have prompted several attempts to improve upon it. One such endeavour was the "Patterns of Reactivity" scheme, first described as long ago as 1959 (4-7), when the Q-e scheme was only about ten years old; despite the indisputably more satisfactory basis of this procedure, it did not achieve popularity but recent revisions have greatly improved both its accessibility and its accuracy (3,8,9). In the Q-e scheme, four parameters (Qi, Q2, e\, e2, two for each monomer) are necessary for the prediction of a monomer reactivity ratio (e.g. r\2 = &11/&12, where subscript 1 refers to the radical and subscript 2 to the monomer) but the same four parameters also facilitate the prediction of the partner monomer reactivity ratio (?2\ — k22/k2\) because identical Q and e parameters are used to characterise both a given monomer and its derived radical. This device is certainly economical on input data but it introduces an approximation of very doubtful validity. In the "Patterns" scheme (to use the abbreviated title), different parameters are designated for the monomer and its conjugate radical. Hence, while four input parameters are
again necessary for the calculation of a single monomer reactivity ratio, eight are required to calculate both r\2 and r2\. The reward for the greater input of data is a substantial increase in the precision of the result; furthermore, all four parameters for each monomer/radical conjugate pair are experimentally determined from polymerization data, specifically monomer reactivity ratios from Greenley's tabulation, so no arbitrary assignment is involved, as it is with the Q-e scheme. The fundamental equation for the calculation of a reactivity ratio, r\2, is given below. log rn = log ris - U2TTi - V2.
(Al)
Here, the symbol S denotes the monomer styrene, and log ris is the counterpart of Q\ in the Q-e scheme. The counterpart of ei is the polarity parameter TTI; this is usually almost exactly equal to the Hammett a parameter for the substituent(s) present on the oc-carbon atom of the radical derived from monomer 1 but it is best calculated (8) from monomer reactivity ratio data according to Eq. (A2). TT1 = 0.385 log[(r 1A )/0.377(n s )]
(A2)
Here, the symbol A denotes the monomer acrylonitrile. It is truly an astonishing fact that the Hammett a parameter, derived originally from studies of the dissociation of substituted benzoic acids, is equal in value to a simple quantity derived from a knowledge of the monomer reactivity ratios for the reactions of a monomer 1 with (separately) acrylonitrile and styrene. The values of U2 and V2, the respective counterparts of the Q-e scheme's e2 and Q2, are determined by reference to data for the (separate) copolymerizations of monomer 2 with the members of a Basic Monomer Set. These are five monomers for which reliable data exist in the literature: styrene (S); methyl methacrylate (MM); methyl acrylate
(MA); methacrylonitrile (MAN); and acrylonitrile (A). Ideally, monomer reactivity ratios should be known for the copolymerization of the monomer of interest (labelled 2 in this case) with each of these five reference monomers. If the reference monomer is monomer 1 in this context, a plot is made of [log r 12 — log ris] against TT\; the slope of the resulting straight line is — Ui and the intercept on the ordinate axis is — V2, in conformity with Eq. (Al). If data for reactions with all five members of the Basic Monomer Set are not available, use can be made of such data as exists, always provided that styrene and acrylonitrile are among the monomers included. This condition ensures that the data are spread over a wide range of radical polarity, represented by TT\, because styrene has a very low value (zero), while acrylonitrile has one of the highest values known (0.701). In Table 1, each monomer is designated either as Basic or assigned to a category according to the number of members of the Basic Monomer Set for which data have been employed in the determination of its U2 and V2; for category 5, all five Basic monomers were involved, and so on down to category 2, where data for only styrene and acrylonitrile are available. Clearly, the higher the category number, the more reliable the w2 and V2 values. The procedure described thus far is known as the Patterns U, V Scheme (3). For Group 2 monomers, there is no need to make a plot because the use of just two data points permits algebraic solutions to be found. In fact, it can be shown (3) that the following relations hold.
(A3) Substitution in Eq. (Al) leads to the following relationships (A4, A5), giving the two monomer reactivity ratios for the copolymerization of any two monomers, 1 and 2.
(A4)
(A5) Application of Eqs. (A3-A5) corresponds to the Patterns A, S Scheme (4), so-called, because data for reaction with only acrylonitrile and styrene are involved. According to the Patterns A,S Scheme, it is possible to calculate the two monomer reactivity ratios for copolymerization of monomers 1 and 2, if each of them has separately been copolymerized with acrylonitrile and styrene. (The two monomer reactivity ratios for copolymerization of acrylonitrile and styrene are also required. These are taken to be: rAS = 0.04, r SA = 0.38 (3).)
The TT, w, and v values listed in the table below have been derived as explained above, with the Patterns U,V Scheme being used for the monomers in categories 3 - 5 and the Patterns A,S Scheme for those in category 2. The r\$ values are mean values from the figures supplied in Greenley's table, making due allowance for the consistency of the data. B. EXAMPLE Suppose one wants to evaluate the monomer reactivity ratios for the copolymerization of 2-chlorobutadiene (CB) and 2-vinylpyridine (VP). To use the Patterns U,V Scheme for this purpose, it is first necessary to consult Greenley's table of monomer reactivity ratios for data characterizing the copolymerizations of each of these monomers with as many members of the Basic Monomer Set as possible. In fact, in both cases, values exist for reactions with styrene, methyl methacrylate, methyl acrylate and acrylonitrile, but not methacrylonitrile. The TT values for the four useful basic monomers are, respectively, 0.000, 0.339, 0.423 and 0.701. The relevant monomer reactivity ratios are listed in the table below. MONOMER REACTIVITY RATIOS FOR 2-CHLOROBUTADIENE AND 2-VINYLPYRIDINE AND MEMBERS OF THE BASIC MONOMER SET Monomer reactivity ratio
2-Chlorobutadiene
2-Vinylpyridine
rxs rXA rs,x rA,x
6.91 5.18 0.038 0.05
1.26 0.44 0.53 0.10
r MM ,x r MA ,x
0.08 0.06
0.35 0.25
X = 2-chlorobutadiene or 2-vinylpyridine.
Plots of [log r 12 — log ris] against TT\, where 2 = CB or VP, are linear with slopes and intercepts that provide the following u and v values (9). For CB, u = - 2.18, v = 1.44, and for VP, u = - 0.982 and v = 0.323. All the data are now available for substitution in Eq. (Al), first for CB = monomer 1 and VP = monomer 2, and secondly with the monomers' roles reversed, to obtain values of r\i and rj\. The results are rn = 4.26 and r2\ =0.04. The Patterns A,S Scheme can be applied by simply substituting the appropriate monomer reactivity ratio data in Eqs. (A4) and (A5), giving ri2 = 4.71 and r 2 i = 0 . 0 5 . The corresponding experimental results are ri2 = 5.19 and 7*21 =0.06, while the Q = e scheme predicts that ri2 = 1.07 and r2i =0.07. C
TRANSFERCONSTANTS
Transfer constants can be predicted by exactly parallel reasoning (3). It is necessary only to realise that whereas the rate constant for the propagation step of a radical with its own parent monomer appears in the numerator of a monomer reactivity ratio (Vi2 = &11A12X where both rate
constants refer to propagation reactions, it figures in the denominator of a transfer constant because (C 2) 1 = kn/kn, where k\2 represents a transfer reaction between the radical derived from a monomer (species 1) and a transfer agent (species 2); the equations for calculating transfer constants are thus easily obtained from the equations above by replacing log rn by - l o g (C2)1. The only formal difference between the two cases is that, for transfer, there is no symmetrical counterpart of the equations representing reaction of a radical of type 2 with a transfer agent of type 1. Thus, the equivalent of Eq. (Al), for transfer is Eq. (A6), and this enables the Patterns U,V Scheme to be applied to chain transfer. (A6) For use of the Patterns A,S Scheme in transfer, a parallel derivation to that used in copolymerization leads to the following equation, where (C2) s a n d (C 2) A are, respectively, the (known) transfer constants for reaction of the same transfer agent (species 2) with radicals derived from styrene and acrylonitrile (species 1). (A7) Since IT A — 0.701 and r A s = 0 . 0 4 , this equation can be reduced to Eq. (A8) for general use. (A8) The transfer constants used here are taken from two tabulations, one due to Eastmond (10) and one in the Polymer Handbook (11). D.
TABLES OF PARAMETERS
As explained above, each monomer or transfer agent is assigned to a category, designated by Basic or the number 2, 3, 4, or 5, according to the number of members of the
Basic Monomer Set with which this reagent has been reacted to obtain data for the evaluation of w, v and (in the case of monomers) TT. Although it must be true that the higher the category, the more reliable the derived parameters, the difference between Categories 2 and 5 is not so great as might appear at first sight. In all cases, two of the basic monomers involved are styrene, S, (the least polar) and acrylonitrile, A, (the most polar), so the role played by other basic monomers is merely to add intermediate points to what should be a straight line joining the data points for S and A; if the data for these two latter monomers are accurate, intermediate points add little or no value beyond confirmation of the slope and intercept. They do contribute valuable weighting when there are some discrepancies in the data, but parameters have not been recorded here in cases where the discrepancies are large. Where either r\$ or r i A was reported as zero, the value 0.05 has been assigned arbitrarily in order to make it possible to calculate an approximate value for the TT parameter but the values of the u and v parameters are not influenced by this device; entries of this type are printed in italics in Table 1. Sometimes both r\s and n A are reported to be zero; when this happens, TT cannot usefully be estimated but u and v can still be determined, if positive values of r$\ and r A i are available. Nomenclature In the tables below, compounds are listed in alphabetical sequence in accordance with the following rules: The primary listing is based on the root name of the compound and the secondary sequence on the name(s) of the substituent(s) or the esterifying moiety. For example, the compounds, p-methyl styrene, N-vinyl carbazole, and ethyl acrylate, will be found listed under Styrene, p-methyl, Carbazole, N-vinyl, and Acrylate, ethyl, respectively. In deciding on the appropriate order of names, all prefixes (alphanumeric, Greek or whatever) and spaces are ignored, and reliance is placed solely on the alphabetical priority of the strictly chemical part of the name. In styrene, p-methyl, for example, the prefix p- plays no part in determining the place of this name in the list; this is governed by the m in methyl.
TABLE 1. MONOMERS Monomer Acenaphthalene Acetylene, phenyl Aconitate, trimethyl Acrolein Acrolein, methyl Acrylamide Acrylamide, iV-methylol Acrylamide, N-octadecyl Acrylate, benzyl Acrylate, butyl Acrylate, 2-chloroethyl Acrylate, oc-chloro-, methyl
Category
rls
r1A
rA1
4 5 2 5 4 3 4 3 3 3 4 3
0.33 0.33
2.56 0.33
0.27 0.60 0.70 0.48 0.54 0.20 0.18 0.12 0.30
1.11 3.10 1.10 2.43 1.40 0.72 0.97 0.87 1.76
0.02 0.27 4.24 0.78 0.15 0.90 0.60 1.03 1.49 1.11 1.03 O.fe
rSi
log(ri S )
n
3.81 0.32 1.026 0.23 0.26 1.20 0.03 2.08 0.49 0.77 0.53 0.25
-0.4815 -0.4815
0.506 0.159
-0.5686 -0.2219 -0.1549 -0.3188 -0.2676 -0.6990 -0.7447 -0.9208 -0.5229
0.397 0.436 0.237 0.432 0.321 0.376 0.443 0.492 0.457
u
v
1.33 -1.88 -2.88 -2.75 -1.73 -1.82 -3.94 -1.56 -2.68 -2.22 -2.38 -1.55
-0.46 0.37 -0.01 0.59 0.77 -0.07 1.18 -0.35 0.28 0.12 0.25 0.64
References page II - 327
TABLE 1. cont'd Monomer
Category
Acrylate, a-cyano-, methyl Acrylate, 3,4-epoxyhexahydrobenzyl Acrylate, P-ethoxy-, ethyl Acrylate, ethyl Acrylate, methyl Acrylate, octadecyl Acrylate, octyl Acrylate, 2-nitrobutyl Acrylate, a-phenyl-, methyl Acrylate, di-zinc Acrylonitrile Acryloyl chloride Allyl acetate AUyI chloride Aniline, N,N-divinyl Benzothiazole, vinylmercaptoButadiene Butadiene-1-carboxylic acid Butadiene- 1-carboxylate, ethyl Butadiene-1,4-dicarboxylic acid Butadiene, 1,4-dicarboxylate-, diethyl Butadiene, 2-chloroButadiene, 2-fluoroButadiene, 2-trimethylsilyloxyCarbazole, TV-vinyl Cinnamonitrile Citraconimide, TV-methylCrotonaldehyde Crotonate, a-acetyl-, methyl Crotonate, a-carboethoxy-, ethyl Crotonate, a-chloro-, ethyl Crotonate, a-cyano-, ethyl Crotonate, ethyl Crotonate, u-methoxy-, methyl Crotonate, OL-methyl-, methyl Crotonicacid Diallyl phthalate Ethylene Ethylene, tetrachloroEthylene, trichloroEthylene, diphenylFumarate, diethyl Fumarate, diisopropyl Hexatriene, tetrachloroImidazole, yV-vinyl Isoprene Isopropenyl isocyanate Isopropenyl methyl ketone Itaconicacid Itaconic anhydride Maleate, diethyl Maleic anhydride Maleimide, N-(2-chlorophenyl)Methacrylamide, /V-phenylMethacrylate, benzyl Methacrylate, 2-bromoethyl Methacrylate, butyl Methacrylate, isobutyl
rls
rlA
rAl
rSi
log(ri S )
n
u
0.61 1.97
0.68 0.39
0.01 0.25
0.05 0.27
-0.2147 0.2945
0.180 -0.110
-1.09 -1.95
1.20 0.57
0.17 0.18 0.26 0.125 0.12 1.28 0.90 0.04 0.02
0.87 0.85 1.20 0.84 1.76 6.70 0.24 1.00 1.00
-0.7696 -0.7447 -0.5850 -2.0000 -0.9208 0.1072 -0.0458 -1.3980 -1.6990
0.436 0.421 0.417 0.482 0.610 0.438 -0.060 0.701 0.815
0.04 0.033 0.42 1.40 5.55 0.3 0.52
0.04 0.05 0.18 0.29 7.5 3.2 4.00
2.42 0.80 1.42 3.15 1.98 0.67 0.08 0.41 1.00 1.20 6.57 2.80 0.246 0.19 0.06 0.12 0.3 0.20
-1.3980 -1.482 -0.3768 0.1461 0.7443 -0.5229 -0.2840
0.162 0.231 0.020 -0.100 0.213 0.559 0.502
-0.16 -1.99 -2.34 -3.01 -3.01 -2.39 -2.13 -1.39 -2.60 -3.50 -0.37 -0.39 -0.08 -0.38 -0.30 -2.00 -2.57 -2.18
-1.67 0.08 0.16 0.24 0.41 0.44 1.20 -0.04 0.42 1.09 -1.97 -1.53 -0.73 -0.38 0.41 0.94 0.92 0.82
2
0.55
2.79
0.29
0.09
-0.2596
0.433
-2.73
1.05
4 3 2
6.91 1.67 1.20
5.18 0.60 0.07
0.05 0.077 0.036
0.038 0.22 0.64
0.113 -0.0095 -0.324
-2.18 -1.32 -0.21
1.44 0.51 0.19
0.05 0.24 0.07
0.36 0.60 0.01
-0.25 -2.74 -2.77 -2.33 -2.72 -2.51
-0.58 -0.41 0.59 -1.17 -0.43 -0.92
0.02
0.06
0.04
-0.71 0.59 -1.43 -1.26
5 2 2 3 B 3 2 3 5 2 B 4 3 3 2 3 5 2 2 2
4 2 3 2 2 2 2 2 2 2 2 2 4 3 3 4 5 3 5 4 3 4 3 2 3 2 3 4 3 3 3 3 4 4
46.98 0.81 0.75 0.61 0.39 0.35 0.06 1.10 0.38 0.10 90 36 5.38 2.6 0.57 0.115 0.12 0.15
0.39 8.46 0.53 25 8.68 18.7
5.82 2.55 0.145 14.7 2.7 8.24
0.05
9.53 11.4 25.2 1.00
5.13 0.26 27 18.4
0.02
0.05
2.97
30.7
0.076 0.05
0.0385 0.05
0.06 0.055 0.85 0.68 1.84 0.096 0.48 0.12 0.55 0.04 0.011 0.021 0.88 0.47 0.41 0.53 0.42
0.05 0.20 4.01 0.832 0.45 0.1 0.95 0.86 4.83 0.05 0.05 1.078 0.71 0.96 2.38 0.98 1.05
21 3.5 7 463 64.5 0.05 9 16 0.234 3.39 0.03 0.24 0.33 0.59 0.034 16 6 0.956 0.381 0.2 0.31 0.291 0.217
20 23.5 14.88 195 14.6 0.335 0.33 0.4 0.123 8.38 0.458 7.48 0.38 0.26 0.031 7.03 0.36 0.0245 1.24 0.52 0.32 0.6 0.54
0.8395 0.2227 0.0792
v
-1.3010 -0.6198 -1.1549
0.491 0.315 -0.164
-1.6990
0.345
-1.3980
0.199
-2.38 -4.35 -1.96 -0.19
-1.699
0.315
-0.55
-1.49
-1.301 -1.12 -1.301
0.048 0.162
-2.03 -0.77 -1.57 - 2.60 -2.87 - 0.74 -4.05 -4.31 -2.39 -1.44 -0.32 0.14 -1.91 -2.50 -2.06 -2.51 -5.20 -4.23 -1.26 -1.40 -1.97 -1.49 -1.43
-1.30 -1.35 -1.23 - 2.36 -1.20 0.23 0.56 0.17 0.86 -0.92 0.34 -0.87 0.42 0.54 1.51 -0.83 1.22 1.32 -0.08 0.26 0.47 0.26 0.27
-1.222 -1.26 -0.0706 -0.1675 0.2648 -1.0177 -0.3188 -0.9208 -0.2596 -1.398 -1.959 -1.688 -0.0555 -0.3279 -0.3872 -0.2757 -0.3768
0.131 0.377 0.421 0.195 -0.074 0.170 0.276 0.491 0.526 0.199 0.416 0.826 0.126 0.281 0.455 0.267 0.315
TABLE 1. cont'd Monomer Methacrylate, 2-chloroethyl Methacrylate, ferrocenylmethyl Methacrylate, glycidyl Methacrylate, 2-hydroxyethyl Methacrylate, methyl Methacrylate, 3,5-dimethyladamantyl Methacrylate, 2,2,6,6-tetramethyl4-piperidinylMethacrylate, phenyl Methacrylic acid Methacrylonitrile Methacryloylacetone Methylenebutyrolactone Naphthalene, 1-vinylOct-l-ene,6,6-dimethyl4,8-dioxaspiro(2,5)Oxazoline, 2,2-isopropenylOxazoline, 2,2-isopropenyl4,4-dimethylPentadienoate, rra^-4-ethoxy2,4-,ethyl Phthalimide, N-vinylPropene, 3,3,3-trichloroPyridazinone, 3-(2-vinyl)-6-methylPyridazinone, 3-(2-vinyl)-6-methyl4,5-dihydroPyridine, 2-methyl-5-vinylPyridine, 2-vinylPyridine, 2-vinyl-5-ethylPyridine, 4-vinylSilane, 3-methacryloxypropyl, trimethoxyStyrene Styrene,/7-acetoxyStyrene, 3-tri-rc-butylstannylStyrene, 2,5-dichloroStyrene, p-chloromethylStyrene, p-1 -(2-hydroxypropyl)Styrene, a-methoxy Styrene, a-methyl Styrene, p-methyl Succinimide, N-vinyl Tetrazole, 1-vinylTetrazole, 5-phenyl-2(4 '-vinyl)-phenylToluenesulfonamide, N,N-methyl-vinylTriallyl citrate Vinyl acetate Vinyl benzoate Vinylbenzoic acid, pVinyl benzyl methyl carbinol Vinyl bromide Vinyl isobutyl ether Vinyl butyl sulfide Vinyl isobutyl sulfide Vinyl tert-butyl sulfide Vinyl chloride Vinyl chloroacetate Vinyl dichloroacetate
Category
rls
r1A
rA1
3 2 3 3 B 3
0.3 0.01 0.5 0.64 0.46 0.63
1.30 0.82 1.32 1 1.32 1.30
2
0.30
3 4 B 2 3 2 2
0.51 0.524 0.33 1.66 0.7 2.02 0.271
4 4
0.64 0.68
2
12.2
rSi
log(ri S )
n
u
v
0.14 0.15 0.14 0.2 0.138 0.19
0.37 3.6 0.415 0.48 0.5 0.89
-0.5229 -2 -0.301 -0.1938 -0.3372 -0.2007
0.406 0.898 0.325 0.238 0.339 0.283
-1.39 -0.03 -1.32 -1.45 -1.18 -1.04
0.42 -0.56 0.34 0.34 0.23 0.10
0.02
0.63
-0.5229
0.806
0.14
0.20
0.46 0.2 1.67 3.74 1.10 0.451 1.484
0.36 0.04 0.43 0.01 0.09 0.107 0.985
0.25 0.24 0.38 0.067 0.09 0.699 1.93
-0.2924 -0.2807 -0.4815 0.2202 -0.1549 0.3054 -0.567
0.146 0.002 0.432 0.297 0.237 -0.089 0.446
-2.22 -0.95 -2.08 -0.82 -1.98 -0.83 -1.58
0.62 0.39 0.44 1.17 0.88 0.16 -0.29
0.52 1.83
0.13 0.24
0.67 0.55
-0.1938 -0.1675
0.127 0.327
-0.95 -1.51
0.19 0.31
5.40
0.01
0.04
1.0864
0.025
-1.14
1.40
14
2 2 3
0.07 0.05 0.85
0.24 0.10 0.19
0.43 12.2 0.32
6.27 6.9 0.90
-1.155 -1.301 -0.0706
0.367 0.277 -0.089
-0.33 -2.35 -1.36
-0.80 -0.84 0.09
3
0.13
0.02
0.74
5.92
-0.8861
-0.151
-0.73
-0.57
4 4 4 4 2
0.85 1.26 1.09 0.69 0.868
0.31 0.44 0.43 0.375 3.79
0.16 0.10 0.04 0.10 0.094
0.70 0.53 0.74 0.52 0.425
-0.0706 0.1004 0.03743 -0.1612 -0.0615
-0.007 -0.014 0.006 0.06 0.408
-1.04 -0.98 -0.20 -0.94 -1.06
0.28 0.32 0.12 0.30 0.37
B 2 2 4 2 3
1.00 1.26 0.03 0.40 1.12 0.91
0.38 0.40 0.001 0.08 0.56 0.53
0.04 0.07 4.88 0.24 0.067 0.10
1.00 0.86 18.5 0.236 0.62 0.97
0 0.1004 -1.5229 -0.3979 0.0492 -0.041
0 -0.030 -0.407 -0.107 0.046 0.071
0.00 -0.44 -1.17 -1.98 -0.62 -0.60
0.00 0.07 -1.27 0.67 0.21 0.16
5 3 4 4 2 2
0.07 0.60 0.993 0.033 0.184 2.2
0.05 0.143 0.33 0.516 0.314 1.4
0.06 0.047 0.05 0.116 0.54 0.32
2.51 1.1 0.891 7.71 3.85 0.48
-1.1549 -0.2219 -0.0031 -1.4815 -0.7352 0.3424
0.105 -0.077 -0.021 0.623 0.251 0.088
0.41 -0.04 -0.20 0.75 -0.78 -1.75
-0.49 -0.03 0.08 -1.02 -0.59 0.32
3
0.05
0.04
0.42
5.6
-1.301
-0.40
-0.66
2 5 3 3 3 3 3 2 4 2 4 2 2
0.076 0.02 0.06 1.03 0.94 0.054 0.32 0.05 0.05 0.158 0.055 0.03 0.28
0.05 0.05 0.019 1.63 0.54 0.06 0.40 0.041 0.027 0.05 0.045 0.09 0.04
1.76 4.78 5.03 0.06 0.11 2.52 0.49 0.086 0.074 0.09 3.29 0.34 3.85
-0.49 -0.44 -0.86 -1.03 -0.66 -0.82 0.41 0.14 0.18 0.41 -0.90 1.04 -0.98
-1.30 -1.56 -1.45 0.50 0.18 -1.27 -1.41 -0.43 -0.36 -0.64 -1.16 -1.65 -1.30
20 48 31.56 0.282 0.98 16.6 24.5 2.69 2.38 4.36 18.7 45 20
-1.12 -1.699 -1.222 0.0124 -0.027 -1.268 -0.495 -1.3.01 -1301 -0.8013 -1.26 -1.523 -0.553
0.126 0.092 0.315 -0.031 0.238 0.069 0.179 0.200 0.128 0.059 -0.029 0.128 0.345 -0.162
References page 11-327
TABLE 1. cont'd Monomer
Category
Vinyl 2-chloroethyl ether Vinyl chloromethyl ketone Vinyl cymantrene Vinyl dodecyl ether Vinylene carbonate Vinyl ethyl ether Vinyl ethyl oxalate Vinyl ethyl sulfide Vinyl ethyl sulfoxide Vinylferrocene Vinyl hendecanoate Vinylidene chloride Vinyl isocyanate Vinyl isothiocyanate Vinyl methyl ketone Vinyl phenyl ether Vinyl phenyl sulfide Vinyl stearate Vinyltriethoxysilane Vinyl-tris(trimethoxysiloxy) silane Vinyltrimethylsilane
ri S
r1A
rA1
rSi
0.07 0.507 0.096
0.05 0.88 0.05
1.09 0.064 0.446 0.82 14.9 0.69 1.34 0.075 1.63 0.173 1.88 0.64 0.19 0.36 0.61 2.50 0.11 4.64 6.59 3.90
160 0.127 2.32 41.5 70 100 5.62 5.38 7.82 3.57 24.89 1.79 8.13 0.725 0.29 1.70 3.8 15.96 20.86 25
-0.740 -1.000 -0.7696 -1.301 -0.9686 -1.097 -0.3615 -0.495 -2.000 -0.854 -1.301 -1.301 -2.301
4.08
10.32
-1.301
4 3 2 2 3 4 3 3 3 3 3 5 3 3 2 3 3 3 2 3
0.05 0.05
0.08 0.06
0.182 0.10 0.17 0.05 0.1075 0.08 0.435 0.32 0.01 0.14 0.05 0.05 0.005
0.055 0.05 0.158 0.09 0.32 0.16 1.40 1.57 0.23 0.03 0.078 0.41 0.075
3
0.05
0.10
log(riS)
n
u
v
-1.155 -0.295 -1.018
0.105 0.255 0.053
-0.038 0.046 0.149 0.260 0.346 0.277 0.357 0.427 0.685 -0.090 0.236 0.513 0.616
1.18 -1.58 -0.97 0.44 -1.03 1.11 -1.11 0.66 -1.02 -0.12 -0.34 -1.34 0.29 -1.56 -2.46 -2.23 0.20 -1.19 -1.28 -0.84
-2.CX 0.9' -0.3 -1.6: -1.9: -2.Ol -0.7 -0.7' -0.9' -0.51 -1.3. -0.2< -0.91 0.1! 0.5< -0.31 -0.5! -LL -1.3: -1.4
0.29 -1.301
0.252 0.192
0.277
-1.41
-1.1:
TABLE 2. TRANSFER AGENT Transfer agent Acetaldehyde Acetamide, N,N-dimethylAcetic acid Acetone Acetonitrile Allyl chloride Aluminium, hydrodiisobutyl Aluminium, triethyl Aluminium, triisobutyl Aniline Aniline, WV-dimethylAnthracene Benzene Benzene, bromoBenzene, tert-butylBenzene, chloroBenzene, ethyl/7-Benzoquinone Borane, tributyl Butanone Butyl alcohol sec-Butyl alcohol tert-Butyl alcohol Butyl mercaptan Butyric acid, 4-hydroxy-y-lactone Cadmium, dibutyl Carbonic acid, cyclic ethylene ester Carbon tetrabromide, Carbon tetrachloride, Chloroform Copper(II) chloride Cumene Cyclohexane
Category 3 2 3 4 2 2 3 4 2 4 4 3 4 3 3 4 4 3 3 3 3 3 3 4 2 2 2 3 5 3 3
Cs 0.00085 0.00046 0.000222 0.000032 0.000044 0.00151 27.5 12.5 28.5 0.0020 0.0053 2 0.000003 0.000178 0.000005 0.000041 0.00007 227 0.00348 0.0005 0.00016 0.000056 0.00003 21.99 0.00004 0.117 0.000024 See methane, tetrabromoSee methane, tetrachloro0.00005 10300 0.00009 0.000005
CA
U
V
0.0047 0.0005 0.000081 0.000113 0.0002 0.000595 0.394 0.059 28 0.0050 0.0547 1.8 0.000246 0.000136 0.000193 0.000079 0.003573 1.3 0.647 0.000643 0.001542 0.009755 0.000044 0.409 0.00007 5.5 0.000013
-0.93 -1.94 -2.61 -1.28 -1.06 -2.57 -4.60 -5.46 -2.01 -1.43 -0.55 -2.29 0.80 -2.07 0.26 -1.49 0.49 -5.19 1.29 -1.82 -0.57 1.23 -1.75 -4.42 -1.66 0.39 - 2.36
-3.12 -3.34 -3.80 -4.59 -4.36 -2.82 1.21 0.79 1.45 -2.70 -2.20 -0.01 -5.65 -4.73 - 5.20 -4.51 -4.28 2.29 -2.95 -3.55 -4.05 -4.62 -4.62 1.23 -4.39 -0.93 - 4.63
0.000577 67.19 0.004141 0.000206
-0.49 -4.61 0.38 0.25
-4.17 4.33 -4.07 -4.63
TABLE 2. cont'd Transfer agent Dimethyl sulfoxide Diphenylamine-T Ethane, 1,2-dichloroEthane, 1,1,2,2-tetrachloroEther, dodecyl vinyl Ethyl acetate Formamide, WV-dimethyloc-D-Glucoside, methyl, 6-deoxy-6-mercaptooc-D-Glucoside, methyl-, di-O-benzyla-D-Glucoside, methyl-, 2,3,4,6-tetra-O-acetyla-D-Glucoside, methyl-, 6-(p-toluene sulfonyl)a-D-Glucoside, methyl-, 6-O-triphenylmethylP-D-Glucoside, methyl-, 6-deoxy-6-dipropylaminoGlycerol Heptanol, dodecafluoroIndium, triethyl Iron(III) chloride Isobutyl alcohol Isobutyronitrile Lead, tetraethyl Mercury, diethyl Methane, dichloroMethane, tetrabromoMethane, tetrachloroMethane, nitroMethanol Octadiene, 2,6-dimethylOxime, acroleinOxime, crotonaldehydeOxime, ethyl isopropenyl ketoneOxime, methacroleinOxime, methylacroleinOxime, methyl isopropenyl ketoneOxime, methyl vinyl ketonePentanol, octafluoroSilane, tetraethyl Stibine, tributyl Tin, tetrabutyl Toluene Triethylamine Tripropylamine Zinc, diethyl
E. 1. 2. 3. 4.
Category
Cs
CA
U
V
3 3 3 3 2 3 2 2
0.00005 0.00009 0.0002 0.00108 0.000372 0.00155 0.0001 5.5
0.000029 0.07 0.000147 0.000311 0.000495 0.000254 0.000278 0.13
-2.32 2.18 -2.17 -2.73 -1.82 -3.07 -1.36 -4.31
-4.44 -4.57 -3.82 -3.39 -3.43 -3.28 -4.00 0.74
2
0.0062
0.009
-1.76
-2.21
2
0.0002
0.003
-0.32
-3.70
2
0.0002
0.001
-1.00
-3.70
2
0.0021
0.008
-1.17
-2.68
2
0.0022
0.11
0.43
-2.66
2 3 3 3 3 2 2 3 2 4 3 3 3 3 3 3 3 3 3 3 3 3 4 3 3 5 4 4 2
0.002864 0.001333 1.76 536 0.00005 0.00027 0.000124 0.000034 0.000015 2.2 0.01 0.001 0.000074 0.0002 1.08 0.15 0.43 1.3 0.04 0.11 0.27 0.001136 0.000812 0.0058 0.000371 0.000012 0.00071 0.00242 0.366
-2.12 -3.20 -3.25 -5.44 0.41 -1.95 1.28 1.35 -0.13 - 4.04 -4.85 -2.30 -2.23 1.37 0.53 -0.35 -1.45 -0.77 1.03 -0.30 -1.06 -3.10 -1.30 2.78 -0.06 0.26 1.85 1.32 -1.08
-2.54 -2.85 -0.08 2.43 -4.54 -3.57 -3.91 -4.60 -4.82 0.37 -2.09 -3.09 -4.18 -3.79 -0.02 -1.06 -0.37 0.13 -1.25 -0.90 -0.67 -2.93 -3.02 -3.27 -3.69 -4.84 -3.04 -2.89 -0.44
0.00235 0.00019 0.222 3.33 0.002406 0.00029 0.0243 0.00722 0.000306 0.085 0.000099 0.0006 0.00005 0.045 62.6 2.05 1.03 9.41 5.35 1.71 1.20 0.00019 0.0021 11.1 0.00808 0.00032 0.304 0.428 1.6
REFERENCES
R. Z. Greenley, "Polymer Handbook", this volume, p. 181. R. Z. Greenley, "Polymer Handbook", this volume, p. 309. A. D. Jenkins, J. Polymer ScL, 34, 3495 (1996). C. H. Bamford, A. D. Jenkins, R. Johnston, Transactions. Farad. Soc, 55, 418 (1959). 5. C. H. Bamford, A. D. Jenkins, J. Polymer ScL, 53,149 (1961). 6. C. H. Bamford, A. D. Jenkins, Transactions. Farad. Soc, 58, 530 (1962).
7. A. D. Jenkins, Eur. Polymer J., 1, 177 (1965). 8. A. D. Jenkins, Macromol. Chem. Phys. Rapid Commun., 17, 275 (1996). 9. A. D. Jenkins, J. Jenkins, Macromol. Chem. Phys., Macromol. Symp., I l l , 159 (1996). 10. G. C. Eastmond, Comprehensive Chemical Kinetics, (C. H. Bamford, C. F. H. Tipper (Eds.)), 14A, 105 (1976). 11. A. Ueda, S. Nagai, "Polymer Handbook", this volume, p. 97.
C o p o l y m e r i z a t i o n M e t a l l o c e n e - C a t a l y z e d
P a r a m e t e r s
o f
C o p o l y m e r i z a t i o n s
G e r h a r d F i n k , W o l f JCirgen R i c h t e r Max-Planck-lnstitut fur Kohlenforschung, Kaiser-Wilhelm-Platz 1, D-45466 Mulheim an der Ruhr, FR Germany
A. Introduction 11-329 B. A Brief Theoretical Outline of Copolymerization Reactions 11-329 1. First-Order Markov Model II-330 2. Second-Order Markov Model II-330 C. Calculation of the Copolymerization Parameters 11-331 1. First-Order Markov Model 11-331 1.1. Copolymerization Parameters Deduced from the Mayo-Lewis Equation 11-331 1.2. Determination of Copolymerization from the Sequence Distribution (Triad Distribution) Parameters 11-331 2. Second-Order Markov Model M-332 3. Example M-332 D. Table of Copolymerization Parameters II-333 E. List of Catalysts/Cocatalysts Used II-336 F. References II-336 A.
the copolymerization behavior, and, in particular, determination of copolymerization parameters requires correct modeling, i.e. adequate Markov-statistics. B. A BRIEF THEORETICAL OUTLINE OF COPOLYMERIZATION REACTIONS
Various mathematical models have been applied to copolymerization reactions induced by Ziegler-catalysts. Wall (1) assumed the velocity of the monomer addition Mi and M 2 to be independent of the previously integrated monomeric unit (zero-order Markov model):
R = Polymer chain This scheme gives rise to the following equation for a copolymerization reaction:
INTRODUCTION
In contrast to radical and ionic polymerization reactions in which the incoming monomer always adds to the end of the growing chain
Mayo and Lewis (2) extended this model by including the influence of the last built-in monomer into the chain during the subsequent step (first-order Markov model):
the most distinct feature of Ziegler-Natta-catalysis is the attachment of a monomer molecule to a highly structured catalyst complex (which may be homogeneously solvated or heterogeneously fixed to a surface) and its insertion between the catalyst complex and the growing chain:
Since the structural features of the catalyst - in particular the steric bulk of ligands, the bite angle of metallocenes, the configuration and conformation on the one hand, and the increasing space-filling demand of the growing chain and of the various monomers on the other do influence the addition of the monomers, elucidation of
This results in the so-called Mayo-Lewis equation,
with ri = k\\/k\2 and r 2 = £22/^21 • Taking the effect of
the last two built-in monomers into account, Merz, et al (3) developed a second-order Markov model. This 'penultimate model' necessarily results in a more complex kinetic scheme:
with P n + P 1 2 = 1 and P 21 + P22 = 1 The proportion of the Mi and M 2 units (1Pi or 1 P 2 ) in the copolymer is also determined by reactivity probabilities: With m = km/km, r2\ = £211/^212, ^22 = &222A221 and 7*12 = k \22/k 121, the following copolymerization equation is obtained:
with x= [Mi]/[M2]. Expanding this model even further to the influence of the last three monomeric units, Ham (4) proposed a third-order Markov model. However, due to the many parameters involved, it has been of little practical use. Thus, most authors restrict themselves to first- or secondorder Markov models when dealing with Ziegler-Nattacatalysis for copolymerization, and this is elaborated below.
1 1 giving Pi - P 2 i/(Pi 2 +P21) and P2 = Pi2/ (Pn+Pn). All the potential sequence distributions can thus be calculated. Consider, for example, the triad distributions:
1. First-Order Markov Model
The Mayo-Lewis equation describes the composition of a copolymer as a function of the composition of the monomer mixture and their respective copolymerization parameters. These parameters not only determine the composition of the resulting copolymer, but also its microstructure, e.g. the distribution of the sequence length. A knowledge of the ratio of the starting monomers and their copolymerization parameters enables the sequence length distribution to be calculated. The reactivity probabilities Ptj are defined (5,6) that give the probability of the monomer j adding to the polymer chain with the terminating monomer /:
The triad distribution allows the calculation of the true copolymerization parameters. For a given polymer, the triad distribution is deduced from experimental 13C-NMR spectra (7) (see below). 2. Second-Order Markov Model
The kinetic scheme for this model gives rise to eight reaction probabilities Pijk that result from the probability of the monomer k adding to the polymer chain with the terminating monomers ij. The reactivity probability P m is
given for instance as
1. First-Order Markov Model
with P1n +Pm = 1, Pm + Piii = 1, ^122+^121 = 1, ^211+^212 = 1. The triad distribution is calculated in a manner analogous to the first-order Markov model:
7.7. Copolymerization Parameters Deduced from the Mayo-Lewis Equation The Mayo-Lewis equation calculates the composition of the copolymer formed as a function of the ratio of the monomer concentration at a given time. At arbitrary intervals these values are generally inaccessible; thus a sufficiently small interval (a small percent of the total conversion) is taken and the relative change of the monomer concentration d[M 2]/d[Mi] is assumed to be the composition of the copolymer ([mi], [1112]) itself according to
l
Pij is the frequency of the diad //, and is calculated as follows:
It is advisable to keep the monomer ratio [M2]/[Mi] constant during polymerization by constantly feeding both monomers, or at least the most reactive monomer. To determine the copolymerization parameters the experiments are run with varying ratios of the starting monomers, and their compositions are subsequently measured. The data obtained can be analyzed by linear or nonlinear methods. Linear Methods: Mayo and Lewis (2), Fineman and Ross (8), Kelen and Tudos (9) Nonlinear Methods: Behnken (10), Tidwell and Mortimer (11), Braunet al. (12) Independent of the analytical methods the copolymerization parameters derived from the Mayo-Lewis equation have some major drawbacks, but do enable a part of the information contained in each copolymerization experiment to be extracted, namely the integral composition of the copolymer. A series of experiments is necessary to obtain the copolymerization parameters. Furthermore, using this approach it cannot be decided whether the application of the first-order Markov model is valid or not. One may even obtain a nearly perfect Fineman-Ross plot, where other methods show that a first-order Markov model cannot be applied.
It results in
and
7.2. Determination of Copolymerization Parameters from the Sequence Distribution (Triad Distribution)
Once the copolymerization parameters of a catalyst system with a given ratio of monomers are known, the composition of the copolymer and all its sequence distributions result, e.g., the complete microstructure of the copolymer is revealed. These parameters characterize any catalyst system and enable different systems to be compared. The major practical problem is the choice of the adequate statistical model.
As mentioned above, a knowledge of the copolymerization parameters enables all the sequence distributions to be calculated. Or inversely, experimentally determined sequence distributions yield the copolymerization parameters. In the simplest case, intensities of appropriate single sequences can be compared. The results are even more reliable, if the determination of the copolymerization parameters is based on the maximal accessible information on the microstructure of the copolymer. To derive the rparameters from the overall triad distribution is the safest way (13). This may be done by calculating a triad distribution based on a first-order Markov model and optimizing by variation of the reaction probabilities Ptj until the best fit between calculated and experimental data
The
diad
frequency
C. CALCULATION OF THE COPOLYMERIZATION PARAMETERS
References page II - 336
is reached. Based on the optimized reaction probabilities the copolymerization parameters r\ and r2 are calculated according to the following equations:
This, procedure for determining the copolymerization parameters is superior to the Mayo-Lewis approach. While the latter requires several experiments, using the above approach, all the information can be obtained from one experiment. To determine the copolymerization parameters from the triad distribution, six variables are available, five of which are independent. The system is over-determined and thus allows critical evaluation.
Randall (7) found a way to avoid this problem by creating a "collective assignment method". Here the complete triad distribution results from combining the experimental spectral information with the relation between different n-ades. In the first step the 13C-NMR spectrum of an ethene/oc-olefin copolymer is split into several spectral areas given by signal overlap. The 13C-NMR spectra of ethene/propene copolymers, for example, are divided into eight appropriate spectral areas A to H, as shown in Fig. 1. The integrals Tx of different spectral areas are expressed by the number of contributing triads ending up in the complete triad distribution by appropriately combining several TVdata. Randall exemplified this method in detail for ethene/propene-, ethene/1-butene-, and ethene/1-hexenecopolymerizations (7). The resulting triad distribution allows the composition of the copolymer
2. Second-Order Markov Model The second-order Markov model gives four copolymerization parameters, which are gained from the sequence distribution (full triad distribution) with a high degree of reliability. The calculated triad distribution from the second-order Markov model is optimized by varying the reaction probabilities P^ until the best fit is reached. The four copolymerization parameters are calculated from reaction probabilities P^ as follows (13-15):
and the average sequence length:
to be calculated. 3. Example
The second-order Markov model results in four copolymerization parameters from six variables based on triad distribution. A higher degree of determination clearly is desirable to justify this copolymerization model. However, the complete distribution is not obtained from 13C-NMR spectra of ethene/oc-olefin copolymers. The full triad distribution does not exhaust the full information of the spectra, since some peaks exhibit tetrad or even pentad sensitivity. Cheng (16,17) suggested that all recorded peaks of a 13C-NMR spectrum should be included to calculate the copolymerization parameters. Arbitrarily chosen reaction probabilities give rise to a polymer chain built at random, and its 13C-NMR spectrum is calculated. This spectrum is superimposed on the experimental one and optimized by varying the starting values, until the minimal difference is reached. Since the 13C-NMR spectra of ethene/oc-olefin copolymers display many overlapping peaks, the quality of the spectra simulation very much influences the success of this method.
To demonstrate which model describes the experimental results best, the following table from a recent publication by Fink is reproduced (15). It is based on ethene/1-octene copolymerization experiments using a homogeneous metallocene/MAO catalyst.
area C area B
area D area F area H area E area G
area A
ppm Figure 1. 13C-NMR spectrum of an ethene/propene copolymer.
COMPARISON BETWEEN THE EXPERIMENTAL MEASURED TRIAD DISTRIBUTION AND THE CALCULATED TRIAD DISTRIBUTION ACCORDING TO THE FIRST- (M1) AND THE SECOND-ORDER (M2) MARKOVIAN-STATISTIC OF THE ETHYLENE (E)/1 -OCTADECENE (O) COPOLYMERIZATION0 [O]/[E] in solution 0.28
1.39
1.41
2.84
7.14
14.18
Model
EEE
EEO+ OEE
OEO
OOO
EOO + OOE
EOE
Exp. Ml M2 Exp. Ml M2 Exp. Ml M2 Exp. Ml M2 Exp. Ml M2 Exp. Ml M2
0.976 0.980 0.976 0.878 0.878 0.878 0.883 0.883 0.882 0.795 0.798 0.795 0.878 0.738 0.731 0.718 0.733 0.718
0.014 0.004 0.014 0.077 0.078 0.078 0.074 0.074 0.072 0.118 0.124 0.117 0.143 0.158 0.143 0.112 0.153 0.111
0.000 0.000 0.001 0.004 0.002 0.003 0.005 0.002 0.003 0.011 0.005 0.010 0.020 0.008 0.019 0.046 0.008 0.045
0.000 0.011 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.006 0.000 0.006 0.011 0.001 0.011 0.010 0.005 0.010
0.001 0.004 0.001 0.004 0.004 0.004 0.005 0.006 0.006 0.008 0.010 0.008 0.011 0.014 0.011 0.030 0.035 0.031
0.008 0.000 0.008 0.038 0.038 0.039 0.033 0.035 0.036 0.063 0.062 0.064 0.084 0.080 0.085 0.084 0.066 0.085
Rb ( x 106)
50 0.22 0 0.3 0 6.27 20 0.64 90 0.27 610 0.60
T p = 60 0C, Kat: iPr(CpFlu)ZrCl2 and MAO, [Zr] = 7.56 x l(r 6 mol/l, Al/Zr = 9800. b R is the sum of the least squares divided by the number of measured values.
Second-order Markov statistics is only applicable when there is a sufficiently high comonomer concentration in solution, and enables the formation of a-olefin/ a-olefin dual-blocks. Now the insertion of another a-olefin unit into this dual-block sequence is preferred to that into in a single-block. The complete triad distribution is gained by this procedure and it has to be performed over a wide range of the monomer/comonomer ratio in solution.
If the experimentally determined triad distribution is compared with the calculated values based on a first-order or alternatively on a second-order Markov model (Mi or M 2 of the table), both models give a reasonable good fit up to a monomer/comonomer ratio in solution of 1.5. Beyond a ratio of 3, however, the second-order Markov model proves to be the better approximation as indicated by the sum of the error squares divided by the number of experimental values (R of the table). D.
TABLE OF COPOLYMERIZATION PARAMETERS
Monomer/ comonomer
r\
r2
Ethene/propene 6.26 6.61 18.6 2.57 2.90 15.7 16.1 20.6 12.43 5.1 1.3 5.60 4.23 25.42 13.75 16.53 19.61 24
0.11 0.06 0.032 0.39 0.28 0.009 0.025 0.074 0.08 0.14 0.2 0.13 0.12 0.18 0.0085
r\\
r2\
r2i
ru
3.4 4.1
2.2 3.9
0.270 0.153
0.153 0.065
Cat./ cocat. 19 28 24 24 2 24 25 1 7 35 29 24 19 24 28 13 12 7 11 4
Remarks
Aa
B^ B B B B B
r Po i y (0C) 25 25 25 50 36 50 50 50 50 50 120-220 0 25 40 40 40 40 40 40 50
Model tested
Analytical method*
Refs.
Ml; M2 Ml; M2 Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml
C.T.A. C.T.A. R-R. E-R. R-R. See Ref. 20 See Ref. 20 See Ref. 20 See Ref. 20 See Ref. 20 R-R. R-R. R-R. See Ref. 24 See Ref. 24 See Ref. 24 See Ref. 24 See Ref. 24 See Ref. 24 R-R.
13 13 18 18 19 20 20 20 20 20 21 22 22 23 23 23 23 23 23 25
*C.T.A. - Complete Triad Analysis (7); D.A. - Diad Analysis (28); R-R. - Pineman-Ross (8); K.-T. - Kelen-Tiidos (9); M.-L. - Mayo-Lewis (2).
References page II - 336
Monomer/ comonomer
r\ 19.5 50 48 24 250 60 3.9 4.4 5.5
ri
20.2 2.5 42.28 43.35 61.56 99.43 4.71 6.36 8.16 10.6 10.1 7.5 10.1 18.9 19.5 10.7
Remarks
B B B
Model tested
Analytical method
Refs.
50 50 50 50 50 50 40 60 40
Ml Ml Ml Ml Ml Ml Ml Ml Ml
E-R. E-R. E-R. E-R. E-R. E-R. see ref. 24 see ref. 24 see ref. 24
25 25 25 25 25 25 26 26 26
Tp0Iy (0C)
2.9 6.8
0.21 0.085
0.041 0.017
19 28 24 24 24 37 37 37
25 25 30 50 70 30 50 70
Ml; M2 Ml; M2 Ml Ml Ml Ml Ml Ml
C.T.A. C.T.A. E-R. E-R. E-R. E-R. E-R. E-R.
13 13 27 27 27 27 27 27
3.2 10.3
2.6 6.4
0.150 0.111
0.065 0.022
19 28
25 25
Ml; M2 Ml; M2
C.T.A. C.T.A.
13 13
0.034 0.024 0.022
26 26 6 6 24 24 12 12 6 6 6 6 19 19 19
60 60 60 60 60 60 60 60 20 40 60 70 25 40 60
Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml; M2 Ml; M2 Ml; M2
E-R. D. A. E-R. D. A. E-R. D. A. E-R. D. A. E-R. E-R. E-R. E-R. C.T.A. C.T.A. C.T.A.
29 29 29 29 29 29 29 29 30 30 30 30 15 15 15
85 85 60 60 60 60 0 20 40 60 40 60 40 40 40 40
Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml
D.A. D.A. E-R. D.A. E-R. D.A. C.T.A. C.T.A. C.T.A. C.T.A. see ref. 24 see ref. 24 C.T.A. C.T.A. C.T.A. C.T.A.
31 31 29 29 29 29 32 32 32 32 26 26 33 33 33 33
4.58 6.60 8.85
0.130 0.109 0.098
0.55 0.035 0 0.03 0 0.23 0.18 0.14 0.11 0.03 0.07 0.118 0.014 0.013 0.076
Ethene/ 1-octadecene
Cat/ cocat.
3.6 7.9
0.027 0 0.003 0 0.013 0 0.005 0 0.004 0.005 0.005 0.005
Ethene/ 1-dodecene
Ethene/styrene Ethene/2-allylnorbornane
r\i
3 8 6 27 10 9 37 37 24
5.93 7.95 10.08 Ethene/ 1-octene
rii
0.05 0.03 0.04 0.17 0.10 0.21
Ethene/ 1-hexene 32.67 44.75 62.31 74.60 31.00 36.00 88.00 86.70 55 54 52 79
rn
0.015 0.007 0.015 0.029 0.002 0.12 0.12 0.11
Ethene/ 1-butene 19.4 23.6 29.2 5.4 6.6 6.8
/*n
6 5 26 26 6 6 32 32 32 32 24 24 32 28 30 31 7.2 12.0
5.0 5.7
11.2 14.7 38.45
6.3 8.4 18.58
B B
2.9 0.3
0.057 0.036
19 28
28 28
Ml; M2 Ml; M2
C.T.A. C.T.A.
34 34
1.6 0.4 0.085
0.044 0.035 0.041
28 28 60 40
Ml; M2 Ml; M2 Ml; M2 Ml
C.T.A. C.T.A. C.T.A. E-R.
34 34 15 35,46
35 35
Ml Ml
E-R. K.-T.
36 36
23.4
0.015
19 28 19 5
43.7 42.6
0.038 0.027
6 6
Monomer/ comonomer Ethene/ cyclopentene
Ethene/ norbornene
ri\
rii
Model tested
Analytical method
-10 0 10 20 0 25
Ml Ml Ml Ml Ml Ml
R-R. R-R. R-R. R-R. R-R. R-R.
39 39 39 39 40 40
28 34 19 23 23 25 25 25 25 6 24 28 19 23 23 22
30 30 30 30 0 -25 0 25 50 25 25 30 30 0 30 30
Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml Ml
R-R. R-R. R-R. R-R. R-R. R-R. R-R. R-R. R-R. R-R. R-R. R-R. R-R. R-R. R-R. R-R.
37 37 37 37 37 38 38 38 38 38 38 40 40 40 40 40
15 16 17 14 19 20 21 22 33 5
70 70 70 70 70 70 70 70 70 70
Ml Ml Ml Ml Ml M2 M2 M2 M2 M2
K.-T. K.-T. K.-T. K.-T. K.-T. C.T.A. C.T.A. C.T.A. C.T.A. C.T.A.
41 41 41 41 41 41 41 41 41 41
28 19
30 30
Ml Ml
M.-L. M.-L.
43 43
23 18 38
50 50 50
Ml Ml Ml
R-R. R-R. R-R.
40,42 40,42 40,42
28 19
30 30
Ml Ml
M.-L. M.-L.
43 43
23 28 30 31 32
50 40 40 40 40
Ml Ml Ml Ml Ml
R-R. D.A. D.A. D.A. D.A.
40 44 44 44 44
28
60
Ml
K.-T.
45
ri
80 120 250 300 1.9 2.2
<0.05 <0.02 <0.02 <0.07 <1 <1
24 24 24 24 25 25
n.d.c n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. n.d. <2 0.06 0.05 0.05 0
2.66 3.44 2.93 2.61 1.85 1.5 1.9 2.2 3.2 20 6.6 2.6 3.4 2.0 3.0 3.1
ru
Cat./ /*i2 cocat.
r\
Remarks
TV0Iy (0C)
Refs.
Ethene/norbornene 0.88 1.14 1.1 0.83 1.3
0.05 0.1 0.026 0.29 0.03 1.2 2.2 2.2 5.2 2.2
Ethene/5-phenyl-2-norbornene 7.8 0.1 7.0 0.05 Ethene/dimethanooctahydronaphthalene 7.8 0.1 7.0 0.05 7.1 0.04 Ethene/phenyldimethanooctahydronaphthalene 11.5 0.05 7.1 0.03 Ethene/trimethanododecahydroanthracene 15.6 0.06 Propene/1-octene 3.3 0.39 3.6 0.32 2.6 0.37 2.4 0.48 Propene/cyclopentene 40 0.001
3.6 2.7 8.9 18.2 54
0 0 0 0 0
0 0 0 0 0
Cd C C C C
°High pressure copolymerization (100-150 MPa). fc [Monomer]/[Comonomer] ratio varied. The cited r-values hold only for a selected ratio of [Ethene]/[Propene]. c Not determined. d Alternating copolymerization, hence, rn = r 22 = 0.
References page II - 336
E. LIST OF CATALYSTS/COCATALYSTS USED 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38
[Cp] 2 TiCl 2 [Cp] 2 TiMe 2 [Cp] 2TiPh 2 [Cp] 2 Ti = CH 2 Me 2 Si[Me 4 CpNt-Bu]TiCl 2 [Cp] 2 ZrCl 2 [Cp] 2 ZrCl 2 ([Cp] 2 ZrCl 2 )O [MeCp] 2 ZrCl 2 [C 5 Me 4 J 2 ZrCl 2 [n-Bu-Cp] 2 ZrCl 2 [lnd] 2 ZrCl 2 [lnd] 2 ZrBenzyl 2 MeCH[Cp] 2 ZrCl 2 Me 2 C[Cplnd]ZrCl 2 Me 2 C[MeCpIiId]ZrCl 2 Me 2 C[3-t-BuCplnd]ZrCl 2 Ph 2 C[Cplnd]ZrCl 2 Me 2 C[CpFIu]ZrCl 2 Me 2 C[3-MeCpFlu]ZrCl 2 Me 2 C[3-PropCpFlu]ZrCl 2 Me 2 C[3-t-BuCpFlu]ZrCl 2 Ph 2 C[CpFIu]ZrCl 2 C 2 H 4 [IiId] 2 ZrCl 2 C 2 H 4 [lndH4] 2 ZrCl 2 Me 2 Si[Cp] 2 ZrCl 2 Me 2 Si[Cp] 2 ZrCl 2 Me 2 Si[lnd] 2 ZrCl 2 Modified silylbridged [lndH4] 2 ZrCl 2 Me 2 Si[2-Melnd] 2 ZrCl 2 Me 2 Si[Benz(e)lnd] 2 ZrCl 2 Me 2 Si[2-MeBenz(e)lnd] 2 ZrCl 2 Me 2 Si[3-t-BuCpFlu]ZrCl 2 Ph 2 Si[IiId] 2 ZrCl 2 [Cp] 2 HfCl 2 Me 2 C[CpFIu]HfCl 2 C 2 H 4 [IiId] 2 HfCl 2 Ph 2 C[CpFIu]HfCl 2
MAO AlMe 3 MAO: AlMe 3 AlMe 2 Cl MAO MAO MAO: AlMe 3 MAO: AlMe 3 MAO: AlMe 3 MAO: AlMe 3 MAO MAO MAO MAO MAO MAO MAO MAO MAO MAO MAO MAO MAO MAO MAO MAO MAO: AlMe 3 MAO MAO MAO MAO MAO MAO MAO MAO MAO MAO MAO
(1:1 mixture) (Tebbe reagent)
( 1 : 1 mixture) ( 1 : 1 mixture) ( 1 : 1 mixture) ( 1 : 1 mixture)
( 1 : 1 mixture)
F. REFERENCES 1. F. T. Wall, J. Am. Chem. Soc, 63, 1862 (1941). 2. F. R. Mayo, F. M. Lewis, J. Am. Chem. Soc, 66, 1594 (1944). 3. E. Merz, T. Alfrey, and G. Goldfinger, J. Polym. ScL, 1, 75 (1946). 4. G. E. Ham, J. Polym. ScL, 45, 169 (1960). 5. F. P. Price, J. Chem. Phys., 36, 209 (1962). 6. K. Ito, Y. Yamashita, J. Polym. ScL, Part A: Gen. Pap., 3, 2165 (1965). 7. J. C. Randall, J. Macromol. ScL, C: Rev. Macromol. Chem. Phys., 29, 201 (1989). 8. M. Fineman, S. D. Ross, J. Polym. ScL, 5, 269 (1950). 9. T. Kelen, F. Tiidos, J. Macromol. ScL, A: Chem., 9, 1 (1975). 10. D. W. Behnken, J. Polym. ScL, Part A: Gen. Pap., 2, 645 (1964). 11. RW. Tidwell, G. A. Mortimer, J. Polym. ScL, Part A: Gen. Pap., 3, 369 (1965). 12. D. Braun, W. Brendlein, G. Mott, Eur. Polym. J., 9, 1007 (1973).
13. N. Herfert, P. Montag, G. Fink, Makromol. Chem., 194, 3167 (1993). 14. J. Koivumaki, G. Fink, Macromolecules, 27, 6254 (1994). 15. P. Muhlenbrock, G. Fink, Z. Naturforsch., B: Chem. ScL, 50, 423 (1995). 16. H. N. Cheng, J. Chem. Inf. Comput. ScL, 27, 8 (1987). 17. H. N. Cheng, J. Appl. Polym. ScL: Appl. Polym. Symp., 43, 129 (1989). 18. H. Drogemuller, K. Heiland, W. Kaminsky, in: W. Kaminsky, H. Sinn (Eds.), "Transition Metals and Organometallics as Catalysts for Olefin Polymerization", Springer, Heidelberg, 1988, p. 302. 19. V. Busico, L. Mevo, G. Palumbo, A. Zambelli, Makromol. Chem., 184, 2193 (1983). 20. J. C. W. Chien, D. He, J. Polym. ScL, Part A: Polym. Chem., 29, (1991). 21. C. Bergemann, R. Cropp, G. Luft, J. MoI. Catal., 102, 1 (1995).
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35. F. G. Sernetz, R. Mulhaupt, R. M. Waymouth, Macromol. Chem. Phys., 197, 1071 (1996). 36. S. Marathe, T. P. Mohandas, S. Sivaram, Macromolecules, 28, 7318 (1995). 37. W. Kaminsky, A. Noll, Polym. Bull. (Berlin), 31, 175 (1993). 38. W. Kaminsky, A. Bark, M. Arndt, Makromol. Chem., Makromol. Symp., 47, 83 (1991). 39. W. Kaminsky, R. Spiehl, Makromol. Chem., 190, 515 (1989). 40. W. Kaminsky, Macromol. Chem. Phys., 197, 3907 (1996). 41. D. Ruchatz, G. Fink, Macromolecules, 31,4681 (1998) and the two preceeding papers by the same authors on pages 4669 and 4674 (1998). 42. W. Kaminsky, R. Engehausen, J. Kopf, Angew. Chem., 107, 2469 (1995), Angew. Chem. Int. Ed. Engl., 34, 2273 (1995). 43. W. Kaminsky, A. Noll, in: G. Fink, R. Mulhaupt, H.-H. Brinzinger (Eds.), Ziegler Catalysts, Springer, Berlin, 1995, p. 149. 44. M. J. Schneider, R. Mulhaupt, Macromol. Chem. Phys., 198, 1121 (1997). 45. M. Arnold, O. Henschke, F. Koller, Macromol. Rep., A33,219 (1996). 46. L. Oliva, P. Longo, L. Izzo, M. DiSerio, Macromolecules, 30, (1997).
R a t e s
o f
P o l y m e r i z a t i o n
A v e r a g e
M o l e c u l a r
W e i g h t
a n d
D e p o l y m e r i z a t i o n ,
W e i g h t s ,
D i s t r i b u t i o n s
o f
a n d
M o l e c u l a r
P o l y m e r s
L. H . Peebles, Jr. Chemistry Division, Naval Research Laboratory, Washington, DC, USA
A. Introduction 11-339 B. Reference Tables for the Calculation of Rates of Polymerization, Average Molecular Weights, and Molecular Weight Distributions of Polymers for Various Types of Polymerization 11-340 Table 1. Addition Polymerization with Termination 11-341 Table 2. Addition Polymerization - "Living" Polymers with Partial Deactivation II-344 Table 3. Linear Condensation Polymerization without Ring Formation II-346 Table 4. Equilibrium Polymerization II-347 Table 5. Nonlinear Polymerization Systems II-348 Table 6. Degradation of Polymers - May be Accompanied by Crosslinking II-350 Table 7. Influence of Reactor Conditions and Design on the Molecular Weight Distribution II-352 C. Some Distribution Functions and Their Properties II-352 1. Normal Distribution Function (Gaussian Distribution) II-353 2. Logarithmic Normal Distribution Function II-353 3. Generalized Exponential Distribution II-354 4. Poisson Distribution II-354 D. Molecular Weight Distribution in Condensation Polymers: The Stockmayer Distribution Function II-354 E. References II-356
A.
INTRODUCTION
An attempt is made to present a systematic guide to the literature dealing with rates of polymerization, average molecular weights, and molecular weight distributions of polymers for various types of polymerization. This chapter is based on a review of molecular weight distributions (1) in which many of the equations are given in detail along with
graphs showing the interrelationship among various distributions; here, we present only references to the literature. In addition, sections have been added on the effects of degradation and reactor design on the reaction rates and the molecular weight distributions. Literature references beyond (312) are those that have been added since the third edition of Polymer Handbook. The theoretical description of the molecular weight distribution of a polymer and its rate of polymerization is dependent on the assumed mechanism of polymerization and on the mathematical simplifications used to obtain analytical expressions. As the number of distinct reactions is increased, such as the various transfer reactions, the mathematical expressions can become quite complex and unwieldy. In general, the equations for the rate of polymerization are the most difficult to describe, the distribution equations are somewhat easier, and the average molecular weights the simplest. In condensation polymerization, many of the distribution formulas are derived by considering the statistics or the probability of a given reaction instead of the kinetics of the reactions. Depending on which assumptions are made, quite different average molecular weights are derived, despite the rigor of the derivation. The emphasis in this section is, therefore, on the distribution functions and their averages; the rates of polymerization are given only if they have been explicitly derived. This chapter is divided into several tables and sections, each treating various types of polymerization. The Stockmayer distribution function for condensation polymers is given in detail because of its general applicability and usefulness. Some general distribution functions are given in Section C. For all the other expressions, the reader must refer to the original literature. Many of the simpler functions are adequately described in textbooks of polymer chemistry. Flory (2), Bamford et al. (3), Odian (4), Billmeyer (5), and Kuechler (6) give extended descriptions of many systems. Bagdasarian (7) gives an extended discussion of methods of determining absolute values of propagation and termination constants, the influence of cage effects on the rate of initiation, and the influence
of retardation, inhibition, and diffusion-controlled termination on the rate of polymerization. A review of the various ways of deriving molecular weight distributions and the moments of a distribution is given by Chappelear and Simon (8). Section B presents a series of tables describing the main assumption or conditions imposed on the theoretical models and references to the articles where the corresponding equations may be found. Tables 1 and 2 present rate equations and the distribution formulas for addition polymerization by a variety of mechanisms. No distinction is made among free radical, cationic, anionic, or coordinationtype polymerization. While Table 1 treats those cases where termination reactions predominate and where steady-state assumptions are usually made, Table 2 treats those cases where termination reactions either do not exist, or may be considered as side reactions, having a minor to major control over the molecular weight distribution. The sequence length distributions for addition-type copolymers are omitted. However, see Kuechler (6) for an extended discussion of copolymerization distributions. Table 3 contains distribution formulas for linear condensation polymers in which the polymer is assumed to be perfectly linear and to contain no rings. Table 4 treats equilibrium polymerization. Table 5 describes nonlinear systems. Table 6 treats those cases where polymers are degraded (or altered) by the application of heat, light, or ionizing radiation. In the latter case, the polymer may undergo scission, crosslinking, or both reactions simultaneously. Several references on crosslinking are included here but not in Table 5. Finally, Table 7 is concerned with the influence of reactor design on molecular weight distribution; the kinetic equations for addition polymerization (with and without termination) and condensation polymerization are considered. Section C lists a number of distribution functions and their properties. Among them is the generalized exponential function which is a good approximation to many real systems (Eq. C29). Section D presents the Stockmayer distribution function for condensation polymerization wherein molecules of various types of kind A react with molecules of various types of kind B. B. REFERENCE TABLES FOR THE CALCULATION OF RATES OF POLYMERIZATION, AVERAGE MOLECULAR WEIGHTS, AND MOLECULAR WEIGHT DISTRIBUTIONS OF POLYMERS FOR VARIOUS TYPES OF POLYMERIZATION
The following symbols are used in this chapter. Rv: rate of polymerization; R^: rate of depolymerization; R\: active, growing polymer containing one monomer unit; R^ and Q*: active, growing polymer chains containing n monomer units; Pr: molecular weight distribution; U1: rate constant for initiation; kv\ rate constant for propagation; /: initiator concentration; M: monomer concentration; Mn and Mw: number-average and weight-average molecular weights,
respectively; 1° and 2° represent first and second order, respectively. No distinction is made among free radical, cationic, anionic, or coordination-type polymerizations. The rate of initiation may be held constant (const) throughout the polymerization, or it may depend on some function of the catalyst and monomer concentrations, or it may be instantaneous (instant), in which case only the total number of initiating species need be known. The rate of propagation is normally only the consumption of monomer; in some cases, the rate of propagation through terminal or pendant double bonds is also considered. Transfer reactions may occur to initiator, momomer, solvent, or polymer. Termination of active species may occur by a first-order deactivation, by second-order combination (comb) or disproportionation (disprop), or not at all ("living" polymers). Confusion exists over the meaning of the transfer-tocatalyst reaction. In free radical systems, it means transfer of the active species to the initiator by a second-order mechanism. In ionic polymerization, it means the expulsion of an active fragment from a growing chain by a first-order mechanism to form dead polymer and an active initiator fragment. The first-order mechanism is called here the "catalyst expulsion reaction" (cat ex). The nomenclature of distribution functions can be quite confusing. In this work, the Flory distribution (Eq. C41) is also known as the Schulz-Flory distribution, the "most probable" distribution, and the exponential distribution. The Schulz distribution (Eq. C36) is also known as the Schulz-Zimm distribution or the generalized Poisson distribution; at large values of k it approximates the Poisson distribution (Eq. C48). The Pearson Type III distribution is a variation of the Schulz distribution. If an addition polymer is made at constant monomer concentration, no transfer reactions occur, termination is only by second-order combination, and the distribution of the polymer is described by the Schulz distribution with k — 2. This distribution is sometimes called the self-convolution distribution or the convoluted exponential distribution. In a uniform distribution, all molcules have the same size - it is monodisperse. A rectangular or box distribution has no molecules below ra, an equal number (or weight) of molecules between r a and Tb, and no molecules whose size is above r\>. In Table 5, systems are treated where branching reactions, ring formation, or gel formation may occur. See also Table 6 for crosslinking reactions during degradation. The symbol RA/ means a monomer containing/reactive A units. The problem of calculating the species distribution of polyfunctional condensation polymers where branched, cyclic, and crosslinked species can be formed is exceedingly complex. Most treatments apply the restriction that ring formation does not occur prior to the gel point, which obviously is incorrect. The restriction is invoked because of the transition from the pre-gel condition, where all unreacted functional groups can react without steric limitations to a condition containing rings in which some of the unreacted groups are sterically unable to react with all of the remaining unreacted groups. The problem is
further compounded because each different reacting monomer will have various degrees of steric hindrance. Therefore, a general treatment must ignore this aspect. An examination of the Stockmayer distribution function in Section D shows that in-depth calculations are required even for simple oligomer species. A number of attempts have been made to provide simpler expressions for the number or weight of individual species and the average
molecular weights before and after the gel point. These include the theory of stochastic processes (271), stochastic graph theory (272), the theory of cascade processes which is based on probability generating functions (151), the use of link distribution functions (273), the recursive nature of branching processes and elementary probability laws (274), Monte Carlo methods (275), graph theory (276), and a kinetic approach (277).
TABLE 1. ADDITION POLYMERIZATION WITH TERMINATION References Set
Initiation
Monomer
Transfer
Termination
Rp
Pr
Mn,M^
1.1. INVARIANT MONOMER CONCENTRATION 1.1.1 1.1.2 1.1.3 1.1.4 1.1.5
Const Const Const Const Const
None Monomer, solvent Monomer, solvent Activator None
2° Disprop or comb 2° Disprop 2° Disprop and comb 2° Comb 2° With catalyst; redox system
1.1.6
Const Const Const Const, redox Const, initiation by activator kxM2
2-4 2,3,10-12 3 13 14
1-4 1-3 1,3 13 -
1-4 1-3 1,3 13 14
Const
2° Term
15
-
15
1.1.7
Instant
Const
Dimer, Monomer Initiator None
2° Term; 1° or 2° reactivation
16
-
16
1.2. VARYING MONOMER CONCENTRATION, NO TRANSFER-TO-MONOMER REACTION 1.2.1 1.2.2 1.2.3 1.2.4
Const Const Photosensitized Const
Varies Varies Varies Varies
None Solvent None None
2° Comb or disprop 2° Comb and disprop 2° Disprop 2° Disprop and comb pseudo 1° with scavenger
3 3 39 17 (rate of scavenger
1,3 1,3 1,3 1,3 39 disappearance)
1.3. VARYING MONOMER CONCENTRATION, TRANSFER-TO-MONOMER REACTION OCCURS 1.3.1 1.3.2 1.3.3 1.3.4 .3.5
Const Const k{M2 kxMl Instant
Varies Varies Varies Varies Varies
Monomer, solvent Monomer, solvent Monomer Monomer, initiator Monomer
2° Disprop or comb 2° Disprop and comb 2° Comb and disprop 2° Disprop; degradative chain transfer Non-steady state conditions, term by comb or disprop
3,18 3,4 20 313
1,3,18 1,3,4 313
1 19 1,3,4 20 313
1.4. 1° TERMINATION OR DEACTIVATION, STEADY-STATE KINETICS 1.4.1 1.4.2 1.4.3 1.4.4 1.4.5 1.4.6
Const kiMI k-xM2 kiMI k-M1 kiMI
Const Const Const Varies Varies Const
Monomer Monomer, solvent Monomer Solvent None None
1° Deactivation 1° Deactivation 1° Deactivation 1° Plus solvent term 1° Deactivation Deactivation by init. expulsion
4 1,4 1,4 4 1.4,21,22 1,4,21,22 4 1,4 1,4 4,23 1,4 1,4 4,23 1,4 1,4 21 1,21 1,21
1.5. TERMINATION BY 2° REACTION WITH MONOMER, STEADY-STATE KINETICS 1.5.1 1.5.2 1.5.3 1.6. 1.6.1 1.6.2 1.6.3
Const kiMI Const
Varies Varies Const
None Monomer Monomer
2° With monomer 2° With monomer 2° With monomer
None Monomer Monomer
2° Disprop 2° Disprop 2° Comb; two active chains couple to form a chain with two active ends
4,23 23 4
1,4 1 1,4
1,4 1 1,4
3 3
1,3 18 1,3
1,3 18 1,3
TWO ACTIVE ENDS PER CHAIN Const Const Const
Const Const Const
1.7. SLOW EXHAUSTION OF INITIATOR, NONSTEADY-STATE KINETICS 1.7.1 1.7.2
kj kj
Const Varies
None None
2° Disprop* or comb 2° Comb
25*,26 27
-
1,25*,26 27
*Data belong together.
References page II - 356
TABLE 1. cont'd References Set
Initiation
Monomer
Transfer
Termination
Rp
Pr
Afn, Mw
1.8. DEAD-END POLYMERIZATION, RAPID DECAY OF INITIATOR, MONOMER CONCENTRATION INVARIANT 1.8.1 1.8.2
kj kj2
Const Const
Monomer, solvent None
2° Disprop or comb 2° Disprop or comb
28 28
1,28 1,28
1,28 1,28
30 30 31
-
1,19* 1 -
40 41
-
-
1,2,3,4,10 32,33 239
34
1,35
239
239
315 -
316
316
37*
1,36
27 42 240 241
240 241
242
242
242
243
243
243
317
-
317
-
1,38
1.9. DEAD-END POLYMERIZATION, SLOW DECAY OF INITIATOR, MONOMER CONCENTRATION VARIES 1.9.1 1.9.2 1.9.3
kj kj kJM
Varies Varies Varies
Monomer, solvent Monomer, solvent None
1.9.4 1.9.5
Instant Redox
Varies Varies
Monomer None
2° Disprop * or comb 2° Comb 1° Term, bimolecular monomer addition. /* and R) do not terminate 1° Term, or 2° with monomer 2° Term
1.10. COPOLYMERIZATION: TWO DIFFERENT MONOMERS PRESENT 1.10.1
Const
Const
Monomer
2° Disprop or comb
1.10.2
Const
Varies
None
1.10.3
Const
Const
None
1.10.4 1.10.5
Const Varies
Const Varies
None Agent
Diffusion controlled and inversely proportional to viscosity Rate const for term is known as fn(conc). Comparison of cross term parameter ^ Alternating copolymerization Various; Monte Carlo calculations; initiation and term influences composition
314
1.11. DIFFUSION-CONTROLLED TERMINATION (see also 1.10.2 and 5.1.4) 1.11.1
Const
Varies
None or solvent*
1.11.2 1.11.3 1.11.4 1.11.5
kj Const kj kj
Varies Varies Varies Varies
None None Monomer None
1.11.6
k[
Varies
None
1.11.7
k{
Varies
Monomer, solvent
1.11.8
kj or none
Varies
Monomer, solvent
1.11.9
Const
Const
Solvent
2° Disprop or comb* and diffusion controlled 2° Comb, Rt = ktMn,n > 1 2° Process 2° Disprop and diffusion controlled 2° Disprop and comb, diffusion controlled 2° Disprop, term rate for long chains depends on entanglement density 2° Disprop, term rate for long chains depends on entanglement density 2° Comb, and disprop term depends on free volume or free volume plus entanglement, CaIc. of gel point kt^m) = ko(nm)~a. Term by comb and disprop.
27
318
1.12. PRIMARY RADICAL TERMINATION 1.12.1
Const
Varies
Monomer
1.12.2
Const
Const
None or init. and monomer*
2° Comb and disprop and primary radicals 2° Term and primary radicals
38 33,43-45
- 44,45,15*
1.13. MIXED SPECIES PROPAGATION 1.13.1
Const
Varies
Monomer
1.13.2
Const
Const
None
1.13.3
Const
Varies
None
*Data belong together.
Propagation, transfer and termination rates depend on species type, i.e. free radical and cationic occurring simultaneously Zwitter-ion polymerization; distance between ions varies as r 3/2 , equilibrium between free and solvated ions; 1° term Bifunctional initiator, term by comb
46 244
46 244
244
47
-
47
319
-
319
TABLE 1. cont'd References Set
Initiation
Monomer
Transfer
Termination
Rv
Pr
Mn,Mw
1.14. EMULSION POLYMERIZATION (see also Tables 2 and 7) 1.14.1
Const
Const within particles
None
1.14.2
Const
None
1.14.3
Const
1.14.4
Const
Const within particles Const within particles Const within particles
1.14.5
Const
1.14.6
Slow and const
1.14.7
Const
1.14.8
None Monomer
Const within Monomer particles varies outside Const None None
Const
Const within particles Const
1.14.9
Varies
Varies
Minimize
1.14.10
Const
Const within particles
Monomer, agent
1.14.11
Const
Monomer, agent
1.14.12
Varies
Const within particles Varies
1.14.13
Const
Const
None
1.14.14
Const
Const
None
None
Monomer
General theory; particles act as independent units; 2° term within particles; number of particles remain constant; number of radicals per particle General theory; Slow-term rate within particles Inst. term within particles; number of particles varies Normal 2° term within particles; rapid interchange between phases of small-sized radicals; number of radicals per particle Rapid exchange between phases of small-sized radicals; term in aq phase and in particles Slow 2° comb; calcn. of number of radicals per particle Const number of particles; term by 2° comb Inst term on entering a particle; const number of particles Adjust initiation and term rates while minimizing transfer to obtain "monodisperse" polymer Instant 2° term when a free radical enters a particle containing two growing chains and reacts with one of them. No term by disprop or comb within particles Same as case 1.14.10 but plus term by disprop or particle by comb Varying rate of entry, desorption of oligometic radicals, term by comb and disprop, Monte Carlo simulation model Any number of chains per particle, 1° term, 2° term by disprop or by comb. Use of Markov chains See 1.14.13. Copolymerization, chain composition distribution
48-54
-
53
55
-
55
56
-
-
-
59
59
60
-
60
-
-
61
72
72
72
245
245
245
245
245
245
-
320
-
-
321
-
322
62
62
62
63
-
63
-
-
68
-
68
69
-
69
57
58
1.15. HETEROGENEOUS POLYMERIZATION 1.15.1
k[MI, I varies
Varies
Monomer
1.15.2
Instant
Varies
None
1.15.3
Const
Const
None
1.15.4
Const
Const
None
Polymerization in monomer rich and monomer poor phases; 2° disprop Term by precipitation onto growing solid particle 2° Comb, 1° occlusion onto particle surfaces, and primary radical term 2° Term in liquid phase, 1° radical precipitation, propagation and 2° term at solid-liquid interface
64 65
1.16. INHIBITION AND RETARDATION 1.16.1
Const
Varies
None
1.16.2
Const
Const
Inhibitor
1.16.3
Const
Const
Retarder
2° Term, 2° addition to inhibitor 2° Term, inhibitor term, inhibitor coupling 2° Term, retarder reinitiation and term
3,66,67,73
References page II - 356
TABLE 1. cont'd References Set
Initiation
Monomer
Transfer
1.16.4
Const
Const
Retarder
1.16.5
Const
Const
Retarder
1.16.6 1.16.7 1.16.8 1.16.9
Const Const Const kj
Const Varies Const Const
Retarder None Inhibitor Inhibitor
1.17.
Termination 2° Term, retarder reinitiation, term and coupling 2° Term, rate of transfer equals rate of reinitiation 2° Term, copolymerization of retarder Pseudo 1° with scavenger 2° Disprop, 2° reaction with inhibitor 2° with inhibitor or with monomer to assess the efficiency of initiation
^p
Pr
Mn, Mw
3,12,70 71,74 10
-
-
-
-
11 17 75 246
-
11 75 -
-
-
247
-
323
-
324
324
324
-
325
-
POLYFUNCTIONAL INITIATOR WITH VARIOUS THERMAL STABILITIES
1.17.1
k\Ml On raising the temp., other peroxide groups can initiate
1.18.
Const
None
2° disproportionate
PERIODIC MODULATION OF TERMINATION OR INITIATION
1.18.1
Const
Varies
None
1.18.2
Varies
Varies
None
1.18.3
Varies
Varies
None
Periodic modulation of term by disprop by addition of an inhibitor or by magnetic or electric fields Periodic modulation of initiation, term by comb and/or disprop, computer calculation Periodic modulation of initiation, term by comb. Calcn. of MWD by generating functions
TABLE 2. ADDITION POLYMERIZATION - "LIVING" POLYMERS WITH PARTIAL DEACTIVATION References Set 2.1.
Initiation
Monomer
Transfer
Termination
kpMI
Varies
None
None
2.1.2
kpMIt
Varies
None
None; initiator added at a constant rate
None
None
2.2.1 2.3. 2.3.1 2.3.2 2.3.3
2.3.4 2.3.5 2.3.6
2A. 2.4.1 2.4.2
Pr
Mn^Mw
103
1,2,101, 102 -
1,2,101, 102 103
102, 104
1,102
1,102
THE POISSON DISTRIBUTION: Jc1 = kp
2.1.1
2.2.
Rp
2,101,102
THE GOLD DISTRIBUTION: Zt1 + kp kiMI
Varies
PARTIAL DEACTIVATION BYA 1° PROCESS OR A 2° PROCESS WITH AN IMPURITY Instant Instant Instant initiator has two active sites Instant Instant Instant
Varies Varies Varies
None None None
1° or 2° Rate of term//?p = const. Rate of term//?p = const.
Varies Varies Const
None None None
Rate of term independent of Rp 1° at infinite time Probability that a chain will terminate rather than propagate is kt/kvM
105 1,106 1,106 - 1,106,107 1,106,107 1,107 1,107
1,106 108,109 -
-
1,106 108,109 248
MULTIPLE PROPAGATING SPECIES: R*n CAN TRANSFORM INTO Ql, ETC. Instant kiMI
Const Varies
None None
None, two propagating species None, two propagating species
1, 77-79
76 1,77,78 80
76 1,77-80
TABLE 2. cont'd References Set
Initiation
Monomer
Transfer
2.4.3 2.4.4
Instant Activated monomer addition
Varies Varies; volume also varies
None None
Termination None, multiple propagating species None; two prop constants kp can increase
Rp
Pr
Mn, M ^
249 -
249 326 327
249 326 327
82,83 84
1,81 81
1,81 83
2.5. SIMULTANEOUS POLYMERIZATION AND DEPOLYMERIZATION 2.5.1 2.5.2 2.5.3
kiMI kiMI JcpM2
Const Varies Varies
None None None
None None None
2.6. THE kp VARIES WITH CHAIN LENGTH (see also 2.4.4, 3.3, and 3.4) 2.6.1
2.6.2 2.6.3 2.6.4 2.6.5
kiMI Varies None None (a) all propagation constants (kT) are different 1,85,86 (b) ki : ki : k2 : k3 :~-kn=m : (m - 1) : (m - 2) : (m - 3) : • • • 1,85 (C) * i ^ * 2 - - - ^ m = W i = ••• = *» 1.85 1,85 (d)*i^*i^*2=*m 1,85 Instant, kx = k2 • • • = km,km+l, etc.= 0 86 86 86 Instant, kp is a linear decreasing function of r 86 86 86 Const Varies None None; kv for monomer, dimer, and 328 328 trimer different from remaining molecules Rate constants can vary with extent of conversion; determination of rate constants from Pr and the use of generating functions; termination by monomolecular decay, disprop and/or comb. 329 -
2.7. DEACTIVATION BY TRANSFER TO MONOMER 2.7.1 2.7.2 2.7.3
kxMI Instant Instant
Varies Varies Varies
Monomer Monomer Monomer
None None None, two active ends per initiator
1,87 1,74,90 1,91
1,87 1,74,87,88 1,89,90 1,74,90 1,91,92 1,91
2.8. DEACTIVATION BY SLOW 1° TERMINATION 2.8.1 2.8.2
Instant Instant
Varies Varies
None Monomer
Slow 1° Slow 1°, at infinite time
1,74 1,74
-
1,74 1,74
None 1° term None
67 250
250
1,93 67 250
95
2.9. DEACTIVATION BY INITIATOR EXPULSION REACTION 2.9.1 2.9.2 2.9.3
Instant kiMI Instant
Varies Varies Varies
None Monomer Monomer
2.10. DEACTIVATION BY DEGRADATIVE CHAIN TRANSFER 2.10.1 2.11. 2.11.1
kiMI
Varies
Degradative transfer to polymer
None
94
-
Varies
None
None
-
96
None; diffusion of monomer through solid polymer 2° Term with monomer; diffusion of monomer through solid polymer Sorption and desorption of chains from the surface; slow 1° term which depends on chain length
97
-
97
98
-
98
-
99
99
100
-
100
COPOLYMERIZATION Instant
2.12. HETEROGENEOUS POLYMERIZATION 2.12.1
Instant
Varies
None
2.12.2
Instant
Varies
None
2.12.3
Const
Const
None
2.13. SPONTANEOUS POLYMERIZATION 2.13.1
Const
Const
None
Vinyl compound and activator form monomer; monomer both initiates and propagates; no term
References page II - 356
TABLE 2. cont'd References Set 2.14.
Initiation
Rev 2° with monomer
k[MI
2.15.2
kM
Const
Monomer
No termination; dead species in equilibrium with living species, irreversible propagation
251
252
Numerical method for calc. of MWD with mono- or polyfunctional transfer agent. Latter leads to branching.
-
330
3-State mechanism consisting of two successive equilibria Equilibrium between dormant aggregated polymer and "living" polymer
-
-
331
332
-
-
-
-
334
-
-
335
SLOW EQUILIBRIA
Varies
Varies
None
POLYMER MICROSTRUCTURE
2.17.1
Varies
Varies
None
2.17.2
NA
NA
NA
TABLE 3.
LINEAR CONDENSATION POLYMERIZATION WITHOUT RING FORMATION
3.7
251
-
2.16.2
3.6
251
-
None
3.5
Mn,Mw
No termination. Transfer creates dead polymer and active initiator
Varies
3.1 3.2 3.3 3.4
Pr
Agent const varies Agent
Varies
Set
Rp
Const or varies Varies
2.16.1
2.17.
Termination
DEACTIVATION BY TRANSFER TO AGENT
2.15.1
2.16.
Transfer
REVERSIBLE INITIATION AND REACTIVATION
2.14.1
2.15.
Monomer
None; concentration of head-to-head and tail-to-tail, sequence length distributions, various dyad and triad fractions Block copolymers
Conditions Condensation of bifunctional monomer AB; the Flory distribution. See Eq. (C41) Bifunctional monomer AA reacting with bifunctional monomer BB; the nylon case of hexamethylene diamine and adipic acid Deviations from the principle of equal reactivity; the "substitution effect" Rate of condensation varies 3.4.1 Rate of condensation proportional to chain size 3.4.2 Condensation requires rotation into colinear orientation prior to reaction 3.4.3 The order of reaction varies with conversion, or a catalytic influence of unreacted A or B groups, or both effects occurring simultaneously Other simple linear condensation cases 3.5.1 AA reacting with BC. BC is an anhydride; within a given molecule, B must react before C 3.5.2 AA reacting with BC. BC is an unsymmetrical acid or glycol; B reacts only with A at a different rate from that of C reacting with A 3.5.3 AB reacting with C and itself. B and C react only with A; C is a terminator or capping material 3.5.4 AA reacting with BB and C; the nylon case again with acetic acid as terminator 3.5.5 AA reacting with BC; A and B react with C 3.5.6 AB reacts with CC or DD kinetics 3.5.7 AA and A reacting with BB and B Further polymerization of polymers with an initial geometric distribution 3.6.1 Further polymerization of AB when the initial distribution is geometric 3.6.2 Further polymerization of AB when the initial distribution is a superposition of two geometric distributions 3.6.3 Further polymerization of AA with BB when the initial distribution of both is geometric Copolymerization of condensation polymers 3.7.1 AB reacting with CD; AB and CD can be hydroxy acids or similar materials 3.7.2 AA reacting with BB and CC. A reacts with B and C only and vice versa; BB and CC can be adipic and sebacic acids 3.7.3 AA and BB reacting with CC and DD; A and B react only with C and D and vice versa 3.7.4 AA reacting with BC and DD; A reacts only with B, C, and D 3.7.5 AA and DD reacting with BC; A and B react only with C and D and vice versa 3.7.6 AA reacting with BC-BC, the latter can be a dianhydride; B must react before C
References 1,2,110 1,24,111 1,112,253,254 1,113,114,134 255 256 1,111 1,111 1,111 1,111 1,111 115 336 1,116 1,116 1,116 1,111 111,257 111 111 111 258,259
TABLE 3. cont'd Set 3.8
3.9 3.10 3.11
Conditions Coupled polymers 3.8.1 AB polymerized to extent of conversion a, then coupled with CC 3.8.2 AB polymerized to extent of conversion a, then coupled with CD. A and B can react with C or D 3.8.3 AA and BB polymerized to extent of conversion a, then coupled with an excess of CC. A and B to react completely on coupling 3.8.4 Poisson-distribution polymer of AA coupled with BC 3.8.5 Monomer AB polymerized to extent of conversion a, then coupled with excess CC to extent of conversion 7, then recoupled with excess DD 3.8.6 Particularly narrow distributions via coupling reaction I. AA and BB (great excess)—^BBAABB, then remove excess BB. CC and BBAABB (great excess)—> BBAABBCCBBAABB, then remove excess BBAABB, and continue in like manner II. AA and 2BC^CBAABC then CBAABC and 2DE^EDCBAABCDE, etc III. AB and CD^ABCD then ABCD and EF^ABCDEF, etc 3.8.7 Blocks of polymers of known distribution are coupled together I. A series of Poisson-type-polymers coupled together II. Poisson-type-polymers coupled to "most probable"-type polymers III. A series of "most probable"-type polymers coupled together AB reacts with CC or CD; rate of reaction of A dependent upon whether or not B has reacted Segmented block copolymers; distribution of block sizes Reacted sequences in homopolymers
TABLE 4. Set 4.1
References
1,117 1,117 1,117 119 119 119
120,118 115 260-262 263, 264
EQUILIBRIUM POLYMERIZATION Conditions
References
The "most probable" distribution of Flory has been derived for condensation polymerization when all reactions are assumed to have the same probability, regardless of chain length, and whether or not exchange reactions occur: P r + P5 = P r + s - i + P t ,
4.2
1,117,118 1,117
Eq. C41
i
Here, P1- can be a byproduct such as water, or a polymer molecule whose size is smaller than r + s. The same distribution results when random scission occurs to infinitely long chains. See also (265) for multifunctional monomers. The theoretical equilibrium molecular weight distribution for the system
2,121 122
rM = Pr
4.3 4.4 4.5 4.6 4.7 4.8 4.9 4.10 4.11 4.12 4.13 4.14 4.15 4.16 4.17
depends upon the thermodynamic definition of the final product. If the change in Gibbs free energy of formation and polymerization is a linear function of molecular size r, then two cases can be considered: 4.2.1 The monomer is polymerized to a pure perfectly ordered state (solid); this gives the "most probable" distribution 4.2.2 The monomer is polymerized to a pure randomly ordered state (liquid); a completely different distribution results If the free-energy change upon disordering of the pure polymer is independent of the molecular weight distribution, a new distribution arises Thermodynamics of living equilibrium polymers Given an initial distribution, find the distribution as a function of time when chain ends react at random with all monomer units Initiation, propagation, and termination reactions are all equilibrium reactions; an initiator is required Initiation, propagation, and termination reactions are all equilibrium reactions; the system is self-initiating Equilibrium initiation and equilibrium propagation with a multifunctional initiator Equilibrium initiation and equilibrium propagation; no termination; nonequilibrium solution. The catalyst can form an active species with any polymer molecule, and the total number of moles of the system is kept constant (constant pressure and volume if all polymer molecules are ideal gases) Addition polymerization, instantaneous initiation, no transfer, no termination, monomer concentration held constant, active species in equilibrium with inactive species Addition polymerization, rate of initiation equals k\MC, no transfer, no termination, two active species in equilibrium, monomer concentration varies Addition polymerization, instantaneous initiation, no transfer, no termination, active species in equilibrium with inactive species, monomer concentration varies Poly(phosphate) equilibria Instantaneous initiation, polymerization and depolymerization, 1° termination Instantaneous initiation, polymerization and depolymerization, degradative transfer to monomer Copolymerization: bimolecular addition of one monomer, equilibrium addition of other monomer Copolymerization: equilibrium growth with monomer A or B adding to a chain with a terminal group of either A or B. Three cases: 2° reaction with initiator; 1° formation of active radical; 2° reaction with another monomer
Eq. C41 123 124 125 126 127 127 128,266 129 130 77 78 77 131 132 133 230 267
References page II - 356
TABLE 4. cont'd Set 4.18 4.19 4.20
Conditions Equilibrium copolymerization of two or more comonomers Polycondensation where groups have different equilibrium constants Equilibrium copolymerization initiated by polymer chains with active sites: average mol. wts, grafting ratio, grafting efficiency, grafting success, branching distribution, frequency of grafts
References 268 269,270 337
TABLE 5. NONLINEAR POLYMERIZATION SYSTEMS Set
Conditions
Vinyl polymerization; self-grafting 5.1.1 General case; molecular weight averages for grafted and ungrafted polymer 5.1.2 Constant rate of initiation, monomer concentration invariant, transfer to monomer and to polymer, termination by 2° disproportionation 5.1.3 Constant rate of initiation, monomer concentration varies, transfer to polymer, termination by 2° combination 5.1.4 Constant rate of initiation, monomer concentration can vary, transfer to monomer and to polymer, termination by 2° disproportionation and/or combination 5.1.5 Instantaneous initiation, monomer varies, either no transfer occurs or transfer to monomer, solvent, or polymer is allowed; termination by coupling and varies with chain length 5.2 Vinyl polymerization; grafting onto a performed polymer whose initial distribution is either (i) of constant length or (ii) a geometric distribution 5.3 Vinyl polymerization; all segments of the backbone chains have equal probability to be grafted 5.4 Vinyl polymerization; terminal double-bond polymerization, monomer concentration varies, transfer to monomer and to polymer, terminal double bond polymerization 5.4.1 Termination predominantly by transfer, constant rate of initiation; batch or continuous polymerization 5.4.2 Termination by disproportionation, constant rate of initiation, includes transfer to solvent 5.4.3 Termination by combination, constant rate of initiation, amount of short and long chain branching, transfer to a tertiary site 5.4.4 Termination by combination, initiator and monomer concentration vary, transfer to monomer and to polymer 5.4.5 Termination by combination, initiator and monomer concentration vary, transfer to monomer and to polymer, characterization following saponification and reacetylation 5.5 Vinyl polymerization; long-chain branching. 5.5.1 constant rate of initiation, monomer concentration invariant, transfer to monomer and to polymer, termination by 2° disproportionation 5.5.2 "Living polymer". Instantaneous initiation, P-hydride or p-methyl elimination to form a terminal double bond, transfer with agent to form a saturated end 5.6 Vinyl polymerizaton; "living" branched polymer; polyfunctional initiator RA/; rate of initiation equals rate of propagation, no transfer, no termination 5.7 Vinyl polymerization; Rp, in a diffusion controlled gelling system; termination by disproportionation or combination, no transfer 5.8 Vinyl polymerization; branching density as a function of conversion; branches formed by polymerization through a vinyl group (diene polymers) or by transfer-to-polymer reaction 5.8.1 Batch polymerization 5.8.2 Continuous polymerization 5.9 Vinyl polymerization 5.9.1 Branching density as a function of conversion of (1) long-chain branching, (2) short-chain branching (backbiting), (3) very short chain branching (radical migration) 5.9.2 Copolymerization with divinyl, no ring formation prior to gelation 5.9.3 Copolymerization with divinyl; ring formation permitted; Monte Carlo calculations for crosslinking density, weight fraction of gel; chain-length distribution between crosslinks 5.9.4 Circuits in a network, elastically active chains 5.10a Emulsion polymerization; branch density 5.10b Emulsion polymerization; Monte Carlo calculations; can account for desorption of oligomers, chain-length dependence of kinetic parameters, chain transfer to monomer and solvent, polymerization through terminal double bonds and long-chain branching 5.11 Cyclopolymerization: the concentration of pendent double bonds per molecule 5.12 Gelation condition in a system when cyclopolymerization also occurs; transfer to monomer reaction occurs. Molecular weight given 5.13 General theory of gelation for poly addition- and poly condensation-type polymers 5.14 The general distribution function for various molecules of type A reacting with various molecules of type B; A can only react with B 5.14.1 All functional groups have equal reactivity, independent of position within the molecule or the size of the molecule. Ring formation excluded
References
5.1
278 1,3,18 135 279 280 18 136 1,137-139 338 338,339 340 341 1,140 355 141 142 1,2 1,138 143 274,281 342,343 282,283 144,344 345 145-149 150 151 Section D 276
TABLE 5. cont'd Set
5.15
Conditions
References
5.14.2 Monomers of type RA/ (/can vary) can only react with monomers of type RBg (g can vary) where the various B's can have different reactivities. No ring formation 5.14.3 Monomers of type RA/ and RB g where/and g can vary, the reactivity of a given B can depend on whether or not an adjacent B on the same molecule has reacted. No ring formation 5.14.4 Monomers of type RA/ and RB g where/and g can vary; no ring formation; calculation of higher distribution moments Crosslinking or coupling of a polymer with a known primary distribution (see also Table 6) 5.15.1 General case. No ring formation prior to gelation 5.15.2 All primary chains have the same size; no ring formation prior to gelation
5.16
5.15.3 Primary chains of the Poisson type, (Eq. C48); no ring formation prior to gelation 5.15.4 Primary chains of the Schulz type, (Eq. C36); no ring formation prior to gelation 5.15.5 Primary chains of the "most probable" type; ring formation allowed prior to gelation 5.15.6 Formation of star-type polymers Homopolymer of ARB r _i. A can react only with B; the B's may have different reactivities. Formation of rings excluded prior to gelation 5.16.1 All B groups have the same reactivity 5.16.2 Let B groups have different reactivities 5.16.3 A controversy over the statistical approach
5.17 5.18
5.19
5.20 5.21 5.22
5.23
5.24
Copolymer of ARB/_i and AB; A can react only with B; formation of rings excluded prior to gelation Homopolymer of RA/; formation of rings excluded prior to gelation 5.18.1 All A's equally reactive
284 285 346 1,152-155, 286 1,2,152, 155-157 155,157 286 287 288 1,2,158,265, 289 1,159,160 161,162,163, 164 1,2,158 1,2,121,158, 165,166, 265,274, 277,281, 290-292 167,273,293
5.18.2 Reactivity of A depends on number of A's previously reacted Various copolymers 5.19.1 Copolymer of RA/ and AA; formation of rings excluded prior to gelation 1,2,165 5.19.2 Copolymer of RA/, AA, and BB; A can react only with B; formation of rings excluded prior to gelation; all branch points completely reacted. See set 5.16.3 for a controversy 1,168,169 5.19.3 A mixture of self-condensing monomers RjA g , RiA/j, etc., no ring formation 277,294,295 5.19.4 A stoichiometric mixture of RA/ and RB/ of the same functionality/, indistinguishable reactivity, no ring formation. Note that different authors get different equations for Mn and Mw 277 5.19.5 A stoichiometric mixture of RA/, RA g ,.. .and RBzn R B / . . . , / , g, h, i being different functionalities, indistinguishable reactivities, no ring formation 277,294 5.19.6 A copolymer of RA/ and BB; no ring formation prior to gelation 274,281,290 5.19.7 A copolymer of RA^, AA, and B'B" where B' has a different reaction rate from B"; no rings prior to gelation 293 5.19.8 Copolymer of RA/, AA, and BB where the A's in RA/ can have different rates of reaction 293 Polymers of RA/B g 5.20.1 Homopolymer of RA/B g ; A can only react with B; formation of rings excluded prior to gelation 170,265 5.20.2 A mixture of monomers RA/B g , where/, g = 0,1, 2 , . . . , stoichiometry not required 295 Branching without gelation; copolymer of RA/ and AB. A can react only with B 1,171 Gelation conditions; formation of rings excluded prior to gelation 5.22.1 AA reacting with B/C g . A can react with B and C, but with different velocities. B cannot react with C 1,172 5.22.2 AA, BB, and C reacting with DDE and FF; A, B, and C individually can react with D, E, and F, but with different velocities 1,172 5.22.3 AAB, RC4, and GC reacting with DE and F. DE is an anhydride or similar material. D must react first and may have a different velocity from E. A, B, C. and G may react with different velocities 1,172 5.22.4 AB and CD reacting with EEF and GG. AB and CD are anhydrides or similar materials, where A must react before B and C must react before D. A, B, C, and D may react with different velocities 1,172 5.22.5 AA and BC reacting with DDE and FG. BC is an anhydride, B reacting first, and FG is like an unsymmetrical glycol 1,172 Ring formation in linear polymers 5.23.1 Homopolymer of type AA 1,173,174 5.23.2 Homopolymer of type AA. Formation of catenanes 296 5.23.3 Homopolymer of type AB 1,173,175 5.23.4 Copolymer of type AABB 1,173,176 5.23.5 Distribution for chain fraction 1,2 5.23.6 Copolymer of AA with BC. BC can be an anhydride; within a given molecule, B must react before C; A single cyclic oligomer is permitted to form 297 5.23.7 Ring-chain equilibrium constant, Rp of rings, cut-off point of monomer cone below which only cyclics formed 347 Crosslinking of a polymer with a known distribution; rings are permitted prior to gelation 153
References page II - 356
TABLE 5. cont'd Set
Conditions
References
5.25 5.26
Gelation conditions for RA/ when rings are permitted prior to gelation Homopolymer of RA/. Ring formation permitted prior to gelation
5.27 5.28 5.29 5.30
Copolymer of RA/ and BB when rings are permitted prior to gelation Gelation condition for RA/, AA, and BB when rings are permitted prior to gelation Monte Carlo calculations on small amounts of crosslinking Monte Carlo calculations for RA3, the reactivity of an A group depends on the number of previously reacted groups on that monomer, no ring formation prior to gelation Monte Carlo calculations for vinyl and divinyl copolymerization Grafting of reactive polymers of the type AA, AAB, BB, and BBA where rings can form prior to gelation; M w and the gel point Star type molecules prepared by anionic polymerization and different precursors (see also 5.19.1, 5.21 and 5.27)
5.31 5.32 5.33
1,177 1,178,179, 298 180 1,181 299 275 300 348 349
TABLE 6. DEGRADATION OF POLYMERS - MAY BE ACCOMPANIED BY CROSSLINKING References Set
Initiation
Mass
Initial distribution
Transfer
Termination
Rd
Pr
Mn, M^
6.1. RANDOM SCISSION ONLY 6.1.1 6.1.2
Proportional to time Const Proportional to time Const
6.1.3
Random at all bonds Random at chain ends Random at all chains Random Random Random
6.1.4 6.1.5 6.1.6 6.1.7 6.1.8 6.1.9 6.1.10 6.1.11 6.1.12
Random Random at normal and weak bonds Gaussian about the midpoint Central
None None
None None
-
183-186 183-187
182-184 183,184,188
Const
Arbitrary Infinite or uniform Uniform
None
None
-
189
189
Const
Uniform
None
None
-
190
Const
Uniform
None
None
-
191
191
Const Const Const
Rectangular Flory Schulz
None None None
None None None
-
184 184,188 187,301
Const Const
Poisson Uniform
None None
None None
-
184,187 184,187 184,187, 301 187 -
Const
Schulz
None
None
301
301
Const
Schulz
None
None
301
301
192
6.2. UNZIPPING-TYPE REACTION 6.2.1 6.2.2 6.2.3 6.2.4 6.2.5 6.2.6 6.2.7 6.2.8 6.2.9 6.2.10 6.2.11 6.2.12
1° end 1° end 1° end 1° end 1° end 1° end 1° end; various rates of initiation Random scission only Random scission only 1° end and random scission
Varies Varies Varies Varies Varies Varies Varies; monomer radicals may evaporate Varies
Uniform Uniform Schulz Schulz Schulz (k = 2) Schulz (k = 2) Flory
None Polymer None None None None None
1° 2° Disprop 1° 2° Disprop 1° 2° Comb 1° or 2° Disprop
193 194 193 195 196 196 197
-
193 194 193 195 196 196 -
Uniform
Polymer
2° Disprop
194
-
194
Varies
Schulz
None
2° Disprop
198
-
198
Varies
Unspecified
None
1° and 2° Process
1° end and random scission 1° end and random scission
Varies
Flory
Polymer
Varies
Flory
Polymer
1° and 2° Disprop 2° Comb
199 (all molecules must terminate) 200 (some molecules can completely disappear) 201 201 201
-
201
TABLE 6. cont'd References Initial Distribution
Set
Initiation
Mass
6.2.13
1° end and random scission
Varies
6.2.14
1° end and random scission
Varies
Uniform
Polymer
6.2.15
1° end and random scission
Polymer
6.2.16
1° end and random scission
6.2.17
Unzipping reactions
Varies; units Uniform other than monomer may evaporate Varies; units Flory other than monomer may evaporate Varies Various
Flory
Transfer Polymer
Termination
Ra
Pr
Mn, M^
1° and 2° Process; comparison of random scission, weak link, and transfer theories. Comparison of various term mechanisms 2° Disprop
202 203
-
203
204
-
-
205
-
205
polymer
1° and 2° Disprop or 2° comb
206
206
206
Various
Various, a review
207
153 208 302 303 209
153 208 282 302 303 210 209
153 208 302
211 208
211 208
211 28
211
211
211
29
-
29
-
-
350
153
153
153
182
182
182
182,212, 213 -
182
182
182
-
153
153
153
6.3. RANDOM SCISSION AND CROSSLINKING 6.3.1
Proportional to time
Const
Arbitrary
None
Unspecified term, with and without ring formation
6.3.2
Varies with depth of penetration
Const
Flory
None
6.3.3
Proportional to time
Const
Arbitrary
None
6.3.4
Proportional to time Proportional to time
Const
Arbitrary
None
Const
Schulz
None
Const
Various
Unspecified
1° and 2° Disprop without ring formation End-linking (grafting) rather than crosslinking; without ring formation End-linking; with ring formation Unspecified term, without ring formation Various initial distributions
6.3.5 6.3.6
Proportional to time
210
6.4. CROSS LINKING ONLY 6.4.1 6.4.2 6.4.3 6.4.4 6.4.5
Proportional time Proportional time Proportional time Proportional time Proportional time
to
Const
Arbitrary
None
to
Const
Uniform
None
to
Const
Schulz
None
to
Const
Beasley (140)
None
to
Const
Arbitrary
None
Ring formation prohibited Ring formation prohibited Ring formation prohibited Ring formation prohibited Ring formation permitted
6.5. RANDOM SCISSION FOLLOWED BY UNZIPPING 6.5.1 6.5.2
Random macromolecular fragmentation to form defective groups which subsequently initiates depolymerization Random macromolecular fragmentation to form defective groups which subsequently initiates depolymerization with bimolecular kinetic chain termination
351 352
References page 11-356
TABLE 7. INFLUENCE OF REACTOR CONDITIONS AND DESIGN ON THE MOLECULAR WEIGHT DISTRIBUTION Set 7.1 7.2
7.3 7.4 7.5 7.6a 7.6b 7.7 7.8 7.9 7.10 7.11 7.12 7.13 7.14 7.15 7.16 7.17
Conditions Comparison of 1° term, 2° term with monomer, 2° disprop, 2° comb, and no term for 1° and 2° self-initiation and initiation by light in a CFSTR°: Rv, Pr and Mn are given Emulsion polymerization 7.2.1 Emulsion polymerization in a CFSTR. Instantaneous 2° termination 7.2.2 Emulsion polymerization in isothermal BR a ; 1° init, termination with initiator, four stages of polymerization Effect of inadequate stirring in a CFSTR; comparison with BR and normal CFSTR. Term, by 2° or no term. Rp, P r M n ' s Control of MWD a by use of temperature variation; term by 2° disprop or 2° comb. M n 's Effect of expanding drop of monomer in a catalyst solution on MWD of "living" polymers Effect of inadequate mixing by a laminar shear model on MWD of "living" polymers Effect of different flow lines spending different times in the reactor on the MWD of "living" polymers; the bimodal MWD changes with reactor length Effect of varying rate of addition of initiator and/or monomer, transfer agent, or terminator, in a BR, neglecting change in volume Effect of varying the rate of addition of an instantaneous initiator on MWD of "living" polymers Effect of back mixing on MWD of "living" polymers prepared in BR, semi-BR, and CFSTR See also Table 3, set 3.6: Further polymerization of polymers with an initial geometric distribution Linear condensation of a multifunctional monomer in a BR "Living" polymer, inst. initiation, no transfer, no termination in a TR a , monomer varies Effect of mixing in a BR Condensation polymerization when monomer is R times more reactive with monomer or with polymer molecules, CFSTR, and references to BRs Effect of recycling a portion of a TR; chain-stopper control Production of monodisperse particles Reversible polymerization with multifunctional monomers. Comparison of MWD from CFSTR with BR
References
214 215 304 216 217 218 219 353 220 103,221 222 305 306,307 308 309,310 311 312 354
a
CFSTR: Continuous-flow, stirred tank reactor; BR: batch reactor; TR: tube reactor; MWD: molecular weight distribution.
C. SOME DISTRIBUTION FUNCTIONS AND THEIR PROPERTIES
The frequency function, F(r), is the fraction of molecules of size r. Furthermore, F(r) is normalized
Thus, by the definitions of F(r) and W(r) (C5) The weight-average degree of polymerization is
(Cl) (C6) The weight fraction of molecules of size r is
(C2)
Averages of any distribution are defined by
The z and z + 1 averages are defined by Eq. (C3) with / set equal to 3 and 4. There is no need to restrict averages of a distribution to positive integers - any useful average can be defined; such as the (—5/2) average. If the intrinsic viscosity of a polymer is related to the degree of polymerization through the equation (C7) where rv is the viscosity-average degree of polymerization, it is related to the frequency function by
(C3)
The number-average degree of polymerization is defined by
(C4)
(C8) As a approaches unity, rv approaches r w . In principle, a distribution function can be determined if sufficient averages of the distribution can be determined. In practice, only the number, weight, and perhaps z averages can be found, which are insufficient to define any distribution without making further assumptions.
The degree of polymerization is a useful concept as long as one is describing polymers made with a single monomer or with monomers of equal molecular weight. When considering copolymers, one must work with the actual molecular weight of the reacted unit. This is done in condensation polymerization. The molecular weight distribution of addition copolymers is not included here because of the extreme complexity of these systems. When performing the summation of a distribution equation to find an average of the distribution, use is frequently made of the following sums:
Values of F(r) and J^ F(r) Ar are found in many statistical tables (223). 2. Logarithmic Normal Distribution Function Under the assumption that the weight distribution of the logarithm of molecular size is normally distributed, we can replace r in the normal distribution function by In r and f by lnrm (C15)
(C9) where
(C16)
or in the alternate form (C17) n is an integer where (C18)
and (C19)
Here r m is the median value of the distribution, that is, onehalf of the values of r are less than r m . (C20) (C21) (C22)
1. Normal Distribution Function (Gaussian Distribution)
(C23) (ClO) (CU)
(C24) Note that (C25)
(C12)
(C26)
(C13)
The logarithmic normal distribution sometimes is given in a "generalized" form (224)
(C14)
(C27) References page II - 356
but Honig (225) has shown that (C28) Thus, the normalized Lansing-Kramer function (s = 0) (226) is identical to the normalized Wesslau function (s = - l ) ( 2 2 7 ) . The generalized logarithmic normal distribution is skewed to large values of r, but Kotliar (237, 238) shows that this distribution is not a good representation of a polymer after either low- or high-molecular weight material is removed or degradation has occurred.
(b) The Weibull (231) or Tung (232) distribution is obtained by setting m = 1 + k and k > 0. This distribution is usually seen in the form
(C40)
Kotliar (233) shows that evaluation of y and k by the Tung method can lead to erroneous values of fw/fn. (c) The Flory distribution, as noted above, occurs when Jc = m = 1, provided that In/? can be replaced by - ( I — /?), i.e. p & 1. The Flory distribution is also written as:
3. Generalized Exponential Distribution (1,228)
(C41) (C29)
(C42)
(C30)
(C43)
(C31)
(C44)
(C32) (C33)
and with the approximation In p = p — 1
(C34)
(C45)
and (C35) where a is defined by equation (C7). The variance of a distribution
For high molecular weights p « 1, hence
4. Poisson Distribution Hence, the preferred measure distribution breadth is fw/rn. (a) The distribution function (229) is obtained by setting m = This distribution is equivalent distribution
of the molecular weight
(C37) The distribution reduces to the "most probable" distribution where k = 1. The cumulative number or weight fraction of the Schulz distribution may be computed from
(C38)
(C39)
(CAl)
(C48) (C49)
of Schulz (9) and Zimm 1 and requiring that k > 0. to the Pearson Type III
(C36)
(C46)
(C50) (C51) D. MOLECULAR WEIGHT DISTRIBUTION IN CONDENSATION POLYMERS: THE STOCKMAYER DISTRIBUTION FUNCTION Stockmayer (234) has presented a generalized distribution formula for a variety of monomers containing end groups of type A which can only react with a variety of monomers containing end groups of type B. In the original mixture there are A \, A 2, A 3 , . . . , A,-,... moles of reactants bearing respectively,/1,/2,/3,...,/,-,... functional groups of type A each, together with Bi, B2, • • •, Bj,... moles of reactants of functionalities gi, g2, • • -gj,- • • in groups of type B. all functional groups of a given type are equally reactive and ring formation does not occur appreciably; which obviously is not true near the gel point. The system reacts until a fraction a of the A groups and a fraction /3 of the B groups
have reacted. Further
If each species / has an effective molecular weight Af1-, which is lower than the original molecular weight by the term Wo / ; / 2 , where Wo is the molecular weight of the byproduct, then
Now N{mn, Hj) represents the number of moles of that species which consists of mi, ra2, . . . , m f , . . . monomer units of the A type combined with n 1, ^ 2 , . . . , rij units of the B type.
(D5)
The number of molecules of the end of the reaction is,
(Dl) where
neglecting byproduct, (D6)
The number-average molecular weight is (D2) (D7) The weight-average molecular weight is
An example will illustrate the use of Eq. (Dl). Suppose we have the monomers acetic acid (CH3COOH, A1, /1 = 1) and adipic acid (HOOC(CH 2 ) 4 COOH, A 2 , /2 = 2) reacting with ethylene glycol (HOCH 2 CH 2 OH, B i , gi = 2)
and
glycerol
(HOCH2CHOHCH2OH,
B 2 , g2 = 3) (all hydroxyl groups of the glycerol are considered equally reactive). What is the number of molecules which contain exactly 1 acetic acid unit, 4 adipic acid units, 3 glycol units, and 2 glycerol units? It is W{1,4,3,2} and
(D8) where
(D3) (D9)
where
(D4)
Simpler expressions for M n and M w are given by Ziegel et al. (235) for the case when only bifunctional B monomers are present. The gel point is (DlO) Extensive computations of N{mi,rij} for the Z1 = IJ2 = 2 , / 4 , and g2 = 2 have appeared (236).
case
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H e a t s C e i l i n g
a n d
E n t r o p i e s
T e m p e r a t u r e s ,
C o n c e n t r a t i o n s , o f
o f
E q u i l i b r i u m
a n d
H e t e r o c y c l i c
P o l y m e r i z a t i o n , M
o
n
o
m
e
r
P o l y m e r i z a b i l i t y C o m p o u n d s *
J. L e o n a r d Departement de Chimie and CERSIM, Universite Laval, Quebec, Canada
A. Heats of Polymerization 11-365 Table 1. Monomers Giving Polymers Containing Carbon Atoms Only in the Main Chain II-365 1.1. With Acyclic Carbons Only in the Main Chain II-365 1.1.1. Dienes M-365 1.1.2. Monomers Giving Polymers With or Without Aliphatic Side Chains that Contain Only C, H M-365 1.1.3. Monomers Giving Polymers With Aliphatic Side Chains that Contain Heteroatoms II-368 1.1.4. Monomers Giving Polymers With Aromatic Side Chains that Contain Only C, H 11-371 1.1.5. Monomers Giving Polymers With Aromatic Side Chains and that Contain Heteroatoms 11-371 1.2. With Aromatic or Cyclic Carbons in the Main Chain II-372 Table 2. Monomers Giving Polymers Containing Heteroatoms in the Main Chain II-373 2.1. Monomers Giving Polymers Containing O in the Main Chain, Bonded to Carbon Only II-373 2.1.1. Ethers and Acetals M-373 2.1.2. Cyclic Esters II-376
2.2.
Monomers Giving Polymers Containing O in the Main Chain, Bonded to other Heteroatoms (S, Si, P) 2.3. Monomers Giving Polymers Containing S in the Main Chain, Bonded in the Chain to Carbon Only 2.4. Monomers Giving Polymers Containing N in the Main Chain, Bonded in the Chain to Carbon Only 2.5. Monomers Giving Polymers Containing N in the Main Chain, Bonded to other Heteroatoms (P) 2.6. Other Monomers Giving Polymers not Listed Above Table 3. Copolymers B. Entropies of Polymerization Table 4. Monomers Giving Polymers Containing Main Chain Carbon Only 4.1. Main Chain Acyclic Carbon Only 4.1.1. Dienes 4.1.2. Monomers Giving Polymers Without or With Aliphatic Side Chains that Contain Only C, H 4.1.3. Monomers Giving Polymers With Aliphatic Side Chains that Contain Heteroatoms
*Based on the tables compiled for the third edition, by W.K. Buslield, School of Sciences Griffith University, Brisbane, Australia.
11-377
II-378
II-378
II-379 II-379 II-380 11-381
II-382 II-382 II-382
II-382
II-384
4.1.4. Monomers Giving Polymers With Aromatic Side Chains that Contain Only C, H II-385 4.1.5. Monomers Giving Polymers With Aromatic Side Chains that Contain Heteroatoms II-385 4.1.6. Other Monomers Giving Polymers not Listed Above 11-386 4.2. With Aromatic or Cyclic Carbons in the Main Chain 11-386 Table 5. Monomers Giving Polymers Containing Heteroatoms in the Main Chain 11-387 5.1. Monomers Giving Polymers Containing O in the Main Chain, Bonded to Carbon Only II-387 5.1.1. Ethers and Acetals II-387 5.1.2. Cyclic Esters II-390 5.2. Monomers Giving Polymers Containing O in the Main Chain, Bonded to Other Heteroatoms (S, Si, P) 11-391 5.3. Monomers Giving Polymers Containing N in the Main Chain, Bonded in the Chain to Carbon Only 11-391 5.4. Other Monomers Giving Polymers not Listed Above II-392 Table 6. Copolymers II-392 C. Ceiling Temperatures and Equilibrium Monomer Concentrations II-393 1. Equilibria Involving Pure Liquid Monomers II-394 Table 7. Monomers Giving Polymers Containing Main Chain Acyclic Carbon Only II-394 Table 8. Monomers Giving Polymers Containing Heteroatoms in the Main Chain II-395 8.1. Monomers Giving Polymers Containing O in the Main Chain, Bonded to Carbon Only II-395 8.2. Monomers Giving Polymers Containing O in the Main Chain, Bonded to Other Heteroatoms (S, P, Si) II-396 8.3. Monomers Giving Polymers Containing S in the Main
Chain, Bonded in the Chain to Carbon Only 8.4. Monomers Giving Polymers Containing N in the Main Chain, Bonded in the Chain to Carbon Only 8.5. Other Monomers Giving Polymers not Listed Above 2. Equilibria Involving Gaseous Monomers 3. Equilibria Involving Monomers in Solution Table 9. Monomers Giving Polymers Containing Main Chain Carbon Only 9.1. Monomers Giving Polymers Containing Main Chain Acyclic Carbon Only 9.2. Monomers Giving Polymers Containing Main Chain Cyclic Carbon Table 10. Monomers Giving Polymers Containing Heteroatoms in the Main Chain 10.1. Monomers Giving Polymers Containing O in the Main Chain, Bonded to Carbon Only 10.2. Monomers Giving Polymers Containing O in the Main Chain, Bonded to Other Heteroatoms (Si, P) 10.3. Monomers Giving Polymers Containing S in the Main Chain, Bonded in the Chain to Carbon Only 10.4. Monomers Giving Polymers Containing N in the Main Chain, Bonded in the Chain to Carbon Only Table 11. Copolymers 11.1. 1:1 Copolymers 11.2. General Copolymers D. Polymerizability of 5-, 6-, and 7-Membered Heterocyclic Ring Compounds Table 12. 5-Membered Ring Compounds Table 13. 6-Membered Ring Compounds Table 14. 7-Membered Ring Compounds Table 15. Comparison of Polymerizability of Unsubstituted 5-, 6- and 7-Membered Ring Compounds E. Notes F. References
II-396
II-397 II-397 II-397 II-398
II-398 II-398
II-399
II-399
II-399
II-400
II-400
II-400 11-401 11-401 11-401 11-401 II-402 II-403 II-404
II-405 M-406 II-407
A.
HEATS OF POLYMERIZATION
Symbols: The subscripts xx to A// denote the state of the monomer (first letter) and the state of the polymer (second letter), as follows: g c c' 1 s
Gaseous state (hypothetical in case of polymer) Condensed amorphous state Crystalline or partially crystalline state Liquid state In solution; solvent specified in the sixth column (Is denotes polymer dissolved in monomer).
For emulsion polymerization the subscript Ic is used and a note added in the sixth column. In all cases where monomer or polymer is present in solution etc., the value of AH will depend on the composition to some extent. Where the polymer is crystalline, AH will depend on the degree of crystallinity. AH values are in kJ per mol of monomer and are generally the limiting values for high degree of polymerization n [1 kcal = 4.187 kJ]. Where more than one value is available in the literature for given states of monomer and polymer and a given method, only one value is shown in the tables. This corresponds to one of the references indicated N1- refers to the ith note given at the end of the table. Example: C 2 H 4 (g) -> ( 1 / ^ ) ( C 2 H 4 ) J g ) ,
AHgg = -93.5kJ
Precision: generally 0.5-4.0 kj/mol (for details see Ref. 1). Methods of determination: These are summarized below, using the numbering system in Ref. 1. 2 3 4a 4b 5
Combustion of monomer or polymer or both. Reaction calorimetry. Thermodynamic (van't Hoff Equation). Semiempirical rules applied to evaluate heat of formation of polymer or monomer or both. Such rules may be found in Refs. 25,143,223,224,335. Heat capacity and heat of transition (Kirchhoff's equation).
TABLE 1. MONOMERS GJVING POLYMERS CONTAINING CARBON ATOMS ONLY IN THE MAIN CHAIN
Monomer 1.1.
State of monomer
-AZZxx
Temp.
and polymer (xx)
(kj/mol)
(0C)
73 78 73 68 59 70.5 75 71 65.5
25 25 25 61.3 - 70 25 25 74.5 34.6
Method
Solvent/Notes
Refs.
WITH ACYCLIC CARBONS ONLY IN THE MAIN CHAIN
1.1.1. DIENES 1,3-Butadiene
Chloroprene Cyclopentadiene Isoprene
gg gg Ic Ic ss gg Ic Is Is
4b 4b 2 3 3 4b 2 3 3
1:2 Polymerization 1:4 Polymerization Ni Methylene chloride
N2
10 10 45 41 190 10 46 15 47
1.1.2 MONOMERS GIVING POLYMERS WITH OR WITHOUT ALIPHATIC SIDE CHAINS THAT CONTAIN ONLY C, H 1.1.2.1. Olefins (listed by increasing carbon number) Ethylene
Propene
gg gc' gc' gc c'c' c'c gc' gc gc' gc gc' gc gl gg gc7 Ic sc
93.5 108.5 107.5 101.5 173 169 212 209 212 209 211 204 198 86.5 104 84 69
25 25 25 25 -173 -173 173 173 25 25 127 127 227 25 25 25 -78
4b 2 3 2 5 5 5 5 4b 4b 5 5 5 4b 2 4b 3
A#fUS (Polymer) taken as 5.0 Polymer is poly(l-butene), iso Polymer is poly(l-butene), iso Polymer is poly(l-butene), iso Polymer is poly(l-butene), iso Polymer is poly(l-butene), iso Polymer is poly(l-butene), iso Polymer is poly(l-butene), iso Polymer is poly(l-butene), iso Polymer is poly(l-butene), iso
n-Butane
2 2,3 183 2,4 385 385 385 385 385 385 385 385 385 5 3 5 6
Notes page 11-406; References page II - 407
TABLEI.
cont'd
Monomer 1-Butene
2-Butene, cis
2-Butene, trans
Isobutene
1-Pentene
-, 4-methyl
2-Pentene, cis
State of monomer and polymer (xx) gg Ic Ic' Ic Ic' Ic gc' gc gc' gc gl gg Ic cV c'c Ic' Ic gc' gc gc' gc gl gg Ic c'c' c'c Ic' Ic gc' gc gc' gc gl gc Ic ss ss c'c' c'c Ic' Ic Ic' Ic gl gl c'c' c'c Ic' Ic Ic' Ic gc' gc gcf gc gl gg c'c' c'c Ic' Ic Ic' Ic
-AHx x (kj/mol) 86.5 83.5 78 74 83 79 108 103 107 99 94 80 75 63 59 75 71 101 96 99 92 86 75.5 71 57 54 71 67 96 91 96 89 83 72 48 53.5 54 84 81 95 93 99 95 117 113 82 79 93 90 97 95 124 117 122 112 105 80.5 75 72 87 85 91 87
Temp. (0C) 25 25 -173 -173 -73 - 73 25 25 127 127 227 25 25 -173 -173 -73 -73 25 25 127 127 227 25 25 -173 -173 -73 - 73 25 25 127 127 227 25 25 25 -35 -173 -173 -73 -73 25 25 127 227 -173 -173 -73 -73 25 25 127 127 227 227 327 25 -173 -173 -73 -73 25 25
Method 4b 4b 5 5 5 5 4b 4b 5 5 5 4b 4b 5 5 5 5 4b 4b 5 5 5 4b 4b 5 5 5 5 4b 4b 5 5 5 2 2 ? 3 5 5 5 5 2,4b 2,4b 5 5 5 5 5 5 4b 4b 5 5 5 5 5 4b 5 5 5 5 2,4b 2,4b
Solvent/Notes
Isotactic Isotactic Isotactic Isotactic Isotactic Isotactic Isotactic Isotactic Isotactic
polymer polymer polymer polymer polymer polymer polymer polymer polymer
Isotactic Isotactic Isotactic Isotactic Isotactic Isotactic Isotactic Isotactic Isotactic
polymer polymer polymer polymer polymer polymer polymer polymer polymer
Isotactic Isotactic Isotactic Isotactic Isotactic Isotactic Isotactic Isotactic Isotactic
polymer polymer polymer polymer polymer polymer polymer polymer polymer
Low polymer Solvent? low polymer CH 2 Cl 2 , polymer swollen, N 3
Refs. 5 5 385 385 385 385 385 385 385 385 385 5 5 385 385 385 385 385 385 385 385 385 5 5 385 385 385 385 385 385 385 385 385 7 3,8 8 9 386 386 386 386 386 386 386 386 387 387 387 387 387 387 387 387 387 387 387 10 386 386 386 386 386 386
TABLE 1. cont'd Monomer
- , 4-methyl
2-Pentene, trans
-,4-methyl
1-Hexene 1-Heptene
State of monomer and polymer (xx) gl gl Ic' Ic gc' gc gc' gc gl gg c'c' c'c Ic' Ic Ic' Ic gl gl Ic' Ic gc' gc gc' gc gl Ic gg
1.1.2.2. Cycloalkanes (listed by increasing ring size) Cyclopropane Ic -,methylIc -, 1,1-dimethylIc Cyclobutane Ic -,methylIc -, 1,1-dimethylIc Cyclopentane Ic -,methylIc - 1,1-dimethylIc Cyclohexane Ic -,methylIc - , 1,1-dimethylIc Cycloheptane Ic Cyclooctane Ic Cyclononane Ic Cyclodecane Ic Cycloundecane Ic Cyclododecane Ic Cyclotridecane Ic Cyclotetradecane Ic Cyclopentadecane Ic Cyclohexadecane Ic Cycloheptadecane Ic 1.1.2.3. Cycloalkenes Cyclobutene Cyclopentene
11 gl Ic c ;(I)c Ic Ic c'(I)c Ic Ic Ic
-AHx x (kj/mol)
Temp. (0C)
109 105 90 88 118 111 116 114 100 75.5 70 68 83 81 87 83 106 103 86 83 115 107 113 103 97 83 86
127 227 25 25 127 127 227 227 327 25 -173 -173 -73 -73 25 25 127 227 25 25 127 127 227 227 327 25 25
113 105 97.5 105 100 93.5 22 17 13.5 -3 -9 -7.5 21.5 34.5 47 48 45 14 22 7 12 8 8.5
25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25
121 145 17.5 11 16 15 23 19 18 18
25 25 25 -173 -73 25 -173 -73 25 77
Method
Solvent/Notes
5 5 4b 4b 5 5 5 5 5 4b 5 5 5 5 2,4b 2,4b 5 5 4b 4b 5 5 5 5 5 4b 4b
Refs. 386 386 387 387 387 387 387 387 387 10 386 386 386 386 386 386 386 386 387 387 387 387 387 387 387 5 5
2 4b 4b 2 4b 4b 2 4b 4b 2 4b 4b 2 2 2 2 2 2 2 2 2 2 2
11 11 11 12 11 11 12 11 11 12 11 11 12 12 13 13 13 13 13 13 13 13 13
2,4b 2,4b 2 5 5 2,4b 5 5 2,4b 5
ds-Polybutadiene ds-Polybutadiene N 66 cw-Polymer cw-Polymer ds-Polymer frans-Polymer rrans-Polymer fraws-Polymer toms-Polymer
388 388 361 388 388 388 388 388 388 388
Notes page 11-406; References page 11-407
TABLE 1. cont'd Monomer
State of monomer and polymer (xx)
Cyclopentadiene Cyclohexene Cycloheptene
ss ss C7CIII)C C7CIII)C' C7CII)C C7CII)C7 Ic Ic 7 11 c 7 (II)c 7 C7CII)C c 7 (I)c 7 c 7 (I)c Ic 7 Ic 11
Cyclooctene
-AHx^ (kj/mol) 59 1 12 18 18 26 18 29 17 18 6 27 19 30 13 13
-
Temp. ( 0 C)
6
-173 5 -173 -173 -73 -73 25 25 51 -173 -173 -73 -73 25 25 57
Method 3 4a 5 5 5 5 2,4b 2,4b 5 5 5 5 5 2,4b 2,4b 5
Solvent/Notes
Refs.
Butyl chloride, N 7 0 Toluene, N 7 8 7 0 % trans, 30% ds-Polymer, 7 0 % trans, 3 0 % ds-Polymer, 7 0 % trans, 30% ds-Polymer, 7 0 % trans, 30% ds-Polymer, 7 0 % trans, 30% ds-Polymer 7 0 % trans, 3 0 % ds-Polymer 7 0 % trans, 3 0 % ds-Polymer 4 8 % trans, 5 2 % ds-Polymer, 4 8 % trans, 5 2 % ds-Polymer, 4 8 % trans, 5 2 % ds-Polymer, 4 8 % trans, 5 2 % ds-Polymer, 4 8 % trans, 5 2 % ds-Polymer 4 8 % trans, 5 2 % ds-Polymer 4 8 % trans, 5 2 % ds-Polymer
N54 N54 N54 N54
N54 N54 N54 N54
371 389 388 388 388 388 388 388 388 388 388 388 388 388 388 388
1.1.3. MONOMERS GIVING POLYMERS WITH ALIPHATIC SIDE CHAINS THAT CONTAIN HETEROATOMS 1.1.3.1. Acrylic Derivatives Acrolein
Acrylamide
- , N-methylol- , AyV 7 -methylene bisAcrylic acid
- , rc-butyl ester
-,ethyl ester - , ethylhexyl ester - , lauryl ester - , methyl ester
Acrylonitrile
(listed alphabetically) Ic ss ss ss Ic ss? sc sc Ic Ic Ic ss sc sc sc Ic ss ss ss ss ss Ic Ic Ic Ic Ic Ic ss ss Ic7 sc7
1.1.3.2. ^-Substituted Acrylic Derivatives (listed alphabetically) a-Chloroacrylic acid, methyl ester Ic a-Cyanoacrilic acid, methyl ether Ic - , ethyl ester c7c c7c Ic Ic Ic - , allyl ester c7c
c7c c7c Ic
80 57.5 81.5 81.5 79.4 70.5 60 57.5 74.5 82.7 67 77.5 73.5 72 74.5 78 77 79 76 75.5 78 78 80.7 78.2 80.5 78 81.8 84.5 81 76.5 77.5
52.7 42 28 29 47 53 54 41
42 43 62
74.5 74.5 74.5 74.5 90 74.5 74.5 74.5 190 190 74.5 20 74.5 74.5 74.5 74.5 74.5 74.5 74.5 74.5 74.5 74.5 90 90 30 76.8 80 20 74.5 74.5 74.5
80 60 173 -73 25 127 177 -173
-73 -8 -8
3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3 3
Hexane Water Water Acetone Benzene Hexane
Water Benzene Carbon tetrachloride Hexane Acetone Butanone Benzene Carbon tetrachloride Hexane
Ethyl alcohol Hexane Benzene
15 17 17 17,14 332 17 17 17 332 332 15 36,37 15 15 15 17,37 17 17 17 17 17 34,37 318 318 352 21,34,37 319 36 34 17,21,38,201 17
3 3 5 5 2 5 5 5
319 354 390 390 390 390 390 391
5 5 5
391 391 391
TABLE 1. cont'd Monomer
- , rc-decyl ester
- , allyloxyethyl
Ethacrylic acid, methyl ester Methacrolein Methacrylamide
Methacrylic acid
-, benzoic acid ester
- , benzyl ester -, /i-butyl ester -, rm-butyl ester -, cyclohexyl ester -, 2-ethoxyethyl ester -, ethyl ester -, p(N-piperidyl)ethyl ester -, rc-hexyl ester -, -, -, -, -,
2-hydroxyethyl ester 2-hydroxypropyl ester isobutyl ester isopropyl ester methyl ester
- , methyl ester deuterated
- , n-octyl ester
State of monomer and polymer (xx)
-AH^ (kj/mol)
Temp. (0C)
Ic Ic c'c c'c Ic Ic cc Ic Ic Ic Is Ic ss ss ss ss Ic Ic ss ss ss sc c'c c'c c'c ss 11 Ic Ic Is Is Ic Is Ic Is Ic Ic Is Ic Ic Is Ic Ic Ic Ic Ic Ic
64 68 29 29 69 74 41 43 49 51 31 65.5 56 42.5 39.5 35 42.5 64.5 66 56.5 54 57 55 56 59 57 90 56 57.5 60 54.5 51 53 57.5 62 60 59.5 57.5 57 58.5 60 50 50.5 60 60 56 55.5
25 127 -173 -73 25 127 -173 -73 25 57 87 74.5 74.5 74.5 74.5 74.5 74.5 25 20 25 25 74.5 -173 -73 25 77 227 76.8 74.5 26.9 26.9 76.8 26.9 74.5 26.9 120 74.5 26.9 40 25 26.9 25 25
Ic Is c'c c'c Ic Ic ss ss ss ss
55 57.5 34 36 55 56 54 58.5 57.5 58.5
25 26.9 -173 -73 25 77 130 74.5 74.5 74.5
2 3 5 5 5 3 4a 3 3 3
c'c c'c Ic Ic Ic
33 35 55 57 57
-173 -73 25 77 65
5 5 5 3 3
74.5 130 74.5
Method 2,4b 5 5 5 2,4b 5 5 5 2,4b 5 4a 3 3 3 3 3 3 2 3 3 3 3 5 5 5 2,3 5 3 3 3 3 3 3 3 3 4a 3 3 3 3 3 3 3 3 3 4a 3
Solvent/Notes
Water Chloroform Acetone Benzene Water Water Dimethylformamide, N 7 Methanol, N 5
1,4 Dioxane N6
Emulsion (aq.) Emulsion (aq.) Emulsion (aq.)
o-Dichlorobenzene Acetonitrile Tetrahydrofuran Hexane
Refs. 391 391 392 392 392 392 393 393 393 393 395 15 17 17 17 17 15 206 36 37 203,316 15 394 394 394 394 394 39 34,37,39 14 14 39 14 34 14 40 34,37 14 188 37 14 37 37 34 34 42,43,29 17,34,36,37, 41,201,235 206 14 414 414 414 414 42,29 34 34 34 414 414 414 414 188
Notes page 11-406; References page II - 407
TABLE 1. cont'd Monomer - , phenyl ester - , rc-propyl ester Methacrylonitrile
State of monomer and polymer (xx)
-AZZxx (kj/mol)
Ic Ic Ic ss
51.5 57.5 56.5 64
Ic?
60
Is gc Ic Ic Ic
Temp. (0C)
Method
Solvent/Notes
76.8 74.5 74.5 130
3 3 3 4a
N6
50
3
N6
74 132 71 111.5 96
74.5 25 25 25 74.5
3 2 4b 2 3
Ic Is ss ss ss Ic Ic
88 89.5 90 86.5 86 86 88
74.5 25 74.5 74.5 74.5 74.5 74.5
3 3 3 3 3 3 3
Is Ic ss
77.5 88 91
74.5 20 20
3 2 3
Benzonitrile
Refs. 39 34 15 44,29
LlJJ. Vinyl Ethers Vinyl n-butyl ether 1.1.3.4. Vinyl Alcohol, Ketones, Halogens Vinyl alcohol Methyl vinyl ketone Vinyl chloride
1.1J.5. Vinyl Esters Vinyl acetate
Vinyl propionate Vinyl 2-ethylhexoate 7.7.3.6. Others (listed alphabetically) AUyI chloride Ethylene, nitro - , tetrafluoroFumaric acid, diethyl ester Itaconic acid, dimethyl ester Maleic anhydride Maleimide
- , phenyl a-Methylene pentanolactone Vinyl cyclohexane
Vinylidene chloride
N-Vinyl succinimide
see Acetaldehyde
gg gc7 Ic' Ic ss Is ss ss ss ss ss ss c'c' c'c Ic' Ic Ic' Ic Ic' Ic Ic' Ic' Ic' c'c' c'c Ic' Ic Ic' Ic gc' gc gc' gc Is
155 172 163 ± 1 7 65 60.5 59 67.5 89.5 88.5 87.5 37 38.8 88 68 100 79 105 85 111 86 60 75.5 73 67 56 77 66 81 70 108 97 107 95 54.7
25 25 25 100 26.9 74.5 74.5 74.5 74.5 74.5 55 83 -173 -173 -73 -73 25 25 127 127 76.8 25 74.5 -173 -173 -73 -73 25 25 25 25 127 127 97
2 2 2 3 3 3 3 3 3 3 4a 4a 5 5 5 5 2,4b 2,4b 5 5 3 2 3 5 5 5 5 2 2 2 5 5 5 3
Atffus (Monomer) taken as 20
Acetone Hexane Benzene
Dimethylformamide, tetrahydrofuran
o-Dichlorobenzene Chlorobenzene Dioxane Acetonitrile Dimethylformamide DMF, N 78 , N 75 DMF
216 195 17 18.19,20 10 18 215 17,34,21 35 17 17 17 17,34 34 15 214 214 22 22,23 1 235 14 15 24 24 24 24 440 315 396 396 396 396 396 396 396 396 21 18 15 397 397 397 397 397 397 397 397 397 397 384
TABLE 1. cont'd Monomer
State of monomer and polymer (xx)
-AZZxx (kj/mol)
Temp. (0C)
Method
Solvent/Notes
Refs.
1.1.4. MONOMERS GIVING POLYMERS WITH AROMATIC SIDE CHAINS THAT CONTAIN ONLY C, H (listed alphabetically) Acenaphthalene
Acenaphthylene Biphenyl, p-isopropenylIndene - , 5-methyl- , 6-methyl-, 7-methyl-, 4,6-dimethyl-, 4,7-dimethyl-, 5,6-dimethyl- , 4,5,6,7-tetramethylNaphthalene, 2-isopropenylStyrene
- a-acetoxy - , o-chloro-,p-chloro-, 2,5-dichloro-, ar-ethyl-,a-methyl-
- , a-methyl, p-tert-buty\- , 2,4,6-trimethyl-
ss ss ss ss ss c'c ss ss ss
87.8 84.8 98.5 67 67 82 43 34 58
0 18 26.9 74.5 74.5 26.9 60 -15 - 30
3 3 3 3 3 3 4a 4a 3
ss ss ss ss ss ss ss ss ss gg Ic Ic Ic Is Is ss ss Ic Ic Ic Ic Ic Ic Ic ss ss ss ss ss Ic
58 57.5 58.5 77.5 65 79 75 36.5 38 74.5 70 68.5 73 73 73 66.5 26 68.5 67 69 68 35 34.5 39 33.5 47.7 15 14 29.7 70
- 50 -60 -70 -40 -40 - 40 -40 —5 10 25 25 26.9 127 25 26.9 -60 64 76.8 76.8 76.8 76.8 25 -20 25 -20 22 -10 -10
3 3 3 3 3 3 3 4a 4a 4b 2 3 4a 2 3 3 4a 3 3 3 3 2 4a
26.9
4a 4a 4a 4a 4a 3
Dichloromethane Dichloromethane o-Dichlorobenzene 6>-Dichlorobenzene Benzene Toluene, N 78 , N 75 Tetrahydrofuran Methylene chloride indep. of 7 [ - 7 O 0 to 10°] Methylene chloride Methylene chloride Methylene chloride Methylene chloride Methylene chloride Methylene chloride Methylene chloride Tetrahydrofuran Toluene, N 7 8
320 320 14 15 15 14 399 16 190
175 175,169 175,169 175 175 175 175 16 400 25 26 14,17,27,201,235 28,29 26 14 Methylene chloride 30,190 Toluene, N 7 8 , N 7 5 401 27 27 27 27 31 32,29 N9 123 Tetrahydrofuran 32,29,33,16 Cyclohexane 341 rc-Heptane, N78 402 Toluene, N 7 8 402 Solvent and temp, not stated 381 14
1.1.5. MONOMERS GIVING POLYMERS WITH AROMATIC SIDE CHAINS AND THAT CONTAIN HETEROATOMS 2-Amino-4-alkyl/aryl-amino-6-isopropenyl-1,3,5-triazine, R 1 = H , R 2 = ethyl Is R 1 = H , R i = propyl Is R i = ethyl, R 2 = ethyl , Is R i = p r o p y l , R 2 = propyl Is R i = methyl, R 2 = phenyl Is R i = methyl, R 2 = phenyl Is R i = H, R 2 = p-methoxyphenyl Is R i = H, R 2 = p-methoxyphenyl Is 2-Amino-4-(7V-R. anilino)-6-isopropenyl-1,3,5-triazine R = «-alkyl = «-propyl Ic = w-hexyl Ic = n-octyl Ic = rc-decyl Ic = n-dodecyl Ic = «-tetradecyl Ic = n-hexadecyl Ic R = alkyl = isopropyl Ic = isobutyl Ic = sec-butyl Ic
64.8 63.5 53.9 47.7 50.2 53.1 50.2 46.8 46 43 42 41 41 40 39 44 44 43
170 160 161 153 140 150 160 160
3 3 3 3 3 4a 3 4a
60 60 60 60 60 60 60 60 60 60
3 3 3 3 3 3 3 3 3 3
N65 N65 N65 N65
370 370 370 370 379 379 378 378 403 403 403 403 403 403 403 404 40 404
Notes page 11-406; References page II - 407
TABLE 1.
cont'd
Monomer
State of monomer and polymer (xx)
= n-pentyl = isopentyl = 1-methylbutyl R = benzyl R = chloro R = -4-methoxyR = -4-ethoxy2-Anilo-4-R-6-isopropenyl-1,3,5-triazine R = methoxy R = ethoxy Atropic acid, methyl ester Atroponitrile Benzoic acid, w-methacryloyloxy- , v i n y l ester Carbazole, JV-vinyl2,4-Hexadiyne-l,6-di(R group) R = -SO3C6H4CH3(p) R = -NHC 6 H 3 (NO 2 ) 2 (2,4posn.) R =-SO3C6H4NNC6H5(P) R =-OCONHCH2COOH
Oxazole, 2-isopropenylPyridine - , 2-isopropenyl- , 2-vinyl-
- , 4-vinylSilane, benzyl dimethyl vinyl-
- , dimethyl phenyl vinyl- , trimethyl vinylAWV',N'-Tetraethyl-4-isopropenylphenylphosphonous diamide Thiazole, 2-isopropenyl/7-[bis(Trimethylsilyl)methyl]isopropenylbenzene 1.2.
-AHxx (kj/mol)
Ic Ic Ic Ic Is Is Is
44 43 42 44 11 14 14
Is Is ss ss Ic Ic sc' ss
Temp. ( 0 C)
Method
Solvent/Notes
Refs.
60 60 60 60 170 183 182
3 3 3 3 3 3 3
404 404 404 404 405 406 406
12 12 28 39 59 84.5 63.5 94.9
174 174 -40 50 25 74.5 74.5 0
3 3 4b 4b 2 3 3 3
406 406 149 149 363 34 15 321
c'c' c'c' c'c'
152.6 77.5 138
187 135 140
3 3 3
C'C'
130
137
Toluene, N i 0 Toluene, N i 0
Hexane Dichloromethane
372 373 374
3
375
ss
39.5
20
4a
Tetrahydrofuran
284
ss ss Ic Is sc Ic ss c'c' Ic Ic Ic Ic ss
26 40 71.5 75.5 73.5 78 78 48.2 66.7 67.1 56.5 65.8 27
20 -15 74.5 74.5 74.5 74.5 74.5 -73 25 77 25 25 -55
4a 4a 3 3 3 3 3 2 3 3 3 3 4a
Tetrahydrofuran Toluene, N 7 8
N62 N62 N62 N62 Tetrahydrofuran
284 407 15 15 15 17 17 355 366 366 362 367 408
ss ss
28.5 30
20 — 30
4a 4a
Tetrahydrofuran Tetrahydrofuran
284 409
Benzene Benzene, hexane
WITH AROMATIC OR CYCLIC CARBONS IN THE MAIN CHAIN
— 11,12-Dicyano-2,6-naphtoquinodimethane ll,12-bis(alkylthio) alkyl = butyl = s-butyl = isopropyl = ethyl = methyl —, 7,8-Dicyanoquinodimethane 7,8-bis(butoxycarbonyl)7,8-diacetyl7,8-dibenzoyl7,8-dibutoxycarbonyl7,8-diisobutyryl7,8-dipropionyl7,8-bis(ethylthio)7,8-bis(phenylacetyl)7,8-bis(phenylthio)Norbornylene
5-Trimethylsilyl-2-
ss ss ss ss ss
67 59 65 69 70
30 30 30 30 30
4a 4a 4a 4a 4a
Oligomer, Oligomer, Oligomer, Oligomer, Oligomer,
benzene, benzene, benzene, benzene, benzene,
N78, N78, N78, N78, N78,
ss ss ss ss ss ss ss ss ss c'(II)c c'(I)c c'(I)c Ic c'c cc
26 25 22 26 23 24 23 25 23 56 62 62 65 38 40
60 55 55 55 55 55 60 55 50 -173 -73 25 57 -173 —173
4a 4a 4a 4a 4a 4a 4a 4a 4a 5 5 4b 5 5 5
Chloroform, N 7 8 , N 8 1 Chloroform, N 7 8 , N 8 i Chloroform, N 7 8 , N 8 i Chloroform, N 7 8 , N 8 1 Chloroform, N 7 8 , N 8 1 Chloroform, N 7 8 , N 8 1 Chloroform, N 7 8 , N 8 1 Chloroform, N 7 8 , N 8 1 Chloroform, N 7 8 , N 8 1 55% cis/45% trans Polymer, 55% c/s/45% trans Polymer, 55% cis/45% trans Polymer, 55% cis/45% trans Polymer, Overcooled monomer
N 8o N 8o N 8o N80 N 8o
410 410 410 410 410
N54 N54 N54 N54
411 412 412 412 413 413 411 413 411 415 415 415 415 416 416
TABLE 1.
cont'd State of monomer and polymer (xx)
Monomer
Af-7,7-Triacyanobenzoquinonemethideimine
TABLE 2.
39 46 52 55 22
Temp. (0C) -73 — 73 25 107 55
Method 5 5 4b 5 4a
Solvent/Notes
Overcooled monomer
Toluene N7g, Ng 2
Refs. 416 416 416 416 438
MONOMERS GIVING POLYMERS CONTAINING HETEROATOMS IN THE MAIN CHAIN
Monomer 2.1.
c'c cc Ic Ic ss
-AZZxx (kj/mol)
State of monomer and polymer (xx)
-AH^x (kj/mol)
Temp. (0C)
Method
Solvent/Notes
Refs.
MONOMERS GIVING POLYMERS CONTAINING O IN THE MAIN CHAIN, BONDED TO CARBON ONLY
2.1.1. ETHERS AND ACETALS (listed by increasing ring size of monomer) 2-RINGS (aldehydes and ketones) Acetaldehyde
-, -, -, -, -, -, -, -, -,
bromochlorofluorobromodichlorobromodifluorodibromochlorodibromofluorodichlorofluorodifluorochlorotribromotrichloro-
- , trifluoro-
Acetone
Butanal
4,7-Dioxaoctanal Formaldehyde
Heptanal
Ic Ic' Ic c'c Ic Ic sc' sc' sc' sc' sc' sc' sc' sc' gc' gc' gc Ic' Ic' Ic' Ic' Ic Ic' cc' ss sc' sc' sc' gc Ic sc sc' gg gc Ic Ic sc sc Ic ss gc'
0 25 64.5 25 62.5 25 31 -173 34 -73 36 25 36.0 31.2 43.4 26.0 29.0 56.2 51.0 19.6 71 ± 8 50 65.5 -50 5 1 - 5 0 17 57 38 ± 8 50 34 25 34.5 -50 20 -50 30 -73 25 -173 14.5 -50 33.5 13 39 10 37.8 64.5 45 47 25 50.8 25 54.9 -12 25 10 25 -25 25 20.5 20 35.5 18 21.5 20 15.9 -80 16.7 -80 66 25
gc' c'c' c'c
55 25 2 0 - 1 7 3 10 -173
4b Nn 2 To poly(vinyl alcohol) 2 To poly(vinyl alcohol) 5 5 2,4b 4a Toluene, N74 4a Toluene, N74 4a Toluene, N74 4a Toluene, N74 4a Toluene, N 7 4 4a Toluene, N74 4a Toluene, N74 4a Toluene, N74 4a 4a 4a 5 4a 3 4a 4a 5 5 4a Tetrahydrofuran 4a Pyridine 4a n-Heptane 4a Toluene, N 7 4 4a 4a Dichloromethane 4a Dichloromethane 4a Toluene, N 7 4 4b 4b 4b 3 4a «-Hexane (9 kbar), Ni 2 3 rc-Hexane (1 bar, IM), N i 2 4a N69 4a THF 4a Nn 2 5 5
48 195 195 417 417 417 233 344 344 344 344 344 344 344 50 166 166 418 50 418 166 166 418 418 167 50 166 344 129 322 322 344 234 144,148 48,234 161 161 161 330 330 49,164, 165,132 7,49 419 419
Notes page 11-406; References page II - 407
TABLE 2.
cont'd
Monomer
Hexanal
Octanal 4-Oxapentanal Pentanal 0-Phthalaldehyde Propanal
- 2,2-dichloro-, 2-chloro, 2-methyl-, 2-methyl-
State of monomer and polymer (xx) c'c' c;c Ic(I) Ic 11 c'c' c'c c'c' c'c 11 11 Ic sc Ic Is Ic sc ss c'c' c'c Ic' Ic Ic' Ic Ic' Ic gc Ic ss gc Ic ss gc Ic ss ss ss
-A/^ (kj/mol)
Temp. (0C)
22 -73 8 - 7 3 39 25 33 25 36 97 8 - 1 7 3 7 - 1 7 3 12 -73 1 0 - 7 3 27 25 28 67 14.7 -75 14.2 -75 19.7 -80 20.1 -80 22.7 -75 22.2 -75 22 -70 5 - 1 7 3 2 - 1 7 3 15 -73 12 -73 19 25 14 25 21 57 15 57 50 -65 20.5 -65 1 7 - 6 5 47 - 65 19.5 -65 19.5 -65 46 - 65 16 -65 15.5 -65 16.5 -65 22 -65
Method
Solvent/Notes
Refs.
5 5 3 3 5 5 5 5 5 3 5 4a 4a 4a 4a 4a 4a 4a 5 5 5 5 3 3 5 5 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a
419 419 N 77 419 419 419 420 420 420 420 420 420 N69 330 THF 330 N69 329 329 N69 328 THF 328 Dichloromethane, cyclopolymer 154 421 421 421 421 421 421 421 421 172 172 Tetrahydrofuran 172 172 172 Tetrahydrofuran 172 166 166 Tetrahydrofuran 167,172 Diethyl ether 166 rc-Pentane 166 422 14 168 306 306 51 14,52 14 14
3-RINGS
Cyclohexene oxide Ethylene oxide
Propylene oxide Styrene oxide - , 3-nitro-
Ic gg gc' gc Ic' Ic gg Ic Ic
97 104 140 127.3 102.4 94.5 75.5 101.5 101
25 25 25 25 25 25 25 26.9 26.9
2 4b 3 2 2 2 4b 3 3
gc Ic ss Ic ss ss
81.8 51.4 81 84.5 67.5 83.5
25 25 —9 26.9 -9 26.9
4a 4a 3 3 3 3
gg gc gc Ic Ic Ic
26 50 52.0 24 17 15
20 25 57 100 90 25
4b 4a 4a 4b 4a 4a
4-RINGS
Oxetane - , 3,3-di(chloromethyl)- , 3,3-dimethyl- 3,3-di(phenoxymethyl)-
Chloromethane + chloroethane o-Dichlorobenzene
325 325 53 14 53 14
N60 Ni 4 N 69 , N 78 Nn
54 292 353 198 437 292
N 17 Chloromethane + chloroethane
5-RINGS
1,3-Dioxolane
TABLE 2. cont'd Monomer
-, 4-ethyl- , 4,4-dimethyl-, as-4,5-dimethyl- , tmns-4,5-dimethy\- , 4-isopropyl- , 4-methyltams-7-Oxabicyclo[4.3.0]nonane 7-Oxa-bicyclo[2.2. l]heptane, 2-alkylR= H R = exo-CH3 R = endo-CH3 Tetrahydrofuran
- , 3-methyl-
State of monomer and polymer (xx)
- A / f xx (kj/mol)
Temp. (0C)
Method
Ic Is ss ss ss ss ss Ic Ic Ic Ic Ic Ic Ic
23 6.5 22 27 15 17.5 8 13.0 9.6 12.1 7.5 12.1 13.4 14.0
40 55 0 20 30 70 75 -24 80 80 80 80 -8
4a 4a 4a/3 4a 4a 3 4a 4a 4b 4b 4b 4b 4a
Ic Ic Ic gg gg gc gc Ic' Ic' Ic Ic Ic Ic Ic Is ss Is
44.3 49.7 45.4 21 12 39.5 47.1 29.6 38 18.6 7.5 12.5 15 25.5 23 23 22.6
25 25 25 20 25 25 50 25 25 25 25 50 30 25 40 40 -6
2 2 2 4b 4b 4a 4a 2 2 2 4a 4a 4a 2 4a 4a 4a
gg Is gg sc' sc' sc' sc' sc' c'c' c'c' c'c' c'c'
0 -4 1.5 17.5 26.5 19.5 12.5 21.5 6 11.5 4.5 5.5
20 20 20 40 58 30 30 30 30 58 25 25
4b 4a 4b 4a 3 3 4a 3 3 3 4a 2
Solvent/Notes N 15 Dichloromethane Chloroethane Benzene Dichloromethane Toluene, N 78
N 61
N 17 N 16 Diethyl ether
Refs. 159 219 133,159,220 293 134 220 423 333 335 335 335 335 334 357 308 308 308 55 56 292 353 358 56,57 358 292 130 231 140,208 57,58,211 211 342
6-RINGS
m-Dioxane /j-Dioxane Tetrahydropyran Trioxane
N 78 1,2-Dichloroethane 1,2-Dichloroethane Dichloromethane Nitrobenzene Nitrobenzene N 18 N 19
54,59,60 436 55,56,59 178 212 182,202 182 202 202 212 164 see 202
7-RINGS
1,3-Dioxepane
- 2-butyl -, 4-methyl-, 2-methyll-Oxa-4,5dithiepane
gg gc Ic ss ss ss ss ss ss ss ss Ic ss ss
19.5 20 53.9 25 13.0 25 12 75 13.5 60 14 0 15 -30 7 - 5 9.3 -15 8.8 -15 9 - 1 0 7.5 9 8
26.9 26.9 26.9
4b 4a 4a 4a 4a 4a 4a/3 4a 4a 4a 4a
N 17 Toluene, N 78 Benzene 1,2-Dichloroethane, N 78 Dichloromethane 1,2-Dichloroethane, N 78 1,2-Dichloroethane 1,2-Dichloroethane 1,2-Dichloroethane, N 78
3 3 3
Dioxane Benzene
54 323 323 423 134,87 424 136 424 339 340 424 61 61 61
Notes page 11-406; References page II - 407
TABLE 2. cont'd Monomer Oxepane
State of monomer and polymer (xx)
—AHXX (kj/mol)
Temp. (0C)
Method
Solvent/Notes
Refs.
gc Ic
38.6 -1.7
25 25
4a 4a
ss gg gc Ic sc' c'c' c'c' gc Ic ss ss
8 53.5 62.1 18.3 26 3.5 4 62.2 12.0 13 22
10 20 25 25 30 30 25 5 25 20 60
4a 4b 4a 4a 3 3 2 4a 4a 4a 4a
ss ss ss
16.7 4.6 00
0 0
4a 4a 4a
Dichloromethane Dichloromethane Dichloromethane
343 343 343
ss ss ss ss
13.4 3.8 3.8 0
0 0 0 0
4a 4a 4a 4a
Dichloromethane Dichloromethane Dichloromethane Dichloromethane
343 343 343 343
ss ss ss
11.3 7.5 0
5 5 5
4a 4a 4a
Dichloromethane Dichloromethane Dichloromethane
343 343 343
ss ss ss
10.5 -2 2.9 -2 0 — 2
4a 4a 4a
Dichloromethane Dichloromethane Dichloromethane
343 343 343
Ic Ic' Ic' Ic
75 82 80.5 74
3 3 2/4b 3
368 368 137 368
3 3 3
368 368 368
N 17
323 323
8- AND LARGER RINGS
2-Butyl-l,3,6-trioxocane 1,3-Dioxocane Tetraoxane 1,3,6-Trioxocane
(1,3,6-Trioxocane) n n=l n=2 rc = 3-8 (1,3,6,9-Tetraoxacycloundecane) „ n=\ n=2 n=3 n = 4~S 1,3,6,9,12-Pentaoxacyclotetradecane)n n=\ n=2 n = 3-l 1,3,6,9,12,15-Hexaoxacycloheptadecane) „ n=l n=2 n = 3-5
Toluene, N 78 N 17 Nitrobenzene
N 17 Toluene, N 78 Benzene
425 54 324 324 202 131,202 see 202 324 324 425 134
2.1.2. CYCLIC ESTERS 4-RINGS
P-Propiolactone
25 25 25 127
5-RINGS
y-Butyrolactone
Ic Ic' Ic
-5 7 -6
25 25 77
c'(II)c'(II) c'(II)c c'(II)c'(H) c'(II)c Ic'(I) 11 c'c' c'c c'c' c'c c'c' c'c 11 c'c c'c c'c c'c
7 - 1 7 3 -9 -173 7 25 -8 25 18 117 12 147 21 -173 6 - 1 7 3 21 -73 6 - 7 3 21 25 4 25 17 127 8.6 -173 9.0 -73 10.1 25 8.3 87
6-RINGS
2,2-Dimethyltrimethylene carbonate
p-Dioxanone
Ethylene oxalate
5 5 4b 4b 5 5 5 5 5 5 2 2 5 5 5 2 5
N 54 , N 63 , N 77 N545N63 N 63 , N 77 N 63
426 426 426 426 426 426 427 427 427 427 427 427 427 312 312 312 312
TABLE 2.
cont'd
Monomer Glycollide DL-Lactide L-Lactide 8-Oxo-7-oxabicyclo[2,2,2]octane Pentanolactone
State of monomer and polymer (xx)
-AZJxx (kj/mol)
Temp. (0C)
Method
Solvent/Notes
Refs.
Ic c'c' cc Ic c'c Ic ss ss c'c' gc' Ic' Ic' Ic Ic
20.0 34.0 10.8 31.4 8.7 27.0 25 23 20.9 90.5 34.5 27.5 10.5 9.9
142 25 25 277 25 127 40 105 25 25 25 25 25 77
2 2 2 2 2 2 4a 4a 2 2 2 2 2 3
Ic Ic' Ic ss
17 31 13.7 15
25 25 77 40
3 3 3 4a
Nitrobenzene, N 78
368 368 368 428
ss ss ss
11 8 5
4b 4b 4b
Dichloromethane Dichloromethane Dichloromethane
430 430 430
ss
7
- 5 0 t o - 1 0 4b
Dichloromethane
430
Nitrobenzene, N 78 1,4-Dioxane, N 78 N53 N53 N53
312 364 364 364 311 311 428 429 307 307 307 314 314 314
7-RINGS
e-Caprolactone
Spiroorthoester 2-R-1,4,6-trioxaspiro[4.6] undecane R= H R = CH 3 R = CH3Br
R = Ph
- 30 to 5 - 5 0 to 5 -35 t o - 5
8-AND LARGER RINGS
Heptanolactone Octanolactone Nonanolactone Decanolactone Undecanolactone Dodecanolactone Tridecanolactone Tetradecanolactone Pentadecanolactone
Hexadecanolactone
Ic Ic Ic Ic Ic Ic' Ic Ic c'c c'c' Ic Ic c'c c'c' Ic c'(II)c Ic
16 19 22 24 28 62 27 17 -2 38 6 2 -10 39 -3 -37 0
127 127 127 127 25 25 127 127 25 25 127 127 25 25 97 -73 127
4b 4b 4b 4b 3 3 3 4b 3 3 3 4b 1 1 1 1 4b
N54
368 368 368 368 368 368 368 368 368 368 368 368 313 313 313 313 368
2.2. MONOMERS GIVING POLYMERS CONTAINING O IN THE MAIN CHAIN, BONDED TO OTHER HETEROATOMS (S, Si, P) Cyclotrisiloxane, 1,1,3,3,5,5-hexaethyl
-, hexamethyl Cyclotetrasiloxane, octamethylAW-Diethylamino1,3,2-dioxaphosphorinane 1,3,2-Dioxaphospholan, 2-methoxy-
c'(IH)c'(II) c'(II)c'(II) c'(II)c c'(I)c'(I) c'(I)c 11 Is Ic Ic c'c Ic Ic Is ss ss
4.6 -173 5 - 7 3 -10 -23 10 -23 1 25 14 25 15 170 14.5 25 23.4 77 2.79 25 -13.4 77 -6.4 25 -6.3 -20 15 14
3 3 3 3 3 3 3 3 3 3 3 3 4a
N 54 , N 63 , N 77 N 54 , N 63 , N 77 N 54 , N 63 N 54 , N 63 , N 77 N 54 , N 63 N 63 95% Conversion N 62 N63 N 62 N63 N 58
431 431 431 431 431 431 431 84 365 365 365 365 346
3 4a
Dichloromethane 1,1,2,2-Tetrachloroethane
309 309
Notes page 11-406; References page 11-407
TABLE 2.
cont'd
Monomer 2-Oxo-1,3,2-dioxaphosphorinane - , 2-alkoxyR = methyl R = methyl R = ethyl R = propyl R = trimethyl silyl Sulfur trioxide
State of monomer
—AH^
Temp.
and polymer (xx)
(kj/mol)
(0C)
Ic
-6.28
90
Method 4a
Solvent/Notes N59
Refs. 347
Is 2.9 140 4a Diglyme or DMSO 348 ss 0.8 100 4a Dichloromethane 356 ss -1.0 100 4a Dichloromethane 356 ss -2.4 100 4a Dichloromethane 356 ss -2.7 100 4a Dichloromethane 356 gc' 56 13 4a 86 Ic' 12.5 25 4a 86 2.3. MONOMERS GIVING POLYMERS CONTAINING S IN THE MAIN CHAIN, BONDED IN THE CHAIN TO CARBON ONLY (listed by increasing ring size) (polysulfones listed under Table 3. Copolymers) Carbon disulflde Thiirane
- , 2,2-dimethyl- , c/s-2,3-dimethyl- , frarcs-2,3-dimethyl- , 2-methylThietane Thioacetone Thiolane 1,2-Dithiolane Thiane oDithiane SS(CH2)3CH2 exo-3,4,5-Trithiatricyclo[5.2.2.02'6]decane exo-3,4,5-Trithiatetracyclo[5.5.1.02'6.0812]tridec-10-ene
Ic' gg Ic sc' gg gg gg gg gg Is gg ss gg Ic
23 81 73 ± 4 80 ± 4 70.5 63 5.5 71 80 10.8 7.5 26.5 -2.5 2
2 4b 3 3 4b 4b 4b 4b 4b 4a 4b 4a 4b 3
N20 Various solvents N20 N20 N20 N20 N20 Monomer N20 Ethyl alcohol N20
179 69,70,71 173 173 69,70,71 69,70,71 69,70,71 69,70,71 69,70,71 327 69,70,71 72 69,70,71 14
ss
5.8
40
4a
Toluene, N 7 8
377
ss
6.6
50
4a
Toluene, N 7 8
376
4b
N20
Thiepane
gg
14.5
1,2-Dithiepane SS(CH2)4CH2
lc
10 5
1,2-Dithiocane SS(CH2)5CH2
25 25 20 20 25 25 25 25 25 50-90 25 30 25 26.9
sc
11.5
lc
16
25 26 9
26.9 26 9 -
69,70,71
3
14
3
Dioxane
14
3
14
2.4. MONOMERS GIVING POLYMERS CONTAINING N IN THE MAIN CHAIN, BONDED IN THE CHAIN TO CARBON ONLY (listed by increasing ring size) 2-RINGS
Butylisocyanate
ss
2 4 — 5 5
4a
Dimethylformamide, N 7 8
432
3-RINGS
Ethyleneimine -,Ar-(P-trimethylsilylethyl)(TEI) - , - Z n C l 2 - ( T E I ) 2 (complex)
Ic Ic c'c
96.2 119 264
27 27 27
2 2 2
Ic c'c
115 258
27 27
2 2
ss Ic Ic Ic' c'c' Ic ss ss ss
24 4.5 3.5 12 -5.5 3.5 145 104 60
38 75 43 43 25 25 15 30 50
4a 2/4b 3 3 2/4b 4b 3 3 3
#
360 360 360
4-RINGS
Trimethyleneimine, - , AKP-trimethylsilylethyl)(TMI) - , - , Z n C l 2 - (TMI)2(complex)
360 360
5-RINGS
8-Oxa-6-azabicyclo[3.2.1]octan-7-one 2-Pyrollidinone
- , 1-methylPyrrole
Dimethylsulfoxide, N 7 8
Acetonitrile Acetonitrile Acetonitrile
433 62 135 135 63 64 434 434 434
TABLE 2. cont'd Monomer
State of monomer and polymer (xx)
-AHx^ (kj/mol)
Temp. (0C)
Method
Solvent/Notes
Refs.
6-RINGS
2-Piperidone - , 1-methyl-
Ic c'c' Ic
9 4.5 -2
75 25 25
2/4b 2/4b 4b
62 63 64
Ic Ic Ic Is c'c' Ic Is Is Is Is Ic Is Ic Is Is Is
16.3 16 15.5 16.5 12.5 9.5 12.5 16 16.5 14.5 16 11 16 16.5 14.5 14.5
186 75 200 250 25 25 260 240 240 240 75 200 75 225 240 240
3 2 3 4a 2 4b 4a 3 3 3 4b 4a 4b 4a 3 3
310 62 65,135,138 68,67,66 63 64 194 191 191 171 62 225 62 226 191 191
Ic Ic cV Ic Is Is
22 22 24 16.5 22 21.5
75 230 25 25 240 240
4b 3 2 4b 3 3
62 138,207 63 64 171 171
Ic Ic c'c' c'c' c'c' Ic Is
10.6 32.5 23.5 11.5 -2 ~0 13
186 230 25 25 25 230 290
3 3 2/4b 2/4b 2/4b 3 4a
310 138,189 138 138 138 138,139 139
7-RINGS
8-Caprolactam
-, -, -, -, -, -,
1-methyl 3-methyl 3-ethyl 3-propyl 4-ethyl 5-methyl
-, 7-methyl -, 7-ethyl -, 7-propyl 8-RINGS
2-Oxo-hexamethyleneimine -, 1-methyl-,4-ethyl-, 7-ethyl9-13-RINGS
Q-Dodecalactam 2-Oxo-heptamethyleneimine 2-Oxo-octamethyleneimine 2-Oxo-nonamethyleneimine 2-Oxo-decamethyleneimine 2-Oxo-undecamethyleneimine
2.5. MONOMERS GIVING POLYMERS CONTAINING N IN THE MAIN CHAIN, BONDED TO OTHER HETEROATOMS (P) Phosphonitrile chloride -, cyclic trimer - , cyclic tetramer -, cyclic pentamer - , cyclic hexamer -, cyclic heptamer
gc Ic gc Ic gc Ic gc Ic gc Ic
61 6 68 4 79.5 3.5 88 1.5 96.5 0
230 230 230 230 230 230 230 230 230 230
3 3 3 3 3 3 3 3 3 3
125 125 125 125 125 125 125 125 125 125
25 60
2
Linear polymer (carbyne) Chloroform, N 78 , N 79
187 435
4a
Dichloromethane, N 67
317
2.6. OTHER MONOMERS GIVING POLYMERS NOT LISTED ABOVE Carbon C (graphite) 4,7-bis[Cyano(ethoxycarbonyl) methylene]-4,7-dihydrobenzofuran 4-(2,3-Diphenyl cyclopropenylidene)cyclohexa-2,5-dienone 1,3-Disilacyclobutane, 1,1,3,3-tetramethylSelenium Se 8
c'c7 ss ss Ic Is
-39.5 21.6
21.2-15 73.9 -9.5
25 400
2 4a
359 85 Notes page 11-406; References page II - 407
TABLE 2. cont'd State of monomer and polymer (xx)
Monomer 1-Silacyclobutane, 1,1-dimethyl-, 1-phenyl, 1-methylSulfur, S 6 -,S7 -,S8 -,S8
Ic' Ic Ic Is Is Is Is
-AH101 (kj/mol)
Temp. (0C)
92.7 85.4 91.5 10 4 -19 -13.5
Method
25 25 25 138 138 160 200
Solvent/Notes
2 2 2 2 2 4a 4a
Refs. 359 359 359 380 380 380 73,74
N 72 N 72 Nn
TABLE 3. COPOLYMERS (listed alphabetically under Monomer A) N 2 i
Monomer A
Monomer B
State of monomer and polymer xx
Acrylonitrile
Methacrylic acid, Methyl ester Styrene Vinyl acetate Vinylidene chloride Maleic anhydride
sc ss ss ss sc ss
Allyl chloride bis-(0-Aminophenyl)-2,2' dibenzymidazoleoxide Terephthalic acid -, dichloride - , dimethylether 1,3-Butadiene 1-Butene
Styrene Sulfur dioxide Sulfur dioxide
-, 3-methyl-
Sulfur dioxide
2-Butene, cis
Sulfur dioxide
- , trans
Sulfur dioxide
Cyclohexene Cyclopentene 1,3-Dioxane
Sulfur dioxide Sulfur dioxide 1,3-Dioxolane
Fumaric acid, diethyl ester Fumaroyl chloride Isobutene
Vinyl acetate Styrene Styrene, a-methylSulfur dioxide
1-Hexadecene
Sulfur dioxide
1-Hexene Isopropenyl acetate Maleic acid, diethyl ester Maleic anhydride
Sulfur dioxide Maleic anhydride Vinyl acetate Allyl chloride Isopropenyl acetate Styrene
-AH11x (kj/mol)
74
c'c c'c c'c c'c c'c c'c c'c c'c c'c Ic
24 18 6.5 136 96 83.5 31.5 16.5 5.5
ss ss Ic' Ic ss ss ss ss ss ss ss
44.5 43.5 46 22 42.5 43.5 39.5 40.5 38 45 16
ss? ss ss Ic Ic ss ss ss sc ss? ss sc ss ss
Temp. (0C) 25 30.5 20 20 25 74.5 -173 -73 25 -173 -73 25 -173 -73 25 25
Method 3 3 3 3 3 3
Solvent/Notes Emulsion (aq.)
Emulsion(aq.), N 22
5 5 2 5 5 2 5 5 2 2
Polymer Polymer Polymer Polymer Polymer Polymer Polymer Polymer Polymer
+ + + + + + + + +
H 2 O (c') H2O (c 0 H 2 O (1) HCl (c') HCl (g) HCl (g) CH3OH (c') CH3OH (1) CH3OH (1)
26.9 55 35 25 26.9 25 26.9 25 25 26.9 20
3 4a 4a 4a 3 4a 3 4a 4a 3 4a
Excess B Excess B From B-rich mixture From A-rich mixture Excess B Excess B Excess B Excess B Excess B Excess B Methylene dichloride, N 78 A ^ B A = - H
78 80 71.5 31 39.5 42 40 43.5 74.5
76.8 74.5 74.5 25 0 26.9 30 26.9 76.8
3 3 3 2 4a 3 4a 3 3
Excess B, N 22 Hexane Excess B
83.5 74 74.5 81 82.5
76.8 74.5 76.8 74.5 74.5
3 3 3 s 3
Excess B, N 22
N 23 Chloroform Chloroform Excess B
Benzene Acetonitrile
Refs. 38 76 76,201 76 75 34 445 445 445 445 445 445 445 445 445 45 197 5 77 199,200 199,200 5 5 5 5 78 5 446 79 34 34 82 83 5 80 5 79 79 34 79 34 34
TABLE 3. cont'd
Monomer A
Maleimide Methacrylic acid - , methyl ester
Propene Styrene
- , a-methyl-
Sulfur dioxide
Monomer B Styrene, a-methylVinyl acetate Vinyl rc-butyl ether Styrene Styrene, a-methylMethacrylic acid, methyl ester Acrylonitrile Methacrylic acid Styrene Vinyl acetate Sulfur dioxide Acrylonitrile 1,3-Butadiene Fumaroyl chloride Maleic anhydride Maleimide Methacrylic, acid, methyl ester Vinyl acetate Fumaroyl chloride Maleic anhydride Maleimide Butadiene 1-Butene - , 3-methyl2-Butene, cis - , trans Cyclohexene Cyclopentene 1-Hexadecene 1-Hexene Isobutene
Vinyl acetate
Vinyl rc-butyl ether Vinylidene chloride
B.
Propene Acrylonitrile Fumaric acid, diethyl ester Maleic acid, diethyl ester Maleic anhydride Methacrylic acid, methyl ester Styrene Maleic anhydride Acrylonitrile
State of monomer and polymer xx
—AHXX (kj/mol)
Temp. (0C)
ss sc ss ss ss
72.5 84.5 90 87.5 72
74.5 76.8 74.5 74.5 74.5
3 3 3 3 3
25 25 30.5 25 24 24 26.9 20 25 74.5 74.5 74.5 74.5 24
2 3 3 2 3 3 3 3 2 3 3 3 3 3
35 74.5 74.5 74.5
3 3 3 3
26.9 55 35 25 26.9 25 26.9 25 25 26.9 26.9 30 26.9 25 0 26.9 20 76.8 76.8 76.8
3 4a 4a 4a 3 4a 3 4a 4a 3 3 4a 3 2 4a 3 3 3 3 3
24 35 74.5 25
3 3 3 3
Ic sc ss Ic ss ss sc ss Ic ss ss ss ss ss ss ss ss ss ss ss Ic7 Ic ss ss ss ss ss ss ss ss ss Ic Ic sc ss ss? ss? sc ss ss ss sc
42.5
80 81 82.5 87.5
71.5 72.5 72 44.5 43.5 92 44.5 42.5 43.5 39.5 40.5 38 45 42 40 43.5 31 39.5 42.5 78 83.5 84.5
90
Method
Solvent/Notes Excess B Excess B Benzene Acetonitrile Acetonitrile
Emulsion (aq.)
Excess B
Hexane Benzene Acetonitrile Acetonitrile
Excess A Excess A Acetonitrile Excess A Excess A From A-rich mixture From B-rich mixture Excess A Excess A Excess A Excess A Excess A Excess A Chloroform Chloroform Excess A N24 Excess A Excess A, N22 Excess A, N 2 2 Excess A
Benzene Emulsion (aq.), N 2 2
Refs. 34 79 34 34 34 206 38 76 206 81 81 5 76,201 45, 34 34 34 34 81 81 34 34 34 197 5 77 199 199 5 5 5 5 78 5 5 80 5 82 83 5 76 79 79 79 81 81 34 75
ENTROPIES O F P O L Y M E R I Z A T I O N
Symbols: The subscripts to AS0 denote the state of the monomer (first letter) and the state of the polymer (second letter) as in Section A. The standard state of the monomer is 1 atm for the gaseous state and IM in solution, unless otherwise stated. In all cases where monomer or polymer is present in solution, the value of AS0 will depend to some extent on the composition. Where the polymer is crystalline, AS0 will depend on the degree of crystallinity. AS values are in (J/K) per mol of monomer and are generally the limiting values for high degree of polymerization (1 kcal = 4.187kJ).
Notes page 11-406; References page 11-407
Precision: generally 0.5-8.0 (J/K/mol) Methods of determination: (numbering conforms with that in Section A) 1 Third law or statistical. 4a Thermodynamic (van't Hoff Equation). 4b Semiempirical rules applied to evaluate entropy of monomer or polymer or both.
TABLE 4. MONOMERS GIVING POLYMERS CONTAINING MAIN CHAIN CARBON ONLY
Monomer
State of monomer
-AS^ x
Temp.
and polymer xx
(J/K/mol)
(0C)
Method
Solvent/Notes
Refs.
4.1. MAIN CHAIN ACYCLIC CARBON ONLY 4.1.1. DIENES 1,3-Butadiene Isoprene
Ic Ic Ic
89 84 101
25 25 25
1 1 1
ds-l,4-Polymer
95,96 97 100,101
4.1.2. MONOMERS GIVING POLYMERS WITHOUT OR WITH ALIPHATIC SIDE CHAINS WHICH CONTAIN ONLY C, H 4.1.2.1. Olefins (listed by increasing carbon number) Ethylene
Propene
1-Butene
2-Butene, cis
c'c' c'c gc' gc gg gc gc gc1 gc' gc' gc gc' gc gl gg gc' gc' Ic Ic Ic Ic' Ic' Ic Ic' Ic gg gc' gc Ic Ic Ic' gc' gc gl c'c' c'c Ic' Ic gg Ic gc' gc gc' gc gl
66 59 338 331 142 155 158 172 174 336 325 334 317 311 167 191 205 113 116 116 136 75 69 114 107 166 213 193 113 112 141 204 187 182 21 14 106 99 163 104 201 190 196 179 172
-173 -173 -73 -73 25 25 25 25 25 25 25 127 127 227 25 25 25 25 25 25 25 -173 -173 -73 - 73 25 25 25 25 25 25 127 127 227 -173 -173 -73 - 73 25 25 25 25 127 127 227
1 1 1 1 4b 4b 1 4b 1 1 1 1 1 1 4b 1 1 4b 1 1 1 1 1 1 1 4b 1 1 4b 1 1 1 1 1 1 1 1 1 4b 4b 1 1 1 1 1
Isotactic Isotactic Isotactic Isotactic
poly(-l-butene) poly(-l-butene) poly(-1-butene) poly (-1-butene)
100% Cryst. polymer Isotactic poly (-1-butene) Isotactic poly (-1-butene) Isotactic poly (-1-butene) Isotactic poly (-1-butene) Isotactic poly (-1-butene) Syndiotactic polymer Isotactic polymer Isotactic polymer Atactic polymer 100% Cryst. isotactic Isotactic polymer Isotactic polymer Isotactic polymer Isotactic polymer Isotactic polymer Isotactic polymer Isotactic polymer 100% Cryst. isotactic Isotactic polymer Isotactic polymer Isotactic polymer Isotactic polymer Isotactic polymer Isotactic polymer Isotactic polymer Isotactic Isotactic Isotactic Isotactic Isotactic
polymer polymer polymer polymer polymer
385 385 385 385 2,87 11 88-91 11 88-91 385 385 385 385 385 5 186 207 5 88 88,92 88,92 385 385 385 385 5 88,385 88,385 5 88 88 385 385 385 385 385 385 385 5 5 385 385 385 385 385
TABLE 4.
cont'd
Monomer -, trans
Isobutene
1-Pentene
-, 4-methyl
2-Pentene, cis
-,4-methyl
2-Pentene, trans
-,4-methyl
State of monomer and polymer xx
-ASJ x (J/K/mol)
Temp. (0C)
Method
c'c' c'c Ic' Ic gg Ic gc' gc gc' gc gl gg Ic Ic
17 10 100 93 159 100 195 194 193 175 170 172 112 121
-173 -173 -73 - 73 25 25 25 25 127 127 227 25 25 25
1 1 1 1 4b 4b 1 1 1 1 1 4b 4b 1
c'c' c'c Ic' Ic Ic' Ic gl gl c'c' c'c Ic' Ic gc' Ic' Ic gc' gc gc' gc gl c'c' c'c Ic' Ic Ic' Ic gl gl Ic' Ic gc' gc gc' gc gl c'c' c'c Ic' Ic Ic' Ic gl gl Ic' Ic gc' gc gc'
24 20 117 113 133 124 198 190 28 28 111 111 216 131 131 214 200 209 188 176 20 16 114 111 129 120 195 185 134 134 220 205 215 215 183 18 14 111 102 127 118 194 186 130 130 216 202 214
-173 -173 -73 -73 25 25 127 227 -173 -173 -73 -73 25 25 25 127 127 227 227 327 -173 -173 -73 -73 25 25 127 227 25 25 127 127 227 227 327 -173 -173 -73 -73 25 25 127 227 25 25 127 127 227
1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1
Solvent/Notes Isotactic Isotactic Isotactic Isotactic
polymer polymer polymer polymer
Isotactic Isotactic Isotactic Isotactic Isotactic
polymer polymer polymer polymer polymer
Isotactic polymer
Refs. 385 385 385 385 5 5 385 385 385 385 385 5 5 11,93 386 386 386 386 386 386 386 386 387 387 387 387 196 387 387 387 387 387 387 387 386 386 386 386 386 386 386 386 387 387 387 387 387 387 387 386 386 386 386 386 386 386 386 387 387 387 387 387
Notes page 11-406; References page 11-407
TABLE 4. cont'd State of monomer and polymer xx
Monomer
1-Hexene 1-Heptene
-ASJJx (J/K/mol)
Temp. (0C)
Method
Solvent/Notes
Refs.
gc gl Ic gg
194 182 113 168
227 327 25 25
1 1 4b 4b
387 387 5 5
Ic Ic Ic Ic Ic Ic Ic Ic Ic Ic Ic Ic Ic Ic
69 85 93 55 72 75 43 64 66 11 32 36 16 3
25 25 25 25 25 25 25 25 25 25 25 25 25 25
4b 4b 4b 4b 4b 4b 4b 4b 4b 4b 4b 4b 4b 4b
11 87 87 11 87 87 11 87 87 11,87 87 87 11,94 11,94
52 131 17 54 52 47.2 18 56 52 51 17 -7 6 37 56 37 70 36 10 -25 49 8 63 9 9
25 25 -173 -73 25 25 -173 -73 25 77 -65 -173 -173 - 73 -73 25 25 5 1 -173 -173 -73 - 73 25 25 57
4.1.2.2. Cycloalkanes (listed by increasing ring size) Cyclopropane - , methyl- , 1,1-dimethylCyclobutane - , methyl- , 1,1-dimethylCyclopentane - , methyl- , 1,1-dimethylCyclohexane -,methyl- , 1,1-dimethylCycloheptane Cyclooctane Cycloalkenes Cyclobutene
11 gl c'(I)c Ic Ic Ic c'(I)c Ic Ic Ic ss c'(III)c c '(HI)C' c'(II)c c'(II)c' Ic Ic' 11 c'(II)c' c'(1I)C c'(I)C7 c r(I)c Ic' Ic 11
Cyclopentene
Cyclohexene Cycloheptene
Cyclooctene
1,4b 1,4b 1 1 1,4b 1 1 1 1,4b 1 4b 1 1 1 1 4b 4b 1 1 1 1 1 1,4b 1,4b 1
N25 N25
ds-Polybutadiene as-Polybutadiene czs-Polymer ds-Polymer ds-Polymer N66 frans-Porymer Jra^-Polymer tarns-Polymer tarns-Polymer Toluene, N 7 8 70% trans, 30% cis Polymer, N 5 4 70% trans, 30% cis Polymer, N 5 4 70% trans, 30% cis Polymer, N 5 4 70% trans, 30% cis Polymer, N 5 4 70% trans, 30% cis Polymer 70% trans, 30% cis Polymer 70% trans, 30% cis Polymer 48% trans, 52% cis Polymer, N 5 4 48% trans, 52% cis Polymer, N 5 4 48% trans, 52% cis Polymer, N 5 4 48% trans, 52% cis Polymer, N 5 4 48% trans, 52% cis Polymer 48% trans, 52% cis Polymer 48% trans, 52% cis Polymer
388 388 388 388 388 361 388 388 388 388 389 388 388 388 388 388 388 388 388 388 388 388 388 388 388
4.1.3. MONOMERS GIVING POLYMERS WITH ALIPHATIC SIDE CHAINS THAT CONTAIN HETEROATOMS Acrylonitrile - , allylester
- , allylloxyethyl
-,
rc-decylester
Ic' c'c c'c c'c Ic Ic Ic cc Ic Ic Ic c'c c'c
109 -6 1 24 97 85 96 16 29 56 60 4 8
25 -173 -73 -8 -8 25 127 -173 -73 25 57 -173 -73
1 1 1 1 1 1 1 1 1 1 1 1 1
193 391 391 391 391 391 391 393 393 393 393 392 392
TABLE 4. cont'd Monomer
State of monomer and polymer xx
- , ethylester
Ethacrylic acid -methyl ester Ethylene, tetrafluoroMethacrylic acid - , ethyl ester - , methyl ester
- , methyl ester deuterated
Methacrylonitrile a-Methylene pentanolactone Vinylidene chloride
"AS^ x (J/K/mol)
Temp. (0C)
Ic Ic c'c C7C Ic Ic Ic
141 155 3 16 88 104 107
25 127 -173 -73 25 127 177
Is gc' Ic' ss Ic Ic c'c c'c c'c' Ic Ic ss c'c c'c Ic Ic ss ss c'c' c'c Ic' Ic Ic' Ic gc' gc gc' gc
105 87 197 -75.7 112 -75.7 146 80 126 120 117 127 9 -173 24.1 -73 40 -63 105 25 115 77 130 127 1 0 - 1 7 3 26 -73 110 25 118 77 151 127 108.8 83 31 -173 25 -173 97 -73 91 -73 112 25 106 25 201 25 195 25 198 127 191 127
Method
Solvent/Notes
1 1 1 1 1 1 1 4b 1 1 4b 4a 4a 1 1 1 1 1 4a 1 1 1 1 4a 4a 1 1 1 1 1 1 1 1 1 1
Refs. 392 392 390 390 390 390 390
o-Dichlorobenzene
Benzonitrile DMF
395 98,99 98,99 316 40 42,43,102 414 414 102,103 414 414 42,49 414 414 414 414 44,29 315 397 397 213,397 397 397 397 397 397 397 397
4.1.4. MONOMERS GIVING POLYMERS WITH AROMATIC SIDE CHAINS THAT CONTAIN ONLY C, H Acenaphtylene Biphenyl,/7-isopropenylNaphthalene, 2-isopropenylStyrene
- , oc-methyl-
-, a-methyl, p-tert-buly\-
ss ss ss ss gg Ic Ic Ic Ic Ic Ic Ic' Ic ss ss ss ss ss
98 118 122 125 149 90 104 116 104 105 112 111 110 130 51 47 163.3 106.6
60 -20 -5 10 25 -23 25 127 127 25 25 25 -20 -20 -10 -10 22
4a 4a 4a 4a 4b 1 1 1 4a 1 1 1 4a 4a 4a 4a 4a 4a
Toluene, N 78 Tetrahydrofuran Tetrahydrofuran Toluene, N 78
N 26 Isotactic polymer 100% Cryst. isotactic Tetrahydrofuran rc-Heptane, N 78 Toluene, N 78 Cyclohexane Solvent and temp, not stated
399 16 16 400 25 104 104 104 28 88 105 88 32 32,29,16 402 402 341 381
4.1.5. MONOMERS GIVING POLYMERS WITH AROMATIC SIDE CHAINS AND THAT CONTAIN HETEROATOMS a-Acetoxystyrene 2-Amino-4-(Af-alkalino)-6-isopropenyl-1,3,5-triazine alkyl = «-propyl isopropyl isobutyl
ss
83
64
4a
Is Is Is
117 114 114
157 151 154
4a 4a 4a
Toluene, N 78
401 402 403 403
Notes page 11-406; References page 11-407
TABLE 4. cont'd
Monomer
State of monomer and polymer xx
sec-butyl Is 1-methylbutyl Is rc-pentyl Is isopentyl Is rc-hexyl Is n-octyl Is rc-decyl Is rc-dodecyl Is rc-tetradecyl Is n-hexadecyl Is benzyl Is 2-Amino-4-alkyl/aryl-amino-6-isopropenyl-1,3,5-triazine Is Ri = H, R 2 = ethyl Is Ri = H, R 2 = propyl Is Ri = ethyl, R 2 = ethyl Is R 1 = propyl, R 2 = propyl Ri = methyl, R 2 = phenyl Is Ri = H, R 2 = p-methoxyphenyl Is Benzoic acid, rc-methacryloyloxyc'c c'c crc 11 Oxazole, 2-isopropenyl, 4,5-dimethylss Pyridine, 2-isopropenylss Silane, benzyl dimethyl vinylc'c Ic Ic - , dimethyl phenyl vinylIc - , trimethyl vinylIc Thiazole, 2-isopropenylss /7-[bis(Trimethylsilyl)methyl] isopropenylbenzene ss AWV',Ar'-Tetraethyl-4isopropenylphenyl-phosphonous diamide ss
-AS^ x (J/K/mol) 112 111 114 113 112 110 109 109 105 102 113 160.5 153.8 137.5 124.6 131.7 117 -2 5 8 85 96 70 0.7 83.5 107.3 127.5 109.5 69
Temp. (0C) 148 146 150 151 149 143 140 134 132 130 157 150 145 130 125 150 160 -173 -73 25 227 20 20 -73 25 77 25 25 20
Method
Solvent/Notes
Refs.
4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 1,4a 4a 4a 4a 1 1 3 1 1 4a
403 403 403 403 402 402 402 402 402 402 403
Tetrahydrofuran
370 370 370 370 379 378 394 394 363,394 394 284 284 355 366 366 362 367 284
Tetrahydrofuran Tetrahydrofuran
110
-30
4a
Tetrahydrofuran
409
10
-55
4a
Tetrahydrofuran
408
4.1.6. OTHER MONOMERS GIVING POLYMERS NOT LISTED ABOVE
Vinylcyclohexane
4.2.
c'c c'c Ic' Ic Ic' Ic Ic' Ic
28 3 95 75 120 85 136 102
-173 -173 -73 -73 25 25 127 127
1 1 1 1 1 1 1 1
396 396 396 396 396 396 396 396
WITH AROMATIC OR CYCLIC CARBONS IN THE MAIN CHAIN
-11,12-Dicyano-2,6-naphtoquinodimethane ll,12-bis(alkylthio) alkyl = butyl = sec-butyl = isopropyl = ethyl = methyl -7,8-Dicyanoquinodimethane 7,8-bis(butoxycarbonyl)7,8-diacetyl7,8-dibenzoyl7,8-dibutoxycarbonyl7,8-diisobutyryl7,8-dipropionyl7,8-bis(ethylthio)-
ss ss ss ss ss
109 109 116 115 114
30 30 30 30 30
4a 4a 4a 4a 4a
Oligomer, Oligomer, Oligomer, Oligomer, Oligomer,
benzene, benzene, benzene, benzene, benzene,
ss ss ss ss ss ss ss
37 37 38 37 39 37 37
60 55 55 55 55 55 60
4a 4a 4a 4a 4a 4a 4a
Chloroform, Chloroform, Chloroform, Chloroform, Chloroform, Chloroform, Chloroform,
N78, N78, N78, N78, N78, N78, N78,
N78, N78, N78, N78, N78,
N8i N8i N 82 Ngi N8i N8i N8i
N 8o N80 N80 N80 N 8o
410 410 410 410 410 411 412 412 412 413 413 411
TABLE 4. cont'd Monomer 7,8-bis(phenylacetyl)7,8-bis(phenylthio)-4,7-Dihydrobenzofuran 4,7-bis-[cyano(ethoxycarbonyl)methylene] Norbornylene
5-trimethylsilyl-2-
Af,7,7-Tricyanobenzoquinonemethideimine
State of monomer and polymer xx
-ASJ x (J/K/mol)
ss ss
37 34
ss c'(II)c c'(I)c c'(I)c Ic c'c cc c'c cc Ic Ic ss
41 5 50 50 58 4 13 14 48 70 81 38
Temp. (0C) 55 50 60 -173 -73 25 57 -173 —173 -73 — 73 25 107 55
Method
Solvent/Notes
4a 4a
Chloroform, N 78 , N 8 i Chloroform, N 78 , N 81
4a 3 3 4b 3 1 1 1 1 1 1 4a
Chloroform, N 78 55% cis/45% trans 55% cis/45% trans 55% cis/45% trans 55% cis/45% trans
Polymer Polymer Polymer Polymer
Overcooled monomer Overcooled monomer Toluene, N 7 8 , N 8 i
Refs. 413 411 N54 N54 N54 N54
435 415 415 415 415 416 416 416 416 416 416 438
TABLE 5. MONOMERS GIVING POLYMERS CONTAINING HETEROATOMS IN THE MAIN CHAIN
Monomer 5.1.
State of monomer
-AS^ x
Temp.
and polymer xx
(J/K/mol)
(0C)
Method
Solvent/Notes
Refs.
MONOMERS GIVING POLYMERS CONTAINING O IN THE MAIN CHAIN, BONDED TO CARBON ONLY
5.1.1. ETHERS AND ACETALS (listed by increasing ring size of monomer) 2-RINGS (aldehydes and ketones) Acetaldehyde c'c -6 Ic 14 Ic 21 -, bromochlorofluorosc' 122 -, bromodichlorosc' 122 -, bromodifluorosc' 135 -, dibromochlorosc' 116 -, dibromofluorosc' 114 - , dichlorofluorosc' 179 - , difluorochlorosc' 152 - , tribromosc' 100 - , trichlorogc' 190 ± 3 0 Ic' 95 ± 3 0 sc' 134 sc' 117 ss 52 sc' 142 - , trichloro cc' 37 Ic' 69 Ic' 80 Ic' 30 - , trifluorogc 187 Ic 97 sc' 155 sc 142.7 Acetone gc 188 Butanal sc 122 4,7-Dioxaoctanal Ic 67.4 ss 77.0 Formaldehyde gg 124 gc' 174 gc; 169 Heptanal c'c' 25 c'c 1 c'c' 32
-173 -73 25
50 50 13 -50 10 -173 -73 25 57 45 25 25 25 10 -80 -80 25 25 25 -173 -173 -73
1 1 1 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 1 1 1 1 4a 4a 4a 4a 4b 4a 4a 4a 1 1 4a 1 1 1
Toluene, Toluene, Toluene, Toluene, Toluene, Toluene, Toluene, Toluene,
N74 N74 N74 N74 N74 N74 N74 N 74
Toluene, N 7 4 Pyridine, N 27 Tetrahydrofuran n-Heptane
Dichloromethane Toluene, N 7 4 Dichloromethane rc-Hexane N 69 THF N28
[9 kbar], N n
417 417 417 233 344 344 344 344 344 344 344 50 50 344 50 167 166 418 418 418 418 129 322 344 322 144,148 161 330 330 141,142 106 164,165 419 419 419
Notes page 11-406; References page II - 407
TABLE 5. cont'd Monomer
Hexanal
Octanal 4-Oxapentanal Pentanal oPhthalaldehyde Propanal
-, 2-chloro 2-methyl-, 2,2-dichloro-, 2-methyl-
State of monomer and polymer xx
"AS^ x (J/K/mol)
Temp. (0C) -73 25 25 97 -173 -173 -73 -73 25 67 -75 -75 -80 -80 -75 -75 -70 -173 -173 -73 -73 25 25 57 57 - 65 - 65 - 65 - 65 -65
Method
c'c Ic'(I) Ic 11 c'c' c'c c'c' c'c 11 11 Ic sc Ic Is Ic sc ss c'c' c'c Ic' Ic Ic' Ic Ic' Ic ss ss ss ss ss
4 Hl 101 110 19 16 43 41 117 121 57.8 65.7 81.6 93.6 97.1 107.6 96 8 6 69 67 85 76 90 77 90 69 74 78 94
1 1 1 1 1 1 1 1 1 1 4a 4a 4a 4a 4a 4a 4a 1 1 1 1 1 1 1 1 4a 4a 4a 4a 4a
gc' gc'
174 189
25 25
gc Ic Ic
162.7 68.4 83
25 25 25
4a 4a 1
gc' gc gc gc Ic' Ic Ic Ic Ic Ic ss ss ss ss Ic Ic Ic Ic Ic Ic Ic Ic Ic
205 167 139 147 100 37 67 63 76 18 78 94 22 59 54.8 55.3 55.3 59.4 60.7 53.2 75.3 96.2 96.2
25 25 25 57 25 25 25 40 100 90 0 20 75 30 80 80 80 -24 80 -8 25 25 25
1 1 4a 4a 1 4a 1 4a 4a 4a 4a 4a 4a 4a b4 4b 4b 4a 4b 4a 4b 4b 4b
Solvent/Notes
Refs.
Tetrahydrofuran Tetrahydrofuran Tetrahydrofuran Diethyl ether rc-Pentane
419 419 419 419 420 420 420 420 420 420 330 330 329 329 328 328 154 421 421 421 421 421 421 421 421 172 172 172 166 166
100% Cryst. polymer Estimated for 100% cryst. polymer
210 210
N 17
325 325 107
N 77
N 69 THF N 69 N 69 THF Dichloromethane
3-RINGS
Ethylene oxide Propylene oxide 4-RINGS
Oxetane -, 3,3-dichloromethyl 5-RINGS
1,3-Dioxolane
- , 4,4-dimethyl- , cis 4,5-dimethyl- , trans 4,5-dimethyl- , 4-ethyl- , 4-isopropyl - , 4-methyl7-Oxa-bicyclo[2,2, l]heptane - , 2-exo-methyl- , 2-endo-methyl-
N 60 N 17 N 15 NM N 69 , N 78 Dichloromethane Chloromethane Toluene, N 78 Benzene
177 177 292 353 177 292 177 159 198 398 133,154 213 423 134 335 335 335 333 335 334 308 308 308
TABLE 5. cont'd Monomer £rarcs-7-Oxabicyclo[4.3.0]nonane Tetrahydrofuran
-, 3-methyl-
State of monomer and polymer xx Ic gc' gc gc gc Ic' Ic' Ic Ic Ic Ic Ic Is ss Is
-AS^ x (J/K/mol)
Temp. (0C)
55.7 177 112 139 143 100 81.9 47.6 16 62 41 49 67 87 100.9
25 25 25 50 25 25 25 25 25 50 30 40 40 - 6
1 4a 1 4a 1 1 1 4a 1 4a 4a 4a 4a 4a
20 25 25 25 25 40 25 25
4a 1 1 1 1 4a 4a 4a
Method
Solvent/Notes
N 61
N 17 N 16 Diethyl ether
Refs. 357 140 292 140 353 140 358 358 292 140 130 231 57,58 211 342
6-RINGS
1,3-Dioxane Paraldehyde Trioxane
Is gc' gc' gg gc' ss sc' c'c'
-23 201 159 64 156 41 42 18 ± 1 6
N 78 , Cyclic oligomer Isotactic polymer Syndiotactic polymer 1,2-Dichloroethane Nitrobenzene
436 184 184 141 141 178 182 164
7-RINGS
1,3-Dioxepane
-, 2-butyl - , 2-methyl-,4-methylOxepane l-Oxa-4,5-dithiepane
gc' gc' gc Ic Ic' Ic ss ss ss ss ss ss ss ss gc Ic ss
181 144 131.4 25.1 77 39 48 39 26 43 33 37.2 39 38.8 91.8 -12.4 > 12
25 25 25 25 25 25 -30 60 75 0 -5 -15 - 10 -15 25 25 25
1 1 4a 4a 1 1 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a 4a
ss gc Ic gg c'c' gc Ic ss ss
16 121.7 10.2 51 -3 129.1 8.0 39 13
10 25 25 25 27 25 25 60 20
4a 4a 4a 1 1 4a 4a 4a 4a
Toluene, N 78
N17 Benzene Toluene, N 78
425 324 324 142 131 324 324 134 425
4a 4a 4a 4a 4a 4a 4a 4a
Dichloromethane Dichloromethane Dichloromethane Dichloromethane Dichloromethane Dichloromethane Dichloromethane Dichloromethane
343 343 343 343 343 343 343 343
N 17 Dichloromethane Benzene Toluene, N 78 1,2-Dichloroethane, N 78 1,2-Dichloroethane, N 78 1,2-Dichloroethane 1,1-Dichloromethene, N 78 1,2-Dichloroethane N 17 Benzene
170 170 323 323 170 170 136 134 423 424 424 340 424 339 323 323 61
8-AND LARGER RINGS
2-Butyl-l,3,6-trioxocane 1,3-Dioxocane Tetraoxane 1,3,6-Trioxocane
(1,3,6-Trioxocane) n n=\ n=2 n=3 n= 4 n=5 n—6 rc = 7 n=S
ss ss ss ss ss ss ss ss
34.3 12.6 36.4 43.1 47.7 51.5 54.8 57.8
0 0 0 0 0 0 0 0
N 17
Notes page 11-406; References page II - 407
TABLE 5.
cont'd
Monomer (1,3,6,9-Tetraoxacycloundecane) n n= \ n=2 n=3 n= 4 n=5 n=6 w= 7 n=$ (1,3,6,9,12-Pentaoxacyclotetradecane) n n= l n= 2 n=3 n=4 n= 5 n=6 n=l (1,3,6,9,12,15-Hexaoxacycloheptadecane) „ n=\ n=2 n=3 n=4 n=5
State of monomer and polymer xx
-ASJ x (J/K/mol)
Temp. (0C)
Method
Solvent/Notes
Refs.
ss ss ss ss ss ss ss ss
13.0 20.1 28.9 48.2 52.3 56.9 59.9 62.8
0 0 0 0 0 0 0 0
4a 4a 4a 4a 4a 4a 4a 4a
Dichloromethane Dichloromethane Dichloromethane Dichloromethane Dichloromethane Dichloromethane Dichloromethane Dichloromethane
343 343 343 343 343 343 343 343
ss ss ss ss ss ss ss
8.4 10.0 43.1 49.8 54.4 58.2 61.1
5 5 5 5 5 5 5
4a 4a 4a 4a 4a 4a 4a
Dichloromethane Dichloromethane Dichloromethane Dichloromethane Dichloromethane Dichloromethane Dichloromethane
343 343 343 343 343 343 343
ss ss ss ss ss
8.4 28.1 44.8 50.7 54.8
-2 -2 —2 -2 -2
4a 4a 4a 4a 4a
Dichloromethane Dichloromethane Dichloromethane Dichloromethane Dichloromethane
343 343 343 343 343
Ic Ic' Ic
54 74 51
25 25 127
1 1 1
368 368 368
Ic Ic' Ic
30 65 29
25 25 77
1 1 1
368 368 368
5.1.2. CYCLIC ESTERS 4-RINGS
P-Propiolactone
5-RINGS
y-Butyrolactone
6-RINGS
2,2-Dimetyltrimethylene carbonate
p-Dioxanone
Ethylene oxalate
Glycollide DL-Lactide L-Lactide 8-Oxo-7-oxabicyclo[2,2,2]octane
c'(II)c'(II) c'(II)c c'(II)c'(II) c'(1I)C Ic'(I) 11 c'c' c'c c'c' c'c c'c' c'c 11 c'c c'c c'c Ic c'c' cc Ic c'c Ic ss ss gg Ic'
7.7 -35.3 5.8 -35.2 38.7 24.0 6 -28 9 -25 10 -32 13 -12 -9 -5 15 0.3 -10.5 17.5 -31.3 13.0 41 25 127.7 76.2
-173 -173 25 25 117 147 -173 -173 -73 -73 25 25 127 -173 -73 25 142 25 25 277 25 127 105 40 25 25
1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 1 4a 4a 4b 4b
N63 N63 N63 N63 N63 N 63
1,4-Dioxane, N 78 Nitrobenzene, N 78 N53 N53
426 426 426 426 426 426 427 427 427 427 427 427 427 312 312 312 312 364 364 364 311 311 429 428 307 307
TABLE 5. cont'd Monomer Pentanolactone
State of monomer and polymer xx
-AS^ x (J/K/mol)
Temp. (0C)
Method
Solvent/Notes
Refs.
Ic' Ic Ic
65 15 13
25 25 77
1 1 1
314 314 314
Ic Ic' Ic
4 54 8
25 25 77
1 1 1
368 368 368
ss ss ss ss
-39.6 -30.7 -20.8 -25.7
7-RINGS
s-Caprolactone Spiroorthoester 2-R-1,4,6-trioxaspiro[4.6] undecane R= H = CH 3 = CH 2 Br = Ph
-10 -25 -20 -30
4a 4a 4a 4a
127 127 127 127 25 25 127 127 25 25 127 127 25 25 97 -73 127
4b 4b 4b 4b 1 1 1 4b 1 1 1 4b 1 1 1 1 4b
Dichloromethane, Dichloromethane, Dichloromethane, Dichloromethane,
N78 N78 N78 N78
430 430 430 430
8-AND LARGER RINGS
Heptanolactone Octanolactone Nonanolactone Decanolactone Undecanolactone Dodecanolactone Tridecanolactone Tetradecanolactone Pentadecanolactone
Hexadecanolactone
Ic Ic Ic Ic Ic Ic7 Ic Ic c'c cV Ic Ic c'c c'c' Ic C7CII)C Ic
1 -5 -12 -18 -24 69 -25 -25 -57 50 -26 -25 —41 86 -23 -109 -21
N54
368 368 368 368 368 368 368 368 368 368 368 368 313 313 313 313 368
5.2. MONOMERS GIVING POLYMERS CONTAINING O IN THE MAIN CHAIN, BONDED TO OTHER HETEROATOMS (S, Si, P) Cyclotrisiloxane, 1,1,3,3,5,5-hexaethyl
hexamethylCyclotetrasiloxane, octamethylAf,7V-Diethylamino1,3,2-dioxaphosphorinane 1,3,2-Dioxaphospholan, 2-methoxy 2-Oxo-1,3,2-dioxaphosphorinane - , 2-alkoxyR = methyl R = methyl R = ethyl R = propyl R = trimethyl silyl Sulfur trioxide
c'(HI)C'(II) c'(H)C7OI) c'(II)c c'(I)c'(I) c'0)c 11 Ic c'c Ic Ic
7 0 -62 9 -22 25 3.03 -51.0 -190 -194.4
-173 -73 -23 -23 25 25 77 25 77 25
1 1 1 1 1 1 1 1 1 1
N54, N63, N77 N54, N63, N77 N54, N63 N54, N63, N77 N54, N63 N63
431 431 431 431 431 431 365 365 365 365
Is ss Ic
-20.9 13.5 -19.3
-20 90
4a 4a 4a
N58 1,1,2,2-Tetrachloroethane N59
346 309 347
Is ss ss ss ss gc'
11.7 2.5 -1.5 -4.5 -6.0 178
140 100 100 100 100 41
4a 4a 4a 4a 4a 4a
Diglyme or DMSO Dichloromethane Dichloromethane Dichloromethane Dichloromethane
348 356 356 356 356 86
5.3. MONOMERS GIVING POLYMERS CONTAINING N IN THE MAIN CHAIN, BONDED IN THE CHAIN TO CARBON ONLY (listed by increasing ring size) 3-RINGS
Ethyleneimine - , MP-trimethylsilyl ethyl)-(TEI)
Ic Ic
51.9 113
27 27
1 1
360 360 Notes page 11-406; References page II - 407
TABLE 5. cont'd State of monomer
-AS^ x
Temp.
and polymer xx
(J/K/mol)
(0C)
Monomer - , - , ZnCl2(TEI)2(complex)
c'c
114
Method
Solvent/Notes
Refs.
27
1
360
360 360
4-RINGS
Trimethyleneimine, iV-(P-trimethylsilyl ethyl)-(TMI) - , ZnCl2(TEI)2(complex)
Ic c'c
83.0 37.2
27 27
1 1
ss c'c'
72 31
38 25
4a l/4b
c'c'
25
25
l/4b
63
c-Caprolactam
Is c'c'
29 -5
250 25
4a 1
68 63
-, 3-methyl-, 5-methyl-, 7-methyl-
Is Is Is
260 200 225
4a 4a 4a
5-RINGS
Bicyclic oxalactam 2-Pyrrolidinone
Dimethylsulfoxide
433 63
6-RINGS
2-Piperidone 7-RINGS
11 16 21
194 225 226
8-RINGS
2-Oxo-hexamethyleneimine c'c' —17 25 1 N. B. Values for 9-13 rings by probably unreliable extrapolation of ASC>C> for 5-8 rings are given in Ref. 138
63
13-RINGS
2-Oxo-undecamethyleneimine 5.4.
Is
16
290
4a
- 15
4a
25 55 200 25 25 25 80 80 160 159 50-90
1 4a 4a 1 1 1 1 1 4a 4a 4a
139
OTHER MONOMERS GIVING POLYMERS NOT LISTED ABOVE
4-(2,3-Diphenyl cyclopropenylidene)cyclohexa-2,5-dienone ss
1,3-Disilacyclobutane, 1,1,3,3-tetramethylTV-Phenylmaleimide Selenium Se g 1-Silacyclobutane, 1,1-dimethyl- , 1-phenyl 1-methylSulfur, S 6 -,S7 -,S8 Thioacetone exo-3,4,5-Trithiatricyclo[5.2.1.02'6]decane exo-3,4,5-Trithiatetracyclo[5.5.1.02'6.08'12]tridec-10-ene
TABLE 6.
69.4
Dichloromethane, N67
317
Ic ss Is Ic' Ic Ic Is Is Is Is Is
18.1 86 - 27 85.4 71.2 57.4 2 -11 -44.7 -31 48.9
ss
31.4
40
4a
Toluene, N 7 6
377
ss
29.3
50
4a
Toluene, N 7 6
376
DMF 9 N 78 From estimated T e
N73 N73 Nn Monomer
359 440 88,111 359 359 359 380 380 380 73,74,111 327
COPOLYMERS (listed alphabetically under Monomer A)
Monomer A Bis-(o-aminophenyl)-2,2' dibenzimidazoleoxide
Monomer B Terephthalic acid
State of monomer and polymer, xx c'c c'c c'c
— A5° x (J/K/mol) 19 -17 -112
Temp. (0C) -173 -73 25
Method 1 1 1
Solvent/Notes Polymer + H 2 O (c') Polymer + H 2 O (c') Polymer + H 2 O (1)
Refs. 445 445 445
TABLE 6. cont'd Monomer A
Monomer B - , dichloride - , dimethylester
1,3-Butadiene 1-Butene
Styrene Sulfur dioxide
-, 3-methyl-
Sulfur dioxide
2-Butene, cis -, trans Cyclopentene 1,3 Dioxane
Sulfur dioxide Sulfur dioxide Sulfur dioxide 1,3 Dioxolane
1-Hexadecene 1-Hexene
Sulfur dioxide Sulfur dioxide
Isobutene Methacrylic acid
Sulfur dioxide Methacrylic acid, methyl ester Sulfur dioxide
State of monomer and polymer, xx
-AS^ x (J/K/mol)
c'c c'c c'c c'c c'c c'c Ic Ic ss Ic Ic ss ss ss ss
-33 -295 -320 -13 -108 -160
Temp. (0C)
Method
Solvent/Notes
1 1 1 1 1 1 1 1 4a 4a 4a 4a 4a 4a 4a
Polymer + HcI (c') Polymer + HcI (g) Polymer + HCl (g) Polymer+ CH 3 OH (c') Polymer+ CH 3 OH(I) Polymer+ CH 3 OH(I)
116 145 162 81 146 140 134 57
-173 -73 25 -173 -73 25 30 25 64 35 25 25 25 102 20
ss Ic ss Ic
139 116 145 134
30 25 60 0
4a 1 4a 4a
Chloroform
Ic sc gc
117 130 172
25 90 25
1 4a 1
Excess B Excess B Excess A Excess B Excess B Excess B Methylene ASBA =
Propene
Ethylene
C.
Refs.
445 445 445 445 445 445 108 109 110 199,200 199,200 5 5 110 dichloride, N 78 , 446 -34
Excess B N 23
Excess B 31 mol% A in copolymer, N 3 0
110 109 110 83 206 109 110 222
CEILING TEMPERATURES A N D EQUILIBRIUM MONOMER CONCENTRATIONS
Most addition polymerization reactions are exothermic and exentropic. The free energy of polymerization per monomer unit therefore becomes less negative as the temperature is raised. At the ceiling temperature Tc, the free energy of polymerization under the prevailing conditions is zero, and above this temperature, polymerization to long-chain polymer is impossible (just as in physical aggregation a liquid cannot form a solid when the temperature is above the melting point). The reverse phenomenon of a floor temperature is also known, e.g., for sulfur. In general a pure liquid monomer which gives an insoluble polymer will have a single well-defined ceiling temperature, given by Tc = AH\C/AS\C. A pure liquid monomer which gives a soluble polymer will have a series of ceiling temperatures corresponding to different percentage conversions of monomer to polymer. The condition for equilibrium is then - A G i + AGic + AG 2 = 0 The partial molar free energy per mol of monomer, AG i and per base mol of polymer, AG 2 are then functions of composition and may be evaluated from an appropriate equation for mixing of monomer and polymer, e.g., the Flory-Huggins equation. For a monomer dissolved in a solvent the situation is more complex and the ceiling temperature at a given monomer concentration (or the equilibrium concentration of monomer at a given temperature) is dependent on the nature of the solvent and the composition of the medium (Refs. 28,29,112,113,114,160). For the case where both monomer and polymer are in solution the variation of Tc with concentration is given to a first approximation by r c =A// s ° s /(A5 s s +RIn[M]) where [M] is the concentration of monomer and A//° s and A5°s refer to the heat and entropy changes in an appropriate standard state. A more general expression may be derived from the free energy condition by insertion of suitable expressions for AG i and AG 2 . These will contain the various interaction parameters appropriate to the polymer-monomer-solvent system. The values of Tc quoted in the table are mostly obtained from experimental values by interpolation or short extrapolation. Some unpolymerizable monomers are included where these are structurally closely related to monomers which do polymerize and where the cause of nonpolymerization appears to be thermodynamic. This is amplified for cyclic monomers in Section D. Section C is divided into three sections 1 Equilibria involving pure liquid monomers (Ic, Ic', Is) 2 Equilibria involving gaseous monomers (gc, gc') 3 Equilibria involving monomers in solution (sc, sc', ss) and copolymerizations For meaning of symbols, see Section A.
Notes page 11-406; References page II - 407
1.
Equilibria Involving Pure Liquid Monomers
TABLE 7. MONOMERS GIVING POLYMERS CONTAINING MAIN CHAIN ACYCLIC CARBON ONLY
Monomer
State of monomer and polymer
2-Amino-4-(7V-alkylanilino)-6-isopropenyl-1,3,5-triazine alkyl = rc-propanyl Ic = n-hexanyl Ic = rc-octanyl Ic = /z-decanyl Ic = n-dodecanyl Ic = rc-tetradecanyl Ic = rc-hexadecanyl Ic = isopropyl Ic = isobutyl Ic = sec-butyl Ic = rc-pentyl Ic = isopentyl Ic = 1-methylbutyl Ic = benzyl Ic 2-Amino-4-alkyl/aryl-amino-6-isopropenyl-1,3,5-triazine Is R 1 = H , R 2 = ethyl Is R i = H , R 2 = propyl Is R i = ethyl, R 2 = ethyl Is R i = propyl, R 2 = propyl Is Ri = methyl, R 2 = phenyl Is R i = H, R 2 =/?-methoxyphenyl 2-Amino-4-(/?-chloroanilino)-6-isopropenyl-1,3-5-triazine Ic 2-Amino-4-methoxy Is -4-ethoxy Is 6-isopropenyl-1 -3,5-triazine 2-Anilo-4-methoxy Is -4-ethoxy Is 6-isopropenyl-1,3,5-triazine Atropic acid, methyl ester Is 1-Butene Ic 2-Butene, cis Ic , trans Ic - , 2-methyl11 - , 2,3-dimethyl11 ot-Cyanoacrilic acid - , allyl ester Ic - , rc-decyl ester Ic - , allyloxyethyl Ic Cyclopentene Ic Ethacrylic acid - , methyl ester Is Ethylene Ic Methacrylic acid - , benzoil acid ester Ic - , methyl ester Ic - , methyl ester deuterated Ic Naphtalene, 2-isopropenyl Is Pentene-1 Ic Pentene-2, cis Ic Pentene-2, trans Ic - , 4-methyl, cis Ic - , 4-methyl, trans Ic Silane, benzyl dimethyl vinylIc - , dimethyl phenyl vinylIc Styrene, a-methylIs Is Is
Tc [0C]
Wt. fraction monomer at equilibrium
157 149 143 140 134 132 130 151 154 148 150 151 146 157
1 1 1 1 1 1 1 1 1 1 1 1 1 1
402 402 402 402 402 402 402 403 403 403 403 403 403 403
181 177 163 161 169 169
1 1 1 1 1 1
370 370 370 370 379 378
170 183 182
1 1 1
404 405 405
174 174
1 1
405 405
—8 247 227 217 -29 -223
1 1 1 1 1 1
Isotactic polymer, N 5 7 Isotactic polymer, N 5 7 Isotactic polymer, N 5 7 Calculated, N 3 1 Calculated, N 3 1
149 385 385 385 143 143
307 217 607 97
1 1 1 1
N57 N57 N57 N66
391 392 393 361
87 367
1 1
N75 Polymer is polybutene-1-iso
395 385
787 102 93 69 317 287 277 317 267 397 197 61 54 170
1 1 1 1 1 1 1 1 1 1 1 1 1 1
N57
394 414 414 400 386 386 386 387 387 366 362 119 341 119
Notes
N43 N57 N57 N57 N57 N57
1 bar 6.57 kbar
Refs.
TABLE 7. cont'd
Monomer Vinylcyclohexane Vinylidenechloride Vinyldimethylbenzylsilane Vinyldimethylphenylsilane Vinyltrimethylsilane
State of monomer and polymer
Tc [ 0 C]
Wt. fraction monomer at equilibrium
Ic Ic Ic Ic Ic
567 387 397 117 327
1 1 1 1 1
Notes N57 N57 N57 N57 N57
Refs. 396 397 367 367 367
N.B. The following compounds are not polymerizable for thermodynamic reasons but can sometimes be copolymerized with other monomers (see Ref. 205): a-trifluoromethyl vinyl acetate, oc-methoxystyrene, 1,1-diphenylethylene, frafts-crotonitrile, trans-stilbene, rrarcs-l,2-di(2-pyridyl)-ethylene, ?raw5-l,2-dibenzoylethylene, /rarcs-l,2-diacetylethylene, oc-stillbazole, methyl 2-terf-butylacrylate, 1-isopropenylnaphthalene, 2,4-dimethyl-a-methyl-styrene.
TABLE 8.
M O N O M E R S G I V I N G POLYMERS C O N T A I N I N G HETEROATOMS I N THE M A I N C H A I N
State of monomer and polymer
Monomer 8.1.
Tc [ 0 C]
Wt. fraction monomer at equilibrium
Notes
Refs.
MONOMERS GIVING POLYMERS CONTAINING O IN THE MAIN CHAIN, BONDED TO CARBON ONLY
Acetaldehyde
—, trichloro- , trifluoro2,2-Dimethyltrimethylene carbonate 4,7-Dioxaoctanal 1,3-Dioxepane
- , 2-phenyl(1,3-Dioxolane) n
n=\
/2=1-8 1,3-Dioxolane, 4,4-dimethyl- , cis 4,5-dimethyl- , trans 4,5-dimethyl- , 4-ethyl- , 4-isopropyl- , 4-methyl- , 4-phenylHeptanal Hexanal L-Lactide Octanal 7-Oxabicyclo[2,2,1 ]heptane - , 2-exo-methyl- , 2-endo-methylfrarcs-7-Oxabicyclo[4,3,0]nonane 4-Oxapentanal 1,2-Oxathiolane-2,2-dioxide Oxepane Oxetane 8-Oxo-7-oxabicyclo[2,2,2]octane
gg Is Is Ic' Ic Ic Ic Ic Is Is Is Is Is Is Is Ic Is
—31 -39 20 58 177 212 227 -38 100 192 144 20 100 165 100 98 60
1 1 1 1 1 1 1 1 0.1 1 1 0.36 0.3 1 1 1
Ic Ic Ic Is Ic Ic Is Ic Is Ic Ic' Ic Ic Ic Ic Ic Ic
-98 -54 -137 -48 -54 -74 -20 -21 20 74 -43 -25 640 -19 320 240 200
1 1 1 4.74 Md/1 1 1 4.47 Md/1 1 1 1 1 1 1 1 1 1 1
Ic Ic Is Is Is Ic Ic Ic7
12 -35 -59 95 41.5 -136 478 180
1 1 1 0.74 1 1 1 1
Atactic polymer (1 bar) Isotactic polymer (1 bar) <10kbar N57 N68 N57 N69 N22 N43 N22
N43 Kn determined for cyclic monomers N57 N57 N57 N56 N57 N57 N56 N57 N57 N57 N57 N 5 7 , calculated N69 N57 N57 N57
N69 N22 N32, N57 N3i N53
115 115 158 233 418 322 426 330 H6 423 398 116 116,219 198 423 353 232 335 335 335 333 333 335 334 334 285 419 420 420 429 330 308 308 308 357 329 329 152 147 323 325 307
Notes page 11-406; References page II - 407
TABLE 8.
cont'd
State of monomer and polymer
Monomer Pentanal Propanal
Spiroorthoester 2-R-1,4,6-trioxaspiro[4,6]undecane R= H = CH 3 = CH2Br = Ph Tetrahydrofuran - , 3-methyl Tri(ethylene terephthalate)
Tc [0C]
Wt. fraction monomer at equilibrium
Ic Is Is Ic' Ic
-42 -31 —39 -48 -83
1 1 1 1 1
Ic Ic Ic Ic Is Is Is Is
172 254 498 258 80 129 4 297
1 1 1 1 1 1 1 0.014
Notes
Refs.
N69 Atactic polymer Isotactic polymer N 57 N 57
328 115 115 421 421
N68 N 68 N68 N68 1 bar 12.5 kbar
430 430 430 430 58,130 146 342 see 174
N.B. The following compounds are not polymerizable for thermodynamic reasons but can sometimes be copolymerized with other monomers (see Ref. 205); benzaldehyde (Refs. 297-299), hexafluoroacetone, 1,1-dimethylpropanal; also numerous cyclic ethers - see Section D. 8.2.
MONOMERS GIVING POLYMERS CONTAINING O IN THE MAIN CHAIN, BONDED TO OTHER HETEROATOMS (S, Si, P)
Sulfur trioxide Sodium metaphosphate Na„(OPO 2 ) n n=3
Ic' Is
800
0.043
n=4 n= 5 Siloxanes (RiR 2 SiO) n Ri, R 2 Me, H /z = 3-5
Is Is
800 800
0.026 0.008
Is
0
0.045
n = 6-18 /i=19-oo n = 3-oo
Is Is Is
0 0 0
0.034 0.046 0.125
/2 = 3-5
Is
110
0.100
n = 6-18 /i=19-oo rc = 3-oo n = 4-40
Is Is Is Is
110 110 110 110
0.036 0.047 0.183
n = 4-30
Is
145
Me, Et
n = 3-5
Is
110
0.170
Me, Pr
n= «= /i = n=
Is Is Is Is
110 110 110 110
0.049 0.039 0.258 0.270
Me, CF 3 (CH 2 ) 2
/i = 3-8 n = 3-5
Is Is
110 110
0.310 0.711
Et, Et
n = 6-18 n =19-oo n = 3-00 n= 3
Is Is Is Ic
110 110 110 247
0.089 0.027 0.827 1
Me, Me
8.3.
6-18 19-oo 3-oo 3-5
30.4
1
86 Kn determined for cyclic monomers, n = 3-l
300,301 300,301 300,301
Kn determined for cyclic monomers, n — 4-15
176 176 176 176
Kn determined for cyclic monomers, n = 4-40
Kn determined for values of n indicated Kn determined for values of n indicated Kn determined for cyclic monomers, n — 4-20
Kn determined for cyclic monomers, n = 4 - 8 Kn determined for cyclic monomers, n — 4-20
Calculated
176 176 176 176 180 180 176 176 176 176 176 176 176 176 176 176 431
MONOMERS GIVING POLYMERS CONTAINING S IN THE MAIN CHAIN, BONDED IN THE CHAIN TO CARBON ONLY
Thiacetone Thioacetophenone
Ic Is Is
95 -52 approx. 40
1 1 1
N 55
148 327 288
N.B. Isothiocyanates (Ref. 295) are not polymerizable for thermodynamic reasons, but can be copolymerized with thiiranes; carbon disulfide (Ref. 296) can also be copolymerized with thianes
TABLE 8. cont'd State of monomer and polymer
Monomer 8.4.
n=l
n=2 n=3 /i = 4 n=5 n=>6 - , 3-methyl- , 3-ethyl- , 3-propyl- , 4-ethyl- , 5-methyl- , 7-methyl- , 7-ethyl- , 7-propyl2,5-Dioxopiperazine 2-Oxo-hexamethylenimine -,4-ethyl- , 7-ethyl- , 8-propyl2-Oxo-undecamethylenimine 2-Piperidone 2-Pyrrolidone
Notes
Refs.
Is Is Is Is Is Is Is Is Is Is Is Is Is Is Is Is Is Is Is Is Is Is Is Ic Is
220 225 277 277 277 277 277 277 225 240 240 240 172 225 240 240 171 240 240 240 240 290 60 76 70
0.055 0.067 0.084 0.0078 0.0052 0.0056 0.0048 0.0076 0.086 0.1 0.1 0.35 0.18 0.107 0.1 0.1 1 0.03 0.06 0.02 0.32 1 1
68 192 See 181 Cyclic monomer See 181 Cyclic monomer See 181 Cyclic monomer See 181 Cyclic monomer See 181 Cyclic monomer See 181 192,194 191 191 171 225,302 226,302 191,302 191,302 From calorimetric data 437 302 171 171 302 139 118 N 75 383 Tc varies with the accelerator, N 75 439
OTHER MONOMERS GIVING POLYMERS NOT LISTED ABOVE
Norbornene 5-trimethylsilyl-2Selenium Se 8 Sulfur S 8
2.
Wt. fraction monomer at equilibrium
MONOMERS GIVING POLYxMERS CONTAINING N IN THE MAIN CHAIN, BONDED IN THE CHAIN TO CARBON ONLY
(s-Caprolactam),,
8.5.
Tc [0C]
Ic Ic Is Is
777 417 83 159
1 1 1 1
Is
157
1
55% cis/45% trans polymer, N57 N32 N33 Effect of pressure N33
415 416 85 73,,111 145 380
Equilibria Involving Gaseous Monomers (listed alphabetically)
Monomer
State of monomer and polymer xx
Tc (0C)
gc' gc gc gc gc gc gc gc'
98 73 -220 149 288 87 560 119
Acetaldehyde, trichloro- , trifluoroAcetone 1,3-Dioxepane 1,3-Dioxocane 1,3-Dioxolane Ethylene, tetrafluoroFormaldehyde Methacrylic acid - , ethyl ester - , methyl ester Oxepane Oxetane Sulfur trioxide
gs gs gc gc gc'
Tetrahydrofuran 1,3,6-Trioxocane
gc gc
173 164 135 319 27.0 0.0 83 243
Equilibrium pressure (mbar)
Notes
1013 1013 Estimated, N 3 6 1013 1013 1013 128 1013 1013 1013 1013 1013 372 40.8 1013 1013
N34 N28 N35 N35
Refs. 50 129 144 323 324 292 23,120 49,164,165 40 43 323 325 86 86 292 324
Notes page 11-406; References page II - 407
3.
Equilibria Involving Monomers in Solution
TABLE 9. MONOMERS GIVING POLYMERS CONTAINING MAIN CHAIN CARBON ONLY Monomer
State of monomer and polymer xx
Tc (0C)
M (mol/i)
Solvent/Notes
Refs.
9.1. MONOMERS GIVING POLYMERS CONTAINING MAIN CHAIN ACYCLIC CARBON ONLY Acrylonitrile Atropic acid - , methyl ester -, ethyl ester - , n-propyl ester - , n-butyl ester -,/?-methyl-, methyl ester Atroponitrile Biphenyl, p-isopropenylCyclohexene Cyclooctene Isobutylene Methacrylamide, N-butyl- , Af-phenylMethacrylic acid, methyl ester - , o-methyl phenyl ester - , phenyl ester - , o-tert-buiy\ phenyl ester - , cKseobutylphenyl ester - , o-chlorophenyl ester -, 2,6-diisopropylphenyl ester - , 2,6-dimethyl phenyl ester - , o-ethylphenyl ester - , o-isopropylphenyl ester - , o-methoxyphenyl ester - , 0-methoxycarbonylphenyl ester - , onitrophenyl ester - , ophenylphenyl ester -, 0-propylphenyl ester 2,4,6-tribromophenyl ester 2,4,6-trichlorophenyl ester 2,4,6-trimethylphenyl ester Methacrylonitrile Methyl-a-/?-chlorobenzylacrylate a-Methylene pentanolactone Methyl-a-p-methoxybenzylacrylate Methylphenylitaconate Naphthalene, 2-isopropenylOxazole, - , 2-isopropenyl-4,5-dimethylPyridine, 2-isopropenylStyrene - , a, acetoxy - , a-methyl- , - , o-methoxyAWA^Af'-TetraethyMisopropenylphenylphosphorous diamide Thiazole, 2-isopropenyl/?-[Bis(Trimethylsilyl)methyl] isopropenylbenzene
25 ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss ss
-40 -67 -72 -80 —37 50 0 -23 20 88 122 125 155.5 135 140 146 81 100 139 33 77 118 112 145 112 108 100 118 92 104 69 145 85 83 55 95 120 0
ss ss ss ss ss ss ss ss ss ss
0 0 150 150 47 0 53 58 -25 10
ss ss
0 1.2
3 x 1 ~8 1.0 1.0 1.0 1.0 1.0 1.0 0.515 5 1.2 0.651 0.611 0.82 0.611 0.64 0.64 0.64 0.64 0.64 0.64 0.64 0.64 0.64 0.64 0.64 0.64 0.64 0.64 0.64 0.64 0.64 0.27 5 1 0.324 5 2,22 0.284 0.0025 0.043 9.1 x 10 ~4 6.5 x l O " 4 1.0 0.76 1.8 1.8 ~2 1.0 0.010 1.0
Estimated from AG]c>
193
Toluene Toluene Toluene Toluene Toluene Toluene Tetrahydrofuran Toluene Benzene, N 38 Supercritical CO 2 Ethyl benzoate Ethyl benzoate o-Dichlorobenzene Ethyl benzoate /?-Xylene Benzene or/?-xylene, N75 /?-Xylene Benzene or p-xylene, N 75 Benzene or/?-xylene, N 75 Benzene or /?-xylene, N75 /?-Xylene Benzene or p-xylene, N 75 Benzene or/?-xylene, N 75 Benzene or p-xylene, N 75 Benzene or p-xylene, N75 Benzene or/?-xylene, N 75 Benzene or/?-xylene, N 75 Benzene or p-xylene, N 75 Benzene or p-xylene, N 75 Benzene or/?-xylene, N 75 Benzene or /?-xylene, N 75 Benzonitrile Toluene DMF DMF Toluene Dichlorobenzene Tetrahydrofuran
149 150 150 150 150 149 16 389 229,230 441 326 326 42 326 345 442 345 442 442 442 345 442 442 442 442 442 442 442 442 442 442 44 443 315 315 443 444 16
Tetrahydrofuran Tetrahydrofuran Benzene Cyclohexane Toluene Tetrahydrofuran, N 37 rc-Heptane Toluene Methylene chloride Tetrahydrofuran
284 284 28 28 401 16,32,33 402 402 155 408
Tetrahydrofuran Tetrahydrofuran
284 409
TABLE 9. cont'd State of monomer and polymer xx
Monomer 9.2.
Tc (0C)
M (mol/1)
Solvent/Notes
Refs.
MONOMERS GIVING POLYMERS CONTAINING MAIN CHAIN CYCLIC CARBON
- , 7,8-Dycyanoquinodimethane 7,8-bis(butoxycarbonyl) 7,8-Diacetyl7,8-Dibenzoyl7,8-Dibutoxycarbonyl
ss ss ss ss ss ss ss ss ss ss ss ss
93 442 87 415 88 301 93 442 79 422 67 481
0.014 1.0 0.018 1.0 0.069 1.0 0.014 1.0 0.014 1.0 0.014 1.1
Chloroform, Chloroform, Chloroform, Chloroform, Chloroform, Chloroform, Chloroform, Chloroform, Chloroform, Chloroform, Chloroform, Chloroform,
N75 N43 N75 N43 N75 N43 N75 N43 N75 N43 N75 N43
411 411 412 412 412 412 412 411 411 411 411 411
TABLE 10. MONOMERS GIVING POLYMERS CONTAINING HETEROATOMS IN THE MAIN CHAIN State of monomer and polymer xx
Monomer 10.1.
Tc (0C)
M (mol/1)
Solvent/Notes
Refs.
MONOMERS GIVING POLYMERS CONTAINING O IN THE MAIN CHAIN, BONDED TO CARBON ONLY
Acetaldehyde - , bromochlorofluoro- , bromodichloro- , bromodifluoro- , dibromochloro- , dibromofluoro- , dichlorofluoro- , chlorodifluoro- , tribromo- , trichloro-
- , trifluoroButanal
4,7-Dioxaoctanal 1,3-Dioxepane
- , 2-butyl - , 2-methyl- , 4-methyl(1,3-Dioxolane)n
n=l
n=l-8
sc sc' sc' sc' sc sc' sc sc' sc sc' sc' ss sc' sc' sc' sc' sc' sc sc sc sc ss ss ss ss ss ss ss ss ss ss ss ss Is
~ - 80 23 —17 48 -40 -19 52 41 70 63 -75 11 12.5 35 18 9 81 9 -18 12 27 -56 78 27 32 -51 -37 -40 -33 1 -8 20 20 60
Is
145
ss
60
6 1 1 1 1 1 1 1 1 1 1 1.0 (0.1) 1.0 1 1 1 1 ~2 1.0 1.0 1 1.0 1.0 1.0 1.0 1 1.0 1 1.0 1.0 2.0 1.0 2.0 10.0
Toluene, N 22 Toluene Toluene Toluene Toluene Toluene Methyl cyclohexane Toluene Methyl cyclohexane Toluene Toluene Tetrahydrofuran Pyridine, N 3 9 , N 4 0 /i-Heptane Methyl cyclohexane Toluene Toluene Dichloromethane Toluene, isotactic polymer n-Hexane [8kbar], Ni 2 n-Hexane [10 kbar], N12 THF Benzene Dichloromethane 1,2-Dichloroethane, N 5 7 1,2-Dichloroethane, N 5 7 1,2-Dichloroethane 1,2-Dichloroethane, N 5 7 1,2-Dichloroethane Dichloromethane Benzene, N 4 i 1,3-Dioxane, N41 Chloroethane A few percent dichloromethane present A few percent dichloromethane present Dichloroethane, N 42
228 233 344 344 337 344 336 344 336 344 338 167 50 166 336 344 344 322 227 161 161 330 116,134 136 424 424 340 424 339 133,159 134,159 159 293 198 198 232
Notes page 11-406; References page 11-407
TABLE 10. cont'd
Monomer Formaldehyde L-Lactide Octanal frans-8-Oxabicyclo[4,3,0]nonane mms-2-Oxabicyclo[3,3,0]octane Oxa-4,5 -dithiepane Oxepane Pentanal o-Phthalaldehyde Propanal, 2-chloro-, 2-methyl- , 2,2-dichloro- , 2-methyl-
Tetrahydrofuran Tetraoxane
Trioxane
1,3,6-Trioxocane - , 2-Butyl10.2.
sc' sc' ss sc ss
30 25 284 -59 -51
ss ss ss sc ss ss ss ss ss ss ss ss ss sc' sc' sc' sc' sc' sc' sc' sc' sc' ss ss ss
0 25 30 -68 -43 -54 -24 approx. 5 -36.6 -63 -61.6 25 20 50 25 25 50 30 30 30 25 25 297 330 220
M (mol/l) 0.06 0.004 1.0 1 1 0.63 < 0.005 0.08 1 1.0 1.0 1.0 (0.25) 1.0 1.0 1.0 4.45 2.8 < 0.008 0.12 0.10 0.20 0.13 0.05 0.19 1.5 2.5 1.0 1.0 1.0
Solvent/Notes
Refs.
Dichloromethane Nitrobenzene 1,4-Dioxane THF Dichloromethane
122 182 429 330 357
Dichloromethane Benzene Dichloromethane THF Dichloromethane, cyclopolymer Tetrahydrofuran Tetrahydrofuran Dichloromethane, N 2 2 , N40 rc-Pentane Tetrahydrofuran Diethyl ether Benzene, N 3 7 , N 4 4 Diethyl ether 1,2-Dichloroethane Dichloromethane Nitrobenzene 1,2-Dichloroethane 1,2-Dichloroethane Benzene Nitrobenzene, N 45 Nitrobenzene, N 4 5 Dichloromethane Benzene, N 4 5 Toluene, N 57 Toluene, N 5 7
357 61 236 328 154 172 172 153 166 172 166 231 211 178 182 182 178 178 178 178 182 182 134 425 425
ss ss ss
157 -33 -37
0.1 1 1
ss ss ss ss
0 110 110 110
(0.2) 0.3 (0.4) (0.9)
1,1,2,2-Tetrachloroethane 1,2-Dichloroethane 1,2-Dichloroethane
Toluene, N 4 6 Toluene, N 47 Toluene, N 4 6 Cyclohexanone, N 4 6
309 339 340
176 217,218 176 176
MONOMERS GIVING POLYMERS CONTAINING S IN THE MAIN CHAIN, BONDED IN THE CHAIN TO CARBON ONLY
1,3-Dithiolane, 2-phenylimino-4-methylexo-3,4,5-Trithiatetracyclo[5,5,l,02'6.0812]tridec-10-ene exo-3,4,5-Trithiatricyclo5.2.1.026]decane
10.4.
Tc (0C)
MONOMERS GIVING POLYMERS CONTAINING O IN THE MAIN CHAIN, BONDED TO OTHER HETEROATOMS (Si, P)
1,3,2-Dioxaphospholan, 2-methoxy1,3-Dioxepane, 4-methyl- , 2-methylSiloxanes (RiR 2 SiO) n R1, R2 H, Me Me, Me Me, Et Me, CF 3 (CH 2 ) 2 10.3.
State of monomer and polymer xx
ss
65
2.7
Benzene
290
ss ss
25 90
2.37 3.72
Toluene, N 7 6 Toluene, N 7 6
376 376
ss ss
10 70
3.8 6.0
Toluene, N 7 6 Toluene, N 7 6
377 377
MONOMERS GIVING POLYMERS CONTAINING N IN THE MAIN CHAIN, BONDED IN THE CHAIN TO CARBON ONLY
Bicyclic oxalactam n-Hexyl isocyanate Pyrrole N,7,7-Tricyanobenzoquinone methide imine
ss sc ss ss
60 —22 77 74
1.0 2 0.017 0.14
Dimethylsulfoxide Dimethylformamide Acetonitrile Toluene, N 7 5 , N 8 i
433 127 434 438
Next Page
TABLE 11. COPOLYMERS Monomer A
Monomer B
State of monomer and polymer
Ta (0C)
[A][B] (mol 2 /I 2 )
Solvent/Notes
Refs.
11.1. 1:1 COPOLYMERS Allyl acetate Allyl alcohol Allyl ethyl ether Allyl formate 1-Butene -, 2-ethyl-, 3-methyl2-Butene, cis -,trans 2-Butene, (50% cis) - , 2-methylCycloheptene Cyclohexene 1,3-Cyclooctadiene Cyclopentene Ethene Ethene oxide Formaldehyde 2-Heptene (88% m ) 1-Hexadecene 1-Hexene -,2-ethylIsobutene 1-Pentene -,2-methyl-, 4,4-dimethyl-, 2,4,4-trimethyl2-Pentene (50% cis) -, 4-methyl4-Pentenoic acid Propene Propene oxide 3-Propenyl phenyl ether Styrene Tetrafluoroethene Vinyl chloride
Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Carbon monoxide Carbon dioxide Sulfur dioxide Carbon monoxide Carbon dioxide Carbon monoxide Carbon dioxide Sulfur dioxide Sulfur dioxide
Sulfur dioxide Sulfur dioxide Carbon monoxide Carbon dioxide Carbon monoxide Carbon dioxide Carbon monoxide
sc sc gg gg gg gg gg
45 76 68 45 64 <-80 36 46 38 34.6 <—80 11 24 37 103 150 (-35) -(50) >135 350 (—127) 220 (-58) 190 (-47) - 1 5 0 (46) -38 69 30 60 <-80 5 63 -34 14 <-80 8.5 <-80 66 90 140 (-39) - 1 2 0 (39) 490 (-129) 180 (-49) 590 (—136)
Carbon Carbon Carbon Carbon Carbon Carbon
gg gg gg gg gg gg
190 (-36) -190 (53) 280 (-74) 30 ( - 2 ) 230 (-55) -45(18)
N 64 N 64 N 64 N 64 N 64 N 64
369 369 369 369 369 369
Is
225
N50
192,194
Sulfur Sulfur Sulfur Sulfur Sulfur Sulfur Sulfur Sulfur
dioxide dioxide dioxide dioxide dioxide dioxide dioxide dioxide
dioixde monoxide monoxide dioxide monoxide dioxide
ss sc ss sc ss sc ss ss ss ss ss ss ss gg gg sc' gg gg gg gg ss sc ss ss sc ss ss sc ss
27 27 27 27 27 27 27 27 27 27 27 10 27 27
33 27 1.15 27 27 27 27 27 32 27 27
Excess B Excess B Excess B Excess B Excess B All compositions Excess B Excess B, N 48 Excess B, N 48 Excess B, N 49 All compositions Excess B Excess B Excess B (1,2 addition) Excess B N 64 N 64 Excess B N 64 N64 N 64 N 64 Excess B, N 49 Excess B Chloroform Excess B All compositions Excess B Excess B Excess B Excess B All compositions N 49 All compositions Excess B Excess B N 64 N 64 N 64 N 64 N 64
110 110 110 110 110 110 110,199 110 110 110 110 124 110 156 110 369 369 110 369 369 369 369 110 110 80 110 110 110 110 110 110 110 110 110 110 110 369 369 369 369 369
11.2. GENERAL COPOLYMERS 8-Caprolactam a
e-Caprolactam, 3-methyl-
Values in parentheses are for AGJ98 in (kJ/mol).
D.
POLYMERIZABILITY OF 5-, 6- AND 7-MEMBERED HETEROCYCLIC RING COMPOUNDS
The free energy of polymerization is generally negative for 3-, 4-, 8-, and higher-membered ring compounds. With heterocyclic rings there is generally an ionic mechanism available which allows these compounds to polymerize. With 5-, 6- and 7-membered ring compounds the sign of AG, and hence the polymerizability, is critically dependent on the nature of the ring and on the extent and position of substitution. Substitution generally makes AG less negative (more positive) and reduces polymerizability in the thermodynamic sense. Tables 12-14 summarize the polymerizability of 5-, 6- and 7-membered rings, respectively, as a function of the nature of the ring and extent of substitution. Table 15 provides a comparison of polymerizability of unsubstituted 5-, 6-, and 7-membered rings.
Notes page 11-406; References page II - 407
Previous Page
TABLE 11. COPOLYMERS Monomer A
Monomer B
State of monomer and polymer
Ta (0C)
[A][B] (mol 2 /I 2 )
Solvent/Notes
Refs.
11.1. 1:1 COPOLYMERS Allyl acetate Allyl alcohol Allyl ethyl ether Allyl formate 1-Butene -, 2-ethyl-, 3-methyl2-Butene, cis -,trans 2-Butene, (50% cis) - , 2-methylCycloheptene Cyclohexene 1,3-Cyclooctadiene Cyclopentene Ethene Ethene oxide Formaldehyde 2-Heptene (88% m ) 1-Hexadecene 1-Hexene -,2-ethylIsobutene 1-Pentene -,2-methyl-, 4,4-dimethyl-, 2,4,4-trimethyl2-Pentene (50% cis) -, 4-methyl4-Pentenoic acid Propene Propene oxide 3-Propenyl phenyl ether Styrene Tetrafluoroethene Vinyl chloride
Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Sulfur dioxide Carbon monoxide Carbon dioxide Sulfur dioxide Carbon monoxide Carbon dioxide Carbon monoxide Carbon dioxide Sulfur dioxide Sulfur dioxide
Sulfur dioxide Sulfur dioxide Carbon monoxide Carbon dioxide Carbon monoxide Carbon dioxide Carbon monoxide
sc sc gg gg gg gg gg
45 76 68 45 64 <-80 36 46 38 34.6 <—80 11 24 37 103 150 (-35) -(50) >135 350 (—127) 220 (-58) 190 (-47) - 1 5 0 (46) -38 69 30 60 <-80 5 63 -34 14 <-80 8.5 <-80 66 90 140 (-39) - 1 2 0 (39) 490 (-129) 180 (-49) 590 (—136)
Carbon Carbon Carbon Carbon Carbon Carbon
gg gg gg gg gg gg
190 (-36) -190 (53) 280 (-74) 30 ( - 2 ) 230 (-55) -45(18)
N 64 N 64 N 64 N 64 N 64 N 64
369 369 369 369 369 369
Is
225
N50
192,194
Sulfur Sulfur Sulfur Sulfur Sulfur Sulfur Sulfur Sulfur
dioxide dioxide dioxide dioxide dioxide dioxide dioxide dioxide
dioixde monoxide monoxide dioxide monoxide dioxide
ss sc ss sc ss sc ss ss ss ss ss ss ss gg gg sc' gg gg gg gg ss sc ss ss sc ss ss sc ss
27 27 27 27 27 27 27 27 27 27 27 10 27 27
33 27 1.15 27 27 27 27 27 32 27 27
Excess B Excess B Excess B Excess B Excess B All compositions Excess B Excess B, N 48 Excess B, N 48 Excess B, N 49 All compositions Excess B Excess B Excess B (1,2 addition) Excess B N 64 N 64 Excess B N 64 N64 N 64 N 64 Excess B, N 49 Excess B Chloroform Excess B All compositions Excess B Excess B Excess B Excess B All compositions N 49 All compositions Excess B Excess B N 64 N 64 N 64 N 64 N 64
110 110 110 110 110 110 110,199 110 110 110 110 124 110 156 110 369 369 110 369 369 369 369 110 110 80 110 110 110 110 110 110 110 110 110 110 110 369 369 369 369 369
11.2. GENERAL COPOLYMERS 8-Caprolactam a
e-Caprolactam, 3-methyl-
Values in parentheses are for AGJ98 in (kJ/mol).
D.
POLYMERIZABILITY OF 5-, 6- AND 7-MEMBERED HETEROCYCLIC RING COMPOUNDS
The free energy of polymerization is generally negative for 3-, 4-, 8-, and higher-membered ring compounds. With heterocyclic rings there is generally an ionic mechanism available which allows these compounds to polymerize. With 5-, 6- and 7-membered ring compounds the sign of AG, and hence the polymerizability, is critically dependent on the nature of the ring and on the extent and position of substitution. Substitution generally makes AG less negative (more positive) and reduces polymerizability in the thermodynamic sense. Tables 12-14 summarize the polymerizability of 5-, 6- and 7-membered rings, respectively, as a function of the nature of the ring and extent of substitution. Table 15 provides a comparison of polymerizability of unsubstituted 5-, 6-, and 7-membered rings.
Notes page 11-406; References page II - 407
TABLE 12. 5-MEMBERED RING COMPOUNDS Ring
Polymerized
Not polymerized
C2N2O
Refs. 237
R = Me, Ph
376
C2S3
377
238,239,433
C3NO R = Me, Ph etc.
239,240
C3NS
C3N2
239 R = Me, MeCO
C3OS
152
C3O2 R = Me, CH2Cl, Ph
R1 R1 R1 R1 R1
= R 2 = R 3 =H = R 2 = R 3 =Me = R 2 = R 3 = CH 2 Ph = R 3 = CH2Ph5R2= H = R 2 = CH 2 Ph 5 R 3 = H
R = Me, Ph
R = Me, CH2Cl
116,133,134, 159,177. 239,241-244, 285-287, 350,351,349, 398,423
331
C3S2
245,246,290
C4N
239,240,243
240,247-249
C4O
51,58,117, 130,140,146, 239,243,250-256, 291,303,304 R' = H,R = H R' = H, R = endo - Me R' = H, R = e x o - M e R' = endo - Me, R = exo - Me
R' = exo-Me R = exo-Me
TABLE 12. cont'd Ring
Polymerized
Not polymerized
Refs. 357
(trans)
(cis)
(trans)
(cis)
(trans)
(cis)
357
357
357 {trans)
(cis)
185,256
C4S
TABLE 13. 6-MEMBERED RING COMPOUNDS Ring
Polymerized
Not polymerized
Refs.
C3N2O
239
C3N3
239
C3O2P
346
R=H
347 348
R = OCH 3
C3O3
141,178,184,257
C3S3
148,258,259,260
C 4 NO
185,239,240
C 4 NS
240
C4N2
239,240,261 R = Me,Ph
Notes page 11-406; References page II - 407
TABLE 13. cont'd Ring
Polymerized
Not polymerized
Refs.
C4OS
152
C4O2
116,136,239,243,262,426,436
239,243,262,263,428,429 R = Me, Ph
R = Me 1 Ph
427
382 246,265
C4S2 C5N
R = H, Et, Ph
118,209,239,240,243,266
153,239,243,264,226-270,283
C5O
331
185,256
C5S
431
Si 3 O 3
TABLE 14. 7-MEMBERED RING COMPOUNDS Ring
Polymerized
Not polymerized
Refs.
C 4 OS 2
61
C5NS
240
C5N2
239,240
TABLE 14. Ring
cont'd Polymerized
Not polymerized
Refs.
C5O2
116,136,170,241, 262,271,423,424
C5S2
246
C6N
63,68,240, 249,272-279 R= 3555-
Me, 4 - Me, R = H, Me Me, 5 - Et, n - propyl, 5-z-propyl Cyclohexyl
R = Me, Ph, CH 2 OH, EtSCH 2
R = Ph, PhCH 2 n - Heptyl
6 - Me, 7 - Me
240,243,276, 277,280,305 C6O
153,239,243, 281,282
C6S
256
TABLE 15. COMPARISON OF POLYMERIZABILITY (+ OR - ) OF UNSUBSTITUTED 5-, 6- AND 7-MEMBERED RING COMPOUNDS0 T^pe of ring
Name of 5-ring
1,3-CnNO
2-Oxazolidinone
1,3-CnN2
2-Imidazolidinone
1,2-CnOS
1,2-Oxathiolane-2,2-dioxide
1,3-CnO2
1,3-Dioxolane
5-Ring
6-Ring
7-Ring
Ethylene carbonate 1,2-CnS2
1,2-Dithiolane
CnN
Pyrrolidine 2-Pyrrolidinone Succinimide
Notes page 11-406; References page II - 407
TABLE 15. cont'd Type of ring
Name of 5-ring
5-Ring
6-Ring
7-Ring
2-Pyrrolidinethione CnO
Tetrahydrofuran (oxolane) Oxolane-2-one (y-butyrolactone) Oxolane-2,5-dione(succinic anhydride)
CnS a
Thiolan-2-one (y -thiobutyrolactone)
The formulae denote rings of any size. Thus in the first line 1,3C4NO is drawn as
and represents
E. NOTES Ni N2 N3 N4
Corrected for end-group effects. Is assumed. Partial allowance for unreacted monomer. Semi-empirical values for a number of other olefins are given in Ref. 143. N5 Value given is for dilute solution. Values determined for complete range of composition; maximum (14.4) at 50 mol% monomer. N 6 No allowance for unreacted monomer. N 7 Strongly dependent on both monomer concentration and temperature. N 9 Corrected for enthalpy of glassy state. N i 0 - AS s s assumed to be 120.3 J/Kmol. N n Zero heat not necessarily in conflict with observed polymerizability below — 40 0 C. Additional loss of free energy may be provided by the crystallization of the polymer. N12 Polymer largely insoluble and remains in suspension. N13 After correction for species in vapour other than formaldehyde. N14 In the presence of a few per cent methylene chloride. N15 From measurements in methylene chloride, benzene and 1,4-dioxane. N i6 From measurements in benzene. N n From measurements on vapor-solid equilibrium. N i8 From measurements in both methylene chloride and nitrobenzene. NI 9 From measurements in 1,2-dichloroethane. N 20 Value calculated by the compiler of this table from data in Ref. cited. N21 Numerical values for heats of copolymerization are listed only for those systems yielding 1:1 copolymers. The values refer to the copolymerization of 0.5 mol of each monomer. In all other cases listed the copolymers have a range of composition; details of the corresponding heats of copolymerization are given in the Ref. cited.
N 22 N 23 N 24 N 25 N 26 N 27 N 28 N 29
N 30 N 31 N 32 N 33 N34 N35
Where no solvent is specified in the seventh column, the symbol AH ss denotes that the measured heat is for a liquid mixture of monomers going to a solution of copolymers. AH\c denotes the heat change for pure liquid monomers going to condensed amorphous polymer. (This symbolism differs from that in Ref. 1.) The states of monomer and/or polymer are not stated in Ref. but are likely to be the ones given. Value calculated from measurements on mixtures containing excess B. Value calculated from measurements on mixtures containing excess A. Value in Ref. 11 corrected using entropy of monomer in Ref. 94. From measurements in both benzene and cyclohexane. Standard state: mol fraction of monomer = 0.1. After correction for species in vapor other than formaldehyde. Numerical values for entropies of polymerizaiton listed are for systems yielding 1:1 copolymers. The values refer to the copolymerization of 0.5 mol of each monomer. The symbolism and standard states are the same as used for the heats of copolymerization (see N 2 i). Value of A5° for the composition of polymer indicated. No allowance for free energy of mixing of polymer and monomer. Floor temperature (hypothetical for supercooled liquid). Floor temperature. Calculated value. Not measurable experimentally because of side reactions. Small amount of vapor dissolved in the polymer: approximately gc.
N 36 Hypothetical value for acetone as a gas at 1013 mbar pressure. N 37 Decreases with increasing polymer concentration (Ref. 112,160,289). N 38 Recognised that polymerization over WCl 6/EtAlCl 2/ EtOH yields an equilibrium mixture of unsaturated cyclic rings (CsH 14)«. Species up to n = 15 have been identified and higher cyclic polymers are also likely to be present. No firm equilibrium data exist as yet. N 3 9 dr c /dP=19deg/kbar. N 40 Value in [M] column is the mol fraction of monomer. N41 Decreases with increasing polymer concentration in methylene chloride, in benzene and in 1,4-dioxane (Ref. 159). N42 Kn values determined for cyclic monomers, n = 1-8. N43 Extrapolated value. N 4 4 For equilibrium concentrations of linear oligomeric species see Ref. 294. N45 Note the substantial discrepancy between the two sets of results with nitrobenzene as solvent. N 46 Value in [M] column is the volume fraction of cyclic monomer (rings of all sizes). N47 Concentration of rings, rc = 13-oo, taking mol. wt. = 74 (value for n— 1); Kn determined for cyclic monomers, n — 3-400. N48 Corrected for isomerization effect. N 49 Uncorrected for isomerization effect. N 50 Equilibrium concentrations of A and B lower than expected from values for homopolymerizations. N51 Polymer is -{CONHN(COMe)f. N 5 2 Polymer is 4CH 2 CH 2 N(COR)J-. N53 cis and trans forms of polymer. N 5 4 c'(I)^(IIXc(III) refer to crystal forms I, II, III of monomer. N 5 5 Standard state is IM, calculated from data in Ref. 148. N56 Polymer dissolved in monomer; equilibrium concentration in mol/L. N 5 7 Tc calculated from AH?JAS°lc or A#S°S/ASS°S. N5g Valid in concentration range 2.3 to 4.6 M. N59 Corrected for monomer-polymer interactions; required temperature variable interaction parameter. N6O Data from Ref. 292, with corrections for monomer adsorbed in polymer. N 6 i Ic data from Ref. 231 combined with vaporization data.
N 62 Calorimetry in solution with adjustments for solution enthalpies. N63 With heat capacity adjustment for T change: may apply to N 62N64 From group method calculations; AG° (298K) value given in brackets in kJ/mol; Tc refers to standard state conditions, PA = PB = I atm. N65 AHP by method 4a in close agreement. N66 Ring opening polymerization giving 78% trans polymer. N 67 Polymer is N 68 Calculated from solution values with experimentally determined data. N 69 Calculated from solution data utilizing monomerpolymer interaction parameters, see Ref. 130. N 70 Mixture of 1,2 and 1,4 polymerization. N71 Includes adjustment for the presence of small concentrations of other cyclics; Sn 7^ S 8 . N 72 Calculations based on standard enthalpies of formation of Sn and AHP (S 8 ). N73 Calculation based on standard entropies of Sn and AS P (S 8 ). N 7 4 Values apply in temperature range below the appropriate ceiling temperature, see Section C, Table 10, under "Monomers Giving Polymers Containing O in the Main Chain, Bonded to C Only." N 7 5 Obtained by extrapolation of kinetic data. N 7 6 Ring opening at S-C bond. N 7 7 c'(I), C7CII) refer to crystal forms I, II of polymer. N 7 8 Average Temperature
N 7 9 Polymer is
N8o Polymer is
N 8 i Polymer is
N82 Polymer is
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A c t i v a t i o n a n d
E n e r g i e s
o f
T e r m i n a t i o n
R a d i c a l
P r o p a g a t i o n i n
F r e e
P o l y m e r i z a t i o n
T. F. M c k e n n a Laboratoire de Chimie et Procedes de Polymerization, Villeurbanne, Cedex, France A . M . Santos Faculdade de Engenharia Quimica de Lorena-Faenquil, Lorena, Sao Paulo, Brazil
A. Introduction B. Tables Table 1. Dienes Table 2. Olefins Table 3. Acrylic Derivatives Table 4. Methacrylic Derivatives Table 5. Vinyl Halogens Table 6. Vinyl Ethers and Vinyl Esters Table 7. Styrene and Derivatives Table 8. Vinyl Heteroaromatics Table 9. Miscellaneous Compounds C. References A.
11-415 11-416 11-416 11-416 11-417 11-418 II-420 11-421 11-421 II-422 II-423 II-424
INTRODUCTION
The conversion of a free radical homopolymerization as a function of time is usually expressed by the following equation:
where x is the conversion, t the time, fep, ku and k& the propagation, termination and initiator decomposition rate constants, respectively, / the initiator efficiency and / the initiator concentration.
It is generally assumed that the temperature dependence of free radical polymerization rate constants can be expressed using the well-known Arrhenius equation:
where Ao is the frequency factor, R the universal gas constant, T the absolute temperature, and E the activation of the reaction in question. Measurement of kp and kt at different temperatures allows one to determine values of the activation energies of the same two reactions, Ep and E1, respectively. If we accept this representation, then the overall activation energy of a homopolymerization can be written as
The value of the activation energy for the initiator decomposition reaction, 2Jd, can often be estimated separately. When data are not available for Ep and Et as separate quantities, the term (Ev —\Et) can be used to model the polymerization reaction. In the following tables, all energies are reported in terms of kJ/mol, and any appropriate remark(s) associated with the data are presented.
B. TABLES TABLE 1. DIENES Monomer
Ep
Butadiene
10.9 38.9 24.3 & 20.9 20.5 35.7
Et
Ev — \Et
8.42
Chloroprene Dimethyl butadiene Isoprene
40.6 37.7 46.0
Refs.
In gas phase In emulsion In gas phase In gas phase Solution polymerization in CCl4; temperature range: 303-333 K For emulsion polymerization, supposing w = 0.5 Thermal and photoinitiation; temperature range: 278-333 K; kp measured by ESR In emulsion In emulsion In emulsion
5.9
38.9 1,3-Hexadiene
Remarks
13 14 16 21 90 91 92 35 45 15
TABLE 2. OLEFINS Monomer
Ev
Acetylene Ethylene
21.4 34.3 18.4 23.9 46.4
Et
£ p -|£ t
1.3
17.8
33.5
29.7 31.0
36.8 29.7 40.0
6.22 10.0 15.2
25.1 20.8 29.7 32.5 36.9 31.4
-1.59 3.13 10.0 4.19 1.05
Refs.
In gas phase In gas phase Calculated using results of Ref. 24 In gas phase High pressure in gas phase (up to 300 NPa); initiated by oxygen; temperature range: 60-250 0 C; conversion found by gravimetry High pressure polymerization (up to 300 MPa); initiated by DTBPO; temperature range: 130-1650C Activation volumes (cal/mol/atm): propagation: — 19.7, termination: 13.0
Estimation for simulation of emulsion copolymerization with vinyl acetate 14.2 31.6
Propene Isoprene
Remarks
30.3
4.2
17.6 ± 0.31
15.3 ± 0.26
30.2 23.4 41.0
6.44
Activation volume = - 26.2£ x 10~6 m3/gmol Activation volume for propagation = — 0.5 cal/mol/atm Activation volumes (cal/mol/atm): propagation: —16.8 ±0.1; termination: 9.2. Optimized from values of industrial runs In gas phase In emulsion
21 21 35 44 73 82 93 94 95 96 97 98 99 100 101 102 103 104 105 106 21 15
TABLE 3. ACRYLIC DERIVATIVES Monomer
Ep
Et
Acrylamide A B C D E
11.7 ± 1.2 16.3 ± 0.8 18.8 ± 1.9 20.5 ±0.8 25.1 ±0.9
11.7 ±0.8 10.9 ± 0.4 10.9 ±0.4 7.9 ±0.4 0±0.8
22 ±0.2 20 ±0.2 11.5 57.8
Ep-\Et 5.8 dz 1.6 10.9 ± 1.3 13.4±0.3 16.9 ±1.0 25.1 ±1.3
6.2 10.46
iVyV-methylene-bis-acrylamide
9.3
Remarks
Refs.
Solution polymerization in H2O/DMSO mixture with potassium persulfate; initiators: H 2 O: DMSO: (A) 100:0 (B) 88:12 (C) 65:35 (D) 38:62 (E) 0:100 pH 1 pH4 Compilation of data, validated for inverse suspension polymerization Compilation from various sources, validated for solution polymerization Aqueous polymerization with temperature range: 293-313 K
68
111 112 113
Acrylic acid 23.4 21.7 14.1 - , sodium salt
(1) 67.5 (2) 72.1
- , chromium salt
33.5
-, zinc salt
13.0
-, butyl ester
8.8 52.3 15.5
0 73.7 38.1
14 ± 6 £ p - ET = 0 9.6 ± 0.56
- , ethyl ester - , methyl ester
41 29.7 19.7 31.8 ±2.5
12.3 22.2 -0 20.1 ±0.8
-, methyl oc-acetoxy ester
35.5
46.8
-, methyl a-butoxy ester
30.5
25.1
Acrylonitrile
17.2 16.2
22.6 15.5
107 108
109 By PLP; temperature range: 288-328 K 110 Thermally induced solid state polymerization; 87 two methods to find Ep: (1) ESR, (2) DSC; temperature range: 60-160 0 C Polymerized with styrene-arsenic sulfide 114 complex initiator in DMF Initiated with an As2S3-styrene complex in 115 DMSO at 363 K 8 At 20% conversion 26 From PLP-GPC; temperature range: 116 (208-266 K); bulk polymerization 109 From PLP; temperature range: (298-353 K); 117 conversion range: (10-80%); bulk polymerization; P = 1 bar. From PLP; conversion = 30% in bulk 118 polymerization By PLP-GPC; bulk polymerization with 119 photoinitiators: benzoin and 2,2dimethoxy-2-phenylacetophenone; temperature range: 298-303 K 109 Gamma ray induced solid state polymerization; temperature range: 243-283 K
40.7 31.8
-, 1,3-hydroxyneopentyl ester
Initiation with APS; temperature range: 309.5-324.5 K; solution polymerization at pH 0 4.38 Precipitation polymerization; temperature range: 313-333 K
5.9 8.5
109 Measured by dilatometry in both benzene 120 and 1,4 dioxane (kp/k®-5 higher in dioxane) By ESR; temperature range: 303-333 K; 121 solution polymerization in 1,1,2-trichloroethane; initiator: 2,2 '-azobis(4-methoxy-2,4dimethylvaleronitrile) (V-70) By ESR; assuming Ed = 109.5; 121 solution polymerization in 1,1,2-trichloroethane; initiator: 2,2 /-azobis(4-methoxy-2, 4-dimethylvaleronitrile (V-70) In water solvent 25 In DMF solvent 32
References page II - 424
TABLE 3. cont'd Monomer
Ep
Et
Ep — \Et
Acrylonitrile {cont'd)
26.8
~0
6.8 21.4
29.6
7.0
Remarks In DMF solvent Estimated from data on solution copolymerization with styrene as azeotrope
42.7
D-Fluoroacrylic acid -, methyl ester
23.9
Polymerization in NaSCN solution with Mn(CsH702)2 as free radical initiator; temperature range: 295-313 K; value estimated from overall activation energy with Ed = 58.6 kJ/mol
9.6
Solution: acrylonitrile; initiator: AIBN; (assume Ed = 128 kJ/mol)
Refs. 37 109 122 123 124
71
TABLE 4. METHACRYLIC DERIVATIVES Monomer
Ep
Et
Methacrylamide
15.5 22.1
16.7
Methacrylic acid
17.7
-, butyl ester - , butyl ester
17.4 18.4 20.4 20.9 21.8 ± 0.27 22.9 ±1.1
4.6 12.7 8.8
Ev -\Et 7.1
16.1 14.1 16.7
23.3 20.4 20.5 ± 0.24 - , i-butyl ester
22.5 ± 0.42 21.5 ± 0.35
-, f-butyl ester
27.7 ± 2.5
-, chloromethyl ester
5.5
-, cyanomethyl ester
~ 8.4
- , dodecyl ester (lauryl ester)
15.5 29.8 21.5 ±0.34 13.7 16.2
- , ethyl ester
23.2
8.9
18.0
21.3
7.1
17.7 16.5
Remarks Solvent: water By PLP; temperature range: (288-328 K); pH 1 By PLP-GPC; 33% monomer in methanol; temperature range: 293-333 K
Refs. 34 110 125
109 Gamma ray initiation 27 Kinetics from calorimetry 55 Temperature range: 35-27°C Quoted in 58 By PLP 131 By PLP-GPC; P = 1000 bars; temperature 141 range: - 10 to 6O0C Temperature range: 25-55°C; by PLP bulk 135 polymerization; photoinitiator: benzoin 126 By PLP-MWD; bulk polymerization; 127 pressure: 1 bar; photoinitiator: benzoin 131 By PLP-MWD; bulk polymerization; 127 pressure: 1 bar; photoinitiator: benzoin Temperature range: 9-66°C; by PLP with 128 benzoinethyl ether as free rapid initiator Ampoule and emulsion polymerization; 78 AIBN initiator Solution: acetonitrile AIBN initiator 87 calculated, assuming Ed of AIBN= 128 kJ/mol from overall activation energy; temperature range: 50-70 0 C Quoted in 58 Bulk polymerization with BPO initiator; 66 temperature range 60-80 0 C; maximum conversion 1% ByPLP 131 135 By PLP-MWD; bulk polymerization; 135 photoinitiator: benzoin Gamma ray initiation; temperature range: 52 — 30 to 55 0 C; kinetics from calorimetry Quoted in 58 Data from bulk and solution (50% DMF); 63 AIBN initiator; kinetics from GLC and gravimetry
TABLE 4. cont'd Monomer Methacrylic acid, ethyl ester {cont'd)
Ev
Et
27.0 22.8 ±0.35 20.46
- 6.6
Ev-\Et 30.4
27.0 22.9 ± 0.46 22.2 16.3 -, hexadecyl ester - , hexyl ester - , methyl ester
20.1 18.0 26.4 18.4 24.3 20.9
18.8 11.9 0 2.1 0-16.7
10.5 ~ 8.4 20.5 18.4 23.2 20.9-12.6
18.8 22.4 22.8
13.2
11.2
22.6 ± 2.5
Tends to 0
22.6 ± 2.5 13.0
19.7 18.2 ± 0.2
3.3 2.9 ± 0.0
18.0 16.7 ± 0.2
23.4 20.4
~ 10.5
15.1
20.9 ±3.3
1.6 ± 0.4
20.1 ±3.6
31.3 21.3 ±0.25 18.2 26.4
11.7
29.1
3.55 22.6 18.9 15.7 18.0 18.2 24.2 18.3 31.3
0 ± 2.5 2.93
2.9 26.9 2.94 21.1 36 -14 ±8 - 1 6 ±15
22.2 ±0.3
Remarks
Refs.
Quoted in 79 ByPLP 131 By PLP; temperature range: 298-328 0 C; 135 bulk polymerization; photoinitiator: benzoin Evaluated for emulsion polymerization 129 By PLP-GPC; bulk polymerization, 127 pressure: 1 bar; photoinitiator: benzoin Bulk polymerization; initiator: AIBN 130 Solution polymerization in benzene; 130 initiator: AIBN Quoted in 58 Quoted in 58 4 7 28 Termination by combination or 30 disproportionation 47 In emulsion 31 Gamma ray induced; temperature range: 48 - 25 to 55 0 C; used a combination of DCS and inhibition with DPPH to find kinetic parameters Polymerization in benzene; DMDM initiator; 49 temperature range: 50-80 0C Bulk polymerization; DBPO initiator; 53 maximum conversion 25%; ESR used to find kinetic parameters Isothermal bulk; polymerization with AIBN 56 initiator; DCS used to follow reaction; value found assuming E& AIBN= 128 kJ/mol Quoted in 58 Bulk polymerization; AIBN initiator 64 temperature range 15-3O 0 C; reaction followed by spatially intermittent polymerization; DP 10000-15000 Bulk polymerization; AIBN initiator; 65 1-butanethiol used as CTA; value assumes Ed AIBN= 128 kJ/mol Solution: benzene; AIBN initiator; kinetic 68 data from molecular weight data; maximum conversion 5% Emulsion data; particle sizes from turbidity; 72 potassium persulfate initiator Solution: benzene; AIBN initiator; kinetic 77 parameters from intermittent illumination Bulk polymerization 85 ByPLP 131 132 133 109 Temperature range: 293-353 K 156 Suspension polymerization 134 Spatially intermittent polymerization/ 164 emulsion polymerization 135 136 137 Solution polymerization in toluene 138 139 1 Bar; temperature range: 323-353 K, 140 low conversion 100 bars 1000 bars 141
References page II - 424
TABLE 4. cont'd Monomer
Ep
Methcrylic acid, methyl ester (cont'd)
22.4
Et
Ev-\Et
Remarks PLP plus GPC for bulk polymerization; temperature range: 272-363 K
22.2 23.9
22.2
nonyl ester octyl ester phenyl ester o-methylphenyl ester 0-ethylphenyl ester 6>-iso-propylphenyl ester /7-methylphenyl ester p-ethylphenyl ester /7-iso-propylphenyl ester /?-te7t-butylphenyl ester ethyl a-Benzoyloxymethyl ester
17.2 15.9
13.0 12.1
- , ethyl a-acetacetoxymethyl ester - , 2-(3-chloro-3-methylcyclobutyl)-2hydroxyethyl ester Methacryloyl fluoride
Methacrylonitrile
10.4
20.9
- , «-Phenyl-a-methylene-p-lactam
TABLE 5.
10.9 9.7 9.2 9.6 12.2 14.4 10.6 9.3 13.2 9.5 11.5 24.55 30.68
48.1 29.7 ±1.5
142 143 144 145
2.9
-, -, -, -, -, -, -, -, -, -, -,
Refs.
37.7
22.8
By PLP-GPC; bulk polymerization; pressure: 1 bar; photoinitiator: 2-hydroxy-2,2-dimethylacetophenone; temperature range: 272-363 K By PLP-GPC; bulk polymerization; 146 pressure: 1 bar; photoinitiator: benzoin; temperature range: 272-363 K Quoted in 58 Quoted in 58 147 147 147 147 147 147 147 147 By ESR, assuming E& = 129; solution 148 polymerization in benzene; initiator: AIBN 149 Polymerization in dioxane using BZ2O2 as 150 initiator Solution: MEK; AIBN initiator; calculated 81 using Ed AIBN = 128 kJ/mol; temperature range: 50-70 0 C 20 By PLP; solution polymerization in 151 benzylactone; temperature range: 283-333K Solution polymerization in n-methyl-2152 pyrrolidone with AIBN (calculated from £ O v assuming Ed of AIBN= 129 kJ/mol)
VINYL HALOGENS
Monomer
Ev
Tetrafluoroethylene
17.4 5.4 30.0 16.0
Vinyl bromide Vinyl chloride
Vinylidene chloride
27.6 104 37.7 ± 5.9
Et 13.6 0.8 16.3 17.6
18.2 167 20.9 ± 10.5
Ep-\Et 10.6 5.0 21.8 7.4 12
20.5 27.2 ±11.1
Remarks
Validated for model of suspension polymerization For suspension polymerization Solvent: hexane Solution: N-methylpyrrolidone; AIBN used as photoinitiator; most runs < 1% conversion
Refs. 46 43 42 17 153 154 9 67
TABLE 6. VINYL ETHERS AND VINYL ESTERS Monomer
Ep
Et
Butyl vinyl ether
Vinyl acetate
E9-\Et 46.4
18.0 30.6 13 18 18 39±3 19.6 ± 2.9
O 21.9 0 <4 0 0
Refs.
Bulk polymerization; initiator DTBPO; assume Ed = 51.5 kJ/mol (Ref. 82) at given conditions; GPC data used to find kinetic parameters
18.0 19.6 13 16-18 0 19.6 ± 2.9 ~ 26.4
20.5 ±0.39 26.4 23.5
Remarks
Bulk polymerization; DBPO and cyclohexyloxyperoxide initiators; ESR used to find kinetics Bulk polymerization; DBPO and cyclohexyloxyperoxide initiators; temperature range: 55-70 0 C; DSC used for kinetics; maximum conversion 20%
11.7 Validated for emulsion copolymerization with ethylene; temperature range: 293-323 K; pressure range: 0-34 bar 14.2 28.1
19.7 ± 2.9 23.7 23.6 24.2 26.4 35.2
0
Temperature range: 293-353 K For emulsion polymerization Emulsion polymerization
4.0 13.4 14.2
Rotating-sector method; bulk polymerization; photoinitiator: benzoin By PLP-MWD; bulk polymerization; photoinitiator: benzoin
27.8
84
1 5 6 18 22 38 53 57
131 133 102 155 109 156 157 158 159 160 155 161
TABLE 7. STYRENE AND DERIVATIVES Monomer Styrene
Ep 49.0 27.2±4.2 26.0 32.5 31.0 & 35.0 54.0 & 59.0 25.0 73.6 29.0
E1
Ep-\Et
11.7±4.2 8.0 9.9
21.3 ±6.3 22.0 27.5 In emulsions In emulsions
2.0
24.0
37.7 9.2 ± 0.5
24.9 ± 0.4
34.1 29.0 ±3.0
Refs.
In emulsion
25.1
29.5 ± 0.1
Remarks
Gamma ray induced; bulk liquid phase polymerization; maximum conversion 10%; temperature range: 19-74 0 C Low conversion; bulk polymerization; ESR spectroscopy used for kinetics Bulk photopolymerization; kinetics from spatially intermittent polymerization technique; temperature range: 15-36 0C DP 2400-2700 AIBN initiator; assume Ed = 128 kJ/mol; bulk polymerization 1-butanethiol as CTA; maximum conversion 0.4% In emulsion; reaction followed by dilatometry
2 3 10 11 15 19 29 36 42 50 51 64
65 70
References page II - 424
Table 7. cont'd Monomer
Ep
Et
Ep-\Et
32.2 32.5
14.5
25.2
17.7 29.6
Remarks Emulsion data; assume N = 0.5, sodium persulfate and sodium bisulfite initiators Bulk polymerization; AIBN initiator; temperature range: 45-100 0 C In emulsion; sodium persulfate initiator
25.2 37.8 ±1.7 39.8 36.1
15.6 18.7
29.5 44.4 29
36.4
37.5 ± 1.6 30.8
10.91
30.0 29.0 32.3
31.5 31.5 31.5 18
9.5 14.2
32.5
/?-Bromostyrene o-Methylstyrene /7-Methylstyrene
32.0 58.2 32.0
a-Methyl styrene Divinylbenzene
29.6 29.6 54.3 35.5
30.5 8.27 8.4 29.8
Ep
Et
By ESR; temperature range: 273-403 K Suspension polymerization; conversion less than 0.8; temperature range: 283-353 K Spatially intermittent polymerization/emulsion polymerization High conversion suspension polymerization Emulsion polymerization; temperature range: 318-338 K ESR; temperature range: 323-363 K By PLP; temperature range: 298-328 K By PLP; temperature range: 293-353 For dp (degree of polymerization) >4 For all chain lengths together Bulk and diluted systems initiated by (p-acetylbenzylidene)triphenylarsonium Measurements by rotating sector method; initiators: AIBN (30-50 0 C), BPO (70-90 °C) Styrene Perdeuterated styrene PLP; temperature range: 303-363 K; in bulk Measurments by ESR; photo and thermal initiation; temperature range: 293-363 0C PLP; temperature range: 261-366 K; bulk polymerization with photoinitiators: benzoin and 2,2-dimethoxy-2phenylacetophenone (DMPA) In emulsion In emulsion
25.4
Searched by EVM
Refs. 76 79 89 132 109 156 162 163 164 165 166 167 168 169 170 171
172 173 174
39 36 36 109 175 176 177 178
TABLE 8. VINYL HETEROAROMATICS Monomer
Ev-\Et
3-Methylene-5,5-dimethyl-2-pyrrolidone
8.2
Methylene-Af-methylpyrrolidone
20.1
N-Vinylcarbazole 2-Vinylpyridine Af-Vinylpyrrolidone (A) (B) (C) (D)
28.9 33.5 29.7 68.0 40.Od= 2.0 31.6 ±3.0 23.0
20.9 6.7 19.0 13.0 9.0 8.0
23.0 26.4 58.5 33.5 ±2.0 27.5 ±3.0 19.0
Remarks Solution polymerization in DMSO with AIBN (calculated from £ov assuming £ d o f AIBN =129 kJ/mol) In bulk and in solution with acetonitrile; AIBN initiator (assume Ed = 128 kJ/mol) Low conversion In various solvents: (A) Water (B) L-Propanol (C) Methanol (D) Ethyl acetate; rates followed by dilatometry
Refs. 179 86 42 40 41 61
Table 8. cont'd Monomer
Ev
E1
E9-±Et 4.8 (1) 12.8 (2) 10.8
65.8 ± 0.1 29.7
Remarks
Refs.
Template polymerization in DMF; AIBN initiator; DSC used to follow reaction Solution polymerization In DMF; assume Ed of AIBN in DMF =142 kJ/mol; reaction followed by DSC in 2 modes: (1) dynamic (2) isothermal Aqueous phase polymerization with potassium peroxydiphosphate Ag + ; temperature range: 293-323 K
6.7
4-Methylene-4H-l,3-benzodioxin-2-one
11.2
Solution polymerization in rc-methyl-2pyrrolidone with AIBN (calculated from Eov assuming Ed of AIBN= 129 kJ/mol)
74 75
180 181 182
TABLE 9. MISCELLANEOUS COMPOUNDS Monomer Acetaldehyde
Ep
Et
Ep-\Et
46.0 ± 6.3
Diethyl fumarate
25.0 ± 2.0
26.5 Diisopropyl fumarate Formaldehyde D-Methylene-y-butyrolactone
16.8 8.4
Vinylferrocene
20.0
16.3 12.1 7.9
N-Vinyl-methylacetamide ot-Ethyl, P-hexafluoroisopropyl itaconate
26.9 18.0
57.4
29.0 21.0 28.5
30.0 24.0 66.1
Diethyl itaconate
Diisopropyl itaconate Di-«-Butyl itaconate (DBI)
0.5 4.35
l,l-bis[(l-adamantyloxy)carbonyl]-2-vinylcyclopropane Diethylene glycol bis-allyl carbonate (DEAC) A^-Acryloyl-2,2-dimethyl-5®-phenyl-l, 3-oxazolidine (ADPO)
87.1 53.6 29
21
Remarks
Refs.
Radiation induced in solid phase; calorimetry used to follow reaction; temperature range: 130-150 0 K Bulk polymerization; AIBN initiator; (assume Ed = 128 kJ/mol) dilatometry used to follow the reaction; temperature range: 60-80 0 C Assuming Ed = 129; by dilatometry; bulk polymerization; initiator: AIBN
54 59
183
184 Quoted in 54 Solution: DMF; AIBN initiator (assume 80 Ed = 128 kJ/mol); E9-E1K 12.1 Note nonclassical kinetics; overall 62 activation energy does not equal Ed + Ep — Et/2\ can approximate Et = that of styrene Solution: methanol; AIBN initiator; 83 maximum conversion 10%; temperature range: 25-75 0C Polymerization in benzene catalyzed by 185 dimethyl 2,2-azobisisobutyrate Polymerization in benzene catalyzed by dimethyl 2,2-azobisisobutyrate 186 (no SnCl4) (0.342 mol/1 SnCl4) Polymerization in benzene catalysed by 187 dimethyl 2,2-azobisisobutyrate Assuming Ed = 129; by ESR; solution 188 polymerization in benzene; initiator: AIBN Assuming Ed = 129.1; By ESR; 188 solution polymerization in benzene; / initiator: 2,2 -azobis(isobutyrate): MAIB Ring-opening solution homopolymerization 189 in benzene; temperature range: 323-343 K; with AIBN (assume £D,AIBN = 123.5 kJ/mol) Rotating sector method; Initiator: BPO 190 Assuming Ed = 124.3; temperature range: 191 323-343 0 C; solution polymerization in benzene; initiator: 2,2'-azobis(isobutyrate): MAIB
References page II - 424
Table 9. cont'd Monomer
Ep
Et
Af-Cyclohexyrmaleimide (CHMIm)
40.9
20.1
Af-Acryloyl-/?-aminobenzoic acid
Ep-\Et
48.3
Remarks By ESR; temperature range: 313-333 K; solution polymerization in benzene; initiator: AIBN Assuming E^= 129; solution polymerization in dioxane; initiator: AIBN
Refs. 192
193
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Activation Volumes of Polymerization Reactions G. Luft n l stiut fur Chem siche Technoo lgei, Technsiche Hochschuel, Darmsad,t FR Gem r any Yh Oag Research n Istiute for Sovlo t.erm loT*echnoo lgy, Takamas tu, Takamas tu, Japan
A IA trocd uo co tinVo 11e 4 -2 9o B..Rn v t i a t i n u l m e s o f S o m e P o y l m z r i a itn e a c o i t n s 1 1 4 3 2 C .. A c v titia o titin V o u llm e s o ff C n I tih aatn o rP D ep co m p oo s itin114 1514 -35 D A c v a o n V o u m e s o i r o a g a o i t n 3 E Ac cv v ao o nV Vo o u me es so off C Ch ha an n Tre m irao itn 114 -36 F.. A titia titin u llm ii T arn se fn Reactions G. Influence of Pressure on Copolymerization Table 1. Copolymerization Parameters Table 2. Reactivity Ratios of Terpolymerization Table 3. Activation Volumes Table 4. Q, e Values H. References A.
11-436 11-437 II-437 II-438 II-439 II-440 II-440
INTRODUCTION
The activation volume is included in the pressure dependence of the reaction rate constant (1-4): (Al) where k is the reaction rate constant, p is the pressure, T, the temperature K the volume, and Av*, the activation volume (analogous to the activation energy). It is the difference between the partial molar volume of the activated complex, as formed in the transition state theory by the efficient collision of molecules, and those of the initial reactants. The sign of the activation volume depends on the type of the chemical reaction. If new bonds are formed in the transition state, the activated complex is larger than the
* Table 3. Activation Volumes.
initial species, and hence the activation volume is positive. Inversely the activation volume is negative if bonds are stretched and broken. For a rough calculation of the activation volume, we can assume that the formation of new bonds as well as stretching occurs along the axis of a cylinder, whose constant cross section is determined by the van der Waal's radii dmA/2, dmB/2, and dmC/2 of the atoms A, B, C:
(A2) with A A B = (0.10-0.35) dmAB, A B ,c = (1.10-1.35)J m B C ^mB,c (see Refs. 2,5,6), N is the Avogadro number, dmAB, dmBC = bond length (values, see Ref. 7), and d mB c is the interatomic distance at the minimum of potential (sum of van der Waal's radii), d mA / 2 , dmB/2 (see Ref. 8). The stretching of the bonds in the transition state is about 0.01-0.1 nm, whereas the change in the distance dmB£ between the unbonded atoms is usually larger (up to 0.25 nm). If the decomposition of the activated complex causes only small changes in the bond length or in the distance between the atoms, its partial molar volume differs from that of the activated complex only slightly. Hence we can assume
where Av is the excess of the partial molar volume of the reaction products over the partial molar volumes of the initial species. This simplification is valid for reactions in which products of cyclic structure are formed, as in the dimerization of cyclopentadiene, with Ai>* ~ Av = — 30cm 3 /mol (9, 10).
A second term is added to the volume change of the reacting molecules in the transition state if a polar solvent is involved. This term takes into account the change in the packing density of the surrounding solvent molecules due to the arising or disappearing of electrostatic charges between the solvent and the reactant species. This volume change is negative in bimolecular association and positive in unimolecular dissociation and tends therefore to counteract the effect of volume change during the reaction. The activation volume can be determined according to Eq. (Al) from rate measurements at different pressures and constant temperature using a semilog plot of reaction rate constant versus pressure. In this evaluation the value of (QV/dp)T/V can often be neglected, because the compressibility of fluid reactants and compressed gases is generally small at pressures above 100-200MPa. At very high pressures the increase of the reaction rate constant at negative activation volume is retarded by the lower mobility of the molecules due to the increased viscosity. This effect was first measured by Hamann (11) in an examination of the alkaline etherification of ethyl bromide at pressures up to 4000MPa. It was also found in the polymerization of styrene by Nicholson and Norrish (12). In order to obtain the reaction rate as an explicite function of pressure, Eq. (Al) can be integrated, neglecting the compressibility and assuming that the activation volume does not change greatly with pressure (13): (A3) where kp is the reaction rate constant at pressure p and fco is the reaction rate constant at reference pressure po. According to Eq. (A3) the reaction rate constant increases exponentially with pressure if the activation volume is negative and decreases if Ai;* is positive. Eq. (A3) is valid only in the high pressure range (p > 50MPa). At low pressures the compressibility cannot be neglected anymore, and the activation volume changes noticeably with pressure, especially in the neighborhood of the critical point. Simmons and Mason (14) studied the dimerization of chlorotrifluoroethylene at pressures up to 10 MPa. They found that the value of the negative activation volume decreases first with pressure and then increases rapidly. It has a maximum at the critical point and after decreasing again it approaches asymptotically a constant value. The authors describe the pressure dependence of the rate constant, taking account of the partial molar volume of the initial reactants as well as that of the activated complex by the use of suitable equations of state (e.g., Redlich-Kwong or virial coefficient equations). In order to appreciate the influence of pressure on the reaction rate constant one can compare it with the influence of the temperature: an increase in pressure (activation volume Av* = —25cm3/mol) at a temperature of 500C from 0.1 to 450MPa corresponds to a temperature increase (activation energy E = 84kJ/mol) from 50 to 1050C.
Experimentally determined overall activation volumes of some polymerization reactions are listed in Section B. The data were determined from the dependence of the overall rate constant of the polymerization reactions on pressure. The values are more or less negative, hence the rate of polymerization increases with pressure. The overall activation volume is composed of the activation volumes of the different polymerization steps, initiation, or initiator decomposition, chain propagation and chain termination: (A4) where Av* is the activation volume of chain propagation, Av^ is the activation volume of initiation with respect to initiator decomposition, and Ai;* the activation volume of chain termination. The activation volumes of initiator decomposition (values in Section C) are always positive because this reaction is a unimolecular dissociation, in which a bond (e.g., the O-O bond in peroxides and peresters or the N-N bond in azo-compounds) is stretched in the transition state and finally broken. As mentioned before, Ai;^ depends on the solvent. It can significantly be influenced by a change of electrostatic charges, viscosity, and cage effects. The activation volume of initiator decomposition is different when induced decomposition is involved at high concentration of the initiator or when the initiator decomposes in a concerted mechanism. Av^ is small for two-bond scission initiators (15). The activation volume is higher for one-bond scission initiator, bulky molecules, and when more bonds brake simultaneously. The data collected in Section C were obtained in separate measurements, observing the decrease of the initiator concentration with time at different pressures. The disappearance of the initiator can also be measured during polymerization by observing the light absorption at a characteristic waver length or using scavenger techniques. In the chain propagation reaction, the decrease in the distance between the radical and the monomer molecule is greater than the increase in length of the double bond of the monomer. Hence the activation volumes Ai;* listed in Section D are always negative. The data for Ai;* are measured at high pressures by the method of the rotating sector together with Ai;*, the activation volume of chain termination. The activation volumes Ai;* are also negative as shown in Section E. Mostly the termination reactions are diffusioncontrolled. The reactant molecules undergo translational diffusion at first to form a collision pair. It follows the movement of the reactive sites on these molecules into a position favorable to chemical reaction. This process has been considered to be the rate-determining step. The activation volume involved in this so-called segment diffusion is observed. When chain termination is governed by translational diffusion, the activation volume, Ai;*is for viscous flow, is the key parameter for the evaluation of the influence of pressure.
The chain transfer of a radical to the monomer, to a "dead" polymer, or to a modifier molecule is mostly favored by the pressure which means that the activation volumes should be negative, whereas the activation volume of the intramolecular transfer (by "back biting"), which initiates the formation of short side chains, can be negative or positive. The activation volumes of these reactions are determined from the change in short- and long-chain branching or from the change of the average molar mass or degree of polymerization of the formed polymers with pressure. Under the assumption that the monomer and the polymer concentration do not change over a wide range and that the temperature is kept constant, the following relation can be derived from kinetic considerations:
modulus increase with pressure: (A7)
(A5)
where v = chain length. The small negative activation volume of the intramolecular chain transfer shows that this reaction step, which determines the short chain branching, is less favored by high pressures, which means that polymers with high density and crystallinity can be synthesized at high pressures. Similar considerations also show that the composition of copolymers and thus their molecular structure is influenced by the synthesis pressure. The pressure dependence of the copolymerization parameters r\ and r2, which determine the composition of a copolymer, is expressed by the relationship
where VZG is the number of branches and Av *r is the activation volume of the chain transfer reaction. Analogously, the influence of the pressure on the chain transfer to a modifier can be described by the expression
(A8)
(A6) where P is the average degree of polymerization obtained in the presence of a transfer agent and P n o is the average degree of polymerization obtained in the absence of a transfer agent. Because of the mostly negative sign of the activation volumes (listed in Section F), the radical transfer to the modifier molecule is often slightly decreased at high pressures. The activation volume of degradation reactions which can occur at high temperatures should be positive because bond cleavage increases the volume of the activated complex more than the formation of double bonds from single bonds decreases it. The difference in the activation volumes of the various component reactions results in a different influence of the pressure on the rate constants and leads to modified polymers. Because of its larger negative activation volume the chain propagation reaction is more favored by high pressures than the termination. The chain length and consequently the tensile strength as well as the tensile
where Av*n, Av* 22 are the activation volumes of the propagation reaction between a monomer molecule and a radical formed from the same monomer, and Av *12, Ai>*21 are the activation volumes of the propagation reaction between a monomer molecule and a radical formed from the comonomer. Equation (A8) is valid if the composition of the initial reaction mixture does not change appreciably with pressure. According to Eq. (A8), an increase in pressure favors the inclusion of monomers, which in homopolymerization show a large negative activation volume (e.g., substituted olefins). Values of copolymerization parameters obtained at different pressures and activation volumes of some copolymerization reactions are listed in Section G. When r\ and Yi should be calculated for high-pressure copolymerization, following Alfrey and Price, the pressure dependence of Q, e data must be taken into account. Some values of Q and e for high pressures are collected in Section G. The dependence of the e data of two monomers on pressure is given by the equation
(A9)
References page 11-440
B. ACTIVATION VOLUMES (cm3/mol) OF SOME POLYMERIZATION REACTIONS
Monomer Acenaphthylene Acetaldehyde
Acrylic acid anhydride Acrylonitrile AUyI acetate /V-(4-Anilinophenyl)acrylamide
3,3-Bis(chloromethyl)oxetane Butadiene
Butyl acrylate Butyl acrylate
Butyl methacrylate
2-Cyclopropylpropene-l Diallyl cyanamide Diallyl phthalate 3,3-Dichloropropene-l l,l-Dichloro-2-vinylcyclopropane Diethyl fumarate 3,3,3-Difluorochloropropene-l l,l-Difluoro-2-vinylcyclopropane
Maximum pressure (MPa) 390 150 844 844 844 400 200 850 100 200 300 500 1500 500 500 500 500 100 100 100 300 460 700 100 100 100 300 460 >460 140 140 600 500 500 1000 1000 1000 300 1400 1000 1000
Temp. (0C) 60 100-200 -60 - 70 -78 50 50 80 60 60 60 60 60 60 50 70 95 30 30 20 20 20 20 60 30 20 20 20 20 70 20 80 70 70 40 80 20 60 30 50 20
2,3-Dimethyl-l,3-butadiene Ethylene
1,2-Epoxycyclohexane Az-Hexyl methacrylate Indene Isobutyl methacrylate Isoprene
Solvent
AIBN Diethyamine
DMF DMF THF
Toluene
Benzene
Toluene Benzene
Heptane DEE 250 760 200 190
129 50-70 225-235 80
100-210 110-220 250 110-550 175 300 840-1250 450 800 800 100 1400 1400 1400 1400
200-300 190 130-165 170-240 127-197 135-165 60 20 20 64 60 20-30 20-30 20 20
Initiator0
Heptane Benzene Toluene Ethyl acetate
A^*
-5.8 -12.5 -11.1 - 8.0 -6.2 AIBN -14 AIBN -22* BPO -13.4 AIBN -36.1 -31.2 - 22.3 -15.4 -6.4 BF3/diethyl ether -16 -8.8 -13.3 -17.2 ACN -26.3 ACN -26.3 Radiation -21.0 -21.2 - 5.7 -11.4 AIBN -25.6 ACN -17.4 Radiation -21 -21.2 -5.7 -14.4 AIBN -23 Stannic chloirde -15 TBPB -14 AIBN - 9 . 9 to -11.8 AIBN -14.3 DCPC 0 to 8* AIBN -14^ Stannic chlorde - 30 to - 70 -14 DCPC -15 AIBN -15 Stannic chloride -45 BuLi -36 BuLi -48 DTBP - 2 0 to - 2 3 AIBN - 3 to - 6 Peroxide - 20 to - 26 DCPC -10 Enanthylperoxide - 5 8 to - 6 8 Methylinobutylketone -18 TBPO - 1 8 to - 2 2 TBPP -22.6 Oxygen - 1 2 to - 1 8 Diphenyl disulfide -29 DTBP -17.5 BPO -13 Radiation - 24 -17.4 -21.0 AIBN -23.9 Oxygen -11.0 BPO - 7 . 9 to 18.0 HLOI2O -7.9 HLW2O -9.8C
Refs. 16 127 142 51 52 17 150
55 141 91 154 147
128 90 94,95 53 53 54 130 57 56 18 58 59 59,60 133 46,20 19 73 74 151 114 61 79 21 85 79 55 94 22 122 23 24
Monomer
Isopropenylcyclopropane Itaconic acid
Maleic anhydride Maleimide Methyl acrylate
Methyl methacrylate
a-Methylstyrene
Octyl methacrylate Propylene
Sodium allylsulfonate Styrene
Maximum pressure (MPa)
Temp. (0C)
1400 1400 1400 500 500 500 500
20 70 20 40 50 60 70
500 100 180 270 400 700 200 300 100
20-40 50 20 20 20 20 40 40 30
300 550 100 100 100 100 100 100 400 100
20 20 50 50 40 50 60 70 50 50
100 100 100 100 100 350 500 500 500 500 100
50 50 50 50 50 60 50 60 70 80 30
1600 1600 1600 800 400 400 400 900 208
21 48 83 80-100 80 90 100 22
Radiation Radiation Radiation AIBN BPO BPO BPO Radiation Radiation
273 400 100
25 30 30
Radiation Radiation ACN
200 280 400 600 300 100 200
40 40 40 40 50 50 60
Radiation Radiation Radiation Radiation AIBN AIBN AIBN
Initiator0
Solvent Dichloromethane DMF DMF DMF DMF Methanol Benzene
HI/H2O AIBN Stannic chloride AIBN AIBN AIBN AIBN BPO AIBN Radiation
Peroxide Peroxide ACN Radiation Acetone Benzene Benzene Benzene Benzene Benzene Butyraldehyde Carbon tetrachloride Dichloroethane Ethanol Ethyl acetate H-Hexane Trichloromethane
Peroxide AIBN Peroxide Peroxide Peroxide Peroxide AIBN AIBN AIBN AIBN Peroxide Peroxide Peroxide AIBN AIBN AIBN AIBN ACN
H2O
\v* -10.8 -23.0 -15.0 - 23.2 -27.4 -30.8 -32.3 —4.6 - 1 5 to - 25 -17.6 -21.4 -22.9 -3.6 -12.8 -19 -19 -15.6 -21.8 C -23.6 -13.7 -26.0 -21.6 -17 -19 -21 -23 -25 -19 -21 -20 - 24 -19 -22 -18 -14.5 -13.8 -11.8 -10.7 -26.3 -25.6 C -9.6 -9.6 -12.2 -14 -9.0 -10.8 -12.7 - 5 to - 7 -20.5 -18.6 C + 5.8 -20.9 -18 -17.1 -17.6 C -15.8 -50.5 -4.3 -29.5 -21 -20.2 -15
Refs.
158 140
132 122 129 147
25 26 87,153 93,95 27 129 27 27 27 27 62 27 27 27 27 27 27 18 135
99 28 144
145 137 136 126 89 146 146 146 146 64 27 149
References page II - 440
Monomer
Maximum pressure (MPa)
Temp. (0C)
293 265 265 274
60 80 80 25
274
l,l,2,2-Tetrachloro-l,3-butadiene Tetrahydrofuran Vinyl acetate
Vinyl chloride
25
200-500 100 100
60 50 50
100 400 400 100
50 50 50 50
300 100 100 100 100 400 100 400 268 293 440 300 300 100-600 1400 250-540 100 600 400 400 300
25-30 50 50 50 50 60 50 60 60 60 60 30 40 72 25-80 60 30 20 40 40 40
400 500 390 390 390 390 250 200 300 200 400
65 60 40 50 60 70 50 60 60 60 60
Initiator0
Solvent
Emulsion Emulsion with SDS SDS Emulsion with aerosol OT Emulsion Emulsion with nonionic emulsifier Emulsion Acetone Benzene Benzene Benzene Butyraldehyde Butyraldehyde Carbon tetrachloride Chlorobenzene Chloroform Dichloroethene Ethanol Ethyl acetate Isopropyl aldehyde Hexane Propionaldehyde Tetrachloroethylene Toluene Triethylamine Triethylamine Triethylamine Triethylamine
Acetone Butyraldehyde Carbon tetrachloride Trichloroethylene
Benzaldehyde Benzene Benzonitrile Toluene
AIBN BPO Thermal Radiation
Av*
Refs.
-18 -17 -25.8 138 - 18.7C - 17.9C -18.3c
29 125 125
Radiation
AIBN AIBN AIBN Peroxide AIBN AIBN AIBN HClO4 AIBN AIBN AIBN AIBN AIBN AIBN AIBN Peroxide AIBN AIBN BPO BPO Thermal BF3/diethyl ether ACN Radiation AIBN AIBN AIBN AIBN BPO BPO BPO BPO LPO AIBN AIBN AIBN AIBN
138 138 138
-21.6
139 139
-11.1 -25.5 -19.2 -23.0 -18 -25 -22 -19.1
35 27 27 63 30 65 63 27
- 2 0 to - 2 5 -21.9 -21.2 -19.6 -24.3 -6.8 -19.1 -15.5 -16 -17 -17 -18 > —11.5 -17.5 -36 -22 -17.2 -9 -19 -21 -13
155 27 27 27 27 157 27 157 31 29 29 32 33 34 159 55 86 148 62 62 36
-10.5 -16.7 -4.6 -6.8 -8.1 -10.4 -18 -4.1 -20.5 -12.0 -8.2
65 131 143
124 98 131 98 98
a Abbreviation: ACN: l,l'-azobiscyclohexane-l-carbonitrile; AIBN: 2,2/-azobisisobutyronitrile; BPO: benzoyl peroxide; DCPC: dicyclohexyl peroxidicarbonate; DEE: diethyl ehter; DMF: dimethylformamide; DTBP: di-terf-butyl peroxide; LPO: lauroyl peroxide; TBPB: terf-butyl perbenzoate; TBPO: te/Y-butyl peroctoate; THF: tetrahydrofuran; SDS: sodium dodecylsulfate; Aerosol OT: sodium dioctyl sulfosuccinate; TBPP: tert-butyl pervivalate. ^Calculated by other authors. c Cationic polymerization.
C. ACTIVATION VOLUMES OF INITIATOR DECOMPOSITION
Initiator
Solvent
AIBN* Azobis-terf-butanolate Benzoyl peroxide
2,2-Bis(tert-butyl peroxy)butane Decanoyl peroxide Dicyclohexyl peroxydicarbonate Di-rc-propyl peroxydicarbonate Dioctanoyl peroxide Di-tert-butyl peroxide
Pentaphenylethane tert-Amyl perneodecanoate tert-Amyl perpivalate tert-Buty\ cyclohexanecarboxylate tert-Buty\ perbenzoate tert-Butyl perneodecanoate tert-Butyl perpivalate tert-Butyl peroxy-2-ethylhexanoate terf-Butyl phenylperacetate 1-Methyl-l propylpentyl perpivalate 1,1,4-Trimethylpentyl perpivalate 1,1,4-Trimethylpentyl perneodecanoate
Toluene Toluene Octane Acetophenone Allyl acetate Carbon tetrachloride Carbon tetrachloride Iso-dodecane Benzene Iso-dodecane Benzene Iso-dodecane Benzene Iso-dodecane Carbon tetrachloride «-Heptane Cyclohexane Toluene Toluene Toluene Iso-dodecane Iso-dodecane Cumene Cumene Benzene Iso-dodecane Iso-dodecane n-Heptane Benzene Cumene Iso-dodecane Iso-dodecane Iso-dodecane
Absolute pressure (MPa)
Temperature (0C)
Activation volume Av J (cm3/mol)
Refs.
0.1-150 0.1-1000 0.1-630 0.1-650 0.1-550 0.1-300 0.1-300 0.1-200 0.1-300 0.1-300 0.1-300 0.1-300 0.1-300 0.1-730 0.1-300 0.1-730 10-230 0.1-730 0.1-730 0.1-150 100-270 0.1-300 0.1-300 0.1-410 0.1-410 0.1-300 0.1-300 0.1-300 0.1-200 0.1-300 0.1-410 0.1-300 0.1-300 0.1-300
70 62.5 55 80 80 60 70 135-212 <100 95-200 <100 80-200 <100 120 143-230 120 140-200 120 120 60 50 100-200 120-200 80 80 <100 100-200 120-200 65-105 <100 80 120-200 120-200 100-200
13.1 3.8* to 9.4C 4.3 4.8 4.7 9.7 8.6 22.3 3 4.3 4 5.9 15 12.6 13.4 13.3 10.1 6.7 5.4 7 5 7.0 9.4 3.9 10 7 6.1 6.1 1.6 6 1 13 14 9
37 37 104 38 17 39 39 81 78 75 78 75 78 40 75 40 77 40 40 37 37 75 75 101 102 78 75 88 78 78 103 76 76 76
Absolute pressure (MPa)
Temperature (0C)
Activation volume Av* (cm3/mol)
Refs.
0.1-100 0.1-100 -40 50-175 0.1-100 0.1-100 0.1-100 0.1-100
30 30 24 130-200 30 30 30 30
-22.5 -23.2 -39 -25.5 -19 -24.7 -17.9 -23.3
91 90 152 85 87 99 89 86
a
Azobisisobutyronitrile. ^Photometric analysis. c By 12 scavenger technique.
D.
ACTIVATION VOLUMES OF C H A I N PROPAGATION
Monomer
Solvent
Butyl acrylate Butyl methacrylate Ethylene Ethylene Methyl methacrylate Octyl methacrylate Styrene Vinyl acetate
/-Butanol -
a
Initiator ACNa ACN Radiation Diphenyl disulfide ACN ACN ACN ACN
ACN: 1,1 -azocyclohexane-1,1' -dicarbonitrile.
References page 11-440
E. ACTIVATION VOLUMES OF CHAIN TERMINATION
Monomer Butyl acrylate Butyl methacrylate Ethylene Methyl methacrylate Octyl methacrylate Styrene Vinyl acetate a
Solvent -
Initiator ACN" ACN Diphenyl disulfide ACN ACN ACN ACN
Absolute pressure (MPa)
Temperature (0C)
Activation volume Av * (cm3/mol)
0.1-100 0.1-100 50-175 0.1-100 0.1-100 0.1-100 0.1-100
30 30 130-200 30 30 30 30
20.8 17.8 7 25.0 20.8 13.1 16.3
Refs. 91 90 85 87 99 89 86
ACN: 1,1 -azocyclohexane-1,1 '-dicarbonitrile.
F.
A C T I V A T I O N V O L U M E S O F C H A I N TRANSFER REACTIONS
Activation volume (cm3/mol) Monomer Acrylonitrile 3,3-Dichloropropene-l Ethylene
Transfer agent Butyraldehyde 3,3-Dichloropropene-l Acetone Butane Butanone Cyclohexane Cyclopentane Ethanol Ethylbenzene Ethylene Isopropanol Polyethylene - intermolecular intramolecular Propane Toluene Xylene
Methyl methacrylate Styrene
Vinyl acetate Vinyl chloride
Butyraldehyde Butyraldehyde Carbon tetrachloride Isobutyraldehyde Triethylamine Butyraldehyde Butyraldehyde
Absolute pressure (MPa)
Temperature (0C)
0.1-400 0.1 136-238 138-240 136-238 136-238 136-238 138-240 198-240 136-238 138-240 136-238 138-240 136-238 -250 138-240 136-238 110-200 110-200 180-300 138-240 136-238 138-240 136-238 138-240 138-238 0.1-400 0.1-400 600 0.1-400 181-440 0.1-400 0.1-400
50 50 130 130-200 130 130 130 130-200 130-200 130 130-200 130 130-200 130 130-255 130-200 130 100-300 100-300 175-275 130-200 130 130-200 130 130-200 130 50 50 60 50 60 50 50
Av*r
-24.9
-24.5 -21.3 -22.9 -19.3 -20.1 -19.9 -23 -21 -22.9 -30.7 4.7 -33.8
Av* - \v*r -6.6 —8 -1.1 -1.1 -3.2 -2.9 -1.5 -1.5 -4.7 -4.7 -3.1 -3.1 -6.7 -6.7 -6.1 -6.1 3 5 20-24 -3.1 -3.1 4.7 4.7 7.8 7.8 -6.6 -15
-11 -6.6 - 2 to - 3 -3.2 -3.8
Refs. 62 62 41 83 41 41 41 83 83 41 83 41 83 41 96 83 41 82,85 82,85 83,84 83 41 83 41 83 83 67 63,65,68 33 68 42 67 67
G.
INFLUENCE OF PRESSURE ON COPOLYMERIZATION
TABLE 1. COPOLYMERIZATION PARAMETERS Copolymerization parameters Monomer 1
Monomer 2
Acrylonitrile
Ethyl cinnamate
Solvent
Absolute pressure (MPa)
Temperature ( 0 C)
0.1 80 280 0.1 300 0.1 300 0.1 300 0.1 300 0.1 300 0.1 300 0.1 200 400 3.5 60 51 102-204 3.5 3.5 3.5 3.5 60 120 3.5 34 102 204 3.5 3.5 3.5 3.5 118 0.1 288 0.1 300 0.1 200 0.1 300 0.1 300 0.1 300 0.1 320 0.1 300 0.1 600 0.1 300 0.1 300
60
-
Ethyl fumarate Methyl acrylate a-Methylstyrene Styrene Vinyl acetate Butyl acrylate
Styrene
Cyclopentene
Maleic anhydride
Benzene
Ethylene
Vinyl acetate
-
Benzene Isopropyl alcohol AyV-Dimethylformamide tert-Butyl alcohol Vinyl butyrate Vinyl chloride
tert-Butyl -
Vinyl formate tert-Butyl Vinyl isobutyrate tert-Butyl Vinyl pivalate tert-Butyl Vinyl propionate tert-Butyl Maleic anhydride
Acenaphthylene 2-Ethyl-l-hexene 1-Hexene 2-Methyl-2-butene a-Methylstyrene Norbornene Thiophene
Methyl acrylate
a-Methylstyrene Croton aldehyde Methyl vinyl ketone Vinyl-2-pyridine
alcohol
alcohol alcohol alcohol alcohol
Acetic anhydride
60 62 62 120 62 62 62 62 62 62 62 74 62 62 62 62 62 60 70 70 70 70 70 70 50 50 50 50
/*i 2.4 2.8 3.9 5.5 9.20 0.65 0.76 0.05 0.04 0.02 0.05 3.10 3.50 0.20 0.17 0.49 0.21 0.10 0.74 0.94 0.6 0.82 0.80 0.77 0.92 0.74 0.79 0.80 0.696 0.16 0.16 0.21 0.586 0.609 0.645 0.674 0.68 0.07 0.10 0.15 0.11 0.15 0.10 0.10 0.005 0.005 0.03 0.03 0.02 0.20 0.15 0.10 0.08 20 20 0.50 0.60 0.20 0.30
r2 0.17 0.21 0.36 0.15 0.10 0.46 0.43 0.15 0.10 0.65 0.53 0.10 0.05 0.62 0.50 0.049 0.041 0.030 1.51 1.20 0.95 0.99 1.39 1.485 1.13 1.50 1.40 1.37 1.505 2.7 2.1 2.0 1.29 1.49 1.49 1.50 1.26 0.43 0.32 0.015 0.011 0.015 0.010 0.035 0.025 0.04 0.03 0.05 0.03 0 0 0.27 0.23 0.02 0.02 1.80 1.20 1.10 1.05
Refs. 69 69 69 105 105 105 105 105 105 105 105 105 105 105 105 100 100 100 97 97 41 41 116 116 116 116 117 118 120 41 41 41 120 120 120 120 115 43 43 106 106 106 106 106 106 106 106 106 106 106 106 105 105 105 105 105 105 105 105
References page II - 440
TABLE 1. cont'd Copolymerization parameters Monomer 1
Monomer 2
Methyl methacrylate
Acenaphthylene
Styrene
Solvent
Absolute pressure (MPa)
Temperature (0C)
0.1
60
Toluene
Acrylonitrile
Toluene
Methyl acrylate
Toluene
Acrylic acid
-
Acrylonitrile
Toluene
Diethyl fumarate
Benzene
Diethyl maleate
Benzene
Ethyl methacrylate
Benzene
190 390 0.1 10 100 3.4 590 118 0.1 100 250 0.1 10 100 0.1 10 100 0.1 10 100 0.1 10 100 0.1 100 300 3.4 59 118 3.4 59 118 0.1 10 100 0.1 150 200 0.1 200 300 0.1 300 0.1 150 250 0.1 200 400
Methyl methacrylate -
Vinyl acetate
Vinylidene chloride
Methyl acrylate
Toluene
Methylacrylate
Toluene
Vinyl acetate
Benzene
Vinylidene chloride
-
Vinylidene chloride
-
Isopropyl acetate Vinylidene chloride
-
Indene
-
rx
r2
Refs.
0.57
3.1
43
0.60 0.58 1.34 1.46 2.01 2.42 2.36 2.40 0.25 0.27 0.31 0.37 0.43 0.55 0.26 0.29 0.32 6.53 7.08 9.50 0.56 0.62 0.72 0.704 0.710 0.718 1.20 1.12 1.10 0.86 0.82 0.77 44 46 47 2.6 2.5 2.5 0.54-0.55 0.560 0.605-0.70 0.90 0.60 0.025 0.025 0.03 0.475 0.500 0.525
70 62 62 62 60 70 60 60 50 60 62 62 62 62 62 62 60 60 60
60 60
1.9 1.6 0.12 0.37 0.45 0.31 0.31 0.30 0.07 0.08 0.095 0.07 0.13 0.14 0.06 0.09 0.15 0.01 0.02 0.02 0.50 0.55 0.67 0.159 0.163 0.171 0.09 0.11 0.13 0.38 0.39 0.41 0.01 0.01 0.01 0.04 0.04 0.01 0.80-1.135 1.145 0.80-1.165 0.30 0.35 3.2 3.1 3.1 0.205 0.215 0.225
43 43 44 44 44 119 119 119 69 69 69 44 44 44 70 70 70 70 70 70 45 45 45 69 69 69 119 119 119 119 119 119 46 46 46 47 47 47 69,105 69 69,105 105 105 47 47 47 69 69 69
TABLE 2. REACTIVITY RATIOS OF TERPOLYMERIZATION" Pressure (MPa)
ri2
r2\
ri3
r$\
r23
r32
0.1 300
5.5 3.2
0.15 0.10
0.02 0.05
0.65 0.53
0.06 0.15
0.15 0.25
a
Monomers: (i) acrylonitrile; (ii) diethyl fumarate; (iii) styrene.
Refs.
107,108
TABLE 3. ACTIVATION VOLUMES Activation volume (cm3/mol) Monomer 1
Monomer 2
Acrylonitrile
Butyl acrylate Cyclopentene Ethylene
Ethylfumarate Methyl acrylate a-Methylstyrene Styrene Vinyl acetate Styrene Maleic anhydride Vinyl acetate
Ethylene Indene
Vinyl acetate Acrylonitrile
Isoprene Maleic anhydride
Solvent
Benzene Heptane Dioxane Heptane Heptane
Methyl vinyl ketone Methyl methacrylate Vinylidiene chloride Acrylonitrile Heptane 2-Ethyl-l-hexene 2,3-Dimethyl-2-butene 1,1-Diphenyl ethylene 1-Hexane Cyclohexene 2-Methyl-2-butene a-Methylstyrene Norbornene Thiophene trans-Stilbene
Absolute pressure (MPa) 0.1-300 0.1-300 0.1-300 0.1-300 0.1-300 0.1-300 0.1 -0.1-600 2.5-60 110-190
0.1-300 0.1-300 0.1-300 0.1-200 0.1-300 0.1-300 0.1-300 0.1-300 0.1-320 0.1-300
Temperature ( 0 C) 50 50 50 50 50 50 60 60 62 240 50 50 50 50 50 70 70 70 70 70 70 70 70 70 60
Av*
Av*n - Av\2
Av^2 - Av^1
-5.0 -1.5 ~0 -8.5 -1.1 0
3.7 ~0 3.7 1.9 6.3 1.0
9.3 -11.3
2.7 11.9
0 0 2.5 0
-4.3 -3.6 -1.0 0
- 2 6 . 4 to - 3 7 . 4
-36 -17.5 -18.0 -24.0 -20.1 - 17.8 to - 19.1 —27.0 -36 -25 - 5 0 to - 6 0 -18 -23 -25 -35 -28 -26 -25
-
-
C O P O L Y M E R I Z A T I O N O F MALEIC A N H Y D R I D E W I T H M O N O - A N D POLY-SUBSTITUTED OLEFINS Substitution mono-
di-(l,2)
gem-
tritetra-
Methyl acrylate
a-Methylstyrene Croton aldehyde Maleic anhydride Methyl vinyl ketone Vinyl-2-pyridine
Comonomer
Refs. 107 105 105 105 105 105 100 100 97 72 48 48 49 48 71 50 106 106 106 106 121 106 106 106 106 106
160
Activation volume (cmVmol)
= CH(Pr) = CH(Bu) = CH(z-Pr) = CH(i-Bu) = CH(J-Bu) = CH(Ph) CH(Me) = CH(Et) CH(Me) = CH(Z-Pr) CH(Me) = CH(J-Bu) CH(Z-Pr) = CH(Z-Pr) CH(Ph) = CH(Ph) = C(Me)(Pr) = C(Me)(Z-Pr) = (MeXf-Bu) = C(Me)(CH2J-Bu) = C(Me)(Ph) = C(Et)(Et) = C(Et)(Bu) = (Ph)(Ph) CH(Me) = C(Me)(Me) CH(Et) = C(Me)(Me) C(Me)(Me) = C(Me)(Me)
0.1-300 0.1-300
50 50
0.1-300 0.1-300
50 50
-16.6 -18.0 -17.0 -17.5 -31 -18.5 -19.0 - 20.0 -35 -18.5 -25.0 -31 -33 -60 -46 -35 -34 -36 -50 - 25 - 31 -25
1.0 0
0.7 0
-1.9 -3.7
1.9 ~0
- 1 8 to - 2 5
105 105 71 105 105
References page II - 440
TABLE 3. cont'd Activation volume (cm3/mol) Monomer 1
Monomer 2
Methyl methylacrylate Styrene
Methyl acrylate
TABLE 4.
Solvent
Absolute pressure (MPa)
Temperature (0C)
3.4-118
62
Diethyl fumarate Methyl acrylate Methyl methacrylate Vinyl-2-pyridine
Av*
Av*n - bv\2
Sv*22 - Av*21
0.9 - 1 8 to - 13.8 to - 1 8 to - 2 3 . 5 to
-25 - 14.5 -25 -26
-2.2
1.8
0
Refs. 119 71,105 71 71 71
Q, e VALUES
Qa Monomer
At 0.1 MPa
Acrylic acid Acrylonitrile rt-Butyl acrylate rc-Butyl methacrylate Crotonaldehyde Diethyl fumarate Diethyl maleate Ethylene Ethyl methacrylate Indene Isobutylene Isopropenyl acetate Methylacrylate Methyl methacrylate oc-Methylstyrene Methyl vinyl ketone Propylene Styrene Vinyl acetate Vinyl chloride Vinyl pivalate 2-Vinylpyridine Vinylidene chloride
0.53(0.83)^ 0.53(0.50) 0.40(0.30) 0.62 (0.66) 0.015(0.02) 0.20 (0.03) 0.03(0.04) 0.015(0.013) 0.62(0.57) 0.30(0.36) 0.025 (0.029) 0.08 (0.02) 0.44(0.44) 0.63(0.74) 1.40(1.00) 1.07 (0.65) 0.010 (0.008) 1.20(1.00) 0.06 (0.03) 0.0450(0.056) 0.023 (-) 1.05(1.03) 0.27(0.26)
ea At 300 MPa 0.45 0.62 0.40 0.70 0.015 0.25 0.03 0.05 0.66 0.28 0.022 0.12 0.44 0.63 1.65 1.03 0.015 1.35 0.05 0.045 0.046 0.95 0.24
At 0.1 MPa +0.91(0.88)* +0.90(1.20) +0.35(0.74) - 0.08 (0.34) +0.80(0.84) +1.35 (2.17) +0.62(1.40) -0.15 (-0.15) 0.00(0.35) -1.10 (-1.03) -1.72 (-1.06) -1.30 ( - 0.34) +0.60(0.60) -0.20(0.38) -1.30 (-1.27) +0.95 (1.11) -1.50 ( - 2.20) -1.10(-0.80) - 0.20 ( - 0.22) +0.16(0.20) -0.19 (-) -0.60(-0.50) +0.42(0.40)
At 300 MPa +0.64 +0.95 +0.35 - 0.54 +0.80 +1.25 +0.40 -0.02 -0.35 -1.05 -1.25 -1.60 +0.60 -0.05 -1.40 +1.15 -1.05 -1.22 - 0.35 +0.19 -0.02 -0.50 +0.43
Refs. 108 105 105 92 105 105,109,25 109 110 92 111,108 112 105 105 108,25 105 105 112 105,108,92 105,108,110 112,41 113 105 108
a Reference monomer is methyl acrylate (105). ^Values in parentheses refer to the values of styrene.
H.
REFERENCES
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A c t i v a t i o n S t e r e o c o n t r o l
E n t h a l p i e s i n
F r e e
a n d
E n t r o p i e s
R a d i c a l
o f
P o l y m e r i z a t i o n s
H a n s - G . Elias Michigan Molecular Institute, 1910 West St. Andrews Rd., Midland, Ml 48640, USA
A. Introduction B. Tables Table 1. Ratios of Some /-ads for Different Mechanisms Table 2. Ratios of Rate Constants for Markov First Order Mechanisms Table 3. AH^. - AHf/s and A S ^ - ASf/s of Free Radical Polymerizations in Different Solvents Table 4. Activation Enthalpy Differences (AH\ - AHl) Calculated from Various Literature Data Table 5. Activation Entropy Differences (ASl-ASl) Calculated from Various Literature Data Table 6. Calculated Compensation Temperatures T0 and Compensation Enthalpies AAHQ for Various Monomers and Modes of Addition, Assuming Markov First Order Trials C. References A.
il-445
II-446 II-446
II-447
(b) The last monomeric unit of the chain, but not the last diad, controls the propagation step. The probabilities for the formation of isotactic and syndiotactic diads are thus different (pi / ps). The process is Bernoullian (zeroth order Markov statistics) with respect to the formation of diads. Consequently, the probability of forming an isotactic diad at an existing isotactic diad equals the probability of forming an isotactic diad at an existing syndiotactic diad (P1J1 = ps/{), and, by analogy, Ps/s = Pi/s• It follows for the diads (6,8)
II-448
II-449
(A3) and for the triads (A4) (A5)
II-449 II-450
INTRODUCTION
In free radical polymerization, the tacticity of the resulting polymer depends on the propagation step, i.e., on stereocontrol by the propagating end. The following simple cases exist: (a) The last monomeric unit does not control the stereospecificity of the propagation step. Isotactic (i) and syndiotactic (s) additions thus exhibit the same conditional probabilities (px — ps). The mole fractions x of the resulting isotactic and syndiotactic diads are equal (x\ = xs). If all steps occur at random, the four conditional probabilities for the formation of triads are equal Q)^1 = p-x/s = ps/-x = /? s / s ), and so are the conditional probabilities for the formation of tetrads, pentads, etc. The resulting polymer is a true atactic polymer. It follows that (Al) (A2)
where xa is the mole fraction of isotactic triads and xss is the mole fraction of syndiotactic triads. ;cht is the mole fraction of heterotactic triads, regardless of whether formed by the formation of an isotactic unit at a syndiotactic one (conditional probability ps/i) or vice versa (conditional probability p i / s ). (c) The last two monomeric units of the chain, i.e., the last monomeric diad, regulate the stereocontrol of the propagation step. The four conditional probabilities do not equal each other (P1J1 ^ pi/s ^ ps/i ^ ps/s)- The mole fractions of isotactic (JCH), syndiotactic (xss) and heterotactic triads (jcht) are thus given by (8,11) (A6) (A7) This process corresponds to a Markov trial of first order. (d) Second order Markov statistics are present if the last two diads (i.e., the last triad or the last three monomeric
units) control the propagation step. In this case (A8) (A9) (AlO) (All) In order to distinguish between Markov second order and Markov first order mechanisms, at least tetrads must be known. The probability of the addition of a 'b' diad (b = i, s) to an existing end 'a' (a = i, s) is given by the corresponding rates R: (A12) with a = i, s or b = i, s, in the Markov first order case, or a = ii, is, si, ss b = ii, is, si, ss, in the Markov second order case. Using these definitions and assuming steady states and the equality of instantaneous and final diad and triad fractions, one can express ratios of all diads, triads, and tetrads in terms of rate constants (Table 1) or ratios of rate constants in terms of diad, triad, etc. fractions (Table 2). The rate constants themselves can be calculated if the rate constants of propagation are known for the corresponding experimental conditions (1). From the temperature dependence of the expressions given in Table 2, differences in activation enthalpies (AHA* — A//g) and differences in activation entropies (AS^ - AS^) can be calculated:
from literature data as very few triad fractions have been reported. For any two modes of addition, the compensation effect between AAH$ and AAS$ (10,12,43) for the polymerization of a given monomer, in different solvents and/or at different monomer/solvent ratios, can be described by (A14) The compensation temperature To has been found to be independent, of the mode of addition (e.g., A = i/i vs. B = i/s) within the limits of error (12,43). However, the compensation enthalpy AAH^ depends on the mode of addition. B. TABLES TABLE 1. RATIOS OF SOME /ADS FOR DIFFERENT MECHANISMS0 Mechanism i-ad Ratio Bernoulli
a
Markov 1st order Markov 2nd order
From Ref. 42.
(AB)
TABLE 2. RATIOS OF RATE CONSTANT FOR MARKOV FIRST ORDER MECHANISMS0
The quantities (AH\ - A # | ) and (AS* - AS^) may reflect activation parameters (2,3), conformation parameters (4,5), or combinations thereof. Table 3 gives the difference AAH^ = AHJ - A # | and AAS^ = AS\ - ASg calculated from the temperature dependence of diad ratios X[/xs. In the case of Bernoulli trials, they represent AHf - AHj and ASf - AS^, respectively. For first order Markov trials, they stand for AHj/{ - AH}/S and ASJ/{ - Asf/s, respectively. In general, both AAH^ and AAS^ depend on the solvent (9,10), and consequently on the monomer/solvent ratio (11,12), but they are nearly independent of monomer conversion. Table 4 gives the differences in activation enthalpies for modes of addition other than s/i vs. i/s, and Table 5 gives the corresponding differences in activation entropies. Only a few of these activation parameters could be calculated
Ratios of rate constants Expressions giving ratios of rate constants
a
From Ref. 43.
TABLE 3.
AHJ/J -
AIfJ1 AND Asjfi - As}/s OF FREE RADICAL POLYMERIZATIONS IN DIFFERENT SOLVENTS*
Monomer (H-additive) Acrylonitrile
Vol.%
30 100 Acrylic acid, isopropyl ester ? ? - , methyl ester ? a-Chloroacrylic acid, methyl ester ? Methacrylonitrile 100 100 - , ( + 1 mol SnCV2 mol monomer) 3:1* - , ( + 1 molSnCVl mol monomer) 2:1* - , ( + 1 molSnCyi mol monomer) 1:1* - , ( + 1 mol SnCl4/2 mol monomer) 1:1* Methacrylic acid 10 20 20 20 -,anhydride ? - , benzyl ester 50 - , j-butyl ester 50 - , f-butyl ester 50 - , p-carboxyphenyl ester ? ? - , cyclohexyl ester 100 - , glycidyl ester 45 50 57 100 - , a-methylbenzyl ester 50 - , methyl ester 9. \d 9Ad 9. ld 9Ad 9.1* 9Ad 9Ad 9Ad 9Ad 9Ad 9Ad 9.1^ 9.1d 9Ad 20 25 25 25 25 25 25 25 28.5 50 100 100 100 100 100 - , - , ( + 8.7 mol ZnCl2A mol MMA) 1.1« - , - , ( + 1 mol ZnCl2A mol MMA) 3.2e - , - , (±0.04 mol ZnCl2A mol MMA) 100 - , - , ( + 1 mol ZnCl2/2 mol MMA) 100 - , - , ( + 1 mol ZnCl2A mol MMA) 100 - , - , ( + 1 mol SnCU/2 mol MMA) 100
Solvent
(J/mol)
Toluene Bulk
3770 ±59 0 0 0 3800 ±190 250 ±50 -4100±71 - 630 ± 54 170±63 251 2350 ± 38 3980 ±92 3850 ±80 7800 ±180 3140±42 13300 ±210 2300 ±130 3430 ±63 2090 ±80 4310 0 1210 ±80 700 ±100 5780 ±42 8600 ±130 9800 ±110 3640 ±59 6280 ± 75 5360 ±75 3480 ±71 3900 ±160 3140 ±88 5100 ±71 3500 ±150 3350 ±96 5317 ± 8 3100 ±67 4860 ±75 5200 ±100 3900 ±110 2810 ±96 2720 ±34 7030 ±75 5860 ±21 9380 ±71 6700 ±46 4980 ±50 5200 ±210 6700 ±29 5650 ±80 2900 ±420 6200 ±110 4480 3800 ±230 2300±54 3560 ±84 2850 ± 71 4100 ±71 2700±190 - 1 3 0 ± 80 - 40 ± 130 800 ± 100
? Toluene Bulk Bulk Toluene Toluene Benzene Benzene 1-Propanol 1-Propanol 2-Propanol Methanol Benzene Toluene Toluene Toluene Dimethylformamide /7-Cetyloxybenzoic acid Bulk Acetone Dimethylformamide Toluene Bulk Toluene Acetone Acetonitrile Benzene Butanone y-Butyrolactone Chloroform Dimethylformamide Dimethyl sulfoxide 1,4-Dioxane Methylene chloride Pyridine Tetrachloroethane Tetrahydrofuran Toluene Paraffin Acetone Carbon tetrachloride Chloroform Dichloroethylene Ethanol ^-Heptane /i-Hexane Toluene Toluene Bulk Bulk Bulk Bulk Bulk Water Ethyl acetate Bulk Bulk Bulk Bulk
(J/mol/K) 2.7 ±0.19 0 -5.9 - 5.9 2.5 ±0.59 3.0 ±0.14 -10.8±0.21 - 0.7 ± 0.18 -0.1±0.18 0.75±0.88 9.76 ± 0.096 - 2 . 2 ±0.32 - 1 . 8 ±0.28 10.5 ±0.63 - 4 . 1 ±0.13 44.4 ±0.63 - 1 . 7 ±3.8 2.0 ±0.22 - 2.6 ± 0.29 2.09 - 6.87 - 5 . 0 ±0.20 9.5 ±0.36 5.0 ±0.15 14.2 ±0.042 17.5 ±0.28 2.2 ±0.22 10.2 ± 0.23 7.3 ±0.26 2.3 ±0.23 4.2 ±0.46 1.4 ±0.27 7.5 ±0.23 3.4 ±0.46 2.5 ±0.28 7.4 ±0.30 2.0 ±0.22 7.7 ±0.22 7.2 ±0.29 4.4 ±0.33 0.8 ±0.26 1.6 ±0.13 9.0 ±0.23 5.36 ±0.067 16.0 ±0.21 8.4 ±0.13 3.6 ±0.14 3.69 ±0.059 8.50 ±0.092 3.9 ±0.26 1.3 ±1.3 9 ±3.8 4.2 -0.04 ±0.63 -1.8±0.16 3.3 ±0.24 2.2 ± 0.20 5.2 ± 0.2 1.13±0.054 - 9.80 ± 0.67 - 6.7 ± 0.46 - 8.2 ± 0.33
Remarks a a
a
c
IR IR IR IR IR IR IR a
-
a
a
-
Refs. 10,14 13 15 15 16 17 18 18 18 18 18 19 19 19 19 20 21 10,22 10,22 23 10,23 10,24 10,25 10,25 10,25 10,25 10,22 12 12 12 12 12 12 12 12 12 12 12 12 12 12 27 9 9 9 9 9 9 9 10,26 21 27 1 25 28 12 10,29 10,29 10,29 27 27 27
*In all cases, except those marked by IR (infrared) (see Remarks column), diad fractions were determined via NMR. References page 11-450
TABLE 3. cont'd Monomer ( +additive)
Vol.%
- , - , ( + 1 mol SnCVl mol MMA) - , L-menthyl ester - , phenetyl ester Trifluorochloroethylene Vinyl bromide Vinyl bromide N-Vinyl carbazole
? ? ? 10 33.3 33.3 100 100 100 100 50d 50 J 50d 100 100 100 ? 100 ?
Vinyl chloride
- P , p-d2 Vinyl formate
Vinyl trichloroacetate
a c e
100 50 50 0.4*" 100 ? 6.5 100 100 ? ? ? ?
Solvent
(J/mol)
Bulk Toluene Toluene Carbon tetrachloride Bulk n-Butyl acetate o-Dichlorobenzene Bulk Bulk Dimethylacetamide Dimethylformamide Dimethylsulfoxide Hexamethylphosphoric triamide Hexane/nonane Methylene dichloride Toluene Cyclohexane Water/ethanol Water Bulk Bulk Bulk Bulk Acetone Chloroform Dimethylformamide Bulk Bulk Bulk w-Butyl acetate Bulk w-Butyl acetate
420 ± 13 960 ± 46 5600 ± 1700 0 710 250 1930 ± 5 4 2140 ±17 1270 ± 3 0 - 4600 ±300 - 2850 ± 100 -3300 ±500 -3400 ±200
-14.07 ± 0.054 0.3 ± 0.18 4.6 ±4.6 -5.8 2.5 2.1 5.3 ±0.17 5.99 ±0.080 2.72 - 20 ± 1 -13.5 ± 0.4 -15.4 ±1.4 -14.7 ±0.7
-1500 ±200 -2650 ±100 -3650 ±1000 1300 ± 8 4 5000 ±1000 1500 ±630 2900 ±160 2260 ± 5 0 1090 ± 2 0 -2650 ± 4 340 ±25 290 ± 5 0 250 ±38 1050 ± 5 4 880 ±25 2830 1800 1590 880
-10.5 ±0.7 -11.7 ±0.4 -16.0 ±0.8 2.5 ±0.42 18 ±4.2 2.9 ±2.0 6.78 ±0.067 5.7 ±0.14 1.9 -6.28 ±0.04 0.21 ±0.80 0.08 ±0.16 0.5 ±0.12 3.3 ±0.17 3.4 ±0.080 84 4.6 4.2 2.1
Data directly from literature, mechanistic assumptions unknown. Literature data, calculated under the assumption of Bernoulli statistics. mol/1.
TABLE 4.
(J/moI/K)
Remarks -
a
a a a
a
IR a
a a a
Refs. 27 30 21 31 32 32 34 34 44 45 45 45 45 45 45 45 36 35 35 37 34 44 34 41 41 41 38 41 32 32 32 32
b
Solvent/monomer molar ratio. mol%. f g/ml. d
ACTIVATION ENTHALPY DIFFERENCE (AH* - AHj|) CALCULATED FROM VARIOUS LITERATURE DATA
\H\ - AHI (J/mol) A = i/i B = i/s
Monomer
Solvent
Glycidyl methacrylate
Acetone Bulk Dimethylformamide Toluene Methanol 1-Propanol 2-Propanol
33000 ±2300 25000 ± 1400 14000 ±1500 27000 ±1800
Bulk Bulk Bulk Ethyl acetate 70% ZnCl2/H2O Acetone Bulk Chloroform Dimethylformamide Water Water/methanol Bulk
2800 ±120 - 1 3 ±110 -20±160 2300±230 700±240 670 ±25 2850 ±84 1700 ±180 0±150 423 3600 ±63 3180 ± 46
Methacrylic acid (20 vol.%) Methyl methacrylate/ZnCl2 9.34/0.369 (mol/mol) 2.00/1.00 (mol/mol) 1.00/1.00 (mol/mol) 3.19/3.19 (mol/mol) 1.10/9.6 (mol/mol) Vinyl formate
Vinyl chloride Vinyl chloride, P, P-d2
A = s/i B = i/i
A = i/i B = s/s
-
-
-
-
38000 ± 2500 20000 ±1800 33000 ±2600
6500 ± 750 300 ±160 5556 ± 8
-130 ±110 -100 ±75 -21±110 1800±180 2200±180 -1060 ±88 -1700 ±100 -3200 ±190 -250 ±190 1210 -1230 ±54 540 ± 46
2430 ±59 - 4 2 ±88 -29±130 2600±170 1400±150 -419 ± 4 650 ±25 -520 ±46 -180 ±200 170 4420 ±29 2860 ±21
A = i/s B = s/s 420 ± 80 -1240 ±75 150 ±29 -340 ±59 - 2 9 ±29 -8±17 370±63 700±92 -1060 ±92 -1900 ±130 -300 ±190 -180 ±200 980 830 ±84 - 330 ± 29
A = s/i B = s/s
Refs.
7100 ±110 9300 ±140 580 ±33 10000 ±1000 3300 ±110 4010 ±96 8000 ±220
25 25 25 25 19 19 19
2310 ±54 -140 ±75 -46±130 4480±54 3550±38 -2150 ±92 -900 ±130 -3700 ±1250 -440 ±230 2500 5600 ±140 2320 ± 25
29 27 27 29 29 41 41 41 41 35 35 39
TABLE 5. ACTIVATION ENTROPY DIFFERENCES (As| - ASj[) CALCULATED FROM VARIOUS LITERATURE DATA AS* - ASJ (J/mol/K)
Monomer
Solvent
A = i/i B = i/s
Glycidyl methacrylate
Acetone Bulk Dimethylformamide Toluene Methanol 1-Propanol 2-Propanol
85 ±8.8 54 ± 4.2 32 ±7.1 75±7.5
Methacrylic acid (20 vol.%) Methyl methacrylate/ZnCl2 9.34/0.369 (mol/mol) 2.00/1.00 (mol/mol) 1.00/1.00 (mol/mol) 3.19/3.19 (mol/mol) 1.10/9.6 (mol/mol) Vinyl formate
Vinyl chloride Vinyl chloride, P, P-d2
Bulk Bulk Bulk Ethyl acetate 70% ZnCl2 in water Acetone Bulk Chloroform Dimethylformamide Water Water/methanol Bulk
4.0±0.34 -7.0±0.46 - 5 . 2 ±0.63 1.4 ±0.88 3.1 ±0.71 5.1 ±0.25 11.1 ±0.25 7.7 ±0.54 4.6 ±0.46 -1.3 11.7 ±0.25 8.3 ±0.17
A = s/i B = i/i
A = i/i B = s/s
A = i/s B = s/s
A = s/i B = s/s
-
-
-
125 ±8.4 72 ±8.0 100±ll
- 1 . 3 ± 2.3 -15.8 ±0.54 -1.84 ±0.04
2.3 ± 0.25 - 3 . 4 ±0.25 .0.7 ±0.13
10.3 ±0.42 16.1 ±0.54 5.8 ±0.13 17 ±3.9 - 1 . 1 ± 0.13 - 0 . 9 ±0.38 11.1 ±0.75
25 25 25 25 19 19 19
-2.9±0.29 -2.8±0.29 -1.7 ±0.38 3.9 ±0.71 5.2±0.54 - 5 . 6 ±0.29 - 7 . 6 ±0.25 -13.0 ±0.63 - 3 . 9 ±0.59 4.6 - 4 . 1 ±0.21 2.1 ±0.17
1.8±0.17 -8.0±0.38 - 6 . 0 ±0.46 1.8 ±0.63 -1.5±0.42 -0.75 ±0.04 2.55 ±0.080 - 1 . 1 ±0.13 - 0 . 3 ±0.13 4.5 15.3 ±0.54 7.03 ±0.080
-2.2±0.17 -1.5±0.13 - 0 . 8 ±0.21 0.4 ±0.25 1.6±0.25 - 5 . 8 ±0.29 - 8 . 6 ±0.34 -13.9 ±0.59 - 4 . 3 ±0.39 3.8 3.6 ±0.34 -1.30 ±0.08
—1.1 ±0.13 -10.8±0.29 -7.7 ±0.42 5.7 ±0.13 3.8±0.13 - 9 . 3 ±0.29 - 5 . 0 ±0.38 -13.9 ±0.75 - 3 . 9 ±0.71 6.8 20.6 ±0.54 4.98 ±0.08
29 27 27 29 29 41 41 41 41 35 35 39
Refs.
TABLE 6. CALCULATED COMPENSATION TEMPERATURES T0 AND COMPENSATION ENTHALPIES AAH* FOR VARIOUS MONOMERS AND MODES OF ADDITION, ASSUMING MARKOV FIRST ORDER TRIALS Modes of addition M o n o m e r
A
Acrylonitrile Methacrylic acid, in alcohols
s/i s/i i/i s/i i/i s/i i/s s/i s/i s/i s/i s/i s/i s/i i/i s/i i/i s/i i/s s/i i/i s/i i/i s/i i/s s/i s/i s/i s/i i/i s/i i/i s/i
- , /-butyl ester - , rc-butyl ester - , /7-carboxyphenyl ester - , glycidyl ester - , hexyl ester - , methyl ester
- , - , ( + ZnCl2)
- , /-propyl ester - , rc-propyl ester Vinyl acetate Vinyl chloride
B
T0 (K) i/s i/s i/i i/i s/s i/s s/s s/s i/s i/s i/s i/s s/s i/s i/s i/i s/s i/s s/s s/s i/s i/i s/s i/s s/s s/s i/s i/s i/s i/s i/i s/s i/s
1400 455 294 ±26 323 ± 5 403 ±140 323 ±10 302 ±74 333 ±23 294 ± 3 236 ± 4 481 345 ± 15 373 ±11 303 ±11 315 ± 49 310 ±20 323 ±124 362 ±15 338 ±51 334 ±54 314 ± 39 321 ± 9 331 ±24 336 ±21 304 ±10 328 ±42 230 ± 54 248 ± 41 1100 283 ±25 282±6 235 ±28 305 ±124
AAHJ (J/mol) 0 2780 6300 ±1260 -2300 ±510 6600 ±200 4480 ±21 - 1 8 0 ±63 4250 ±25 3304 ± 4 3576 ± 8 3308 3800 ± 200 3500 ±120 3260 ± 29 120 ± 160 2600 ±130 1440 ±84 1470 ±50 1400 ±92 4010 ±75 1650 ± 67 540 ±33 1930 ±42 2250 ±50 243 ± 4 2530 ±80 3420 ± 67 3300 ± 176 -2050 820 ±130 -75±17 900 ±160 - 2 2 0 ±420 References page 11-450
TABLE 6. cont'd Modes of addition M o n o m e r
Vinyl formate
N-Vinyl carbazole Vinyl chloroacetate Vinyl trifluoroacetate
A i/s s/i i/i s/i i/i s/i i/s s/i s/i s/i s/i
B
T0 (K) s/s s/s i/s i/i s/s i/s s/s s/s i/s i/s i/s
248 ± 9 219 ± 1 0 362 ± 2 3 315 ± 1 6 323 ± 2 7 330 ± 9 5 320 ± 1 8 316 ± 5 - 243 300 340
AA/fJ (J/mol) - 1 3 ±33 1130 ± 5 9 -1400 ±130 850 ± 8 0 -200 ±25 -290 ±42 970 ± 9 6 740 ± 2 1 288 419 167
"Based on data in Tables 3-5; see also Refs. 40,43.
REFERENCES
1. H. -G. Elias, Makromol. Chem. 137, 277 (1970). 2. J. W. L. Fordham, J. Polym. ScL, 39, 321 (1959). 3. C. E. H. Bawn, W. H. Janes, A. M. North, J. Polym. Sci. C 4, 427 (1963). 4. H. Fischer, Kolloid-Z., 206, 131 (1965). 5. P. L. Luisi, R. M. Mazo, J. Polym. Sci. A-2, 7, 775 (1969). 6. F. A. Bovey, G. V. D. Tiers, J. Polym. Sci., 44, 173 (1960). 7. T. G. Fox, H. W. Schnecko, Polymer 3, 575 (1962). 8. F. A. Bovey, "Polymer Conformation and Configuration", Academic Press, New York, 1969. 9. H. Watanabe, Y. Sono, Kogyo Kagaku Zasshi, 65, 273 (1962). 10. H. -G. Elias, P. Goeldi, V. S. Kamat, Makromol. Chem., 117, 269 (1968). 11. E. L. Miller, SPE Trans., 3, 1 (1963). 12. P. Goeldi, H. -G. Elias, Makromol. Chem., 153, 81 (1972). 13. G. Svegliado, G. Talamini, G. Vidotto, J. Polym. Sci. A-I, 5, 2875 (1967). 14. H. Murano, R. Yamadera, J. Polym. Sci. B, 5, 333 (1967). 15. C. Schuerch, W. Fowells, F. P. Hood, F. A. Bovey, cited in Ref. 36. 16. K. Matsuzaki, T. Uryu, K. Ito, Makromol. Chem., 126, 292 (1969). 17. K. Matsuzaki, T. Uryu, J. Polym. Sci. B, 4, 255 (1966). 18. H. Hirai, T. Ikegami, S. Makishima, J. Polym. Sci. A-1,7,2059 (1969). 19. J. B. Lando, J. Semen, B. Farmer, Polym. Preprints, 10, 586 (1969). 20. W. L. Miller, W. S. Brey, G. B. Butler, J. Polym. Sci., 54, 329 (1961). 21. K. Yokota, Y. Ishi, Kogyo Kagaku Zasshi, 69, 1966 (1966). 22. K. Matsuzaki, A. Ishida, N. Tateno, T. Asakura, A. Hasegawa, T. Tameda, Kogyo Kagaku Zasshi, 68, 852 (1965). 23. Y. B. Amerik, I. I. Konstantinov, B. A. Krentsel, IUPAC, International Symposium, Macromolecular Chemistry, Tokyo, 1966, Preprint 1.1.09. 24. K. Matsuzaki, A. Ishida, N. Tateno, IUPAC, International Symposium, Macromolecular Chemistry, Prague, 1965, Preprint 265.
25. Y. Iwakura, F. Toda, T. Ito, K. Aoshima, Makromol. Chem., 104, 26 (1967). 26. Y Kato, A. Nishioka, Bull. Chem. Soc. Japan, 37, 1614 (1964). 27. S. Okuzawa, H. Hirai, S. Makishima, J. Polym. Sci. A-I, 7, 1039 (1969). 28. F. A. Bovey, J. Polym. Sci., 46, 59 (1960). 29. T. Otsu, B. Yamada, M. Imoto, J. Macromol. Chem., 1, 61 (1966). 30. H. Sobue, K. Matsuzaki, S. Nakano, J. Polym. Sci. A, 2, 3339 (1964). 31. EA. Bovey, G. V. D. Tiers, Fortschr. Hochpolym. -Forschg., 3, 139 (1963). 32. M. Uoi, M. Sumi, S. Nozakura, S. Murahashi, cited in Ref. 33. 33. S. Murahashi, in: IUPAC, International Symposium, Makromol. Chem., 3, 435 (1967) ( = Pure Appl. Chem., 15, nos. 3-4 (1967)). 34. G. Talamini, G. Yidotto, Markromol. Chem., 100, 48 (1967). 35. J. Bargon, K. H. Hellwege, U. Johnsen, Makromol. Chem., 95, 187 (1966). 36. F. A. Bovey, F. D. Hood, E. W. Anderson, R. L. Kornegay, J. Phys. Chem., 71, 312 (1967). 37. H. U. Pohl, D. O. Hummel, Makromol. Chem., 113, 203 (1968). 38. K. C. Ramey, D. C. Lini, G. Statton, J. Polym. Sci. A-I, 5, 257 (1967). 39. L. Cavalli, G. C. Borsini, G. Carraro, G. Confalonieri, J. Polym. Sci. A-I, 8, 801 (1970). 40. H. -G. Elias, P Goeldi, Makromol. Chem., 144, 85 (1971). 41. H. -G. Elias, M. Riva, P. Goeldi, Makromol. Chem., 145, 163 (1971). 42. B. L. Johnson, H. -G. Elias, Makromol. Chem., 155, 121 (1972). 43. H. -G. Elias, P. Geoldi, B. L. Johnson, Adv. Chem. Ser., 128, 21 (1973). 44. R. E. Cais, W. L. Brown, Macromolecules, 13, 801 (1980). 45. D. R. Torrell, F. Evers, Makromol. Chem., 183, 863 (1982).
P r o d u c t s
o f
T h e r m a l
D e g r a d a t i o n
o f
P o l y m e r s
John Liggat Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, Scotland A. Introduction B. Tables Table 1. Main-Chain Acyclic Carbon Polymers Table 2. Main-Chain Carbocyclic Polymers Table 3. Main-Chain Heteroatom Polymers Table 4. Main-Chain Heterocyclic Polymers Table 5. Cellulose and Its Derivatives C. References A.
11-451 11-451 11-451 II-464 II-465 II-473 II-475 II-475
INTRODUCTION
Polymer degradation is a complex phenomenon, and the nature of the chemistry occurring during thermal decomposition can be difficult to determine precisely. The observed products of degradation can be the result of a mixture of primary, secondary or even tertiary decomposition processes, and as a consequence, the distribution of products will depend on such factors as sample thickness and melt viscosity, in addition to the more obvious factors such as temperature, atmosphere and the chemical structure of the polymer itself. It is often overlooked that abnormal structures (terminal unsaturation, head-to-head structures, peroxide links etc.) can also markedly effect polymer stability and product distribution. Products are of three types. Firstly, there are the volatile small molecules (typically of the size of monomer or smaller) which are fairly readily separated and character-
ized. Secondly, there are the larger molecules that represent fragments of the chain. These species are volatile at the degradation temperature but condense outwith the degradation zone. Generally produced as a complex spectrum of oligomers, these fragments are more difficult to separate and characterize in detail, particularly as internal rearrangements of the backbone often occur before and during fragmentation. In many cases, identification is limited to key functionalities but the advent of sophisticated chromatographic and mass spectrometric techniques is leading to increasingly detailed analyses. In particular, the smaller fragments such as dimer and trimer are in principle more readily fully characterized than the larger fragments; nevertheless there often remains some uncertainty, particularly in relation to end groups. The most intractable product is the third type, the residue, which is often (but not always) insoluble, and characterization may again be limited to identification of key functionalities. Naturally, most of the information in the literature relates to the easily identified low molecular weight species, and the data in this section reflects this. In addition, most thermal degradation studies focus on inert rather than oxidizing environments. Following the lead of the previous author, Norman Grassie, the vast majority of the entries included here are concerned with products of the first two types from purely thermal degradation processes under inert atmospheres.
B. TABLES TABLE 1. MAIN-CHAIN ACYCLIC CARBON POLYMERS Polymer
Temperature range (0C)
Degradation products
Refs.
1.1. UNSATURATEDPOLYMERS Poly(acetylene)
650
Poly(butadiene)
325-475 20°C/min to 15% weight loss
Methane (0.87 moles relative to benzene= 1), ethylene (0.47), ethane 82 (0.26), propylene (0.27), propane (0.047), 1,3-butadiene (0.19), cyclopentadiene (0.086), cyclopentene (0.063), benzene (1.0), toluene (0.18), m-xylene (0.091), /?-xylene (0.015), styrene (0.041), o-xylene (0.013), methylstyrene (0.010), frans-p-methylstyrene (0.011), indane (0.0074), indene (0.036), methylindene (0.0072), naphthalene (0.052), 2-methylnaphthalene (0.015), 1-methylnaphthalene (0.018), biphenyl (0.0091), fluorene (1.0), anthracene (0.005) 14.1% of products are volatile at 25°C including 1.5% of monomer 16 among other saturated and unsaturated hydrocarbons; 85.9% of products are larger fragments involatile at 250C Effect of cisltrans ratio; increasing trans content gives more cyclopentene 83 and 1,3-cyclohexadiene and less 4-vinyl-l-cyclohexene and 1,3-butadiene
TABLE 1. cont'd Polymer Poly(butadiene-co-acrylonitrile) (70/30) 25-100 mol% butadiene
Poly(butadiene)-£/ewd-poly(styrene) (0-100wt.%) Poly(butadiene-co-sytrene) (75/25) Poly(chloroprene)
Poly(chloroprene)-fc/em/ poly(methyl methacrylate) Poly(isoprene), synthetic 97% c/s-1,4; 3%, 3,4
natural rubber
Temperature range (0C) 310-400 350-400
Ambient to 500 327-430
chlorinated rubber-blendpoly(vinyl chloride) Poly(perfluoro-4-chloro-l,6-heptadiene)
14.5% of products are volatile at 25°C, consisting of saturated hydrocarbons Main product is structurally modified chain fragments; ammonia and hydrogen cyanide increasing with acrylonitrile content to approximately 4% each by weight of copolymer containing mole 75% acrylonitrile; traces of hydrogen and hydrocarbons up to C 7 Volatile products as for individual polymers
Refs. 10 98
84
160-350
11.8% of products are volatile at 25°C; 1.9% butadiene with 10,16 other saturated and unsaturated hydrocarbons Hydrogen chloride 19 HCl (90% of theoretical), ethylene, chloroprene (trace), chloroprene 85 dimers and other modified chain fragments HCl (trace), methane, ethylene, propylene (trace) 85 Methyl methacrylate, HCl, CO 2 , CO, 86 methyl chloride, methanol. 3.4% isoprene, 8.8% dipentene, small amounts of p-menthene. 2,16,31 In helium; methane (0.04 wt.%), ethylene (0.08), ethane (0.03), 87 propylene (0.15), propane (0.06), isobutylene (0.09), butenes (0.07), methyl butene (0.09), isoprene (29), toluene (0.02), 2,3-dimethyl cyclopentene (1.2), octene (0.05), 2,4-dimethyl cyclohexene (0.16), m-xylene (0.33), l-methyl-4-ethyl cyclohexene (0.18), l,5-dimethyl-5-vinyl cyclohexene (2.5), dipentene (60), C n H i 8 (0.2), C 12 H 18 (0.2), C 15 H 24 (3.5), C 16 H 26 (1.8) 3.9% isoprene, 13.2% dipentene, small amounts of /?-menthene 2,16,31 Dipentene main product at 4500C, optimum yields of isoprene in 32 range 675-8000C, e.g., 58% at 7500C and 13mbar Monomer, dimers (l,7,7-trimethyl-2,2,l-bicyclohept-2-ene, 259 2,5,6-trimethyl 1,3,6-heptatriene, dipentene/d,l-limonene), trimers 3.0% Isoprene, 15.6% dipentene, small amounts of/?-menthene 2,16,31 Styrene, isoprene, dipentene larger chain fragments of both 88 polymers, traces of ethylene, ethane, and propane HCl (almost quantitative), CH 4, C 2 H 4 , and H 2 are minor products 89 formed in the later stages of reaction HCl 90
320-400
Completely volatilized - products unknown.
335-450
Continuous spectrum of saturated and unsaturated hydrocarbons 13,16 from C 2 -C90; lower temperature favors larger fragments Continuous spectrum of saturated and unsaturated hydrocarbons 243 C 1 -C 1 5 ; trace of hydrogen In air; CO 2 , H2O, ethene, propene, propane, cyclopropane, butene, 91 butane, pentene, pentane, hexene, hexane, heptene, heptane, octene, octane, methanol, ethanol, furan, tetrahydrofuran, formaldehyde, acetaldehyde, propanal, acrolein, butanal, isobutanal, pentanal, acetone, methyl vinyl ketone, methyl ethyl ketone, 2-pentanone, 2-hexanone, 2-heptanone, formic acid, acetic acid, propionic acid, acrylic acid, butyric acid, isovaleric acid, hydroxyvaleric acid, crotonic acid, caproic acid, butyrolactone, valerolactone CO, H2O, ethene, series of ketones with general structure 270 R_[_CO-CH 2 -CH 2 -] n -CO-R / where R, R' = - C H 3 , -CH 2 -CH 3 or -CH=CH 2 Broad spectrum of saturated and unsaturated hydrocarbons, ethyl esters 243 and carboxylic acids; ethanol, ethylene, CO2, CO and small amounts of ketene and ethyl acrylate Acetic acid, ketene, CO 2 , ethylene, saturated and usaturated 92 hydrocarbons, chain fragment fraction containing some vinyl acetate units Acetic acid > 99% 93 18.1% monomer together with methane, isobutane, and C 5 and 16 higher saturated and unsaturated hydrocarbons As temperature is increased the yields of fragments smaller than 28 monomer increase at the expense of larger fragments
377 170-400 400-500 Ambient to 500 287-400 384
287-400 450-800 500
gutta percha Poly(isoprene)-&/ew
Degradation products
287-400 Ambient to 500 Ambient to 500
49
1.2. POLY(ALKENES) Poly(ethylene) - , low density
Ambient to 500 264-289
Poly(ethylene-co-carbon monoxide) Alternating copolymer
500
Poly(ethylene-c0-ethyl acrylate) 18:1 mole ratio
Ambient to 500
Poly(ethylene-c0-vinyl acetate) (12-33 mol% vinyl acetate) (38.5% (wt.%) of ester groups) Poly(isobutene)
Ambient to 500 260-290 288-425 Up to 1200
TABLE 1. cont'd Polymer
Temperature range (0C) 325 345 365 300-320
Poly(isopropenylcyclohexane)
400-900
Poly(isopropenylcyclohexane-co-amethylstyrene) (92/8 and 33/67)
400-900
Poly(4-methyl-l-pentene)
291-341
Poly(propylene)
328-410 400-1200 360-400
120-280
200-356 Poly (propylene)-£/end-poly (methyl methacrylate)
Poly(vinylcyclohexane)
Ambient to 500
335-391 360-380
Poly(chlorotrifluoro-ethylene)
Ambient to 500
Degradation products
Refs.
At 4.9% weight loss, products are isobutene (64.3%), CH4 (13.6%), 29 neopentane (10.3%); remainder C2-C12 hydrocarbons At 15.7% weight loss, products are isobutene (78.9%), CH4 (5.9%), 29 neopentane (4.7%); remainder C 2-C12 hydrocarbons At 46.8% weight loss, products are isobutene (81.6%), CH4 (3.9%), 29 neopentane (3.1%); remainder C2-C12 hydrocarbons Two types of f-butyl ended and two types of isopropyl ended terminal 249 monoolefins in range 2-mers to 12-mers Methylenecyclohexane and/or methyl-1-cyclohexene, ethylcyclohexane, 94 toluene, isopropenylcyclohexane, isomer of isopropenylcyclohexane, ethyl benzene, isopropylcyclohexadiene, pentadienylcyclohexane (5 isomers), dicyclohexylpropane, 3-cyclohexenyl-l-cyclohexylpentadiene, dicyclohexylhexadiene Methylenecyclohexane and/or methyl-1-cyclohexane, benzene, toluene, 94 isopropenylcyclohexane, ethylbenzene (92/8 only), decalin (92/8 only), cumene (33/67 only), oc-methylstyrene, styrene, (33/67 only), pentadienylcyclohexane (92/8 only), indene and methyleneindene (33/67 only), naphthalene, dicyclohexylhexadiene (92/8 only). The following from the 33/67 copolymer only: 2-methylnaphthalene, 1-methylnaphthalene, biphenyl, methylstilbene, a-methylstilbene, anthracene/phenanthrene, dihydropyrene After 22 hours at 341°C, 20% residue, 71% saturated and 43 chain fragments; 9% of products volatile at 25°C, comprising isobutene (56%), propane (34%), traces of monomer, and hydrocarbons Saturated and hydrocarbons from C2 upwards, monomer yield 0.17% 13 As temperature is raised, yield of small fragments increases at 28 expense of large fragments At 4000C, chain fragments with 7.05 wt.% of volatile products 95 comprising principally, methane 0.057 wt.%, ethane 0.13, propane 0.078, propene 0.83, isobutene 0.16, butane 0.004, 2-methyl-l-butene 0.010, 1-pentene 0.008, pentane 1.62, 2-pentene (cis and trans) 0.015, 2-methyl pentane 0.074, 2-methyl-1-pentene 1.19, 2,4-dimethylpentane 0.032, 2,4-di-methyl-1-pentene 0.089, 4-methylheptane 0.24, 2,4-dimethyl-l-heptene 2.20, 4,6-dimethylnonane (threo form) 0.042 (erythro form) 0.052, 2,4,6-trimethyl-l-nonene (threo form) 0.055 (erythro form) 0.066 In air; ethene, ethane, propene, propane, isobutene, butane, isobutane, 96 pentadiene, 2-methyl-1-pentene, 2,4-dimethyl-1-pentene, 5-methyl-l-heptene, dimethylbenzene, methanol, ethanol, 2-methyl-2-propene-l-ol, 2-methyl furan, 2,5-dimethylfuran, formaldehyde, acetaldehyde, acrolein, propanal, methacrolein, 2-methyl propanal, butanal, 2-vinyl crotonaldehyde, 3-methyl pentanal, 3-methyl hexanal, octanal, nonanal, decanal, ethenone, acetone, 3-buten-2-one, 2-butanone, l-hydroxy-2-propanone, 1-cyclopropylethanone, 3-methyl-2-buten-2-one, 3-penten-2-one, 2-pentanone, 2,3-butanedione Under 254 nm radiation; additional methane and ethylene are formed 97 compared with the thermal reaction Poly (methyl methacrylate) stabilized by blending with polypropylene; 99 pre-irradiation with 2537 A radiation at ambient temperature reduces amount of methyl methacrylate formed on subsequent thermal degradation; missing methyl methacrylate units appear in a chain fragment fraction Small amounts of cyclohexane, cyclohexane, methylcyclohexene, methyl 2,3 cyclohexane, vinylcyclohexene, vinylcyclohexane, ethylcyclohexane with larger chain fragments Cyclohexane (main product), cyclohexene, vinylcyclohexane, vinylcyclo 100 hexane oligomers, methane, ethane, ethylene, propane, propylene, butane, butylene, hydrogen Monomer, traces of dichlorodifluoroethene, chloropentafluoropropene, 261 trichlorotrifluoroethane
References page II - 475
TABLE 1. cont'd Polymer
Temperature range (0C)
Degradation products
Refs.
1.3. POLY(ACRYLICS), POLY(METHACRYLICS) Poly(acrylic acid)
- , methyl ester
Ambient to 500
292-399
Up to 980
50 - , ethyl ester
300-500 50 Ambient to 500
- , w-propyl ester
300-500
- , isopropyl ester
250-500
- , n-butyl ester
300-500 50
- , tert-butyl ester -, 2-ethyl hexyl ester - , benzyl ester
>160 300-500 260-300
-, 1,1,5-trihydroperfluoroamyl ester
300-315
- , 2,2,2-trichloroethyl ester
319
- , oc-bromo-, methyl ester - , a-chloro-, methyl ester - , a-chloro-, .sec-butyl ester -, a-cyano-, methyl ester - , a-phenyl-, methyl ester Poly (acrylic acid, magnesium salt)
110-150 600 600 190 > 180 210-280 Ambient to 500
Poly(acrylic acid, calcium salt)
Ambient to 500
CO, CO 2 , H 2 O, CH 4 , acetone, ketene, ethene, propylene, 1-butene, 297 methyl vinyl ketone, benzene, acrylic acid, toluene, xylene, short chain fragments such as dimer to octamer with unsaturated and anhydride functionalities 26% of products are volatile at 25°C, mainly methyl alcohol and 2,3 carbon dioxide with traces of monomer and methyl methacrylate and C 4-C 6 oxygenated compounds (74% of products are large chain fragments involatile at 250C) Methanol (1.9%), methyl formate (trace), methyl acetate (1.4%), methyl 101 acrylate (19.0%), methyl methacrylate (1.9%), saturated ester (2.1%), dimethyl glutarate (7.5%), methyl 4-methoxycarbonyl-pent-4-enoate (11.6%), trimethyl pentane 1,3,5-tricarboxylate (0.6%) methyl 4,6-di-methoxycarbonylhept-6-enoate (53%), saturated and tetramers (1.0%) Irradiated with high-pressure mercury lamp; methanol, formaldehyde, 102 methyl acetate, methyl formate, CO 2 , CO, H 2 , CH 4 Major products, carbon dioxide, ethylene, ethanol, and chain fragments; 103 minor products, ethane, ethyl acrylate, and ethyl methacrylate Irradiated with high-pressure mercury lamp; CO, CO 2 , ethanol, acetalde- 104 hyde, ethane, ethyl formate, acetal, ethyl propionate Ethylene, carbon dioxide, trace of ketene, ethanol (major product), 243 various ethyl esters (see Ref.) Major products carbon dioxide, propene, propanol, and chain fragments; 103 minor products, propane, carbon monoxide, hydrogen, rc-propyl acrylate, and w-propyl methacrylate Major products carbon dioxide, propene; minor products isopropanol 105 with trace carbon monoxide Major products carbon dioxide, 1-butene, butanol, and chain fragments; 103 minor products, butane, /i-butyl acrylate, and n-butyl methacrylate Irradiated with high-pressure mercury lamp. CO, CO 2 rc-butanol, 104 butyraldehyde, «-butene, n-butyl formate, n-butyl valerate (after prolonged exposure) 86% isobutylene, 11% water, 3% carbon dioxide 4 Carbon dioxide, 2-ethyl-l-hexene, 2-ethyl-l-hexanol 103 Major products are benzyl alcohol, chain fragments, partially crosslinked 1 residue; minor products are CO 2 , toluene, CO, CH 4 , H 2 CO 2 , benzyl alcohol, and low polymers 106 Oligomers, 1,1,5-trihydroperfluoroamyl alcohol, monomer, 1,1,5-trihydro- 107 perfluoroamyl methacrylate 2,2,2-Trichloroethanol (80%), monomer (9%), 1,1-dichloroethene, 263 2-chloroethanal, 2,2-dichloroethanal, 1,1-dichloropropane, 1,1,1 -trichloroethane, 2,2,2-trichloroethylethanoate, 2,2,2-trichloroethyl chloromethanoate, 2,2,2-trichloroethylpropanoate, 2,2,2-trichloroethylmethacrylate, 2,2,2-trichloroethyl chloroethanoate, 2,2,2-trichloroethyl-2-chloroacrylate Methylbromide, hydrogen bromide 5 CO 2 , propene, methyl bromide, vinyl bromide 305 CO 2 , propene, methyl chloride, monomer 306 sec-Butyl chloride, butylene, hydrogen chloride 7 Yellows and some monomer formed 6 Monomer is the sole product 8 CO, CH 4 , CO 2 , acetone, ketene, ethene, propene, 1-butene, benzene, 312 toluene, xylene, cyclopentene, methyl ethyl ketone, diethyl ketone, methyl-«-propyl ketone, di-w-propyl ketone, methyl vinyl ketone, methyl isopropenyl ketone, methyl isopropyl ketone, ethyl vinyl ketone, trace amounts of methyl-w-butyl ketone, cyclopentanone, cyclohexanone, acrolein, ethanal and butanal, chain fragments, some monomer CO, CH 4 , CO 2 , acetone, ketene, ethene, propene, 1-butene, benzene, 312 toluene, mesitylene, xylene, methyl ethyl ketone, diethyl ketone, methyl-H-propyl ketone, methyl-fl-butyl ketone, ethyl vinyl ketone, methyl propenyl ketone (trace), ethyl propyl ketone (trace), 3-methyl-cyclopentanone, cyclohexanone (trace), cyclohexa-2-enone,
TABLE 1. cont'd Polymer
Temperature range (0C)
Poly (acrylic acid, sodium salt)
Ambient to 500
Poly(acrylic acid, potassium salt)
Ambient to 500
Poly(methyl acrylate-co-methyl methacrylate) (mole ratios 112/1-2/1)
Ambient to 500
Poly (methyl acrylate-co-acryloyl chloride) 6, 15, 41, 83 mol% AC
Ambient to 500
Poly (methyl acrylate-co-2-bromoethyl methyacrylate) (10-82 mol% methyl acrylate) Poly(methyl acry\ate)-blendpoly((2-bromoethyl methacrylate) (50/50, w/w) Poly(/i-butyl acrylate-co-methyl methacrylate) (3.9-93.4 mol% butyl acrylate)
Ambient to 500
Ambient to 500
313-332
165
Poly(terf-butyl acrylate-co-glycidyl methacrylate) (34/66) Poly(methyl-oc-chloroacrylatec0-2,2,2-trifluoroethyl methacrylate) (70/30) Poly(methyl-a-chloroacrylate-co-2,2,2trifluoroethyl methacrylate) (70/30) Poly(acrylonitrile)
0-700 Ambient
Ambient <200 250-280
280-450 250-350 235 - , a-chloro - , a-phenyl Poly (aery lonitrile-co-2-bromoethyl methacrylate (50/50, mol/mol) Poly(acrylonitrile-co-methyl methacrylate)( 1/410-1/8)
150-200 Ambient to 500 Ambient to 500 Below 310 310-500 220-280
Degradation products
Refs.
2-methyl-cyclohexanone, l-methyl-cyclohexa-l-ene-3-one (trace), acrolein, mesityl oxide, ethanal, propanal, butanal, chain fragments, some monomer CO, CH 4 , CO 2, ketene, 1-butene, propene, acetone, methyl ethyl ketone, 303 methyl isopropyl ketone, methyl-fi-propyl ketone, diethyl ketone, methyl propenyl ketone, 3-hexanone, toluene, 2-hexanone, 1,3-cyclopentadiene, cyclopentanone, 2-methyl cyclopentanone, mesityl oxide, xylenes, benzene, propionaldehyde, acrolein, acetaldehyde, ethene, short chain fragments, traces of monomer CO, CH4, CO2, ketene, 1-butene, propene, acetone, methyl ethyl ketone, 303 methyl rc-propyl ketone, 1,4-cyclohexadiene, toluene, 1-methyl-1,3-cyclohexadiene, 2-hexanone, cyclopentene, 1-methyl cyclopentene, mesityl oxide, xylenes, benzene, ethene, cyclopentanone, 1,3-cyclopentadiene, diethyl ketone, short chain fragments, traces of monomer Monomers, CO2, chain fragments larger than monomer, H2; 108,109 more stable than poly(methyl methacrylate); rapid decrease in molecular weight; products of phtodegradation at 170° by 254 nm radiation are qualitatively similar Acrylic acid, HCl, H2O, CO, CO 2, acryloyl chloride, methyl acrylate, 262 methyl acrylate chain fragments, anhydride and y-lactone structures, chloro-methane, methyl methacrylate, methanol, 3,5-(6-chloro-2-pyrone) and fragments thereof, C6, C9, C12, C15 fragments. Relative yields depend upon copolymer composition CO 2, ketene, methyl bromide, acetaldehyde, methyl acrylate, methanol, 110 1,2-dibromoethane, methyl methacrylate, 2-bromoethanol, ethyl methacrylate, CH 4 , CO, H 2 modified chain fragments CO2, ketene (minor), methyl bromide, vinyl bromide (minor), acetalde111 hyde, methanol, methyl methacrylate, methyl acrylate, 1,2-dibromoethane, 2-bromoethyl methacrylate 1-Butene, carbon dioxide, butanol methyl methacrylate, butyl acrylate, 112 and butyl methacrylate; small quantities of methane, ethane, propane, butane, ethylene, propene, cis, and trans 2-butene, hydrogen, and carbon monoxide increase with butyl acrylate content of the copolymer Under 2537 A radiation; methyl methacrylate with smaller quantities of 113 n-butyl acrylate, n-butanol, n-butyraldehyde, hydrogen, carbon monoxide, and methane; a chain fragment fraction increases with rc-butyl acrylate content CO, CO 2, propene, ethanal, isobutene, acrolein, allyl alcohol 114 Gamma Radiolysis; CH 4 , CO, ethylene, ethane, CH 3 OH, CHF3, HCl, C 3 H 6 , CO 2 , C 2 H 3 F, CH 3 Cl, methyl formate, CH 3 CH 2 Cl, CHF3, CH 3 CF 3 , C H 2 = C ( C H 3 ) C O O C H 2 C F 3 Gamma Radiolysis; CH 4 , CO, ethylene, ethane, CH 3 OH, HCl, C 3 H 6 , CO 2 , CH 3 Cl, methyl formate, CH 3 CH 2 Cl, CH 2 Cl 2 , CHCl3 Colours through yellow, orange, red, and black 12% of products are volatile at 25°C, consisting of hydrogen cyanide, acrylonitrile, and vinyl acetonitrile; 88% of products are involatile at room temperature Five major volatile products are cyanogen, HCN, acrylonitrile, acetonitrile, vinyl acetonitrile; involatile residue remains NH 3 , HCN HCN, hydrogenated acrylonitrile, dimer and trimer, acetonitrile, methacrylonitrile Hydrogen chloride Hydrogen chloride and small amount of HCN at higher temperatures High yields of monomer Ethylene, CO 2 , vinyl bromide acetaldehyde, 1,2-dibromoethane Propane, isobutene, CO 2 , HCN, isocyanic acid, yellow-chain fragment fraction Only methyl methacrylate from 410/1 and 40/1 (molar ratio) copolymers; methyl methacrylate and small amounts of acrylonitrile from 16/1 and 8/1 copolymers; rapid decrease in the molecular weight of all copolymers
115
115 9 10,11
12 116 117 118 119 119 120 121 121
References page II - 475
TABLE 1. cont'd Polymer
Temperature range (0C) 160
Poly(acrylonitrile-c0-methyl vinyl ketone) Poly(acrylonitrile-co-styrene) (0/100-50/50, mol/mol)
(1.86-96.62 mol% acrylonitrile)
Poly(acrylonitrile-co vinyl acetate) (7.5 wt.% vinyl acetate) Poly(acrylonitrile-co-methyl acrylate-co-vinyl bromide) (methyl acrylate, 10 wt.%; vinyl bromide, 5 wt.%) Poly(a-chloroacrylonitrile-co methyl methacrylate) (0-50 mol% a-chloroacrylonitrile) Poly (aciylonitrile)-We/idpoly(methyl methacrylate) (50/50, w/w) Poly(acryloyl chloride) Poly(methacrylic acid)
292
500
260 180-320
> 150 Ambient Up to 320 320-500 Ambient to 500 200 900
- , methyl ester
- , ethyl ester - , rc-propyl ester - , iso-propyl ester - , fz-butyl ester - , wo-butyl ester - , s^c-butyl ester - , tert-butyl ester
-, -, -, -, -, -, -, -,
n-amyl ester wo-amyl ester 1,2-dimethylpropyl ester neopentyl ester 3,3-dimethylbutyl ester 1,3-dimethylbutyl ester 2-bromoethyl ester 2-sulfoethyl ester
- , 2-chloroethyl ester
170-300 246-400 160 100-400 250 245 250 250 250 170 250 250 180-200 < 180 250 250 250 250 250 250 Ambient to 500 50-600 600 600 268
Degradation products Photodegradation by 254 nm radiation gives methyl methacrylate from 410/1 to 8/1 copolymers with a 8/1 copolymer; rapid decrease in the molecular weight of all copolymers Production of water from poly(methyl vinyl ketone) accelerated by copolymerization with acrylonitrile Acrylonitrile causes increase in rate of chain scission; proportion of acrylonitrile among degradation products greater than from pure polyacrylonitrile; chain fragments increase with acrylonitrile content of copolymer; styrene, acrylonitrile, toluene, benzene, four dimers, and four trimers Hydrocyanic acid, acetonitrile, acrylonitrile, propionitrile, toluene, ethyl benzene, styrene, methane, ethylene, ethane, C 3 hydrocarbons, but-1-ene, prop-l-ene-3-nitrile, isopropylnitrile, benzene HCN, hydrogenated acrylonitrile, dimer and trimer, acetonitrile, methacrylonitrile, acetic acid CH3Br, HBr, H 2 O, CO 2 , CH 3 OH, NH 3 , HCN, hydrogenated acrylonitrile, dimer and trimer, acetonitrile, methacrylonitrile, naphthyridine fragments Hydrogen chloride, methyl methacrylate, oc-chloroacrylonitrile
Refs. 121
122 123
124
117 117
125
Under 254 nm radiation. HCl, CO 2 , methyl chloride, methyl formate, 126 methanol, methyl methacrylate, CO, CH 4, H 2 NH 3 , HCN, MMA 127 Chain-fragment fraction and small amounts of CO, CO 2 , methanol, CH 4 Acrylic acid, HCl, H 2 O, CO, acryloyl chloride, 3,5-(6-chloro-2-pyrone) 262 and fragments thereof, C6, C9, Cj 2 , C15 fragments Almost quantitative yields of H 2 O, traces of monomer, residue of 33 poly(methacrylic anhydride) CO 2 , propene, butenes, pentenes, pentadienes, hexene, hexadienes, 128 hexatrienes, benzene, toluene, heptene, heptatriene, methacrylic acid, xylene, octatriene, octadienyne, nonatriene, hexadienoic acid, decatriene, decatetraene, decapentaene, undecatriene, methylbenzoic acids, trimethylbenzoic acid 100% monomer 34, 35 As temperature is raised fragmentation increases to give complex 2 series of products and monomer yields correspondingly decreases 100% monomer under 253.7nm radiation 36 Under 254 nm radiation; 100% monomer 129 Monomer 37 Monomer, ethanol, ethanoic acid 300 Monomer 37 Monomer 37 40% monomer and traces of 1-butene 38 100% monomer under 253.7nm radiation 38 Monomer 37 Monomer and small amount of olefin by cracking of side chain 37 High yields of isobutylene and water, 1% monomer, trace of methacrylic 39 acid, residue of poly(methacrylic anhydride) 100% monomer under 253.7 nm radiation Monomer 37 Monomer 37 Monomer and small amount of olefin by side chain cracking 37 Monomer 37 Monomer 37 Monomer and small amount of olefin by side chain cracking 37 2-Bromoethyl methacrylate (>95%), CO 2 (< 1%), vinyl bromide (< 1%) 130 CO, CO 2 , H 2 O, SO 2 , ethene 290 CO, CO 2 , propene, acetaldehyde, methyl bromide, butene, 305 vinyl bromide, ethyl bromide, methyl methacrylate CO 2 , propene, acetaldehyde, vinyl chloride, ethyl chloride, monomer 306 Monomer (99%), traces of acetaldehyde, methyl methacrylate, 268 1,2-dichloroethane, ethylene methacrylate
TABLE 1. cont'd Polymer
Temperature range (0C)
Degradation products
Refs.
Poly(methacrylic acid), 2-fluoroethyl ester - , 2,2-dichloroethyl ester
600
CO 2, vinyl fluoride, acetaldehyde,
242
- , 2-methoxyethyl ester
Ambient to 300 Ambient to 500
Monomer (90.7%), chloroacetaldehyde (8%), 1,1,2-trichloroethane (0.5%), 268 2,2-dichloroethanol, methacrylic acid (0.1%), 2-chloroethylene methacrylate (0.1%) Monomer, CO 2 309 Monomer, CO 2 , CO, CH4, ethene, formaldehyde, isobutene, methyl 309 vinyl ether, methanol CO 2 , propene, acetaldehyde, methyl bromide, butene, ethyl bromide, 305 bromocyclopropane or 2-bromopropane 2-Hydroxyethyl methacrylate (20% at 5000C), ethylene dimethacrylate 131 (6%at 500°C)(main products), ethylene glycol, 3-methyl-5-hydroxy6-valerolactone (probably), 1,2-di-iospropenyl-oxyethane (probably), CO, CO2, methane, ethylene, ethane, propane, H2O Gamma radiolysis; CH4, CO, ethylene, ethane, CH3OH, CH3F, C 3 H 6 , 115 CO 2 , C 2 H 3 F, methyl formate, CH3CHFOH, CHF3, CF3CH3, CF3OH, CH2 = C(CH3)-COOCH2CF3 CO 2 , vinylidene fluoride, trifluoroacetaldehyde, trifluorethanol, 310 monomer CO 2 , propene, vinyl chloride, vinylidene chloride 306 1,1-Dichloroethene, chloroform, methyl methacrylate, methacrylic acid, 300 2,2,2-trichloroethanol, 2,2,2-trichloroethyl acrylate, 2,2,2-trichloroethyl methacrylate, 2,2-dichloroethyl methacrylate, CH2 = C(CH3)-COOCHI=CCl2 or CH2 = C(CH3)-COOCCl = CHCl CO 2 , trifluoracetaldehyde, acetaldehyde, 1,1,1,3,3,3-hexafluoropropane, 310 hexafluoro-isopropylformate CO 2 , SO 2 , phenol, bisphenol S, hydroquinone, fragments of backbone, 248 benzene sulfonic acid CO 2 , CH4, CO, H 2 , propene, isobutene, dimethyl ketene, acrolein, 283 diallyl ether, allyl methacrylate monomer and dimer, chain fragments including anhydride structures from side-group cyclization and an aliphatic ketone in the vicinity of unsaturation Monomer, some CO2 314 CO, CO 2 , dimethyl ketene, isobutene, propene, acrolein, allyl alcohol, 302 glycidyl methacrylate, glycidol, short chain fragments with some unsaturation Isocyanic acid, NH 3 , HCN, isobutene, CO2 (trace), methacrylonitrile 132 (trace) Ethylene, butene-1, isobutene, acetylene, CO 2 , CH4, CO, acetone, 133 isopropylaldehyde, methacrolein, butyraldehyde, methyl ethyl ketone, benzene (trace), methyl isopropyl ketones, methyl isopropenyl ketone, diethyl ketone, methyl rc-propenyl ketone, cyclopentanone, methyl cyclopentanone, dimethyl cyclopentanone, dimethyl cyclopentenone and traces of toluene, di-isopropyl ketone, mesitylene, mesityl oxide CO2, dimethyl ketene trace amounts of CO, CH4, isobutene, butene-1, 134 ethylene, acetylene, benzene toluene isobutyraldehyde, methyl ethyl ketone, methyl isopropenyl ketone, diethyl ketone, methyl isopropenyl ketone, di-isopropyl ketone, cyclopentanone, 2-methyl cyclopentanone, 2,5-dimethyl-cyclopentanone, 2,5-dimethylcyclopent-3-ene-l-one, methacrolein, butyraldehyde Monomer 194 Monomer, phthalic anhydride, diethylene glycol, C 2 H 4 , propylene, CO2 194 CO 2 , alkenes, CH4, CO, propanal methanol (major), acetone, 2-methyl 135 propanal, methacrolein, butanal, methyl ethyl ketone, methyl isopropyl ketone, methyl isopropenyl ketone, methyl methacrylate (major), methyl prop-2-enyl ketone, toluene, di-isopropyl ketone, cyclopentanone, 2-methyl cyclopentanone, 2,5-dimethyl cyclopentanone, 2,5-di-methyl cyclopent-3-enone. Relative yields depend upon salt and copolymer composition Methyl methacrylate, 2-bromoethyl methacrylate, traces of vinyl bromide 130 and CO2
- , 2,3-dibromopropyl ester
600
-, 2-hydroxyethyl ester
375-500
- , 2,2,2-trifluoroethyl ester
Ambient 600
- , 2,2,2-trichloroethyl ester
600 240
- , hexafluoroisopropyl ester
600
- , bisphenol S ester
464
- , allyl ester
Ambient to 500
- , phenyl ester - , glycidyl ester
Ambient to 500 Ambient to 500
- , ammonium salt
Ambient to 500
- , Li, Na, K, and Co salts
Ambient to 500
- , Mg, Ca, Sr, and Ba salts
Ambient to 500
Poly[a-co-(diethylene glycol phthalate)dimethacrylate] Poly(methyl methacrylate-co-alkali (metal methacrylates) (Li, Na, K) (0-100 mol%)
300 400 Ambient to 500
Poly (methyl methacrylate-co2-bromoethyl methacrylate) (50/50, mol/mol) Poly(methyl methacrylateco-methacrylamide)
Ambient to 500 Up to 340
fluoroacetaldehyde
> 35 mol% methacrylamide. MMA, methanol, NH3, H 2 O
310
146
References page 11-475
TABLE 1. cont'd Polymer
Temperature range (0C) >340
Poly(methyl methacrylate-comethacrylic acid)
Poly(methyl methacrylate-co2-chloroethylmethacrylate) 22 mol% CEMA Poly (methyl methacrylateco2,2,2-trichloroethyl methacrylate) 24 mol% TCEMA Poly (methyl methacrylatecomethyl-oc-chloroacrylate) 38 mol% MCA Poly(methyl methacrylatec6>-2-bromoethyl methacrylate) 22 mol% BEMA Poly (methyl methacrylateco-2,3-dibromopropyl methacrylate) 16 mol% DBPMA Poly (methyl methacrylateco-methyl-a-bromoacrylate) 22 mol% MBA Poly(methyl methacrylateco-chlorotrifluoroethylene) 7.7 mol% MMA 77.7 and 85.7 mol% MMA Poly(methyl methacrylateco-2-sulfoethyl methacrylate) 20, 40, 60 mol% MMA Poly(methyl methacrylateco-4-vinylpyridine) 22, 35, 46, 56 mol% 4vinyl pyridine Poly (methyl methacrylatecophenyl methacrylate) 9, 18, 47, 88 mol% PMA
<300 >300 900
600
Degradation products Methacrylamide; chain fragments and small amounts of CH4, CO2, CO, HCN, methacrylonitrile and isobutene < 10 mol% methacrylamide. Degradation becomes progressively more like that of PMMA Water and methanol Methyl methacrylate, CO2, CO, CH4 (50/50 and 75/25); CO2, propene, butenes, pentenes, pentadienes, hexene, hexadienes, hexatrienes, benzene, methyl isobutyrate, methyl methacrylate, toluene, heptene, heptatriene, methyl pentenoate, methacrylic acid, xylene, octatriene, octadienyne, nonatriene, hexadienoic acid, decatriene, decatetraene, decapentaene, undecatriene, methylbenzoic acids CO2, propene, acetaldehyde, vinyl chloride, ethyl chloride, methyl methacrylate
Refs. 146 146 136 128
306
600
CO2, propene, vinyl chloride, vinylidene chloride, dichloroacetaldehyde, methyl methacrylate
306
600
CO2, propene, methyl chloride, methyl methacrylate
306
600
CO2, propene, acetaldehyde, methyl bromide, butene, vinyl bromide, methyl methacrylate
305
600
CO, CO 2 , ethene, propene, methyl bromide, butene, vinyl bromide, ethyl bromide, 1-bromopropene, 2-bromopropene, cyclopropyl bromide, methyl methacrylate
305
600
CO 2 , acetaldehyde, methyl bromide, butene, vinyl bromide, unidentified alkenyl bromides, methyl methacrylate
305
Ambient to 500
HCl, CO 2 , CH3Cl, C 2 F 3 Cl (monomer), C3F5Cl, C 2 F 3 Cl 3 , methyl methacrylate, chain fragments possibly with some lactonization
281
Ambient to 500 50-600
HCl, CO 2 , CH3Cl, C 2 F 3 Cl (monomer), methyl methacrylate CO, CO2, H2O, SO2, ethene, methanol, methyl methacrylate (only 60 and 80 mol% methyl methacrylate copolymers)
281 290
Ambient to 500
4-vinyl pyridine, methyl methacrylate, traces of pyridine and 4-methyl pyridine
260
Ambient to 500
CO 2 , isobutene, ketene, formaldehyde, methanol, methyl methacrylate, phenyl methacrylate, chain fragments including six-membered anhydride ring structures. Product distribution varies with copolymer composition with non-monomer products most pronounced at low PMA contents CH4, CO, CO 2 , propene, isobutene, dimethyl ketene, acrolein, allyl alcohol, glycidol, glycidyl methyl ether, methyl methacrylate, glycidyl methacrylate, chain fragments. Distribution varies with copolymer composition CO, CH4, CO 2 , ethene, propene, isobutene, aziridine, methanol, methyl methacrylate, a-methylstyrene, 2-phenyl-2-butene, l-r-butylamino-2-isopropenylamino-ethane, 2-r-butylaminoethyl-ethylisopropenylamine, 2-aminoethyl-2-?-butylaminoethylisopropenylamine, oligomers - principally butylaziridine based
314
Poly(methyl methacrylatecoglycidyl methacrylate)
Ambient to 500
Poly (methyl methacrylate -/?/6>c£-j-butylaziridine) ABA type copolymer with MW 12000 butylaziridine (B) and MW 16000 MMA (A) Poly(methyl methacrylate-co-styrene)
Ambient to 600
Poly (methyl methacrylate-covinyl acetate) (5-40 mol% vinyl acetate)
Ambient to 500
260-340
286
287
Methyl methacrylate, styrene and oligomers of styrene; formation of 137 oligomers of styrene strongly inhibited by presence of methyl methacrylate units Acetic acid, methyl methacrylate, methyl acetate, chain fragment fraction, 92 ketene, CO2
TABLE 1. cont'd Polymer
Temperature range (0C)
Poly(methyl methacrylate-co-vinyl bromide) (6-75 mol% vinyl bromide)
Ambient to 500
Poly(2-bromoethyl methacrylateco-styrene) (50/50, mol/mol) Poly(methyl methacrylate)-blendammonium polyphosphate
Ambient to 500 Ambient to 450
Poly (methyl methacrylate)-&/e/2
Ambient to 500
Poly(methyl methacrylate)-&/endpoly (vinyl acetate) (10/1-1/1, w/w) Poly(methyl methacrylate)-£/era/poly(vinyl bromide) (50/50, mol/mol) Poly(methyl methacry\ate)-blendpoly(vinyl chloride) Poly(methacrylamide)
Ambient to 500
Poly(methacrylonitrile)
Ambient to 500 Ambient to 500 Up to 340 Above 340 Ambient to 500 < 200 220-270 Ambient to 500
Poly(methacrylonitrile-c0styrene) 10:1 mole ratio
Ambient to 500
Poly(methacrylonitrileco-styrene) 1:1 mole ratio
Ambient to 500
Poly(methacrylonitrileco-styrene) 1:10 mole ratio
Ambient to 500
1.4.
Degradation products
Refs.
Methyl methacrylate, methyl bromide, methanol, CO2, methanol, HBr, CO, H2 and other unidentified minor products. Relative amounts depend upon copolymer composition Styrene, 2-bromoethyl methacrylate, modified chain fragement fraction. Minor products; ethylene, CO 2, HBr, vinyl bromide, acetaldehyde H2O and NH3 from ammonium polyphosphate. Methyl methacrylate (major product), CO, CO2, methanol, dimethyl ether, hydrocarbons, high boiling chain fragments Polymers degrade separately without interaction to give same products as polymers degraded separately; copolymers and mixtures of the same molar compositions can be distinguished by degradation behavior Methyl methacrylate, acetic acid, methyl acetate, methanol, CO2, butene, benzene, ketene Methyl methacrylate, HBr, CO, CO 2 and other unidentified products
138
139 140
141
142 143
Major products: HCl, methyl methacrylate; minor products: CO 2 , 144,145 methyl chloride, benzene NH 3 and H 2 O 146 Chain fragments (50%) in which a high proportion of amide groups have 146 been converted to cyclic imides; small amounts of CO 2, CH 4, HCN NH 3 , HCN, isobutene, CO 2 (trace), methacrylonitrile (trace) 132 Non-volatile material, coloration through yellow, orange, and red 40 50-100% monomer depending upon pretreatment and purity of polymer 40 Ethene, propene, isobutene, HCN, CO 2 (from benzoyl peroxide end 277 groups), methacrylonitrile (major product), 2-cyanobutane, 2-cyanopentene, CH 4 Ethene, isobutene, HCN, methacrylonitrile, styrene, toluene, 279 a-methylstyrene, p-methylstyrene, 2-phenylbutene, 4-cyano2,4-dimethylpentene, 4-phenyl-2-methylbutene, 3-phenyl2-propenenitrile, chain fragments Ethene, isobutene, HCN, methacrylonitrile, styrene, toluene, 279 a-methylstyrene, 4-phenylbutene, 4-phenyl-2-methylbutene, 3-phenyl-2-propenenitrile, chain fragments Ethene, isobutene, HCN, methacrylonitrile, styrene, toluene, 279 a-methylstyrene, p-methylstyrene, 4-phenylbutene, allylbenzene, 4-phenyl-2-methylbutene, 3-phenyl-2-propenenitrile, chain fragments
POLY(VINYLS)
Poly(tert-butyl-Af-vinyl carbamate) Poly(chlorotrifluoroethylene) (KEL-F)
185-220 347-418
Poly(l,l-dichloro-2,2-difluoroethylene) Poly(perfluoroheptene) Poly(perfluoropropylene) Poly(tetrafluoroethylene)
240 210-270 280-400 504-538 1200 600-700
Poly(trifluoroethylene) Poly(vinyl acetate)
380-800 213-235 300 280-350
Poly (vinyl acetate) in presence of zinc bromide Poly(vinyl acetate-comaleic anhydride) alternating copolymer Poly (vinyl acetate-cocrotonic acid) alternating copolymer
Ambient to 500
Equal amounts of CO 2 and isobutylene, in yields ranging from 43 to 60% 196 25% of products volatile at 25°C-monomer with traces of C 3 F 5 Cl 14 and C 3 F4C1 2 ; 72.1% of larger chain fragments involatile at 25°C 20% black involatile residue; 80% monomer 22 100% monomer 49 100% monomer 49 >95% monomer, 2 - 3 % C 3 Fe, no larger fragments (in vacuum) 14 Monomer yield drops, larger fragments appear (in vacuum) 23 At 6.66 mbar pressure; pure monomer; at 1013 mbar pressure, 24 15.9% monomer, 25.7% C 3 F 6 , 58.4% C 4 F 8 High yields of HF and products involatile at 25°C 23 Quantitative yields of acetic acid 71 Small amounts of aromatics including benzene 71 Acetic acid, benzene, naphthalene, toluene, styrene, ethyl benzene, 147 propenyl benzene, propylbenzene, methylnaphthalene, ethylnaphthalene, propenylnaphthalene, propylnaphthalene, anthracene, methylanthracene, ethylanthracene, propylanthracene Acetic acid produced as low as 1000C 148
Ambient to 500
Acetic acid, CO 2, H 2 O, maleic anhydride, CO
240
Ambient to 500
Ethene, propene, acetic acid, CO 2 , propanoic acid, 2-methylpropanoic acid, butanoic acid, cyclopentanone, some unsaturated cyclic and acyclic aliphatic ketones, some chain fragments containing lactones
241
References page 11-475
TABLE 1. cont'd Polymer Poly (vinyl acetate-comethylvinylidene cyanide) Alternating with 10-15 mol% VA homosequence Poly (vinyl acetate-co-styrene) (5-20 mol% vinyl acetate) Poly(vinyl acetate-co-vinyl alcohol) (50-99 mol% vinyl alcohol) Poly (vinyl acetate-co-vinyl chloride)
0
Temperature range ( C) 285-350
Ambient to 500 0-600 Ambient to 500
180 Poly (vinyl acetate-co-vinyl fluoride) (91:9 to 1:89) (80:20 to 23:77) Poly (vinyl acetate)-blendpoly(styrene) (1/1, w/w) Poly(vinyl acetate-blendpoly (vinyl chloride) Poly (vinyl alcohol)
Poly (vinyl bromide) Poly(vinyl butyrate) Poly(A^-vinylcarbazole)
200-500
Vinyl acetate, acetonitrile, HCN, acetic acid, acetamide, 2-methyl1-aminonaphthalene, 3-cyano-3-pentene Acetic acid, styrene, chain fragment fraction, ketene, CO 2 Acetaldehyde, acetone, benzene, crotonaldehyde, acetic acid
Refs. 266
92 154
Bulk polymer; hydrogen chloride and acetic acid in the proportions of 155 the monomers in the copolymer; at each end of the composition range, incorporation of the comonomer results in a copolymer less stable than the homopolymer; minimum stability at 40-50 mol% vinyl acetate In tritolyl phosphate solution; similar to bulk polymer with minimum in 156 stability at 30-40 mol% vinyl acetate Hydrogen fluoride, acetic acid, hydrocarbons 150
200-500 Ambient to 500
Hydrogen fluoride, HCl, hydrocarbons Products as for individual polymers
Ambient to 500
Ambient to 500
Acetic acid, HCl, and traces of CO 2, ketene, acetyl chloride, CO 157 and CH 4 Quantitative yields of H 2 O 72 Main products H 2 O and C 2 H 5 OH, with aldehydes 73 CH 3 -(CH = CH) n -CHO and ketones C H 3 - ( C H = C H ) n - C O C H 3 where n = 0,1,2, etc. HBr, ethylene, benzene, and other unidentified minor products 143 Butyric acid 74 Below 350°, monomer; above 350°, monomer and low-molecular 175 weight oligomers Monomer (49% of total volatiles at 3000C, 39% at 5000C) ethane, 244 ethene, propene, n-butane, isobutene, cis and trans but-2-ene, 1,3-butadiene, 2-methylbutadiene, trace amounts of C 5 and C 6 hydrocarbons Monomer (83% of total volatiles at 3000C, 67% at 5000C), ethane, 244 ethene, propene, w-butane, isobutene, cis and trans but-2-ene, 1,3- butadiene, 2-methylbutadiene, trace amounts of C 5 and C 6 hydrocarbons Monomer (48% of total volatiles at 3500C, 40% at 500°C), ethane, 244 ethene, propene, /i-butane, isobutene, cis and trans but-2-ene, 1,3-butadiene, 2-methylbutadiene, trace amounts of C 5 and C 6 hydrocarbons Quantitative yields of HCl 75 Saturated and unsaturated, aliphatic and aromatic hydrocarbons are 75 produced with benzene and toluene in high yield In helium; quantitative yield of HCl, remainder residue and 76 hydrocarbons; benzene is major volatile hydrocarbons product Aliphatic hydrocarbons, benzene (major product), toluene, ethylbenzene, 149 o-xylene, monochlorobenzene, styrene, vinyl toluene, p-dichlorobenzene, o-dichlorobenzene, indene, 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, naphthalene, a-methylnaphthalene, (3-methylnaphthalene; effect of ZnO, SnO 2 , and Al 2 O 3 on the yields of products is also recorded HCl, CO 2 , ethene, ethane, propane, 1-butene, 2-butene, 1-pentene, 267 cyclopentene, n-pentane, 2-methylbutane, 1,3-pentadiene, 2-methyl-1,3-pentadiene, complex series (60 identified) of aromatic and polyaromatic species, including benzene, styrene, methylstyrenes, toluene, o-xylene, m-xylene, /?-xylene, biphenyl, naphthalene, anthracene, phenanthrene, pyrene, etc. (see Ref.) HCl, a-methyl styrene 159
Ambient to 500
HCl, styrene
159
Ambient to 500 Ambient to 500
Products as for individual polymers CO 2 , HCl, benzene, traces of toluene, phenol and other phenolic compounds, bisphenol A, polycarbonate chain fragments
160 291
250 240
300-325 230-410 300-500
Poly(3,6-dichloro N-vinylcarbazole)
300-500
Poly(3,6-dibromo 7V-vinylcarbazole)
350-500
Poly(vinyl chloride)
200-300 400 600 200-800
Ambient to 1000
Poly (vinyl chloride)-&/era/poly(a-methylstyrene) Poly (vinyl chloride)-№ra/poly(styrene) (10/1 to 1/10, w/w) PVC 1:1 blend with bisphenol A polycarbonate
Degradation products
150 158
TABLE 1. cont'd Temperature range (0C)
Polymer PVC 1: 1 blend with poly(dimethylsiloxane) Poly(vinyl fluoride)
Poly(vinylidene chloride) Poly(vinylidene cyanide) Poly(vinylidene
fluoride)
Poly(vinylidene fluorideco-chlorotrifluoroethylene) 80 mol% vinylidene fluoride 3, 10 mol% vinylidene fluoride Poly(vinyltrimethylsilane)
Ambient to 500 372-480 200-500 450
225-275 170 >160 400-530 Ambient to 500 Ambient to 500 Ambient to 500 300-600 in argon
Poly(4-vinyl pyridine) Poly(vinylacetophenone)
Ambient to 500 380
PolytN-acryloyl-N'cyanoacetohydrazide)
600
Degradation products
Refs.
HCl, benzene, traces of toluene, octamethylcyclotetrasiloxane, 292 oligomeric siloxanes High yields of HF and products involatile at 25°C - little carbonization 23 Hydrogen fluoride, C 2 -C9 fractions 150 85% wt. loss, 33 ± 5% volatile products, remainder was oily green liquid; 151 Volatile products: HF (82 mol%), CH4 (5.2), C 2 H 6 (0.6), ethylene (0.8), acetylene (0.03), fluoroethylene (0.07), propene (0.5), C 3 H 5 F (0.4), butane (0.06), butene (1.1), 1,4-butadiene (0.2), 1,3-butadiene (0.7), C 4 H 5 F (0.06), Cyclopentadiene (0.05), benzene (4.5), fluorobenzene (0.3), toluene (1.0), C 6 H 4 (CH 3 )F (0.04), C 6 H 5 C 2 H 5 or C 6 H 4 (CH 3 ) 2 , and styrene (0.9), rc-propylbenzene (0.2), iso-propylbenzene (0.3), C 6 H 5 -C 3 H 5 (0.2), indene (0.3), naphthalene (0.8), fluoronaphthalene (0.3) High yields of HCl 77 Polymer prepared in presence of oxygen; phosgene, formaldehyde, HCl 152 High yields of monomer 78 35% HF and high yields of products involatile at 25°C - some 23 carbonization Monomer, dimer (C 4 F 3 H 3 ), SiF4, (from reaction of HF with glass) 265 HCl, HF, vinylidene fluoride, chlorotrifluoroethylene, dimer (C 4 F 3 H 3 ) 265 HCl, chlorotrifluoroethylene, dichlorodifluoroethene, chloropentafluoropropene, trichlorotrifluoroethane, dimer (C 4 F 3 H 3 ) Tetramethylsilane, trimethylvinylsilane, 2-trimethylsilylpropene, 1,3-tri-methylsilylpropane, 1,3-trimethylsilylpropene, 2,4-trimethylsilylbutene-1,2,4,6-trimethylsilylhexene-1 Monomer, traces of pyridine and 4-methyl pyridine CO, CH4, ethane, 4-acetyl styrene, 4-acetyl toluene, styrene, toluene, 4-vinyl acetaldehyde, a-methylstyrene, a-methyl-4-acetylstyrene, 4-methylstyrene Cyanoactetamide
265 153 260 307 289
1.5. POLY(VINYL KETONES), POLY(VINYL ETHERS) Poly(methyl isopropenyl ketone)
Poly(methyl vinyl ketone) Poly(trifluorovinyl phenyl ether) 1.6.
270-360 Ambient to 500 150-190 270-360 Ambient to 500 275-500
H2O 41 Methyl isopropenyl ketone (50%), modified chain fragments, water, 161 small amounts of CH4 and CO Monomer under 313 nm radiation 42 H2O, 3-methyl-2-cyclohexene-l-one and other six-membered ring ketones 44 Water, modified chain fragments, small amounts of CH4 and CO 161 Maximum of 75% volatilization-products unknown 49
POLY(STYRENES)
Poly(styrene)
300-400 500-1200 300-570
-, (crosslinked) -, (head-to-head)
Ambient to 500 346-450 320 500 under N2
40.6% monomer, 2.0% toluene, 0.1% CO, remainder dimer, trimer, 62,63 and tetramer - monomer yield increases with pressure of nitrogen - 62% at 1013 mbar Small hydrocarbon fragments appear (Ci-C 6 ) - fragmentation is greater 28 the higher the temperature and the greater the pressure of inert gas Pulsed pyrolysis and 40 jig of polymer. Styrene (92.4-99.8% depending 163 upon temperature), benzene, toluene, and ethyl benzene Thin films (1000 A or less), monomer yield about 55% 164 Crosslinking with increasing quantities of divinyl or trivinyl benzene 11,64 progressively decreases the styrene yield-the yield of larger chain fragments and the amount of carbonization also increase Monomer, dimer, trimer, tetramer, pentamer, stilbene 165 Hydrocarbons (Ci-C 4 ) (2.2 relative GC peak intensity), benzene (0.4), 166 toluene (3.3), ethylbenzene (2.0), styrene (20.4), 3-phenyl-1-propene (1.5), 1-pheny!propane (2.3), a-methylstyrene (0.3), 1-phenylbutadiene (1.0), diphenylmethane (0.3), 1,1-diphenylethylene (2.6), 1,2-diphenylethane (1.3), 1,2-diphenylpropane, (0.7), 1,2-diphenyl-l-propene (0.5), 2,3-diphenyl-l-propene (2.2), 3,4-diphenyl-l-butene (0.5), 2,3-diphenylbutadiene (2.0), 1,2-diphenylethylene (6.5), 1,4-diphenylbutane (3.5), 1,4-diphenyl-l-butene (3.8), 1,4-diphenyl-l-pentene (1.3),
References page II - 475
TABLE 1. cont'd Polymer
-, -, -, -,
(poly(divinyl benzene)) (poly(trivinyl benzene)) a-acetoxym-amino-
- , /7-chloro-a-methyl-
-, a-deutero- , p-deutero- , p-fluoro-oc-methyl-
-, /7-methoxy-a-methyl-
-, 3-methyl-, 4-methylPoly(o-propionylstyrene) - , oc-methyl-
-, /?-7VyV-diethylamino-
- , m-A^Af-dimethylamino-
Temperature range (0C)
Degradation products
Refs.
1,3-diphenylpropadiene (2.1), 1,2-diphenylbutadiene (1.8), 1,4-diphenylbutadiene (1.9), 1,3,4-triphenylbutene (0.6), 1,2,5-triphenylpentane (1.5), 1,2,5-triphenyl-l-pentene (4.6), 2,3,6-triphenyl-l-hexene and 2,5,6-triphenyl-l-hexene (8.9), 1,4,5-triphenyl-l-pentene (4.4) Ambient to 600 Styrene, 1,2-diphenylethene, 1,2-diphenylpropane, 1,4-diphenylbutane, 271 1,4-diphenyl-1 -butene, 1,4-diphenylpentane, 4,5-diphenyl-1,8-octadiene, 2,3,6-triphenyl-l-hexene, 1,4,5-triphenyl- 1-pentene 385-450 Volatile products include toluene, benzene, styrene, and xylene 11,64 470-500 Mixture of aliphatic and aromatic hydrocarbons 11,64 270 Acetic acid (99%), mixture of a-acetoxystyrene and acetophenone (1%) 167 340-500 Gaseous fraction CO2, CH4, C 2 H 6 , C 3 H 6 , C 3 H 8 ; liquid fraction 65 m-aminostyrene, m-toluidine; gum fraction mainly dimer and trimer; crosslinked residue remains 320-500 Monomer yield rises from 41% (32O0C) to 61%(500°C); minor product is 66 m-toluidine, with traces of aniline, m-ethylaniline, oc-methylm-aminostyrene, H 2 , CO2, CH4; remainder comprises chain fragments and residue Ambient Gamma radiolysis: CH4 (12.9 relative mass spec, ion current), C 2 H 6 168 (21.8), C 3 H 6 (13.6), C 3 H 8 (10.5), C 4 Hi 0 (61), HCl (4.2), CH3Cl (17.4), C 3 H 4 Cl (20), C 2 H 5 Cl (28.1), C 3 H 7 Cl (3.3), CH2Cl2 (9.9), C 6 H 5 Cl (3.0), p-chlorostyrene (1.5), p-chloro-a-methyl styrene (12.5) 334-387 68.4% monomer, 1.5% a-deuterostyrene, 0.6% a-methylstyrene, 2,13 29.5% larger chain fragments 345-384 39.7% monomer, 1,2% toluene, 0.1% deuterotoluene, 59% larger 2,13 chain fragments Ambient Gamma radiolysis: CH4 (0.4 relative mass spec, ion current), C 3 H 4 168 (3.0), C 3 H 6 (0.6), C 3 H 8 (0.8), C 4 H 4 (3.5), C 4 H 6 (6.0), C 3 H 7 F (3.2), C 4 H 3 F (6.0), C 4 H 9 F (14.5), C 5 H 5 F (9.37), C 6 H 5 F (29), p-fluorotoluene (23), /?-fluorostyrene (6.45), /?-fluoro-a-methyl styrene (175.5), /?-fluoro-isopropyl benzene (11.5) Ambient Gamma radiolysis: CH4 (32 relative mass spec, ion current), H2O (26), 168 C 2 H 4 (35), C 3 H 4 (7.3), C 3 H 6 (15.2), C 3 H 8 (68.7), C 4 H 10 (8.2), CH3OH (24.2), phenol (63.8), methoxybenzene (38.6), p-methoxytoluene (19.6) 309-399 44.4% monomer, 7.3% xylene, 48.3% larger chain fragments 3 200-350 Ratio of monomer to oligomer rises from 40% at 2000C to 95% at 35O0C 79 560 C i - C 4 hydrocarbons, benzene, toluene, ethylbenzene, styrene, 278 ethyltoluene, vinyltoluene, naphthalene, ethylstyrene 385 CO, CH4, ethane, ethene, butane, 2-propionylstyrene, 2-propionyltoluene, 313 styrene, toluene, a-methylstyrene, a-methyl-2-propionylstyrene, various dimeric and trimeric species not fully characterized 200-500 95-100% monomer 28 520-1200 Fragments both larger and smaller than monomer appear in increasing 28 amounts the higher the temperature, particularly CH4, C 2 H 4 , and C 6 H 6 until at 12000C the monomer yield is only 33.9% Ambient Gamma radiolysis: CH4 (1.0 relative mass spec, ion current) C 2 H 6 (1.2), 168 C 3 H 4 (6.7), C 3 H 6 (1.8), C 3 H 8 (2.7), C 4 H 4 (22), C 4 H 10 (9.9), cyclopentadiene (6.1), benzene (72.8), toluene (20), styrene (50.5), oc-methyl styrene (184), isopropyl benzene (10) 400-900 Benzene, toluene, ethylbenzene, cumene, styrene, a-methyl styrene, 169 indene/phenylpropyne, methyl-1,2-dihydronaphthalene, methylene indene, naphthalene, 2-methylnaphthalene, 1-methylnaphthalene, biphenyl, anthracene/phenanthrene, dihydropyrene 350-500 Toluene, styrene, /?-ethylstyrene, 7VyV-diethyl-/?-toluidine, WV-diethyl170 /?-ethylaniline, p-TVyV-diethylaminostyrene, a-methyl-A^Af-diethylaminostyrene, 2-(p-Af,iV-diethylaminophenyl) butane, a-propyl-p-AW-diethylaminostyrene, N-ethyl-p-toluidine, Af-ethyl-p-toluidine, Af-ethyl/?-ethylaniline, Af-ethyl-/?-aminostyrene and closely related compounds 350-500 ra-iVyV-Dimethylaminostyrene, A^TV-dimethyl-m-toluidine, m-xylene, 171 styrene, AUV-dimethyl-m-ethylaniline, toluene, m-methylstyrene, a-methyl-m-A^,A^-dimethylaminostyrene, trans- fi-methy\-m-N,Ndimethylaminostyrene, a-emyl-ra-Af,Af-dimethylaminostyrene, N-methyl-m-toluidine, Af-methyl-ra-ethylaniline, Af-methyl-ra-aminostyrene, oligomers of m-A^Af-dimethylaminostyrene and closely related compounds
TABLE 1. cont'd Polymer
Temperature range (0C)
- , /?-Af,N-dimethylamino-
Poly(/?-(2,4-dichlorobenzyl)styrene)
-, /?-isopropyl-a-methyl- , 2,3,4,5,6-pentafluoro- , a,p,(3-trifluoroPolystyrene (chain brominated on a-position) Poly(styrene-co-methylene) ~ ~ CH-CH 2 -CH 2 -CH-(CH 2 ) „ ~ ~ ' I _ Qi 3 4 d 5 ' ' Poly(styrene-a?-SO2) (1.85 :1) Poly(styrene-c0-methacrylic acid) 18, 44 and 72 mol% MAA Poly(styrene-co-chlorotrifluoroethylene) 7.7, 14, 20 mol% CTFE
500 for 30min
Ambient to 500
Ambient 390-446 333-382 150-300 300-500 Ambient to 500 350 for 4hr
200 Ambient to 500 Ambient to 500
Poly(styrene-co-glycidyl methacrylate) 10, 23, 51, 62, 78, 86 mol% GMA
Ambient to 500
Poly(styrene-cc>-phenyl methacrylate) 10-90 mol% PMA
Ambient to 500
Poly(styrene-co-1,2,2,2,-tetrachloroethyl acrylate) (4.7/1)
310 and 500
Poly(styrene-c
310 and 500
Poly(styrene-c0-bis-(l,2,2,2-tetrachloroethyl)fumarate) (8.9/1)
310 and 500
Poly(styrene-c6>-bis-(l,2,2,2-tetrachloroethyl) muconate) (7.72/1)
310 and 500
Poly(styrene-co-iV-(2,4,6-tribromophenyl)maleimide) (6.4/1)
310 and 500
Degradation products
Refs.
iV,iV-dimethylaniline (0.2% of original polymer weight), A^Af-dimethylp-toluidine (2.8%), N-methylaniline (0.4%), AyV-dimethyl-/?-ethylaniline (0.4%), N-methyl-/?-toluidine (0.4%), JV-methyl-o-toluidine (0.4%), p-toluidine (0.4%), Af-methyl-p-ethylaniline (0.4%), p-N,JV-dimethylaminostyrene (36.3%), a-methyl-/?-A^,A^-dimethylaminostyrene (0.7%) Benzene, toluene, ethylbenzene, styrene, a-methylstyrene, 1,3-dichlorobenzene, 2,4-dichlorotoluene, monomer (major product), complex series of halogenated and dehalogenated chain fragments (see Ref.) Gamma radiolysis: CH4 (8, relative mass spec, ion current), C 2 H 4 (4.6), C 3 H 4 (7.2), C 3 H 6 (21.2), C3H8 (108), C 4 Hi 0 , (57.4) 63% of the products are volatile at 25°C - contains some monomer 72% monomer, 28% larger chain fragments HBr, trace styrene Styrene, HBr, toluene, benzene HBr, styrene, traces of toluene and benzene, /?-bromostyrene Benzene, toluene, ethylbenzene, styrene (major volatile product), n-propylbenzene (except with n = 2), phenylpropene, butylbenzene (except with n = 0), phenylbutene (with n = 4 and 5 only), amylbenzene ^ wittl n ~ 4 a n c l ^ o m ^ hexylbenzene (with n = 4 and 5 only), chain fragment fraction (major product) At 26.7 mbar pressure; 40% weight loss; main product is 2,4-diphenyl thiophene; at least 11 unidentified minor products CO 2 , H2O, butene, isobutene, dimethyl ketene, styrene, methacrylic acid, succinic-type 5-membered cyclic anhydrides Chlorotrifluoroethylene, styrene, HCl, chloropentafluoropropene, ethene, chloroethene, toluene, a-methylstyrene, dimer and trimer structures with some unsaturation; SiF4 (from reaction of HF with glass). Distribution of products varies with polymer composition CO, CO2, propene, isobutene, dimethyl ketene, acrolein, allyl alcohol, toluene, styrene, a-methylstyrene, ethylbenzene, glycidol, glycidylmethacrylate; product distribution depends on copolymer composition CH4, CO, CO 2 , propene, dimethyl ketene, toluene, styrene, 4-phenylbutene, 4-phenyl-2-methylbutene, phenyl methacrylate, a-methylstyrene, short chain fragments Styrene, benzene, toluene, ethylbenzene, a-methyl styrene, diphenyl, 5,6-benzo-2-methyl-3,5-cyclohexadienone, diphenylethane, 1,3-diphenylpropane, dimers and trimers of styrene, chloroacetaldehyde, dichloroacetaldehyde, trichloroacetaldehyde, trichloropropanal Styrene, benzene, toluene, allylbenzene, a-methylstyrene, indane, isopropenylstyrene, 5,6-benzo-2-methyl-3,5-cyclo-hexadienone, propyl-propenylbenzene, diphenylethane, 1,3-diphenylpropane, dimers and trimers of styrene chloroacetaldehyde, dichloroacetaldehyde, trichloroacetaldehyde, trichloropropanal, benzyl chloride, 2-chloroethylstyrene, 2,2-dichloroethenyl methacrylate, 1,2,2,2-tetrachloroethyl methacrylate Styrene, benzene, toluene, ethylbenzene, allylbenzene, a-methylstyrene, indane, diphenyl propylpropenylbenzene, diphenylethane, 1,3-diphenylpropane, dimers and trimers of styrene, chloroacetaldehyde, dichloroacetaldehyde, trichloroacetaldehyde, benzyl chloride Styrene, benzene, toluene, ethylbenzene, a-methylstyrene, diphenyl, propylpropenylbenzene, diphenylethane, 1,3-diphenylpropane, dimers and trimers of styrene, chloroacetaldehyde, dichloroacetaldehyde, trichloroacetaldehyde, trichloropropanal, benzyl chloride Styrene, benzene, toluene, ethylbenzene, allylbenzene, a-methylstyrene, indane, diphenylethane, 1,3-diphenylpropane, dimers and trimers of styrene, N-(2,4,6-tribromophenyl) maleimide, N-dibromophenyl maleinimide
172
275
168 67 14 271 271 271 173
68 294 261
264
280 174
174
174
174
174
References page II - 475
TABLE 1. cont'd Temperature range (0C)
Polymer Poly(styrene-co-AKpentachlorophenyl)maleimide) (4.9/1)
310 and 500
Poly(styrene) 1:1 (w/w) blend with bisphenol A polycarbonate
Ambient to 500
Poly(vinyl toluene-codivinyl benzene) 10-50% DVB
560
Poly(4-methoxystyrene) 1:1 (w/w) blend with bisphenol A polycarbonate
TABLE 2.
Ambient to 500
Degradation products
Refs.
Styrene, benzene, toluene, ethylbenzene, allylbenzene, oc-methylstyrene, indane, diphenylethane, 1,3-diphenylpropane, dimers and trimers of styrene, pentachlorophenyl isocyanate, Af-pentachlorophenyl formamide, Af-tetrachlorophenyl maleinimide, N-(pentachlorophenyl) maleimide, methyl maleic acid pentachlorophenylimide CO 2 styrene, a-methylstyrene, p-cresol, phenol, /?-ethylphenol, p-vinylphenol, p-isopropylphenol, polystyrene short chain fragments with vinylidene and saturated ends, polycarbonate cyclic dimer and chain fragments, bisphenol A C i - C 4 hydrocarbons, benzene, toluene, ethylbenzene, styrene, ethyltoluene, a-methylstyrene, vinyltoluene, divinylbenzene, naphthalene, ethylstyrene; distribution varies with copolymer composition CO 2, 4-methoxystyrene, a-methyl-4-methoxystyrene, p-cresol and other phenols in small amounts, poly (4-methoxy styrene) dimer and trimer with vinylidene and saturated ends, polycarbonate cyclic dimer and chain fragments, bisphenol A
174
272
278
272
MAIN-CHAIN CARBOCYCLIC POLYMERS
Polymer Poly((E,E)[6.2]paracyclophane-l,5-diene)
Temperature range (0C) 460, 515, 620
Poly(perfluoro-m-phenylene)
700
Poly(perfluoro-p-phenylene) high molecular weight (15000)
700
low molecular weight (3700)
700
Poly(l,4-phenylene)
250-620
- , 2-hydroxy-
300-620
Poly(l,4-phenylene ethylene)
420-465
408-515 436-475 Poy(l,3-phenylene-hexafluorotrimethylene
660 for 30 s
PoIy(1,4-phenylenemethylene)
386-416
Poly a-(ethoxycarbonyl-vinyl)-oo[4-(ethoxycarbonyl-vinyl)-phenyl] (1,4-phenylene-2,4-bis-ethoxycarbonyl1,3-cyclobutylene)
320-360 for 1 h under N 2
Degradation products
Refs.
Primary product is monomer; in addition, a series of secondary products 251 based on ring-opened monomer are formed by H-abstraction (see Ref.); also detected: toluene (not 4600C) and p-xylene Volatiles comprise SiF4 (from silica vessel), CO2, with traces of C6F6 50 and C6F5H; white sublimate on vessel walls; residue contains 1% fluorine Volatiles comprise SiF4 (from silica vessel), CO2, with traces of 50 C-(Fe and C 6 F 5 H; white sublimate on vessel walls; residue contains 1% fluorine Volatiles comprise SiF4 (from silica vessel), CO2, with traces of 50 C 6Fe and CeF5H; no white sublimate; residue contains 33-41% fluorine 79% residue, 10% chain fragments, 11% volatiles comprising H 2 , CH4, 55 H2O, HCl (from catalyst) 60% residue, 24% chain fragments, 16% volatiles comprising CO, CO2 55 H 2 , CH4 3.6% of products are volatile at 25°C and consist of 2.83% xylene, 13,14,80 0.29% toluene, 0.28% methylethyl benzene, 0.14% methylstyrene, 0.06% benzene, products involatile at 250C consist of dimericoctameric fragments Mainly chain fragments (dimer-pentamer); traces of H 2 , monomer 81 H 2 , CH4, C 2 H 4 , C 2 H 6 , toluene, p-xylylene, p-ethyltoluene, p-methyl176 bibenzyl, l,2-di-/?-torylethane, 4,4'-dimethylstilbene C 2 F 4 (21.6% of original weight of polymer), HF (17), 177
C 6 H 6 (8.5%), C 6 H 5 (CF 2 ) 3 C 6 H 5 (7.9%) 7.4% of products are volatile at 25°C; 5.9% toluene, 1.4% benzene, 0.1% xylene Low-molecular-weight polymer and small amount of monomer
13,14 195
TABLE 3. MAIN-CHAIN HETEROATOM POLYMERS Temperature range (0C)
Polymer
Degradation products
Refs.
3.1. POLY(OXIDES) AND POLY(KETONES) Poly(fluoro ethers)
510-540
178
b.
c.
d.
Poly(oxybutylethylene)
321-365
Poly(oxy-2,5-dimethoxy-l,4-phenylene)
100-550
Poly(oxy-2,6-dimethyl-l,4-phenylene)
100-550 400-550
Poly(oxyethylene)
324-363 280
Poly(oxymethylene)
222 100-180
Poly(oxymethyleneoxyethylene) Poly(oxy-2-methylphenylene)
314-338 250-500
Poly(oxy-l,3-phenylene)
300-620
Poly(oxy-l,4-phenylene)
550
Poly(oxy-l,4-phenylene)blend-polystyrene (60: 40) Poly(oxypropylene) atactic isotactic Poly(oxytetramethylene) Poly(oxytrichloromethyl methylene) (Poly(trichloro acetaldehyde))
585 300-360
270-330 275-355 347 Ambient
Mixture of saturated and hydrocarbons (Ci-C 6), aldehydes (C 1 -C 6 XH 2 5 H 2 O 41% residue, 29% fragments, 30% volatiles comprising H 2 , CH4, CO, CO 2 , CH3OH, traces of H 2 O, C 2 H 6 , other hydrocarbons 26% residue, 66% chain fragments, 8% volatiles comprising H 2 , CH4, H2O, CO, CO2 0-Cresol, 2,6-dimethyl phenol, 2,4-dimethyl phenol, 2,4,6-trimethyl phenol, various ketones, dimers, and more complicated structures (see Ref.), various combinations of the monomeric skeletons 9.7% of products volatile at 25°C-3.9% monomer with smaller amounts of CO2, formaldehyde, ethanol, and saturated and C i - C 7 compounds Diethyl ether, ethyl methyl ether, acetaldehyde, formaldehyde, CO 2 , CO, ethene, cyclohex-3-ene-l-one 100% Monomer 100% Formaldehyde; inverse relationship between molecular weight and rate for hydroxyl terminated polymers; acetylation of terminal hydroxy groups inhibits the reaction Major volatile products CH4, C 2 H 6 , C 2 H 4 , C 2 H 2 , HCO 2 C 2 H 5 p-Xylene, phenol, 2-methylphenol, 4-methylphenol, 2,4-dimethylphenol, and a variety of more complex structures (see Ref.) 34% Residue, 53% chain fragments, 13% volatiles comprising H2O, CO, H 2 , CH4, CO 2 , trace of C 6 H 6 Hydroquinone, phenol, benzene, diphenylether, 4,4/-dihydroxydiphenylether, 4-phenoxyphenol. In addition, a broad spectrum of phenyl and phenolic terminated oligomers with up to 10 aromatic units As 5500C plus dibenzofuran and dibenzofuran-containing oligomers Ethylbenzene, styrene, a-methylstyrene, 2-methylphenol, 2,6-dimethylphenol, 2,4-dimethylphenol, 2,4,6-trimethylphenol, 1,3-diphenylpropane, 2,4-diphenyl-1 -butene, 2,4,6-triphenyl-1 -hexene, PPO dimers 12.8% of products volatile at 25°C, including 4.00% acetaldehyde, 2.22% acetone, 1.43% dipropyl ether and 0.75% propylene 20% of products volatile at 25°C, including 6.34% acetaldehyde, 2.39% acetone, 2.19% dipropyl ether, and 2.22% propylene Volatiles comprise a mixture of CH4, C 2 H 6 , C 3 H 8 , C 4 Hi 0 , C 2 H 4 , C 3 H 6 , CH3CHO, C2H5CHO, C3H7CHO Monomer
20 55 55 179
25 252 27 181 20 180 55 255
255 318
25 25 20 182
References page II - 475
TABLE 3. cont'd Polymer
Temperature range (0C)
Poly(oxy- 1,4-phenylenecarbonyl-l,4-phenylene) (Poly(ether ketone), PEK)
390, 490, 530
506 Poly(oxy-1,4-phenyleneoxy-1,4-phenylene -carbonyl-1,4-phenylene) (Poly(ether ether ketone), PEEK) Poly(etherketone-coethersulphone) Mole ratio 1:3, 3:1, 1:1 (random), 1:1 (alternating) 3.2.
506
Degradation products
Refs.
Low MW polymer at 4900C produces benzene, phenol, benzaldehyde, 4-hydroxybenzaldehyde, diphenyl ether, biphenylene, benzophenone, series of -H, -OH and -CHO terminated chain fragments containing < 8 aromatic units and fragments containing dibenzofuran units. High MW polymer at 53O°C as above. Low MW polymer at 3900C produces significant quantities of 4-hydroxy benzaldehyde and benzophenone-4,4 '-diol Phenol, dibenzofuran, benzofuran derivatives, mixtures of oligomers mostly hydroxy terminated Phenol, dibenzofuran, benzofuran derivatives, mixtures of oligomers mostly hydroxy terminated
250
315 315
All polymers have same products with distribution varying with 250 composition. Biphenyl, hydroquinone, 4-phenoxyphenol, benzaldehyde, 4-hydroxybenzaldehyde, diphenyl sulphone, diphenylether, phenol, benzophenone-4,4'-diol. Also two series of chain fragments containing PEK and PES units with -H, -OH and -CHO ends. Analogous fragments with biphenyl units
POLY(ESTERS)
Poly(3-oxybenzoyl) Poly(4-oxybenzoyl) Poly(oxycarbonyl-l,3-phenylenehexafluoroisopropylidene-1,3-phenylene carbonyloxy-1,3-phenylene-hexafluoroisopropylidene-1,3-phenylene) Poly(oxycarbonyl-l-chloroisopropylidene) Poly(oxycarbonylcyclohexylidene) Poly(oxycarbonylcyclopentylidene) Poly(oxycarbonyl-3-pentylidene) Poly(oxyethyleneoxyterephthaloyl) (Poly(ethylene terephthalate))
330 505-565
Monomer, cyclic dimer-heptamer CO, CO 2 , phenol, p-hydroxy phenyl benzoate HF (12%), cyclic structures (see Ref.)
187 197 177
253-384 200-500 200-500 200-300 283-306
HCl and a compound with a glycollidic structure Cyclohexen-1-carboxylic acid, cyclohexanone Cyclopenten-1-carboxylic acid, cyclopentanone, dicyclopentyl glycollide Cw- and trans-2-tthy\ crotonic acid (major products) Acetaldehyde major gaseous product with CO 2 , CO, C 2 H 4 , H2O, CH4, benzene, 2-methyl-dioxolane, terephthalic acid, and more complex chain fragments CO, CH4, CO 2 , ethylene, acetylene, ethane, H2O, propylene, ethanal, acetone, propanal, ethanol, benzene, toluene, ethyl benzene, styrene, /?-vinyl toluene, benzaldehyde, p-ethyl toluene, acetophenone, methyl benzoate, vinyl benzoate, ethyl benzoate, /?-methyl acetophenone, benzoic acid, p-methyl vinyl benzoate, /?-vinyl acetophenone, propyl benzoate, /?-ethyl vinyl benzoate, p-vinyl vinyl benzoate, biphenyl, 1-hydroxy ethyl benzoate, diacetyl benzene, p-acetyl vinyl benzoate, divinyl terephthalate, ethyl vinyl terephthalate, ethyl vinyl terephthalate, /7-acetyl benzoic acid, methyl 1-hydroxyethyl terephthalate, ethylene dibenzoate CO, CH4, CO 2 , ethene, ketene, acetaldehyde, 1,4-dioxane, toluene, benzaldehyde, vinylbenzoate, divinylterephthalate, benzoic acid, terephthaldehydic acid, terephthalic acid, hydroxyethyl methyl terephthalate, short chain fragments CO, CH4 (trace), CO 2 , ethene (trace), formaldehyde, acetaldehyde, 1,3-dioxalane, ethoxyacetaldehyde, 1,4-dioxane, glycidol, diethylether, 1,2-dimethoxyethane, 2-methoxyethanol, 2-ethoxyethanol, -CH2CH2COCH 2 -(ring), HOCH2CH2OCH2CHO, CH3OCH2CH2OC2H5, terephthalic acid, triethylene glycol, tetraethylene glycol, chain fragments CO, CH4 (trace), CO 2 , ethene (trace), formaldehyde, acetaldehyde, 1,3-dioxalane, methoxyacetaldehyde, 1,4-dioxane, 7-membered cyclic ether, methyl benzoate, ethyl benzoate, benzaldehyde,
185 198 198 188 26
900
Ambient to 500
Polyester from terephthaloyl chloride and n = 4 polyethylene glycol
Polyester from terephthaloyl chloride and n = 22 polyethylene glycol
Ambient to 500
-CH 2 CH 2 COCH 2 -(ring), H O C H 2 C H 2 O C H 2 C H O ,
CH3OCH2CH2OC2H5, -(CH 2 CH 2 O) 2 CH 2 CO-(ring), CH2 = CHOCH 2CH 2OCH2CHO, HO(CH 2CH2O) 2C 2H5 , C 2 H 5 (OCH 2 CH 2 ) 3 H, terephthalic acid, triethylene glycol, tetraethylene glycol, chain fragments
192
298
274
274
TABLE 3. cont'd Polymer
Temperature range (0C)
Poly(oxyisophthaloyl-oxy-l,3-phenylene)
330
Poly(oxyisophthaloyl-oxy-l,4-phenylene)
330
Poly(oxy-l-oxohexamethylene) Poly((D)-oxy-l-oxo-3-methyl-trimethylene) (Poly(3-hydroxybutyrate))
220 Ambient to 338
250 400 600 350 Poly((D)-oxy-l-oxotetramethylene) (Poly(4-hydroxybutyrate)) Poly(oxy-l-oxo-2methylethylene) (Poly(l-lactic acid)) Poly(oxy-l-oxo-2,2-dimethyltrimethylene (Poly(a,a-dimethyl-p-propiolactone)) Poly(oxy- 1-oxo-trimethylene) (Poly(p-propiolactone)) Poly(oxyterephthaloyloxy1,2-phenylene) Poly(oxyterephthaloyloxy-l,3-phenylene)
320 500
Poly(oxytetramethyleneoxyterephthaloyl) (Poly(butylene terephthalate))
187 187 184 186
245 245 245 246 257
250-600 180-220
Acrylic acid
189
CO2, benzene, phenol, benzaldehyde, catechol, cyclic dimer
285
Ambient to 500 345
350
Ambient to 500 240-280 200-400 Ambient to 500
Poly(oxydecamethyleneoxyterephthaloyl) Poly(oxyethyleneoxyadipoyl) Poly(oxytetramethyleneoxysebacoyl) Polyester from maleic anhydride, hexolic acid and butanediol; mole ratio 1:1:2.2
Cyclic monomer (10 relative abundance), cyclic dimer (83.5), cyclic trimer (24.5), benzoic acid, isophthalic acid, resorcinol and various fragments of the main chain (see Ref.) Cyclic dimer (17), cyclic trimer (4), m-phthalic acid (26), benzoic acid (7.5), hydroquinone (46), and various fragments of the main chain (see Ref.) Monomer (e-caprolactone) Dimer (41.2 wt.%), crotonic acid (35.3), trimer (12.5), tetramer (2.9), iso-crotonic acid (0.9). Small amounts of CO 2, propene, ketene, acetaldehyde, and P-butyrolactone are formed at higher temperatures due to decomposition of primary products Crotonic acid (64.4% of original polymer), dehydrated dimer (7.2%), dehydrated trimer (1.2%) Crotonic acid (65.4% of original polymer), dehydrated dimer (8.2%), dehydrated trimer (2.1%) Crotonic acid (58.3% of original polymer), dehydrated dimer (9.0%), dehydrated trimer (2.7%) Crotonic acid (trans), dehydrated dimer (trans), dehydrated trimer and tetramer (cisltrans not resolved) Cyclic oligomers (y-butyrolactone and higher homologues)
282
Ambient to 500
Poly(oxyterephthaloyloxy-4,4/diphenylene)
Refs.
CO, CO2, acetaldehyde, acetone, acrylic acid, acetic acid, DL-lactide, meso-lactide, cyclic oligomers up to nonamer, 2,3 pentanedione (?), lactoyl lactic acid (?) Isobutylene and CO2
Ambient to 500
Poly(oxyterephthaloyloxy-l,4-phenylene)
Degradation products
Ambient to 500 Ambient to 500 Ambient to 500 100-440
183
Cyclic dimer (2), cyclic trimer (0.3), terephthalic acid (0.4), benzoic acid 187 (1.5), resorcinol (20) and various fragments of the main chain (see Ref.) CO2, benzene, phenol, benzaldehyde, biphenyl, benzoic acid, 285 3-hydroxyphenylbenzoate, resorcinol, mono and di(3-hydroxyphenyl) terephthalate, terephthalic acid, terephthaldehydic acid, short chain fragments Cyclic dimer (0.1), terephthalic acid (0.5), benzoic acid (6), hydroquinone 187 (40.5), and various fragments of the main chain (see Ref.) Benzene, phenol, benzaldehyde, biphenyl, benzoquinone, 285 4-hydroxyphenylbenzoate, benzoic acid, mono and di(4-hydroxyphenyl) terephthalate, terephthalic acid, terephthaldehydic acid, short chain fragments CO2, benzene, phenol, benzaldehyde, biphenyl, 4-phenylphenol, 285 /?,/?'-dihydroxybiphenyl, 4-hydroxybiphenylbenzoate, di(4-hydroxybiphenyl) terephthalate Butadiene, terephthalic acid, mono-3-butenyl terephthalate, and 190 di-3-butenyl terephthalate Tetrahydrofuran, 1,3-butadiene, CO2, CO, H2O, benzoic acid, tereph191 thalic acid, terephthalic acid mono-3-butenyl, toluene, phenol, benzene CO, CO 2 , butadiene, tetrahydrofuran, toluene, benzene, 1,5-hexadiene, 298 dihydrofuran, 4-vinyl cyclohexene, 1,4-butane diol, benzaldehyde, benzoic acid, terephthaldehydic acid, terephthalic acid, mono-3-butenyl terephthalate, cyclic dimer, short chain fragments CO, CO 2 , 1,9-decadiene, 1,10-decane diol, l-decene-10-ol, benzoic acid, 298 terephthalic acid, mono-decenyl terephthalate Cyclic oligomers, CO, CO2, acetaldehyde, 2-ethylacrolein 269 CO 2 , H2O, butadiene, tetrahydrofuran 299 Tetrahydrofuran, 1-butanol, toluene, maleic anhydride, chlorosuccinic 311 acid isomers, chlorovalerolactone isomers, hydroxypyran, allylpyran, trichlorocylopentadiene, tetrachlorocylopentadiene, pentachlorocylopentadiene, hexachlorocylopentadiene, phthalic anhydride, 1,4-butanediol, 1,4-butanediol dibenzoate, benzoic acid, 4-cyclohexene-l,2-dicarboxylic acid anhydride, benzoic acid butenyl ester, cyclohexadiene carboxylic acid propyl ester, hexolic anhydride,
References page II - 475
TABLE 3. cont'd Polymer
Temperature range (0C)
Degradation products
Refs.
unidentified butenyl ester, compound containing C 5 HCl 5 unit, CH3-CH=CH-CH2-O-CH3, C H 3 - C H = C H - C H 2 - O - C H = CH2,
Polyester from maleic anhydride, phthalic anhydride and butanediol; mol ratio 1:1:2.2
100-440
Unsaturated polyester resins a. Maleic acid-phthalic acid-propylene glycol-styrene
300-800
Cl-CH=CH-O-CH2-CH3 Tetrahydrofuran, 1-butanol, 3-butene-l-ol, toluene, maleic anhydride, 311 phthalic anhydride, 1,4-butanediol, 1,4-butanediol dibenzoate, phthalic acid butenyl ester, various esters containing butenyl, maleate and phthalate units, C H 3 - C H = C H - C H 2 - O - C H 3 , C H 3 - C H = C H - C H 2 - O - C H = CH2
b. Maleic acid-tetrabromophthalic acid-phthalic acid-propylene glycolstyrene c. Maleic acid-phthalic aciddibromoneopentyl glycol-styrene 3.3.
Ethane (above 5000C), propionaldehyde (above 4000C), styrene (major product), phthalic anhydride (major product), benzene (above 5000C), toluene (above 5000C), xylene (above 5000C)
193
Cyclic trimer, tetramer, and pentamer, and various chain fragments Major products: CO 2 , bisphenol A; minor products: CO, CH4, 4-alkyl phenols CO, CO 2 , CH 4 , phenol, diphenyl carbonate, 4-(4-hydroxyphenyl)-2phenyl propane Cyclic dimer, cyclic trimer, bisphenol A, and other chain fragments CO, CH4, CO 2 , H 2 O, phenol, /?-cresol, /?-ethyl phenol, /?-isopropyl phenol, p-vinyl phenol, bisphenol A, cyclic dimer, chain fragments including some ester structures Phenol, /7-cresol CO2, phenol, /?-cresol Cyclic monomer and dimer, and higher cyclic fragments
226 60
304 304 226
HF (3%), cyclic dimer
177
270
Cyclic dimer and trimer, and higher cyclic fragments
226
350
CO 2 , CO, O 2 , H 2 O, phenol, fluorenone, diphenyl carbonate, xanthone, anthraquinone, 2-hydroxyanthraquinone, 2-benzoxyanthraquinone, phenolphthalein, traces of benzoxyphenol and hydroquinone CO2/H2O (possibly desorbed), trimethylene carbonate, cyclic oligomers CO 2 , monomer, oligomer CO, CO 2 , H 2 O (possibly desorbed), a-methylstyrene, chain fragments (85%, w/w)
227
POLY(CARBONATES)
Poly(oxycarbonyloxy-l,3-phenylene) Poly(oxycarbonyloxy-l,4-phenyleneisopropylidene-l,4-phenylene)
270 300-389 200^00 290 Ambient to 500
Poly(oxycarbonyloxy-l,4-phenyleneisopropylidene-1,4-phenylene-oxy-carbonyltetramethylene) Poly(oxycarbonyloxy-l,3-phenylene hexafluorotrimethylene-1,3-phenylene) Poly(oxycarbonyloxy-l,4-phenyleneoxycarbonyloxy-tetramethylene) Poly(oxycarbonyloxy-l,4-phenylenephthalidylidene-l,4-phenylene) Poly(trimethy}ene carbonate) Poly(neopentylene carbonate) Poly(2-phenyl trimethylene carbonate) 3.4.
Ethane (above 6000C), propionaldehyde (above 4000C), styrene (major 193 product), phthalic anhydride (major product), benzene (above (4500C), toluene (above 5000C), xylene (above 4000C) Styrene (major product), phthalic anhydride (major product), benzene 193 (above 5500C), toluene (above 4500C), xylene (above 5000C)
300 375 240
Ambient to 500 Ambient to 500 Ambient to 500
225 226 304
295 296 296
POLY(ANHYDRIDES)
Poly(oxycarbonyl-1,3-phenylenehexafluorotrimethylene-1,3-phenylenecarbonyl) Poly(maleic anhydride-co-frans stilbene) (alternating copolymer)
350 Ambient to 500
Cyclic dimer
177
CO 2 , styrene, maleic anhydride; small amounts benzene, cyclohexadiene, 242 dimethylbutene, ethylcyclobutanol and 4-methoxystyrene; major products (79%) are chain fragments, including aromatic, ketonic and unsaturated structures
3.5. POLY(SULFIDES) AND POLY(SULFONES) Poly(thioacetone) Poly(thioethylene) Poly(thio-l,4-perfluorophenylene)
145 220-260 500
Poly(thiomethylene-1,4phenylene-methylene)
250-350
Main product is cyclic trimer [(CH3) 2CS] 69 Ethylene, H 2 S, ethanethiol 199 73% Residue; remainder, chain fragments, H 2 , SiF 4 (from silica vessel), 51 CO 2 Sulphur, styrene, thiobenzaldehyde, 4-methyl styrene, /?-xylene, 254 4-ethyl toluene, H 2 S, 4-methyl thiobenzaldehyde, stilbene and chain
TABLE 3. cont'd Polymer
Temperature range (0C)
650 Poly(dithiomethylene-1,4phenylene-methylene)
250-350
650 Poly(thio-l,2-phenylene) Poly(thio-l,3-phenylene) Poly(thio-l,4-phenylene)
430 540 460 300-620 325-625 560
Degradation products
Refs.
fragments containing stilbene units, chain fragments containing polymer repeat units with -CH 2 SH, -CH = S and -CH 3 terminal units Toluene, ethylbenzene, p-xylene, 1,4-diethylbenzene, 4-ethyltoluene; series of polycyclic aromatics containing phenanthrene and dihydrophenanthrene Sulphur, styrene, thiobenzaldehyde, 4-methyl styrene, /?-xylene, 4-ethyl toluene, H 2 S, 4-methyl thiobenzaldehyde, stilbene and chain fragments containing stilbene units, chain fragments containing polymer repeat units with -CH 2 SH, - C H = S and -CH 3 terminal units Toluene, ethylbenzene, p-xylene, 1,4-diethylbenzene, 4-ethyltoluene; series of polycyclic aromatics containing phenanthrene and dihydrophenanthrene Cyclic dimer (thianthrene), some cyclic trimer Cyclic oligomers (trimer to heptamer) in decreasing yield 72% Residue; remainder chain fragments, H 2 , dibenzthiophene 38% Residue, 47% chain fragments, 15% volatiles comprising mainly H2S and H 2 Benzene, thiophenol, diphenyl, diphenylsulfide, dibenzothiophene, chlorobenzene (from polymers with terminal chlorine atoms) Cyclic oligomers tetramer to heptamer (pentamer dominates)
254 254
254 258 258 51 59 200 258
Poly(oxy-1,4-phenylene-sulfonyl1,4-phenylene-oxy-1,4-phenyleneisopropylidene-1,4-phenylene) 380
350-450 470 for 2 h 800 Poly(oxy-1,4-phenylene-sulfonyl1,4-phenylene)
470 for 2h 550-600
800 Poy(tris-(oxy-l,4-phenylene)-sulfonyl-l,4phenylene) Poly(oxy-4,4'-diphenylene-oxy-l,4-phenylene sulfonyl-1,4-phenylene) Poly(oxy-l,4-phenylene-sulfony 1-1,4-phenyleneoxy-1,4-phenylenemethylene-1,4-phenylene) Poly(sulfur dioxide-co-1-butene) Poly(sulfur dioxide-co-1-hexene) Poly(sulfur dioxide-co-1-octadecene) Poly(sulfur dioxide-co-bicycloheptene)
700-800 700-800 700-800 700-800
Poly(sulfur dioxide-co-cyclopentene)
700-800
Poly(sulfur dioxide-co-c/s-2-butene)
700-800
Poly(sulfur dioxide-co-methyl methacrylate-co-1-hexene) (24.2/1) Poly(sulfur dioxide-co-methyl methacrylate-co-bicycloheptene) (2.5/1)
700-800 700-800
Phenol with smaller amounts of/7-cresol, /?-ethyl phenol, /?-isopropylphenyl phenol, bisphenol A, diphenyl ether, p-tolyl phenyl ether, p-ethyl diphenyl ether, p-isopropenyl diphenyl ether, isomers of tolyl (ethyl-phenyl)ether In 90min at 4500C, 15% (of initial weight) of gaseous products are formed; SO2 (76% of gaseous products), CO2 (15%), CO (4.5%), CH4 (4.5%) Benzene, toluene, /?-xylene, isopropylbenzene, phenol (main product), diphenyl oxide, diphenyl sulfide SO2, benzene, toluene, styrene, phenol, methylphenol, diphenylether, methyl diphenylether Phenol (main product), diphenyl oxide
201
SO2, diphenylsulfone, phenol, diphenylether, hydroquinone, benzenesulfonic acid, 4-hydroxybenzenesulfonic acid, 4,4/-dihydroxydiphenylether, 4-phenoxyphenol; series of -H and -OH terminated fragments up to trimer, series of compounds containing consecutive diphenylether and dibenzofuran units, fragments containing biphenyl units as a result of SO2 elimination; complex ring structures with sulfonate links SO2, benzene, phenol, diphenyl ether, dibenzofuran Benzene, phenol (major product), diphenyl oxide, p-hydroxydiphenyl, or /?-hydroxydiphenyl oxide Phenol (main product), diphenyl oxide
255
202 203 288 203
288 203 203
Benzene, toluene, /7-xylene, phenol (main product), diphenyl oxide
203
Monomers Monomers Monomers SO2, bicycloheptene, cyclopentadiene, ethylene, methyl cyclohexadiene, benzene, indene, naphthalene, dihydronaphthalenes SO2, cyclopentene, xylenes, ethylbenzene, styrene, indene/decadienes, dihydronaphthalenes, tetralin, napthalene SO 2 , butenes, benzene, toluene, octadienes, xylenes, styrene, indene, naphthalene SO2, hexenes, hexadienes, methyl methacrylate, toluene, naphthalene, dodecadienes SO2, ethylene cyclopentadiene, benzene, methyl methacrylate, bicycloheptene, methylcyclohexa-2,4-diene, ethylbenzene, xylenes, styrene, indene, naphthalene, dihydronaphthalenes
204 204 204 204 204 204 204 204
References page II - 475
TABLE 3. cont'd Polymer
Temperature range (0C)
Degradation products
Refs.
3.6. POLY(AMIDES) Poly(2,5-dimethyl-l,4-piperazinediylisophthaloyl)
475
Poly(2,5-dimethyl-1,4-piperazinediyloxaloyl)
475
Poly(2,5-dimethyl-l,4-piperazinediylterephthaloyl)
475
Poly(iminoisophthaloylimino1,3-phenylene) (Nomex)
300-500 300-500 450-550
PolyOminoisophthaloylimino1,3-perchlorophenylene)
550
Poly(iminoisophthalylimino1,4-phenylene) Poly(iminoisophthaloyl-co-terephthaloylimino-1,4-phenylene) Poly(imino(l-oxohexamethylene) (Nylon 6)
Poly(iminohexamethyleneiminoadipoyl) (Nylon 66)
300-500 250-620 327
310-380 305 305
400
Poly(imino(l-oxoundecamethylene) (Nylon 11)
800
Poly(imino(l-oxododecamethylene) (Nylon 12)
800
Poly(iminoterephthaloylimino1,3-phenylene) Poly(iminoterephthaloylimino1,4-phenylene) (Kevlar)
300-500 300-500 370-450 450-550 527
Poly(2-methylpiperazinediylterephthaloyl)
475
Poly(l,4-piperazinediylterephthaloyl)
475
After 1 h, 5.1% residue, 73.8% chain fragments, 20.5% volatiles comprising mainly CO, H2O, CH4, CO2, H2, with traces of hydrocarbons, pyrazines, pyrroles After Ih, 1% residue, 73.5% chain fragments, comprising mainly CO, with traces of H2, CO2, H2O, hydrocarbons, pyrazines, pyrroles After Ih, 9.4% residue, 3.2% chain fragments 87.4% volatiles comprising mainly CO, H2O, CO2, CH4, NH3, with traces of hydrocarbons, pyrazines, and pyrroles Mixture of H 2 , CO, CO 2 , H2O, HCN, benzene, toluene, benzonitrile CO2, H2O, CO Benzene, HCN, toluene, benzonitrile, H 2 CO, CO 2 , H2O, benzene, benzonitrile, 1,3-dicyanobenzene, 3-cyanobenzoic acid, other trace compounds Water (46 mol%), CO (18), CO2 (31), CH4 (1.2), HCN (1.3), and smaller quantities of, N 2 O, NO, CH3CI, ethylene, acetylene, cyanogen, acetonitrile, acetone, acetic acid, cyanogen chloride, propenenitrile, benzene, toluene, benzonitrile, phenol, chlorobenzene Mixture of H 2 , CO, CO 2 , H2O, HCN, benzene, toluene, benzonitrile
30 47 47 57 205 205 319 206
57
36% residue, 24% chain fragments, 40% volatiles comprising H 2 , CO, 58 CO2, CH 4 Cyclic monomer, acetonitrile, HCN, NH 3, acrylonitrile, 3-cyanopropene, 293 4-cyanobutadiene, 4-cyano-1 -butene, 5-cyano-1,3-pentadiene, 4-pentenal, 5-cyano-l-pentene, 3,5-hexadienal, 5-isocyanato1-pentene, linear dimer H2O, CO 2 , cyclopentanone, traces of saturated and hydrocarbons; 45,46 purification from water and acid polymerization catalysts increases stability and decreases yield of CO2 H2O, CO2, NH 3, cyclic monomer, cyclopentanone, cyclopentylidine207 cyclopentanone, cyclopentylcyclopentanone, hexylamine, hexamethyleneimine, hexamethylenediamine CO 2 , NH3, H2O, cyclic monomer, cyclopentanone, 207 2-cyclopentylidenecyclo pentanone, 2-cyclopentylcyclopentanone, hexylamine, hexamethyleneimine, hexamethylenediamine, 1,2,3,5,6,7-hexahydro dicyclopenta[b,e]pyridine Hexamethylenediamine, aminohexamethylene isocyanate, 247 hexamethylenediamine-monocyclopentanimine, hexamethylenediaminedicyclopentanimine and larger oligomers related to above; cyclopentanone CO 2 , HCN, saturated and olefinic hydrocarbons C5-Cn, 308 saturated and olefinic mononitriles CwH(2n+1)CN and CwH(2n_i)CN, undecalactam, hydrocarbons and nitriles containing amide units CO2, HCN, saturated and olefinic hydrocarbons C 5 - C n , 308 saturated and olefinic mononitriles CnH(2n+1)CN and CnH(2n_!)CN, dodecalactam, hydrocarbons and nitriles containing amide units Mixture of H 2 , CO, CO2, H2O, HCN, benzene, toluene, benzonitrile 57 Mixture of H 2 , CO, CO2, H2O, HCN, benzene, toluene, benzonitrile 57 CO 2 , H2O, CO 205 Benzene, HCN, toluene, benzonitrile, H 2 Cyanobenzene, dicyanobenzene, aniline, 1,4-diaminobenzene, 293 4-cyanoaniline, benzaldehyde, benzene, CO, NH3, CO2, H2O, benzamide, benzoic acid, phenylisocyanate, terephthaldehyde, benzanilide, NH 2 -Ph-NH-CO-Ph, NC-Ph-NH-CO-Ph, NH 2 -Ph-NH-CO-Ph-CN, Ph-NH-CO-Ph-CHO After Ih, 11.3% residue, 46.2% chain fragments, 42.5% volatiles 30 comprising mainly CO, H2O, CO2, CH4, NH3, H 2 , with traces of hydrocarbons, pyrazines, and pyrroles After Ih, 21.1% residue, 45.6% chain fragments, 33.3% volatiles 30 comprising mainly H2O, CO, H 2 , CO2, NH3, with traces of hydrocarbons, pyrazines, and pyrroles
TABLE 3. cont'd Polymer 3.7.
Temperature range (0C)
Degradation products
Refs.
POLY(SILOXANES)
Poly(oxy-dimethylsilylene) (Poly(dimethyl siloxane))
Ambient to 500
470
Poly(oxy-methylphenylsilylene)
Ambient to 500
Poly(oxy-methyl-3,3,3-trifluoropropylsilylene)
400 615 for 30 s
Poly(oxy-phenylbutoxysilylene) Poly(dimethyl siloxane-codiphenyl siloxane)
430-500 Ambient to 500
Poly(dimethyl siloxane-co phenylmethyl siloxane)
Ambient to 500
Poly (dimethyl-1,4-silphenylene)
400 in argon
Predominantly cyclic trimer with smaller amounts of cyclic tetramer and 208 higher cyclics; threshold degradation temperature of about 3000C reduced to 1000C by 5% KOH and CH 4 formed as additional product Distribution of cyclic oligomers, n = 3 (243.9 relative mass spec. 317 intensity), n = 4 (100), n = 5 (35.6), n = 6 (37.6), n = 1 (13.1), n = 8 ( l . l ) , n = 9(0.2) Mixture of all possible stereoisomeric cyclic trimers and tetramers with 209 small amounts of pentamer, benzene, and two more complex oligomers Low-molecular-weight cyclic oligomers, CF 2 = CH-CH 3 , CHF 3 70 Cyclic methyl-(3,3,3-trifluoropropyl)siloxanes, CH 4 , CHF3, CF 2 = CH-CH 3 , CH 2 = CH-CF 3 CO, H 2 and hydrocarbons Complex mixture of cyclic oligomers, which have been individually identified, whose composition varies with the dimethyl/diphenyl ratio; small amounts of benzene Complex mixture of cyclic oligomers, which have been individually identified, whose composition varies with the dimethyl/methyl phenyl ratio; small amounts of benzene Methane, dimethylsilane, benzene, dimethylphenylsilane,
210 211 212
213
214
dimethyldiphenylsilane,
Poly(oxy-methylphenyl1,4-silphenylene-silylene) Poly(oxy-tetramethyl-
Ambient to 500 500 in argon
1,4-silphenylene-silylene)
Benzene, diphenylmethylsilane, triphenylmethylsilane, and higher linear oligomers CH3 CH3
214
Methane, H - S i - O - S i - H , benzene, cyclic trimer of dimethylsiloxane, CH3 Ambient to 500
Poly(oxy-tetramethyl-l,3-silphenylene615 for 30s silylene-hexafluoropropylenephenylene) Poly(oxy-tetramethyl-l,3-silphenylene615 for 30s silylene-tetrafluoroethylenephenylene) Poly(oxy-tetramethyl-l,3-silphenyleneAmbient to 500 siloxane-co-dimethylsiloxane) Poly(boron tri(dimethylsiloxane)), nonlinear 250-350
3.8.
215
CH3
and various higher chain fragments (see Ref.) Cyclic trimer and tetramer of dimethylsiloxane and a complex mixture of higher linear and cyclic oligomers HF (15-18%), methane, methyltrifluorosilane, dimethyldifluorosilane, benzene, toluene, phenyldifluoromethane HF (15-18%), methane, methyltrifluorosilane, dimethyldifluorosilane, benzene, toluene, phenyldifluoromethane Cyclic trimer and tetramer of dimethylsiloxane and a complex mixture of higher linear and cyclic oligomers Molecular weight increases; traces of cyclic products [(CH 3 ) 2 Si0] 3 and [(CH 3 ) 2 Si0] 4
216 210 210 216 15
POLY(URETHANES)
Poly(oxy-2,2-dimethyltrimethylene) oxycarbonyl-Af-imino-1,4-phenylenemethylene1,4-phenylene-A/-iminocarbonyl) Poly(oxy-l,4-phenyleneisopropylidene1,4-phenyleneoxycarbonylimino-l ,4-phenylene methylene-1,4-phenylene-iminocarbonyl) Poly(oxy-l,4-phenyleneisopropylidene1,4-phenylene-oxycarbonyl-A^methylimino1,4-phenylenemethylene-1,4-phenyleneAf-methyliminocarbonyl) Poly(oxy-l,4-phenyleneisopropylidene1,4-phenylene-oxycarbonyl-Af-methyliminohexamethylene-Af-methyliminocarbonyl) Poly((oxy-l,4-phenyleneisopropylidene1,4-phenylene-oxycarbonyl-piperazine1,4-diyl-carbonyl)
350
Various fragments of the main chain (see Ref.)
231
190
4,4/-Diphenylmethane diisocyanate, bisphenol A
231
Bisphenol A, 4,4/-J/V-methyldiphenyl methane and linear and cyclic fragments of the main chain (see Ref.)
231
330
Cyclic monomer and dimer, and various chain fragments
232
330
Cyclic dimer, bisphenol A and various chain fragments
232
References page II - 475
TABLE 3.
cont'd
Polymer
Temperature range (0C)
Poly(oxy-l,3-phenylene-oxycarbonyl320 Af-methylimino-hexamethyleneAf-methyliminocarbonyl) Poly(oxy-l,4-phenyleneoxycarbonyl325 Af-methylimino-1,4-phenylenemethylene1,4-phenylene-A^methyliminocarbonyl) Poly(oxy-l,3-phenylene-oxycarbonyl360 piperazine-1,4-diyl-carbonyl) Poly(oxytetramethylene oxycarbonylAmbient to 500 imino-1,4-phenylenemethylene1,4-phenylene-iminocarbonyl) with 10% (w/w) ammonium Ambient to 500 polyphosphate Poly(oxy-xylylene-oxycarbonylimino300 xylylene-iminocarbonyl) Polyurethane from methylene bis600 (4-phenyl isocyanate) (105 parts) and propoxylated trimethyl propane (100 parts) 250-350 350-500 500-650 Polyurethane from butane diol, phenylphosphonic dichloride, and methylene bis-(4-phenyl isocyanate) Polyester urethane from an ethylene/ propylene glycol/adipic acid polyester, butane diol and methyl bis(4-phenyl isocyanate) Poly(urethane-cocarbonates)
650-800 Ambient to 500 Ambient to 500
330
290
Degradation products
Refs.
Cyclic monomer, dimer and trimer, resorcinol
232
Cyclic dimer, 4,4/-Af-methyldiphenylmethane, hydroquinone, and higher chain fragments (see Ref.)
232
Cyclic dimer and trimer, resorcinol, and various chain fragments (see Ref.) 1,4-Butanediol, methylene bis-(4-phenyl isocyanate), tetrahydrofuran, CO2, H2O, butadiene, HCN, CO
232
Methylene bis-(4-phenyl isocyanate), tetrahydrofuran, H2O, aniline, formaldehyde, CO2 CO 2 , frajis-l,4-cyclohexane-dimethanol, 4-methylene-cyclohexanemethanol, xylylene diamine Methane, CO 2 , ethylene ethane, H2O, propene, propane, ethanol, isobutene, acrolein, propanal, 2-methyl-l-butene, 2-methylpropenal, 2-butanone, benzene, dihydropyran, 2,2,4-trimethyl-l,3-dioxalane CO2, propene, some methane and propanal Methane, ethane, ethene, propane, propene, ethanal, propanal, diminishing quantities of CO2 Methane (max. rate of production at 6000C), ethane, ethene, propene, ethanal, propanal Methane, ethane, ethene, propene, ethanal, propanal CO 2 tetrahydrofuran, dihydrofuran, aniline, /?-toluidine, TV-phenyl pyrrolidine, N-(p-io\y\) pyrrolidine, cyclobutylene phenylphosphonate, butane diol, methylene bis-(4-phenyl isocyanate), 4,4/-methylene dianiline Modified chain fragments, ethylene, propylene, CO2, ethylene oxide, propylene oxide, acetaldehyde, tetrahydrofuran, water, cyclopentanone, ethylene, glycol, propylene glycol, adipic anhydride (trace), aniline (trace) Cyclic monomer, bisphenol A and higher linear and cyclic fragments of the chain (see Ref.)
228 229 230 234 256 256 256 256 235 236
237
Cyclic monomer, resorcinol, and various fragments of the chain (see Ref.)
237
Ethene, propane, propene, isobutane, isobutene, ethylamine, aziridine, 1-r-butyl-perhydro-l,4-diazine, N-t-b\xty\ ethylamine, 1 -?-butyl-4-isopropenyl-1,2,3,4-tetrahydro-1,4-diazine, 1,4-di-(/-butyl)-perhydro-1,4-diazine, oligomers
276
Butadiene, tetrahydrofuran, dihydrofuran, H2O, cyclic ester of phenylphosphonic acid and 1,4-butanediol, phenylphosphonic acid, butane diol Butadiene, tetrahydrofuran, dihydrofuran, H2O, cyclic ester of phenylphosphonic acid and butanediol, phenylphosphonic acid, butane diol, CO2, aniline
233
Cyclic trimer, tetramer, pentamer, hexamer, and higher oligomers, l,l,l-trifluoro-2-chloroethane (due to residual chlorine in the polymer) Cyclic tetramer, trimer and higher oligomers, chlorobenzene (due to residual chlorine in the polymer), phenol, triphenylphosphate
238
3.9. OTHER NITROGEN CONTAINING POLYMERS Poly(£-butyl aziridine)
Ambient to 500
3.10. PHOSPHOROUS CONTAINING POLYMERS Poly(oxytetramethylene oxyphenyl phosphono)
Ambient to 550
Poly(oxytetramethylene oxyphenylAmbient to 500 phosphono) capped with phenylisocyanate)
Poly(bis(trifluoroethoxy)phosphazene)
150-400
Poly(diphenoxyphosphazene)
100-400
233
239
TABLE 3. cont'd Polymer Poly(diphenoxy-phosphazene) (residual chlorine content: <0.05%) Poly(diphenoxy-phosphazene) (residual chlorine content: 2.4%) Poly(diphenoxy-phosphazene) (residual chlorine content: 9.9%)
Temperature range (0C) Ambient to 480 Ambient to 480 Ambient to 480
Degradation products
Refs.
Traces of phenol, phenoxy cyclic trimer and monochlorophenoxy 316 cyclic trimer Phenoxy cyclic trimer and tetramer, monochloropentaphenoxy cyclic 316 trimer, monochloroheptaphenoxy cyclic tetramer, dichlorohexaphenoxy cyclic tetramers Phenoxy cyclic trimer and tetramer, monochloropentaphenoxy cyclic 316 trimer, monochloroheptaphenoxy cyclic tetramer, dichlorohexaphenoxy cyclic tetramers, dichlorotetraphenoxy cyclic trimers, trichloropentaphenoxy cyclic tetramers, HCl
TABLE 4. MAIN-CHAIN HETEROCYCLIC POLYMERS Polymer Phenol-formaldehyde resin PoIy(I-methylene-2-imidazolidinone) (Poly(ethyleneurea formaldehyde))
Temperature range (0C) 250-400 240 Ambient to 600
Poly(7V-phenylmaleimide)
100-400
Poly(5,5/-bibenzimidazole-2,2/-diyl1,4-phenylene)
400-700 570, 700, 1000
Poly(5,5/-bibenzimidazole-2,2/-diyl1,3-phenylene)
599-667
PoIy(1,3,5,7-tetraoxo-2,3,6,7-tetra700 hydro-(lH,5H)-2,6-benzo[l,2-c: 4,5-c']dipyrroldiyl-1,4-phenylene-carbonyl1,4-phenylene) (Poly(pyromellitimide)) Poly(l,3,5,7-tetraoxo-2,3,6,7-tetra700 hydro-(lH,5H)-2,6-benzo[l,2-c:4,5-c']dipyrroldiyl-1,4-phenylene-methylene1,4-phenylene) (Poly(pyromellitimide)) PoIy(1,3,5,7-tetraoxo-2,3,6,7-tetra700 hydro-( 1 H,5H)-2,6-benzo[ 1,2-c: 4,5-c']dipyrroldiyl-1,4-phenylene-oxy1,4-phenylene) (Poly(pyromellitimide)) Poly(l,5-diimino-3,7-dioxo450-500 2,3,6,7-tetrahydro-(lH,5H)-2,6-benzo [1,2-c: 4,5-c'] dipyrroldiyl- 1,3-phenylene) PoIy(1,5-diimino-3,7-dioxo450-500 2,3,6,7-tetrahydro-(lH,5H)-2,6-benzo [1,2-c: 4,5-c']dipyrroldiyl-l,4-phenyleneoxy1,4-phenylene)
Degradation products
Refs.
Volatiles comprise xylene (76%), traces of phenol, cresol, benzene 53 Formaldehyde (trace) 253 Low boiling fraction consists of NH 3 , CO 2 , HCN, CH 4 , CO (trace); 253 IR data also suggests presence of isocyanate, ketamine and carbodiimide or cyanogen compounds; high boiling fraction (77% of total volatiles) consists of chain fragments up to pentamer, including Af-methylethylene urea, corresponding unsaturated compounds and higher homologues; similarly, AUV'-dimethylethylene urea and homologues Aniline, P h - N = C H - C H 2 - C H 3 , Af-phenylsuccinimide, 301 N-phenylmaleimide (trace), P h - N = C H - C H = CH-CO-NH-Ph Phenol, terephthalodinitrile, benzonitrile, 4,4/-diaminodiphenyl, H 2 , CO, 56 NH 3 , HCN, traces of aniline, carbonaceous residue H 2 (700 and 1000°C), NH 3 (570 and 700), N 2 O, HCN, cyanogen (570 217 only), CH 4 , C 2 H 6 , ethylene, acetylene (700 and 1000), acetonitrile (700 and 1000), propene (570 and 700), benzene, toluene, benzonitrile (700 only), ethylbenzene, methylbenzonitrile (700 only) Gaseous products; H 2 , NH 3 , HCN, and CH 4 ; products involatile at 218 ambient temperature after approx. 50% weight loss; benzimidazole (29.8%), benzoxazole (4.9%), 2-methylbenzimidazole (7.3%), 2-phenyl-benzimidazole (24.3%), 2-(3-methylphenyl)benzimidazole (5.3%), 5-(3-aminophenyl)benzimidazole (9.6%), 2-(3-cyanophenyl)benzimidazole (7.8%), 5,5'-bibenzimidazole (4.4%), 2-phenyl-5-(3-aminophenyl)-benzimidazole (4.4%), 2-phenyl-5,5/-bibenzimidazole (1.9%), 2-phenyl-5-(benzoxazolo)benzimidazole (0.3%) H 2 , CO, CH 4 , CO 2 , H 2 O, benzene, benzonitrile, chain fragments, 60% 61 residue H 2 , CO, CH 4 , CO 2 , H 2 O, benzene, toluene, benzonitrile, chain fragments, 60% residue
61
H 2 , CO, CH 4 , CO 2 , H 2 O, benzene, benzonitrile, phenol, chain fragments, 60% residue
61
CO, CO 2 , HCN, NH 3 , H 2 and traces of CH 4 and C 6 H 6 ; NH 3 is the main product at 4400C, CO increases at higher temperatures
219
CO, CO2 HCN, NH3, H2 and traces of CH4 and C6H6; NH3 is the main product at 4400C, CO increases at higher temperatures
References page II - 475
TABLE 4. cont'd Polymer
Temperature range (0C)
Degradation products
Refs.
Poly(triazines)
Poly(perfluoropyridine)
415-505
C 2 F 4 , C 2 F 6 , and smaller amounts of C 3 H 6 and C 3 H 8 and larger chain fragments
48
430-503
C 2 F 4 with traces of CF4, C 3 H 6 , and larger chain fragments
48
305-465 480-660 690-760
Only volatile product is benzonitrile HCN and NH3 H 2 and carbonaceous residue
54 54 54
424-550
Perfluoroethane, perfluoromethane, perfluoroethylene, 220 perfluoropropane, perfluoropropylene, acetal fluoride, carbonyl fluoride
600
Volatiles comprise CO2, CO, SiF4 (all from silica vessel); carbonaceous residue remains
300
CO 2 , CO, NO
52
Poly(parabanic acid)
221
Poly(bismaleimides)
Poly(3-(4-octylphenyl)2,2/-bithiophene) Poly(3-octylthiophene) Poly(3-octyl-2,2'-bithiophene) Poly(3-(4-octylphenyl)thiophene)
350-500
Aliphatic: C 2 - C 6 fractions, maleimide (MI), succinimide (SI) 222 MI-CH 3 , SI-CH 3 , MI-C 2 H 5 , SI-C 2 H 5 , MI-C 3 H 7 , SI-C 3 H 7 , MI-C 4 H 9 , SI-C 4 H 9 , MI-C 5 Hn, SI-C 5 Hn, MI-(CH 2 ) 2 -MI, SI-(CH 2 ) 2 -SI, MI-(CH 2 ) 6 -MI, MI-(CH 2 )S-MI, MI-(CH 2 )I 0 -MI, MI-(CH 2 )I 2 -MI
350-500
Benzene, toluene, aniline, SI, methylaniline, phenylisocyanate, tolylisocyanate, and various other products (see Ref.)
222
350-500
Aniline, phenol, SI, anisidine, phenylisocyanate, and various other products (see Ref.)
222
H 2 S, COS, SO2, CH3SH, CS 2 , S 8 , C i - C 8 alkanes and alkenes, benzene, ethylbenzene, toluene, styrene, octylbenzene, thiophene, methylthiophene, bithiophene C i - C 8 alkanes and alkenes, H 2 S, CS 2 , benzene, toluene C i - C 8 alkanes and alkenes, H 2 S, CS 2 , benzene, toluene C i - C 8 alkanes and alkenes, H 2 S, CS 2 , benzene, toluene
284
800 550-1400 550-1400 550-1400
284 284 284
Next Page
TABLE 5. CELLULOSE AND ITS DERIVATIVES Polymer
Temperature range (0C)
Cellulose
250-397 Ambient to 500
- , a form
330-440
Cellulose (oxidized)
180-331
Cellulose triacetate
250-310 250-900
Ethyl cellulose
C.
230-320 306
Degradation products
Refs.
H 2 O with smaller amounts of CO2 and CO and a tar containing 17,18 principally levoglucosan H 2 , CO, CO2, H2O, furan, furancarboxyaldehyde, methylfurans, acetone, 273 hydroxypropanone, butenal, butanone, butanedione, levoglucosan Fixed gases (not identified), pentene, acetaldehyde, furan, 162 propionaldehyde, acetone, acrolein, 2-methylfuran, butyraldehyde, methyl ethyl ketone, benzene, 2,5-dimethylfuran, methyl vinyl ketone, 2,3-butanedione, toluene, crotonaldehyde, H2O, cyclopentanone, cyclooctatetraene, acetol, pyruvaldehyde, acetic acid, furfural, formic acid, 5-methyl-2-furfural, furfuryl alcohol, butyrolactone, 2-hydroxy-3-methyl-3-cyclopenten-2-one, phenol, o-cresol, m-cresol, p-cresol, 2,5-dimethylphenol, 3,4-dimethylphenol, 5-hydroxymethylfurfural Mainly H 2 O and CO2, smaller amounts of CO, formaldehyde, methanol, acetic acid, ethanol and acetaldehyde, and very little tar Product fraction volatile at 25°C contains acetic acid, CO2, CO, CH4, 18 H 2 , acetaldehyde and acetone; heavier fractions do not contain levoglucosan acetate Main products: acetic acid, water, CO, CH4, H 2 , CO 2 ; minor products: 223 ketene, acetaldehyde, acetone, acetylene, ethylene, ethane, propylene, and C 4 , C 5 and C 6 hydrocarbons Acetic acid, acetyl derivatives of D-glucose 224 H2O, CO, CO2, C 2 H 4 , C 2 H 6 , C2H5OH, CH3CHO, aliphatic 224 compounds, furan derivatives
REFERENCES
1. G. G. Cameron, D. R. Kane, Polymer, 9, 461 (1968). 2. S. Straus, S. L. Madorsky, J. Res. Natl. Bur. Std., 50, 165 (1953). 3. S. L. Madorsky, J. Polym. Sci., 11, 491 (1953). 4. J. R. Schaefgen, I. M. Sarasohn, J. Polym. Sci., 58, 1049 (1962). 5. C. S. Marvel, J. C. Cowan, J. Am. Chem. Soc, 61, 3156 (1939). 6. A. J. Canale, W. E. Goode, J. B. Kinsinger, J. R. Panchak, R. L. Kelso, R. K. Graham, J. Appl. Polym. Sci., 4, 231 (1960). 7. J. W. C. Crawford, D. Plant, J. Chem. Soc, 4492, 1952. 8. G. G. Cameron, G. P. Kerr, J. Polym. Sci. A-I, 7, 3067 (1969). 9. W. J. Burlant, J. L. Parsons, J. Polym. Sci., 22, 249 (1956). 10. S. Straus, S. L. Madorsky, J. Res. Natl. Bur. Std., 61, 77 (1958). 11. S. L. Madorsky, S. Straus, J. Res. Natl. Bur. Std., 63A, 261 (1959). 12. A. R. Monahan, J. Polym. Sci. A-I, 4, 2391 (1966). 13. S. L. Madorsky, S. Straus, J. Res. Natl. Bur. Std., 53, 361 (1954). 14. S. L. Madorsky, S. Straus, J. Res. Natl. Bur. Std., 55, 223 (1955). 15. M. A. Verkhotin, K. A. Andrianov, M. N. Yermakova, S. R. Rafikov, V. V. Rode, Polym. Sci. USSR, 8,2369 (1966). 16. S. L. Madorsky, S. Straus, D. Thompson, L. Williamson, J. Res. Natl. Bur. Std., 42, 499 (1949). 17. S. L. Madorsky, V. E. Hart, S. Straus, J. Res. Natl. Bur. Std., 56, 343 (1956).
18. S. L. Madorsky, V. E. Hart, S. Straus, J. Res. Natl. Bur. Std., 60, 343 (1958). 19. R. F. Schwenker, Jr., L. R. Beck, Textile Res. J., 624, (August, 1960). 20. A. B. Blyumenfel'd, B. M. Kovarskaya, Polym. Sci. USSR, 12, 710 (1970). 21. L. G. Kaufman, R T. Funke, A. A. Volpe, Macromolecules, 3, 358 (1970). 22. J. L. Cotter, G. J. Knight, W. W. Wright, J. Polym. Sci. B, 6, 763 (1968). 23. S. L. Madorsky, V. E. Hart, S. Straus, V. A. Sedlek, J. Res. Natl. Bur. Std., 51, 327 (1953). 24. E. E. Lewis, M. A. Naylor, J. Am. Chem. Soc, 69, 1968 (1947). 25. S. L. Madorksy, S. Straus, J. Polym. Sci., 36, 183 (1959). 26. E. P. Goodings, Soc. Chem. Ind. (London), Monograph, 13, 211 (1961). 27. C. E. Schweitzer, R. N. MacDonald, J. O. Punderson, J. Appl. Polym. Sci., 1, 158 (1959). 28. S. Straus, S. L. Madorsky, J. Res. Natl. Bur. Std., 66A, 401 (1962). 29. Y. Tsuchiya, K. Sumi, J. Polym. Sci. A-I, 7, 813 (1969). 30. S. D. Bruck, Polymer, 7, 231 (1966). 31. S. Straus, S. L. Madorsky, Ind. Eng. Chem., 48, 1212 (1956). 32. B. S. T. Boonstra, G. J. Van Amerongen, Ind. Eng. Chem., 41, 161 (1949). 33. D. H. Grant, N. Grassie, Polymer, 1, 125 (1960). 34. N. Grassie, H. W. Melville, Proc Roy. Soc A, 190, 1 (1949). 35. R D. Zemany, Nature, 171, 391 (1953).
Previous Page
TABLE 5. CELLULOSE AND ITS DERIVATIVES Polymer
Temperature range (0C)
Cellulose
250-397 Ambient to 500
- , a form
330-440
Cellulose (oxidized)
180-331
Cellulose triacetate
250-310 250-900
Ethyl cellulose
C.
230-320 306
Degradation products
Refs.
H 2 O with smaller amounts of CO2 and CO and a tar containing 17,18 principally levoglucosan H 2 , CO, CO2, H2O, furan, furancarboxyaldehyde, methylfurans, acetone, 273 hydroxypropanone, butenal, butanone, butanedione, levoglucosan Fixed gases (not identified), pentene, acetaldehyde, furan, 162 propionaldehyde, acetone, acrolein, 2-methylfuran, butyraldehyde, methyl ethyl ketone, benzene, 2,5-dimethylfuran, methyl vinyl ketone, 2,3-butanedione, toluene, crotonaldehyde, H2O, cyclopentanone, cyclooctatetraene, acetol, pyruvaldehyde, acetic acid, furfural, formic acid, 5-methyl-2-furfural, furfuryl alcohol, butyrolactone, 2-hydroxy-3-methyl-3-cyclopenten-2-one, phenol, o-cresol, m-cresol, p-cresol, 2,5-dimethylphenol, 3,4-dimethylphenol, 5-hydroxymethylfurfural Mainly H 2 O and CO2, smaller amounts of CO, formaldehyde, methanol, acetic acid, ethanol and acetaldehyde, and very little tar Product fraction volatile at 25°C contains acetic acid, CO2, CO, CH4, 18 H 2 , acetaldehyde and acetone; heavier fractions do not contain levoglucosan acetate Main products: acetic acid, water, CO, CH4, H 2 , CO 2 ; minor products: 223 ketene, acetaldehyde, acetone, acetylene, ethylene, ethane, propylene, and C 4 , C 5 and C 6 hydrocarbons Acetic acid, acetyl derivatives of D-glucose 224 H2O, CO, CO2, C 2 H 4 , C 2 H 6 , C2H5OH, CH3CHO, aliphatic 224 compounds, furan derivatives
REFERENCES
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R a d i a t i o n
C h e m i c a l
Y i e l d s :
G
V a l u e s
M . C. Senake Perera Magnetic Resonance Facility, School of Science, Griffith University, Nathan, QId 4111, Australia D a v i d J. T. H i l l Department of Chemistry, University of Queensland, St Lucia, QId 4072, Australia
A. Introduction B. Tables of G values Table 1. Homopolymers 1.1. Polydienes 1.2. Polyolefins 1.3. Polyacrylates 1.4. Poly(methacrylates) 1.5. Poly(styrenes) 1.6. Poly(vinyls) 1.6.1. Acrylamides and Nitriles 1.6.2. Vinyl Monomers 1.7. Miscellaneous Polymers 1.7.1. Cellulose and Derivatives 1.7.2. Poly(siloxanes) 1.7.3. Poly(amino acids) 1.7.4. Polyesters 1.7.5. Polysulfones 1.7.6. Polyketones 1.7.7. Fluoropolymers 1.7.8. Others Table 2. Copolymers 2.1. Copolymers with Ethylene 2.2. Copolymers with Methyl Methacrylate 2.3. Copolymers with Styrene 2.4. Copolymers with Sulfur Dioxide 2.5. Other copolymers Table 3. Polymers Blends Table 4. Composites C. References
11-481 11-481 M-482 M-482 II-482 II-483 II-484 II-485 II-486 II-486 M-486 II-487 II-487 II-487 II-487 II-488 II-488 II-488 II-488 II-489 II-490 II-490 II-490 11-491 11-491 II-492 II-493 II-493 II-493
A.
INTRODUCTION
The G values quoted in the following tables are defined as the radiation chemical yields of individual atomic or molecular events for 100 eV of energy absorbed by the system. G(R) represents the yield of free radicals, G(X) the yield of crosslinks, G(S) the yield of main chain scission, and G(products) the yield of product molecules per 10OeV of absorbed radiation. This table has been compiled from the polymer literature that has been published since the third edition of the "Polymer Handbook" (i.e. 1986-1997). In many cases, the tabulated data are only representative of the total data in the paper, and the original publication should be consulted. B. TABLES OF G VALUES Notes to the Tables General: Unless otherwise stated, the conditions applying are y-rays, vacuum, room temperature (ambient). Symbols/Abbreviations + — vac RT e
cation radical anion radical vacuum room temperature electron beam
d.b. t-v Y X n
double bond trans-vinylene crosslinks crosslinks neutron
TABLE 1. HOMOPOLYMERS Polymer 1.1.
G(R)
G(X)
G(S)
G(products)
Radiation conditions
38.7 (d.b.)
e, 263 K
Refs.
POLYDIENES
Polybutadiene 610 (1,2) 0.0054
2.1 Various
Polyisoprene
0.009 0.5-0.8 Various
NR latex Polychloroprene
77 K 9.3 105 3.36/9.4 5.3
112 (Vinyl) Various 0.34/0.19 90
Various
Various
41 7.2
Poly(2-phenyl butadiene)
1.2.
Comments
3.0
1.6-2.1 Various Various 3.9
e 77K/RT Air, 295 K
Excitation scavenger 1, 2-PBD Radical pairs, isotactic Syndiotactic cis 1,4
64 138 74 97 84 98 104
Effect of pressure Various Review 186 G(Cy) > G(X) 261 G(X) depend on MW G (initiation), 262 G(X) increases G(Cy), G(db) decreases with Crosslinker Vac, 303 K 180 Vac/303 K, ethyl178 ene dichloride 77 K Radical pairs 74 Var cis content 15
94-168 (d.b.), CH 4 , H 2 Various
Various
2.8 (-Cl)
Vac/77, 303 K
186 248 179
RT, vac
235 226
Review +acrylate
POLYOLEFINS
Squalene Poly(butene-l)
1.0
Poly(ethylene)
1.09-1.39 0.63
3.2
4 4.1
4 1.4 15-30 0.25 1.50-2.40
3.0 (H 2 ) 13.9 (-isotactic pentad) 7 (COOH) 9.1 (O 2 ) - 2 (MO
e, air Vac/O2 300K
0.48 8-15
Carries
Air, 300/450K
Pressure effects
1.08-1.69
Various
303-373 K He, 77K O 2 , CCl 4
e pre-irradiated
2.8, 5.8 (C 2 D 4 ) 2.4
Fibers,
89 101 107 172 116 169 30 63 52 147 151
G(S)ZG(X) = 1
1.1-2.8
0.05-2.7 Various gases
1.1 1.5
<0.05 0.48
2.6/0.56 (alkyl) 0.74 G (H) 0.27 G (Y) 1.0
Air
e, N 2 Various compounds e, N 2 Gamma/n
Gamma/alpha, 77 K Vac, molten state 0.2
3.9(H 2 ) 3.5 (damage)
155 70 87 174 163 183
Crystalline region units
228 270
TABLE 1. cont'd Polymer -,LDPE
G(R)
G(X)
G(S)
G(products)
2.5(alkyl) 12.4-15.4 (O 2 ) 4.45 (butanes) Various -1.9(MO
Radiation conditions 77 K O2 air 303 K 298-423 K
Comments
Refs.
G(S)/G(X) = 1.6 +I2 +CH 3 SH antioxidants
Alkanes 77 K
129 164
Various
Air
231 105 184
0.16 (butanes)
Air 77 K 77 K 303 K
3.0 (total) 2.8 (alkyl) Various G(M) -,LLDPE
2.4
-, HDPE
0.4
1.3 2.9-3.6 2.3-4.5(alkyl) 0.3* 0.21
-,HDLPE
5.5
0.3,0.43
Alkanes Y, C = C, (M)
3.7 0.76 (bulk)
- 9 . 6 (f-v)
88 92 177 10 28 32 125 45
Morphology
Monolayer crystals 303 K Air, 77K/RT
1.6* 0.76
Wanning, morphology *G(X/unsat.) 77 K
2.4 (trans) 0.7 (cis) 4-5 (gas) 4.0 2.5 3.8-11.1 Various 2.1
Poly(4-methylpentene-l) polypropylene
Butene-1, hexene-1
Allylic
- , Chlorosulfonated polyisobutylene
Various 3.6
Various Various 0.3,0.6*
4.8, 2.7(dPP) 3.1/0.64 9.4
e 77 K Various temperatures Various Vac/77, 303 K N2/air He, e, 77 K Air/vac O 2 + CCl 4
2.9 (H 2 ) 2.19*
/-Polypropylene
177 96 117 10 27 71
+CCl 4
47 134 75 79 240
119 131 133 78,90,100 186 *G(S)/G(X) Also 373-623 K Also O 2 Decreases with dose *G(S)-G(X)
43 52 129 147 158 159
Various Various 94 (-/-pentad) Various (pentad sequences) 220 (-/-pentad)
Air Air Gamma
118 40 244
e
245
Various gases
Vac/air
Various
293-308 K Vac 77, 300K
Various
Gamma, aq.
H 2 , CO, CO 2 , CH 4 etc.
195-423
170 2 4 185 189 190 233 59 126
1.3. POLYACRYLATES Poly(acrylic acid) 3.6 3.49
Poly(acrylic anhydride) Poly(methyl acrylate)
0.0
0.44
0.47
0.62 1.1*
*G(S)- S(X)
References page II - 493
TABLE 1. cont'd Polymer Poly (methyl bromoacrylate) Poly(methyl a-chloroacrylate)
G(R)
G(X)
G(products)
6.98 5.1
Radiation conditions
Comments
77 K 0.3-0.9 0.8
Poly(methyl a-cyanoacrylate) Poly(methyl oc-fluoroacrylate)
G(S)
1.6 1.0
3.2-7.4 6.0 6.7*
Dose dependent *G(S)-G(X) 77 K 77 K
0.05
Refs. 139 133 24 62 17 133 65
1.4. POLY (METHACRYLATES) Poly(benzyl methacrylate) 0 Poly(f-butyl methacrylate) Poly(cyclohexyl methacrylate) Poly(glycidyl methacrylate) Poly(hexafluoroisopropyl methacrylate) Poly(hexyl methacrylate) Poly(isobutyl methacrylate)
0.29* 0 0.14 1.28* 0.44* 2.4*
e 300K
*G(S)-G(X) Syndiotactic
e e
*G(S)-G(X) *G(S)-G(X) * G(S)-G(X)
Various
9.2
0.1 0.5
Poly(2-methyl heptyl methacrylate) Poly(methacrylic acid)
2.6 0.38* 1.1* 0.8 0.3 3.4 Various
0.2
0.6/2.9 4.8 6.0
0.04
6
Poly(methacrylic anhydride) Poly(methyl methacrylate) 1.1-1.5( + ) 0.7-0.9(-)
7K e e 300K 300K N2 Gamma/e 77/273 K 77 K
Various
77, 303 K
Various
Gamma/e
1.8-2.9 1.9 (DMF) 1.3 (THF) 1.5
SoIn. 77 K
0.5, 1.5( + )
77 K
2.8-4.1
303, 343 K 1.3 1.31 1.9
Aromatic additives Aromatic additives Absorbed on zeolite
77 K
1.63, 1.09 1.4 1.5/0.33 1.2
Gamma/X Various
0.71-1.63 1.9/4.1 1.04/1.11 1.9,4.4 1.5 Various 15.8 (units) 0.34 (H2) 18.6 0.22,0.46,1.08 Various
Si wafers
e/gamma, 303-383K Gamma/n, vac/air 77/273 K Vac/air, 273 K 77 K
Bulk, alcohol
Air
*G(S)-G(X) 4- ethane diol Isotactic
1.5*
Vac, 363 K Deep UV, e, X-ray
73 57 51 53 65 50 131 132 135
e 77 K Gamma/n, vac/air 206 K
0.58 1.42
*G(S)-G(X) *G(S)-G(X) Syndiotactic Syndiotactic Aq. solution
22 192 238 22 22 120 246 65 22 22 192 192 91 176 123 133 185 189 195 176 59 59
139 152 161 176 86
Various radicals
Isotactic
173 146 171 162 17 14 23 33 187 188
TABLE I.cont'd Polymer
G(R)
G(X)
G(S)
G(products)
1.5 1.1 1.7 1.7 1.6 0.99, 0.4 0.77 5.1 (soln.) 0.89 (amorphous solid) 0.48 (crystalline solid) 1.21 (333K) 0.89 (303 K) 0.46(195K) G(damage) = 8.8
1.0
300K N 2 , RT Vac N2 Vac
0.14
Poly(2-naphthyl methacrylate) Poly(2,2,2-trichloroethyl methacrylate)
0.14 0.19 3.7
1.5.
0 0.4
Refs.
Isotactic Syndiotactic
190 192 222 223 224 225 238 249
Protons, gamma e, gamma C5 + , O5 + ions i-PMMA
Morphology effects, racemization Benzene solution
1.7 1.3
300K 300K 77, 300K
1.2, 1.7
258
264 1 238 238 175
Gamma/e, 298-416K
3.7 Poly(ethyl methacrylate) Poly(w-butyl methacrylate) Poly(2-hydroxyethyl methacrylate) Poly(phenyl methacrylate)
Comments
Air, RT
PoIy(I-naphthyl methacrylate)
0.03
Radiation conditions
Dioxane solution Syndiotactic Syndiotactic
0.44
11 192 192 193 238
POLY(STYRENES)
Poly(oc-methyl styrene)
0.3 0.33
e Gamma/e, 77-373K 273-319 K
0.78 0
0.29 0.48,0.89, 0.97, 1.13
303, 353, 373, 383, 393 K
0.105,0.05 Poly(/?-methyl styrene)
0.1
Poly(styrene)
0.45-7.9
77, 298 K Gamma/e, 77-373K 303 K
0.022 0.17
0.022 1.09, 2.12
0.035-0.042 0.043
0.010-0.051 0.0009
0.043-0.027 0.048, 0.021
0.086-0.074 0.2* 0.27, 0.07
0.03/0.2
0.02/0.2
0.043
0.00086 3.9
0.05
0.02
0.1
Air
0.032 (H 2 )
303-373 K 303 K 303-423 K 77 K Air 77 K Gamma/n, vac/air, 206 K
131 38 Benzene solution + Depolymerization
194
197 38 Emulsion polymerization Sheet absorbed on silica gel Includes lit. review * G(S)-G(X) Various doses
Sheet O 2 + CCl 4 373-623K Air
25
48 56 58 60 61 67 73 130 132 135 136 147 157
References page II - 493
TABLE 1. cont'd Polymer
G(R)
G(X) 0.077
G(S)
G(products)
Radiation conditions
Comments
0.055
0.0009 0.094 Various
0.0027 Various
0.018,0.15
0.06,0.07
0.0174 0.0425
0.0012
0.014-0.05
0.105
77 K 313 K Gamma/n, vac/air 77 K Gamma/n/alpha, air 77 K
1.8
0.5
Radical pairs
0.05
Various
24.7-30.4 G(degradation) 0.01 0.03 (H 2 ) H 2 , CH 4 , C 2 H 2 , C3H4, C6H6 Various (-O 2 ) Various Various hydrogen
Warming
Gamma/e, 77-373 K Abs of air Various dose rates
Various sources + Crosslinking agents
Ion beam
Deuterium subs
Vac, various temp.
Variable temp. dose rate Tacticity, crystallinity effect Gamma, X-ray,
0.03-0.05
161 74 81 85 98 112
0.033 (H 2 )
0.03-0.05 6.7-15.2
Refs.
19 6 7 33 38 195 196 228 234
250 257
255
Ne, Ar 1.6.
POLY(VINYLS)
1.6.1. ACRYLAMIDES AND NITRILES Poly(acrylamide)
2.5 0.04
0.88
5 1.33/0.62
Poly(methacrylamide)
0.45/0.52 1.2*
Poly(acrylonitrile)
3.7-4.1
Poly(methacrylonitrile)
0.15-3.0 2.8,4.2 2.2,2.8
303 K
0.59
0.0 0.4-3.3 3.3 gamma 3.6 X 0.5Ne 0.4 Ar
Poly(a-chloroacrylonitrile)
Various
AhYH2O e, O 2 Aq. soln, 304 K Vac/air, 77-393K
1.4
77, 300K 77, 300K Absence of O 2
Aq. soln. Hydrogel
149 103 108 167
* G(S)-GQQ
141
Absorbed on zeolite
53
Various sources
77 K 2.7* 1.1-7.2 3.2 2.1-3.3* 3.1-3.3 3.3*
Vac/air
* G(S)-G(X) Solution + bulk *G(S)-G(X) *G(S)- G(X)
5 198 200 195 255
133 59 99 145 59 62 17
1.6.2. VINYL MONOMERS Poly(r-butyl crotonate) Poly(f-butyl vinyl ether) Poly(ethyl vinyl ether) Poly(isobutyl vinyl ether) Poly(isopropyl vinyl ether)
0.66
0.59 3.6,10.3 0.36,0.50 0.39,1.73 0.86,1.50
273, 273, 273, 273,
348 K 348 K 348 K 348 K
Liquid
54 122 122 122 122
TABLE 1. cont'd Polymer Poly(methyl vinyl ether) Poly(tetrafluoroethylene) Poly(vinyl acetate)
G(R)
G(X)
0.31,0.64 0.5 2.4-4.1
Poly(vinyl alcohol) Poly(vinyl bromide) Poly(vinyl butyral) Poly (vinyl carbazole) Poly (vinyl chloride)
G(S)
1.08 1.02 0.71 0.35
0.6
0.7 (holes) 1.7 2.36 10-11
20-115
G(products)
Radiation conditions
273, 348 K O 2 + CCl4 K 243-273 K 0.9-2.4 gel dose Absence of O 2 O2 Air N2 39-55(HBr) e, N 2 e 77 K Air Various Vac/O2 7.7 (HCl) Vac/O2 (d.b.) 17(HCl) e, N2/vac 0.24 (H2) Vac/O2 8 (HCl) 2.8-3.5(Py + ) 0-1.2 (Phenyl + ) 3.0 (-Cl)
Poly(vinyl imidazole) Poly(vinyl pyrrolidone)
10-54 0.41-0.75
Aq
3.3
77 K 0.01-1.32
Comments
Also 373-623 K
Solution
Underpressure THFsoln. + additives
Refs. 122 147 21 195 236 9 241 168 165 113 115 119 8,44 154 160
G(cation) 247 273 K G(X) Increases 263 with crosslinker 269 +Crosslinker 256 Aq. soln. 12 +Warming 13 Various 205 solutions
1.7. MISCELLANEOUS POLYMERS 1.7.1. CELLULOSE AND DERIVATIVES Cellulose 13-186 7.1
Cellulose acetate
CO, CHO, COOH Vac/air Vac/air Air
Post irrad. H2O incr. G(S)
111 26 156
1.7.2. POLY(SILOXANES) Poly(oxydimethyl diphenylsilylene) Poly(oxydimethyl silylene)
Various Poly(methyl phenyl silane) Poly(cyclohexyl methyl silane)
Various 2.48
N 2 , 303 K
18.5/120
Air
2.7 3.0 2.8 Various
Various
Various
0.01-0.21 1
Poly(dimethyl siloxane) Silicon containing poly(acetylene)
1.8-17.4 1.7 0.3-2.3
Liq. 94 Also blends with 143 PS Effect of 104 pressure 76 80 Liquid 82 186 G(X) increases 265 with crosslinker LET 230 dependence Dose 232 dependence 243 Effect of various 252 pendent groups
1.7.3. POLY (AMINO ACIDS) Poly(alanine) Poly(glycine) Poly(tyrosine) Poly(valine)
2.9 3.6 2.2 < 0.4
3.8-7.0 3.0-3.3 0.12
Various Various Various Various 0.04-0.12 (NH3) Air/N2/N2O Various
Aq. soln.
95 128 95 95 102 95
References page II - 493
TABLE 1. cont'd Polymer
G(R)
G(X)
G(S)
G(products)
Radiation conditions
Comments
Refs.
1.7.4. POLYESTERS Poly(hydroxybutyrate) Poly(L-lactic acid) PoIy(D, L lactic acid)
1.65
Air 77, 300K 77, 300K 77, 300K
2.0,1.5 2.37-1.23 2.4, 1.2
Pressure and temp, effect on G(S) and G(X) Poly(glycolic acid)
1.72,1.47
77, 300K Pressure and temp, effects on G(S) and G(X)
191 201 203 201 274
203 274
1.7.5. POLYSULFONES Bis-A-PSF Hydroquinone PSF Biphenol PSF Bis-S-PSF PES (Polyethersulfone)
0.13 0.13 0.57 0.19 0.14 0.56 0.084 0.084 0.51 0.128 0.24
0.13-1.34
0.11-0.67
Various gases 0.14 (SO2) 0.145 (SO2) 0.136 (SO2) 0.14 (SO2) 0.14(SO2) 0.063 (SO2) 0.06 (SO2) 0.6(SO 2 ) 0.198 (SO2) 0.243 (SO2)
Various temp
207 208 211 207 208 211 207 208 211 207 207
1.7.6. POLYKETONES PEEK
PEEKK
PEEK-Me PEEKK-Me PEK-Ar
0.11 0.004 0.001 1.0e20 spin/kG 0.11 0.12 0.004 0.001 Lle20spin/kG 0.28 0.009 0.001 0.37 0.012 0.001 0.42 0.039 0.005
Vac, 77 K Vac, 300K Air, 300K 77 K
209 211
0.00054 gases
212 209
Vac, 77 K Vac, 300K Air, 300K 77 K Vac, 77 K Vac, 300K Air, 300K Vac, 77 K Vac, 300K Air, 300K Vac, 77 K Vac, 300K Air, 300K
211 209 209 209
1.7.7. FLUOROPOLYMERS Fluoro elastomers Poly(perfluoroethers)
Various
Various
Various
G(S) Poly(tetrafluoroethylene)
2.15 6.0
Various Various Various gases e, argon 9 K G(decomposition) e = 0.2-1.2 G(wt. loss), G(gas)
Review Structure, temp. effects
186 202 259 260
As polymerized 237 sintered, low crystalline Dose rate 267 effects on G(S)
TABLE 1. cont'd Polymer
G(R)
G(X)
G(S)
G(products)
Radiation conditions
0.3 at 373 0.57 at 473 0.89 at 573 1.33 at 673 2.07 at 773 Poly(vinyl Poly(vinylidene
fluoride) fluoride)
0.22 0.37 0.46-0.78 0.6-0.78
0.38-0.86 0.29
Various
Various
Comments
Refs.
+Dose effects 271
0.07 (Polyvinyl) 0.11 (Polyvinyl) 1-4 (HF)
46 46 49 254
293 K +Crosslinker
1.7.8. OTHERS Aromatic polymers Alkyl aromatic poly amides
Various
Aryloxyphosphazenes -[(R-Ph-O)2-PN]n-biphenol 0.6,0.19 -bis phenol 0.6,0.22 -hydroquinone 0.6,0.35 Poly(bis(phenoxy)phosphazene) Poly(bis(4-methyl-phenoxy)phosphazene) Poly(bis(4-r-butyl-phenoxy)phosphazene) Poly(bis(4-cumyl-phenoxy)phosphazene) PoIy(I-(f-butoxycarbonylthio)ethylene) 3.39 Poly(f-butyl isopropenyl ketone) Poly(butylene), l,4-disubstituted(urethane side chain) Poly(epoxide)(Araldite) 0.59 Poly(ether imide) (Ultem) 0.01 Hyaluronic acid
PoIy(I-mercapto ethylene) 2.65 Poly(oxadiazole-2,5-diyl-l,4-phenylenephthalidylidene-1,4-phenylene) Poly (oxycarbonyl-1,1 -dimethy 1-2isopropylidene-ethylene) Poly(oxycarboxyethylene) Poly(oxyethylene)
Various gases
0.22(R = Me) 2.12(R = Et)
G(S)ZG(X) Reduces with increase in methylene 0.26 0.26 77, 300K 77, 300K 77, 300K
0.9 3.5 0.1 0.2
0.7 2.0 0.1 0.2 77 K
0.33 0.139
77 K 77 K
0.00528 5.0-6.7 (O2) 2.0 (H 2 O 2 ) 0-0.1 (peroxide) Vac/air
0.0014
Warming 39
1.9 0.4-11
Poly(oxyethyleneoxyterephthaloyl) 0.023 Poly(oxymethylene) Poly (oxy-l,4-phenylenesulfonyl-l,4-phenelene 0.05 oxy-1,4-phenylene-isopropylidene-1,4phenylene) Poly(oxy-1,4-phenylenesulfony-1,4-phenylene) Poly(oxysebacoyloxy-1,4-phenylene) isopropylidene-1,4-phenylene) Poly(phenylene oxide) 5.7e20 spin/kG 0.6,0.33
Poly(thiopropylene)
pH dependence
77 K Various
0.015/0.067
110 110 210 210 210 273 273 273 273 13 142 93 36 114 253
19 50
14.5,40.5 2.6
N 2 air e, O 2 air 200K
36
0.16,0.04
Warming
1.5
5
Poly(phenylene sulfide) Poly(thiophenylene)
204,211 251
Aq. soln.
57-144
Various
8 0.012
320 (HCHO) 0.04 gas
423 K 300-423 K
29 37 153
0.04 gas
300-423 K Air
153 68
77 K 77, 300K
211 206
77, 300K Gamma/e, vac/air 77 K
206 109
9 0.08H 2 0.015 CH4 0.03H2 0.030/0.15
Dose rate dependence Also e
35 103 83 55
Radical pairs
74
References page 11-493
TABLE 2. COPOLYMERS Copolymers 2.1.
G(R)
G(X)
G(S)
Radiation conditions
Comments
Refs.
303-423 K
+Additives
10 125 89 125 10 127
COPOLYMERS WITH ETHYLENE
Poly(ethylene-co-l-butene)
Various Various
Poly(ethylene-c0-ethyl acrylate) Poly(ethylene-co-hexene)
2.53-3.2
Poly(ethylene-co-propylene)
0.43,0.83
Butyl rubber Halogenated butyl rubber
e, air Various Various
2.92
2.2.
G(products)
0.11,0.35
0.69 1.1 0.9/3.2
1.2 0.33 3.2
0.26
0.16
Various
Various
Various
2.3 (total) 0.19 (allyl) 3.7-4.0
0-0.6
3.9-6.09
Dose dependent
Dose dependent
Various Various Various 8.6-11.0(O 2 ) 5(COOH)
Various gases, O2 Various 0.07-0.62 gel dose Various chain ends Various gases
303-423 K 303 K Air
+Additives 23%, 36% Propylene +Additives
303-423 K Air Air
+Additives
Air
2.0 GPa + variation In terpolymer
293-298 Various
16 182
Review 186 various sources 195
77-398 K 77 K
70 125 10 96 101 116 104
219 Chloro and bromo
220
COPOLYMER WITH METHYL METHACRYLATE
Poly(methyl methacrylate-cobromomethyl methacrylate) Poly(methyl methacrylate-cochlorotrifluoroethylene)
0.2-1.4
0.06-0.1
0.7-1 2.1
139 77 K
65
2.1 Poly(methyl methacrylate-codichlorostyrene) Poly(methyl methacrylate-codimethyl itaconate) Poly(methyl methacrylate-cohexafluoroisopropyl methacrylate) Poly(methyl methacrylate-cohexyl methacrylate) Poly(methyl methacrylate-comethacrylic acid)
50 3.2-3.5* 1.0* 2.0-3.1
0.4 0.53-0.87
77 K
17 59 65 137
22
1.8,2.06
2.0
*G(S)-G(X) * G(S)-G(X)
3.6
273 K
2.9 Poly(methyl methacrylate-comethacrylic acid-styrene) Poly(methyl methacrylate-comethacrylic acid-co-cumyl phenyl methacrylate) Poly(methyl methacrylate-comethacrylic acid-co-2-naphthyl methacrylate) Poly (methyl methacrylate-comethacrylic acid) Poly(methyl methacrylate-co-2 naphthyl methacrylate) Poly(methyl methacrylate-comethacrylonitrile, vinylidene chloride, methyl-a-chloroacrylate, a-chloronitrile ter polymers) Poly(methyl methacrylate-co-methyl bromoacrylate)
137
1.3
77 K
146
1.2
20% MAA 238
1.6
238
133
1.09
238
2.0
238
1.06
238
0.06
1.9-3.1
145
0.41
4.16
139
TABLE 2. cont'd Copolymer
G(R)
Poly(methyl methacrylate-ctf-methyl3.1 oc-chloroacrylate) Poly(methyl methacrylate-co-methyloc-chloroacrylate) Poly(methyl methacrylate-comethyl2-chloroacrylate) Poly(methyl methacrylate-co-methyla-chloroacrylonitrile) Poly(methyl methacrylate-ctf-methyl5.9 a-cyanoacrylate) Poly(methyl methacrylate-co-methyloc-fluoroacrylate) Poly(methyl methacrylate-comethyl fluoroacrylate) Poly(methyl methacrylate-co3-oximino-2-butanone methacrylate) Poly(methyl methacrylate-cotribromophenyl methacrylate) Poly(methyl methacrylate-cotrichloroethyl-alpha-chloroacrylate) Poly(methyl methacrylate-cotrichlorophenyl methacrylate) Poly(methyl methacrylate-cotrifluoroethylene methacrylate) Poly(methyl methacrylate-covinylidene chloride) Poly(methyl methacrylate-covinylidene fluoride) Poly(glycidyl methacrylate-co-ethyl methacrylate) Poly(glycidyl methacrylate-coethyl acrylate) 2.3.
G(X)
0.06
G(S)
G(products)
Comments
Refs.
77 K
14% MCA
133
3.1
24
2.8*
*G(S)-G(X)
6.6
0-0.44
1.0-2.2
14% CAN
133
77 K
20% MCA
133
77 K
65
2.4 > 0.55 0.07-0.19
137 1.4-2.4
0.38-2.2
Various
69
Air
72
3.8 0.05-0.7
17
77 K
Also TFEM
140
0.4-4.4
72
1.9
77 K
2.8-3.4*
65 *G(S)-G(X)
17
1.6
137
1.35-8.5
1.6 1.51-5.5
77 K
0.077 0.04-0.59
Various 0.055 0.0-0.09
Vac
4.3/33
2.8/17
Air
0.3-3.0 Various
Various
313 K 77 K
0.04-0.38
2.18-2.47
Various compositions 246
6.5
65 246
COPOLYMERS WITH STYRENE
Poly(styrene-coacrylates) Poly(styrene-c<9-acrylonitrile) 0.4-2.8 77 K 0.14-4.2 300 K Poly(styrene-co-butadiene)
Poly(styrene-co-cyanoacrylates) Poly(styrene-co-l-mercaptoethylene) Poly(styrene-co-methyl acrylate)
Various CO, CH 4 , CO 2 etc.
Poly(styrene-co-methyl methacrylate)
0.40-2.76 77 K 0.14-1.39 300K 0.18
Poly(styrene-co-methacrylonitrile)
0.31-2.16
0.83 (gases)
Poly(styrene-co-butyl vinyl ketone) Poly(styrene-co-methyl isopropyl ketone) 2.4.
Radiation conditions
77 K Various temperatures Vac 77K/(R), 300 K/(gas)
e e
73 34 Various 215,221 compositions Effect of 104 pressure 3 Block 98 copolymers 73 19 12-80% sty 126 Various compositions 51% sty
216
Various compositions
199
132
239 239
COPOYMERS WITH SULFUR DIOXIDE
Poly(1 -butene-co-sulfur dioxide)
Various gases 12
Poly(2-butene-co-sulfur dioxide) Poly(cyclohexene-co-sulfur dioxide) Poly(4,4-dimethylpentene-co-sulfur dioxide)
Various gases Various gases Various gases
273 -423 K e 273-423 K 273-423 K 273-423 K
31,124,150 131 31,124 31,124 31,124
References page II - 493
TABLE 2. cont'd Copolymer Poly(ethylene-co-sulfur dioxide) Poly(hexene-l-co-sulfur dioxide) Poly(isobutene-co-sulfur dioxide) Poly(3-methyl-l-butene-co-sulfur dioxide) Poly(propylene-co-sulfur dioxide)
G(products)
Radiation conditions
1.8
Various gases Various gases Various gases Various gases
273-423 K 273-423 K 273-423 K 273-423 K
124 31,124 31,124 Poly(31,124, 150
2.2
Various gases
273-423 K
31,124,150
G(R)
G(X)
G(S)
Comments
Refs.
2.5. OTHER COPOLYMERS Poly (butyl methacrylate-col-naphthyl methacrylate) Poly(glutamic acid-co-tyrosine) Poly(glycolic acid-co-1 -lactic acid) Poly(glycidyl methacrylate-co3-chlorostyrene) Poly(hydroxy butyrate-co-valerate)
0.14 0.03-0.5 2.23-2.36 1.49-1.53 1.0
0-0.5
300K 77 K 300K
Various 2.7-3.4
Various gases 1,4-ester
77, 263, 273, 303 K e, gamma
3.2-43.*
Different compositions
77 K 20/150
+ Warming
Air
3.3 0.42 0.6-5.2(HF)
N2 240C
30 (d.b.) 2.3-2.7 1.2
0.9
Various
203
Vac/air/H2O
217
17 13 104 119 106
3.5 (Gas)
Poly(vinyl chloride-coethylglycodimethacrylate) Poly(vinylidene chloride-co-dimethyl itaconate) Poly(vinylidene chloride-co-hexafluoropropylene) Tetrafluoroethylene, perfluoro methyl vinyl ether copolymer 2:1
214
218 *G(S)- G(X)
3.01
1.3
1
144
1.16
Polysulphone-polydimethyl siloxane block copolymer
Various compositions Various compositions
0.42
3.0-0.5 Poly(methacrylonitrile-c0-methyl2-chloroacrylate) Poly (N- vinylpyrrolidone-c0-/-buty I5-vinyl thiocarbonate) Poly(acrylonitrile-co-butadiene) Poly(acrylonitrile-co-chloroprene) Poly(tetrafluoroetnylene-c0hexafluoropropylene) Poly(tetrafluoroethylene-co-propylene)
Benzene soln.
Emulsion 121 polymer + H 2O 116 266 8 *G(S)-G(X)
17
+Additives
166
0.93 (CF4) e 0.31 (COF2) 0.055 (CO2) 0.14 (CF3 OCF3) 1.43 (total gas) 0.34 (acid fluoride) New chain ends 1 (_CF 2 -CF 3 ) 0.09 (-CF 2 -O-CF 3 ) 0.5 (CF2-COOH) 0.2(-CF = CF2)
229
268
Dose and molecular weight effects
272
TABLE 3. POLYMERS BLENDS Polymer Blends
G(X)
Poly (methyl methacrylate)/ Poly (1 -naphthyl(methacrylate) Poly(methyl methacrylate)/ Poly(styrene-co-acrylonitrile) Poly (methyl methacrylate)/styreneacrylonitrile Poly(methyl methacrylate)/Acrylonitrile
G(S)
Comments
Refs.
0.14
Benzene
1
0.025
0.051
50% PMMA
161
0.041 0.034 0.02 0.008 0.042 0.036 0.009 0.01
0.027 0.15 0.21 0.23 0.14 0.25 0.34 0.88
SAN 100 85 50 15 ACNlOO 85 50 15
242
242
TABLE 4. COMPOSITES Polymer Composites
G(products)
Radiation conditions
Refs.
Glass-DGEBA-DDM Color-DGEBA-DDM
H 2 , CO, CO2 H 2 , CO, CO2
77 K, RT 77 K, RT
227 227
C
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S E C T I O N
P H Y S I C A L M
O
N
O
M
E
R
III
P R O P E R T I E S S
A
N
D
S
O
L
O V
E
N
F T
S
P h y s i c a l
P r o p e r t i e s
o f
M o n o m e r s
D a n i e l R. B l o c h Lakeshore Research, 5536 W. Branch Trail, Racine, Wl 53402, USA
A. Introduction B. Tables of Physical Properties Table 1. Acetylenes Table 2. Acid Dichlorides Table 3. Acroleins Table 4. Acrylamides/Methacrylamides 4.1. Acrylamides 4.2. Methacrylamide Table 5. Acrylates/Methacrylates 5.1. Acrylate, Acids/Esters 5.2. Methacrylate, Acids/Esters Table 6. Alcohols 6.1. Alkanediols 6.2. Ether Diols Table 7. AIIyI Functional Table 8. Amines, Difunctional Table 9. Anhydrides 9.1. Monoanhydrides 9.2. Dianhydrides Table 10. Butadienes 10.1. 1,2-Butadienes 10.2. 1,3-Butadienes Table 11. Butenes 11.1. 1-Butenes 11.2. 2-Butenes Table 12. Epoxides 12.1. Monoepoxides 12.2. Diepoxides Table 13. Ethylene Halides Table 14. Fumaric, Acids/Esters Table 15. lsocyanates Table 16. Lactams Table 17. Lactones Table 18. Maleic, Acids/Esters Table 19. Propenes Table 20. Styrenes Table 21. Vinyl Functional 21.1. Aryl 21.2. Esters 21.3. Ethers
111-1 ill-4 III-4 III-4 III-4 III-4 III-4 III-6 III-8 III-8 111-12 111-16 111-16 111-18 111-18 III-20 III-20 III-20 III-24 III-24 III-24 III-24 III-26 III-26 III-26 III-26 III-26 III-28 III-28 III-30 III-30 III-32 IM-32 III-32 III-32 III-34 III-36 III-36 III-36 III-38
21.4. /V-substituted 21.5. Sulfonates
A.
III-38 III-40
INTRODUCTION
This chapter contains some of the principal properties of the more common monomers. The monomers are arranged alphabetically, in groups, with derivatives listed alphabetically within the groups. Compounds are listed under their most commonly used names in polymer chemistry. Therefore, some names are not in agreement with the nomenclature rules of the International Union of Pure and Applied Chemistry. Data are taken from a variety of published literature, including the 3rd edition of the "Polymer Handbook", "The Brandon Worldwide Monomer Reference Guide and Sourcebook", the "Aldrich Catalog Handbook of Fine Chemicals", and "Polysciences Monomers/Polymers, Scientific Polymer Products", "TCI America", "Lancaster and Janssen Chemica" catalogs. Where a range is reported in the literature, the average value is used here for melting points and boiling points. No attempt was made to verify the reported values experimentally. Linear structures are given for most monomers. Molecular formulas are provided when linear structures cannot be unambiguously drawn. Molecular weight is calculated based on the International Atomic Weight values. Boiling point is given in degrees Celsius (0C), at 760mmHg, unless indicated otherwise by the value in mmHg following a slash (/). Melting point is given in degrees Celsius (0C), at 760 mmHg, unless indicated otherwise by the value in mmHg following a slash (/). Refractive index is given at 200C, unless indicated otherwise by the temperature in Celsius following a slash (/). Density is relative to water at 4°C and measured at 200C, unless otherwise indicated by the value following a slash (/). Flash point was determined by the closed-cup method, using a Setaflash apparatus.
RTECS# is the reference to the Registry of Toxic Effects of Chemical Substances. R&S is the reference found in the "Sigma-Aldrich Library of Regulatory & Safety Data", available from Aldrich Chemical Company. FT-NMR is the reference to spectra in the "Aldrich Library of 13C and 1H FT-NMR Spectra", available from the Aldrich Chemical Company. FT-IR is the reference to spectra in the "Aldrich Library of FT-IR Spectra", available from the Aldrich Chemical Company.
Merck Index is the reference to "The Merck Index", Merck & Co., Inc., Whitehouse Station, NJ. Beilstein is the reference to "Beilsteins Handbuch der Organischen Chemie", Springer-Verlag, New York, NY. Fieser is the reference to L. F. Fieser and M. Fieser, "Reagents for Organic Synthesis", John Wiley, New York, NY. Abbreviations: (d) decomposes; (s) sublimes; (aq) aqueous.
B. TABLES OF PHYSICAL PROPERTIES TABLE 1. ACETYLENES Formula RC = CR' Name Acetylene - , Chloro - , Dichloro- , Diphenyl- , Phenyl-
R
CAS Registry Number
R'
-H -Cl -Cl -C 6 H 5 -C 6 H 5
-H -H -Cl -C 6 H 5 -H
74-86-2 501-65-5
MoL wt. 26.04 60.48 94.93 178.23 102.14
Boiling point (0C) -82 -32 60 143
Melting point (0C) - 84(s) -126 -66 170/19
TABLE 2. ACID DICHLORIDES Formula ClC(O)RC(O)Cl Name Adipoyl Azelaoyl Diethylmanoyl Dodecanedioyl Glutaryl Isophthaloyl Malonyl Methylpimeloyl Oxalyl Phthaloyl Pimeloyl Sebacoyl Suberoyl Succinyl Terephthaloyl Thionyl
CAS Registry Number
R -(CH 2 ) 4 -(CH 2 ) 7 -C(CH 2 CH 3 ) 2 -(CH 2 ) 1 0 -(CH 2 ) 3 -C6H4-CH2-(CH 2 ) 2 CH(CH 3 )(CH 2 ) 2 -CO-CO-C6H4-(CH 2 ) 5 -(CH 2 ) 8 -(CH 2 ) 6 -(CH 2 ) 2 -C6H4ClC(S)Cl
111-50-2 123-98-8 54505-72-5 4834-98-4 2873-74-7 99-63-8 1663-67-8 44987-62-4 79-37-8 88-95-9 142-79-0 111-19-3 10027-07-3 543-20-4 100-20-9 7719-09-7
MoI. wt.
Boiling point (0C)
183.03 255.12 197.06 267.20 169.01 203.02 140.95 197.06 126.93 203.02 197.06 239.14 211.09 154.98 203.02 118.97
106/2 166/18 198 140/0.5 217 276 54/19 118/10 61 270 113/5 168/12 162/15 190 266 79
MoI. wt.
Boiling point (0C)
Melting point (0C)
43 -8 12 -2.5 16 80 -105
TABLE 3. ACROLEINS Formula HC(O)CR = CHR' Name Acrolein -, 2-Chloro- , 2-Methyl- , 3-Methyl-, fra/w-(Crotonaldehyde) - , 2-Chloro-3-methyl-
R
CAS Registry Number
R'
-H -Cl -CH 3
-H -H -H
107-02-8
-H -Cl
-CH 3 -CH 3
123-73-9
78-85-3
56.06 90.51 70.09
53 40/30 68
70.09 104.54
148
Melting point (0C) -87 -81 104
TABLE 4. ACRYLAMIDES/METHACRYLAMIDES Name
R
4.1. ACRYLAMIDES H2C=CHC(O)NRR' Acrylamide -H -, Acetyl-, N-C(O)CH3 - , Adamantyl-, N-Ci 0 H 5 -,AlIyI-, N-CH2CH=CH2 - , Benzyl-, N-CH 2 C 6 H 5 - , Butoxymethyl-, N-CH2O(CH2)3CH3 - , terf-Butyl-, N-C(CH 3 ) 3 - , Cyclohexyl-, N-C 6 Hn - , Cystamine-bis-, NJf'-CH 2 CH 2 SSCH 2 CH 2 - , Diacetone-, N-C(CH3)2CH2C(O)CH3 - , Diallyl-, N,N-CH2CH=CH2 - , Di-n-butyl-, N9N-(CH 2 ) 3 CH 3
R' -H -H -H -H -H -H -H -H -H -H -CH2CH=CH2 -(CH 2 ) 3 CH 3
CAS Registry Number
MoI. wt.
79-06-1 1432-45-7 19026-83-6 2555-13-7 13304-62-6 1852-16-0 107-58-4 3066-72-6 60984-57-8 2873-97-4 3085-68-5 2274-13-7
71.08 113.12 205.30 111.14 161.20 157.21 127.19 153.23 260.38 169.23 151.21 183.29
Boiling point (C)
Melting point (0C)
125/25 129 155 120/19 125/0.3
93/0.1 108/3 97/1
70 -9 128 113 123 55
Density (at 200C)
Refractive index (at 200C)
Flash point (°C)
1.000 0.990 0.929
Density (at 200C) 1.259 1.143 1.145 1.069 1.324
R and S
FT-NMR
FT-IR
Fieser 1,11
1(2),2711I
Refractive index (at 200C) 1.4700 1.4680 1.4590 1.4680 1.4720
1.631
1.5190
1(3), 533A
1(2),946B
Refractive index (at 200C)
Flash point (0C) >110 >110 74 >110 107 180 47 >110 None >110 >110 >110 >110 77 180 None
RTECS Number
R and S
WN4900000 WZ1797000 XM515OOOO
1(1), 867J 1(1),869C 1(1),867G 1(1),869E 1(1),867I 1(2),1981H 1(1),867F 1(1),867K 1(1),867D 1(2),1981G 1(1),869A 1(1),869D 1(1),869B 1(1),867H 1(2),1981I 1(2),3197F
Flash point (°C)
RTECS Number
R and S
NT2625000 KI2950000
FT-NMR
FT-IR
11,9428
1(1),1211B 1(1)1212C 1(1),1212A
5,656
1,335
Beilstein
Fieser
1(1),1211A 1(1),1212B
1(1),1211C
FT-NMR
l(l),740D 1(2),352A l(l),740A 1(1),741B 1(1),739C 1(2),351D 1(1),741C 1(1),742B 1(1),741D l(l),740C 1(2),352B 1(2),1227B
FT-IR
-19
AS105000
1(1),515A
1(1),733B
l(l),470D
-16
OZ2625000
1(1),515B
1(1),733C
1(1),471A
0.846 1.478
1.4365
9
GP9625000
1(1),515G
RTECS Number
R and S
AS3325000
1(1),877K
Flash point (°C)
1.122
1.4620
> 110
>110
1(1),472C
FT-NMR 1(1),1221A
2,653 2,709 2,687 2(4),2127 2,634 9,834 2(1),252
l(l),740B
1.4025 1.463 1.4160
Refractive index (at 200C)
Merck
1(1),741A
0.839 1.199 0.847
0.9790
Beilstein
1.548
1.4650 1.4720 1.4290 1.5684 1.4690 1.4680 1.4680 1.4680
Density (at 200C)
Merck
AO9600000
1.449 1.217 1.455 1.409 1.205 1.121 1.172 1.407
Density (at 200C)
RTECS Number
FT-IR 1(1),749B
11,6867 11,7439
11,8844 11,9278
Merck 11,122
13,297
Beilstein
Fieser
1,725
10,2
11,2599
Merck 11,123
1,728
Beilstein 2,400
4(4),664 1(1),887I
1(1),1236A
l(l),750C
17,241 14,263
1(3),2981
AS3450000 AS3460000 AS3475000
2,542 9,805 2,671 2,719 2,694 2,613 9,844
12,291
11,2943
Fieser
TABLE 4.
cont'd
- , Diethyl-, N9N- , 1,2-Dihydroxyethylenebis-,N,N' - , Diisopropyl-, N,N- , 4,4-Dimethoxybutyl-, N- , Dimethyl-, N9N- , 3-(Dimethylamino)propyl-, N-, l,l-Dimethyl-2sulfoethyl-, N-(AMPS) - , Diphenylmethyl-,7V- , Ethylenebis-,WV'- , Ethylhexyl-,iV- , 2-Glycolic acid, N- , 2-Glycolic acid methyl ester, N- , Hexamethylenebis-, N,Nf - , tert-Hexyl-, N- , Hydroxymethyl-, N- (solution) - , Isobornyl-, N-, Isobutoxymethyl-, N-, Isopropyl-, N-, Isopropylidenebis-, N9N1- , 3-Methoxypropyl-, N- , Methyl-, N- , Methylenebis-, N,Nf- , (1-Methoxy) - , (Methoxy)acetoxymethyl-, N- , Morpholinoethyl-, N- , 1-Naphthyl-, N- , Octadecyl-, N- , Octamethylenebis-, NJ*'- , tert-Octyl-, N- , Phthalamidomethyl-, N- , 2,2,2-Trichloro-lhydroxyethyl-, N- , Tri(hydroxymethyl)methyl-, N -, 1,1,3-Trimethylbutyl-, N- , Trimethylenebis-, N,N'- , Triphenylmethyl-, N4.2.
R;
R
Name
Boiling point (0C)
CAS Registry Number
MoI. wt.
2675-94-7 868-63-3
127.19 200.19
93/19 54/0.4 135/0.7 82/21 117/2
Melting point (0C)
-CH 2 CH 3 -CH(OH)CH(OH)-
-CH 2 CH 3 -H
-CH(CHs) 2 -(CH 2 ) 3 CH(OCH 3 ) 2 -CH3 -(CH 2 ) 3 N(CH 3 ) 2
-CH(CH 3 ), -H -CH3 -H
44975-46-4 38486-53-2 2680-03-7 3845-76-9
155.24 187.24 99.13 156.23
-C(CH 3 ) 2 CH 2 SO 3 H
-H
15214-89-8
207.25
-CH(C 6 H 5 ), -CH2CH2-CH 2 CH(CH 2 CH 3 ) (CH 2 ) 3 CH 3 -CH(OH)C(O)OH -CH(OH)C(O)OCH3
-H -H -H
10254-08-7 2956-58-3 91625-16-0
237.30 168.20 183.30
-H -H
6737-24-2 77402-03-0
163.13 173.17
-(CH2)6-
-H
7150-41-6
224.28
135
-CH 2 CH 2 C(CH 3 ), -CH 2 OH
-H -H
51330-07-5 924-42-5
155.24 101.11
100
- C H)H 17
-CH 2 OCH 2 CH(CH 3 ) 2 -CH(CH 3 ), -C(CH3)2-
-H -H -H -H
17159-04-5 16669-59-3 2210-25-5
207.31 157.21 113.16 182.22
-(CH 2 ) 3 OCH 3 -CH3 -CH2-
-H -H -H
107374-86-7 1187-59-3 110-26-9
143.19 85.11 154.17
-C(OCH 3 )C(O)OCH 3
-H
77402-03-0
173.17
-CH 2 CH 2 NC 4 H 8 O -Ci0H7 -(CH 2 ) 17 CH 3 -(CH2)8-
-H -H -H -H
5117-12-4 22302-62-1 1506-54-3 2945-02-0
141.17 197.24 323.56 252.35
-(CH 2 ) 4 C(CH 3 ) 3 -CH 2 NC 8 H 4 O 2 -CH(OH)CCl 3
-H -H -H
4223-03-4 80500-94-3
183.29 230.22 218.47
58 190 170
-C(CH 2 OH) 3
-H
13880-05-2
175.18
139
-C(CH 3 ) 2 CH 2 CH(CH 3 ) 2 -(CH2),-C(C 6 H 5 ),
-H -H -H
25269-93-6 4887-13-2 102548-89-0
169.27 182.22 313.40
156(d)
18
195(d)
178 140
123/0.5 95 74
135
108 90/2
61 210
99/0.3 106/4 >300 73
158/50
125/25
>110 138 75 138
55 112 204
METHACRYLAMIDES H2C=C(CH3)C(O)NRR'
215 76/1.2
Methacrylamide - , Acetyl-, N- , Acetylphenyl-, N- , AlIyI-, N- , 3-Aminopropyl-, N-, hydrochloride - , Benzyl-, N-, Bis(diethylaminoethyl)-, N9N- , Butoxymethyl-, N-
-H -C(O)CH 3 -C 6 H 4 C(O)CH 3 -CH 2 CH=CH 2 -(CH 2 ) 3 NH 2 HC1
-H -H -H -H -H
79-39-0 44810-87-9 58813-69-7 2186-33-6 72607-53-5
85.11 127.14 203.24 125.17 178.66
-CH 2 C 6 H 5 -CH 2 CH 2 N(CH 2 CH 3 ) 2
3219-55-4 76392-05-7
175.23 183.28
122/0.4
-CH 2 O(CH 2 ) 3 CH 3
-H -CH 2 CH 2 N(CH 2 CH 3 ), -H
171.24
105/0.3
-, ^rr-Butyl-, N- , 2-Cyanoethyl-, N- , 2-Cyanoethyl-, N-, methyl-, N
-C(CH 3 ), -CH 2 CH 2 CN -CH 2 CH 2 CN
-H -H -CH3
5153-77-5 28384-61-4 6554-73-0 24854-94-2
142.20 138.17 152.20
163
109 138 138
90/2.2 124 82
113/1
60 46 46
Density (at 200C)
0.962 0.949
Refractive index (at 200C)
1.4730 1.4820
Flash point (0C)
71 > 110
RTECS Number
AU3230000
160
R and S
FT-NMR
1(1),885K
1(1),1233C
1(1),893I
1(1),1244C
l(l),1065K
1(1),1438C
FT-IR
1(3),784B
1(1),915E 1(1),913D
1(1),885J
1.074
1.4130
None
AS3600000
0.970
1.4610
79
AS3630000 AS3675000
1.122
1.5120
Beilstein
4(3),130 4(4), 1268
4(3),526
1(1),883K
AI8967330
Merck
1(1),1276B 1(1),1272B
1(1),781A
l(l),750A
2(4), 1472
4(4),517
AS3678000
1(1),883J
l(l),1230C
AI8967330
1(1),913D
1(1),1272B
> 110
1(1),749D
1.10
UC6475000
1(1),883M
1(1),1231B
1(1),877L
1(1),1221B
27(4),278
2(2),399 1.4702 0.96
1.46
1.4755
122
1(1),749C
Fieser
TABLE 4.
cont'd R
Name -, -, -, -, -, -, -, -, -, -, -, -,
Cyclohexyl-, NDiallyl-, N,NDibenzyl-, N,NDibutyl-, NJf3-Di(butyl)aminopropyl-, NDiethyl-, NJf3-(Diethylamino)propyl-, NDiisopropyl-, NJf2,2-Dimethoxyethyl-, NDimethyl-, NJf2-(Dimethylamino)ethyl-, N3-(Dimethylamino)propyl-, N- , Dodecyl-, N-, Ethylenebis-, NJf'- , 2-Ethylhexyl-, N-, 2-Hydroxyethyl-, N- , Hydroxymethyl-, N- , 4-Hydroxyphenyl-, N- , Isobutoxymethyl-, Af- , Isopropyl-, N-, Methoxymethyl-, N- , Methyl-, N- , Methylenebis-, NJf'- , Methyl-, N-, Phenyl-, N-, Methyl-, N-, 2,2-dimethoxyethyl-, N-, 3-(Af-morpholino)propyl-, A^- , 2-(2-Oxo-l-imidazolidinyl)ethyl-, N- , Phenyl-, N- , Phenyl-, N-, Phenylethyl-, N-, 3-(Trifluoromethyl)phenyl-, A^- , 3-(Trimethylammonium)propyl-, chloride, N- (eq. solution)
TABLE 5.
-C6Hn -CH2CH=CH2 -CH 2 C 6 H 5 -(CH 2 ) 3 CH 3 -(CH2)3N((CH2)3CH3)2 -CH 2 CH 3 -(CH 2 ) 3 N(CH 2 CH 3 ) 2 -CH(CH 3 ) 2 -CH2CH(OCH3)2 -CH 3 -CH 2 CH 2 N(CH 3 ) 2 -(CH 2 ) 3 N(CH 3 ) 2
-H -CH2CH=CH2 -CH 2 C 6 H 5 -(CH 2 ) 3 CH 3 -H -CH 2 CH 3 -H -CH(CH 3 ) 2 -H -CH 3 -H -H
-(CH 2 )nCH 3 -CH 2 CH 2 -CH2CH(CH2CH3)(CH2)3CH3 -CH2CH2OH -CH 2 OH -C 6 H 4 OH -CH2OCH(CH3)2 -CH(CH 3 ), -CH 2 OCH 3 -CH 3 -CH2-CH 3 -CH 3
-H -H -H -H -H -H -H -H -H -H -H -C 6 H 5 -CH2CH(OCH3)2
