Pyrolysis - GC MS Data Book of Synthetic Polymers: Pyrograms, Thermograms and MS of Pyrolyzates

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Author: Shin Tsuge | Hajima Ohtani | Chuichi Watanabe

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PYROLYSIS-GC/MS DATA BOOK OF SYNTHETIC POLYMERS

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PYROLYSIS-GC/MS DATA BOOK OF SYNTHETIC POLYMERS Pyrograms, Thermograms and MS of Pyrolyzates

TSUGE Shin, OHTANI Hajime, WATANABE Chuichi

Amsterdam • Boston • Heidelberg • London • New York • Oxford Paris • San Diego • San Francisco • Singapore • Sydney • Tokyo

Elsevier The Boulevard, Langford Lane, Kidlington, Oxford OX5 1GB, UK Radarweg 29, PO Box 211, 1000 AE Amsterdam, The Netherlands First edition 2011 Copyright Ó 2011 Elsevier B.V. All rights reserved. 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 or otherwise without the prior written permission of the publisher Permissions may be sought directly from Elsevier’s Science & Technology Rights Department in Oxford, UK: phone (+44) (0) 1865 843830; fax (+44) (0) 1865 853333; email: permissions@ elsevier.com. Alternatively you can submit your request online by visiting the Elsevier web site at http://elsevier.com/locate/permissions, and selecting Obtaining permission to use Elsevier material Notice No responsibility is assumed by the publisher for any injury and/or damage to persons or property as a matter of products liability, negligence or otherwise, or from any use or operation of any methods, products, instructions or ideas contained in the material herein British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library Library of Congress Cataloging-in-Publication Data A catalog record for this book is available from the Library of Congress ISBN: 978-0-444-53892-5 For information on all Elsevier publications visit our web site at elsevierdirect.com

Printed and bound in Great Britain 11 12 13 10 9 8 7 6 5 4 3 2 1

CONTENTS

xiii

Preface

Part 1 Introduction 1.1 History and scope of analytical pyrolysis 1.2 Expanded applicability of GC/MS by combining with pyrolysis 1.3 Py-GC/MS measuring process for polymer characterization

Part 2 Pyrograms and thermograms of 163 high polymers, and MS data of the major pyrolyzates 2.1 Experimental conditions for measuring pyrograms and thermograms of high polymers, and MS data for the major pyrolyzates by means of pyrolysis-GC/MS and evolved gas analysis (EGA)-MS techniques 2.1.1 Polymer samples 2.1.2 Measuring conditions for the pyrograms of the polymers and the MS data of the major peaks on each pyrogram, and the thermograms of the polymers 2.1.3 Data descriptions for the pyrograms and the MS data of the major peaks on the pyrograms, and the thermograms for 163 polymer samples 2.2 Data compilation of pyrograms, thermograms and MS data of major pyrolyzates for 163 typical polymer samples 2.2.1 Polyoleﬁns (homopolymers) 001 Polyethylene (high density); PE(HDPE) 002 Polypropylene (isotactic); iso-PP 003 Polypropylene (atactic); at-PP 004 Polypropylene (syndiotactic); syn-PP 005 Polybutene-1 (isotactic) 006 Poly(4-methyl-1-pentene); PMP 007 Isobutylene-isoprene rubber; IIR 2.2.2 Vinyl polymers with ethylene units (copolymers) 008 Ethylene-propylene copolymer; P(E-P) 009 Ethylene-propylene-diene rubber; EPDM 010 Ethylene-methyl methacrylate copolymer; P(E-MMA) 011 Ethylene-acrylic acid copolymer; P(E-AA)

1 1 3 4

7

7 7

7

10 12 12 12 14 16 18 20 22 24 26 26 28 30 32

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012 Ethylene-vinyl acetate copolymer; EVA 013 Ethylene-ethyl acrylate copolymer; P(E-EA) 014 Ethylene-vinyl alcohol copolymer; P(E-VA) 015 Polyethylene ionomer; IO 2.2.3 Vinyl polymers with styrene units 016 Polystyrene; PS 017 Styrene-methyl acrylate copolymer; P(S-MA) 018 Styrene-methyl acrylate alternating copolymer 019 Styrene-methyl methacrylate copolymer; P(S-MMA) 020 Styrene-methyl methacrylate alternating copolymer 021 Methyl methacrylate-butadiene-styrene copolymer; MBS 022 Acrylonitrile-styrene copolymer; AS 023 Acrylonitrile-styrene alternating copolymer 024 Acrylonitrile-butadiene-styrene copolymer; ABS 025 Acrylonitrile-acrylate-styrene copolymer; AAS 026 Acrylonitrile-EPDM-styrene copolymer; AES 027 Styrene-maleic anhydride copolymer; P(S-Mah) 028 Styrene-divinylbenzene copolymer; P(S-DVB) 2.2.4 Vinyl polymers with styrene units’ derivatives 029 Poly(a-methylstyrene); P-a-MS 030 Polydivinylbenzene; PDVB 031 Poly(p-chlorostyrene) 032 Poly(p-methylstyrene); PMS 033 Poly(2-vinylpyridine) 034 Acrylonitrile-p-chlorostyrene copolymer 035 Chloromethylated styrene-divinylbenzene copolymer 2.2.5 Acrylate-type polymers 036 Poly(methyl methacrylate); PMMA 037 Poly(n-butyl methacrylate); PBMA 038 Poly(2-hydroxyethyl methacrylate); PHEMA 039 Poly(methyl acrylate); PMA 040 Poly(ethyl acrylate); PEA 041 Poly(butyl acrylate); PBA 042 Poly(acrylic acid; isotactic); PAA 043 Methyl methacrylate-methyl acrylate copolymer; P(MMA-MA) 044 Higher methacrylate copolymer 045 Acrylic rubber; ACM 046 Polyacrylonitrile; PAN

34 36 38 40 42 42 44 46 48 50 52 54 56 58 60 62 64 66 68 68 70 72 74 76 78 80 82 82 84 86 88 90 92 94 96 98 100 102

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047 Acrylonitrile-methyl acrylate copolymer 048 Polyacrylamide; PAAm 049 Poly(maleic anhydride); PMAH 2.2.6 Chlorine-containing vinyl polymers 050 Poly(vinyl chloride); PVC 051 Vinyl chloride-vinylidene chloride copolymer; P(VC-VdC) 052 Chlorinated poly(vinyl chloride); CPVC 053 Chlorinated polyethylene; CM 054 Vinyl chloride-vinyl acetate copolymer; P(VC-VAc) 055 Chlorosulfonated polyethylene; CSM 056 Acrylonitrile-vinyl chloride copolymer; P(AN-VC) 057 Acrylonitrile-vinyl chloride alternating copolymer 058 Methyl acrylate-vinyl chloride copolymer; P(MA-VC) 059 Methyl acrylate-vinyl chloride alternating copolymer 2.2.7 Fluorine-containing vinyl polymers 060 Polytetraﬂuoroethylene; PTFE 061 Tetraﬂuoroethylene-hexaﬂuoropropylene copolymer; FEP 062 Polychlorotriﬂuoroethylene; PCTFE 063 Poly(vinyl ﬂuoride); PVF 064 Poly(vinylidene ﬂuoride); PVDF 065 Vinylidene ﬂuoride-hexaﬂuoropropylene rubber 066 Propylene-tetraﬂuoroethylene rubber 2.2.8 The other vinyl polymers 067 Poly(vinyl alcohol); PVA 068 Poly(vinyl butyral); PVB 069 Poly(vinyl acetate); PVAc 070 Poly(vinyl pyrrolidone); PVP 2.2.9 Diene-type elastomers 071 High cis-butadiene rubber; BR 072 Poly(1,2-butadiene) 073 Natural rubber; NR 074 Chloroprene rubber; CR 075 Hydrogenated natural rubber 076 Acrylonitrile-butadiene rubber; NBR 077 Hydrogenated acrylonitrile-butadiene rubber 078 Polynorbornene 079 Styrene-butadiene rubber; SBR 080 Styrene-butadiene-styrene block copolymer; SBS(TPS)

104 106 108 110 110 112 114 116 118 120 122 124 126 128 130 130 131 132 134 136 138 140 142 142 144 146 148 150 150 152 154 156 158 160 162 164 166 168

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081 Styrene-ethylene-butadiene-styrene block copolymer; hydrogenated SBS (SEBS) 2.2.10 Polyamides 082 Polycaproamide; Nylon-6 083 Polyundecanoamide; Nylon-11 084 Polylauroamide; Nylon-12 085 Poly(tetramethylene adipamide); Nylon-4,6 086 Poly(hexamethylene adipamide); Nylon-6,6 087 Poly(hexamethylene sebacamide); Nylon-6,10 088 Poly(dodecamethylene adipamide); Nylon-12,6 089 Caproamide-hexamethylene adipamide copolymer; Nylon-6/66 090 Poly(m-xylene adipamide); Nylon-MXD6 2.2.11 Polyacetals and polyethers 091 Polyoxymethylene; POM 092 Polyoxymethylene(copolymer) 093 Poly(ethylene oxide) 094 Epichlorohydrin rubber; CHR 095 Epichlorohydrin-ethylene oxide rubber; CHC 2.2.12 Thermosetting polymers 096 Phenol formaldehyde resin (novolak); PF 097 Phenol formaldehyde resin (resol); PF 098 Cresol formaldehyde resin (novolak) 099 Diallyl phthalate resin; DAP 100 Poly(ethylene glycol bisallyl carbonate); CR-39 101 Urea formaldehyde resin; UF 102 Melamine formaldehyde resin; MF 103 Xylene resin 104 Unsaturated polyester; UP 105 Epoxy resin; EP 106 Brominated epoxy resin 2.2.13 Polyimide and polyamide-type engineering plastics 107 Bismaleimide triazine resin; BT resin 108 Polyetherimide; PEI 109 Polypyromellitimide; PI 110 Polyaminobismaleimide; PABM 111 Polyamideimide; PAI 112 Poly(p-phenylene terephthalamide); Kevlar 113 Poly(m-phenylene isophthalamide); Nomex

170 172 172 174 176 178 180 182 184 186 188 190 190 192 194 196 198 200 200 202 204 206 208 210 212 214 216 218 220 222 222 224 226 228 230 232 234

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114 Poly(p-phenylene/3,4-diphenylene ether terephthalamide) 2.2.14 Polyesters 115 Poly(ethylene terephthalate); PET 116 Poly(butylene terephthalate); PBT 117 Poly(ethylene naphthalate); PEN 118 Poly(p-hydroxybenzoic acid); type A 119 Poly(p-hydroxybenzoic acid); type B 120 Polyarylate; PAR 121 Poly(1,4-cyclohexanedimethylene terephthalate) 122 Poly(lactic acid); PLA 123 Poly(3-caprolactone); PCL 124 Poly(butylene succinate / adipate); PBSA 125 Poly(3-hydroxybutylic acid); PHB 126 Poly(butylene succinate / carbonate); PEC 2.2.15 The other engineering plastics with phenylene skeletons 127 Polycarbonate(melt method); MM-PC 128 Polycarbonate(solvent method); SM-PC 129 Bisphenol Z polycarbonate 130 Polycarbonate (thermally stabilized) 131 Brominated polycarbonate; Br-PC 132 Polysulfone; PSF 133 Poly(phenylene oxide); PPO 134 Modiﬁed poly(phenylene oxide); Modiﬁed PPO 135 Polyethersulfone; PESF 136 Poly(ether ether ketone); PEEK 137 Poly(phenylene sulﬁde); PPS 138 Poly(arylether nitrile); PEN 2.2.16 Silicone polymers 139 Polydimethylsiloxane; PDMS 140 Polymethylphenylsiloxane; PMPS 141 Dimethylsiloxane-methylphenylsiloxane copolymer 142 Polymethylsilsesquioxane; PMSQ 143 Poly(methyl-phenyl) silsesquioxane; PMPSQ 2.2.17 Polyurethanes 144 TDI-polyester polyurethane; PU 145 TDI-polyether polyurethane; PU 146 MDI-polylactone polyurethane; PU 147 Urethane rubber; U 2.2.18 Cellulose-type polymers

236 238 238 240 242 244 246 248 250 252 254 256 258 260 262 262 264 266 268 270 272 274 276 278 280 282 284 286 286 288 290 292 294 296 296 298 300 302 304

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148 Cellulose 149 Methylcellulose; MC 150 Ethylcellulose 151 Cellulose acetate; CA 152 Cellulose acetate-propionate; CAP 153 Cellulose acetate-butyrate; CAB 154 Hydroxyethylcellulose; HEC 155 Carboxymethyl cellulose; CMC 2.2.19 The other natural polymers, etc 156 Glue 157 Shellac 158 Chitin 159 Chitosan 160 Ivory 161 Synthetic lignin; DHP 162 Wood powder 163 Gluten

Part 3 Pyrograms for 33 condensation polymers and MS data of the major pyrolyzates obtained in the presence of organic alkaline 3.1 Experimental conditions for measuring pyrograms and MS data of the major pyrolyzates for the condensation polymers by means of reactive pyrolysis-GC/MS in the presence of organic alkaline 3.1.1 Polymer samples 3.1.2 Measuring conditions for the pyrograms of the polymers and the MS data of the major peaks on each pyrogram by use of reactive pyrolysis in the presence of organic alkaline 3.1.3 Data descriptions for the reaction pyrograms and the MS data of the major peaks on the pyrograms for 33 condensation polymer samples 3.2 Data compilation of pyrograms of 33 condensation polymers through reactive pyrolysis

304 306 308 310 312 314 316 318 320 320 322 324 326 328 330 332 334

337

337 337

337

339 340

[ The number in [xyz] corresponds to that in the Chapter 2.2. ] R01 [042] Poly(acrylic acid; isotactic); PAA R02 [099] Diallyl phthalate resin; DAP R03 [100] Poly(ethylene glycol bisallyl carbonate); CR-39 R04 [104] Unsaturated polyester; UP R05 [105] Epoxy resin; EP R06 [107] Bismaleimide triazine resin; BT resin

340 342 343 344 346 348

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R07 [108] Polyetherimide; PEI R08 [109] Polypyromellitimide; PI R09 [110] Polyaminobismaleimide; PABM R10 [115] Poly(ethylene terephthalate); PET R11 [116] Poly(butylene terephthalate); PBT R12 [117] Poly(ethylene naphthalate); PEN R13 [118] Poly(p-hydroxybenzoic acid); type A R14 [119] Poly(p-hydroxybenzoic acid); type B R15 [120] Polyarylate; PAR R16 [121] Poly(1,4-cyclohexane dimethylene terephthalate) R17 [122] Poly(lactic acid); PLA R18 [123] Poly(3-caprolactone); PCL R19 [124] Poly(butylene succinate / adipate); PBSA R20 [125] Poly(3-hydroxybutylic acid); PHB R21 [126] Poly(butylene succinate / carbonate); PEC R22 [127] Polycarbonate (melt method); MM-PC R23 [128] Polycarbonate (solvent method); SM-PC R24 [129] Bisphenol Z polycarbonate R25 [130] Polycarbonate (thermally stabilized) R26 [132] Polysulfone; PSF R27 [135] Polyethersulfone; PESF R28 [136] Poly(ether ether ketone); PEEK R29 [151] Cellulose acetate; CA R30 [152] Cellulose acetate-propionate; CAP R31 [153] Cellulose acetate-butyrate; CAB R32 [157] Shellac R33 [161] Synthetic lignin; DHP APPENDIX Monographs and reviews for pyrolysis-GC of polymers Index

350 352 354 356 357 358 359 360 361 362 363 364 365 366 367 368 369 370 371 372 373 374 375 376 378 380 382

385 387

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PREFACE

Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) as evidenced by ever increasing numbers of publications in various fields is a rapidly growing scientific area. Especially, in the field of polymer characterization, it is now widely recognized as one of the most promising and practical techniques. Among important factors enabling the rapid advancement of the modern analytical pyrolysis technique are the developments of: a) Various specific pyrolyzers such as the resistively heated self-sensing Pt filaments, the Curie point devices and the functional micro-furnace ones, b) Highly efficient and specific capillary columns such as fused-silica and deactivated stainless steel capillary ones enabling separation of up to fairly polar compounds with higher boiling points to yield high-resolution pyrolysis-gas chromatogram (pyrogram) characteristic of the sample, c) Specific on-line identification techniques for separated components on the pyrograms by means of GC/MS, GC/AED (atomic emission detector), GC/IR (infrared spectrometer), etc. among which GC/MS has played the most important role, d) On-line chemolysis combined with thermal decomposition of condensation polymers in the pyrolysis chamber, typically in the presence of an organic alkaline such as tetramethylammonium hydroxide (TMAH), and e) Sophisticated data searching and handling systems aided by modern computer with abundant memory capacity and processing speed. However, not a few scientists have been skeptical to some extent against the reported data of modern analytical pyrolysis, especially concerning to interlaboratory specificity and reproducibility of the resulting data. Therefore, the standardization of the analytical conditions by use of well characterized samples, and the publication of well qualified data compilation for a series of standard samples have been eagerly requested for a long time. In the end of the 1980’s, the authors published a trial standard database for the pyrograms of 135 typical synthetic polymer samples taken under the same conditions for Py-GC with flame ionization detector (FID) (Tsuge S, Ohtani H. “Pyrolysis-gas chromatography of polymers - fundamentals and data compilations”. Techno System Co., Tokyo, 1989). Recently, we launched a revised database for the pyrograms of 165 typical standard polymers by use of Py-GC/MS together with those for 33 condensation polymers taken by reactive pyrolysis (RP) in the presence of TMAH, where all pyrograms were monitored by total ion current of MS rather than by FID (Tsuge S, Ohtani H, Watanabe C. “Pyrolysis-GC/MS of high polymers - fundamentals and pyrogram compilations”. Techno System Co., Tokyo, 2006). Both of the above mentioned data books, however, were written in Japanese. xiii

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Therefore, the authors have been frequently requested to publish their English editions. In this new data book, the authors compiled the comprehensive pyrolysis data for representative synthetic polymers along with some natural polymers, not only pyrograms taken by conventional Py-GC/MS and RP, but also thermograms and mass spectra taken by evolved gas analysis (EGA) under programmed degradation temperatures. Furthermore, the mass spectra of the up to top 10 major pyrolyzates observed on each pyrogram, and the retention index data for each peak on a given pyrogram were also compiled, for the sake of users’ convenience and promotion of interlaboratory reproducibility and reliability. The authors would be in supreme bliss if this data book could contribute to move up the status of Py-GC/MS in the field of polymer characterization through overcoming its potential skepticism.

ACKNOWLEDGMENTS The authors wish to acknowledge with thanks so many suppliers of the standard polymer samples used for the data measurements of this compilation. We wish to extend our sincere gratitude to Frontier Laboratories Ltd (FLL) and Nagoya Institute of Technology (NIT) for their instrumental and scientific contribution, especially to Ms. MATSUI Kazuko, Mr. HOSAKA Akihiko and Ms. KUNII Sayuri (FLL), and Ms. AOI Hiromi and Ms. KATO Shino (NIT), for collecting, interpreting and compiling huge pyrolysis data properly with patience. TSUGE Shin Nagoya University

OHTANI Hajime Nagoya Institute of Technology

WATANABE Chuichi Frontier Laboratories Ltd

October 1, 2010

PART 1

Introduction In this data book, both conventional Py-GC/MS where thermal energy alone is used to cause fragmentation of given polymeric materials, and reactive Py-GC/MS in the presence of organic alkaline for condensation polymers are compiled. Before going into detailed presentation of the data, however, acquiring a firm grip on the proper understanding about the situation of Py-GC/MS would promote better utilization of the following pyrolysis data for various polymer samples.

1.1 HISTORY AND SCOPE OF ANALYTICAL PYROLYSIS Figure 1.1 shows a brief chronological diagram of modern analytical pyrolysis after the advent of organic MS with an electron impact (EI) ion source followed by the appearance of GC, together with various developments in related techniques and the associated international conferences.1–3 In 1948, the first reports on the off-line pyrolysis-MS (Py-MS) of polymers were published by Madorsky and Straus, and Wall. In 1953, Bradt et al. described on-line Py-MS for which pyrolysis of polymer samples was affected within the instrument in vacuo. Thus valuable structural information about the samples became obtainable. Two years after the introduction of GC by James and Martin in 1952, Davison et al. reported the first work on off-line Py-GC of polymers. These workers demonstrated that Py-GC was quite effective for the characterization of polymeric materials. In 1959, online Py-GC systems and their applications to polymer analysis were reported independently by three research groups: Lehrle and Robb, Radell and Strutz, and Martin. These achievements triggered a boom in Py-GC. Moreover, the dissemination of GC–MS after 1965 strongly accelerated the development of Py-GC. In 1966, Simon and co-workers reported the first directly coupled Py-GC/MS system using a rapid scanning MS. The high-resolution capillary columns introduced by Golay in 1958 had a strong impact on Py-GC. However, general application of their effectiveness was held back until the advent of the chemically inert fused silica capillary columns in 1979, since the earlier metal capillary columns were not suitable for the separation of polar and/or higher boiling point compounds. The chemical inertness and thermal stability of capillary separation columns are among the most important factors in achieving highresolution pyrograms of polymer samples by Py-GC/MS since the thermal degradation products of polymers usually consist of compounds with a wide range of boiling points Pyrolysis-GC/MS Data Book of Synthetic Polymers/Tsuge ISBN 978-0-444-53892-5, Doi:10.1016/B978-0-444-53892-5.10001-X

Ó 2011 Elsevier B.V. All rights reserved.

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[Analytical pyrolysis]

[Related techniques] 1945

Madorsky, et al., and Wall, et al., (1948)

Organic MS (EI) 1950

Bradt, et al., (1953)

GC (1952)

Davison, et al., (1954) Lehrle, et al., Radell, et al. and 1960 Martin (1959) Simon (1964)

Capillary GC/FID (1959)

[Intl. Symposium] 1st (1965) Paris

Simon (1966) Hummel, et al., (1968)

GC/MS (1965-1970) 1970

Meuzelaar, et al., (1973)

3rd (1976) Amsterdam

Tsuge (1973) <Micro-furnace pyrolyzer> J. Anal. Appl. Pyrol. <Elsevier>

2nd (1972) Paris

1980

4th (1979) Budapest th

Fused-silica capillary for GC (1979)

5 (1982) Vail, CO 6th (1984) Weisbaden

GC/FT-IR (1980-1990)

7th (1986) Reading

Tsuge, Ohtani (1989)

1990

8th (1988) Lund

GC/AED (1989)

9th (1990) Noordwijkerhout

Deactivated stainless steel capillary GC (1991)

10th (1992) Hamburg 11th (1994) Nagoya 12th (1996) Venice 2000

13th (1998) Munich 14th (2000) Seville 15th (2002) Leoben

Tsuge, Ohtani, Watanabe (2006)

16th (2004) Alicante 17th (2006) Budapest 18th (2008) Canary Islands

2010

Figure 1.1 Chronicle of analytical pyrolysis.

which often contain fairly polar compounds such as carboxylic acids, amines, nitriles, epoxides, and so on. Modern fused silica capillary columns and recently developed metal capillary ones with deactivated inner walls have drastically improved the situation of Py-GC/MS. During such developments in analytical pyrolysis, a number of books and commentaries have been released (most of these are listed in Appendix). In recent years, comprehensive monographs of analytical pyrolysis by Moldoveanu were published by focusing on natural4 and synthetic polymers,5 respectively. These books systematically discuss the latest trends in theory and techniques in analytical pyrolysis with featuring the representative applications. On the other hand, standardization and reliable compilation of

3

Introduction

a standard database for various series of standard samples have been left among the important factors to promote interlaboratory data comparison in Py-GC. In the early stage of Py-GC, however, significant interlaboratory discrepancies between pyrolysis data (pyrograms) were reported even for the same polymer types. This was mainly caused by a diversity of pyrolysis devices operated under varied conditions. Owing to continued improvement of pyrolyzers and fundamental studies to control the operating conditions and obtain reproducible and characteristic degradation of the studied materials, most of the commercially available pyrolyzers (flash filament-, furnace-, and Curie-point types) have made the interlaboratory discrepancies, a minor problem. In this situation, a trial standard database for 136 kinds of typical synthetic polymers compiled under the same refined conditions using Py-GC was published by the authors in 1989,6 and its expanded revision was then issued in 2006.7 These data books, however, were written in Japanese. In order to respond to the international request, the authors have compiled a new English version Py-GC/MS data book covering most of the typical synthetic polymers.

1.2 EXPANDED APPLICABILITY OF GC/MS BY COMBINING WITH PYROLYSIS Modern GC/MS is widely recognized as one of the most powerful methodologies, where mass resolving and mass determining capabilities of MS are synergistically enhanced through direct combination with high-resolution ability of GC even for complex mixture samples provided that they might have moderate volatility. However, we have to comprehend that the ordinary limitation of GC/MS lies in the volatility of given samples. Generally speaking the samples to be fed on GC/MS analysis should have vapor pressure (volatility) at least in order of a few mmHg at the maximum GC column temperatures around 300 C. Here, you should notice that ordinary high polymers in the category of non-volatiles should be out of GC/MS application. Figure 1.2 illustrates the situations of Py-GC (Py-GC/MS) together with ordinary GC (GC/MS) and LC (LC/MS) as a function of hypothetical volatility [molecular weight (MW) or polarity]. As shown at the top, the substances around us exist at ambient temperature as either gas, liquid or solid, mostly depending on their MW. Although, the substances called “molecules” are in the range between A and B have some solvents, and are in the applicability of either GC or LC depending on their volatility or solubility in given solvents. Roughly speaking among the whole molecules (100%), about 30% of them could be treated with GC, including those formed through derivatization to enhance volatility or thermal stability, while LC can be applied about 85% of them provided that some proper solvents can be found even for polymers. However, the insoluble substances between the ranges above B cannot be treated by any chromatographic techniques.

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Molecules

Insoluble substances [+α]

[ 100 % ]

Infinitive MW

MW / Polarity

Gas Liquid

[at ambient temp.]

Solid

Application range of LC, GC and Py-GC

LC (LC/MS)

[ 85 % ]

GC (GC/MS)

Non accessible by GC and LC

[ 30 % ] by derivatization

Py-GC (Py-GC/MS)

A

B

C

Figure 1.2 How “Pyrolysis” expanded the applicability of GC/MS for material characterization.

Three-dimensional polymeric materials, coal, lignin, soil, and most of biomass would be included in these category substances. However, the applicability of GC (GC/MS) combined with pyrolysis, Py-GC (Py-GC/MS) ranges the entire area of the organic substances if they could yield fragment by thermal energy or chemically assisted thermolysis. Thus, the modern Py-GC (Py-GC/ MS) is on the new horizon for the polymer characterization including intractable materials by conventional methodologies.

1.3 PY-GC/MS MEASURING PROCESS FOR POLYMER CHARACTERIZATION Figure 1.3 illustrates the flow diagram in Py-GC/MS and its complementary evolved gas analysis (EGA)–MS for polymer characterization. In Py-GC/MS measurements, usually a given polymer sample weighing about 10–100 mg is instantaneously pyrolyzed at about 400–600 C with or without catalytic and/or reactive reagents under a flow of N2 or He carrier gas. The resulting decomposition products transferred into the separation column are separated to yield a pyrogram. The pyrolysis products of a given polymer sample are usually composed of very complex components each of which might reflect the original structures. Even for these conditions, Py-GC/ MS utilizing a chemically inert capillary column often provides highly efficient

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Introduction

Polymer sample

Pyrolysis (with/without reagent)

Decomposition products

Vaporization and thermal decomposition by programmed heating

Evolved compounds

EGA-MS

Py-GC/MS

Separative analysis by GC/MS

On-line monitoring by MS

Specific pyrogram

Thermogram

Compositional and structural characterization, and thermal behaviors of polymer

Figure 1.3 Flow diagram for polymer characterization by Py-GC/MS and EGA/MS.

separation. The individual components on the pyrogram are continuously identified by use of the observed mass spectra. In addition, total ion monitoring (TIM) and selected ion monitoring (SIM) often provide supplemental and/or complement information of peak identification on the pyrogram. On the other hand, in EGA–MS, evolved gases formed during the programmed heating of the sample are directly transferred into MS to achieve on-line monitoring of the components. For the EGA–MS measurements, the separation column in Py-GC/ MS is replaced with a deactivated open transfer line connecting directly between a temperature programmable pyrolyzer and an ion source of MS. The resulting thermogram monitored by MS during the programmed heating reflects the evolved gas profile of the sample as a function of temperature. The observed specific pyrograms and/ or thermograms often provide valuable information regarding the composition and/or chemical structures of the original polymer sample as well as on the degradation mechanisms and related kinetics.

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REFERENCES 1. Tsuge S. J Anal Appl Pyrol 1995;32:1–6. 2. Tsuge S, Ohtani H. Polym Degrad Stab 1997;58:109–30. 3. Tsuge S, Ohtani H. Pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS). In: Montaudo G, Lattimer RP, editors. Mass spectrometry of polymers. Boca Raton: CRC Press; 2002. 4. Moldoveanu SC. Analytical pyrolysis of natural organic polymers. Amsterdam: Elsevier; 1998. 5. Moldoveanu SC. Analytical pyrolysis of synthetic organic polymers. Amsterdam: Elsevier; 2005. 6. Tsuge S, Ohtani H. Pyrolysis-gas chromatography of polymers - fundamentals and data compilations. Tokyo: Techno System Co; 1989. 7. Tsuge S, Ohtani H, Watanabe C. Pyrolysis-GC/MS of high polymers - fundamentals and pyrogram compilations. Tokyo: Techno System Co; 2006.

PART 2

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates 2.1 EXPERIMENTAL CONDITIONS FOR MEASURING PYROGRAMS AND THERMOGRAMS OF HIGH POLYMERS, AND MS DATA FOR THE MAJOR PYROLYZATES BY MEANS OF PYROLYSIS-GC/MS AND EVOLVED GAS ANALYSIS (EGA)–MS TECHNIQUES 2.1.1 Polymer samples In the following data acquisition, the same 163 standard polymer samples used in the former editiony were adopted as a set of representative ones utilized in versatile fields, which include representative synthetic polymers [a) polyolefins (homopolymers) (001– 007), b) vinyl polymers with ethylene units (copolymers) (008–015), c) vinyl polymers with styrene units (016–028), d) vinyl polymers with styrene derivatives (029–035), e) acrylate-type polymers (036–049), f) chlorine-containing vinyl polymers (050–059), g) fluorine-containing vinyl polymers (060–066), h) the other vinyl polymers (067–070), i) diene-type elastomers (071–081), j) polyamides (082–090), k) polyacetals and polyethers (091–095), l) thermosetting polymers (096–106), m) polyimides and polyamide-type engineering plastics (107–114), n) polyesters (115–126), o) the other engineering plastics with phenylene skeletons (127–138), p) silicone polymers (139–143), and q) polyurethanes (144–147)] along with some natural polymers [r) cellulose-type polymers (148–155) and s) the other some natural polymers (156–163)].

2.1.2 Measuring conditions for the pyrograms of the polymers and the MS data of the major peaks on each pyrogram, and the thermograms of the polymers Figures 2.1 and 2.2 illustrate the schematic flow diagrams of the measuring systems of the pyrolysis (Py)-GC/MS and evolved gas analysis (EGA)–MS, respectively. In both systems, the vertical micro-furnace pyrolyzer (Frontier Lab., PY-2020iD) mounted on y Tsuge S, Ohtani H, Watanabe C. “Pyrolysis-GC/MS of high polymers - fundamentals and pyrogram compilations”. Techno System Co., Tokyo, 2006.

Pyrolysis-GC/MS Data Book of Synthetic Polymers/Tsuge ISBN 978-0-444-53892-5, Doi:10.1016/B978-0-444-53892-5.10002-1

Ó 2011 Elsevier B.V. All rights reserved.

7

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Tsuge, Ohtani and Watanabe

He

Pyrolyzer

pyrolysis tube micro furnace

He

interface heater sample cup GC splitter vent separation column

separation column GC/MS adaptor

GC Oven

Q-MS

Figure 2.1 Schematic ﬂow diagram of Py-GC/MS System (from the upper to the lower ﬂow). (a) Carrier gas: 100 ml/min of He ﬂow at the pyrolyzer, 1 ml/min at the separation column through a splitter (1/ 100); (b) pyrolyzer: a micro-furnace pyrolyzer (Frontier Lab., PY-2020iD) at 600 C; (c) pyrolyzer/GC interface temp.: 320 C; (d) GC injection temp.: 320 C; (e) sample size: ca. 0.2 mg of a sample cup (ECO cup-L: o.d. 4.2 i.d. 4 8 mm height, deactivated stainless steel cup); (f) GC separation column: Ultra ALLOY-5 (0.25 mm 30 m; 0.25 mm ﬁlm of 5%diphenyl–95%dimethylpolysiloxane); (g) GC oven temp. programmed from 40 C (2 min hold) – (20 C/min) – 320 C (13 min hold); (h) GC/MS adapter (Frontier Lab, Vent-free adapter); (i) GC/MS interface temp.: 320 C; (j) EI source (70 eV) temp.: 230 C; (k) MS, scan range: 29–600 (m/z) at 2000 amu/sec.

either a Shimadzu GCMS-QP2010 or an Agilent 6890 GC & 5975 MS was used under a flow of He carrier gas, and data search libraries of Frontier Lab., F-search (pyrolyzates MS08) and NIST/EPA/NIH (version 2.0f) were mostly used for the peak identification of the pyrolyzates together with their retention index (RI) data. However, any other GC/MS systems equipped with any type of pyrolyzers such as resistively heated filament devices and inductively heated ones could provide basically the same tendency data as those in this compilation. Pyrograms and MS data measurements The measurements of the pyrograms for the 163 polymer samples were carried out by the Py-GC/MS system shown in Figure 2.1. The flash pyrolysis temperature was fixed at 600 C throughout the entire data acquisition, and the resulting pyrolyzates of the

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

He

Pyrolyzer

sample cup vent

transfer tube

GC Oven

GC/MS adaptor

Q-MS

Figure 2.2 Schematic Flow Diagram of EGA/MS System (from the upper to the lower ﬂow). (a) Carrier gas: 50 ml/min at the pyrolyzer, 1 ml/min in the interface through a splitter (1/50); (b) pyrolyzer: the same pyrolyzer as in Figure 2.1, its temperature programmed from 100 to 700 C at a rate of 20 C/ min; (c) sample size: ca. 0.2 mg weighed into the same sample cup as in Figure 2.1; (d) deactivated and uncoated stainless steel transfer tube (i.d. 0.15 mm 2 m length); (e) GC/MS adapter/MS interface temp.: 300 C; (f) MS scan range: 29–600 (m/z) at 70 amu/sec.

polymer sample weighing ca. 0.2 mg were separated by a stainless steel capillary column (Frontier Lab. Ultra ALLOY-5) coated with 5%diphenyl–95%dimethylpolysiloxane liquid phase under a programming temperature condition; 40 C (2 min hold) – (20 C/ min) – 320 C (13 min hold). The other experimental conditions are supplemented at the bottom of the figure. The resulting mass spectrometric data for all the peaks on the pyrograms stored as the total ion chromatogram (TIC), and the selected mass spectra for the top 10 major peaks at most were compiled on this data book, together with the RI data of the main peaks on the pyrograms. Here, the RI data for the components were estimated by comparison of the retention data for a series of hydrocarbon peaks with known carbon numbers appearing on the pyrogram of polyethylene observed under the same condition. As shown in Figure 2.2, the measurements of the EGA–MS thermograms for the polymer samples weighing ca. 0.2 mg were carried out separately by replacing the separation column with a deactivated and uncoated stainless steel transfer tube (i.d. 0.15 mm 2 m length), where the column oven temperature was maintained at 300 C to prevent condensations of less-volatile pyrolyzates in the transfer tube, and the temperature of the pyrolyzer was programmed from 100 to 700 C at a rate of

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Tsuge, Ohtani and Watanabe

20 C/min to obtain the thermogram as a function of temperature. Here, in the mode change from the Py-GC/MS system to the EGA/MS system, the Vent-free adapter (Frontier Lab) played an important practical role enabling the rapid replacement of the separation column with the transfer tube without venting the working Q-MS under a high vacuum.y Thus obtained thermogram data of the polymer samples by monitoring the total ion current of MS are compiled in the upper right corner of the averaged mass spectrum for each thermogram as a function of the programmed temperature from 100 to 700 C.

2.1.3 Data descriptions for the pyrograms and the MS data of the major peaks on the pyrograms, and the thermograms for 163 polymer samples In the following Chapter 2.2, two facing pages were allocated for each polymer sample. For example, two facing pages (pp. 12–13) are accommodated for polyethylene. On the left hand page (p. 12), you can find at the top:

001 Polyethylene (high density); PE(HDPE) CH2CH2

n

where the sample number, 001 is followed by the full name with its abbreviation, and then its chemical structure is given. The upper display is its pyrogram at 600 C separated by the capillary separation column followed by TIC monitoring mentioned in Chapter 2.1.2 where C10, for example, designates hydrocarbons containing ten carbon atoms. The horizontal retention time scale can easily be converted into temperature axis by knowing the programmed temperature conditions for the separation column [from 40 C (2 min hold) – (20 C/min) – 320 C (13 min hold)]. In the bottom, you can see the peak identification table for the pyrogram together with molecular weight, relative peak intensity, and retention index data. As the footnote, related references in which the concerned pyrolysis information is included were listed. On the right hand page (p. 13), its EGA thermogram taken as a function of temperature from 100 to 700 C at a rate of 20 C/min is shown at the right hand shoulder of its averaged mass spectrum for the temperature range (4) shown above the thermogram monitored by its TIC between 29 and 600 (m/z). By the thermogram profile, you can easily understand the whole thermal behavior, that the thermal decomposition of PE(HD) starting at ca. 400 C passes through the peak top at ca. 480 C, finishing at ca. 530 C, which also tells us useful information to determine the y http://www.frontier-lab.com/product/catalogue/Vent-free_adapter.pdf.

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

optimum pyrolysis temperature to measure its pyrogram. Furthermore, by use of the average mass spectrum data search mentioned above, you could often make rapid identification of the polymeric materials. At the bottom on the right hand page, the selected mass spectra for the top 10 major peaks are compiled. (In some cases, where only a few significant pyrolyzates are observed, typically for depolymerizing polymers, the number of the mass spectra should be less than 10.)

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2.2 DATA COMPILATION OF PYROGRAMS, THERMOGRAMS AND MS DATA OF MAJOR PYROLYZATES FOR 163 TYPICAL POLYMER SAMPLES 2.2.1 Polyoleﬁns (homopolymers) 001 Polyethylene (high density); PE(HDPE) CH2CH2

n

C10 C28 C26

C22 C11

C14 C15 C12

C18 C20

C16

C13

C24

C30 C32 C34

C9

C36

C6 LB

C7

C8

C40

C41

TIC

0

10

Peak Notation LB C6 C7

C8

C9

C10

C11

C14

C20 C30 C40 C41

30 [min]

20

Assignment of Main Peaks

Molecular Weight

propylene + propane CH2=CH(CH2)3CH3 CH2=CH(CH2)4CH3 CH3(CH2)5CH3 CH2=CH(CH2)4CH=CH2 CH2=CH(CH2)5CH3 CH3(CH2)6CH3 CH2=CH(CH2)5CH=CH2 CH2=CH(CH2)6CH3 CH3(CH2)7CH3 CH2=CH(CH2)6CH=CH2 CH2=CH(CH2)7CH3 CH3(CH2)8CH3 CH2=CH(CH2)7CH=CH2 CH2=CH(CH2)8CH3 CH3(CH2)9CH3 CH2=CH(CH2)10CH=CH2 CH2=CH(CH2)11CH3 CH3(CH2)12CH3 CH2=CH(CH2)16CH=CH2 CH2=CH(CH2)17CH3 CH3(CH2)18CH7 CH2=CH(CH2)27CH3 CH2=CH(CH2)37CH3 CH2=CH(CH2)38CH3

42; 44 84 98 100 110 112 114 124 126 128 138 140 142 152 154 156 194 196 198 278 280 282 420 560 574

[ Related References ] 1) Michajlov, L.; Zugenmaier, P.; Cantow, H.-J. Polymer 1968, 9, 325. 2) Sugimura, Y.; Tsuge, S. Anal. Chem. 1978, 50, 1968. 3) Sugimura, Y.; Tsuge, S. Macromolecules 1979, 12, 512. 4) Ohtani, H.; Tsuge, S.; Usami, T. Macromolecules 1984, 17, 2557. 5) Duc, S.; Lopez, N. Polymer 1999, 40, 6723.

Retention Relative Index Intensity 300 583 689 700 782 791 800 883 892 900 983 991 1000 1083 1092 1100 1385 1392 1400 1985 1993 2000 2993 3997 4096

43.7 91.8 42.4 19.3 2.1 25.1 14.3 5.8 30.4 10.3 6.6 64.2 10.4 7.1 49.8 16.1 12.3 49.2 13.5 25.3 38.0 16.2 100.0 94.1 82.8

13

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

001

EGA thermogram

Averaged mass spectrum 41

55

83

69

100

200

300

400

500

97

600

700 ºC

programming rate: 20ºC/min

111 125

30 50

139

100

154

168

182

196

150

200

250 [m/z]

( m/z range : 29 - 600 amu )

C7 : 1-heptene

C10 : 1,9-decadiene 41

55

56 41

67 81

70

29

95

29

98

83

110 123

C10 : n-decane

C10 : 1-decene 41

57

43

56 70

29

71

83 111

98

140

C11 : 1-undecene 41

85

29

97

113

142

C14 : 1-tetradecene 41

55

55

70

69

83 97

83 29

29

97

111 111 126

125

154

140 153 168

196

C30 : 1-triacontene C20 : 1-eicosene

(mixed with 1,29-triacontadiene and n-triacontane) 57

43 55

83

43

97

69

97 69

111 29

111 125 139

168

196

224

252

418

C41 : 1-hentetracontene

(mixed with 1,39-tetracontadiene and n-tetracontane)

(mixed with1,40-hentetracontadiene and n-hentetracontane)

57

57

71

43 71 97

97

29

153

280

C40 : 1-tetracontene

43

125

29

111 125

153

559

29

111 125

153

572

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Tsuge, Ohtani and Watanabe

002 Polypropylene(isotactic); iso-PP CH2CH(CH3 )

n

C15 C9

C12 C’13 C13

C’34 C16 C21 C18 C’25 C’28 C’31 C’37 C’22 C’16 C’19 C’40 C24

C’43

C11 C3 C10 C’10

C5 TIC

10

C’46

C’49

20

C6

0

10

Peak Notation

Assignment of Main Peaks

C3 C5 C6 C9 C10 C10’ C11

propylene n-pentane 2-methyl-1-pentene 2,4-dimethyl-1-heptene 2, 4, 6-trimethyl-1-heptene 2, 4, 6-trimethyl-1, 6-heptadiene 4, 6-dimethyl-2-nonene (meso form) 2, 4, 6-trimethyl-1-nonene (meso form) 2, 4, 6-trimethyl -1-nonene (racemic form) 2, 4, 6, 8-tetramethyl-1-nonene (meso form) 2, 4, 6, 8-tetramethyl-1, 8-nonadiene (meso form) 2, 4, 6, 8-tetramethyl-1-undecene (isotactic) 2, 4, 6, 8- tetramethyl-1-undecene (heterotactic) 2, 4, 6, 8- tetramethyl-1-undecene (syndiotactic) 2, 4, 6, 8, 10-pentamethyl-1-undecene (isotactic) 2, 4, 6, 8, 10-pentamethyl-1, 10-undecadiene (isotactic) 2, 4, 6, 8, 10-pentamethyl-1-tridecene (isotactic) 2, 4, 6, 8, 10, 12-hexamethyl-1, 12-tridecadiene (isotactic) 2,4,6,8,10,12,14,16,18,20,22-undecamethyl-1,22tricosadiene (isotactic)

C12 C13 C13’ C15 C16 C16’ C18 C19’ C34’

30 [min]

20

Molecular Retention Weight Index 42 72 84 126 140 138 154 168 168 182 180 210 210 210 224 222 252 264 476

295 500 584 844 895 916 996 1083 1087 1132 1156 1312 1320 1329 1356 1385 1531 1605 3397

[ Related References ] 1) Michajlov, L.; Zugenmaier, P.; Cantow, H.-J. Polymer 1968, 9, 325. 2) Tsuchiya, Y.; Sumi, K. J. Polym. Sci., Part-A1 1969, 7, 1599. 3) Seeger, M.; Cantow, H. -J. Makromol. Chem. 1975, 176, 2059. 4) Kiran, E.; Gillham, J. K. J. Appl. Polym. Sci. 1976, 20, 2045. 5) Kiang, J. K. Y.; Uden, P. C.; Chien, J. C. W. Polym. Degrad. Stab. 1980, 2, 113. 6) Sugimura, Y.; Nagaya, T.; Tsuge, S.; Murata, T.; Takeda, T. Macromolecules 1980, 2, 113. 7) de Amorim, M. T. S. P.; Comel, C.; Vermande, P. J. Anal. Appl. Pyrolysis 1982, 4, 73. 8) Ishiwatari, M. J. Polym. Sci., Polym. Lett. Ed. 1984, 22, 83. 9) Ohtani, H.; Tsuge, S.; Ogawa, T.; Elias, H. -G. Macromolecules 1984, 17, 465.

Relative Intensity 14.6 10.0 8.1 100.0 6.8 2.6 2.9 9.5 3.3 4.0 4.1 18.5 2.6 10.6 3.4 3.9 6.4 5.4 9.7

15

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

002

EGA thermogram

Averaged mass spectrum 41 69

55

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

83 111

97

125

30 50

137

100

154

167

150

250 [m/z]

200

( m/z range : 29 - 600 amu )

C5 : n-pentane

C6 : 2-methyl-1-pentene 43

39 56 84

69

29 29 55

72

C10 : 2,4,6-trimethyl-1-heptene

C9 : 2,4-dimethyl-1-heptene 43

41

70

83

55

69 55

29

29 83 126 111

91

97

C12 : 2,4,6-trimethyl-1-nonene (meso form)

125

140

C12 : 2,4,6-trimethyl-1-nonene (racemic form)

41

41 55

69 55

29

83

111

69 83

29

112

125

97

C15 : 2,4,6,8-tetramethyl-1-undecene (isotactic)

125

97

153 168

168

C15 : 2,4,6,8-tetramethyl-1-undecene (heterotactic)

43 55 69

43 55 69 83

111 111

83

29

29 125

97

154 140

97 167

125

154

210

C34’ : 2,4,6,8,10,12,14,16,18,20,22-undecamethyl C15 : 2,4,6,8-tetramethyl-1-undecene (syndiotactic)

-1,22-tricosadiene (isotactic)

43 55

69 69 111

85

55

29

43 97

125

154 139

167

83 125 97111 153 139 165 179

283

313 327 355

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Tsuge, Ohtani and Watanabe

003 Polypropylene(atactic); at-PP CH2CH(CH3 )

n

C15 C9 C12

C’13 C13

C18

C21

C’16

10

C3 C5

TIC

0

10

Assignment of Main Peaks

C3 C5 C6 C9 C10 C10’

propylene n-pentane 2-methyl-1-pentene 2,4-dimethyl-1-heptene 2, 4, 6-trimethyl-1-heptene 2, 4, 6-trimethyl-1, 6-heptadiene 2, 4, 6-trimethyl-1-nonene (meso form) 2, 4, 6-trimethyl-1-nonene (racemic form) 2, 4, 6, 8-tetramethyl-1-nonene (meso form) 2, 4, 6, 8-tetramethyl-1-nonene (racemic form) 2, 4, 6, 8-tetramethyl-1, 8-nonadiene (meso form) 2, 4, 6, 8-tetramethyl-1, 8-nonadiene (racemic form) 2, 4, 6, 8-tetramethyl-1-undecene (isotactic) 2, 4, 6, 8-tetramethyl-1-undecene (heterotactic) 2, 4, 6, 8-tetramethyl-1-undecene (syndiotactic) 2, 4, 6, 8, 10-pentamethyl-1, 10-undecadiene (isotactic) 2, 4, 6, 8, 10-pentamethyl-1, 10-undecadiene (heterotactic) 2, 4, 6, 8, 10-pentamethyl-1, 10-undecadiene (syndiotactic)

C13 C13’

C15

C16’

30 [min]

20

Peak Notation

C12

20

15

C10 C’10

C6

Molecular Retention Index Weight 42 72 84 126 140 138 168 168 182 182 180 180 210 210 210 222 222 222

295 500 584 845 896 916 1083 1087 1132 1138 1156 1159 1311 1320 1329 1385 1392 1401

[ Related References ] 1) Seeger, M.; Cantow, H. -J. Makromol. Chem. 1975, 176, 2059. 2) Sugimura, Y.; Nagaya, T.; Tsuge, S.; Murata, T.; Takeda, T. Macromolecules 1980, 13, 928. 3) de Amorim, M. T. S. P.; Comel, C.; Vermande, P. J. Anal. Appl. Pyrolysis 1982, 4, 73. 4) Ishiwatari, M. J. Polym. Sci., Polym. Lett. Ed. 1984, 22, 83. 5) Ohtani, H.; Tsuge, S.; Ogawa, T.; Elias, H. -G. Macromolecules 1984, 17, 465.

Relative Intensity 19.5 13.7 11.6 100.0 7.2 2.7 7.3 7.6 2.1 2.6 2.3 1.9 11.0 11.1 8.8 1.5 1.7 1.8

17

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

003

EGA thermogram

Averaged mass spectrum 43

69 55 100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

83 111 97

125

153

139 50

100

200 [m/z]

150

( m/z range : 29 - 600 amu )

C5 : n-pentane

C3 : propylene 39

41

29 55

72

29

131

C9 : 2,4-dimethyl-1-heptene

C6 : 2-methyl-1-pentene 39

70

43 56

55

69 84

29

29

83

221

C12 : 2,4,6-trimethyl-1-nonene (meso form)

C10 : 2,4,6-trimethyl-1-heptene 41

41 69

55

83

69

55

83

29

29 91

109

125

111 125

97

140

C12 : 2,4,6-trimethyl-1-nonene (racemic form)

139 153 168

C15 : 2,4,6,8-tetramethyl-1-undecene (isotactic)

41

43 55

126 111

97

55

69

69

29

83

83 111 97

125 132

125

97 168

C15 : 2,4,6,8-tetramethyl-1-undecene (heterotactic)

139

154

167

210

C15 : 2,4,6,8-tetramethyl-1-undecene (syndiotactic) 43

43 55 69

55 69

85

111

83

111

29

111

29

29 97

97

125

154 139

167

210

125

154 139

167

210

18

Tsuge, Ohtani and Watanabe

004 Polypropylene (syndiotactic); syn-PP CH2CH(CH3 )

n

C15 C9 C12

C11

C’13 C13

C’16 C18 C16 C’19

C21 C’22

C’25 C24

C’28

C3 C5 TIC

10

C10

0

10

Assignment of Main Peaks

C3 C5 C6 C9 C10 C10’ C11

propylene n-pentane 2-methyl-1-pentene 2,4-dimethyl-1-heptene 2, 4, 6-trimethyl-1-heptene 2, 4, 6-trimethyl-1, 6-heptadiene 4, 6-dimethyl-2-nonene (racemic form) 2, 4, 6-trimethyl-1-nonene (meso form) 2, 4, 6-trimethyl-1-nonene(racemic form) 2, 4, 6, 8-tetramethyl-1-nonene (racemic form) 2, 4, 6, 8-tetramethyl-1, 8-nonadiene(racemic form) 2, 4, 6, 8-tetramethyl-1-undecene (isotactic) 2, 4, 6, 8-tetramethyl-1-undecene (heterotactic) 2, 4, 6, 8-tetramethyl-1-undecene (syndiotactic) 2, 4, 6, 8, 10-pentamethyl-1-undecene (syndiotactic) 2, 4, 6, 8, 10-pentamethyl -1, 10-undecadiene (syndiotactic) 2, 4, 6, 8, 10-pentamethyl -1-tridecene (syndiotactic) 2, 4, 6, 8, 10, 12-hexamethyl-1, 12-tridecadiene (syndiotactic)

C15 C16 C16’ C18 C19’

20

30 [min]

20

Peak Notation

C13 C13’

C’34

C’10

C6

C12

C’31

15

Molecular Retention Weight Index 42 72 84 126 140 138 154 168 168 182 180 210 210 210 224 222 252 264

295 500 586 844 895 916 1000 1081 1086 1138 1159 1312 1318 1327 1377 1399 1568 1641

[ Related References ] 1) Seeger, M.; Cantow, H. -J. Makromol. Chem. 1975, 176, 2059. 2) Sugimura, Y.; Nagaya, T.; Tsuge, S.; Murata, T.; Takeda, T. Macromolecules 1980, 13, 928. 3) Ohtani, H.; Tsuge, S.; Ogawa, T.; Elias, H. -G. Macromolecules 1984, 17, 465.

Relative Intensity 59.5 32.5 18.5 100.0 10.0 1.9 1.8 3.3 8.7 2.0 1.5 9.0 2.1 11.4 1.0 1.2 2.6 1.1

19

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

004

EGA thermogram

Averaged mass spectrum 41 55

69

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

83 111 97

125 137

30 50

100

153

167

150

250 [m/z]

200

( m/z range : 29 - 600 amu )

C5 : n-pentane

C3 : propylene

43

41

55 29

72

29

C6 : 2-methyl-1-pentene

C9 : 2,4-dimethyl-1-heptene 43

56

70 55

41 84 69

83

29 29

126 91

C10 : 2,4,6-trimethyl-1-heptene

111

C12 : 2,4,6-trimethyl-1-nonene (meso form) 43

43

55 69

69

84 84

55

111 91

29

140

106

C12 : 2,4,6-trimethyl-1-nonene (racemic form) 43

168

193

C15 : 2,4,6,8-tetramethyl-1-undecene (isotactic)

69

69

43

55

55 85

84

111

112 97

29

125 132

168

C15 : 2,4,6,8-tetramethyl-1-undecene (heterotactic)

97

125

30

154

C15 : 2,4,6,8-tetramethyl-1-undecene (syndiotactic) 43

43

69 55

69

55 85 111

85 111

154 97

126

154 160

97 30

125 160

195 210

20

Tsuge, Ohtani and Watanabe

005 Polybutene-1 (isotactic) CH2CH(CH2CH3)

n

C20

C12 C16

C29 C25 C28

C24 C17

C15

C19

C33

C37

C32

C41 C45

10

C4 TIC C3

C21

C5

C7

C8

C6

20

C13 C9

C11

0

10

Peak Notation

Assignment of Main Peaks

C3 C4 C5 C6 C7 C8

propane + propylene 1-butene (monomer) 2-methyl-1-butene 1-hexene n-heptane 2-ethyl-1-hexene (dimer) 2-ethyl-4-methyl-1-hexene 2, 4-diethyl-1, 4-pentadiene 5-ethylnonene 5-ethylnonane 2, 4-diethyl-1-octene (trimer) 2, 4-diethyl-6-methyl-1-octene 2, 4, 6-triethyl-1, 6-heptadiene 2, 4, 6-triethyl-1-decene (meso form) 2, 4, 6-triethyl-1-decene (racemic form) 2, 4, 6, 8-tetraethyl-1-dodecene (isotactic) 2, 4, 6, 8-tetraethyl-1-dodecene (syndiotactic) 2, 4, 6, 8, 10-pentaethyl-1-tetradecene (isotactic) 2, 4, 6, 8, 10, 12-hexaethyl-1, 12-tridecadiene (isotactic)

C9 C11 C12 C13 C16 C20 C24 C25

C49

[ Related Reference ] 1) Seeger, M.; Cantow, H. -J. Makromol. Chem. 1975, 176, 2059.

30 [min]

20

Molecular Retention Weight Index 44; 42 56 70 84 100 112 126 124 154 156 168 182 180 224 224 280 280 336 348

300 385 480 585 700 790 853 858 1024 1056 1124 1176 1190 1424 1428 1707 1725 1983 2053

Relative Intensity 0.9 36.0 15.5 3.2 21.3 19.4 5.9 3.7 3.3 4.5 100.0 14.9 3.7 17.7 5.5 21.4 16.1 22.4 15.7

21

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

005

EGA thermogram

Averaged mass spectrum 55 41 100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

69 83

97 111

125

30 50

100

139

153

168

181

195

150

207 250 [m/z]

200

( m/z range : 29 - 600 amu )

C7 : n-heptane

C4 : 1-butene (monomer) 41

43

71 57

56 29 29

100 85

C8 : 2-ethyl-1-hexene (dimer)

C12 : 2,4-diethyl-1-octene (trimer)

70

55

57 70

41

98

41 29 29

83

112 83

111

95

95

83 57 71 81

41 55 29

151 29 126 137

153

166

123 137

182

166

C16 : 2,4,6-triethyl-1-decene (racemic form)

C16 : 2,4,6-triethyl-1-decene (meso form) 57

57 41

41

69

69 83

83

97 112

29

125

97

112

29

154 139

167

195

125

224

C20 : 2,4,6,8-tetraethyl-1-dodecene (isotactic)

154 137

167

57

41

97

69 83

97

69 83

111 153 125139

112 181 167

29 210

251

280

195

C20 : 2,4,6,8-tetraethyl-1-dodecene (syndiotactic)

57

29

110

69

112 97

41

168

C13 : 2,4,6-triethyl-1,6-heptadiene

C13 : 2,4-diethyl-6-methyl-1-octene 41

139 125

153 125139

181 167

210

251

22

Tsuge, Ohtani and Watanabe

006 Poly(4-methyl-1-pentene); PMP CH2CH(CH2CH(CH3)CH3)

n

C18

C4 C3 TIC

C20 C24 C19

C12 C6

C7 C8

C10 C’10

C11 C13 C14

0

C30

C36

C43 C37

10

Peak Notation

Assignment of Main Peaks

C3 C4 C6 C7 C8 C10’ C10

propane + propylene 1-butene 4-methyl-1-pentene 2, 4-dimethyl-1-pentene 6-methyl-1-heptene 2-isobutyl-4-methyl-1-pentene ? 8-methyl-1-nonene ? 2, 8-dimethyl-4-nonene ? 2, 8-dimethyl-3-nonene ? 2, 8-dimethylnonane 2-isobutyl-6-methyl-1-heptene (dimer) 2-isobutyl-4, 6-dimethyl-1-heptene 2-isobutyl-8-methyl-1-nonene ? 2, 4-diisobutyl-8-methyl-1-nonene (trimer) 2, 4-diisobutyl-6, 8-dimethyl-1-nonene C20H40 2, 4, 6-triisobutyl-10-methyl-1-undecene 2, 4, 6, 8-tetraisobutyl-12-methyl-1-tridecene

C11 C12 C13 C14 C18 C19 C20 C24 C30

C49

C55

C61 30 [min]

20

Molecular Retention Weight Index

[ Related Reference ] 1) Shimono, T.; Tanaka, M.; Shono, T. J. Anal. Apply. Pyrolysis 1980, 1, 189.

44; 42 56 84 98 112 140 ? 140 ? 154 ? 154 ? 156 168 182 194 ? 252 266 280 336 420

300 388 548 638 756 886 960 1016 1023 1031 1088 1119 1288 1497 1523 1693 1861 2194

Relative Intensity 20.0 100.0 29.5 19.6 15.4 6.6 6.3 3.3 5.9 4.7 18.4 6.7 5.3 79.8 13.7 21.4 15.1 10.8

23

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

006

EGA thermogram

Averaged mass spectrum 41 57 69

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

83 111

97

123 50

137

100

154

182 193

167

150

207 250 [m/z]

200

( m/z range : 29 - 600 amu )

C4 : 1-butene

C6 : 4-methyl-1-pentene 41

41

56 56 69

84

C8 : 6-methyl-1-heptene

C7 : 2,4-dimethyl-1-pentene 56

55

41

69

41

70 83

30

C12 : 2-isobutyl-6-methyl-1-heptene (dimer)

30

112

C18 : 2,4-diisobutyl-8-methyl-1-nonene (trimer) 57

56 43

41

97

84

98

69 111

83

83

69

97 29

126

57 69

167

195

252

C20 : C20H40

111

83

126 139

154 168

C19 : 2,4-diisobutyl-6,8-dimethyl-1-nonene 43

154

29

97 111

43

57 69 111 83

97

29

97

125

182

168 137 153

29

139

C24 : 2,4,6-triisobutyl-10-methyl-1-undecene

197

223

280

C30 : 2,4,6,8-tetraisobutyl-12-methyl-1-tridecene

57 43

154167

125

205

57 69

43

111 83 97

69

111 85 97

182

125 139

154168

238 251

279

29

154 168 125 139 182 210 196

237 265 251

322

24

Tsuge, Ohtani and Watanabe

007 Isobutylene-isoprene rubber; IIR CH2C(CH3)2

CH2C(CH3)

CHCH2

n

C12 C4 C16 C8 C7

C20

C24 C28

C10 C9

C11

C13

C19

C15

C23

C27

C32 C31

C36 C35

C39

C40 20

10

TIC

0

10

Peak Notation

Assignment of Main Peaks

C4 C7

1-butene 2, 4-dimethyl-1, 3-pentadiene 2, 4, 4-trimethyl-1-pentene (dimer) 2, 4, 4-trimethyl-2-pentene 2, 2, 4, 4-tetramethylpentane 2, 2, 4, 4-tetramethyl-1-pentene 2, 4, 6-trimethyl-1, 3-heptadiene 2, 4, 4, 6-tetramethyl-1-heptene 2, 4, 4, 6-tetramethyl-2-heptene 2, 4, 4, 6, 6-pentamethyl-1-heptene (trimer) 2, 4, 4, 6, 6-pentamethyl-2-heptene C13H24 ? 2, 4, 4, 6, 6, 8-hexamethyl-1-nonene 2, 4, 4, 6, 6, 8-hexamethyl-2-nonene 2, 4, 4, 6, 6, 8, 8-heptamethyl-1-nonene (tetramer) 2, 4, 4, 6, 6, 8, 8-heptamethyl-2-nonene

C8 C9 C10 C11 C12 C13 C15 C16 C 20

30 [min]

20

2,4,4,6,6,8,8,10,10-nonamethyl-1-undecene 2,4,4,6,6,8,8,10,10-nonamethyl-2-undecene

[ Related References ] 1) Tsuchiya, Y.; Sumi, K. J. Polym. Sci., Part A1 1969, 7, 813. 2) Warren, D.; Gates, S.; Driscoll, L. J. Polym. Sci., Part A1 1971, 9, 717. 3) Seeger, M.; Cantow, H. -J. Makromol. Chem. 1975, 176, 2059. 4) Kiran, E.; Gillham, J. K. J. Appl. Polym. Sci. 1976, 20, 2045. 5) Smith, D. A.; Youren, J. W. Br. Polym. J. 1976, 8, 101. 6) Grimbley, M. R.; Lehrle, R. S. Polym. Degrad. Stab. 1995, 49, 223. 7) Grimbley, M. R.; Lehrle, R. S. Polym. Degrad. Stab. 1995, 48, 441.

Molecular Retention Weight Index 56 96 112 112 128 126 138 154 154 168 168 180 ? 210 210 224 224 280 280

398 702 710 726 769 774 873 970 984 1040 1065 1190 1289 1320 1368 1403 1703 1741

Relative Intensity 100.0 5.9 8.5 6.1 1.7 3.1 4.7 2.3 1.8 18.9 4.2 3.2 3.6 3.0 9.2 5.8 8.2 3.8

25

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

007

EGA thermogram

Averaged mass spectrum 97 41 57

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

69

83

50

113

123

137

100

155

168

150

250 [m/z]

200

( m/z range : 29 - 600 amu )

C4 : 1-butene

C8 : 2,4,4-trimethyl-1-pentene 41

57 56 41 29

29

C8 : 2,4,4-trimethyl-2-pentene

112

97

69

81

C10 : 2,4,6-trimethyl-1,3-heptadiene 95

97 55

110

67

41

112

69

41

79

30

C12 : 2,4,4,6,6-pentamethyl-1-heptene (trimer)

57

55 41

41 69 81

112

69

97

41 111

224

C20 : 2,4,4,6,6,8,8,10,10-nonamethyl-1-undecene

69

29

169

57

97 41 69 81

153

C20 : 2,4,4,6,6,8,8,10,10-nonamethyl-2-undecene

57 41

113

83 125 137

97

29

168

57

57 69 81

113

83

C16 : 2,4,4,6,6,8,8-heptamethyl-2-nonene (tetramer)

97

29

97

29

168

C16 : 2,4,4,6,6,8,8-heptamethyl-1-nonene (tetramer)

41

77

C12 : 2,4,4,6,6-pentamethyl-2-heptene (trimer)

97

29

55

30

111

153

280

29

69

113

83 123 137 153

169

224

26

Tsuge, Ohtani and Watanabe

2.2.2 Vinyl polymers with ethylene units (copolymers) 008 Ethylene-propylene copolymer; P(E-P) CH2CH2 C10

C’9

C11

C’12

C12

C’11

C’14 C’15 C15 C14 C16

C’10

CH2CH(CH3 )

n

C18 C20 C22 C24 C26 C28 C30 C32 C34

C3 C4 TIC

C36

C8 C5 C6

10

20

C9

C7

0

10

Peak Notation

Assignment of Main Peaks

C3 C4 C5 C6 C7 C8 C9’

propylene 1-butene 1-pentene 1-hexene 1-heptene 2-methylheptene 2, 4-dimethyl-1-heptene (P trimer) 1-nonene 2, 4, 6-trimethyl-1-heptene n-nonane 4-methylnonane 2-methyl-1-nonene 1-decene dimethylnonene dimethylnonene 2, 4, 6-trimethyl-1-nonene (P tetramer; meso form) 1-undecene 2-methyl-1-undecene 1-dodecene n-dodecane 2, 6, 8-trimethyl-1-undecene 2, 4, 6, 8-tetramethyl-1-undecene (isotactic) (P pentamer) 2, 4, 6, 8-tetramethyl-1-undecene (syndiotactic) 1-tetradecene

C9 C10’ C10 C11’ C12’ C11 C12 C14’ C15’ C14

30 [min]

20

Molecular Retention Weight Index 42 56 70 84 98 112 126 126 140 128 142 140 140 154 154 168 154 168 168 170 196 210 210 196

295 385 492 585 690 787 844 893 896 900 964 987 992 1037 1047 1083 1092 1186 1192 1200 1290 1311 1329 1394

[ Related References ] 1) Michajlov, L.; Zugenmaier, P.; Cantow, H.-J. Polymer 1968, 9, 325. 2) Michajlov, L.; Cantow, H. -J.; Zugenmaier, P. Polymer, 1971, 12, 70. 3) Tsuge, S.; Sugimura, Y.; Nagaya, T. J. Anal. Appl. Pyrolysis 1980, 1, 221. 4) Wampler, T.; Zawodny, C.; Mancini, L.; Wampler, J. J. Anal. Appl. Pyrolysis 2003, 68-69, 25

Relative Intensity 100.0 60.3 43.6 25.5 39.9 90.7 9.8 8.6 6.3 5.9 3.7 17.3 7.0 7.3 11.9 14.9 7.1 10.7 8.7 15.0 13.4 5.2 11.8

27

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

008

EGA thermogram

Averaged mass spectrum 41 55 69 100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

83 97

111

30 50

125

139

100

154 165

182

196

150

250 [m/z]

200

( m/z range : 29 - 600 amu )

C5 : 1-pentene

C6 : 1-hexene 39

39

56 55

29

84

69

29

70

C9’ : 2,4-dimethyl-1-heptene (P-trimer)

C8 : 2-methylheptene 56

43

41

70 55

29

29

83

69

126

112 84

97

111

91

C9 : 1-nonene

C10’ : 4-methylnonane 41

41

57

29

55

29

70

98

69 83

97 81

126

104

112

127

C12’ : 2,4,6-trimethyl-1-nonene (P-tetramer; meso form)

C10 : 1-decene 41

41

55

29

55

69

29

70 83

83

97 111

111 125

97

168

139

140

C15’ : 2,4,6,8-tetramethyl-1-undecene (isotactic) C14’ : 2,6,8-trimethyl-1-undecene 41

29

142

(P-pentamer) 43 55

55

69

83

97

69

83

111

29 97

140 109

125

196

125 141

154

28

Tsuge, Ohtani and Watanabe

009 Ethylene-propylene-diene rubber; EPDM CH2CH2

C3

C5

CH2CH(CH3)

X

n

C4

C6 C7

C10

C8

C11 C9

C12 C13

C15 C17

C20

C25

TIC

0

10

Peak Notation

Assignment of Main Peaks

C3 C4 C5 C6 C7 C8 C9 C10 C11 C12 C13

propylene 1-butene 1-pentene 1-hexene 1-heptene 2-methyl-1-heptene 1-nonene 1-decene 1-undecene 2-methyl-1-undecene 1-tridecene

30 [min]

20

Molecular Retention Index Weight 42 56 70 84 98 112 126 140 154 168 182

[ Related References ] 1) Smith, D. A.; Youren, J. W. Br. Polym. J. 1976, 8, 101. 2) Tsuge, S.; Sugimura, Y.; Nagaya, T. J. Anal. Appl. Pyrolysis 1980, 1, 221. 3) Kretzschmar, H. -J.; Tobisch, K.; Gross, D. Kautsch. Gummi Kunstst. 1987, 40, 447. 4) Yamada, T.; Okumoto, T.; Ohtani, H.; Tsuge, S. Rubber Chem. Technol. 1990, 63, 191. 5) Yamada, T.; Okumoto, T.; Ohtani, H.; Tsuge, S. Rubber Chem. Technol. 1991, 64, 708.

295 382 492 592 693 788 892 992 1091 1186 1292

Relative Intensity 100.0 41.1 32.8 34.4 17.3 7.7 11.1 8.8 7.7 4.2

29

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

009

EGA thermogram

Averaged mass spectrum 55

41

69 100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

83

97 111 125

50

137

151

100

168 200 [m/z]

150

( m/z range : 29 - 600 amu )

C3 : propylene

C4 : 1-butene 41

41

56

29

29

C5 : 1-pentene

C6 : 1-hexene 56

42 41

55

70 69

84

104

126

29 29

C8 : 2-methyl-1-heptene

C9 : 1-nonene 41

56

56

69 41 84

29

69

29

97

112 84

97

C10 : 1-decene

C11 : 1-undecene 41

41

55

55

70

70

83 83

29

97 29

97 111

111

140

126

154

125

140 154

C13 : 1-tridecene

C12 : 2-methyl-1-undecene

41

56

55 69

83 97

41 29

69 83

97

112 125

140 153 168

29

111 182

30

Tsuge, Ohtani and Watanabe

010 Ethylene-methyl methacrylate copolymer; P(E-MMA) CH2CH2

CH2C(CH3)(COOCH3)

n

C10 C11

C14 C15

C12 C6

C9

MMA LB C7

C13

C26

C30 C32

C8

a

C28

C24

C20 C22

b TIC

C18

C16

c

C34 C36

d

0

C39 10

Peak Notation LB C6 C7 MMA a C8

C9 b C10 c C11 d C14 C20 C30 C39

30 [min]

20

Assignment of Main Peaks

Molecular Weight

propylene, isobutene 1-butene CH2=CH(CH2)3CH3 CH2=CH(CH2)4CH3 CH3(CH2)5CH3 CH2=C(CH3)COOCH3 unidentified* CH2=CH(CH2)5CH3 CH3(CH2)6CH3 CH2=CH(CH2)5CH=CH2 CH2=CH(CH2)6CH3 CH3(CH2)7CH3 unidentified* CH2=CH(CH2)7CH3 CH3(CH2)8CH3 2-methyloctanoic acid methylester CH2=CH(CH2)7CH=CH2 CH2=CH(CH2)8CH3 CH3(CH2)9CH3 unidentified* CH2=CH(CH2)10CH=CH2 CH2=CH(CH2)11CH3 CH3(CH2)12CH3 CH2=CH(CH2)17CH3 CH2=CH(CH2)27CH3 CH2=CH(CH2)36CH3

42, 56 56 84 98 100 100 112 114 124 126 128 140 142 172 152 154 156 194 196 198 280 420 546

* bonding in MMA and C1-C5 alkyls.

[ Related Reference ] 1) Sugimura, Y.; Tsuge, S.; Takeuchi, T. Anal. Chem. 1978, 50, 1173.

Retention Relative Intensity Index 298 385 591 693 700 710 777 790 800 882 895 900 982 991 1000 1054 1085 1092 1100 1151 1385 1392 1400 1993 2995 3895

100.0 76.1 35.6 8.2 45.8 8.1 26.5 8.3 4.9 25.4 4.7 7.5 47.6 5.1 13.9 7.9 35.7 7.0 6.5 12.2 31.9 5.4 16.9 33.1 18.6

31

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

010

EGA thermogram

Averaged mass spectrum 41 55 100

69

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

88 97 111 30 50

125

139

157

100

200 [m/z]

150

( m/z range : 29 - 600 amu )

C7 : 1-heptene

C6 : 1-hexene 41

56

56

41

70

29

29

84

69

98 83

MMA : methyl methacrylate

C8 : 1-octene

41

55

41 69

70

O

O

100 59

29

83

29

112

85

97

C11: 1-undecene

C10 : 1-decene 41

41

55

55

70

70 83 83

29

29

97 111

111

140

C14 : 1-tetradecene 41

97 154

C20 : 1-eicosene

55

83 97

43 57 69

126

83 69

97

111 29

111

125

29 125

140 154 168

57

83 97

69 43 111

29

280

(mixed with 1,38-nonatriacontadiene and n-nonacosane)

(mixed with 1,29-triacontadiene and n-triacontane) 43

252

C39 : 1-nonatriacontene

C30 : 1-triacontene 57

139 153 168182

196

125 153 167

418

29

71 97

111 125 139 153 167

504

545 552

32

Tsuge, Ohtani and Watanabe

011 Ethylene-acrylic acid copolymer; P(E-AA) CH2CH2

CH2CH(COOH)

n

C10

C11

C14 C15

C12 C13

C16 C18

C9

C20

C22

C24 C28 C26

C30 C32

LB C6

C7

C8

C34

C36

TIC

0

10

Peak Notation LB C6 C7 C8

C9

C10

C11

C13

C14

C18 C34

30 [min]

20

Assignment of Main Peaks

Molecular Retention Index Weight

propylene + propane 1-butene CH2=CH(CH2)3CH3 CH2=CH(CH2)4CH3 CH3(CH2)5CH3 CH2=CH(CH2)5CH3 CH3(CH2)6CH3 CH2=CH(CH2)5CH=CH2 CH2=CH(CH2)6CH3 CH3(CH2)7CH3 CH2=CH(CH2)6CH=CH2 CH2=CH(CH2)7CH3 CH3(CH2)8CH3 CH2=CH(CH2)7CH=CH2 CH2=CH(CH2)8CH3 CH3(CH2)9CH3 CH2=CH(CH2)9CH=CH2 CH2=CH(CH2)10CH3 CH3(CH2)11CH3 CH2=CH(CH2)10CH=CH2 CH2=CH(CH2)11CH3 CH3(CH2)12CH3 CH2=CH(CH2)14CH=CH2 CH2=CH(CH2)15CH3 CH3(CH2)16CH3 CH2=CH(CH2)31CH3

42; 44 56 84 98 100 112 114 124 126 128 138 140 142 152 154 156 180 182 184 194 196 198 250 252 254 476

300 385 597 694 700 794 800 882 893 900 984 993 1000 1084 1093 1100 1285 1293 1300 1386 1393 1400 1787 1794 1800 3398

Relative Intensity 100.0 84.5 38.3 16.7 36.2 13.4 5.2 36.7 9.5 8.2 68.8 8.1 8.4 50.5 10.8 10.8 35.9 8.5 10.5 47.6 8.3 14.7 34.4 8.4 41.1

33

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

011

EGA thermogram

Averaged mass spectrum 41 55 100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

71 83

97 111

30 50

125

138

152

100

165 200 [m/z]

150

( m/z range : 29 - 600 amu )

C7 : 1-heptene

C6 : 1-hexene 41

41

56

29 56

29

70 84

69

83

C8 : 1-octene

98

C9 : 1-nonene 41

41

55

29

55

29 70

69 83 97

83

112

C10 : 1-decene

97

104

126

C11 : 1-undecene

41

41

55

55

29

29

70

69 83

97

111

83 97 111

140

126

154

125

140 154 168

C14 : 1-tetradecene

C13 : 1-tridecene 41

41 55 55

29

69

83

29

69

97

83

97 111

111 125 139

154

182

196

C34 : 1-tetratriacontene (mixed with 1,33-tetratriacontadiene and n-tetratriacontane)

C18 : 1-octadecene 41

43

57

55 69 69 83 97 29

111 125

29 139 153 168

224

97 83 111 125 153 195 139 165 207

269 282

343 356

405 429

34

Tsuge, Ohtani and Watanabe

012 Ethylene-vinyl acetate copolymer; EVA CH2CH2

CH2CH(OCOCH3)

n

C10 C11

LB

C14 C15

C12 C13

C16 C18

C6 C9

AC

C20

C24 C26 C22 C28

C7

C30

C8

C32 C34

TIC

0

10

Peak Notation LB C6 AC C7

C8

C9 C10

C11

C12

C14

C16

C19 C21

C36

30 [min]

20

Assignment of Main Peaks

Molecular Retention Index Weight

propylene, butane etc. CH2=CH(CH2)3CH3 CH3COOH CH2=CH(CH2)4CH3 CH3(CH2)5CH3 CH2=C(CH2)4CH=CH2 CH2=CH(CH2)5CH3 CH3(CH2)6CH3 CH2=CH(CH2)6CH3 CH3(CH2)7CH3 CH2=CH(CH2)6CH=CH2 CH2=CH(CH2)7CH3 CH3(CH2)8CH3 CH2=CH(CH2)7CH=CH2 CH2=CH(CH2)8CH3 CH3(CH2)9CH3 CH2=CH(CH2)8CH=CH2 CH2=CH(CH2)9CH3 CH3(CH2)10CH3 CH2=CH(CH2)10CH=CH2 CH2=CH(CH2)11CH3 CH3(CH2)12CH3 CH2=CH(CH2)12CH=CH2 CH2=CH(CH2)13CH3 CH3(CH2)14CH3 CH2=CH(CH2)15CH=CH2 CH2=CH(CH2)16CH3 CH3(CH2)17CH3 CH2=CH(CH2)19CH3

42, 58 84 60 98 100 110 112 114 126 128 138 140 142 152 154 156 166 168 170 194 196 198 222 224 226 264 266 268 294

[ Related Reference ] 1) Haeussler, L.; Pompe, G.; Albrecht, V.; Voigt, D. J. Thermal Anal. 1998, 52, 131.

298 595 606 689 700 782 792 800 894 900 986 994 1000 1087 1095 1100 1188 1195 1200 1388 1396 1400 1590 1593 1600 1892 1898 1900 2094

Relative Intensity 81.8 51.4 100.0 27.7 8.9 4.0 23.5 10.7 25.2 7.6 6.5 44.8 8.3 7.1 33.9 8.3 6.1 24.4 9.7 5.8 27.7 7.7 6.4 21.6 10.3 7.7 21.3 9.8 35.7

35

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

012

EGA thermogram

Averaged mass spectrum 43 55 100

69

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

83

97

29

111 50

123

135

149

100

165 200 [m/z]

150

( m/z range : 29 - 600 amu )

AC : acetic acid

C8 : 1-octene 43

43

O

55

60

70

OH 29

83

29 67

112

97

82

C9 : 1-nonene

C10 : 1-decene 43

41

56

56

70 69

29

29 83

83 97

97

111

126

108

C12 : 1-dodecene

C11 : 1-undecene 43 55

43 55 70

69 83 29

97 111

111 126 134

125

154

140

168

C16 : 1-hexadecene

C14 : 1-tetradecene

43

43 55

55 83 97

83 69

69

97

29

111

29

111 125

125 140 154 168

139 154 168

196

196

224

C21 : 1-heneicosene

C19 : 1-nonadecene

43

57

97

83

83 69

69 111

29

83 97

29

43 57

140

125 139 154168182

29 238

266

97

111

125 139 153 168 182 196

36

Tsuge, Ohtani and Watanabe

013 Ethylene-ethyl acrylate copolymer; P(E-EA) CH2CH2

CH2 CH(COOC2 H5)

n

C10 C14 C11

C15 C12

C16 C13

C28 C18 C20

C9

C26 C22 C24

C30 C32

LB C6 TIC

C8 C7

C34 a

C36

b

0

10

30 [min]

20

Peak Notation

Assignment of Main Peaks

LB C6

propylene, 1-butene 42, 56 CH2=CH(CH2)3CH3 84 CH2=CH(CH2)4CH3 98 CH3(CH2)5CH3 100 CH2=CH(CH2)4CH=CH2 110 CH2=CH(CH2)5CH3 112 CH3(CH2)6CH3 114 ethyl (2E)-2-methyl-2-butenoate CH3CH=C(COOC2H5)CH3 128 CH2=CH(CH2)4CH=CH2 124 CH2=CH(CH2)6CH3 126 CH3(CH2)7CH3 128 CH2=CH(CH2)6CH=CH2 138 CH2=CH(CH2)7CH3 140 CH3(CH2)8CH3 142 unidentified* CH2=CH(CH2)7CH=CH2 152 CH2=CH(CH2)8CH3 154 CH3(CH2)9CH3 156 CH2=CH(CH2)8CH=CH2 166 CH2=CH(CH2)9CH3 168 CH3(CH2)10CH3 170 CH2=CH(CH2)9CH=CH2 180 CH2=CH(CH2)10CH3 182 CH3(CH2)11CH3 184 CH2=CH(CH2)11CH=CH2 208 CH2=CH(CH2)12CH3 210 CH3(CH2)13CH3 212 *bonding in ethyl acrylate and alkyls

C7

C8 a C9

C10 b C11

C12

C13

C15

[ Related Reference ] 1) McNeil, I. C.; Mohammed, M. H. Polym. Degrad. Stab. 1995, 48, 175.

Molecular Retention Weight Index 300 593 694 700 782 794 800 876 885 893 900 984 993 1000 1056 1084 1093 1100 1185 1193 1200 1286 1294 1300 1486 1494 1500

Relative Intensity 100.0 74.9 33.6 14.9 5.4 32.4 16.0 5.1 5.0 30.7 10.7 5.6 61.4 7.5 6.7 11.7 48.2 9.6 10.1 38.0 9.7 11.8 35.3 8.0 12.9 40.3 9.3

37

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

013

EGA thermogram

Averaged mass spectrum 41 55 100

83

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

69 97 111

125

31 50

100

139

152

169 179

194

150

250 [m/z]

200

( m/z range : 29 - 600 amu )

C6 : 1-hexene

C8 : 1-octene 41

41

56

55

29

70

29 69

83

84

112

97

a : ethyl(2E)-2-methyl-2-butenoate

C9 : 1-nonene O

55 29

41

O

83

55

39

29

113 100

69 83

67

97

128

104

C10 : 1-decene

126

b : unidentified 29 39

41

87

55

55

111

70

29

69 83

128

99

97 111 125

156 141

140

C12 : 1-dodecene

C11 : 1-undecene

41

41

55

55 29

69

69

29

83

83

97 111

126

97 111

154

C13 : 1-tridecene

125

140

168

C15 : 1-pentadecene 41

41

55 55 29

69

83

69 83 97 29

97

111

111 125

141 154

182

125

140 154 169 182

210

38

Tsuge, Ohtani and Watanabe

014 Ethylene-vinyl alcohol copolymer; P(E-VA) CH2CH2

CH2CH(OH)

n

c

A

a

d e

b B

DF TIC

C

20

10

H DP

0

10

Peak Notation

Assignment of Main Peaks

A B DF C DP H a b c d e

acetaldehyde acetone 2,5-dihydrofuran crotonaldehyde 6-methyl-3,4-dihydro-2H-pyran 3-hexene-2,5-diol

kinds of aldehyde?

30 [min]

20

Molecular Retention Weight Index 44 58 70 70 98 116 -

408 465 571 637 772 997 1183 1200 1269 1388 2010

Relative Intensity 39.6 20.6 2.6 4.6 2.9 100.0 10.9 5.3 11.5 15.8 7.3

39

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

014

EGA thermogram

Averaged mass spectrum 43

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

55

29

69 81

98

50

105

123

139

149

100

200 [m/z]

150

( m/z range : 29 - 600 amu )

A : acetaldehyde

B : acetone 43

44

O

O

58 30

30

C : crotonaldehyde

DF : 2,5-dihydrofuran 39

39

O

70

O

70 50

30

DP : 6-methyl-3,4-dihydro-2H-pyran 43

50

30

H : 3-hexene-2,5-diol 43

55

O

OH

98 OH

83

58 31

70

30

71

98 83

112

c : unidentified

a : unidentified 69

41

43

55 58 31 84 68

31 97

83

112

43

55

126

95

71 55

71 97

31

111

e : unidentified

d : unidentified 41

97

81

81

111

31 111

170 125 137 152

129 133

151 169 185197

224

40

Tsuge, Ohtani and Watanabe

015 Polyethylene ionomer; IO CH2CH2

CH2C(CH3)(COO)

n

Zn OCO C10

C11 C12

C14 C15 C13

C16 C18 C20 C22 C26 C28 C24

C9

LB C6 C7

C30

C8

C32 C34 C36

TIC

0

10

Peak Notation LB C6 C7

C8

C9

C10

C11

C12

C13

C14

C18 C22

30 [min]

20

Assignment of Main Peaks

Molecular Retention Index Weight

propylene, 1-butene 2-butene CH2=CH(CH2)3CH3 CH2=CH(CH2)4CH3 CH3(CH2)5CH3 CH2=CH(CH2)4CH=CH2 CH2=CH(CH2)5CH3 CH3(CH2)6CH3 CH2=CH(CH2)5CH=CH2 CH2=CH(CH2)6CH3 CH3(CH2)7CH3 CH2=CH(CH2)6CH=CH2 CH2=CH(CH2)7CH3 CH3(CH2)8CH3 CH2=CH(CH2)7CH=CH2 CH2=CH(CH2)8CH3 CH3(CH2)9CH3 CH2=CH(CH2)8CH=CH2 CH2=CH(CH2)9CH3 CH3(CH2)10CH3 CH2=CH(CH2)9CH=CH2 CH2=CH(CH2)10CH3 CH3(CH2)11CH3 CH2=CH(CH2)10CH=CH2 CH2=CH(CH2)11CH3 CH3(CH2)12CH3 CH2=CH(CH2)14CH=CH2 CH2=CH(CH2)15CH3 CH3(CH2)16CH3 CH2=CH(CH2)19CH3

42, 56 56 84 98 100 110 112 114 124 126 128 138 140 142 152 154 156 166 168 170 180 182 184 194 196 198 250 252 254 308

300 385 593 693 700 783 792 800 884 892 900 983 992 1000 1083 1091 1100 1184 1192 1200 1284 1292 1300 1384 1392 1400 1786 1793 1800 2194

Relative Intensity 100.0 60.5 29.4 18.0 4.7 26.5 12.3 4.2 22.0 7.9 8.0 36.3 8.9 9.0 30.7 10.0 8.6 25.8 12.4 10.3 25.9 7.2 10.0 30.8 10.7 13.5 25.5 7.9 40.1

41

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

015

EGA thermogram

Averaged mass spectrum 41 55 100

69

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

83

97 111

30 50

124

100

139

155 165

180

150

250 [m/z]

200

( m/z range : 29 - 600 amu )

C8 : 1-octene

C6 : 1-hexene 56

41

41

55 70

84

69

83

29

29

112 97

C10 : 1-decene

C9 : 1-nonene 56

41

41 55

70

69

83

29

97 111

126

104

125

140

C12 : 1-dodecene

C11 : 1-undecene 41

83

29

97

41

55

55

70

69 83

83

97 97

29

29 111

111 126

154

125

C13 : 1-tridecene 41

140

168

C14 : 1-tetradecene 41

55 69

55 69

83

83 97

97

29

125

140 154

125

182

C18 : 1-octadecene

97 55 83 43 69

43 69 111

29

196

139 153 168

C22 : 1-docosene

83 97

55

111

29

111

111 125 139153168

224

252

29

125 139 153 182 167196

308

403

553

42

Tsuge, Ohtani and Watanabe

2.2.3 Vinyl polymers with styrene units 016 Polystyrene; PS CH2CH(C6 H5)

n

SSS

SS S AB

D4

D2 D3 D1

αS

D5 D7 D6

10

20

TIC

T 0

10

30 [min]

20

Peak Notation

Assignment of Main Peaks

Molecular Retention Weight Index

T S AB αS D1 D2 D3 D4 SS D5 D6 D7 SSS

toluene 92 styrene 104 allylbenzene 118 α methylstyrene 118 C(Ph)-C-Ph 182 C-C(Ph)-C-Ph 196 C=C-C(Ph)-C-Ph 208 C(Ph)-C-C-Ph 196 C=C(Ph)-C-C-Ph (dimer) 208 C=C(Ph)-C-C(Ph)-C 222 C(Ph)=C-C-C-Ph 208 C=C(Ph)-C-C-C(Ph)=C 234 C=C(Ph)-C-C(Ph)-C-C-Ph (trimer) 312 * bonding hydrogen is omitted ; Ph represents C6H5 (phenyl group)

765 898 952 988 1542 1579 1647 1678 1749 1759 1851 1924 2488

Relative Intensity 1.9 100.0 0.3 0.7 0.6 0.3 0.2 0.3 10.2 0.9 1.2 1.0 26.7

[ Related References ] 1) Tsuge, S.; Okumoto, T.; Takeuchi, T. J. Chromatogr. Sci. 1969, 7, 250. 2) Sugimura, Y.; Tsuge, S. Anal. Chem. 1978, 50, 1968. 3) de Amorim, M. T. S. P.; Bouster, C.; Vermande, P.; Veron, J. J. Anal. Appl. Pyrolysis 1981, 3, 19. 4) Sugimura, Y.; Nagaya, T.; Tsuge, S. Macromolecules 1981, 14, 520. 5) Schroeder, U. K. O.; Ebert, K. H. Makromol. Chem. 1984, 185, 991. 6) Dean, L.; Groves, S.; Hancox, R.; Lamb, G.; Lehrle, R. S. Polym. Degrad. Stab. 1989, 25, 143. 7) Ohtani, H.; Yuyama, T.; Tsuge, S.; Plage, B.; Schulten, R. -H. Eur. Polym. J. 1990, 26, 893. 8) Atkinson, D. J.; Lehrle, R. S. J. Anal. Appl. Pyrolysis 1991, 19, 319. 9) Gardner, P.; Lehrle, R. Eur. Polym. J. 1993, 29, 425. 10) Ito, Y.; Ohtani, H.; Ueda, S.; Nakashima, Y.; Tsuge, S. J. Polym. Sci., Part A 1994, 32, 383. 11) Nonobe, T.; Ohtani, H.; Usami, T.; Mori, T.; Fukumori, H.; Hirata, Y.; Tsuge, S. J. Anal. Appl. Pyrolysis 1995, 33, 121. 12) Yang, M.; Shibasaki, Y. J. Polym. Sci. A, Polym. Chem. 1998, 36, 2315. 13) Liu,Y.; Guo, S.; Qian, J. Petrol. Sci. Technol. 1999, 17, 1089.

43

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

016

EGA thermogram

Averaged mass spectrum 104

91 78

100

200

300

400

500

39

600

700 ºC

programming rate: 20ºC/min

51 117

63

130 143 50

100

165 179 194 207 221

150

200

250

350 [m/z]

300

( m/z range : 29 - 600 amu )

S : styrene

T : toluene

104

91

103

78 51 39

65

51

63

39

89

αS : α-methylstyrene

D1 : 1,2-diphenylethane 91

118 117 103 78

182

51

39

65

63

39

D2 : propane-1,2-diyldibenzene

51

77

39

51

65

77

91

91 152 165 178

39 51

196

104

65 77

141152 165 180

105

91

208

130 193

D6 : (E)-1-butene-1,4-diyldibenzene

D5 : 1-pentene-2,4-diyldibenzen

77

128 141 152 165

SS : 3-butene-1,3-diyldibenzene (styrene dimer)

105

32

104

117

91

115

115

194

39 51 65

144 165 152

179 205

222

D7 : hexa-1,5-diene-2,5-diyldibenzene

39 51 65 77

208 139 152 165 178 189

SSS : 5-hexene-1,3,5-triyltribenzene (styrene trimer) 91

130

115 117

91 77 39

51 65

194 207

143 234 156 178 165 189 205 219

39

51 6577

115

221

297 312

44

Tsuge, Ohtani and Watanabe

017 Styrene-methyl acrylate copolymer; P(S-MA) CH2CH(C6H5)

CH2CH(COOCH3)

n

SMS

S

SMM MMS MSM SM MS

MM MM’

SS

SSM

MMM

SSS

MS’ 20

10

TIC

M T

αS 10

0

30 [min]

20

Peak Notation

Assignment of Main Peaks

M T S αS MM’ MM MS’ MS SM MMM SS MSM MMS SMM

methyl acrylate 86 toluene 92 styrene 104 α-methylstyrene 118 C(COOC)-C-C-COOC 160 C=C(COOC)-C-C-COOC (M dimer) 172 C(COOC)-C-C-Ph 178 C=C(COOC)-C-C-Ph (hybrid dimer) 190 C=C(Ph)-C-C-COOC 190 C=C(COOC)-C-C(COOC)-C-C-COOC (M trimer) 258 C=C(Ph)-C-C-Ph (S dimer) 208 C=C(COOC)-C-C(Ph)-C-C(COOC) 276 C=C(COOC)-C-C(COOC)-C-C-Ph 276 C=C(Ph)-C-C(COOC)-C-C-COOC (hybrid trimer) 276 C=C(Ph)-C-C(Ph)-C-C-COOC 294 + C=C(COOC)-C-C(Ph)-C-C-Ph 294 C=C(Ph)-C-C(COOC)-C-C-Ph 312 C=C(Ph)-C-C(Ph)-C-C-Ph (S trimer) * bonding hydrogen is omitted ; Ph represents C6H5 (phenyl group)

SSM SMS SSS

Molecular Retention Weight Index

Relative Intensity

610 766 892 987 1118 1189 1386 1438 1465 1659 1737 1913 1925 1932

12.6 1.6 100.0 1.7 1.1 2.1 2.0 5.4 7.4 6.1 0.5 11.5 10.8 20.1

2191

8.1

2213 2482

25.1 0.7

[ Related References ] 1) Tsuge, S.; Hiramitsu, S.; Horibe, T.; Yamaoka, M.; Takeuchi, T. Macromolecules 1975, 8, 721. 2) Blazso, M.; Varhegyi, G. Eur. Polym. J. 1978, 14, 625. 3) Tsuge, S.; Kobayashi, T.; Sugimura, Y.; Nagaya, T.; Takeuchi, T. Macromolecules 1979, 12, 988. 4) Blazso, M.; Ujszaszi, K.; Jakab, E. Chromatographia 1980, 13, 151.

45

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

017

EGA thermogram

Averaged mass spectrum 91 104 117 78

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

129

51

65

39

143

31 50

100

212 216

177 190 157 170

150

244

200

263

294 300 [m/z]

250

( m/z range : 29 - 600 amu )

M : methyl acrylate

S : styrene 55

104

O

O 42

29

103

78

85

51 74

39

68

MMM : trimethyl hex-5-ene-1,3,5-tricarboxylate SM : methyl 4-phenylpent-4-enoate

(M trimer)

131

O

59

O 91

115

O

O

O

167

190 132

63

O

194

106

O

77 51

29 39

O

134

79

125

39

SS : 3-butene-1,3-diyldibenzene (styrene dimer)

227

97

67

29

160 176 159

153

MSM : dimethyl 2-methylene-4-phenylheptanedioate

91

117 O

O

O

O

177 39 51

115 130

65 77

91

208 165 180 193

39

MMS : dimethyl 2-methylene-4-phenethylpentanedioate

129

59 77 65

145

216

157 171

244

SMM : dimethyl 2-(2-phenylallyl)pentanedioate

112

142 O

91

O

O

O

O

O

O

O

129

212

115 140

170

77 91 39

65 59 77

129

157

244

213

185 172

29

39

157

59 65

184 244

276

SSM :methyl 4,6-diphenylhept-6-enoate SMS : methyl 2-phenethyl-4-phenylpent-4-enoate

+ methyl 2-methylene-4,6-diphenylhexanoate

91

117 O

O

O

131

O

+

115 O

91

O

115 39 51 65

77

145

177 189

65 207220

262

294

39 51

77

176 190 143 158 171

203

263

294

46

Tsuge, Ohtani and Watanabe

018 Styrene-methyl acrylate alternating copolymer CH2 CH(C6H5 )

CH2CH(COOCH3)

n

SMS S MSM MS SM MM

SS SSM

MS’

20

10

TIC

M T

αS

0

10

30 [min]

20

Peak Notation

Assignment of Main Peaks

M T S αS MM MS’ MS SM SS MSM

methyl acrylate 86 toluene 92 styrene 104 α-methylstyrene 118 C=C(COOC)-C-C-COOC (M dimer) 172 C(COOC)-C-C-Ph 178 C=C(COOC)-C-C-Ph (hybrid dimer) 190 C=C(Ph)-C-C-COOC 190 C=C(Ph)-C-C-Ph (S dimer) 208 C=C(COOC)-C-C(Ph)-C-C-COOC 276 C=C(Ph)-C-C(Ph)-C-C-COOC (hybrid trimer) 294 + C=C(COOC)-C-C(Ph)-C-C-Ph C=C(Ph)-C-C(COOC)-C-C-Ph 294 * bonding hydrogen is omitted ; Ph represents C6H5 (phenyl group)

SSM SMS

Molecular Retention Weight Index

Relative Intensity

615 766 892 983 1189 1385 1438 1465 1737 1913

15.9 3.0 100.0 4.2 1.7 3.1 8.9 7.2 5.6 14.4

2191

0.7

2212

27.8

[ Related Reference ] 1) Tsuge, S.; Kobayashi, T.; Sugimura, Y.; Nagaya, T.; Takeuchi, T. Macromolecules 1979, 12, 988.

47

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

018

EGA thermogram

Averaged mass spectrum 117 91 104 100

78

300

400

500

600

700 ºC

programming rate: 20ºC/min

129

55 39

200

65

177

143 157

31 50

100

171

150

190

203 216

244

200

263 300 [m/z]

250

( m/z range : 29 - 600 amu )

M : methyl acrylate

T : toluene 55

91

O

O 85

42

29

39 68

65

51

89

32

αS : α-methylstyrene

S : styrene

118 117

104

103 103

78

78

51

51

39

63

39

MS' : methyl 4-phenylbutanoate 91

63

MS : methyl 2-methylene-4-phenylbutanoate 91

O

O

O

104

O

74

147 29

43 51

130

178

117

78

29

39

65 51

77

158

115

190

SS : 3-butene-1,3-diyldibenzene (styrene dimer)

SM : methyl 4-phenylpent-4-enoate 131

91

O O

115

91

190

77 29 39

51

159

63

39 51

176

MSM : dimethyl 2-methylene-4-phenylheptanedioate

115 130

65 77

208 180 193

SMS : methyl 2-phenethyl-4-phenylpent-4-enoate 91

117 O

O

O

O

O

O

131 115 177 91 39

59 65 77

129 145

157 171

216 212 230 244

65 39 51

77

143 158

176 190 203 234

263

294

48

Tsuge, Ohtani and Watanabe

019 Styrene-methyl methacrylate copolymer; P(S-MMA) CH2 CH(C6H5)

CH2 C(CH3)(COOCH3 )

SS

S

SMS

n

SSS SSM

SM M

MS’ MS 20

TIC

0

10

30 [min]

20

Peak Notation

Assignment of Main Peaks

M S MS’ MS SM SS

methyl methacrylate 100 styrene 104 C(COOC)=C-C-Ph 176 C=C(COOC)-C-C-Ph (hybrid dimer) 190 C=C(Ph)-C-C(COOC)-C 204 C=C(Ph)-C-C-Ph (S dimer) 208 C=C(Ph)-C-C(Ph)-C-C(COOC)-C 308 (diastereoisomer) C=C(Ph)-C-C(Ph)-C-C(COOC)-C 308 C=C(Ph)-C-C(C)(COOC)-C-C-Ph 308 C=C(Ph)-C-C(Ph)-C-C-Ph (S trimer) 312 * bonding hydrogen is omitted ; Ph represents C6H5 (phenyl group)

SSM SMS SSS

Molecular Retention Weight Index 709 892 1338 1438 1483 1737 2166 2195 2294 2482

[ Related References ] 1) Shimono, T.; Tanaka, M.; Shono, T. J. Anal. Appl. Pyrolysis 1979, 1, 77. 2) Tsuge, S.; Kobayashi, T.; Nagaya, T.; Takeuchi, T J. Anal. Appl. Pyrolysis 1979, 1, 133. 3) Tsuge, S.; Kobayashi, T.; Sugimura, Y.; Nagaya, T.; Takeuchi, T. Macromolecules 1979, 12, 988. 4) Shadrina, N. E.; Dmitrenko, A. V.; Pavlova, V. F.; Ivanchev, S. S. J. Chromatogr. 1987, 404, 183. 5) Dean, L.; Groves, S. ; Hancox, R. ; Lamb, G. ; Lehrle, R. S. Polym. Degrad. Stab. 1989, 25, 143. 6) Atkinson, D. J.; Lehrle, R. S. J. Anal. Appl. Pyrolysis 1991, 19, 319. 7) Wang, F. C.-Y. ; Smith, P. B. Anal. Chem. 1996, 68, 3033. 8) Ohtani, H.; Suzuki, A.; Tsuge, S. J. Polym. Sci., A, Polym. Chem. 2000, 38, 1880. 9) Wang, F. C.-Y. J. Anal. Appl. Pyrolysis 2004, 71, 83.

Relative Intensity 50.1 100.0 0.5 0.3 0.9 1.9 1.3 1.1 1.9 1.8

49

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

019

EGA thermogram

Averaged mass spectrum 104

78

100

103

39

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

69

50

91

131

30 50

145

100

172179

191

221

208

150

250 [m/z]

200

( m/z range : 29 - 600 amu )

M : methylmethacrylate

S : styrene

41

104 O

69

O

100

103

78 51

29

59

85

63

39

MS' : (E)-methyl 4-phenylbut-2-enoate

MS : methyl 2-methylene-4-phenylbutanoate 91

116

O

O

O O

91 31

39

51

176

144

89

65

39

161

51

115 130

65 89

32

SM : methyl 2-methyl-4-phenylpent-4-enoate

145

158

176 190

SS : 3-butene-1,3-diyldibenzene (styrene dimer)

145

91 O

O

117129 77 91

204

39 51 63

39 51

173

115

65 77

130

208 151 165 180 193

SMS : methyl 2-methyl-2-phenethyl-4-phenylpent SSM : methyl 2-methyl-4,6-diphenyl hept-6-enoate

-4-enoate 91

131 O

145 O

O

O

91 118 115

44

65

77

191

115 159

221 208

65 248

276

SSS : 5-hexene-1,3,5-triyltribenzene (styrene trimer) 91

117 3951

6577

129

178

194 207 221

297312

39 51

190

77

204

158172 217

277

50

Tsuge, Ohtani and Watanabe

020 Styrene-methyl methacrylate alternating copolymer CH2CH(C6H5)

CH2C(CH3)(COOCH3)

n

SMS S

SS

MS SM MS’

M

SSM

SSS

10

20

TIC

T 0

10

30 [min]

20

Peak Notation

Assignment of Main Peaks

M T S MS’ MS SM SS

methyl methacrylate 100 toluene 92 styrene 104 C(COOC)=C-C-Ph 176 C=C(COOC)-C-C-Ph (mixture of dimer) 190 C=C(Ph)-C-C(COOC)-C 204 C=C(Ph)-C-C-Ph (S dimer) 208 C=C(Ph)-C-C(Ph)-C-C(COOC)-C 308 (diastereoisomer) C=C(Ph)-C-C(Ph)-C-C(COOC)-C 308 C=C(Ph)-C-C(C)(COOC)-C-C-Ph 308 C=C(Ph)-C-C(Ph)-C-C-Ph (S trimer) 312 * bonding hydrogen is omitted ; Ph represents C6H5 (phenyl group)

SSM SMS SSS

Molecular Retention Weight Index 711 766 892 1338 1437 1482 1736 2166 2194 2294 2480

[ Related Reference ] 1) Tsuge, S.; Kobayashi, T.; Sugimura, Y.; Nagaya, T.; Takeuchi, T. Macromolecules 1979, 12, 988.

Relative Intensity 47.3 0.4 100.0 0.6 0.4 0.4 2.6 0.2 0.2 4.7 0.1

51

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

020

EGA thermogram

Averaged mass spectrum 104

78

100

103

39

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

69

51

91 131

30 50

145

100

158

190

172

204

150

250 [m/z]

200

( m/z range : 29 - 600 amu )

M : methyl methacrylate

S : styrene 104

41

O

69

O

100

103

78 51

29

59

85

63

39

MS' : (E)-methyl 4-phenylbut-2-enoate

MS : methyl 2-methylene-4-phenylbutanoate 91

115

O

O

O O 176

91 39

51

32

65

144

89

161

32

39

51

115

65

145 158

176 190

SS : 3-butene-1,3-diyldibenzene (styrene dimer)

SM : methyl 2-methyl-4-phenylpent-4-enoate 145

91 O

O

115 129 39 51 63 29

130

77

77 91

204

39 51

173

SSM : methyl 2-methyl-4,6-diphenyl hept-6-enoate

65

115 130 77

165 180 193

208

SMS : methyl 2-phenylethyl-4-phenylpent-4-enoate

131

91 O

145

O

O

O

91 118 115 32

65 77

115

44 59

77

159

191

221

41 51

SSS : 5-hexene-1,3,5-triyltribenzene (styrene trimer) 91

117 44 32 51 6977

129

165178 194

281

190 204 158172

277

52

Tsuge, Ohtani and Watanabe

021 Methyl methacrylate-butadiene-styrene copolymer; MBS CH2 C(CH3)(COOCH3 )

CH2 CH

CHCH2

CH2 CH(C6H5)

n

SSS S

SS M

D 20

10

EB TIC B

T 0

V

αS 10

Peak Notation

Assignment of Main Peaks

B M T V EB S αS D SS SSS

1,3-butadiene methyl methacrylate toluene 4-vinylcyclohexene ethylbenzene styrene α -methylstyrene C(Ph)-C-C-Ph C=C(Ph)-C-C-Ph (S dimer) C=C(Ph)-C-C(Ph)-C-C-Ph (S trimer)

30 [min]

20

Molecular Retention Weight Index 54 100 92 108 106 104 118 196 208 312

*bonding hydrogen is omitted ; Ph represents C6H5 (phenyl group)

395 710 766 835 866 892 983 1668 1736 2482

Relative Intensity 5.0 59.1 2.7 3.4 0.9 100.0 2.5 0.9 3.2 9.3

53

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

021

EGA thermogram

Averaged mass spectrum 91 104 39 78

100

200

300

400

500

69

600

700 ºC

programming rate: 20ºC/min

117

51

129 30 50

143

100

165

150

194 207 221

312

200

250

350 [m/z]

300

( m/z range : 29 - 600 amu )

M : methyl methacrylate

B : 1,3-butadiene 39

41 O

69 54 O

100 29

59

85

31

V : 4-vinylcyclohexene

T : toluene

79

91

39

54 93

66 39

65

51

89

108

29

S : styrene

EB : ethylbenzene 91

104

103

78 106 51 39

51

65

78

63

39

32

αS : α−methylstyrene

D : 1,3-diphenylpropane 118 117

92

103 105 39

196

65 77

78

51 63

41 51

SS : 3-butene-1,3-diyldibenzene (styrene dimer)

128 141 152

170

SSS : 5-hexene-1,3,5-triyltribenzene (styrene trimer)

91

91

117 39 51

65

115 130 77

208 180 193

51

6577

129

194207 178

297 312

54

Tsuge, Ohtani and Watanabe

022 Acrylonitrile-styrene copolymer; AS CH2CH(C6H5)

CH2CH(CN)

ASA

S

AS SA

n

SAS

AAS SAA SSA

SA’ αS

SS

AA

ASS

20

10

TIC

A

T

0

10

30 [min]

20

Peak Notation

Assignment of Main Peaks

Molecular Retention Weight Index

A T S αS AA AS SA SA’ SS AAS ASA SAA ASS SSA SAS

acrylonitrile 53 toluene 92 styrene 104 α-methylstyrene 118 C=C(CN)-C-C-CN (A dimer) 106 C=C(CN)-C-C-Ph 157 C=C(Ph)-C-C-CN (hybrid dimer) 157 C-C(Ph)-C-C-CN 159 C=C(Ph)-C-C-Ph (S dimer) 208 C=C(CN)-C-C(CN)-C-C-Ph 210 C=C(CN)-C-C(Ph)-C-C-CN 210 C=C(Ph)-C-C(CN)-C-C-CN (hybrid trimer) 210 C=C(CN)-C-C(Ph)-C-C-Ph 261 C=C(Ph)-C-C(Ph)-C-C-CN 261 C=C(Ph)-C-C(CN)-C-C-Ph 261 * bonding hydrogen is omitted ; Ph represents C6H5 (phenyl group)

565 766 892 983 1059 1342 1424 1435 1737 1812 1846 1866 2129 2175 2200

[ Related References ] 1) Vukovic, R. ; Gnjatovic, V. J. Polym. Sci. A-1 1970, 8, 139. 2) Tsuge, S.; Kobayashi, T.; Sugimura, Y.; Nagaya, T.; Takeuchi, T. Macromolecules 1979, 12, 988. 3) Blazso, M.; Varhegyi, G.; Jakab, E. J. Anal. Appl. Pyrolysis 1980, 2, 177. 4) Blazso, M.; Ujszaszi, K.; Jakab, E. Chromatographia 1980, 13, 151. 5) Nagaya, T.; Sugimura, Y.; Tsuge, S. Macromolecules 1980, 13, 353. 6) Shadrina, N. E.; Dmitrenko, A. V.; Pavlova, V. F.; Ivanchev, S. S. J. Chromatogr. 1987, 404, 183.

Relative Intensity 5.6 1.0 100.0 1.2 2.7 9.3 8.4 2.5 2.9 7.2 19.1 7.4 3.1 2.9 15.1

55

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

022

EGA thermogram

Averaged mass spectrum 91

104

78

100

39

65

300

400

500

170

700 ºC

150

261 255

210 220

182 193 100

600

programming rate: 20ºC/min

156

129

50

200

144

115

51

200

300 [m/z]

250

( m/z range : 29 - 600 amu )

A : acrylonitrile

S : styrene 104

53

N 103

78 38

51 63

39

SA : 4-phenylpent-4-enenitrile

AS : 2-methylene-4-phenylbutanenitrile 91

115

N

N

157

91 103

77

130

51 39

51

65 77

128

AAS : 2-methylene-4-phenethylpentanedinitrile 91

ASA : 2-methylene-4-phenylheptanedinitrile 144

N

N

65 51

91 104 117

77

119

143

156 195

118 115

77

77

39 51

209

N

103

129

210

170

39 51

182

210

N

65 77

128

156169

91

N

261

N 170

115 118

91 115 118

65 220 233 205

195

SAS : 2-phenethyl-4-phenylpent-4-enenitrile

144

77

182

117 142 156

SSA : 4,6-diphenylhept-6-enenitrile

39 51 65

157

91

N

91

65

127

ASS : 2-methylene-4,6-diphenylhexanenitrile

SAA : 2-(2-phenylallyl)pentanedinitrile

39 51

N

N

105 39

142

63

39

157

261

39 51

77

105

156 142 246261

56

Tsuge, Ohtani and Watanabe

023 Acrylonitrile-styrene alternating copolymer CH2CH(CN)

CH2CH(C6H5)

S

ASA

AS SA SA’ αS

AA

AAS SAA SS

n SAS

SSA ASS 20

10

TIC

A

T

0

10

Peak Notation

Assignment of Main Peaks

A T S αS AA AS SA SA’ SS AAS ASA SAA ASS SSA SAS

acrylonitrile toluene styrene α-methylstyrene C=C(CN)-C-C-CN (A dimer) C=C(CN)-C-C-Ph C=C(Ph)-C-C-CN (hybrid dimer) C-C(Ph)-C-C-CN C=C(Ph)-C-C-Ph (S dimer) C=C(CN)-C-C(CN)-C-C-Ph C=C(CN)-C-C(Ph)-C-C-CN C=C(Ph)-C-C(CN)-C-C-CN (hybrid trimer) C=C(CN)-C-C(Ph)-C-C-Ph C=C(Ph)-C-C(Ph)-C-C-CN C=C(Ph)-C-C(CN)-C-C-Ph

30 [min]

20

Molecular Retention Weight Index 53 92 104 118 106 157 157 159 208 210 210 210 261 261 261

566 765 892 983 1058 1341 1422 1434 1734 1809 1844 1863 2126 2172 2199

* bonding hydrogen is omitted ; Ph represents C6H5 (phenyl group) [ Related Reference ] 1) Tsuge, S.; Kobayashi, T.; Sugimura, Y.; Nagaya, T.; Takeuchi, T. Macromolecules 1979, 12, 988.

Relative Intensity 5.5 1.1 100.0 0.9 2.0 8.8 7.4 2.0 2.8 1.2 19.2 0.9 1.7 1.6 18.2

57

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

023

EGA thermogram

Averaged mass spectrum 104

91

78

100

200

300

400

500

144

51

600

700 ºC

programming rate: 20ºC/min

117 39

65

156

129

50

170 210

182 193

100

150

261

200

300 [m/z]

250

( m/z range : 29 - 600 amu )

S : styrene

A : acrylonitrile

104

53

N 103

78 51

38 39

AS : 2-methylene-4-phenylbutanenitrile

AA : 2-methylpentanedinitrile (A dimer) 66

N

39

63

91

N

N

106

52 79

39

92

51

65 77

157

SS : 3-butene-1,3-diyldibenzene (styrene dimer)

SA : 4-phenylpent-4-enenitrile 115

N

128 140

91 157

77

51 39

91 103 129 142

63

39 51

165 180 193

91

N

N

115 130 104

77

208

ASS : 2-methylene-4,6-diphenylhexanenitrile

ASA : 2-methylene-4-phenylheptanedinitrile 144

65

91

N

117 117

39 51 63

77

128

157

182

65 77 39 51

210

SSA : 4,6-diphenylhept-6-enenitrile

156169

91

N

115 77

65 205

220233

261

N 170

115 118

91

118

195

SAS : 2-phenethyl-4-phenylpent-4-enenitrile

144

39 51 65

128

260

39 51

77

105

156 142 246261

58

Tsuge, Ohtani and Watanabe

024 Acrylonitrile-butadiene-styrene copolymer; ABS CH2CH

CHCH2

m

+

CH2CH(CN)

CH2 CH(C6H5)

n

SAS

S

AS

SA

AAS ASA

SS

SA’

SSA ASS

SAA SSS

AA 10

TIC

B

A

T

0

V

20

S 10

Peak Notation

Assignment of Main Peaks

B A T V S S AA AS SA SA’ SS AAS ASA SAA ASS SSA SAS SSS

1,3-butadiene acrylonitrile toluene 4-vinylcyclohexene styrene -methylstyrene C=C(CN)-C-C-CN (A dimer) C=C(CN)-C-C-Ph C=C(Ph)-C-C-CN (hybrid dimer) C-C(Ph)-C-C-CN C=C(Ph)-C-C-Ph (S dimer) C=C(CN)-C-C(CN)-C-C-Ph C=C(CN)-C-C(Ph)-C-C-CN C=C(Ph)-C-C(CN)-C-C-CN (hybrid trimer) C=C(CN)-C-C(Ph)-C-C-Ph C=C(Ph)-C-C(Ph)-C-C-CN C=C(Ph)-C-C(CN)-C-C-Ph C=C(Ph)-C-C(Ph)-C-C-Ph (S trimer)

30 [min]

20

Molecular Retention Weight Index 54 53 92 108 104 118 106 157 157 159 208 210 210 210 261 261 261 312

* bonding hydrogen is omitted ; Ph represents C6H5 (phenyl group)

395 560 766 835 892 983 1058 1342 1424. 1435 1736 1811 1843 1865 2129 2175 2200 2479

Relative Intensity 0.7 3.4 1.9 0.4 100.0 1.8 1.0 7.6 5.7 1.5 5.1 1.5 6.2 1.7 4.3 3.6 10.1 0.7

59

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

024

EGA thermogram

Averaged mass spectrum 104

91

78

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

51 39

117

144

65

156

129

50

100

170

150

182 193

261 255

210 220 233 200

300 [m/z]

250

( m/z range : 29 - 600 amu )

A : acrylonitrile

S : styrene 104

53

N 103

78 51

38

63

39

68

AS : 2-methylene-4-phenylbutanenitrile 91

SA : 4-phenylpent-4-enenitrile 115

N

N

157

39

51

77

39

157

115 128 140

129 142

63

32

SA' : 4-phenylpentanenitrile

SS : 3-butene-1,3-diyldibenzene (styrene dimer)

103

91

N 169

77 39

103

77

51 65

154 115

51

141

63

128

39 51

ASA : 2-methylene-4-phenylheptanedinitrile 144

65

180 193

208

ASS : 2-methylene-4,6-diphenylhexanenitrile 91

N

N

115 130 104 77

N

91 117

104 39 51

77

128

66

157 170182

194 210

39 51

SSA : 4,6-diphenylhept-6-enenitrile 144

65 77

77

156 169

91

65 260 202220233244

261

N 115 118

115 118 157 170

195

SAS : 2-phenethyl-4-phenylpent-4-enenitrile N

91

39 51 65

128

39 51

77

105

170 156 142 178

246 261

60

Tsuge, Ohtani and Watanabe

025 Acrylonitrile-acrylate-styrene copolymer; AAS CH2CH(COOC4 H9)

m

+

CH2CH(CN)

CH2CH(C6 H5 )

n

SAS

S

SSA AS αS AA

SA

AAS SS

SA’

ASA ASS SAA SSS 20

10

TIC

B A

BO T

0

10

Peak Notation

Assignment of Main Peaks

B A BO T S αS AA AS SA SA’ SS AAS ASA SAA ASS SSA SAS SSS

1-butene acrylonitrile 1-butanol toluene styrene α-methylstyrene C=C(CN)-C-C-CN (A dimer) C=C(CN)-C-C-Ph C=C(Ph)-C-C-CN (hybrid dimer) C-C(Ph)-C-C-CN C=C(Ph)-C-C-Ph (S dimer) C=C(CN)-C-C(CN)-C-C-Ph C=C(CN)-C-C(Ph)-C-C-CN C=C(Ph)-C-C(CN)-C-C-CN (hybrid of trimer) C=C(CN)-C-C(Ph)-C-C-Ph C=C(Ph)-C-C(Ph)-C-C-CN C=C(Ph)-C-C(CN)-C-C-Ph C=C(Ph)-C-C(Ph)-C-C-Ph (S trimer)

30 [min]

20

Molecular Retention Weight Index 56 53 74 92 104 118 106 157 157 159 208 210 210 210 261 261 261 312

* bonding hydrogen is omitted ; Ph represents C6H5 (phenyl group)

383 568 657 765 892 982 1057 1341 1422 1434 1734 1809 1842 1864 2128 2172 2199 2478

Relative Intensity 1.6 3.3 1.1 1.6 100.0 1.6 0.9 6.4 5.4 1.1 5.1 1.5 7.0 1.7 6.0 5.1 11.1 1.0

61

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

025

EGA thermogram

Averaged mass spectrum 104

91 78

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

51

117

39

144

65

129

50

100

170

156

31

150

193

208 220 233 246 200

260 300 [m/z]

250

( m/z range : 29 - 600 amu )

B : 1-butene

A : acrylonitrile 39

53

N

56 38 29

S : styrene

AS : 2-methylene-4-phenylbutanenitrile 91

104

103

78 51 39

39

63

SA : 4-phenylpent-4-enenitrile

51

65

157

77

115 128 140

SS : 3-butene-1,3-diyldibenzene (styrene dimer)

115

N

N

91 157

103 77

51

129

63

39

142

39 51

91 39 51

91

N

N

N

117

77

128

66

157

182

210

39 51

65 77

128

156 169

195

261

SAS : 2-phenethyl-4-phenylpent-4-enenitrile

144

91

N

N 115 118

91

77

208

104 117

SSA : 4,6-diphenylhept-6-enenitrile

39 51 65

165 178 193

ASS : 2-methylene-4,6-diphenylhexanenitrile

ASA : 2-methylene-4-phenylheptanedinitrile 144

115 130

65 77

105

115 118

170 156

77 65 170

203

220 233

260

39 51

142 246261

62

Tsuge, Ohtani and Watanabe

026 Acrylonitrile-EPDM-styrene copolymer; AES CH2CH2

CH2CH(CH3)

X

m

+

CH2CH(CN)

CH2CH(C6H5)

n

SAS S ASA AS SA

AAS SS

SSA SAA ASS

SA’ S AA

SSS 10

20

TIC

A

T

0

10

Peak Notation

Assignment of Main Peaks

A T S S AA AS SA SA’ SS AAS ASA SAA ASS SSA SAS SSS

acrylonitrile toluene styrene -methylstyrene C=C(CN)-C-C-CN (A dimer) C=C(CN)-C-C-Ph C=C(Ph)-C-C-CN (mixture of dimer) C-C(Ph)-C-C-CN C=C(Ph)-C-C-Ph (S dimer) C=C(CN)-C-C(CN)-C-C-Ph C=C(CN)-C-C(Ph)-C-C-CN C=C(Ph)-C-C(CN)-C-C-CN (mixture of trimer) C=C(CN)-C-C(Ph)-C-C-Ph C=C(Ph)-C-C(Ph)-C-C-CN C=C(Ph)-C-C(CN)-C-C-Ph C=C(Ph)-C-C(Ph)-C-C-Ph (S trimer)

30 [min]

20

Molecular Retention Weight Index 53 92 104 118 106 157 157 159 208 210 210 210 261 261 261 312

* bonding hydrogen is omitted ; Ph represents C6H5 (phenyl group)

563 766 891 982 1057 1341 1422 1434 1734 1809 1842 1864 2126 2172 2197 2478

Relative Intensity 3.9 1.9 100.0 1.4 1.7 8.8 7.5 1.8 4.8 2.9 9.3 3.4 4.6 4.1 12.2 0.5

63

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

026

EGA thermogram

Averaged mass spectrum 91

104

78 100

200

300

400

500

117

39

65

144 129

50

156

100

600

700 ºC

programming rate: 20ºC/min

51 170

150

261 255

210 220

182 193 200

300 [m/z]

250

( m/z range : 29 - 600 amu )

S : styrene

A : acrylonitrile 53

104

N 103

78 38

51 63

39

SA : 4-phenylpent-4-enenitrile

AS : 2-methylene-4-phenylbutanenitrile 91

N

115

N

157

91 103

77

130

51 39

51

65 77

157

128

104

SS : 3-butene-1,3-diyldibenzene (styrene dimer)

142

63

39

AAS : 2-methylene-4-phenethylpentanedinitrile

91

91

N

N

105 39 51

65

104115 130

77

39

208 180 193

ASA : 2-methylene-4-phenylheptanedinitrile 144

65 77

51

91

91

66

128

157168 182

210

39 51

SSA : 4,6-diphenylhept-6-enenitrile

182

209

N

65 77

128

169

91

N

N 115 118

91

105

115 104

65

77 220233

261

SAS : 2-phenethyl-4-phenylpent-4-enenitrile

144

39 51 65

156

117

104 117 39 51

77

143

ASS : 2-methylene-4,6-diphenylhexanenitrile N

N

119

260

39 51

77

170 156

142 129

246261

64

Tsuge, Ohtani and Watanabe

027 Styrene-maleic anhydride copolymer; P(S-Mah) CH2 CH(C6H5)

CH(CO) CH(CO)

n

O S

SSS

SS

D1

D5 D2 MS D6

MA

TIC

T

20

10

αS AB

0

10

Peak Notation

Assignment of Main Peaks

T MA S AB αS D1 D2 MS SS D5 D6 SSS

toluene maleic anhydride styrene allyl benzene α-methylstyrene C(Ph)-C-Ph C-C(Ph)-C-Ph (hybrid dimer) C=C(Ph)-C-C-Ph (S dimer) C=C(Ph)-C-C(Ph)-C C(Ph)=C-C-C-Ph C=C(Ph)-C-C(Ph)-C-C-Ph (S trimer)

30 [min]

20

Molecular Retention Weight Index 92 98 104 118 118 182 196 202 208 222 208 312

* bonding hydrogen is omitted ; Ph represents C6H5 (phenyl group) [ Related References ] 1) Yamaguchi, S. ; Hirano, J. ; Isoda, Y. J. Anal. Appl. Pyrolysis 1989, 16, 159 2) Wang, F. C.-Y. J. Chromatogr. A 1997, 765, 279. 3) Wang, F. C.-Y. J. Anal. Appl. Pyrolysis 2004, 71, 83.

764 848 892 947 982 1536 1568 1661 1735 1746 1837 2181

Relative Intensity 2.0 1.3 100.0 0.7 1.8 2.1 1.9 1.5 7.1 1.2 1.6 8.1

65

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

027

EGA thermogram

Averaged mass spectrum 104 91

78

100

200

300

400

500

39

600

700 ºC

programming rate: 20ºC/min

51 117

63

129 50

141 153 165 179 194 207 221

100

150

200

312 250

350 [m/z]

300

( m/z range : 29 - 600 amu )

MA : maleic anhydride

S : styrene 54

O

O

104

O 103

78 51 98

44

29

αS : α-methylstyrene

39

63

D1 : 1,2-diphenylethan 91

118 117 103 78 51

39

91

182

65

63

39

D2 : propane-1,2-diyldibenzene

89

51

104

128 139 152 165

MS : (hybrid dimer) 129

105 115

202 174

51 39

51

65

77

39

91 165 178

63 77

SS : 3-butene-1,3-diyldibenzene (styrene dimer)

D5 : 1-pentene-2,4-diylbenzen

91

39 51

105

115

115 130 104

65 77

208 180 193

77

115

179

194 222

117

65 77

165

91

117

39 51

91

39 51 65

SSS : 5-hexene-1,3,5-triyltribenzene (styrene trimer)

D6 : (E)-1-butene-1,4-diyldibenzene

91

145 156

102

196

152

178190

208

39 51

6577

129

194207 221

297312

66

Tsuge, Ohtani and Watanabe

028 Styrene-divinylbenzene copolymer; P(S-DVB) CH2CH(C6H5 )

CH2CH(C6 H4)

CH2CH(C6H4 CH2CH3)

n

CHCH2 SS

S

SSS ES DV D5 αS MS

DS D7

D1 D4

TS

D6

10

20

TIC

T 0

10

Peak Notation

Assignment of Main Peaks

T S αS

D1 D4 SS D5 D6 D7

toluene styrene α-methylstyrene m-methylstyrene p-methylstyrene m-ethylstyrene p-ethylstyrene m-divinylbenzene p-divinylbenzene C(Ph)-C-Ph C(Ph)-C-C-Ph C=C(Ph)-C-C-Ph (S dimer) C=C(Ph)-C-C(Ph)-C C(Ph)=C-C-C-Ph C=C(Ph)-C-C-C(Ph)=C

DS

(hybrid dimer)

SSS TS

C=C(Ph)-C-C(Ph)-C-C-Ph (S trimer) C=C(Ph)-C-C(Ph)-C-C-Ph (hybrid trimer)

MS ES DV

30 [min]

20

Molecular Retention Weight Index 92 104 118 118 118 132 132 130 130 182 196 208 222 208 234 248 234 312 312

* bonding hydrogen is omitted ; Ph represents C6H5 (phenyl group) [ Related References ] 1) Nakagawa, H.; Tsuge, S. Macromolecules 1985, 18, 2068. 2) Nakagawa, H.; Matsushita, Y.; Tsuge, S. Polymer 1987, 28, 1512.

766 892 983 944 998 1087 1104 1116 1129 1536 1666 1735 1747 1836 1910 1940 1947 2487 2582

Relative Intensity 1.2 100.0 1.1 0.5 0.1 4.8 1.4 4.1 1.6 1.2 0.2 7.1 0.7 0.5 1.3 0.8 0.8 6.5 0.4

67

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

028

EGA thermogram

Averaged mass spectrum 104 78

91 100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

51 117

39

63

130

50

152 165 178 193 207

100

150

200

234

312 250

350 [m/z]

300

( m/z range : 29 - 600 amu )

ES : m-ethylstyrene

S : styrene

117

104

103

78

132 115

51 39

63

51

39

ES : p-ethylstyrene

91

77

63

DV : m-divinylbenzene 117

130

132

115

115 51

39

91

77

63

51

39

DV : p-divinylbenzene

102

91

115 51

63

SS : 3-butene-1,3-diyldibenzene (styrene dimer) 130

39

77

77

63

103

39 51

DS : (hybrid dimer)

104115 130

65 77

208 193

DS : (hybrid dimer)

91

117 131

115 65 39 51

130

91

77

234 141

234 205 248 220

SSS : 5-hexene-1,3,5-triyltribenzene (styrene trimer)

77

39 51 65

143 156

TS : (hybrid trimer) 129

91 91

207 117 6577 39 51

65 77

129

178

194207 221

297 312

32 39 51

105 143

178 191 165

219

254

312

68

Tsuge, Ohtani and Watanabe

2.2.4 Vinyl polymers with styrene units’ derivatives 029 Poly(α α-methylstyrene); P-α-MS CH2C(CH3)(C6H5)

n

αS S PX

PP

T BA

B

2

3

4

5

6

7

8

9

TIC

0

10

Peak Notation

Assignment of Main Peaks

B T PX S BA αS PP

benzene toluene p-xylene styrene benzaldehyde α-methylstyrene 2-phenylpropenal [ Related Reference ] 1) Okumoto, T.; Takeuchi, T. Bull. Chem. Soc. Jpn 1973, 46, 1717.

30 [min]

20

Molecular Retention Weight Index 78 92 106 104 106 118 132

658 764 869 890 961 985 1158

Relative Intensity 0.02 0.02 0.03 0.03 0.02 100.0 0.03

69

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

029

EGA thermogram

Averaged mass spectrum 118 117 103 100

78

51

200

300

400

500

39

600

700 ºC

programming rate: 20ºC/min

91

63

50

100

200 [m/z]

150

( m/z range : 29 - 600 amu )

B : benzene

T : toluene 78

91

39 51

63 32

PX : p-xylene

S : styrene 104

91

106 78 103

77

39

51

50

65 38

63

αS : α-methylstyrene

BA : benzaldehyde 105

118

O

77

117 103

51

78 39

PP : 2-phenylpropenal 103

O

104 77 51 44

63

132

51

63

91

70

Tsuge, Ohtani and Watanabe

030 Polydivinylbenzene; PDVB CH2CH(C6H4)

CH2CH(C6H4CH2CH3)

n

CHCH2 dimer D2

ES

DV D1

MS 10

EB

20

PS

S

TIC

PB

0

DD 10

Peak Notation

Assignment of Main Peaks

EB S PB

ethylbenzene styrene isopropylbenzene m-methylstyrene p-methylstyrene m-ethylstyrene p-ethylstyrene m-divinylbenzene p-divinylbenzene m-isopropenylstyrene 1-dodecanol dimer (DVB) dimer (DVB)

MS ES DV PS DD D1 D2

[ Related Reference ] 1) Nakagawa, H.; Tsuge, S. Macromolecules 1985, 18, 2068.

30 [min]

20

Molecular Retention Index Weight 106 866 104 896 120 969 118 999 118 1006 132 1097 132 1104 130 1120 130 1140 144 1210 186 1478 264 2083 262 2124

Relative Intensity 3.3 2.8 7.6 21.6 9.5 100.0 36.6 61.2 27.4 12.7 5.8 1.9 9.0

71

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

030

EGA thermogram

Averaged mass spectrum 117

100

39

51

77

63

300

400

500

600

700 ºC

programming rate: 20ºC/min

103

50

200

132 130

91

144

100

169

150

205

236 248

200

262 300 [m/z]

250

( m/z range : 29 - 600 amu )

EB : ethylbenzene

S : styrene 104

91

106

103

78 51

51

39

63

77

63

39

MS : m-methylstyrene

PB : isopropylbenzene

117 118

105

91

120 39

51

65

77

91

39

ES : m-ethylstyrene

51

63

77

DV : m-divinylbenzene 130

117

132 115

115 91 51

39

63

51

77

39

PS : m-isopropenylstyrene

63

77

102

DD : 1-dodecanol 144

55 41

OH

69 83

128

97 29

104 51

39

63

77

111

103

125

D1 : dimer (DVB)

91 41 51 65

155 168

D2 : dimer (DVB) 117

119

77

140

91 117 132

235 158

219

248

264

248 262

130 39 51 65

77

156

233

72

Tsuge, Ohtani and Watanabe

031 Poly(p-chlorostyrene) CH2CH(C6 H4 Cl)

n

CC

C

CCC CB

IC

d

b a

c 20

10

TIC

CT

C’

0

10

Peak Notation

Assignment of Main Peaks

CT C’ C CB IC a b CC c d CCC

p-chlorotoluene chlorostyrene ( m- and o- ) p-chlorostyrene p-chlorobenzaldehyde 4-chloroisopropenylbenzene C(Ph)=C-C-PhCl ? C(PhCl)-C-PhCl C=C(PhCl)-C-C-PhCl (dimer) C(PhCl)=C-C-C-PhCl C=C(PhCl)-C-C-C(PhCl)=C C=C(PhCl)-C-C(PhCl)-C-C-PhCl (trimer)

30 [min]

20

Molecular Retention Weight Index 126 138 138 140 152 228 ? 250 276 276 302 414

958 1071 1080 1130 1170 1906 1975 2168 2288 2328 3150

* bonding hydrogen is omitted ; PhCl represents C6H4Cl (4-chlorophenyl group) ; Ph represents C6H5 (phenyl group) [ Related References ] 1) Okumoto, T.; Takeuchi, T.; Tsuge, S. Macromolecules 1973, 6. 922. 2) Okumoto, T.; Tsuge, S.; Yamamoto, Y.; Takeuchi, T. Macromolecules 1974, 7, 376. 3) Bertini, F.; Audisio, G.; Kiji, J. J. Anal. Appl. Pyrolysis 1994, 28, 205. 4) Zuev, V. V.; Bertini, F ; Audisio, G. Polym. Degrad. Stab. 2001, 71, 213.

Relative Intensity 0.8 1.7 100.0 0.3 0.5 0.4 1.3 9.4 0.6 1.4 5.6

73

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

031

EGA thermogram

Averaged mass spectrum 138

103

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

77 51 63

39

112125 151164

50

100

241

150

200

250

276

414 300

350

400

450 [m/z]

( m/z range : 29 - 600 amu )

CT : p-chlorotoluene

C' : m-chlorostyrene and o-chlorostyrene 91

103

138

Cl + Cl 126 63 39

Cl

77 75

51

89

50

39

C : p-chlorostyrene

CB : p-chlorobenzaldehyde 138

139

O

103 111

Cl 51

75

50

77 75

Cl

77

112

39

38

123

a : 1-chloro-4-cinnamylbenzene ? 165 178

b : 1,2-bis(4-chlorophenyl)ethane 125

228

193

Cl Cl

Cl 115 125

75 89

39 51 32

139

89

152 39 51 63

99

139

250

178

CC : 4,4'-(but-3-ene-1,3-diyl)bis(chlorobenzene) (dimer)

c : (E)-4,4'-(but-1-ene-1,4-diyl)bis(chlorobenzene) Cl

125

Cl

151

Cl

115 Cl 125

51

75

89

115 89 101

138

39 51 63

276

241

101

276

202

CCC : 4,4',4''-(hex-5-ene-1,3,5-triyl) d : 4,4'-(hexa-1,5-diene-2,5-diyl)bis(chlorobenzene) 129

tris(chlorobenzene) (trimer) 125

Cl

Cl

Cl

Cl

115 138

3951

101 75 89

164 151 177

Cl 202

302

89 115 138 51 75

275 262

416

74

Tsuge, Ohtani and Watanabe

032 Poly(p-methylstyrene); PMS CH2CH(C6H4 CH3)

n

MMM

M

MM c IP

a

d

b

20

10

S

TIC

X

ET

0

10

Peak Notation

Assignment of Main Peaks

X S ET M IP

p-xylene styrene p-ethyltoluene p-methylstyrene p-isopropenyltoluene C(PhC)-C-C-PhC C(PhC)=C-C-PhC C=C(PhC)-C-C-PhC (dimer) C(PhC)=C-C-C-PhC ? C=C(PhC)-C-C(PhC)=C C=C(Ph)-C-C(PhC)-C-C-PhC C=C(PhC)-C-C(PhC)-C-C-PhC (trimer)

a MM b c d MMM

30 [min]

20

Molecular Retention Weight Index 106 104 120 118 132 224 222 236 236 248 340 354

870 890 964 1000 1090 1877 1882 1946 2295 2084 2663 2745

* bonding hydrogen is omitted ; PhC represents C6H4CH3 (p-tolyl group) ; Ph represents C6H5 (phenyl group)

[ Related References ] 1) Schroeder, U. K. O.; Ederer, H. J.; Ebert, K. H. Makromol. Chem. 1987, 188, 561. 2) Nakagawa, H.; Tsuge, S.; Mohanraj, S.; Ford, W. T. Macromolecules 1988, 21, 930. 3) Luda, M. P.; Guaita, M.; Chiantore, O. Makromol. Chem., Macromol. Symp. 1989, 25, 101. 4) Zuev, V. V. ; Bertini, F. ; Audisio, G. Polym. Degrad. Stab. 2001, 71, 213.

Relative Intensity 2.1 6.2 0.1 100.0 0.6 0.4 0.4 2.8 0.3 2.1 0.6 6.8

75

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

032

EGA thermogram

Averaged mass spectrum 117

100

200

300

400

500

91

600

700 ºC

programming rate: 20ºC/min

105 39 51 63 77 144156 50

100

207 221 236248

178

150

200

354

250

300

400 [m/z]

350

( m/z range : 29 - 600 amu )

X : p-xylene

S : styrene 91

104

106

51

39

78

77

65

63

39

M : p-methylstyrene

a : 1,3-bis(4-tolyl)propane 106

117 118

91

51

119

224

77

91 39

103

51

65

63

39 51 32

89

132

MM : 4,4'-(but-3-ene-1,3-diyl)bis(methylbenzene) (dimer)

a : 1,3-bis(4-tolyl)-1-propene 117

105

105

40 50 64 89

222 130

255

327

405

b : (E)-4,4'-(but-1-ene-1,4-diyl)bis(methylbenzene)

39 51 65

77 91

236 91

77 144

51 65

248 233

MMM : (Z)-4,4',4''-(hex-5-ene-1,3,5-triyl)tris

(methylbenzene)

(methylbenzene) (trimer)

105

115 131 143

130 156 141

3951 65 77

d : 4,4''-(5-phenylhex-5-ene-1,3-diyl)bis

91

221

117

91 106

77 65

144

105

207221 193

340

403

236

c : 4,4'-(penta-1,4-diene-2,4-diyl)bis(methylbenzene)

117

39

118

91 6577

131 143

222235

354

76

Tsuge, Ohtani and Watanabe

033 Poly(2-vinylpyridine) CH2CH(C5H4N)

n

VV

V

IP

VVV

c b d

a

e

10

TIC

20

MP

0

10

Peak Notation

Assignment of Main Peaks

MP V IP a VV b c d e VVV

2-methylpyridine 2-vinylpyridine 2-isopropenylpyridine C(C5N)-C-C-C5N C=C(C5N)-C-C-C5N (dimer) C=C-C(C5N)=C-C-C5N C(C5N)=C-C-C-C5N C=C(C5N)-C=C-C5N C=C(C5N)-C-C(C5N)=C C(C5N)=C-C(C5N)-C-C-C5N (trimer)

30 [min]

20

Molecular Retention Weight Index 93 105 119 198 210 222 210 208 222 301

811 933 1023 1613 1832 1921 1935 1988 2101 2619

Relative Intensity 1.9 100.0 1.9 1.8 29.1 1.2 0.6 2.4 0.7 27.1

* bonding hydrogen is omitted ; C5N represents 2-pyridyl group [ Related Reference ] 1) Ohtani, H. ; Kotsuji, ; H. Momose, H. ; Matsushita, Y. ; Noda, I. ; Tsuge, S. Macromolecules 1999, 32, 6541.

77

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

033

EGA thermogram

Averaged mass spectrum 79 105 51

100

93

200

300

210

65

144 154

50

500

600

700 ºC

programming rate: 20ºC/min

132

39

400

118

100

169

223

195

182

150

250 [m/z]

200

( m/z range : 29 - 600 amu )

V : 2-vinylpyridine

MP : 2-methylpyridine 93

N

105

N 79

66 51

39

78

51

39

74

a : 1,3-bis(4-pyridyl)propane

IP : 2-isopropenylpyridine 118

106

N N

N 184

79

51

39

93

63

N

65

N

51 39

169

N

130

118 117 78

130 141 154

92

b : (Z)-4,4-(penta-2,4-diene-1,3-diyl)dipyridine

VV : 4,4'-(but-3-ene-1,3-diyl)dipyridine (dimer) 132

78

51

39

N

117 144

78

195 209

93

51

65

39

154 169181

c : 1,4-di(pyridin-4-yl)butane

195

104 93

65

221 210

168

d : (Z)-4,4-(buta-1,3-diene-1,3-diyl)dipyridine

93

N

N

193

N

117 132 N 130 39

51 65 78

195 210

106

51 63 78 39

96

140

208

165

VVV : (Z)-4,4',4''-(pent-1-ene-1,3,5-triyl)tripyridine e : 4,4'-(penta-1,4-diene-2,4-diyl)dipyridine N

N

(trimer) 210

144

223

N

N

N

118 93 130

39

51

78 63

90

78

222

117 130 105 167

194206

39

51 65

106

144

195 169 286

315

78

Tsuge, Ohtani and Watanabe

034 Acrylonitrile-p-chlorostyrene copolymer CH2CH(CN)

CH2 CH(C6H4Cl)

n

CAC

C ACA AC CA’ AAC

CAA CC

CCA ACC

AC’ CB

IC

CCC

A

S

20

10

AA TIC

CT

0

10

Peak Notation

Assignment of Main Peaks

A S CT AA C CB IC AC AC’ CA’ AAC ACA CAA CC ACC CCA CAC CCC

acrylonitrile styrene p-chlorotoluene C=C(CN)-C-C-CN (A dimer) p-chlorostyrene p-chlorobenzaldehyde 4-chloroisopropenylbenzene C=C(CN)-C-C-PhCl C(PhCl)-C-C-CN (hybrid dimer) C=C(PhCl)-C-C(CN)-C C=C(CN)-C-C(CN)-C-C-PhCl C=C(CN)-C-C(PhCl)-C-C-CN (hybrid trimer) C=C(PhCl)-C-C(CN)-C-C-CN C=C(PhCl)-C-C-PhCl (C dimer) C=C(CN)-C-C(PhCl)-C-C-PhCl C=C(PhCl)-C-C(PhCl)-C-C-CN (hybrid trimer) C=C(PhCl)-C-C(CN)-C-C-PhCl C=C(PhCl)-C-C(PhCl)-C-C-PhCl (C trimer)

30 [min]

20

Molecular Retention Weight Index 53 104 126 106 138 140 152 191 179 205 244 244 244 276 329 329 329 414

570 889 957 1056 1081 1128 1168 1562 1558 1644 2051 2075 2101 2179 2597 2629 2657 3144

* bonding hydrogen is omitted ; PhCl represents C6H4Cl (4-chlorophenyl group) [ Related Reference ] 1) Okumoto, T.; Tsuge, S.; Yamamoto, Y.; Takeuchi, T. Macromolecules 1974, 7, 376.

Relative Intensity 2.1 0.1 1.2 1.1 100.0 0.7 1.0 6.3 0.7 7.5 4.1 8.2 3.3 4.2 2.9 2.4 9.7 0.4

79

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

034

EGA thermogram

Averaged mass spectrum 138 103 125 100

200

300

400

500

600

77 75

51

700 ºC

programming rate: 20ºC/min

178

115

39 50

152 165

100

190

150

244

202 216 200

276

329

250

350 [m/z]

300

( m/z range : 29 - 600 amu )

C : p-chlorostyrene

A : acrylonitrile

138

53

N 103

38

Cl

77 75

51

112

39

AC : 4-(4-chlorophenyl)-2-methylenebutanenitrile 125

CA' : 4-(4-chlorophenyl)-2-methylpent-4-enenitrile

N

Cl

115 N

75 39

89

51 63

99

115

138

39 51 63

191

156

191

129 151 137

Cl 101 89

168 176

203

AAC : 2-(4-chlorophenethyl)ACA : 4-(4-chlorophenyl)-2-methyleneheptanedinitrile

4-methylenepentanedinitrile 125

N

N

178

Cl N

Cl 89 39 51 63

77

125 103115

N

139

106 103

156

244

190

77

39 51

138 151 244

CC : 4,4'-(but-3-ene-1,3-diyl)bis(chlorobenzene) CAA : 2-(2-(4-chlorophenyl)allyl)pentanedinitrile 115

152

(C dimer)

Cl

Cl

125 N

39 51

75 89

102

127137

163

177 190 204

N 244

75

39 51

ACC : 4,6-bis(4-chlorophenyl)-

115 89 101

Cl 138

164

241

276

CAC : 2-(4-chlorophenethyl)-4-

2-methylenehexanenitrile

(4-chlorophenyl)pent-4-enenitrile

125

125

Cl

Cl

115

N

N 152

75 39 51 75

89103 115 138

263

329 355

Cl

39 51

89 101

139 204 190 177

Cl 329

80

Tsuge, Ohtani and Watanabe

035 Chloromethylated styrene-divinylbenzene copolymer CH2CH(C6H5)

CH2CH(C6H4)

CS

S

X

TIC

LB B

T

S EB

CH2CH(C6H4CH2Cl)

n

CHCH2

MS ET ME DE DM ES

0

D dimers

10

Peak Notation

Assignment of Main Peaks

LB B T EB X S ET S MS ME DE DM ES CS D

hydrogen chloride etc. benzene toluene ethylbenzene p-xylene styrene p-ethyltoluene -methylstyrene p-methylstyrene p-isopropyltoluene p-diethylbenzene ,p-dimethylstyrene p-ethylstyrene p-chloromethylstyrene unidentified

30 [min]

20

Molecular Retention Weight Index 36 78 92 106 106 104 120 118 118 134 134 132 132 152 210

[ Related References ] 1) Nakagawa, H.; Tsuge, S.; Mohanraj, S.; Ford, W. T. Macromolecules 1988, 21, 930. 2) Boinon, B.; Ainad-Tabet, D.; Montheard, J. P. J. Anal. Appl. Pyrolysis 1988, 13, 171. 3) Mao, S.; Tsuge, S.; Ohtani, H ; Uchijima, S.; Kiyokawa, A. Polymer 1998, 39, 143.

655 767 866 875 895 968 989 1005 1033 1065 1098 1102 1265 1767

Relative Intensity 43.6 1.7 42.9 30.0 81.6 107.7 78.8 7.7 100.0 8.7 11.2 8.5 15.9 161.8 13.0

81

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

035

EGA thermogram

Averaged mass spectrum 91

105117

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

39 51 63

77 152

132 50

100

165 178 195

150

232 246 265 279 296 310 324 338

200

250

300

400 [m/z]

350

( m/z range : 29 - 600 amu )

LB : hydrogenchloride

T : toluene

36

H

91

Cl

39

65

51

89

X : p-xylene

EB : ethylbenzene 91

91

106 106 39

51

65

77

51

39

65

77

ET : p-ethyltoluene

S : styrene

105

104

103

78

120 51 63

39

39

MS : p-methylstyrene

51

65

77

91

ES : p-ethylstyrene 117

117 118

132

91 39

51

63

89

39

CS : p-chloromethylstyrene

51

77

63

91

D : unidentified 181

117

210

152 39

51 63

165

Cl

91 39 51 63

77

105

118

141152

195

82

Tsuge, Ohtani and Watanabe

2.2.5 Acrylate-type polymers 036 Poly(methyl methacrylate); PMMA CH2C(CH3)(COOCH3)

n

M T D2 D1 D3 D4 d2 d4

5

10

15

20

TIC

0

10

Peak Notation M d2 d4 D1 D2 D3 D4 T

Assignment of Main Peaks methyl methacrylate C=C(C)-C-C(C)(COOC)-C ? C=C(C)-C=C(COOC)-C ? C=C(COOC)-C-C(C)(COOC)-C ? C-C(COOC)=C-C(COOC)-C ? C-C(COOC)=C-C(C)(COOC)-C C11H18O4 ? C-C(COOC)=C-C(C)(COOC)-C-C(C)(COOC)-C * bonding hydrogen is omitted

30 [min]

20

Molecular Retention Index Weight 100 156 140 200 186 200 214 300

? ? ? ? ? ?

710 1035 1090 1256 1274 1310 1332 1830

Relative Intensity 100.0 <0.1 <0.1 0.1 <0.1 0.1 <0.1 0.1

[ Related References ] 1) Haken, J. K.; Mckay, T. R. Anal. Chem. 1973, 45, 1251. 2) Ohtani, H.; Ishiguro, S.; Tanaka, M.; Tsuge, S. Polym. J., 1989, 21, 41. 3) Ohtani, H.; Tanaka, M.; Tsuge, S. J. Anal. Appl. Pyrolysis, 1989, 15, 167. 4) Ohtani, H.; Tanaka, M.; Tsuge, S. Bull. Chem, Soc. Jpn. 1990, 63, 1196. 5) Ohtani, H.; Luo, Y. F.; Nakashima, Y.; Tsukahara, Y.; Tsuge, S. Anal. Chem. 1994, 66, 1438. 6) Ito, Y.; Tsuge, S.; Ohtani, H.; Wakabayashi, S.; Atarashi, J.; Kawamura, T. Macromolecules 1996, 29, 4516 7) Nonobe, T.; Tsuge, S.; Ohtani, H.; Kitayama, T.; Hatada, K. Macromolecules 1997, 30, 4891. 8) Ohtani, H.; Takehana, Y.; Tsuge, S. Macromolecules 1997, 30, 2542.

83

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

036

EGA thermogram

Averaged mass spectrum 41 69

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

100 59

30

85

50

150 [m/z]

100

( m/z range : 29 - 600 amu )

M : methyl methacrylate

d2 : methyl 2,2,4-trimethylpent-4-enoate

41

125

81 69

O

O

39

O

59

29

109

53

32 100

140

O

85

d4 : (Z)-methyl 2,4-dimethylpenta-2,4-dienoate

D1 : dimethyl 2,2-dimethyl-4-methylenepentanedioate

127

81

140 109

O

59

O

O

O

O

O 41

69

39

99

101

53 29

D2 : (Z )-dimethyl 2,4-dimethylpent-2-enedioate 67

67

125

D3 : (Z)-dimethyl 2,4,4-trimethylpent-2-enedioate 69

127

41

95 O

O

O

O

O

O

O

O

115 41

99

59

111

59

154

88

32

D4 : C11H18O4

T : (Z)-trimethyl 4,6-dimethylhept-2-ene-2,4,6-tricarboxylate 121

81

O

39

41

95 55

69

O

O

O

O

O

149

123 109 139

59

32 67

79

111 93

167 139

181

212 241

84

Tsuge, Ohtani and Watanabe

037 Poly(n-butyl methacrylate); PBMA CH2 C(CH3 )(COOC4H9)

n

M MMA

PB Be MA

BT 2

4

DP

6

8

10

12

B TIC

0

10

Peak Notation

Assignment of Main Peaks

B BT Be MMA MA M DP PB

1-butene n-butanal benzene methyl methacrylate methacrylic acid n-butyl methacrylate diphenyl phenyl benzoate

30 [min]

20

[ Related References ] 1) Haken, J. K.; Mckay, T. R. Anal. Chem. 1973, 45, 1251. 2) Mao, S.; Ohtani, H.; Tsuge, S. J. Anal. Appl. Pyrolysis, 1995, 33, 181. 3) Bertini, F.; Audisio, G.; Zuev. V. V. Polym. Degrad. Stab. 2005, 89, 233.

Molecular Retention Weight Index 56 72 78 100 86 142 154 198

386 600 656 709 788 979 1390 1668

Relative Intensity 1.8 0.2 0.5 1.3 1.1 100.0 0.1 0.4

85

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

037

EGA thermogram

Averaged mass spectrum 41 69

87 100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

56 100

31 50

113 150 [m/z]

100

( m/z range : 29 - 600 amu )

BT : n-butanal

B : 1-butene

29

41

41

O 72 56 57 29

Be : benzene

MMA : methyl methacrylate 78

39 O 69 O

50

100

43 63

33

59

85

30

M : n-butyl methacrylate

MA : methacrylic acid

69

39

87 O

41

OH 86

O

56 O 29 58

68 99

DP : diphenyl

113

127

143

PB : phenyl benzoate 105

154

O O

77

39 50

63

76

102

115 128

139

39

51

65

93

198

86

Tsuge, Ohtani and Watanabe

038 Poly(2-hydroxyethyl methacrylate); PHEMA CH2C(CH3)(COOCH2CH2OH)

M’

n

ED

M

TIC

8

LB A

9

10

11

12

MA

0

10

Peak Notation

Assignment of Main Peaks

LB A MA M M’ ED

CO2 acetaldehyde methacrylic acid 2-hydroxyethyl methacrylate CH2=CHCH(CH3)COOCH2CH2OH CH2=C(CH3)COOCH2CH2OCOC(CH3)=CH2

[ Related References ] 1) Razga, J. R.; Petranek, J. Eur. Polym. J. 1975, 11, 805. 2) Choudhary, M. S.; Lederer, K. Eur. Polym. J. 1982, 18, 1021. 3) Braun, D.; Steffan, R. Polym. Bull. 1983, 3, 111. 4) Cascaval, C. N.; Poinescu, Ig. Polym. Degrad. Stab. 1995, 48, 55.

30 [min]

20

Molecular Retention Weight Index 44 44 86 130 144 198

150 408 798 1029 1284 1315

Relative Intensity 2.2 1.6 5.3 100.0 2.9 2.6

87

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

038

EGA thermogram

Averaged mass spectrum 69

41

100

87

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

31 59

100

50

100

150

[m/z]

( m/z range : 29 - 600 amu )

LB : carbon dioxide O

C

A : acetaldehyde 44

O

44

O

30

29

MA : methacrylic acid

58

M : 2-hydroxyethyl methacrylate 69

86

41

O 41

OH

OH

O 87

O 57

69 31

100

59

31

ED : ethane-1,2-diyl bis(2-methylacrylate)

M' : 2-hydroxyethyl-2-methylbut-3-enoate 69

O

69 O

41

O

OH

O 101

31 55

112

O

O 41

113

113

88 131

143

31

53

82

99

125 136

155

170

88

Tsuge, Ohtani and Watanabe

039 Poly(methyl acrylate); PMA CH2CH(COOCH3)

n

M3

M2 M5

M2’

M1

M4

M’ TIC

MO

M6

M

0

10

Peak Notation MO M1 M M’ M 2’ M2 M3 M4

M5 M6 M7

Assignment of Main Peaks

M7 30 [min]

20

Molecular Retention Weight Index

methanol methyl acrylate methyl methacrylate C=C-C(COOC)-C C(COOC)-C-C-COOC C=C(COOC)-C-C-COOC (dimer) C=C(COOC)-C-C(COOC)-C-C-COOC (trimer) C=C(COOC) C-C(COOC) C-C-COOC (meso (m)) 2 (tetramer) C=C(COOC) C-C(COOC) 2 C-C-COOC (racemic (r)) C=C(COOC) C-C(COOC) 3 C-C-COOC (mm) (pentamer C=C(COOC) C-C(COOC) 3 C-C-COOC (mr) ;diastereomer) C=C(COOC) C-C(COOC) 3 C-C-COOC (rr) C=C(COOC) C-C(COOC) 4 C-C-COOC (hexamer) C=C(COOC) C-C(COOC) 5 C-C-COOC (heptamer) *bonding hydrogen is omitted

32 86 100 114 160 172 258 344 344 430 430 430 516 602

310 607 711 804 1138 1198 1675 2101 2111 2521 2526 2530 2932 3328

[ Related References ] 1) Yamamoto, Y.; Tsuge, S.; Takeuchi, T. Macromolecules 1972, 5. 325. 2) Haken, J. K.; Mckay, T. R. Anal. Chem. 1973, 45, 1251. 3) Tsuge, S.; Hiramitsu, S.; Horibe, T.; Yamaoka, M.; Takeuchi. T. Macromolecules 1975, 8, 721. 4) Gunawan, L.; Haken, J. K. J. Polym. Sci., Polym. Chem. Ed. 1985, 23, 2539. 5) Haken, J. K.; Tan, L. J. Polym. Sci., Part A, 1988, 26, 1315. 6) Lehrle, R. S.; Place, E. J. Polym. Degrad. Stab. 1997, 56, 215. 7) Bertini, F.; Audisio, G ; Zuev. V. V. Polym. Degrad. Stab. 2005, 89, 233.

Relative Intensity 5.5 24.0 3.5 6.8 15.4 28.4 100.0 8.0 7.8 6.3 12.4 4.9 7.6 4.0

89

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

039

EGA thermogram

Averaged mass spectrum 59

79 41

100

31 67

300

400

500

153

100

600

700 ºC

programming rate: 20ºC/min

125

50

200

134

100112

194

167

227 215

186

150

200

275

306

250

334

300

399

366

350

[m/z]

400

( m/z range : 29 - 600 amu )

MO : methanol

M1 : methyl acrylate H

31

O

O

H

H

41

55

O

H

85

42

31

56

68

M' : methyl-2-methylbut-3-enoate

M : methyl methacrylate

55

41

O

O

O

69

83 O 100

59

29

O

M2 : dimethyl 2-methylenepentanedioate

59

O

114

71

M2' : dimethyl glutarate O

99

39

29

85

O

100

O

O

112 O

129

140 O

42

53 87

29

39

74

O

O

O

O

(meso form) (tetramer) O

194

134

79

59 106

167

59

67

29

153

179

O

O

O

O

O

O

O

O

O

O

220 252

313

280

67

M6 : hexamethyl dodec-11-ene-1,3,5,7,9,11-hexacarboxylate

O

O

O

O

O

O

O

O

O

O

O

O

O

59

59 172

275 306 334

100 79 41 67 29

O

(hexamer)

(pentamer; diastereoisomer ) O

O

79

29

211

M5 : pentamethyl dec-9-ene-1,3,5,7,9-pentacarboxylate O

192

O

100 41

97

O

161 133

227

125

41

125

M4 : tetramethyl oct-7-ene-1,3,5,7-tetracarboxylate

M3 : trimethyl hex-5-ene-1,3,5-tricarboxylate O

97

71

31

113

O

81

112 139

399

79

247

187

172

100 112

215 366

41 67

227

361

138

128

185 213

273

301

333

420

485

392 452

380

31

90

Tsuge, Ohtani and Watanabe

040 Poly(ethyl acrylate); PEA CH2CH(COOC2H5)

n

M3

M2 M1

M2

EO LB

M5 TIC

M4

M’

0

10

Peak Notation LB EO M1 M M2’ M2 M3 M4

M5

30 [min]

20

Assignment of Main Peaks CO2 ethanol ethyl acrylate ethyl methacrylate C(COOC2)-C-C-COOC2 C=C(COOC2)-C-C-COOC2 (dimer) C=C(COOC2)-C-C(COOC2)-C-C-COOC2 (trimer) C=C(COOC2) C-C(COOC2) 2C-C-COOC2 (meso form) C=C(COOC2) C-C(COOC2) 2C-C-COOC2 (racemic form) (tetramer) C=C(COOC2) C-C(COOC2) 3C-C-COOC2 (pentamer) *bonding hydrogen is omitted

[ Related References ] 1) Haken, J. K.; Mckay, T. R. Anal. Chem. 1973, 45, 1251. 2) Haken, J. K.;Tan, L. J. Polym. Sci, Part-A, 1988, 26, 1315. 3) Mao, S.; Ohtani, H.; Tsuge, S. J. Anal. Appl. Pyrolysis. 1995, 33, 181. 4) McNeil, I. C.; Mohammed, M. H. Polym. Degrad. Stab. 1995, 48, 175. 5) Bertini, F.; Audisio, G.; Zuev. V. V. Polym. Degrad. Stab. 2005, 89, 233.

Molecular Retention Weight Index

Relative Intensity

44 46 100 114 188 200 300 400 400

150 462 695 786 1280 1333 1846 2301 2309

19.5 28.6 30.7 28.6 26.1 21.8 100.0 2.2 1.8

500

2738

10.6

91

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

040

EGA thermogram

Averaged mass spectrum 31

100

45

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

55 69

79

98

50

134 125

114

100

154 166 150

181

200

208

226

255

243

200

300 [m/z]

250

( m/z range : 29 - 600 amu )

EO : ethanol

LB : carbon dioxide O

C

44

O

31

OH 45

29

M' : ethyl methacrylate

M1 : ethyl acrylate 55

69

O

O

O

41

O

29

29

45

73

M2 : diethyl 2-methylenepentanedioate (dimer) 98

143 O

O

114

58

M2' : diethyl glutarate

O

115

O 42

43

101

O

127

29

55 73

O

O O 154

87 29

99

86

99

82

53 69

129

81

109

143

172

200

M4 : tetraethyl oct-7-ene-1,3,5,7-tetracarboxylate M3 : triethyl hex-5-ene-1,3,5-tricarboxylate (trimer) 208

134 O

O

O

O

O

(meso form) (tetramer) 29

255

O

O

O

O

O

O

O

O

200

29

79

181

106 152

55 41

67

97

226

125

206 234 262280 308

M5 : pentaethyl dec-9-ene-1,3,5,7,9-pentacarboxylate (pentamer)

(racemic form) (tetramer)

455

29

29 O

O

O

O

O

O

55

105 91 79

206 179

O

O

O

O

355

161 133

O

355

179

79

41

M4 : tetraethyl oct-7-ene-1,3,5,7-tetracarboxylate

41

105 133

55

200

161

235

55 280 308 262

O

O

O

O

200 114 79

98

187 155 215 131 167

O

O

O

O

289 334

261 306

362 380 408

92

Tsuge, Ohtani and Watanabe

041 Poly(butyl acrylate); PBA CH2CH(COOC4H9)

n

M3

M2

M1

B

M2

BO TIC

BT

A

M4

0

10

Peak Notation B BT BO A M1 M2’ M2 M3 M4

30 [min]

20

Assignment of Main Peaks 1-butene n-butanal 1-butanol acrylic acid n-butyl acrylate C(COOC4)-C-C-COOC4 C=C(COOC4)-C-C-COOC4 (dimer) C=C(COOC4)-C-C(COOC4)-C-C-COOC4 (trimer) C=C(COOC4) C-C(COOC4) 2C-C-COOC4 (meso form) C=C(COOC4) C-C(COOC4) 2C-C-COOC4 (racemic form) (tetramer) *bonding hydrogen is omitted

[ Related References ] 1) Haken, J. K.; Mckay, T. R. Anal. Chem. 1973, 45, 1251. 2) Haken, J. K.;Tan, L. J. Polym. Sci, Part A, 1987, 25, 1451. 3) Haken, J. K.;Tan, L. J. Polym. Sci, Part A, 1988, 26, 1315. 4) Bertini, F.; Audisio, G.; Zuev. V. V. Polym. Degrad. Stab. 2005, 89, 233.

Molecular Retention Weight Index 56 72 74 72 128 244 256 384 512 512

392 605 657 697 892 1648 1696 2352 2929 2938

Relative Intensity 64.6 5.3 43.8 1.3 47.3 44.7 46.0 100.0 1.5 1.1

93

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

041

EGA thermogram

Averaged mass spectrum 41

100

56

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

31

98

115 127 134

73 79 50

100

181 236 171 199 208 226

153 150

255

200

311

282

250

300

350

[m/z]

( m/z range : 29 - 600 amu )

BT : n -butanal

B : 1-butene

29

41

41

O 72

56 57 29

BO : 1-butanol

A : acrylic acid 31

56

41

OH

72

55

OH O 45

74 78

M1 : n-butyl acrylate

M2' : dibutyl glutarate

55

115

O O

O

O

O

57

70

O

73 41

29

99

113

M2 : dibutyl 2-methylenepentanedioate (dimer)

171

87

41

29

85

142 98

181 O

O

O

O

29

154

109

201

79

67

256

124 98109

311 170

208 226 199

255 282 267

M4 : tetrabutyl oct-7-ene-1,3,5,7-tetracarboxylate

M4 : tetrabutyl oct-7-ene-1,3,5,7-tetracarboxylate

(rasemic form)(tetramer)

(meso form)(tetramer)

41

41 O

29

153

57

183

81

O O

236

41 71

O O

O O

134

41

98

57

189

M3 : tributyl hex-5-ene-1,3,5-tricarboxylate (trimer)

127

29

129

O

O

O

O

O

O

O

29

57

O

O

O

57 161 73 98

127 151

179

207 253 223 262 290308 336

439

98115 78

O

O

O

O

O

207

133 160

181

234253

439 290

327

364

403

94

Tsuge, Ohtani and Watanabe

042 Poly(acrylic acid; isotactic); PAA CH 2CH(COOH)

n

h e

LB d b

c

j

f g i

X

a

T MA

5

3

A TIC

7

11

9

13

17

15

B

0

10

Peak Notation LB B A T MA X a b c d e f g h i j

Assignment of Main Peaks

30 [min]

20

Molecular Retention Weight Index

CO2 1-butene acrylic acid toluene methacrylic acid xylene 3-methyl-2-cyclohexenone o-cresol 2,6-xylenol

unidentified (these pyrolyzates are expected to be cyclic ketones, esters, and acid anhydrides)

[ Related References ] 1) McGaugh, M. C.; Kottle, S. Polym. Lett. 1967, 5, 817. 2) Fyfe, C. A.; Mckinnon, M. S. Macromolecules 1986, 19, 1909. 3) Maurer, J. J.; Eustace, D. J.; Ratchliffe, C. T. Macromolecules 1987, 20, 196. 4) Lattimer, R. T. J. Anal. Appl. Pyrolysis 2003, 68-69, 3.

44 56 72 92 86 106 110 108 122 162 160 174 178 210 246 260

150 382 709 768 790 874 999 1057 1113 1478 1543 1610 1769 1880 2323 2340

Relative Intensity 100.0 10.3 0.8 3.2 1.0 5.5 4.4 6.4 6.2 10.9 13.4 11.5 6.7 12.9 4.6 10.4

95

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

042

EGA thermogram

Averaged mass spectrum 44

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

51

77

91 115 131

65

50

165 178 195 202 216

146

100

150

239 246 260 272 286

200

250

350 [m/z]

300

( m/z range : 29 - 600 amu )

LB : carbon dioxide O

C

B : 1-butene 44

O

41

56

29

A : acrylic acid

64

X : xylene 72

OH

91

55

O

106 45 29 81

b : o-cresol

51

39

29

65

77

c : 2,6-xylenol

OH

OH

108

122 107

79

77

90 29

39

51

63

119

134

29

39

51

91

65

e : unidentified

d : unidentified 162

160

134

91

132

120 39

51

65 77

51

105

152

63

39

178

77

103 150

j : unidentified

f : unidentified 145

260

174

146 163

39

51 63

77

91

115

41

131

55 29

69

91

134 105 121

189

204

232

96

Tsuge, Ohtani and Watanabe

043 Methyl methacrylate-methyl acrylate copolymer; P(MMA-MA) CH2C(CH3)(COOCH3)

CH2CH(COOCH3)

n

A2’ M

D1 A2 d4 d1 d2

D3

HT D4

T

d5

5

TIC

HT ’

10

15

A

0

10

Peak Notation A M d1 d2 d4 d5 A2 A2’ D1 D3 D4

HT

HT’ T

Assignment of Main Peaks methyl acrylate methyl methacrylate C=C(C)-C-C(COOC)-C ? C=C(C)-C-C(C)(COOC)-C ? C=C(C)-C=C(COOC)-C ? C-C(C)-C-C(C)(COOC)-C ? C-C(COOC)-C-C-COOC (MA dimer) C=C(COOC)-C-C-COOC C=C(COOC)-C-C(COOC)-C ? C=C(COOC)-C-C(C)(COOC)-C ? C-C(COOC)=C-C(C)(COOC)-C ? C11H18O4 ? either one of the following: C-C(COOC)=C-C(COOC)-C-C(COOC)-C C=C(COOC)-C-C(COOC)-C-C(COOC)-C C-C(COOC)=C-C(C)(COOC)-C-C-COOC C=C(COOC)-C-C(C)(COOC)-C-C-COOC C=C(COOC)-C-C(C)(COOC)-C-C(C)(COOC)-C C-C(COOC)=C-C(C)(COOC)-C-C(C)(COOC)-C *bonding hydrogen is omitted

30 [min]

20

Molecular Retention Weight Index 86 100 142 156 140 158 174 172 186 200 200 214 272 272 272 272 300 300

? ? ? ?

? ? ? ?

Relative Intensity

613 710 937 984 1035 1088 1166 1187 1209 1256 1309 1327

4.5 100.0 0.1 0.1 0.2 0.1 0.1 0.2 0.5 0.4 0.2 0.2

1648 1655 1671 1728 1735 1829

0.2 0.1 0.2 0.2 0.1 0.2

[ Related References ] 1) Haken, J. K.; Mckay, T. R. Anal. Chem. 1973, 45, 1251. 2) Kiura, M ; Atarashi, J.; Ichimura, K.; Ito, H.; Ohtani, H.; Tsuge, S. J. Appl. Polym. Sci. 2000, 78, 2140.

97

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

043

EGA thermogram

Averaged mass spectrum 41

100

69

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

100

55

85

31

113

50

126

153

100

150

250 [m/z]

200

( m/z range : 29 - 600 amu )

A : methyl acrylate

M : methyl methacrylate 41

55

O

O

69

O O

100 85

42

29

59

29

68

A2' : dimethyl 2-methyl-4-methylenepenatanedioate

85

D1 : dimethyl 2,2-dimethyl-4-methylenepentanedioate 81

126

140 109 O

O

O 67

O

O

41

O

O

O

111 59

95

39

59

29

83

HT : trimethyl hept-1-ene-2,4,6-tricarboxylate

93

79 O

152 120

59 79

29

O

O

O

O

O

32 41

125

95

O

O

O

O

113 121

141 O

O

O

241 111

181

137

29

O

-2,4,6-tricarboxylate 121

107 O

59 69

O

O

O

O

O

O

O

O

127 79

O

T : (Z)-trimethyl 4,6-dimethylhept-2-ene

-2,4,6-tricarboxylate

40

O

213

212

HT' : trimethyl 4,6-dimethylhept-1-ene

O

186 153

55 67

39

120 81

67

O

166

79 41

O

227

93

93

29

O

198

HT : trimethyl 3-methylhex-5-ene-1,3,5-tricarboxylate

-1,3,5-tricarboxylate

59

O

241

HT : (Z)-trimethyl 3-methylhex-4-ene

O

O

134

68

180

152

O

106

59

172

113

69

125 169

HT : (Z)-trimethyl hept-2-ene-2,4,6-tricarboxylate

41

101 67

155

95

O

O

149

O

59 139

155

186 194

139

41 32

79 65

97 111

167 176

241

98

Tsuge, Ohtani and Watanabe

044 Higher methacrylate copolymer CH2C(CH3)(COOR)

n

R=C1, C12 – C16, C18 (including branched isomers) M13 M12 M14 M13’ C13 TIC

M1

MA

C12

0

M15

M12’ C14

M14’ M16

M15’ M18

10

Peak Notation

Assignment of Main Peaks

M1 MA C12 C13 C14 M12’ M12 M13’ M13 M14’ M14 M15’ M15 M16 M18

methyl methacrylate methacrylic acid 1-dodecene 1-tridecene 1-tetradecene 2-methylundecyl methacrylate dodecyl methacrylate 2-methyldodecyl methacrylate tridecyl methacrylate 2-methyltridecyl methacrylate tetradecyl methacrylate 2-methyltetradecyl methacrylate pentadecyl methacrylate hexadecyl methacrylate octadecyl methacrylate [ Related References ] 1) Ohtani, H.; Asai, T.; Tsuge, S. Macromolecules 1985, 18, 1148.

30 [min]

20

Molecular Retention Index Weight 100 86 168 182 196 254 254 268 268 282 282 296 296 310 338

711 801 1193 1292 1393 1714 1776 1814 1876 1914 1976 2014 2075 2175 2377

Relative Intensity 7.9 1.6 7.8 11.5 6.8 7.3 70.3 10.9 100.0 6.3 55.1 3.2 25.2 6.1 1.9

99

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

044

EGA thermogram

Averaged mass spectrum 41

69 87

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

55 97

111

31 50

125

140

100

153

168

182

196

150

211 250 [m/z]

200

( m/z range : 29 - 600 amu )

MA : methacrylic acid

M1 : methyl methacrylate 41

39 O 69

29

OH 86

O

O

100

59

85

58

29

C13 : 1-tridecene

68

M12' : 2-methylundecyl methacrylate 69

41 41

55

O 56

69

29

O

83 97 111

29 125 139

154

M12 : dodecyl methacrylate 41

83

O

41

O

O

56

55 97

29

111 125140 152 168 181195 211

83

29

111

126

139

154 167 182 195

M14 : tetradecyl methacrylate

69

41

69

O

87

97

255

M13 : tridecyl methacrylate

O

87

O

O

55

55 97

29

97

29 111

125 182 139 154 169 195

111 125 139

269

M15 : pentadecyl methacrylate

196

239

69

41

O

O

87 O

55

168

M18 : octadecyl methacrylate

69 87

O

55 97

97 29

140 153 168

69 O 87

41

111 125

M13' : 2-methyldodecyl methacrylate

69

41

97

182

111

29 125 139153

182

210

237 253

297

111

125

139

207

283

100

Tsuge, Ohtani and Watanabe

045 Acrylic rubber; ACM CH2CH(COOC2H5)

CH2CH(COOC2H4OCH3)

CH2CH(COOC4H9)

B

EB’

EBM EBB

BM’ EM’ BA

VM LB

BO

BB’

EEB

EE’ EE

BMA

ME

n

BBB BBM

EEM

BMM

EEE EMM

M

MMM

E 8

6

12

10

14

16

TIC

0

10

Peak Notation LB B VM ME BO E BA M BMA EE’ EE EB’ EM’ BB’ BM’ EEE EEB

EEM

EBB

EBM

EMM BBB BBM BMM MMM

Assignment of Main Peaks CO2 1-butene vinyl methyl ether 2-methoxy ethanol 1-butanol ethyl acrylate n-butyl acrylate 2-methoxy ethylacrylate n-butyl methacrylate C(COOC2)-C-C-COOC2 C=C(COOC2)-C-C-COOC2 (E dimer) C(COOC2)-C-C-COOC4 C(COOC2)-C-C-COOC2OC C(COOC4)-C-C-COOC4 C(COOC4)-C-C-COOC2OC C=C(COOC2)-C-C(COOC2)-C-C-COOC2 (E trimer) Either one of the C=C(COOC2)-C-C(COOC2)-C-C-COOC4 following C=C(COOC2)-C-C(COOC4)-C-C-COOC2 C=C(COOC4)-C-C(COOC2)-C-C-COOC2 C=C(COOC2)-C-C(COOC2)-C-C-COOC2OC Either one of the following C=C(COOC2)-C-C(COOC2OC)-C-C-COOC2 C=C(COOC2OC)-C-C(COOC2)-C-C-COOC2 C=C(COOC2)-C-C(COOC4)-C-C-COOC4 Either one of the following C=C(COOC4)-C-C(COOC4)-C-C-COOC2 C=C(COOC4)-C-C(COOC2)-C-C-COOC4 C=C(COOC2)-C-C(COOC4)-C-C-COOC2OC Either one of the following C=C(COOC2OC)-C-C(COOC2)-C-C-COOC4 C=C(COOC2OC)-C-C(COOC4)-C-C-COOC2 C=C(COOC2)-C-C(COOC2OC)-C-C-COOC2OC Either one of the following C=C(COOC2OC)-C-C(COOC2)-C-C-COOC2OC C=C(COOC2OC)-C-C(COOC2OC)-C-C-COOC2 , etc. C=C(COOC4)-C-C(COOC4)-C-C-COOC4 (B trimer) C=C(COOC4)-C-C(COOC4)-C-C-COOC2OC + 2 isomers C=C(COOC4)-C-C(COOC2OC)-C-C-COOC2OC + 2 isomers C=C(COOC2OC)-C-C(COOC2OC)-C-C-COOC2OC (M trimer) *bonding hydrogen is omitted

[ Related References ] 1) Haken, J. K.; Mckay, T. R. Anal. Chem. 1973, 45, 1251. 2) Yamaguchi, S.; Hirano, J.; Isoda, Y. Polym. J. 1985, 17, 1105.

30 [min]

20

Molecular Retention Weight Index 44 150 56 388 58 390 76 627 74 657 100 696 128 892 130 913 142 976 188 1269 200 1322 216 1459 218 1475 244 1648 246 1664 300 1828 328 1996 328 2004 328 2008 330 2018 330 2021 330 2029 356 2170 356 2177 356 2187 358 2319 358 2199 358 2204 360 2211 360 2219 360 2223 384 2352 386 2370 388 2391 390 2412

Relative Intensity 30.9 100.0 13.4 42.5 34.6 32.9 54.3 39.1 6.1 10.8 7.1 25.8 16.3 15.4 21.1 11.2 9.1 9.4 8.5 8.6 5.0 5.9 11.0 8.9 18.0 6.6 9.2 8.9 3.1 4.9 6.0 9.4 21.1 15.2 3.7

101

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

045

EGA thermogram

Averaged mass spectrum 41 56 31

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

98

79 73 50

115

134 127

152

100

181 164

150

208 199

227236

255

200

283

313

250

300

350

[m/z]

( m/z range : 29 - 600 amu )

B : 1-butene

VM : vinyl methyl ether 43

41

O 29

58

56 29

ME : 2-methoxyethanol

BO : 1-butanol

45

O

56

41

31

OH

OH 29

76

58

69

78

BA : n-butyl acrylate

E : ethyl acrylate O

55

O

55

O

O 73

29 45

72

41

29

99

82

85

M : 2-methoxyethyl acrylate

99

113

EB' : butyl ethyl glutarate O

55

115

O

143 O

O

45

O

O

O 87

42

29

29 71

55

87

99

70

98

171

129

BBM : 3,5-dibutyl 1-(2-methoxyethyl) hex-5-eneBM' : butyl 2-methoxyethyl glutarate

1,3,5-tricarboxylate

115

O

59 29

181

O

O

O

87

42

O

41 59 29

134 79

173 70

98

118

142

69 159

106125 153 97 162

O

O

O

O

O

O

236 199 225

313 258 284 329 355

O

102

Tsuge, Ohtani and Watanabe

046 Polyacrylonitrile; PAN CH2CH(CN)

n

AA2 AAA2 AA3 AAA1

AAA3 AAA4

LB TIC

AAA5 T1

AA1 A

MA

T2

T3

AA’ 0

10

Peak Notation LB A MA AA’ AA1 AA2 AA3 AAA1 AAA2 AAA3 AAA4 AAA5 T1 T2 T3

Molecular Retention Weight Index

Assignment of Main Peaks low boiling point components acrylonitrile (monomer) methacrylonitrile C(CN)=C-C-CN C-C(CN)-C=C-CN + C=C(CN)-C-C(CN)-C C=C(CN)-C-C-CN + C(CN)-C-C-CN + C=C(CN)-C-C(CN)=C C-C(CN)-C-C-CN C=C(CN)-C-C(CN)-C-C-CN C-C(CN)-C-C(CN)-C-C-CN (trimer) C(CN)-C-C(CN)-C-C-CN C-C(CN)-C-C(CN)-C=C-CN C9H9N3 (isomer of trimer) C=C(CN)-C-C(CN)-C-C(CN)-C-C-CN C=C(CN)-C-C(CN)-C-C(CN)-C-C(CN)=C C(CN)-C-C(CN)-C-C(CN)-C-C-CN? *bonding hydrogen is omitted

30 [min]

20

(dimer)

(tetramer)

53 67 92 106; 120 106 94; 118 108 159 161 147 159 159 212 224 200

470 567 602 834 1045

Relative Intensity 1.4 6.2 1.1 0.9 1.2

1059

64.9

1071 1513 1540 1564 1655 1743 2022 2155 2294

24.4 23.9 100.0 35.9 39.9 13.5 23.9 12.0 9.9

[ Related References ] 1) Yamamoto, Y.; Tsuge, S.; Takeuchi, T. Macromolecules 1972, 5, 325. 2) Tsuchiya, Y.; Sumi, K. J. Appl. Polym. Sci. 1977, 21, 975. 3) Nagaya, T.; Sugimura, Y.; Tsuge, S. Macromolecules 1980, 13, 353. 4) Usami, T.; Itoh, T.; Ohtani, H.; Tsuge, S. Macromolecules 1990, 23, 2460. 5) Minagawa, M.; Onuma, H.; Ogita, T.; Uchida, H. J. Appl. Polym. Sci. 2001, 79, 473. 6) Sanchez-Soto, P. J.; Aviles, M. A.; del Rio, J. C.; Gines, J. M.; Pascual, J.; Perez-Rodriguez, J. L. J. Anal. Appl. Sci. 2001, 58-59, 155.

103

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

046

EGA thermogram

Averaged mass spectrum 54 66 39 100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

106 119 79

94 133

50

147

100

160

174 200 [m/z]

150

( m/z range : 29 - 600 amu )

AA2 : 2-methylenepentanedinitrile (+ glutaronitrile + 2,4-dimethylenepentanedinitrile) (dimer)

A : acrylonitrile 53

66 N

N

N

N

+ 41

N

N

N

+

54 106

38 79

29

AAA1 : hex-5-ene-1,3,5-tricarbonitrile (trimer)

AA3 : 2-methylpentanedinitrile N

91

N

39

N

171

118

N

143 156

205

AAA3 : pentane-1,3,5-tricarbonitrile (trimer) N

106 66

N

105 78 91

78

N

66 52

64

AAA2 : hexane-1,3,5-tricarbonitrile (trimer) N

N

119

39 52

91

N

N

107

54

119 41

39

80

52

66

92 78

29

AAA4 : (Z)-hex-1-ene-1,3,5-tricarbonitrile (trimer) N

106

N

93

29

132

N

119

146

T1 : oct-7-ene-1,3,5,7-tetracarbonitrile (tetramer) N

N

N

119

N

54

106

66

39

66

79 92

29

39

119 132

32

158

T2 : nona-1,8-diene-2,4,6,8-tetracarbonitrile (tetramer) N

N

N

N

78

172 107

107 66

159

172

N

N

145

145 131

79

145

54

39

32

92

T3 : heptane-1,3,5,7-tetracarbonitrile (tetramer)

171

54

54

39

158

158

66 79

92

119 91

183

29

208

N

N

104

Tsuge, Ohtani and Watanabe

047 Acrylonitrile-methyl acrylate copolymer CH2CH(CN)

M2A

CH2CH(COOCH3)

n

M3

MAA

A2M

A MO LB

MMA

M

A

AM

MA AA

TIC

MM

AM

MM

M

0

pentamers

MA

trtramers

10

Peak Notation LB MO A MA M A’ MMA M’ AA AM’ AM MM’ MA’ MM

A2M MAA

M2A M3

30 [min]

20

Assignment of Main Peaks CO2 methanol acrylonitrile methacrylonitrile methyl acrylate C-C-C=C-CN methyl methacrylate C=C-C(COOC)-C C(CN)-C-C-CN + C=C(CN)-C-C-CN (A dimer) C(CN)-C-C-COOC + C=C(CN)-C-C(CN)=C C=C(CN)-C-C(COOC) (hybrid dimer) C(COOC)-C-C-COOC + C-C(CN)-C=C(COOC) C=C(COOC)-C-C(CN)=C C=C-C(COOC)-C-C-COOC (M dimer) Either one of the following: C=C(CN)-C-C(CN)-C-C-COOC C=C(CN)-C-C(COOC)-C-C-CN C=C(COOC)-C-C(CN)-C-C-CN (hybrid trimer) Either one of the following: C=C(COOC)-C-C(COOC)-C-C-CN C=C(COOC)-C-C(CN)-C-C-COOC C=C(CN)-C-C(COOC)-C-C-COOC C=C(COOC)-C-C(COOC)-C-C-COOC *bonding hydrogen is omitted

[ Related References ] 1) Yamamoto, Y.; Tsuge, S.; Takeuchi, T. Macromolecules 1972, 5, 325. 2) Saglam, M. J. Appl. Polym. Sci. 1986, 32, 5719.

Molecular Retention Weight Index

Relative Intensity

44 32 53 67 86 81 100 114 94; 106 127; 118 139 160; 139 151 186

150 320 567 602 608 699 714 803 1063 1076 1088 1134 1150 1194

27.6 38.6 33.8 5.4 47.1 6.6 6.5 5.9 14.6 23.2 9.2 34.4 5.2 16.5

192 192 192

1522 1545 1563

2.0 41.1 51.4

225 225 225 258

1582 1619 1628 1667

100.0 69.6 34.8 83.4

105

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

047

EGA thermogram

Averaged mass spectrum 39

55 106

79 31

100

66

200

300

400

500

94

50

600

700 ºC

programming rate: 20ºC/min

134 120

161 152

100

194 187 203

150

227 235246 261274

200

305

250

333

366

300

400 [m/z]

350

( m/z range : 29 - 600 amu )

A : acrylonitrile

MO : methanol H

31

53

H

H

H

41

N

O

38

29

56

74

MM' : dimethyl glutarate

M : methyl acrylate

( + (Z)-methyl 4-cyanopent-2-enoate) 55

O

O

59

N O

O

O

100

O

108

29

68

A2M : methyl 4,6-dicyanohept-6-enoate (hybrid trimer) 106

N

66

O

129

69

138

MAA : methyl 4,6-dicyano-2-methylenehexanoate (hybrid trimer) O

N

O

80

42

85

42

29

O

+

N

O

N

106

92

133

O

119 55

55

79

O

177

192

M2A : dimethyl 4-cyano-2-methyleneheptanedioate (hybrid trimer)

4-methylenepentanedioate (hybrid trimer) O

152

29

192

M2A : dimethyl 2-(2-cyanoethyl)O

161 131

177

149

N

66

161

134

92

29

O

79

39

39

106

O

N

O

O

161

O 133 106

79

194

99

59 41

152

65

O

O

79

59 39 29

O

69

O

134

O

106 99

120

185

O

O

O

79

194 152 161

67

153

M3 : trimethyl hex-5-ene-1,3,5-tricarboxylate

(hybrid trimer) N

125

93

29

177

M2A : dimethyl 2-(2-cyanoallyl)pentanedioate

194

79

120

39 29

165

134

59

O

O

194

134

106

167

59 210

41

178 224

29

227

125 67

97

153

230

106

Tsuge, Ohtani and Watanabe

048 Polyacrylamide; PAAm CH2CH(CONH2)

n

D3

D2 D5 T1

AN

D1 AN2

LB

TIC

T3

AN3

D4

MA

T4

a T2

P

0

10

Peak Notation LB AN P MA

AN2

D1 a D2 D3

D5 AN3

T2 T3

T4

CO2 etc. acrylonitrile propanenitrile methacrylonitrile C-C(CN)-C=C-CN C(CN)-C-C-CN C=C(CN)-C-C-CN C-C(CN)-C-C-CN

Molecular Retention Weight Index

Relative Intensity

44 53 55 67 106 94 106 108

150 560 567 602 1045 1053 1057 1073

27.9 17.3 3.3 18.1 7.8 18.6 30.7 4.9

113

1176

53.4

C7H9NO ?

123

1202

C-C-C-C | | O=C-N-C=O

6.5

127

1216

38.2

125

1228

100.0

141

1252

18.3

139

1261

60.6

159 147

1528 1551

41.9 5.0

178

1679

36.0

192

1692

8.1

166

1697

69.5

180

1713

35.9

C-C-C | | O=C-N-C=O

C-C-C=C | | O=C-N-C=O C-C-C-C-C | | O=C-N-C=O

D4

T1

Assignment of Main Peaks(*bonding hydrogen is omitted)

30 [min]

20

C-C-C-C=C | | O=C-N-C=O

C=C(CN)-C-C(CN)-C-C-CN C(CN)-C-C(CN)-C-C-CN C=C(CN)-C-C-C-C | | O=C-N-C=O C=C(CN)-C-C-C-C-C-C | | O=C-N-C=O C(CN)-C-C-C-C | | O=C-N-C=O C-C(CN)-C-C-C-C | | O=C-N-C=O

*bonding hydrogen is omitted [ Related References ] 1) Leung, W. M.; Axelson, D. E. J. Polym. Sci., Polym. Chem. Ed. 1987, 25, 1825. 2) Tutas, M.; Saglam, M.; Yuksel, M. J. Anal. Appl. Pyrolysis 1991, 22, 129. 3) Wang, F. C.-Y. J. Chromatogr. A 1996, 753, 101. 4) Ishida, Y.; Tsuge, S.; Ohtani, H.; Inokuchi, F.; Fujii, Y.; Suetomo, S. Anal. Sci. 1996, 12, 831.

107

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

048

EGA thermogram

Averaged mass spectrum 42

56 100

67

200

300

400

500

96

700 ºC

125

82

139

154 164 176

30 50

600

programming rate: 20ºC/min

113

100

192

150

210

225 235

200

300 [m/z]

250

( m/z range : 29 - 600 amu )

AN : acrylonitrile

MA : methacrylonitrile 53

N

41

N

67 52 38

AN2 : 4-methylpent-2-enedinitrile

D1 : piperidine-2,6-dione

79

N

N

42

O

52

N

O

113

66

106

39

70

92

120

55

30

84

D3 : 3-methylenepiperidine-2,6-dione

D2 : 3-methylpiperidine-2,6-dione 56

125 54

99

42

O

N

O

O

N

O 39

127 29

70

84

82

112

70

29

T1 : 2-(2,6-dioxopiperidin-3-yl)but-3-enenitrile

D5 : 3-methyl-5-methylenepiperidine-2,6-dione 67

N

106

O

39

N

111

123

39

O

96

66 133

178

O

150 161

T4 : 3-(2,6-Dioxopiperidin-3-yl)2-methylpropanenitril

T3 : 3-(2,6-dioxopiperidin-3-yl)propanenitrile 113

N

O

92

29

124

81

79

55

139

53

29

96

N

127 55 39 O

55

N

67 95

29 123 137 149

166

192

N

O

N

99

67 29

O

O

85

42

112 78

145

161

190

108

Tsuge, Ohtani and Watanabe

049 Poly(maleic anhydride); PMAH CH(CO)CH(CO)

n

O M

LB D B

X1 EB S X2

TIC

0

SM

10

Peak Notation LB B A M EB X1 S X2 SM D

Assignment of Main Peaks CO2 butene acrylic acid maleic anhydride ethylbenzene xylene (m- or p-) styrene o-xylene styrene-maleic anhydride (hybrid dimer) unidentified unidentified unidentified

30 [min]

20

Molecular Retention Weight Index 44 56 72 98 106 106 104 106 202 204 204 204

150 389 702 849 862 869 890 892 1614 1693 1707 1732

Relative Intensity 51.5 3.4 8.7 100.0 10.5 22.1 5.3 4.6 8.2 18.3 19.2 33.9

109

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

049

EGA thermogram

Averaged mass spectrum 44 54

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

91 65

31

105

77

128

50

145

100

150

165 178 189

204 200

300 [m/z]

250

( m/z range : 29 - 600 amu )

LB : carbon dioxide O

C

B : 1-butene 44

O

39

56 29 29

A : acrylic acid

M : maleic anhydride

OH

54

72 55

O

O

O

45

29

98

44

29

81

69

X1 : xylene

EB : ethylbenzene 91

91

106 106 39

51

65

77

39

51

32

63

77

X2 : o-xylene

S : styrene 104

78

39

51

91

103

106 39

74

SM : styrene-maleic anhydride (hybrid dimer)

51

65

77

D : unidentified

115

105 129

174 39

O

51 63 77

162 202

103

39 145157

29

51

65

77

91

204 132 186

110

Tsuge, Ohtani and Watanabe

2.2.6 Chlorine-containing vinyl polymers 050 Poly(vinyl chloride); PVC CH2CHCl

n

N HCL

S E X1

B TIC

5

MI

I

MN

X2

6

AC

7

8

9

AN

F

10

11

12

13

T

0

10

Peak Notation HCL B T E X1 S X2 I MI N MN AC F AN

Assignment of Main Peaks hydrogen chloride benzene toluene ethylbenzene xylene (m- or p-) styrene o-xylene indene 1-methylindene 3-methylindene naphthalene 2-methylnaphthalene 1-methylnaphthalene acenaphthene fluorene anthracene

30 [min]

20

Molecular Retention Weight Index 36 78 92 106 106 104 106 116 130 130 128 142 142 154 166 178

651 766 867 875 896 898 1057 1167 1183 1204 1320 1338 1403 1622 1832

[ Related References ] 1) Tsuge, S.; Okumoto, T.; Takeuchi, T. Makromol. Chem. 1969, 123, 123. 2) Chang, E. P.; Salovery, R. J. Polym. Sci., Polym. Chem. Ed. 1974, 12, 2927. 3) Lattimer, R. P.; Kroenke, W. J. J. Appl. Polym. Sci. 1980, 25, 101 4) Lattimer, R. P.; Kroenke, W. J. J. Appl. Polym. Sci. 1982, 27, 1355. 5) Matsusaka, K.; Tanaka, A.; Murakami, I. Polymer 1984, 25, 1337. 6) Dadvand, N.; Lehrle, R. S.; Parsons, I. W.; Rollinson, M. Polym. Degrad. Stab. 1999, 66, 247. 7) Tienpont, B.; David, F.; Vanwalleghem, F. ; Sandra, P. J. Chromatogr. A 2001, 911, 235. 8) Starnes Jr., W. H. Prog. Polym. Sci. 2002, 27, 2133.

Relative Intensity 100.0 16.0 4.3 0.5 0.8 1.3 1.0 1.8 1.8 1.3 3.5 1.7 1.2 0.9 0.8 0.8

111

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

050

EGA thermogram

Averaged mass spectrum

36 100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

78 51 31

91 115 128 141 152 165 178 191 202

63

50

100

150

229 239

258

200

300 [m/z]

250

( m/z range : 29 - 600 amu )

HCL : hydrogen chloride

B : benzene 36

78

Cl

H

52

39

T : toluene

74

S : styrene 91

104

103 78

51 39

65

51

39

89

63

MI : 1-methylindene

l : indene

130

116 115

57 63

39

119

90

64

51 39

132

N : naphthalene

132 77

91

MN : 1-methylnaphthalene 142

128

115 39

51

64

77

102

116

132

57

36

146

71

91

129

158

AN : anthracene

AC : acenaphthene 154

76 36

51 63

102 115 128

178

36

143

- 127 -

50

75

89 91

115 128 141

152

165

194

112

Tsuge, Ohtani and Watanabe

051 Vinyl chloride-vinylidene chloride copolymer; P(VC-VdC) CH2CHCl

CH2CCl2

n

LB

P3 TIC

CN

V

BO

O

CB DC TC

0

CS

TN

10

Peak Notation LB V BO O CB DC TC CS TN CN P3

Assignment of Main Peaks hydrogen chloride vinylidene chloride 1-butanol C8H16 ? C8H16 ? C8H16 ? chlorobenzene m-dichlorobenzene 1,3,5-trichlorobenzene trichlorostyrene(2,4,6- ?) trichloronaphthalene tetrachloronaphthalene plasticizer of fatty acid ester

30 [min]

20

Molecular Retention Weight Index 36 96 74 112 112 112 112 146 180 206 230 264 -

530 652 787 798 810 850 1014 1149 1367 1762 2000 2407

Relative Intensity 100.0 9.9 2.3 1.2 2.1 0.7 0.9 4.9 3.8 1.9 0.6 0.9 12.9

[ Related References ] 1) Tsuge, S.; Okumoto, T.; Takeuchi, T. Makromol. Chem. 1969, 123, 123. 2) Tsuge, S.; Okumoto, T.; Takeuchi, T. Bull. Chem. Soc. Jpn. 1969, 42, 2870. 3) Montaudo, G.; Puglisi, C.; Scamporrino, E.; Vitalini, D. J. Polym. Sci., Polym. Chem. Ed. 1986, 24, 301. 4) Wang, F. C.-Y.; Smith, P. B. Anal. Chem. 1996, 68, 425. 5) Wang, F. C.-Y. J. Anal. Appl. Pyrolysis 2004, 71, 83.

113

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

051

EGA thermogram

Averaged mass spectrum 36 100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

57 31

129 112 101

70 83

50

185

147

100

150

213

259

241

200

250

350 [m/z]

300

( m/z range : 29 - 600 amu )

LB : hydrogen chloride

V : vinylidene chloride 36

Cl

61

Cl

H

96

Cl 63 36

BO : 1-butanol

82

O : C8H16 55

56 31

OH

41

41 70 78

112

146

Cl

Cl

Cl

77 51

111 75

50

74

37

TC : 1,3,5-trichlorobenzene

85

CS : trichlorostyrene 180

Cl

171 Cl

Cl

Cl

Cl

37

84 90

136

145 147

109

74

50

Cl 50 36

119

TN : trichloronaphthalene

85 99 109

206 159

175

Cl

266 Cl

Cl

Cl

Cl

62

74

CN : tetrachloronaphthalene 230

Cl

36

112

DC : m-dichlorobenzene

CB : chlorobenzene

36

83

29

160 80

98

116 125

159

194

Cl 195

98 222

36

61 74

123 133 115

159

231

114

Tsuge, Ohtani and Watanabe

052 Chlorinated poly(vinyl chloride); CPVC CH2CHCl

CHClCHCl

CH2CCl2

n

N HCL I

DP

DC

CN

MN

CB

B

TIC

6

7

8

AN

F

9

10

12

11

13

T

0

10

Peak Notation HCL B T CB DC I N MN DP CN F AN

Assignment of Main Peaks

30 [min]

20

Molecular Retention Weight Index

hydrogen chloride benzene toluene chlorobenzene m-dichlorobenzene p-dichlorobenzene o-dichlorobenzene indene naphthalene 2-methylnaphthalene 1-methylnaphthalene diphenyl 2-chloronaphthalene fluorene anthracene [ Related References ] 1) Tsuge, S.; Okumoto, T.; Takeuchi, T. Bull. Chem. Soc. Jpn. 1969, 42, 2870. 2) Tsuge, S.; Okumoto, T.; Takeuchi, T. Macromolecules 1969, 2, 277. 3) Okumoto, T.; Ito, H.; Tsuge, S.; Takeuchi, T. Makromol. Chem. 1972, 151, 285.

36 78 92 112 146 146 146 116 128 142 142 154 162 166 178

650 766 850 1015 1021 1047 1057 1205 1319 1338 1403 1405 1622 1831

Relative Intensity 100.0 9.9 2.8 7.9 0.9 1.1 1.1 1.2 3.5 0.7 0.6 2.1 2.6 1.0 1.0

115

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

052

EGA thermogram

Averaged mass spectrum 36

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

78 74

50

91

112

50

128

100

141 152

165

178 188

202

150

216

200

250

[m/z]

( m/z range : 29 - 600 amu )

HCL : hydrogen chloride

B : benzene 36

78

Cl

H

52 39

T : toluene

74

CB : chlorobenzene 91

112

Cl

77 39

65

51

32

51 38

89

DC : o-dichlorobenzene

74

97

I : indene

Cl

116

146 Cl

111 37

75

50

118

85

57 63

39

140

N : naphthalene

89

CN : 2-chloronaphthalene 128

162

Cl

127

39

51

64

77

102

50

F : fluorene

68

81

99

136

AN : anthracene 166

178

82 39 51

69

98

115126 139

196

76 39

51

98 111

126 139

152 191

116

Tsuge, Ohtani and Watanabe

053 Chlorinated polyethylene; CM CH2CHCl

CH2CH2

n

C10 LB

C11 S

C12

C13

C14

C15 C16

I

C4

5

B TIC

6

10

Peak Notation

S C10 I C11 MI C12 C13 C14 C15 C16 C17

8

9

10

11

12

13

14

15

T

0

LB C4 B T

7

C17

MI

Assignment of Main Peaks

30 [min]

20

Molecular Retention Weight Index

hydrogen chloride 1,3-butadiene benzene toluene 1-nonene styrene o-xylene 1-decene indane 1-undecene 1-methylindene tetrahydronaphthalene 3-methylindene 1-dodecene 1-tridecene 1-tetradecene 1-pentadecene 1-hexadecene 1-heptadecene [ Related References ] 1) Tsuge, S.; Okumoto, T.; Takeuchi, T. Macromolecules 1969, 2, 200. 2) Tsuge, S.; Okumoto, T.; Takeuchi, T. Bull. Chem. Soc. Jpn. 1969, 42, 2870. 3) Wang, F. C.-Y.; Smith, P. B. Anal. Chem. 1997, 69, 618.

36 54 78 92 126 104 106 140 118 154 130 132 130 168 182 196 210 224 238

395 653 767 894 896 899 995 1048 1096 1166 1180 1183 1196 1295 1396 1496 1592 1697

Relative Intensity 100.0 16.7 4.4 4.4 2.1 1.6 1.2 3.5 2.1 2.7 2.3 1.4 1.0 2.2 2.3 2.0 1.8 1.6 1.6

117

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

053

EGA thermogram

Averaged mass spectrum 41 55

67

91

79

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

105 129

50

100

141

155 165

178 189

150

202

216

231 250 [m/z]

200

( m/z range : 29 - 600 amu )

LB : hydrogen chloride

C4 : 1,3-butadiene 36

39

Cl

H

54

29

B : benzene

64

T : toluene 91

78

52

39

39

74

32

S : styrene

79

65

51

29

C10 : 1-decene 104

56

41

70 103 78

51 29

29

83 97

39

111

63

I : indane

140

MI : 1-methylindene 117

130 115

118 132 32 39

58 65

79

91

39

136

MI : tetrahydronaphthalene

51

64 81

91

MI : 3-methylindene

104

91

130

132 115

39 29

51

65 77

131

148 29

39

51

64 77

102

134

118

Tsuge, Ohtani and Watanabe

054 Vinyl chloride-vinyl acetate copolymer; P(VC-VAc) CH2CHCl

CH2CH(OCOCH3)

n

N LB

S X I MN

A 5

6

7

8

9

10

11

B TIC

T

0

10

Peak Notation LB A B T S X I N MN

Assignment of Main Peaks

30 [min]

20

Molecular Retention Weight Index

hydrogen chloride acetic acid benzene toluene styrene o-xylene indene naphthalene 2-methylnaphthalene 1-methylnaphthalene [ Related Reference ] 1) Okumoto, T.; Takeuchi, T.; Tsuge, S. Bull. Chem. Soc. Jpn. 1970, 43, 2080.

36 60 78 92 104 106 116 128 142 142

605 650 766 895 899 1057 1204 1320 1339

Relative Intensity 100.0 20.8 13.8 3.3 1.2 0.6 1.7 3.4 1.0 0.9

119

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

054

EGA thermogram

Averaged mass spectrum 36

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

78

60 29

91 115 128 141 152 165 178 189 202

67 50

100

150

229 239 252

200

300 [m/z]

250

( m/z range : 29 - 600 amu )

LB : hydrogen chloride

A : acetic acid 36

43

Cl

H

60

29

B : benzene

62

T : toluene 91

78

52

39

39

74

S : styrene

65

51

89

I : indene 104

115

103 78

51 44

63

39

57 63

89

118

MN : 2-methylnaphthalene

N : naphthalene

142

128

115 39

51

64

102

77

44 115

MN : 1-methylnaphthalene 142

115 44

57

71

91

129

158

132

146

57

7177

91

129

158

120

Tsuge, Ohtani and Watanabe

055 Chlorosulfonated polyethylene; CSM CH2

CH2(SO2Cl)

n

MI

C10

T

LB

CHCl

S

C11

I

MD

N

ID

C14

P

C4 3

TIC

4

5

6

7

8

10

9

C6 B

0

10

Peak Notation LB C4 C6 B T S P C10 I ID C11 MI

N MD C14 C15

Assignment of Main Peaks hydrogen chloride 1,3-butadiene 1-hexene benzene toluene 1-nonene styrene o-xylene phenol 1-decene indane indene 1-undecene 1-methylindene 3-methylindene tetrahydronaphthalene naphthalene C11H12 ? 1-tetradecene 1-methylnaphthalene

[ Related Reference ] 1) Smith, D. A.; Youren, J. W. Br. Polym. J. 1976, 8, 101.

30 [min]

20

Molecular Retention Index Weight 36 54 84 78 92 126 104 106 94 140 118 116 154 130 130 132 128 144 ? 196 210

395 594 653 767 894 897 899 986 995 1048 1057 1096 1167 1173 1179 1204 1296 1397 1497

Relative Intensity 100.0 17.4 5.3 4.9 4.3 1.6 2.1 1.5 0.9 2.1 1.7 1.6 1.7 2.7 1.4 1.6 1.3 1.5 1.0 0.7

121

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

055

EGA thermogram

Averaged mass spectrum 41 55

91

67 81

100

105

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

131 141 32 50

100

155 165 178 189 202 216 150

239 252

200

300 [m/z]

250

( m/z range : 29 - 600 amu )

LB : hydrogen chloride

C4 : 1,3-butadiene

36

H

39

Cl

54

64

48

29

B : benzene

T : toluene 78

91

52

39

39

74

29

79

65

51

29

S : o-xylene

S : 1-nonene

91

56 43

106 69

29

83

97

39

108

126

C10 : 1-decene 41

51

29

65

77

ID : indene 116

56

70 29

83

97 111 122

C11 : 1-undecene 43

140

39

57 63

89 90

132

N : naphthalene 128

56 70 83

29

97 111119 134

154

43

57 64

85

102 117

132 146

122

Tsuge, Ohtani and Watanabe

056 Acrylonitrile-vinyl chloride copolymer; P(AN-VC) CH2CH(CN)

CH2CHCl

n

b BN

LB

AA

PN

TN

a

BA

P

MA B A TIC

7

6

CB

8

0

10

Peak Notation LB A MA B CB T CB BN AA TN BA PN a P b

9

10

11

12

13

14

T

Assignment of Main Peaks hydrogen chloride acetonitrile acrylonitrile methacrylonitrile benzene cyanobutadiene toluene cyanobutadiene cyanobenzene CH2(CN)CH2CH2CN CH2=C(CN)CH2CH2CN tolunitrile (m- ?) benzoic acid isophthalonitrile unidentified diethyl phthalate dibutyl phthalate

30 [min]

20

(A dimer)

[ Related Reference ] 1) Tanaka, M.; Nishimura, F.; Shono, T. Anal. Chim. Acta 1975, 74, 119.

Molecular Retention Weight Index 36 41 53 67 78 79 92 79 103 94 106 117 122 128 132 222 278

470 567 605 652 748 767 774 991 1065 1068 1101 1169 1276 1413. 1610 1980

Relative Intensity 100.0 4.6 7.3 2.5 1.5 3.5 1.3 4.1 3.9 1.5 1.8 2.0 3.8 3.2 3.2 1.6 3.0

123

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

056

EGA thermogram

Averaged mass spectrum 36

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

51

67

77

91 116

130

144 156

168

30 50

100

181

195

150

207

220

233

200

250

[m/z]

( m/z range : 29 - 600 amu )

LB : hydrogen chloride

A : acrylonitrile 36

53

Cl

H

N

38

29

67

B : benzene

MA : methacrylonitrile 41

78

N

67 52

52 39

63

29

29

BN : cyanobenzene

T : toluene 91

103

N

76 39

50

65

51

39

89

TN : m-tolunitrile

AA : 2-methylenepentanedinitrile (A dimer) 66

N

117

N

39

N

106 52 79

90 89 63

51

118

PN : isophthalonitrile

BA : benzoic acid O

39

119

91

105

OH

128

122

77

N

N 51 39

104

75

91 50 66

92

38

76 116

144

124

Tsuge, Ohtani and Watanabe

057 Acrylonitrile-vinyl chloride alternating copolymer CH2CH(CN) CH2CHCl

n

c

LB

a CP

A

b PN

AV

6

5

TIC

VAV BN TN 7

0

10

Peak Notation LB A CB CP AV a BN TN PN VAV b c

8

9

10

11

12

CB

30 [min]

20

Assignment of Main Peaks hydrogen chloride acetonitrile acrylonitrile cyanobutadiene cyanobutene cyanobutadiene cyanopentadiene CH2=C(CI)CH2CH2CN (hybrid dimer) unidentified cyanobenzene tolunitrile (m- ?) isophthalonitrile CH2=C(CI)CH2CH(CN)CH2CH2CI (hybrid trimer) unidentified unidentified

[ Related Reference ] 1) Tanaka, M.; Nishimura, F.; Shono, T. Anal. Chim. Acta 1975, 74, 119.

Molecular Retention Weight Index 36 41 53 79 81 79 93 115 103 117 128 177 -

470 563 747 759 774 904 940 978 991 1100 1277 1289 1303 1457

Relative Intensity 100.0 6.8 17.3 8.7 13.5 10.2 3.0 4.7 6.5 6.0 2.6 4.5 7.7 6.0 26.5

125

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

057

EGA thermogram

Averaged mass spectrum 36

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

52

67

77

91

116

29 50

130

100

144

157 169

181

207

195

150

250 [m/z]

200

( m/z range : 29 - 600 amu )

LB : hydrogen chloride

A : acrylonitrile 36

53

Cl

H

N

38

29

CB : cyanobutadiene

67

CB : cyanobutene 52

41

79

N

N

54

81

39 75

66

CB : cyanobutadiene

AV : 4-chloropent-4-enenitrile 52

75

N N

Cl 39

115

79

53

77

39

118

75

29

90

TN : m-tolunitrile

BN : cyanobenzene (+ unidentified) 103

117

N

41

N

76

39

50 104

75

118

29

122

PN : isophthalonitrile

90 89

63

51

VAV : 4-chloro-2-(2-chloroethyl)-4-pentenitrile 128

128

N Cl

Cl 75

N

N

39

44

50

64

81

76 49

101 116

135

153

29

106 102 142

177

126

Tsuge, Ohtani and Watanabe

058 Methyl acrylate-vinyl chloride copolymer; P(MA-VC) CH2CH(COOCH3)

CH2CHCl

n

MN’ MC

MMM LB P B MMA TIC

7

8

9

10

11

12

M T

0

10

Peak Notation

Assignment of Main Peaks

LB MC M B MMA T MM’ P MMM

hydrogen chloride + CO2 methyl chloride methyl acrylate benzene methyl methacrylate toluene CH2(COOCH3)CH2CH2COOCH3 diethyl phthalate CH2=C(COOCH3)CH2CH(COOCH3)CH2CH2COOCH3

30 [min]

20

[ Related Reference ] 1) Tanaka, M.; Nishimura, F.; Shono, T. Anal. Chim. Acta 1975, 74, 119.

Molecular Retention Weight Index 36; 44 50 86 78 100 92 160 222 258

150 327 607 653 711 767 1138 1610 1671

Relative Intensity 46.5 100.0 8.3 1.5 2.2 1.7 8.8 2.1 4.7

127

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

058

EGA thermogram

Averaged mass spectrum 50

44 100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

31

91

79

67 50

115

129 141 152

100

165

178 189

202

150

250 [m/z]

200

( m/z range : 29 - 600 amu )

LB : hydrogen chloride ( + carbon dioxide ) Cl

H

MC : methyl chloride

44

50

Cl

+ O

C

O

47

B : benzene

M : methyl acrylate 55

78

O

O

85

42

31

39

68

52 74

31

MMA : methyl methacrylate

T : toluene

41

91 O 69 O 100 59

31

85

29

MM' : dimethyl glutarate O

O

65

51

79

P : diethyl phthalate

59

O

149

O O

O

100 O

39

129

O

42 87 29

177

74

132

MMM : trimethyl hex-5-ene-1,3,5-tricarboxylate O

O

O

O

O

194

79

106

59

167

125

41 29

134

O

67

93

227 153

29

50 65 76

93 105 121

222

128

Tsuge, Ohtani and Watanabe

059 Methyl acrylate-vinyl chloride alternating copolymer CH2CH(COOCH3)

CH2CHCl

n

F MC I

LB

TIC

5

TM E M

6

7

8

9

12

11

10

T 0

10

Peak Notation

Assignment of Main Peaks

LB MC TM M E T F I

hydrogen chloride + CO2 methyl chloride trichloromethane methyl acrylate ethyl acrylate toluene furfuryl methyl ether indene

30 [min]

20

Molecular Retention Weight Index

O

CH2OCH3

[ Related Reference ] 1) Tanaka, M.; Nishimura, F.; Shono, T. Anal. Chim. Acta 1975, 74, 119.

36; 44 50 117 86 100 92 112 116

150 327 605 607 694 767 867 1057

Relative Intensity 44.5 100.0 2.8 1.1 1.2 2.2 0.7

129

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

059

EGA thermogram

Averaged mass spectrum 50

100

44

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

91

77

67

31

115

50

128

100

145152

165

178 189

202

150

226 250 [m/z]

200

( m/z range : 29 - 600 amu )

LB : hydrogen chloride (+ carbon dioxide)

MC : methyl chloride 50

44

Cl

H

H

+ O

C

H

O

Cl H

47 29

29

TM : trichloromethane

M : methyl acrylate 83

55

Cl

O

Cl O

Cl 47 29

120

70

E : ethyl acrylate 43

42

85

68

T : toluene 91

O

55

O 29

71

85

100

39 31

F : furfuryl methyl ether

65

51

79

I : indene

53

O 81

116 O

112

97 31 39

69

39 32

57

63

89

124

130

Tsuge, Ohtani and Watanabe

2.2.7 Fluorine-containing vinyl polymers 060 Polytetrafluoroethylene; PTFE CF2CF2

n

M

TIC

0

10

30 [min]

20

Peak Notation

Assignment of Main Peaks

M

tetrafluoroethylene

Molecular Retention Weight Index 100

Relative Intensity

-

100.0

[ Related References ] 1) Madorsky, S. L.; Hart, V. E.; Straus, S.; Sedlak, V. A. J. Res. Nat. Bur. Std. 1953, 51, 327. 2) Morisaki, S. Thermochim. Acta. 1978, 25, 171. 3) Pidduck, A. J. J. Anal. Appl. Pyrolysis 1985, 7, 215. 4) Lonfei, J.; Jingling, W.; Shuman, X. J. Anal. Appl. Pyrolysis 1986, 10, 99.

EGA thermogram

Averaged mass spectrum 81 31 100

200

300

400

100

50 69

43

500

600

700 ºC

programming rate: 20ºC/min

131

50

100

150

[m/z]

( m/z range : 29 - 600 amu )

M : tetrafluoroethylene 81

F

F

F

F

100 31 50 43

69

131

150

131

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

061 Tetrafluoroethylene-hexafluoropropylene copolymer; FEP CF2CF2

CF2CF(CF3)

n

M

TIC

0

10

30 [min]

20

Peak Notation

Assignment of Main Peaks

Molecular Retention Index Weight

M

tetrafluoroethylene, hexafluoropropylene

100, 150

Relative Intensity

-

100.0

[ Related References ] 1) Morisaki, S. Thermochim. Acta. 1978, 25, 171. 2) Pidduck, A. J. J. Anal. Appl. Pyrolysis 1985, 7, 215. 3) Lonfei, J.; Jingling, W,; Shuman, X. J. Anal. Appl. Pyrolysis 1986, 10, 99. 4) Shadrina, N. E.; Dmitrenko, A. V.; Pavlova, V. F.; Ivanchev, S. S. J. Chromatogr. 1987, 404, 183.

EGA thermogram

Averaged mass spectrum 81

31

100

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

50

131

69

150

44 132 50

100

150

181 200

250 [m/z]

( m/z range : 29 - 600 amu )

M : tetrafluoroethylene (+ hexafluoropropylene) 131

F

F

100

F

150

31

F

F

F F F

50 44 112

F

+

69 81

132

181

200

F

132

Tsuge, Ohtani and Watanabe

062 Polychlorotrifluoroethylene; PCTFE CF2CFCl

n

B6 M TF M’

C4

A2

B3

B2 C2 D

A3

B5

C6 A6

B4 C5

C3 A4

B7 C7 A7

A5

B8

B9

C9 A9 B10 C8 A8

10

20

TIC

0

10

30 [min]

20

Peak Notation

Assignment of Main Peaks

Molecular Retention Weight Index

M TF M’ A2 B2 C2

CF2=CFCI + C3CI F5 (monomer) CFCl3 C3CI2F4 CF2CI-CFCI2 C4CI2F6 (dimer) C5CI2F8

116; 166 136 182 186 232 282

D

C7CI2F10 ?

344

A3 B3

C4CI4F6 ? C6CI4F9 (trimer)

304 383

C3

C7CI3F11 ?

398

A4

C6CI5F12

475

B4

C8CI4F12 (tetramer)

464

C4 A5 B5

C9CI4F14 ? C8CI6F15 ? C10CI5F15 (pentamer)

514 591 580

C5

C11CI5F17 ?

630

C6 B6 B7

C12CI6F20 ? C12CI6F18 (hexamer) C14CI7F21 (heptamer)

734 696 812

[ Related References ] 1) Pidduck, A. J. J. Anal. Appl. Pyrolysis 1985, 7, 215. 2) Lonfei, J.; Jingling, W,; Shuman, X. J. Anal. Appl. Pyrolysis 1986, 10, 99.

280 400 440 461 693 696 742 746 764 819 863 865 1054 1086 1088 1114 1343 1359 1372 1373 1628 1635 1915

Relative Intensity 100.0 3.3 2.5 4.7 3.3 0.3 0.8 0.6 0.7 0.6 1.0 2.5 1.0 0.9 0.6 1.9 1.2 2.0 0.7 3.2 0.8 1.0 0.3 5.7 2.6

133

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

062

EGA thermogram

Averaged mass spectrum 131

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

31

85

69

50 50

116

101

135

147

100

163

150

181

203 217

243

200

259 300 [m/z]

250

( m/z range : 29 - 600 amu )

M : chlorotrifluoroethylene

TF : trichlorofluoromethane

(+ 3-chloropentafluoropropene) F

F F Cl +

Cl

101

116

Cl

F Cl

F

Cl

F

F 31

F

85

66

F

118

97

47 50

31

M' : 1,2-dichlorotetrafluoro propane

66

47

105 119

82

147

A2 : 1,1,2-trichloro-1,2,2-trifluoroethane (+ unidentified)

147

162

F F

Cl

101

Cl

F

Cl 85

93

116

163

132

182 193

F

Cl

69

47

Cl

F

151

F

31

182

243 259

31 278

A3 : C4Cl4F6

F

85 47

116

66

143

259

193 209

243

278 293

B3 : C6CI4F9 (trimer) 101

131

85 116 31

47

69

118 147

197

217 230

275

309

344

B4 : C8CI4F12 (tetramer)

31 47

69 85 101 116

69 85 101 116

B6

147 163

197

263

297

131

69

225

263

348

131

: C12CI6F18 (hexamer)

31

181197

B5 : C10CI5F15 (pentamer)

131

31

147

85 101 147 116 135 163

201217

247

279

335

31

69 85 101

147

163

247

297

134

Tsuge, Ohtani and Watanabe

063 Poly(vinyl fluoride); PVF CH2CHF

n

N I

LB

MI S

MN

X

B

AN

E

FB T

TIC

F AC

6

5

7

8

9

10

11

12

13

CP

0

10

Peak Notation LB CP B FB T E S X I MI N MN AC F AN

Assignment of Main Peaks low boiling point components cyclopentadiene benzene fluorobenzene toluene ethylbenzene styrene o-xylene indene 1-methylindene 3-methylindene naphthalene 2-methylnaphthalene 1-methylnaphthalene acenaphthene fluorene anthracene

30 [min]

20

Molecular Retention Index Weight 66 78 96 92 106 104 106 116 130 130 128 142 142 154 166 178

[ Related References ] 1) Madorsky, S. L.; Hart, V. E.; Straus, S.; Sedlak, V. A. J. Res. Nat. Bur. Std. 1953, 51, 327. 2) Chatfied, D. A. J. Polym. Sci., Polym. Chem. Ed. 1983, 21, 1681. 3) Pidduck, A. J. J. Anal. Appl. Pyrolysis 1985, 71, 215. 4) Nguyen, T. J. Macromol. Sci., Rev. Macromol. Chem. Phys. 1985, C25, 227.

510 659 675 769 865 894 897 1054 1163 1179 1200 1315 1333 1402 1614 1823

Relative Intensity 100.0 4.1 20.8 3.1 13.5 2.1 5.9 3.0 8.2 5.0 5.0 9.9 4.5 3.5 1.1 3.2 3.4

135

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

063

EGA thermogram

Averaged mass spectrum 85

100

200

300

400

500

600

91 39 33

51

115 129 141

65

50

700 ºC

programming rate: 20ºC/min

100

153 165 178 191 150

216 230 200

300 [m/z]

250

( m/z range : 29 - 600 amu )

CP : 1,3-cyclopentadiene

B : benzene

66

78

39 61

29

79

39

163

T : toluene

51 74

114

S : styrene 91

104

103

78 39

51

65

51

79

63

39

I : indene

MI : 1-methylindene 130

115 115

89 90

57 63

39

39

133

MI : 3-methylindene

51

64

77

132

102

N : naphthalene 128

130

115

39

51

64

102

77

39

MN : 2-methylnaphthalene

51

64

102

77

MN : 1-methylnaphthalene 142

142

115 39

57

71

89

146

115 129

159

196

39

57

71

89 98

126

159

176

136

Tsuge, Ohtani and Watanabe

064 Poly(vinylidene fluoride); PVDF CF2CH2

n

F5’ F6 FN

TS

F7 F8

T

F9 FA F10

F5

F11 F12

F13

F14

F15 F16 F17

FB VF 2

4

6

8

10

12

14

16

18

TIC

0

10

Peak Notation

Assignment of Main Peaks

VF FB T F5 F5’ F6 FN F7 F8 F9 FA F10 F11

vinylidene fluoride 1,3,5-trifluorobenzene CF2=CHCF2CH=CF2 C11H10F10 C11H9F11 C13H12F12 C10H4F4 (tetrafluoronaphthalene) C15H14F14 C17H16F16 C19H18F18 C14H5F5 (pentafluoroanthracene) C21H20F20 C23H22F22

30 [min]

20

Molecular Retention Weight Index 64 132 176 332 350 396 200 460 524 588 268 652 716

[ Related References ] 1) Madorsky, S. L.; Hart, V. E.; Straus, S.; Sedlak, V. A. J. Res. Nat. Bur. Std. 1953, 51, 327. 2) Hagiwara, M.; Ellinghorst, G.; Hummel, D. O. Makromol. Chem., 1977, 178, 2913. 3) Nguyen, T. J. Macromol. Sci., Rev. Macromol. Chem. Phys. 1985, C25, 227. 4) Pidduck, A. J. J. Anal. Appl. Pyrolysis 1985, 7, 215. 5) Lonfei, J.; Jingling, W,; Shuman, X. J. Anal. Appl. Pyrolysis 1986, 10, 99.

625 805 970 1062 1119 1147 1316 1488 1658 1681 1827 1994

Relative Intensity 100.0 5.9 5.0 2.5 3.8 3.2 3.1 3.0 2.6 2.6 1.3 2.1 2.5

137

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

064

EGA thermogram

Averaged mass spectrum 85

100

113 51 65

95

121

300

400

500

100

600

700 ºC

programming rate: 20ºC/min

159169177189

3139 50

200

133

150

213 223 241

200

261

287 305

250

300

400 [m/z]

350

( m/z range : 29 - 600 amu )

TS : tetrafluorosilane

FB : 1,3,5-trifluorobenzene 85

F F

F

132

Si

F F

F 47 51

33

64

102

63 57

31 39

F

F

154

172

115

F

F

F

153

101 112

F5 : C11H10F10

T : 1,1,3,3,5,5-hexafluoropenta-1,4-diene 108

81

F

133

F

51

236 64

39

83

57

103 133

172

203217

46

290

64

95

113

223

243

269

121

115

51 51 69

197

F6 : C13H12F12

F5' : C11H9F11

39

159 179

77

65 101 77

133 157 179 197

95

223 238

39

285 311

165 133 159 185

215 235

279 299 325

364

F7 : C15H14F14

FN : tetrafluoronaphthalene 200

115

F

133

F F 51

F 61 75

31

169 180 100111 129 150

64 218

46

274

FA : pentafluoroanthracene F

268

F F F 31

86

134 151

237 217 248 198

F

414 439 477

95

159 179197 223 287 243 261

351

397

138

Tsuge, Ohtani and Watanabe

065 Vinylidene fluoride-hexafluoropropylene rubber CF2CF2

CF2CH2

CF2CF(CF3)

n

LB E A

D B

TIC

7

6

0

10

Peak Notation LB A B C D E

8

9

10

11

C

Assignment of Main Peaks (vinylidene fluoride + tetrafluoroethylene + hexafluoropropylene) CF2=CHCF2CF2CH=CF2 unidentified C8H5F9 unidentified C12H2F10 ?

30 [min]

20

Molecular Retention Weight Index 64; 100 150 226 222 272 336

[ Related References ] 1) Blackwell, J. T. Anal. Chem. 1976, 48, 1883. 2) Nguyen, T. J. Macromol. Sci., Rev. Macromol. Chem. Phys. 1985, C25, 227. 3) Pidduck, A. J. J. Anal. Appl. Pyrolysis 1985, 7, 215. 4) Lonfei, J.; Jingling, W,; Shuman, X. J. Anal. Appl. Pyrolysis 1986, 10, 99.

710 761 853 941

Relative Intensity 100.0 23.7 4.4 4.5 3.2 7.5

139

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

065

EGA thermogram

Averaged mass spectrum 113

163 69 51

100

200

300

400

500

77

600

700 ºC

programming rate: 20ºC/min

133 95

31 45

157

131

50

100

197 207

175

150

229 241

200

259

277

250

350 [m/z]

300

( m/z range : 29 - 600 amu )

LB : vinylidene fluoride (+ tetrafluoroethylene + hexafluoropropylene) 44

F

85 64

F +

+

F

114

F

F

F

F

F

F F

95

131

163 F

150 164

182

B : unidentified

51 69

51 77

95

119 144

95

39

F

F 189

228

257

307

C : C8H5F9

113

113

133 163 179 213 229

39

F

F

F

51

F

113

F

F

31

A : 1,1,3,3,4,4,6,6-octafluorohexa-1,5-diene

F

269

319

357

409

D : unidentified

39

51 69 95 77

160

133

245

273

319

E : C12H2F10 163

113

163 133 113 51

77

95

197 229

263

307

371 391 423

51

133

77 95

177

224

285

317

367

140

Tsuge, Ohtani and Watanabe

066 Propylene-tetrafluoroethylene rubber CH2CH(CH3)

CF2CF2

n

TE H

P

H’

TE’ HP LB

FP’ FP T

TIC

O

P’

T’

P’’

T’’

0

10

Peak Notation LB FP FP’ T T’ T” TE TE’ P P’ P’’ H H’ HP O

Assignment of Main Peaks propylene, tetrafluoroethylene C5H6F4 (hybrid dimer) C6H6F6 C7H6F8 (FPF hybrid trimer) C8H12F6 ? C8H6F10 C8H8F8 C8H10F6 C10H12F8 (FPFP hybrid tetramer) C11H12F10 C12H12F12 (FFPFP hybrid pentamer) C12H12F12 (FPFPF hybrid pentamer) C13H12F14 C13H16F10 C15H18F12 (FPFPFP hybrid hexamer) C16H18F14 C17H18F16 (FPFPFPF hybrid heptamer) C20H24F16 (FPFPFPFP hybrid octamer) * F : unit of tetrafluoroethylene ; P : unit of propylene

30 [min]

20

Molecular Retention Index Weight 42, 100 142 192 242 222 292 256 220 284 334 384 384 434 362 426 476 526 568

295 648 675 724 738 760 920 979 1028 1034 1088 1153 1300 1349 1396 1671

Relative Intensity 25.7 100.0 47.0 67.5 34.9 11.9 7.9 14.5 75.1 55.2 22.3 35.1 18.8 11.3 60.2 34.4 36.6 35.3

141

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

066

EGA thermogram

Averaged mass spectrum 91

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

65 51 47

77

109

33 50

127 141

100

161

181 193

150

223

263

200

250

350 [m/z]

300

( m/z range : 29 - 600 amu )

FP : C5H6F4

FP' : C6H6F6 91

65

91

41 51

142

77

65

41

192

51 33

110 123

151 160

178

77

33

T : C7H6F8 (FPF hybrid trimer)

109

127 141

156 171

TE : C10H12F8 (FPFP hybrid tetramer) 91

91

65 65 242

51

41

77

33

109 123 139

171 183

39 51

206

P : C12H12F12 (FFPFP hybrid pentamer)

77

156 173 193

216

284

245

91

65 109 133 159

77

133

P : C12H12F12 (FPFPF hybrid pentamer)

91

3951

215 109

315 209

273 293

345

51

384

H : C15H18F12 (FPFPFP hybrid hexamer)

65 77

109

159 141 173

223

255 274

384 315 345

H' : C16H18F14 91

91

65

47

77

109

173193 153

357 231

295

335

426

HP : C17H18F16 (FPFPFPF hybrid heptamer)

65 51

109 141 161

199

263 295 243

366

476 407 437

O : C20H24F16 (FPFPFPFP hybrid octamer)

91

91

65

65 77 109

51

141161183

223

273

345

395

416 457 487 526

47

77 109

173 193 141 213

499 231 263 295

347

437 457

142

Tsuge, Ohtani and Watanabe

2.2.8 The other vinyl polymers 067 Poly(vinyl alcohol); PVA CH2CH(OH)

A

n

C

C7 AC D H EA

TIC

B

MB

0

10

Peak Notation

Assignment of Main Peaks

A AC D C EA H C7 B MB

acetaldehyde acetone 2,5-dihydrofuran crotonaldehyde CH3CH=CHCHO ethylidene acetone CH3CH=CHCH=CHCHO C7H12 (methyl hexadiene ?) benzaldehyde methylbenzaldehyde [ Related Reference ] 1) Wang, F. C.-Y. J. Chromatogr. A 1996, 753, 101.

30 [min]

20

Molecular Retention Weight Index 44 58 70 70 70 96 96 106 120

404 463 573 640 740 901 912 965 1075

Relative Intensity 100.0 9.7 14.9 95.9 4.1 2.9 46.6 5.8 3.2

143

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

067

EGA thermogram

Averaged mass spectrum 39

100

200

300

400

500

81

700 ºC

91

70

53

600

programming rate: 20ºC/min

105

31 50

122 133

100

155 165

178

150

250 [m/z]

200

( m/z range : 29 - 600 amu )

A : acetaldehyde

AC : acetone 43

29

O

44

O

58 29

D : 2,5-dihydrofuran

70

EA : ethylidene acetone 41

O

69

O 41

70 84 29 50

29

C : crotonaldehyde

50

H : 2,4-hexadienal 70

O

81

41

O

39 29

C7 : methylhexadiene

91

O

120

65 51

108

O

77

105

106

77

51

29

MB : methylbenzaldehyde

39

95

96

67

53

29

29

67

B : benzaldehyde 81

39

53

29

50

39

74

95

144

Tsuge, Ohtani and Watanabe

068 Poly(vinyl butyral); PVB CH2CHCH2CH

n

OCHO C3H7

B

BT

BA LB

C

F 3

TIC

A

4

5

6

7

AP

0

10

Peak Notation

Assignment of Main Peaks

LB A F BT C BA B AP

propylene acetaldehyde O 2,5-dihydrofuran n-butanal crotonaldehyde CH3CH=CHCHO butyric acid benzaldehyde acetophenone

30 [min]

20

Molecular Retention Weight Index 42 44 70 72 70 88 106 120

295 408 571 610 639 816 965 1072

Relative Intensity 11.2 10.0 9.4 100.0 24.8 1.5 4.1 1.2

145

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

068

EGA thermogram

Averaged mass spectrum 43

100

29

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

72 57 77

92

50

105

143

123

100

155

169

150

200

250

[m/z]

( m/z range : 29 - 600 amu )

A : acetaldehyde

LB : propylene

29

41 44

O

29 56

F : 2,5-dihydrofuran

BT : n-butanal 41

O

44

72

O 29 70

57

29 50

C : crotonaldehyde

BA : butyric acid 70

O

60

O

41

OH 41 29

73

29

55

88 94

B : benzaldehyde

AP : acetophenone 106

77

105

O 77 O

51

120 51

29

39

74 95

43

74

91

146

Tsuge, Ohtani and Watanabe

069 Poly(vinyl acetate); PVAc CH2CH(OCOCH3)

n

N

A I

EA

MI

X1 S

B E

LB

MN X2

5

T

AC

I’

6

7

8

9

11

10

TIC

0

10

Peak Notation LB EA A B T E X1 S X2 I’ I MI N MN AC

Assignment of Main Peaks

30 [min]

20

Molecular Retention Weight Index

ketene, etc. ethyl acetate acetic acid benzene toluene ethylbenzene p-xylene styrene o-xylene indane indene 1-methylindene 3-methylindene naphthalene 2-methylnaphthalene 1-methylnaphthalene acenaphthene [ Related Reference ] 1) Sellier, N.; Jones, C. E. R.; Guichon, G. J. Chromatogr. Sci. 1975, 132, 383.

42 88 60 78 92 106 106 104 106 118 116 130 130 128 142 142 154

150 606 643 657 768 864 873 894 896 1048 1054 1162 1178 1200 1315 1333 1398

Relative Intensity 6.6 20.4 100.0 11.6 3.3 0.6 0.3 1.7 0.4 0.6 2.2 1.4 2.3 4.5 1.1 0.9 1.4

147

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

069

EGA thermogram

Averaged mass spectrum 43

100

60

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

29 67

77

91

50

115

128

100

141 152

165

178

191 202

150

250 [m/z]

200

( m/z range : 29 - 600 amu )

EA : ethyl acetate

A : acetic acid O

43

43

O 60

OH

O

29

61

70

29

88

B : benzene

62

T : toluene 91

78

51

39

39

74

I' : indane

65

51

89

I : indene 115

117 118

91 31

39

51

63

78

58 63

39

MI : 1-methylindene

89 90

MI : 3-methylindene 129

130

115 115

51 39

64

77

102

132

N : naphthalene

39

64

51

77

102

AC : acenaphthene 128

39

146

51

64

77

102

154

39

51 63

76

102 115 128 139

148

Tsuge, Ohtani and Watanabe

070 Poly(vinyl pyrrolidone); PVP CH2 CH N

n

O

C

F B

E

H

D

A

TIC

G

0

10

Peak Notation A

Assignment of Main Peaks CH 3 N O

H N

B

O

CH=CH 2 N O

C

30 [min]

20

(monomer)

Molecular Retention Weight Index

Relative Intensity

99

1043

5.3

85

1088

14.5

111

1118

100.0

125

1181

3.7

222

2079

13.3

210

2101

9.6

234

2120

3.5

333

2974

20.1

CH2=C- CH3 N

D

O

CH2= C - CH 2 - CH2

E

N

O N

O

(dimer)

CH2 CH2 CH2

F

N

N

O

O

CH2=C - CH2 -C=CH2

G

H

N

O

N

O

CH2=C - CH2 - CH- CH2 - CH2 N O N O N O

(trimer)

[ Related Reference ] 1) Ericsson, I.; Ljunggren, L. J. Anal. Appl. Pyrolysis 1990, 17, 251.

149

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

070

EGA thermogram

Averaged mass spectrum 56

100

200

300

400

500

600

41 68

30

700 ºC

programming rate: 20ºC/min

111 98

85

124

50

137

100

150

163

210

150

222

200

250

[m/z]

( m/z range : 29 - 600 amu )

A : 1-methyl-2-pyrrolidinone

B : 2-pyrrolidinone 99

H N N

85

O

O

44

41 30 71

56

30

56 66

82

C : 1-vinyl-2-pyrrolidinone (monomer) 56

D : 1-(prop-1-en-2-yl)pyrrolidin-2-one 125

70

111

N

O

N

O 42 82

68

41

82

96

30 54

29

E : 1,1'-(but-3-ene-1,3-diyl)dipyrrolidine-2-one (dimer)

111

F : 1,1'-(propane-1,3-diyl)dipyrrolidin-2-one 112

98 137 N

O

N

N

O

99

70 41 82 30

109

O

N

O

70

124

204

55

151 166

179 194

41 222

84

56

210

125

30

139 154

182

H : 1,1',1''-(hex-5-ene-1,3,5-triyl)tripyrrolidin-2-one G : 1,1'-(penta-1,4-diene-2,4-diyl)dipyrrolidin-2-one)

(trimer)

126

124 N

O

N

N

O

178

N

O

O

N

O

98 234

41 56 30

82 96107 69

149 136

206 164

191

41 219

283

30

56

70

82

163 110 136150

193

209 221

248 262

305

333

150

Tsuge, Ohtani and Watanabe

2.2.9 Diene-type elastomers 071 High cis-butadiene rubber; BR CH2CH

CHCH2

n

T3

M D

T2

T4 TE

T1

C5 15

10

TIC

B

trimers

T

0

10

tetramers

pentamers

hexamers

heptamers

30 [min]

20

Peak Notation

Assignment of Main Peaks

Molecular Retention Weight Index

M C5 B T D T1 T2 T3 T4

1,3-butadiene 1,3-pentadiene benzene toluene 4-vinylcyclohexene (dimer) C11H16 C12H18 (trimer) C12H18 C12H18

54 68 78 92 108 148 162 162 162

TE

C16H26 (tetramer)

218

[ Related References ] 1) Shono, T.; Shinra, K. Anal. Chim. Acta 1971, 56, 303. 2) Alexeeva, K. V.; Kharanova, L. P.; Solomatina, L. S. J. Chromatogr. 1973, 77, 61. 3) Braun, D.; Canji, E. Angew. Makromol. Chem. 1974, 35, 27. 4) Ericsson, I. J. Chromatogr. Sci. 1978, 16, 340. 5) Haeusler, K. G.; Schroeder, E.; Huster, B. J. Anal. Appl. Pyrolysis 1980, 2, 109. 6) Radhakrishnan, T. S.; M. R. J. Polym. Sci., Polym. Chem. Ed. 1981, 19, 3197. 7) Schrafft, R. Kautsch. Gummi Kunstst. 1983, 36, 851. 8) Choi, S.-S. J. Anal. Appl. Pyrolysis 2001, 57, 249.

395 490 650 766 834 1091 1139 1164 1237 1553 1567 1580 1604

Relative Intensity 100.0 4.6 8.2 6.3 77.9 7.1 6.7 6.3 6.4 1.5 2.2 1.8 1.9

151

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

071

EGA thermogram

Averaged mass spectrum 79 91

67 41

100

55

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

105 119

50

133

147

100

161 175

150

189 202

216 230

200

300 [m/z]

250

( m/z range : 29 - 600 amu )

M : 1,3-butadiene

B : benzene 78

54

39

52

39

29

D : 4-vinylcyclohexene

74

T2 : C12H18 (trimer)

54

79

79

93

119 133 66

39

93

41

67 147

53

108

29

162

29

T3 : C12H18 (trimer)

T4 : C12H18 (trimer) 79

79 93

93 119 119

105

106

67

41

133

147

54

147

53

162

29

133

67

41 29

TE : C16H26 (tetramer)

162 176

TE : C16H26 (tetramer) 55

55

67

67 79

79

91

41

107

29

41 121

153 168

189

93 109

29 216

230

TE : C16H26 (tetramer)

147 161

189

159

187

228

TE : C16H26 (tetramer) 79 91

79 91 55 41

67

119 29

67

41

105 145

106 55

165 187

216

230

29

119

133

202 216

230

152

Tsuge, Ohtani and Watanabe

072 Poly(1,2-butadiene) CH2CH(CH CH2)

n

D

M

T2

X2 X1

C10

TE

T3

a

C9

b

EB S

10

TIC C3

C5

trimers

B C7 T

0

10

Peak Notation

Assignment of Main Peaks

C3 M C5 B C7 T D EB X1 S X2 C9 C10 T2 T3 TE a b

propylene etc. 1,3-butadiene pentadiene benzene cycloheptadiene toluene 4-vinylcyclohexene (dimer) ethylbenzene p-xylene styrene o-xylene C9H12 C10H14 C12H18 (trimer) C12H18 C15H24 (tetramer) unidentified unidentified

15

tetramers

pentamers

30 [min]

20

Molecular Retention Weight Index 42 54 68 78 94 92 108 106 106 104 106 120 134 162 162 204 320 ?

[ Related References ] 1) Shono, T.; Shinra, K. Anal. Chim. Acta 1971, 56, 303. 2) Braun, D.; Canji, E. Angew. Makromol. Chem. 1974, 35, 27. 3) Haeusler, K. G.; Schroeder, E.; Huster, B. J. Anal. Appl. Pyrolysis 1980, 2, 109. 4) Radhakrishnan, T. S.; Rao, M. R. J. Polym. Sci., Polym. Chem. Ed. 1981, 19, 3197.

295 395 492 650 703 765 836 865 874 895 896 926 1013 1183 1211 1481 1694 2789

Relative Intensity 11.3 100.0 4.5 1.7 3.8 5.9 8.1 1.8 1.6 0.6 0.9 2.3 2.9 3.8 1.6 5.7 2.0 1.1

153

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

072

EGA thermogram

Averaged mass spectrum 91 79 41 55

100

105

67

300

400

500

600

700 ºC

programming rate: 20ºC/min

119

50

200

133

147

100

165 178 189 202

150

216 230

256 270

200

250

300 [m/z]

( m/z range : 29 - 600 amu )

M : 1,3-butadiene

C5 : 1,4-pentadiene 39

67

54

53 39

31

29

B : benzene

C7 : cycloheptadiene 66

78

79

39 52

39 32

67

T : toluene

91

51

29

D : 4-vinylcyclohexene 91

54

79 39

66

79

39

55

32

93

65

108

29

C10 : C10H14

T2 : C12H18 (trimer) 79

41 79

93

67 91 39

105

66

53

55 133

29

T3 : C12H18 (trimer)

29

147

TE : C15H24 (tetramer) 79

41 94

107 67

41 29

119 93

55

67

133 162

79

55

105 119

119

29

105 119

133 147

133 147 173

162

201

154

Tsuge, Ohtani and Watanabe

073 Natural rubber; NR CH2C(CH3) CHCH2

n

M T1 D

MP

TE1

T2 T3

TE2

C10

D’’ D’ TIC LB

T

20

10

trimers

tetramers

pentamers

hexamers

X

0

10

Peak Notation

Assignment of Main Peaks

LB M T X D’ D’’ D MP

propylene etc. isoprene toluene m-xylene 2,4-dimethyl-4-vinylcyclohexene C10H16 dipentene methylisopropylbenzene ?

C10

C10H16

T1 T2 T3 TE1 TE2

C15H24 C15H24 C15H24 C20H32 C20H32

(trimer)

(tetramer)

30 [min]

20

Molecular Retention Weight Index

(dimer)

42 68 92 106 136 136 136 134 136 136 204 204 204 272 272

[ Related References ] 1) Alexeeva, K. V.; Khranova, L. P.; Solomatina, L. S. J. Chromatogr. 1973, 77, 61. 2) Braun, V. D.; Canji, E. Angew. Makromol. Chem. 1974, 36, 67. 3) Chien, J. C. W.; Kiang, J. K. Y. Eur. Polym. J. 1979, 15, 1059. 4) Naveau, J.; Dieu, H. J. Anal. Appl. Pyrolysis 1980, 2, 123. 5) Schrafft, R. Kautsch. Gummi Kunstst. 1983, 36, 851. 6) Groves, S. A.; Lehrle, R. S. J. Anal. Appl. Pyrolysis 1991, 19, 301. 7) Choi, S.-S. Bull. Korean Chem. Soc. 1999, 20, 445. 8) Chen, F.; Qian, J. Fuel 2002, 81, 2071.

295 470 766 874 965 1019 1038 1122 1135 1149 1452 1472 1484 1941 2002

Relative Intensity 3.6 100.0 3.4 3.6 7.9 4.0 68.3 1.0 0.5 0.4 0.9 1.1 1.0 1.5 1.0

155

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

073

EGA thermogram

Averaged mass spectrum 67

79

53

39

93

100

200

300

400

500

600

107

700 ºC

programming rate: 20ºC/min

121 136 147 50

100

150

161 175

189

204

272

200

300 [m/z]

250

( m/z range : 29 - 600 amu )

X : m-xylene

M : isoprene

91

67 53

106

39

39

29

51

D' : 2,4-dimethyl-4-vinylcyclohexene

77

65

32

D'' : .2,5-dimethyl-3-methylene-1,5-heptadiene

68

107 91

93 79 41 107 41

53

121

79

121

53

29

136

67

136

29

D : dipentene

T1 : C15H24 (trimer) 68

121 93 93

41

107

81 79 53

39

55 107

121

136

67

133

29

147

204 175

T2 : C15H24 (trimer)

T3 : C15H24 (trimer) 107

119 41

41

93 55

93 55

119

79

133

67

29

147 161

147 161 175 189 204

TE1 : C20H32 (tetramer)

93 41 55

93 107

175

189 204

TE2 : C20H32 (tetramer)

121

29

107

79

134

67

41 55

189

161

29

81

107 119

134 67

81 29 149 161

203

229

272

132 161175 203

257

156

Tsuge, Ohtani and Watanabe

074 Chloroprene rubber; CR CH 2 CCl

CHCH 2

n

DC

HCL

T

D M C4

TIC

CB M’ a T CT CX S B b

0

15

10

D’

10

Peak Notation

Molecular Retention Weight Index 36 54 88 90 78 102 121 92 112 104 126 140 176

395 550 618 653 722 740 766 850 896 962 1101 1255

Relative Intensity 100.0 7.8 19.2 1.3 1.6 1.3 3.8 2.4 1.3 1.1 1.4 1.4 4.4

C8H9Cl3

176 210

unidentified

254 ?

1259 1444 1950 2031 2068 2104

19.8 5.5 1.7 2.9 2.5 4.4

Assignment of Main Peaks

HCL C4 M M’ B a b T CB S CT CX D’

hydrogen chloride 1,3-butadiene chloroprene chlorobutene (C-C(Cl)=C-C ?) benzene C5H7Cl (C=C(Cl)-C=C-C ?) C4H4Cl2 (Cl-C=C-C=C-Cl ?) toluene chlorobenzene styrene chlorotoluene ( or isomer ) chloroxylene (or isomer ) Cl Cl ) C8H10Cl2 (dimer

D DC

C8H10Cl2 (dimer

T

30 [min]

20

Cl

Cl

)

* bonding hydrogen is omitted

[ Related References ] 1) Gardner, D. L.; McNeill, I. C. Eur. Polym. J. 1971, 7, 593. 2) Fuh, M.-R. S.; Wang, G.-Y. Anal. Chim. Acta 1998, 371, 89. 3) Lehrle, R. S.; Dadvand, N.; Parsons, I. W.; Rollinson, M.; Horn, I. M.; Skinner, A. R. Polym. Degrad. Stab. 2000, 70, 395.

157

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

074

EGA thermogram

Averaged mass spectrum 91

36

105

77

53

100

128 141

200

300

400

500

600

155

178 189 202

31 50

100

700 ºC

programming rate: 20ºC/min

165

65

150

239 285 289 300

229 244 258

200

250

350 [m/z]

300

( m/z range : 29 - 600 amu )

HCL : hydrogen chloride

M : chloroprene 36

Cl

H

53

Cl

88

90 62

39

30

b : 1,4-dichloro-1,3-butadiene

D' : 1-chloro-5-(1-chloroethenyl)-cyclohexene (dimer)

Cl 51

Cl

Cl

113 87

122

Cl 88 53 39

90

65

141

73

37

176

D : 1-chloro-4-(1-chlorovinyl)cyclohexene (dimer) 88

DC : C8H9Cl3 88

Cl Cl

147

51 53 39

90 105 65

141

139

90 176

127

T : unidentified

39

122

175

63

210

T : unidentified 239

239

254

41

91

67

141 112 131 155

225

183197

211

41 55

91

141

112

165

197

T : unidentified

T : unidentified 239

239

131 141

254 43

53

81 91

254

223

129 117 141 159

199 183

225

258

169

55

91

211 195

117

43

178

254

158

Tsuge, Ohtani and Watanabe

075 Hydrogenated natural rubber CH2CH(CH3)CH2CH2

C8

C12

n

C13

C4 C7

C9

LB

C10 C5

S

C14

C17

C16

T C9’

C6

C15

C18

C20 C19

C11

C21

C25 C24 C26 C23

C22

C31

C30 C36

TIC

0

10

Peak Notation LB C5 C6 C7 T C8 C 9’ C9 C10 C11 S C12 C13 C14 C15 C16 C17 C18

30 [min]

20

Assignment of Main Peaks propylene etc. 1-pentene methylbutane 4-methyl-1-hexene toluene 2-methyl-1-heptene 2,6-dimethyl-1-heptene 3-methyloctane 4-methyl-1-nonene 4-methylnonane 2,6-dimethyl-1,8-nonadiene 2,6-dimethyl-1-nonene 4-methyl benzenthiol 4,8-dimethyl-1-decene 2,6-dimethyl-1-undecene 2,6,10-trimethyl-1-undecene 3,7-dimethyldodecane 4,8-dimethyltridecane 4,8-dimethyl-1-tridecene 2,6,10-trimethyl-1,12-tridecadiene 2,6,10-trimethyl-1-tridecene 4,8,12-trimethyl-1-tetradecene 2,6,10-trimethyl-1-pentadecene

[ Related Reference ] 1) Tsuge, S.; Sugimura, Y.; Nagaya, T. J. Anal. Appl. Pyrolysis 1980, 1, 221.

Molecular Retention Weight Index 42 70 72 98 92 112 126 128 140 142 152 154 124 168 182 196 198 212 210 222 224 238 252

295 495 580 656 765 787 853 874 960 966 1040 1048 1082 1124 1239 1298 1321 1403 1407 1484 1489 1566 1677

Relative Intensity 88.1 76.1 10.6 81.2 42.2 100.0 30.7 38.7 21.9 7.2 10.5 14.7 10.0 52.8 54.2 23.8 21.8 47.6 7.1 22.0 12.7 33.0 28.8

159

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

075

EGA thermogram

Averaged mass spectrum 41 55 69

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

81

97

111

30 50

125 137

100

151

167

182

196

150

250 [m/z]

200

( m/z range : 29 - 600 amu )

C7 : 4-methyl-1-hexene

C4 : butane (+ butene) 43

41

57

+ 29 29 56

70

98

78

64

C8 : 2-methyl-1-heptene

C12 : 4,8-dimethyl-1-decene 43

56

57 71 85

41 29

29

69 84

97

97

112

111

139

C17 : 4,8,12-trimethyl-1-tetradecene

C13 : 2,6-dimethyl-1-undecene

57

56

43

41

125

71

69

29

85 97

83

111

29 126

97

182

154

C18 : 2,6,10-trimethyl-1-pentadecene

111 125

140 154

196

C26 : 2,6,10,14,18-pentamethyl-1-henicosene

57

55 69

43

43

69

97

83 83 97 111

29

126 140

123 137

252

182

C31 : 2,6,10,14,18,22-hexamethyl-1-pentacosene

151 165 179

C36 : 2,6,10,14,18,22,26-heptamethyl-1-nonacosene 57

57

43

111

29

69

69 43 83 97 111

83 97 111 125

137 179

208

29

123 137

179

209

160

Tsuge, Ohtani and Watanabe

076 Acrylonitrile-butadiene rubber; NBR CH2CH CHCH2 AB

M

CH2CH(CH CH2)

CH2CH(CN)

n

ABA1 ABA2 TQ AB’’

CB N7

ABA3 ABA5 ABA’

AB’ A N6

LB

D B

TIC

10

N6’

14

18

T

0

10

Peak Notation

Assignment of Main Peaks

LB M A B T D

propylene etc. butadiene acrylonitrile benzene toluene 4-vinylcyclohexene (B dimer)

N6

C6H9N (C-C=C-C-C-CN ?)

N 6’ N7 CB

C=C-C-C(CN)=C C7H11N cyanobenzene C7H9N (AB mixture of dimer; C=C-C=C-C-C-CN C=C-C-C-C-(CN)=C etc. ?) C8H11N C8H9N C9H11N (tetrahydroquinoline)

AB AB’ AB’’ TQ ABA1 ABA2 ABA3 ABA4 ABA5 ABA’

C10H12N2 (ABA mixture of trimer; C=C(CN)-C-C=C-C-C-C-CN etc.) C11H13N3 * bonding hydrogen is omitted

30 [min]

20

Molecular Retention Weight Index 42 54 53 78 92 108 95 95 93 109 103 107 107 121 119 133

160

187

Relative Intensity

295 395 568 654 767 838 863 880 925 977 991 1004 1023 1083 1125 1190 1301 1319 1340 1350 1376 1488

[ Related References ] 1) Shimono, T.; Tanaka, M.; Shono, T. Anal. Chim. Acta 1978, 96, 359. 2) Balyan, A. K.; Fedtke, M.; Hausler, K.-G. Plaste Kautschuk 1982, 29, 569. 3) Kondo, A.; Ohtani, H.; Kosugi, Y.; Kubo, Y.; Inaki, H.; Asada, N.; Yoshioka, A. Macromolecules 1988, 21, 2918. 4) Fuh, M.-R. S.; Wang, G.-Y. Anal. Chim. Acta 1998, 371, 89. 5) Hiltz, J. A. J. Anal. Appl. Pyrolysis 2000, 55, 135. 6) Shield, S. R.; Ghebremeskel, G. N.; Hendrix, C. Rubber Chem. Technol. 2001, 74, 803.

15.2 100.0 65.9 7.6 7.7 17.2 10.5 5.9 7.4 4.4 8.7 7.8 14.5 4.6 8.8 10.1 11.6 9.7 9.3 4.5 7.6 2.9

161

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

076

EGA thermogram

Averaged mass spectrum 41

79 67

91

53 100

133

108

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

118 147

161

30 50

100

150

184 193

214 225

240 251

200

266 279 300 [m/z]

250

( m/z range : 29 - 600 amu )

M : 1,3-butadiene

B : benzene 39

78

54

52

41

74

29

T : toluene

D : 4-vinylcyclohexene 91

54

79 39 39

66

79

93

65

55

108

29

N6 : (E )-hex-4-enenitrile

N6' : 2-methylenepent-4-enenitrile

55

66

N

41

39 29

67

79

93

108

79

29

AB : C7H9N (AB hybrid dimer)

108

122

ABA : C10H12N2 (ABA hybrid trimer) 67

54

41

41 107

80 67

54 79

92

29

120

ABA : C10H12N2 (ABA hybrid trimer) 67 41 54

93 79

133 104

30

93

54

119

146 160

29

93 105 119

133

146

160

162

Tsuge, Ohtani and Watanabe

077 Hydrogenated acrylonitrile-butadiene rubber CH2CH

CHCH2

CH2CH2CH2CH2

CH2CH(C2 H5 )

CH2 CH(CN)

n

N7

N11’’ N11 N7’ LB TIC

B A

C8

N7

C6

N10

N 8’

N6

N8

N9

0

N11’

X

DN

10

Peak Notation LB B A C6 C8 N6 N 7’ N7 N8’ N8 N9 N10 N11’’ N11’ N11 DN X

Assignment of Main Peaks low boiling point components 1-butene acrylonitrile 1-hexene 1-octene CH2=CH(CH2)3CN CH3(CH2)4CN CH3(CH2)3C(CN)=CH2 CH2=CH(CH2)4CN CH3(CH2)5CN CH3(CH2)4C(CN)=CH2 CH2=CH(CH2)5CN CH3(CH2)6CN CH2=CH(CH2)6CN CH3(CH2)7CN CH2=CH(CH2)7CN CH3(CH2)8CN CH3(CH2)3CH(CN)(CH2)3CH CH2 CH3(CH2)7C(CN)=CH2 CH2=CH(CH2)8CN CH3(CH2)9CN NC(CH2)7CN CH3(CH2)6C(CN)=CH2 unidentified

30 [min]

20

Molecular Retention Weight Index 56 53 84 112 95 97 109 109 111 123 123 125 137 139 151 153 165 165 165 167 150 151 -

[ Related Reference ] 1) Kondo, A.; Ohtani, H.; Kosugi, Y.; Kubo, Y.; Inaki, H.; Asada, N.; Yoshioka, A. Macromolecules 1988, 21, 2918.

384 565 597 791 864 881 892 976 982 992 1079 1085 1181 1188 1284 1290 1292 1296 1387 1392 1509 1514 1923

Relative Intensity 26.8 48.8 27.7 17.3 35.1 11.6 17.5 42.3 100.0 10.6 10.0 13.0 9.8 11.4 14.2 16.2 20.9 30.7 19.2 31.8 14.4 14.4 12.3 50.3

163

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

077

EGA thermogram

Averaged mass spectrum 41 55 100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

67

94

82

108

122

136

30 50

100

150

164

180 190

203

150

220

234

248

200

250 [m/z]

( m/z range : 29 - 600 amu )

B : 1-butene

A : acrylonitrile 53

41

N

56

29

38

31

C8 : 1-octene

67

N7 : 6-heptenenitrile 43

41

55

N 70 29

55 80

83

68 94

29

112

N7 : heptanenitrile

108

94

N10 : decanenitrile

41

41

N

N 54

55

82

82

29

96 110

69

29

124

68 96

108

134 148 162

120

N11'' : 2-butylhep-6-tenenitrile

N11' : 2-methylenedecanenitrile 43

41 94 109

108 122

N 55 29

57

83

29 67

122

N

136 95

69 81

150 164

136 150 164

N11 : 1-undecenenitrile

N11 : undecanenitrile 41

55 41

N

122

N 55

136 69 29

82

94

29 108 150 164

94 69

82

109 122 134

148 162 176

164

Tsuge, Ohtani and Watanabe

078 Polynorbornene CHCH2 CHCH

n

CH2CH2

I

LB

CH

MI

C8

C5 C4

C6

TIC

T

C7

0

10

Peak Notation LB C4 C5

C6

T C7 C8 I MI

20

10

Assignment of Main Peaks propylene etc. butene 1,3-cyclopentadiene cyclopentene methylcyclopentane methylcyclopentadiene 3-methylcyclopentene benzene 1,3-cyclohexadiene toluene unidentified unidentified indene 1-methylindene

30 [min]

20

Molecular Retention Weight Index 42 56 66 68 84 80 82 78 80 92 84 108 116 130

295 382 626 580 642 642 606 654 626 765 763 809 1055 1163

Relative Intensity 100.0 20.9 14.2 7.3 2.2 9.9 6.0 3.1 10.7 3.7 9.8 17.3 8.0 7.9

165

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

078

EGA thermogram

Averaged mass spectrum 67 39

79 91

55

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

115

128 141

31 50

100

152 165 178 189 202 216 150

233

200

252 264 276 300 [m/z]

250

( m/z range : 29 - 600 amu )

C5 : 1,3-cyclopentadiene

C5 : cyclopentene 67

66

39

39 53 61

31

29

C6 : benzene

79

C6 : 1,3-cyclohexadiene 79

78

51

39

39

67

29

C7 : unidentified

82

39

84

53

41 29

29

91

69

I : indene

62

107

MI : 1-methylindene 116 55

39

65

C8 : unidentified 55

29

51

130 115

84

68

55 29 153

211

285

82 98

132 153

238

405

166

Tsuge, Ohtani and Watanabe

079 Styrene-butadiene rubber; SBR CH2CH

CHCH2

CH2CH(C6H5 )

n

SBB

S S T

SB

PB’

Y

PB

M

Z D LB TIC

C5 B

20

10

TO

0

10

Peak Notation

Assignment of Main Peaks

30 [min]

20

Molecular Retention Weight Index

TO D S PB PB’ S

propylene etc. 1,3-butadiene pentadiene benzene cyclohexadiene toluene 4-vinylcyclohexene (B dimer) styrene propenylbenzene propylbenzene -methylstyrene

42 54 68 78 80 92 108 104 118 120 118

T

C12H18 (B trimer)

162

LB M C5 B

SB

C12H14 (mixture of dimer)

158

SBB

C16H12 (SBB mixture of trimer)

204

Y

unidentified

302 ?

Z

unidentified [ Related References ] 1) Alexeeva, K. V.; Khramova, L. P.; Solomatina, L. S. J. Chromatogr. 1973, 77, 61. 2) Trojer, L.; Ericsson, I. J. Chromatogr. Sci., 1978, 16, 345. 3) Schrafft, R. Kautsch. Gummi Kunstst. 1983, 36, 1983. 4) Choi, S.-S. J. Anal. Appl. Pyrolysis 2000, 55, 161. 5) Shield, S. R.; Ghebremeskel, G. N.; Hendrix, C. Rubber Chem. Technol. 2001, 74, 803. 6) Choi, S.-S. J. Anal. Appl. Pyrolysis 2002, 62, 319.

295 395 495 654 663 767 837 896 954 961 988 1164 1194 1354 1654 1671 2456 2470 2528 3083 3100

Relative Intensity 9.8 76.9 5.1 5.4 5.8 14.8 30.7 100.0 3.4 3.5 5.2 7.7 4.0 6.2 7.7 3.8 1.3 1.6 2.0 1.3 0.7

167

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

079

EGA thermogram

Averaged mass spectrum 91

100

79 41

55

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

104

67 129

50

143

100

157165 178 197 202 217

150

200

239 252

287285 302

250

300

350 [m/z]

( m/z range : 29 - 600 amu )

M : 1,3-butadiene

TO : toluene 39

91 54

39 29

D : 4-vinylcyclohexene

65

51

29

89

S : styrene 104

54

79 103

39

66

78

51

93 39

108

29

S : -methylstyrene

63

T : C12H18 (B trimer) 91

118 117

103 39

129 115

78

51

39

63

T : C12H18 (B trimer)

65

77

132

SB : C12H14 (SB hybrid dimer)

79

93

104

119 133

41 106

67 29

55

32

147

53

158 162

SBB : C16H12 (SBB hybrid trimer)

29 39

51

65

78

91

128

143

172

SBB : C16H12 (SBB hybrid trimer) 104

104

91

41 53 65 79

91

129 143 169

183

212

41 53 65

79

143

169

198

146

168

Tsuge, Ohtani and Watanabe

080 Styrene-butadiene-styrene block copolymer; SBS(TPS) CH2CH(C6H5)

p

CH2CH

CHCH2

q

CH2CH(C6H5)

r

SSS

S

S T2 T1 B

SS’ SS

20

10

V

TIC

EB

T

0

10

Peak Notation

Assignment of Main Peaks

B T V EB S S T1 T2 SS’ SS SSS

butadiene toluene 4-vinylcyclohexene (B dimer) ethylbenzene styrene -methylstyrene C12H18 (B trimer) C12H18 (B trimer) CH2(C6H5)CH2CH2C6H5 CH2=C(C6H5)CH2CH2C6H5 (S dimer) CH2=C(C6H5)CH2CH(C6H5)CH2CH2C6H5 (S trimer)

30 [min]

20

Molecular Retention Weight Index 54 92 108 106 104 118 162 162 196 208 312

[ Related Reference ] 1) Hacaloglu, J.; Ersen, T.; Ertugrul, N.; Fares, M. M.; Suzer, S. Eur. Polym. J. 1997, 33, 199.

395 767 837 867 897 989 1170 1194 1678 1738 2490

Relative Intensity 25.4 7.2 13.6 1.6 100.0 4.6 1.0 1.4 2.4 2.2 11.8

169

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

080

EGA thermogram

Averaged mass spectrum 104 91

78

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

51

39

118

63

133 147 161 50

100

187194 207216

150

312

200

250

350 [m/z]

300

( m/z range : 29 - 600 amu )

B : 1,3-butadiene

T : toluene 39

91

54

39 29

V : 4-vinylcyclohexene

65

51

29

89

S : styrene 104

54

79 103 39

78

66 51

93 108

29

39

S : -methylstyrene

63

T1 : C12H18 (B trimer) 118

79

117

103

91

105 119 133

41 53

78

67

51

39

147 63

162

T2 : C12H18 (B trimer)

SS' : propane-1,2-diyldibenzene

79

92 93

41

106

119

133 105

67

196

53

147

29

162

SS : but-3-ene-1,3-diyldibenzene (styrene dimer)

29

39

51

145

165

187

91

104 65 77

118

SSS : 5-hexene-1,3,5-triyltribenzene (styrene trimer)

91

39 51

65 77

117 130 152 165

193

208 39

65 77

118143

194 207 221

312

170

Tsuge, Ohtani and Watanabe

081 Styrene-ethylene-butadiene-styrene block copolymer; hydrogenated SBS (SEBS) CH2CH(C6H5)

CH2CH2

p

CH2CH

q

CHCH2

r

CH2CH(C6H5)

s

SSS

S

S C10

SS

C11 C12 C13 C14

E

C4 TIC

C15 C16

20

10

T C8

LB

0

10

Peak Notation LB C4 T C8 E S S C10 C11 C12 C13 C14 C15 C16 SS SSS

Assignment of Main Peaks propylene etc. butadiene etc. toluene 1-octene ethylbenzene styrene -methylstyrene 1-decene 1-undecene n-undecane 1,11-dodecadiene 1-dodecene 1-tridecene 1-tetradecene 1,14-pentadecadiene 1-pentadecene n-pentadecane 1,15-hexadecadiene 1-hexadecene CH2=C(C6H5)CH2CH2C6H5 (S dimer) CH2=C(C6H5)CH2CH(C6H5)CH2CH2C6H5 (S trimer)

30 [min]

20

Molecular Retention Weight Index 42 54 92 112 106 104 118 140 154 156 166 168 182 196 208 210 212 222 224 208 312

295 395 767 791 867 896 988 994 1094 1100 1189 1195 1294 1394 1494 1496 1500 1591 1594 1737 2491

[ Related References ] 1) Lamb, G. D.; Lehrle, R. S. J. Anal. Appl. Pyrolysis 1989, 15, 261. 2) Dean, L.; Groves, S.; Hancox, R.; Lamb, G.; Lehrle, R. S. Polym. Degrad. Stab. 1989, 25, 1

Relative Intensity 3.7 6.2 5.2 4.1 1.4 100.0 3.0 1.4 1.1 1.3 1.2 1.4 0.7 0.7 0.3 0.8 0.6 0.8 0.8 2.7 9.7

171

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

081

EGA thermogram

Averaged mass spectrum 104

78 100

91

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

51 39

118

63

165 178 194 207

143 50

100

150

200

312 250

300

350 [m/z]

( m/z range : 29 - 600 amu )

T : toluene

C8 : 1-octene 91

55

41

70

29 83 39

65

51

32

89

112

97

S : styrene

S : -methylstyrene 104

118 117

103

103 78

78

51 39

51

39

63

63

C12 : 1-dodecene

C10 : 1-decene

43

56

41

55

70 70 29 83

83 97

29 97 111118

111

140

SS : but-3-ene-1,3-diyldibenzene (styrene dimer)

125

168

SSS : 5-hexene-1,3,5-triyltribenzene (styrene trimer)

91

91

117 104 39 51

65

77

130 165 179 193

208 51 6577

118 143

194 207 221

312

172

Tsuge, Ohtani and Watanabe

2.2.10 Polyamides 082 Polycaproamide; Nylon-6 NH(CH2)5CO

n

M

NA5 LB TIC

N6

N5

AN

0

NA4 NA3 NA1

NAA3 NAA1

10

Peak Notation LB N5 N6 AN M NA1 NA3 NA4 NA5 NAA1 NAA3 NAA5

Assignment of Main Peaks propylene etc. CH2=CH(CH2)2CN CH2=CH(CH2)3CN CH3(CH2)4CN NC(CH2)5NH2 (CH2)5CONH CH3CONH(CH2)5CN CH3(CH2)2CONH(CH2)5CN CH2=CH(CH2)2CONH(CH2)5CN CH2=CH(CH2)3CONH(CH2)5CN CH3(CH2)4CONH(CH2)5CN CH3CONH(CH2)5CONH(CH2)5CN CH3(CH2)2CONH(CH2)5CONH(CH2)5CN CH3(CH2)4CONH(CH2)5CONH(CH2)5CN

NAA5

30 [min]

20

Molecular Retention Weight Index 42 81 95 97 112 113 154 182 194 208 210 267 295 323

[ Related References ] 1) Ohtani, H.; Nagaya, T.; Sugimura, Y.; Tsuge, S. J. Anal. Appl. Pyrolysis 1982, 4, 117. 2) Levchik, S. V.; Weil, E. D.; Lewin, M. Polym. Int. 1999, 48, 532.

295 737 838 855 1110 1265 1530 1689 1780 1883 1892 2603 2758 2958

Relative Intensity 2.6 0.4 1.5 1.1 1.4 100.0 2.0 2.1 3.9 5.4 2.6 6.4 4.8 7.1

173

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

082

EGA thermogram

Averaged mass spectrum 55 113

30

41 100

200

300

400

500

600

85

700 ºC

programming rate: 20ºC/min

68 96 50

124

139

100

151

164

179

150

250 [m/z]

200

( m/z range : 29 - 600 amu )

N6 : 1-pentenenitrile

N6 : pentanenitrile

55

N

41

N 54

41 68

82

29 29

96

67

80

95

110

143

143

M : ε -caprolactam

AN : 6-aminohexanenitrile N

30

O

113

55

NH 2

NH 85

30

41

42

67

54

67

84

94

111

98

124

NA3 : N-(5-cyanopentyl)butyramide

NA5 : N-(5-cyanopentyl)hex-5-enamide O

114

O

71

41

43

N H

30

55

N

N H

69

114 128

55

100

30

154

83

168

87 142 167

126 140

188

NA5 : N-(5-cyanopentyl)hexanamide 154

O

114 N H

43

179 193 208

NAA1 : 6-acetamido-N-(5-cyanopentyl)hexanamide

O

114

N

154

100

N

H N N H

N

O

99 55 30

71

167 83 128 139

167 181

30 43 55 72 86 96

190 210 229

114

128 140

273

NAA3 : 6-butyramido-N-(5-cyanopentyl)hexanamide H N

N H

267

NAA5 : N-(5-cyanopentyl)-6-hexanamide O

114

O

224 181195 213 238

154

N H

N

H N

N O

O

43 30 55 71 96 86

167 142 154

128

224 41 55 69 30

181 206

295

419

96 86

168 154 126 140

224 195 181 209

292

321

174

Tsuge, Ohtani and Watanabe

083 Polyundecanoamide; Nylon-11 (CH2)10 CONH

N11

C6 LB

C10 C7

C9 C8

TIC

N7

N10 N9

NA10 NA5 HA19 HA20 NA6 HA18 HA17 NA7 HA16 NA8 NA1 NA9

HA15 HA14 HA13 N11’ M

10

LB C6 C7 C8 C9 C10 N9 N10 N11 N11’ M NA1 HA17

HA18

NA5 HA20 NA8 NA9 NA10 D

D

N8

0

Peak Notation

n

Assignment of Main Peaks

30 [min]

20

Molecular Retention Weight Index

42 propylene etc. 84 1-hexene 98 1-heptene 112 1-octene 124 1,8-nonadiene 126 1-nonene 140 1-decene 137 CH2=CH(CH2)6CN 139 CH3(CH2)7CN 151 CH2=CH(CH2)7CN 165 CH2=CH(CH2)8CN 167 CH3(CH2)9CN 165 C11H19N 183 (CH2)10CONH 224 CH3CONH(CH2)10CN 279 CH2=CH(CH2)m -2CONH(CH2)n-2CH=CH2 281 CH2=CH(CH2)m-2CONH(CH2)n-1CH3 (m+n=17, m<10, n<9) 283 CH3(CH2)m-1CONH(CH2)n-1CH3 293 CH2=CH(CH2)m-2CONH(CH2)n-2CH=CH2 295 CH2=CH(CH2)m-2CONH(CH2)n-1CH3 297 CH3(CH2)m-1CONH(CH2)n-1CH3 (m+n=18, m<10, n<10) 278 CH2=CH(CH2)3CONH(CH2)10CN 280 CH3(CH2)4CONH(CH2)10CN 321 CH2=CH(CH2)8CONH(CH2)8CH=CH2 CH2=CH(CH2)8CONH(CH2)9CH3 + CH3(CH2)9CONH(CH2)9CH3 323, 325 CH2=CH(CH2)6CONH(CH2)10CN + CH3(CH2)7CONH(CH2)11CN 320, 322 334 CH2=CH(CH2)7CONH(CH2)10CN 348 CH2=CH(CH2)7CONH(CH2)11CN 366 (CH2)10CONH(CH2)10CONH

[ Related References ] 1) Ohtani, H.; Nagaya, T.; Sugimura, Y.; Tsuge, S. J. Anal. Appl. Pyrolysis. 1982, 4, 117. 2) Levchik, S. V.; Weil, E. D.; Lewin, M. Polym. Int. 1999, 48, 532.

295 595 691 790 882 891 992 1175 1181 1279 1383 1388 1512 1710 2098 2226 2231 2242 2327 2333 2339 2453 2462 2531 2537 2774 2875 2981 3384

Relative Intensity 27.5 28.3 18.4 9.3 6.0 10.9 13.2 3.8 7.7 13.4 35.4 20.3 12.2 15.2 12.5 7.2 11.5 1.9 9.7 13.2 1.2 5.7 10.5 7.4 12.3 25.2 32.3 82.9 100.0

175

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

083

EGA thermogram

Averaged mass spectrum 30 41 55 100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

69

86 98

50

114 122

142

100

156

170 182 193

150

200

250 [m/z]

( m/z range : 29 - 600 amu )

N11 : 10-undecenenitrile

C6 : 1-hexene 41

56

55 41

N

122 136 94

69

84

69

82

108

29

29

150 164

NA1 : N-(10-cyanodecyl)acetamide

M : azacyclododecan-2-one 83

O

41 55

O

30

H N

72

12

96

69

97 86

55

30 110 138

114 142 128

183 277

238

357

55

N H

237 240 224

73

252 321

NA9 : N-(10-cyanodecyl) -9-decenamide 97

O

184

83

110 141 128 171

N

+

O

O

196

340

H N

97

184

73 86100 114 140 128 156168

274

N-(10- cyanodecyl) -8-nonenamide (+ N-(11- cyanoundecyl)nonanamide)

NA8 :

H N

41

184 166

476

HA17 : N-(non-8-enyl) -8-nonenamide

30

N N H

43

N

198 224

282 265

322

362

NA10 : N-(11-cyanoundecyl)-9-decenamide H N

97

O

N

N N H

55 83 41

55

237

184

110 142 166

30

294 334

266

521

D : 1,13-diazacyclotetracosane-2,14-dione O

184

55

41 30

184 237

41

69 30

O

83

HN

69 100 86

140 156 168

196

366

NH

238

294 323 280 309 337

O

351

429

69 110

224 209

308 356

176

Tsuge, Ohtani and Watanabe

084 Polylauroamide; Nylon-12 (C H 2 ) 1 1 C O N H

n

N12

N12’ C10

TIC

LB C6 C7

C8

N7 C9 N6

N11

C11 N8 N9 N10

0

HA20 HA19 HA18 HA17 NA1 HA16 HA15 HA14 M

LB C6 C7 C8 C9

C10 C11 N10 N11 N12 N12’ M’ M NA1 HA19

HA20

NA5 HA22 NA9 NA10 NA11 D

NA7 NA11 NA8 NA9 NA10

M’

10

Peak Notation

NA5 HA21 HA22

D 30 [min]

20

Assignment of Main Peaks propylene etc. 1-hexene 1-heptene 1-octene 1,8-nonadiene 1-nonene n-nonane 1,9-decadiene 1-decene 1-undecene CH2=CH(CH2)7CN CH3(CH2)8CN CH2=CH(CH2)8CN CH2=CH(CH2)9CN CH3(CH2)10CN C12H21N unidentified (CH2)11CONH CH3CONH(CH2)11CN CH2=CH(CH2)m -2CONH(CH2)n-2CH=CH2 CH2=CH(CH2)m-2CONH(CH2)n-1CH3 (m+n=19, m<11, n<10) CH3(CH2)m-1CONH(CH2)n-1CH3 CH2=CH(CH2)m-2CONH(CH2)n-2CH=CH2 CH2=CH(CH2)m-2CONH(CH2)n-1CH3 CH3(CH2)m-1CONH(CH2)n-1CH3 (m+n=20, m<11, n<11) CH2=CH(CH2)3CONH(CH2)11CN CH3(CH2)4CONH(CH2)11CN CH2=CH(CH2)9CONH(CH2)9CH=CH2 + CH2=CH(CH2)9CONH(CH2)10CH3+CH3(CH2)10CONH(CH2)10CH3 CH2=CH(CH2)7CONH(CH2)11CN +CH3(CH2)8CONH(CH2)11CN CH2=CH(CH2)8CONH(CH2)11CN +CH3(CH2)9CONH(CH2)11CN CH2=CH(CH2)9CONH(CH2)11CN +CH3(CH2)10CONH(CH2)11CN (CH2)11CONH(CH2)11CONH

Molecular Retention Weight Index 42 84 98 112 124 126 128 138 140 154 151 153 165 179 181 179 196 197 238 307 309 311 321 323 325 292 294 349 351, 353 348, 350 362, 364 376, 378 394

[Related References ] 1) Ohtani, H.; Nagaya, T.; Sugimura, Y.; Tsuge, S. J. Anal. Appl. Pyrolysis. 1982, 4, 117. 2) Levchik, S. V.; Weil, E. D.; Lewin, M. Polym. Int. 1999, 48, 532.

295 593 692 792 886 894 900 986 994 1094 1284 1290 1387 1490 1496 1615 1764 1825 2210 2438 2443 2471 2540 2545 2549 2565 2574

Relative Intensity 59.4 44.5 17.5 15.6 4.4 16.0 2.5 9.1 26.9 12.2 8.8 10.9 26.9 77.5 29.9 27.5 15.0 23.3 25.8 9.0 17.0 9.0 13.6 3.3 8.7 11.8

2747

18.6

2991 3095 3200 3590

31.8 33.8 100.0 17.7

177

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

084

EGA thermogram

Averaged mass spectrum 41 30

55 100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

86

69

96 50

112 122

136

100

156 166

197 207

180

150

224

200

250 [m/z]

( m/z range : 29 - 600 amu )

N11 : 10-undecenenitrile

C10 : 1-decene 56

41

55 N

41 122 70

136

29

83

94

69

97

82

29

111

108 150 164

140

N12 : dodecanenitrile

N12 : 11-dodecenenitrile N

55

N

41

41 122 136

97

55

110 82

69 82

29

94

108

150

124

69

29

138 152

164 178

166 180

NA1 : N-(11-cyanoundecyl）acetamide

M : Azacyclotridecan-2-one 30 41

55

73

86

NH 112 126

140

43

168

156

O N H

N

+

55

N H 110

N

198 251 212 185 238

128 142 156 198 170 181

(+ N-(11-cyanoundecyl)undecanamide) 97

O

73

114

NA10 : N-(11-cyanoundecyl)undec-10-enamide

N H

55

86

55

O

83

97

182

(+ N-(11-cyanoundecyl)decanamide ) 97

N

72

197

154

NA9 : N-(11-cyanoundecyl)dec-9-enamide

30

N H

O

100

43

O

30

13

O

83

41 30 69

110 128 156

310 321

198 180

N

+

N H 251 238

N 362

NA11 : N-(11-cyanoundecyl)dodec-11-enamide

( + N-(11-cyanoundecyl)dodecanamide ) 97

55 N H

O

N

+

30 41

N H

83

55 41 30

D : 1,14-diazacyclohexacosane-2,15-dione

O

198

N 69

69

110

198

251

336

376

83

100 114

156

210 184

O HN

252

26 280 309

NH O

351 365

394

178

Tsuge, Ohtani and Watanabe

085 Poly(tetramethylene adipamide); Nylon-4,6 NH(CH2 )4NHCO(CH2 )4 CO

n

CP c

b e Pr B TIC LB

BA

0

BD

d

a CC

10

Peak Notation

Assignment of Main Peaks

LB B BA Pr CP BD CC a b c d e

CO2 1,3-butadiene 1-butanamine pyrrolidine cyclopentanone 1,4-butanediamine 2-cyanocyclopentanone unidentified CH2=CH(CH2)2NHCO(CH2)4CN unidentified (CH2)4NHCO(CH2)4CONH unidentified

30 [min]

20

Molecular Retention Weight Index 44 54 73 71 84 88 109 133 180 180 198 263

150 395 637 686 790 882 1150 1366 1612 2006 2059 2499

Relative Intensity 3.1 3.7 13.3 33.6 100.0 31.6 5.4 35.5 19.7 39.3 9.9 24.5

179

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

085

EGA thermogram

Averaged mass spectrum 30

100

55

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

44 70

84

96

110

136

124 50

100

158 173180 150

198 202 216 200

300 [m/z]

250

( m/z range : 29 - 600 amu )

BA : 1-butanamine

Pr : pyrrolidine H N

43

30

NH2

70 41

30

73

56

54

79

BD : 1,4-butanediamine

CP : cyclopentanone 55

O

30

NH2

H2N 84

41 29

43 59

67

CC : 2-cyanocyclopentanone

71

87

a : unidentified O

54

30

N

39

109

114

41

80 66

30

56

120

93

b : N-(but-3-enyl)-5-cyanopentanamide

69

86

99

151

c : unidentified

O

55 N H

41

180 125

123

30

N

72

96 67

29

82

110

137

152 41 53

80 95 109

180 165

156 98 114

141

82

170

185

96

30

N H

128

84

224

55

H N 70

196

110

O

55

41

163

e : unidentified

d : 1,6-diazacyclododecane-7,12-dion

30

137 151

41 O 225

70 124 136 154

181

196

263

286

180

Tsuge, Ohtani and Watanabe

086 Poly(hexamethylene adipamide); Nylon-6,6 NH(CH 2 )6 NHCO(CH2 ) 4 CO

n

CP

DA

AA4 AA3 NA6

A6 TIC LB

CA

A5

0

AA2 AA1

DN

M HD

L6 10

Peak Notation LB A5 CP A6 CA DA DN L6 AA1 AA2 AA3 AA4 NA6 M HD

Assignment of Main Peaks CO2 etc. CH2=CH(CH2)3NH2 (CH2)4CO CH2=CH(CH2)4NH2 CH3(CH2)5NH2 NC(CH2)4NH2 ? H2N(CH2)6NH2 NC(CH2)4CN (CH2)5CONH CH3CONH(CH2)6NH2 CH2=CHCONH(CH2)6NH2 CH2=CHCH2CONH(CH2)6NH2 CH2=CH(CH2)2CONH(CH2)6NH2 CH2=CH(CH2)4NHCO(CH2)4CN CH3(CH2)5NHCO(CH2)4CN (CH2)6NHCO(CH2)4CONH CH2=CH(CH2)4NHCO(CH2)4CONH(CH2)5CH3 ?

30 [min]

20

Molecular Retention Weight Index 44 85 84 99 101 98 ? 116 108 113 158 170 184 198 208 210 226 310 ?

150 729 788 832 841 907 1087 1183 1257 1532 1608 1704 1799 1905 1912 2295 2733

[ Related References ] 1) Ohtani, H. ; Nagaya, T. ; Sugimura, Y. ; Tsuge, S. J. Anal. Appl. Pyrolysis. 1982, 4, 117. 2) Mac Kerron, D. H. ; Gordon, R. P. Polym. Degrad. Stab. 1985, 12, 277. 3) Ballistreri, A.; Garozzo, D.; Giuffrida, M.; Montaudo, G. Macromolecules 1987, 20, 2991. 4) Levchik, S. V.; Weil, E. D.; Lewin, M. Polym. Int. 1999, 48, 532. 5) Schaffer, M. A.; Marchildon, E. K.; McAuley, K. B.; Cunningham, M. F. J. Macromol. Sci., Rev. Macromol. Chem. Phys. 2000, C40, 233.

Relative Intensity 27.3 7.4 100.0 20.0 10.2 7.0 21.1 2.5 4.0 9.2 3.3 3.2 6.8 12.3 4.3 31.5 18.0

181

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

086

EGA thermogram

Averaged mass spectrum 30

44

55

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

84 96

68 50

110

124

152

138

100

166

176 200 [m/z]

150

( m/z range : 29 - 600 amu )

A6 : hex-5-en-1-amine

CP : cyclopentanone O

55

30

NH2 39 84 39 56

29

67

67

A6 : hexan-1-amine

82

DA : hexane-1,6-diamine 30

30

41

42

56

56 87

70

O

41

H N

30

NH2

N H

43

100

AA4 : N-(6-aminohexyl)pent-4-enamide

AA1 : N-(6-aminohexyl)acetamide 30

NH2

H2 N

NH2

NH 2

55

O 82

73

56

86 100

82

O

41 30

N H

55

N H

55

N

N

82 110

110 100

67

55

O

41

NH O 168 181

198

181

226

30

152 O

82 96 110

55

112 128 141 154

167

H N

N H

HN

41

86 98

128 140

HD : N1-(hex-5-enyl)-N6-hexyladipamide

O

30

100

73

167

127 139

M : 1,8-diazacyclotetradecane-2,7-dione

69

152

NA6 : 5-cyano-N-hexylpentanamide

O

41

139

129

114

NA6 : 5-cyano-N-(hex-5-enyl)pentanamide

30

100 110

73

67 124138

166

209

251

291

182

Tsuge, Ohtani and Watanabe

087 Poly(hexamethylene sebacamide); Nylon-6,10 NH(CH 2 )6 NHCO(CH 2 )8 CO

n

M HA14 NA1 HA13 HA12 A DN

N8

NA5 NA4 HD

L6

LB TIC

NA6

N7

C6

N9

N6

C7

0

10

Peak Notation LB C6 C7 N6 N7 N8 N9 L6 DN A HA12

HA13 NA1 HA14

NA4 NA5 NA6 M HD

Assignment of Main Peaks

1-butene 1-hexen 1-heptene CH2=CH(CH2)3CN CH3(CH2)4CN CH2=CH(CH2)4CN CH3(CH2)5CN CH2=CH(CH2)5CN CH2=CH(CH2)6CN CH3(CH2)7CN (CH2)5CONH NC(CH2)8CN NC(CH2)8COOH CH2=CH(CH2)m-2CONH(CH2)n-2CH=CH2 (m+n=12, m<8, n<6) CH2=CH(CH2)m-2CONH(CH2)n-1CH3 (m+n=12, m<8, n<6) + CH2(CH2)n-2CONH(CH2)m-1CH3 CH2=CH(CH2)m-2CONH(CH2)n-2CH=CH2 (m+n=13,m<8, n<7) CH2=CH(CH2)m-2CONH(CH2)n-1CH3 (m+n=13, m<8, n<7) + CH2=CH(CH2)n-2CONH(CH2)m-1CH3 CH3NHCO(CH2)8CN CH2=CH(CH2)6CONH(CH2)4CH=CH2 CH2=CH(CH2)6CONH(CH2)5CH3 + CH2=CH(CH2)4NHCO(CH2)7CH3 CH3(CH2)3NHCO(CH2)8CN CH2=CH(CH2)3NHCO(CH2)8CN CH2=CH(CH2)4NHCO(CH2)8CN CH3(CH2)5NHCO(CH2)8CN (CH2)6NHCO(CH2)8CONH CH2=CH(CH2)4NHCO(CH2)8CONH(CH2)5CH3 ?

30 [min]

20

Molecular Retention Weight Index 56 84 98 95 97 109 111 123 137 139 113 164 183 209 211 211 223 225 225 196 237 239 239 238 250 264 266 282 366 ?

[ Related References ] 1) Ohtani, H. ; Nagaya, T. ; Sugimura, Y. ; Tsuge, S. J. Anal. Appl. Pyrolysis. 1982, 4, 117. 2) Levchik, S. V.; Weil, E. D.; Lewin, M. Polym. Int. 1999, 48, 532.

Relative Intensity

385 595 694 863 880 975 982 1079 1079 1187 1263 1617 1670 1717

31.1 31.0 7.7 6.7 4.1 8.8 10.4 37.4 8.4 5.0 14.9 33.5 48.6 10.9

1726

17.2

1820

15.3

1828

15.5

1909 1923

18.6 6.5

1931

9.0

2152 2246 2353 2359 2776 3097

18.6 21.3 68.3 13.4 100.0 47.4

183

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

087

EGA thermogram

Averaged mass spectrum 55

41 30

100

200

300

400

500

82

67

600

700 ºC

programming rate: 20ºC/min

96 114 50

124

142

100

156 165

184

198 207

150

223

200

250 [m/z]

( m/z range : 29 - 600 amu )

DN : decanedinitrile

N8 : 7-octenenitrile 55

82

N

41

N

41

N 55

94

96 29

82

67

73

58

137 30

154 166

NA4 : N-butyl-9-cyanononanamide

30

N

55

30

O 166

N 30

166

55 N H 41

N

73 138 126 154 113

86

223 183196 210

156 100

114

128 143

O

30

O

55

100

86

86

41

NH

72 282 253267

H N

N H

128

69

237

HD : N5-(hex-5-enyl)-N10-hexyldecanediamide H N

128 O 140 156 114 210 168 184196 225 239

223 182 196 209

264

235

97

41

195 208

NA6 : 9-cyano-N-hexylnonanamide

M : 1,8-diazacyclooctadecane-9,18-dione 55

85

138 156 112 127

98 73 82

N 166

198 209 223

O N H

156166

99

128 138 156

NA6 : 9-cyano-N-(hex-5-enyl)nonanamide 55

114 128 138

O 73

100

100

H N

73

86

30

86

41

N H 166

41

41

NA5 : 9-cyano-N-(pent-4-enyl)nonanamide

O

115

55

N O

97 108

41

H N

124

84

30

163

OH

N

29

135

NA1 : 9-cyano-N-methylnonanamide O

55

69

124 110

A : 9-cyanononanoic acid 41

69

29

122 108

O

140 114

166 157

196 210

251 241

323

184

Tsuge, Ohtani and Watanabe

088 Poly(dodecamethylene adipamide); Nylon-12,6 NH(CH 2 )12 NHCO(CH 2 ) 4 CO

n

CP M DA

LB

C11

C6

A12 NA10

A11 A10

C9 C10

C7

TIC

A7 A8 A9

0

10

Peak Notation LB C6 C7 CP C9 C10 C11 A9 C12 A10 A11 A12 DA NA10 NA11 NA12 M

NA12 NA11

C12

Assignment of Main Peaks propylene etc. CH2=CH(CH2)3CH3 CH2=CH(CH2)4CH3 (CH2)4CO CH2=CH(CH2)6CH3 CH2=CH(CH2)7CH3 CH2=CH(CH2)7CH=CH2 CH2=CH(CH2)8CH3 CH2=CH(CH2)7NH2 CH3(CH2)8NH2 CH2=CH(CH2)9CH3 CH2=CH(CH2)8NH2 CH3(CH2)9NH2 CH2=CH(CH2)9NH2 CH3(CH2)10NH2 CH2=CH(CH2)10NH2 CH3(CH2)11NH2 H2N(CH2)12NH2 CH3(CH2)9NHCO(CH2)4CN CH2=CH(CH2)10NHCO(CH2)4NH2 CH2=CH(CH2)9NHCO(CH2)4CN + CH3(CH2)11NHCO(CH2)4CN (CH2)12NHCO(CH2)4CONH

30 [min]

20

Molecular Retention Weight Index 42 84 98 84 126 140 152 154 141 143 168 155 157 169 171 183 185 200 266 282 278 294 310

[ Related References ] 1) Ohtani, H.; Nagaya, T.; Sugimura, Y.; Tsuge, S. J. Anal. Appl. Pyrolysis. 1982, 4, 117. 2) Tsuge, S.; Ohtani, H.; Matsubara, H.; Ohsawa, M. J. Anal. Appl. Pyrolysis 1987, 11, 181.

Relative Intensity

295 596 690 790 891 991 1093 1093 1151 1158 1193 1241 1250 1343 1352 1446 1454 1717 2335 2438

10.2 15.1 6.3 95.8 18.8 7.2 2.9 6.3 4.8 3.4 3.1 3.9 10.2 14.7 6.2 24.5 20.8 54.7 12.0 17.0

2548

42.1

2982

100.0

185

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

088

EGA thermogram

Averaged mass spectrum 30

100

200

300

400

500

55

600

700 ºC

programming rate: 20ºC/min

44 84

97

69

152 128 142

110

50

100

171 184

150

194 208 222 236 250 200

266

250

300 [m/z]

( m/z range : 29 - 600 amu )

CP : cyclopentanone

C6 : 1-hexene 56

55

O

41

84 41

69

29

84 29

C10 : 1-decene

67

A10 : 1-decanamine 30

41

NH2 55 70 29 83

97

41

111

140

A11 : undec-10-en-1-amine

55

69

86

100 114

132

157

A12 : dodec-11-en-1-amine

30

30

NH2

41

55

NH2

41 67

86 95

114 128 140 154

55

169

67

86

100 112

128 142 154 168

183

DA : 1,12-dodecanediamine

A12 : 1-dodecanamine

30

30

NH2

41

55

44 86

69

100 114 128 142 156

184

NA12 : 5-cyano-N-(undec-10-enyl)pentanamide H N

55

+

82 41 73

100

127

86 100 114 128 142 156 171 184 201

O N H

O O

30 41 N

139 153 167181195 212

69

55

N

N H

110

56

M : 1,8-diazacycloicosane-2,7-dione

(+ 5-cyano-N-dodecylpentanamide ) 30

NH2

H2N

294

20 HN

112 84100 69 128

O

156 182 212 238 265

310 364

186

Tsuge, Ohtani and Watanabe

089 Caproamide-hexamethylene adipamide copolymer; Nylon-6/66 NH(CH2)5CO

NH(CH2)6NHCO(CH 2)4CO

n

L6

CP

CA N6 LB A5

TIC

A6

NA5 AN

0

10

Peak Notation LB A5 CP A6 N6 CA AN L6 NA5

Assignment of Main Peaks propylene etc. CH2=CH(CH2)3NH2 (CH2)4CO CH2=CH(CH2)4NH2 CH3(CH2)5NH2 CH2=CH(CH2)3CN CH3(CH2)4CN NC(CH2)4NH2 ? NC(CH2)5NH2 (CH2)5CONH CH2=CH(CH2)3NHCO(CH2)4CN ?

30 [min]

20

Molecular Retention Weight Index 42 85 84 99 101 95 97 98 ? 112 113 194 ?

[ Related References ] 1) Senoo, H.; Tsuge, S.; Takeuchi, T. J. Chromatogr. Sci., 1971, 9, 315. 2) Ohtani, H.; Nagaya, T.; Sugimura, Y.; Tsuge, S. J. Anal. Appl. Pyrolysis. 1982, 4, 117.

295 732 788 839 850 861 878 912 1159 1268 1821

Relative Intensity 5.3 1.6 28.0 2.1 0.8 1.3 1.3 2.9 0.8 100.0 11.8

187

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

089

EGA thermogram

Averaged mass spectrum 55

30 41

100

200

300

400

500

84

600

700 ºC

programming rate: 20ºC/min

113 68

96 122

50

136

100

150

179

164

200 [m/z]

150

( m/z range : 29 - 600 amu )

CP : cyclopentanone

A5 : pent-4-enylamine 30

55

O

NH2

84 41 39

56 68

29

A6 : hex-5-en-1-amine

63

A6 : hexan-1-amine

30

30

NH2

NH2

56 39

39 70 56

82

N6 : hexanenitrile

N6 : hex-5-enenitrile 55

54

41

N

N

41 68 82 29 67

29

93

80

L6 : ε -caprolactam

AN : 6-aminohexanenitrile 43

30

N

O

55

113

NH2 30 72

60

NH

41

85

85 67 98

NA5 : 5-cyano-N-(pent-4-enyl)pentanamide H N O 95 108 41 29

55

179

N

67

80

123

136 150 164

188

Tsuge, Ohtani and Watanabe

090 Poly(m-xylene adipamide); Nylon-MXD6 NHCH2

CH2NHCO(CH2)4CO

n

G

X

CP LB TIC

H

TA TN AL MS CB

0

J

NO DN A

C B

F D

E

10

Peak Notation

Assignment of Main Peaks

LB CP X CB MS AL TN TA NO DN A B C D E F G H I J

CO2 (CH2)4CO m-xylene cyanobenzene m-methylstyrene m-tolualdehyde ? m-tolunitrile CH3C6H4CH2NH2 C6H7NO adiponitrile C10H11N ? C10H9N ? unidentified unidentified unidentified unidentified CH3C6H4CH2NHCO(CH2)4CN unidentified unidentified CH3C6H4CH2NHCO(CH2)4CONHCH2C6H4CH3

* C6H4 represents m-phenylene group

I

30 [min]

20

Molecular Retention Weight Index 44 84 106 103 118 120 ? 117 121 109 108 145 ? 143 ? 126 210 212 231 230 352

150 786 871 988 998 1074 1098 1122 1131 1187 1340 1407 1434 1718 1933 2000 2208 2517 3021 3314

Relative Intensity 42.5 59.6 100.0 1.4 4.2 1.3 15.5 7.5 9.4 8.1 10.7 4.6 30.2 23.3 19.2 23.6 124.1 108.3 30.0 80.8

189

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

090

EGA thermogram

Averaged mass spectrum 91 55

39

106 100

77

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

120

65

132

30

147 170 50

100

187188

208

150

223 250 [m/z]

200

( m/z range : 29 - 600 amu )

X : m-xylene

CP : cyclopentanone 55

O

91

84

106

41 29

51

39

66

C : unidentified

77

65

D : unidentified 59

105

44 210 82 29

72

98

110

77

39 51 65

E : unidentified

103

118

139 152 165 178189

F : unidentified 105

119 231

55 77

39 51 65

212 103

29

128 144 158170 185

G : 5-cyano-N-(3-methylbenzyl)pentanamide

77

41

98105 132 146 160

65

188

229

H : unidentified

O

105 120

203

174

120

N H

N 230

105 77 91

55

162

65

29 41

132 148

176 190

44 55 65 77 91 29

215

132 146 160 174 190 203 220 231 248

J : N1,N6-bis(3-methylbenzyl)adipamide

I : unidentified

120

105

O N H

105

120 334

163

30

77 91 5565

H N O

158

176191

212

355

30

657791

132

229

324

352

190

Tsuge, Ohtani and Watanabe

2.2.11 Polyacetals and polyethers 091 Polyoxymethylene; POM CH 2O

n

M

MO TIC

a

0

10

Peak Notation

Assignment of Main Peaks

M MO a

formaldehyde methanol unidentified

30 [min]

20

Molecular Retention Weight Index 30 32 -

245 320 615

[ Related References ] 1) Grassie, N.; Roche, R. S. Makromol. Chem. 1968, 112, 16. 2) Ishida, Y.; Ohtani, H.; Abe, K.; Tsuge, S.; Yamamoto, K.; Katoh, K. Macromolecules 1995, 28, 6528.

Relative Intensity 100.0 7.7 5.6

191

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

091

EGA thermogram

Averaged mass spectrum 29

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

50

100

[m/z]

( m/z range : 29 - 600 amu )

MO : methanol

M : formaldehyde 29

H

H

H

31

H

O H

O 44

a : unidentified 45

31 61 75

89

44

56

H

192

Tsuge, Ohtani and Watanabe

092 Polyoxymethylene(copolymer) CH2CH2O

CH2O

n

M MO

TIC

DO PG

EA

A

0

10

Peak Notation

Assignment of Main Peaks

M MO DO PG EA A

formaldehyde + ethylene oxide methanol O O 1,3-dioxolane propylene glycol CH3O(CH2CH2O)2CH3 unidentified

30 [min]

20

Molecular Retention Weight Index 30; 44 32 74 76 134 -

245 260 603 616 807 988

[ Related References ] 1) Burg, K. H.; Fischer, F.; Weissermel, K. Makromol. Chem. 1967, 103, 268. 2) Ishida, Y.; Ohtani, H.; Abe, K.; Tsuge, S.; Yamamoto, K.; Katoh, K. Macromolecules 1995, 28, 528.

Relative Intensity 100.0 64.0 2.5 5.3 8.6 4.2

193

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

092

EGA thermogram

Averaged mass spectrum 30

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

44 75

55

87 98

50

135

100

150

200

250

350 [m/z]

300

( m/z range : 29 - 600 amu )

DO : 1,3-dioxolane

MO : methanol 29

H H

O

O H

73

29

O

44

H

45

PG : propylene glycol

EA : 1-methoxy-2-(2-methoxyethoxy)ethane 45

45

OH HO

O

O O

31

31 61

61 75

A : unidentified 45

31 61

75

89

105

119

89

74 90

119

194

Tsuge, Ohtani and Watanabe

093 Poly(ethylene oxide) CH 2 CH 2 O

n

M

HP3 HP2 HP1 H4 P4

D2 EE D3

D4

T4 T2 T3

TIC

TE4

T1

TE3 TE2 TE1

0

P2 P1

P3

H3 H2 H1

10

Peak Notation M EE D2 D3 D4 T1 T2 T3

T4 TE1 TE2 TE3

TE4 P4 HP4 O4 N4 DE4 DO4

HP4 O4 O3 O2 O1

N4 DE4

N1

U4 DO4

30 [min]

20

Assignment of Main Peaks ethylene oxide CH3CH2OOCH2CH3 + CH2=CHOCH2CH3 CH3CH2OCH2CH=O CH2=CHOCH2CH2OH CH2=CHOCH2CH2OCH3 CH2=CHOCH2CH2OCH2CH3 CH3OCH2CH2OCH2CH=O CH2=CHOCH2CH2OCH2CH=O CH3CH2OCH2CH2OCH2CH=O CH2=CHO(CH2CH2O)2H CH2=CHO(CH2CH2O)2CH3 CH3CH2O(CH2CH2O)2CH3 CH2=CHO(CH2CH2O)2CH2CH3 CH3CH2O(CH2CH2O)2CH2CH3 CH3O(CH2CH2O)2CH2CH=O CH2=CHO(CH2CH2O)2CH2CH=O CH3CH2O(CH2CH2O)2CH2CH=O CH2=CHO(CH2CH2O)3H CH2=CHO(CH2CH2O)3CH3 CH3CH2O(CH2CH2O)3CH3 CH2=CHO(CH2CH2O)3CH2CH3 CH3CH2O(CH2CH2O)3CH2CH3 CH2=CHO(CH2CH2O)4CH=CH2 + CH2=CHO(CH2CH2O)4CH2CH3 CH3CH2O(CH2CH2O)4CH2CH3 CH3CH2O(CH2CH2O)6CH2CH3 CH3CH2O(CH2CH2O)7CH2CH3 CH3CH2O(CH2CH2O)8CH2CH3 CH3CH2O(CH2CH2O)9CH2CH3 CH2=CHO(CH2CH2O)11CH=CH2 CH2=CHO(CH2CH2O)11CH2CH3 CH3CH2O(CH2CH2O)11CH2CH3

Molecular Retention Weight Index 44 74, 72 88 88 102 116 118 130 132 132 146 148 160 162 162 174 176 176 190 192 204 206 246, 248 250 336 380 424 468 554 556 558

[ Related References ] 1) Madorsky, S. L.; Straus, S. J. Polym. Sci. 1959, 36, 183. 2) Voorhees, K. J.; Baugh, S. F.; Stevenson, D. N. J. Anal. Appl. Pyrolysis 1994, 30, 47. 3) Fares, M. M.; Hacaloglu, J.; Suzer, S. Eur. Polym. J. 1994, 30, 845.

360 490 657 719 726 802 862 961 971 1004 1015 1019 1084 1090 1173 1238 1251 1284 1296 1308 1358 1363 1629 1634 2169 2439 2703 2975 3506 3511 3518

Relative Intensity 100.0 22.9 23.3 16.1 9.3 20.7 2.6 4.4 3.5 2.0 5.2 4.2 13.6 5.9 1.6 4.5 5.2 2.4 11.4 0.9 15.4 7.8 18.7 8.7 31.6 32.3 31.8 31.5 3.6 13.3 6.5

195

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

093

EGA thermogram

Averaged mass spectrum 45

100

29

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

59 73 87

103

50

117

131133

100

200 [m/z]

150

( m/z range : 29 - 600 amu )

M : ethylene oxide

EE : diethyl ether + ethoxyethene 43

29

O

O

+

29

O 72

44 59

D2 : 2-ethoxyacetaldehyde

D3 : 2-(vinyloxy)ethanol

31

45

O

OH

O

O 59 31 45 57

D3 : (2-methoxyethoxy)ethene

D4 : (2-ethoxyethoxy)ethene

45

45

O

O

58

29

88

69

O

O 31 72 59

87

72

102

86

HP4 : 3,6,9,12,15,18,21-heptaoxatricos-1-ene O

O

O

O

45

O

O

O

89

117 101

133

147 161

O

177

89

59

29

N4 :3,6,9,12,15,18,21,24,27-nonaoxanonacos-1-ene

O

O

O

O

O

117 133

101

161 177

201

DE4 : 3,6,9,12,15,18,21,24,27,30-decaoxadotriacont-1-ene

45

45

O

O

O

O

O

O

O

O

O

O

73 59 29

O

73

73 59

29

116

O4 : 3,6,9,12,15,18,21,24-octaoxahexacos-1-ene

45

O

101

O

O

O

O

O

O

O

O O

73 117

89 101

133

147 161 177

203 221

29

59

117

89 101

133

147 161 177

221

196

Tsuge, Ohtani and Watanabe

094 Epichlorohydrin rubber; CHR CH 2 CH(CH 2 Cl)O

n

D2 LB

D1

T3 T1

P2

P1

T2

TE3

AC

TE1

CP

15

10

TIC

0

10

Peak Notation

Assignment of Main Peaks

LB AC CP D1 D2 T1 T2 T3 TE1 TE3 P1 P2

hydrogen chloride, propylene acrolein CH2=CHCHO 3-chloropropylene CH2=CHCH2Cl C6H9ClO2 C6H11ClO2 C9H13ClO3 C9H14Cl2O3 C9H16Cl2O3 C12H18Cl2O4 C12H21Cl3O4 C15H23Cl3O5 C15H26Cl4O4 [ Related References ] 1) Pidduck, A. J. J. Anal. Appl. Pyrolysis 1985, 7, 215. 2) Mcguire, J. M.; Bryden, C. C. J. Appl. Polym. Sci., 1988, 35, 537.

30 [min]

20

Molecular Retention Weight Index 36, 42 56 76 148 150 204 240 242 296 334 388 410

295 490 530 1023 1090 1258 1392 1531 1721 1910 2134 2675

Relative Intensity 100.0 8.0 13.7 6.7 8.2 3.4 2.9 4.6 1.0 2.4 2.8 4.1

197

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

094

EGA thermogram

Averaged mass spectrum 43

57

29

100

200

300

400

500

93

600

700 ºC

programming rate: 20ºC/min

75 77

121 107

50

135

100

149

171175

188

150

205

229 250 [m/z]

200

( m/z range : 29 - 600 amu )

AC : acrolein

LB : hydrogen chloride (+ propylene) 36

Cl

H

O

56

+

29

37 67

32

CP : 3-chloropropylene

76

D2 : C6H11ClO2 41

39

Cl

76 49

32

31

119

77 101

63

T3 : C9H16Cl2O3

115

TE3 : C12H21Cl3O4

41

41

55

121 29

57

75

5763

91 77

29 149

106

77 75

169

P1 : C15H23Cl3O5

93

111 121

137 149

175 169

P2 :C15H26Cl4O4

41

41 93 75 93

29

57

77

29

111121 141 149

169

203

259

121

57 77 75

107

149 137

169 185 189

241

198

Tsuge, Ohtani and Watanabe

095 Epichlorohydrin-ethylene oxide rubber; CHC CH2CH2O

CH2CH(CH2Cl)O CE3

LB

D2

CE2

A

b c AC

D1

CEE

CEE1 T3

a

CP EP TIC

n

10

5

CE1

0

10

Peak Notation

Assignment of Main Peaks

LB A AC CP EP CE1 CE2 CE3 a b c D1 D2 CEE CEE1 T3

hydrogen chloride + propylene acetaldehyde acrolein CH2=CHCHO 3-chloropropylene CH2=CHCH2Cl epichlorohydrin ? C5H8O2 C5H9ClO (mixture of dimer) C6H11ClO unidentified unidentified unidentified C6H9ClO2 C6H11ClO2 C6H13ClO3 C8H15ClO3 C9H16Cl2O3

[ Related References ] 1) Pidduck, A. J. J. Anal. Appl. Pyrolysis 1985, 7, 215. 2) McGuire, J. M.; Bryden, C. C. J. Appl. Polym. Sci., 1988, 35, 537.

30 [min]

20

Molecular Retention Weight Index 36; 42 44 56 76 92 ? 100 120 134 132 150 148 148 150 168 194 242

295 408 490 530 637 679 754 774 802 837 883 910 986 1090 1371 1648

Relative Intensity 100.0 42.2 10.5 8.9 15.2 2.6 4.8 9.6 2.3 3.5 2.5 1.6 9.3 2.7 1.4 2.1

199

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

095

EGA thermogram

Averaged mass spectrum 45

100

29

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

57

87

63

93 107

50

121

137

100

151

165 175

150

250 [m/z]

200

( m/z range : 29 - 600 amu )

LB : hydrogen chloride

A : acetaldehyde 36

H

29

Cl O

44

32

56

AC : acrolein

62

CP : 3-chloropropylene 56

O

39

Cl

29

76 37 49

67

75

CE3 : C6H11ClO

CE2 : C5H9ClO (mixed dimer)

43

99 73 45 29

55 100 29 55

D1 : C6H9ClO2

72

85

D2 : C6H11ClO2 87

79

29 107

29

43

41 49

55

CEE : C6H13ClO3

136 121

T3 : C9H16Cl2O3

41

31

92

63

94

66

41

57

119

77 63

29

93

57 63

101

84

121

200

Tsuge, Ohtani and Watanabe

2.2.12 Thermosetting polymers 096 Phenol formaldehyde resin (novolak); PF OH CH2 n

P D1 D2 PC OC

D3 X2 HQ

BQ

TIC

A

HA

X1

0

PP XT MX

10

Assignment of Main Peaks

BQ P OC PC X1 X2

benzoquinone phenol o-cresol p-cresol 2,6-xylenol 2,4-xylenol

HA PP XT MX A

T2 T1

30 [min]

20

Peak Notation

HQ

D4

Molecular Retention Weight Index

O H HO

p-hydroxybenzaldehyde o-phenylphenol O xanthene 2-methylxanthene unidentified OH

D1

OH

O

Relative Intensity

108 94 108 108 122 122

920 986 1060 1081 1115 1155

0.8 100.0 32.0 43.7 2.2 11.3

110

1275

9.5

122 170 182 196 -

1369 1540 1687 1808 1998

9.5 2.4 2.3 3.3 8.3

200

2034

60.7

200

2101

73.5

214

2119

10.2

214

2164

10.1

306

3099

7.0

320

3178

12.3

OH C H2

OH CH 2

D2

OH OH

OH

C H3

C H2

D3 OH

C H2

D4

OH OH

OH CH 2

T1 OH

T2

C H3

OH CH 2

OH CH 2

OH CH 2

CH 3

[ Related References ] 1) Jones, S. T. Analyst. 1984, 109, 823. 2) Morterra, C.; Low, M. J. D. Carbon 1985, 23, 525. 3) Blazso, M.; Toth, T. J. Anal. Appl. Pyrolysis 1991, 19, 251. 4) Cohen, Y.; Aizenshtat, Z. J. Anal. Appl. Pyrolysis 1992, 22, 153. 5) Lytle, C. A.; Bertsch, W.; McKinley, M. J. Anal. Appl. Pyrolysis 1998, 45, 121. 6) Sobera, M.; Hetper, J. J. Chromatogr. A 2003, 993, 131.

201

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

096

EGA thermogram

Averaged mass spectrum 94

107

100

66

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

39

200

77 51 121

141

31 50

100

152

181

165

214

150

228

200

250 [m/z]

( m/z range : 29 - 600 amu )

OC : o-cresol

P : phenol OH

94

108

OH

66

39

77

55

29

79

PC : p-cresol

90

63

X2 : 2,4-xylenol 107

OH

122

OH

107

77 29

51

39

29

51

39

77

39

90

63

51

29

91

65

HA : p-hydroxybenzaldehyde

HQ : hydroquinone 110

OH

121

O

HO

29

OH

81

53

39

63

D1 : 2,2'-methylenebisphenol OH

OH

93

65

39 53

29

95

77

D2 : 2,4'-methylenediphenol

107

107

OH

200

200

OH 94

29

77

39 51 63

152 181 128 141 165

202

29

T1 : 2,2'-(2-hydroxy-1,3-phenylene) OH

55 63

183 152 128 141 165

94

202

T2 : 2-(2-hydroxy-3-(2-hydroxybenzyl)benzyl)

bis(methylene)diphenol 107

39

77

-6-methylphenol OH

OH

OH

OH

OH 306 199

107 306 199 213 39 5565

77 94

213

181 255

287

320

3139

55 65

77

94

128

152

181 334

202

Tsuge, Ohtani and Watanabe

097 Phenol formaldehyde resin (resol); PF OH CH2 n

D1

P PC

OC

D2

XT

D3 MX

D4

X2 15

TIC

20

X1

0

10

30 [min]

20

Peak Notation

Assignment of Main Peaks

P OC PC X1 X2 XT

phenol o-cresol p-cresol 2,6-xylenol 2,4-xylenol xanthene

MX

2-methylxanthene

O

Molecular Retention Weight Index

Relative Intensity

94 108 108 122 122 182

986 1061 1081 1116 1155 1687

100.0 38.6 43.9 3.6 14.2 3.1

196

1807

2.2

200

2029

11.4

200

2093

10.0

214

2116

1.6

214

2163

1.7

O

OH

D1

OH C H2

OH CH 2

D2

OH OH

D3

OH C H2

C H3

C H2

C H3

OH

D4

OH

[ Related References ] 1) Martinez, J.; Guiochon, G. J. Gas Chromatogr. 1967, 51, 146. 2) Jones, S. T. Analyst. 1984, 109, 823. 3) Morterra, C.; Low, M. J. D. Carbon 1985, 23, 525. 4) Prokai, L. J. Anal. Appl. Pyrolysis 1987, 12, 265. 5) Sobera, M.; Hetper, J. J. Chromatogr. A 2003, 993, 131.

203

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

097

EGA thermogram

Averaged mass spectrum 94

66

107

100

200

300

400

500

600

39

700 ºC

programming rate: 20ºC/min

77 51 122

31 50

152

100

181

165

195

150

200

250 [m/z]

( m/z range : 29 - 600 amu )

OC : o-cresol

P : phenol OH

94

108

OH

77

66

39 55

29

79

PC : p-cresol

51

39

29

90

63

X1 : 2,6-xylenol

OH

122

OH

107

107

77

77 29

51

39

39

90

63

X2 : 2,4-xylenol

91

65

132

XT : xanthene

OH

107

77 29

51

31

39

51

122

181

O

91

65

39

MX : 2-methylxanthene

76

51 63

152 90

115 127 139

D1 : 2,2'-methylenediphenol 195

O

107

OH

OH

200 94

181 97 39

69

51

152 165 115 126 139

82

202

D4 : 4-(2-hydroxybenzyl)-2-methylphenol

D2 : 2,4'-methylenediphenol 107

OH

152 181 128 141 165

77 29 39 51 63

214

OH 200

39

55 63 77

107 121

HO

OH 94

183 152 128 141 165

214

39

55 65

77

91

199

181 141152 165

216

204

Tsuge, Ohtani and Watanabe

098 Cresol formaldehyde resin (novolak) CH3 OH CH2 OC

n

D1 D3

X2

D4

X1 TP

D5 D2 T1

PC TIC

T2

P

0

10

Peak Notation

Assignment of Main Peaks

P OC PC X1 X2 TP

phenol o-cresol p-cresol 2,6-xylenol 2,4-xylenol 2,4,6-trimethylphenol C

D1

HO

D2

HO

C C C

HO

HO C

HO

C

2140

99.7

242

2191

14.8

242

2233

100.0

C

256

2269

18.9

242

2286

26.2

348

3211

30.8

376

3308

43.6

OH C

C C HO

C HO

C HO

C C

T2

228

C

HO

T1

6.6 88.9 6.6 44.8 64.6 32.0

C

C

D5

985 1060 1079 1116 1155 1215

C HO

C

94 108 108 122 122 136

C

C

D4

Relative Intensity

C HO

C

D3

Molecular Retention Weight Index

C HO

C

30 [min]

20

C C

C

HO

HO

HO

C

C

C

C

* bonding hydrogen is omitted [ Related References ] 1) Blazso, M.; Toth, T. J. Anal. Appl. Pyrolysis 1991, 19, 251. 2) Cohen, Y.; Aizenshtat, Z. J. Anal. Appl. Pyrolysis 1992, 22, 153.

205

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

098

EGA thermogram

Averaged mass spectrum 121 107 77

100

200

300

400

500

91 39

51

65

700 ºC

228

135

152 165

31 50

600

programming rate: 20ºC/min

100

150

213

181 195

242 256

200

250

300 [m/z]

( m/z range : 29 - 600 amu )

OC : o-cresol

X1 : 2,6-xylenol OH

108

OH

122 107

77 29

51

39

90

77

63

29

X2 : 2,4-xylenol

51

OH

77 39

51

122

121 136

91

91

65

29

39

51

122

HO

108

HO

228

77 91

165 141152 181 195 213

242 77 29 39 51 65

230

D3 : 2-(4-hydroxy-3-methylbenzyl)-4,6-dimethylphenol

91 107

135 152 165 181 197 211 227

121

227 242

HO

213

OH

121 108 77 91

135 152

165 181 197

242

T1 : 4,6'-(4-hydroxy-5-methylene)

244

D5 : 4-(4-hydroxy-3-methylbenzyl)-2,6-dimethylphenol

228

HO

51 65 29 39

117

D2 : 4-(2-hydroxy-3-methylbenzyl)-2,6-dimethylphenol

HO

HO

77

65

121

29 39 51 65

132

OH

D1 : 4,6-methylenebis(2-methylphenol) HO

91

65

TP : 2,4,6-trimethylphenol 107

29

39

29 39 51 65

77 91

135

115

152

165 181 197 211

244

T2 : 4-(2-hydroxy-3,5-dimethylbenzyl)-2-(4-hydroxy-3,5 -dimethylbenzyl)-6-methylphenol

bis(methylene)bis(2-methylphenol)

121

121

HO

HO

HO

348 HO

HO

HO

225 240 348

29 53

108 77 91

228 240

197 7791 108 135 165 152 181 211 43 65

376

206

Tsuge, Ohtani and Watanabe

099 Diallyl phthalate resin; DAP CH2CHCH2OCO

COOCH2CHCH2

n

PA

AB

C6 LB TIC

BA B

M

T

0

10

Peak Notation

Assignment of Main Peaks

LB C6 B T BA AB PA M

propylene etc. C6H12 benzene toluene benzoic acid C6H5COOH allyl benzoate C6H5COOCH2CH=CH2 phthalic anhydride C6H4COOCO CH2=CHCH2OCOC6H4COOCH2CH=CH2 (monomer)

30 [min]

20

Molecular Retention Weight Index 42 84 78 92 122 162 148 246

* C6H5 represents phenyl group ; C6H4 represents o-phenylene group

295 598 658 767 1183 1264 1343 1755

Relative Intensity 11.73 0.27 5.25 2.66 22.87 1.26 100.00 1.47

207

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

099

EGA thermogram

Averaged mass spectrum 104 76

100

200

300

400

500

600

50

700 ºC

programming rate: 20ºC/min

74 31

37

91 50

122

141

100

148

165

178

150

250 [m/z]

200

( m/z range : 29 - 600 amu )

C6 : 1-hexene

B : benzene 44

55

78

84

69

29

39

T : toluene

51 74

BA : benzoic acid 91

O

105

OH

122 77

51 39

65

51

79 29

AB : allyl benzoate

104

O

76

77 29 39

50

74

131

91

162

147

29

M : diallyl phthalate O O

41

O

O 149

76

146

104 98

189 132 121

180

203

226 246

38

O O 148 O

74

51

50 65

94

PA : phthalic anhydride 105

O

29

74

39

208

Tsuge, Ohtani and Watanabe

100 Poly(ethylene glycol bisallyl carbonate); CR-39 CH2CHCH2OCOOCH2CH2OCH2OCOOCH2 CHCH2

n

LB

EV

A

CD DG

TIC

AA

DO

0

BD VD VE

AB

M B

C

10

Peak Notation

Assignment of Main Peaks

LB AA DO EV DG VE AB CD VD BD M A B C

CO2 + propylene etc. allyl alcohol 1,4-dioxane ethylene glycol monovinyl ether C=C-O-C-C-OH diethylene glycol HO-C-C-O-C-C-OH C=C-O-CO-O-C-C-OH allyl benzoate C6H5COO2CH=CH2 C=C-C-O-CO-O-C-C-O-C-C-OH C=C-O-CO-O-C-C-O-C-C-OH C6H5COO-C-C-O-C-C-OH C=C-C-O-CO-O-C-C-O-C-C-O-CO-O-C-C=C (monomer) unidentified unidentified unidentified (initiator)

30 [min]

20

Molecular Retention Weight Index

* bonding hydrogen is omitted ; C6H5 represents phenyl group

44; 42 58 88 88 106 132 162 190 176 210 274 238 264 -

150 562 705 720 983 1152 1268 1369 1569 1711 1776 1799 1930 2395

Relative Intensity 100.0 2.9 2.9 24.3 55.9 6.5 0.5 16.9 8.8 4.0 1.4 13.3 2.1 1.0

209

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

100

EGA thermogram

Averaged mass spectrum 45

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

31 89 91

75

55

105 119

50

133

149

100

165

178 200 [m/z]

150

( m/z range : 29 - 600 amu )

EV : ethylene glycol monovinyl ether

DG : diethylene glycol

O

O

45

OH

45

HO

OH

31 57

OH

O

O 29

105

O

102

O

58

AB : allyl benzoate

VE : 2-hydroxyethyl vinyl carbonate O

75 76

31

88

73

43 77

58 73

132

104

89

146

CD : 2-(2-hydroxyethoxy)ethyl vinyl carbonate 45

O

O

29

67

91

131

O

75

105

119

141

29

160

105

O

O

102 116

41

O

O

O

91

O

O

89

149

180

135

45

89 75

177

O

O

122 75

133 147

129

51

58

71

OH

A : pentaethylene glycol

31

58

77

45 31

OH

M : diallyl 2,2'-oxybis(ethane-2,1-diyl) dicarbonate (monomer)

BD : 2-(2-hydroxyethoxy)ethyl benzoate O

O

O

89

89 54

162

O

45

O

31

146

VD : allyl 2-(2-hydroxyethoxy)ethyl carbonate OH

O

51

39

102 116120133 148 164 178

208

29

57

73

90

117

133

159 173

210

Tsuge, Ohtani and Watanabe

101 Urea formaldehyde resin; UF CH2NCONCH2

MI

e

LB TIC

n

b TA EN

0

a

c

d f

g

10

Peak Notation

Assignment of Main Peaks

LB MI TA EN a b c d e f g

CO2 N N-methylethyleneimine ? N 1,3,5-triazine N N N,N-dimethylaminoethanenitrile ? (CH3)2NCH2CN 1,3,5-trimethyl-1,3,5-triazinane N hexamethylenetetramine N N N unidentified unidentified unidentified unidentified unidentified

30 [min]

20

Molecular Retention Weight Index 44 57 ? 81 84 ? 129 140 -

150 460 666 746 982 1236 1259 1276 1369 1443 1612

Relative Intensity 24.8 100.0 7.0 2.4 5.9 15.3 9.3 2.0 55.2 11.1 16.8

211

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

101

EGA thermogram

Averaged mass spectrum 43

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

57

30

70

81

112

94

50

128

143 149

100

200 [m/z]

150

( m/z range : 29 - 600 amu )

MI : N-methylethylenimine

TA : 1,3,5-triazine

43

81

N N

57

N

54

N

29 29

EN : 2-dimethylaminoacetonitrile

38

a : 1,3,5-trimethyl-1,3,5-triazinane 44

83

N

N 58

42

N

N

86

N

128

57 67

30

30

b : hexamethylenetetramine

71

c : unidentified N

42

N

112

N

140

42

N

30

71

56

58

85 96

112

29

e : unidentified

71

98 85

128

f : unidentified 114

128 44 44

58

30

71

30 85

99

112

g : unidentified 128

42 29

58

70

83

101

160

56

71

85 99

128 140

157

140

212

Tsuge, Ohtani and Watanabe

102 Melamine formaldehyde resin; MF N

H 2CN N DM

NCH 2

n

N N

MI M

TM

TIC

DT

0

10

Peak Notation

Assignment of Main Peaks

MI DT TM DM

formaldehyde 2,4-diamino-1,3,5-triazine N,N,N-trimethylmelamine ? N,N-dimethylmelamine ?

M

melamine

H2 N

NH 2

N N

30 [min]

20

N NH2

Molecular Retention Weight Index

Relative Intensity

30 111 ? 168 ? 154 ?

261 1287 1554 1598

8.9 3.7 9.2 68.3

126

1677

100.0

213

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

102

EGA thermogram

Averaged mass spectrum 43

69 100

111

57

300

500

600

700 ºC

154

98 50

400

programming rate: 20ºC/min

125

83

30

200

140

168

182

150

100

200 [m/z]

( m/z range : 29 - 600 amu )

MI : formaldehyde H

H

DT : 2,4-diamino-1,3,5-triazine

29

N

111

N N

H2N

NH2

O

43 70 53

29

DM : N,N-dimethylmelamine H N N

H N

140

126

N NH

111

69

43

126 85

55

30

85 154

97

68 29

M : melamine 126

N

H 2N N

NH 2 N

43 NH 2 85 68 29

53

99 111

120

H N

N N

N NH 2 43

94

TM : N,N,N-trimethylmelamine

H N

N

84

140 154 168

56

99

110

214

Tsuge, Ohtani and Watanabe

103 Xylene resin CH3 (CH2 O)mCH2 CH3 n

D1 D2

D3

D4

A B D 1’ C DA

TM

TA

DO TE

TIC

X 0

10

Peak Notation

Assignment of Main Peaks

X TM TE DA DO TA

m-xylene 1,2,4-trimethyl benzene 1,2,4,5-tetramethyl benzene 2,4-dimethyl benzaldehyde 2,4-dimethyl benzyl alcohol 2,4,5-trimethyl benzaldehyde C H3

D 1’

30 [min]

20

Molecular Retention Weight Index

Relative Intensity

106 120 134 134 136 148

873 999 1127 1198 1250 1339

0.6 7.0 3.6 6.8 2.6 4.9

224

1838

19.0

224

1866

100.0

238

1961

36.0

268

2129

23.0

CH3

252

2195

32.6

( C H 3) 2 C H3 C H3

266

2222

42.8

254

2282

31.6

-

3152

21.8

C H3 C H2

CH3

CH3 CH3

D1

C H3 C H2

CH3

CH3 C H3

D2

C H3 C H2

C H3 C H3

C H3

A

unidentified C H3

C H3 C H2

D3

C H3 C H3

D4

( C H 3) 2 CH

C H2

H3 C C H3 C H3

3

C H2 O C H 2

B C

C H3

unidentified

C H3

215

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

103

EGA thermogram

Averaged mass spectrum 118

91 100

77

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

117

39

51

65

132

31 50

100

146

165

179

209

193

150

224

236 250 [m/z]

200

( m/z range : 29 - 600 amu )

TM : 1,2,4-trimethylbenzene

TE : 1,2,4,5-tetramethylbenzene 119

105

134

120

39

51

77

65

91 29

39

91

77

65

51

117

TA : 2,4,5-trimethylbenzaldehyde

DA : 2,4-dimethylbenzaldehyde O

133

147

O 105 119 77 29

51

39

91

63

29 39

119

51

65

91

77

105 133

D1 : bis(2,4-dimethylphenyl)methane

D1' : C17H20

118

118

209 224

224 209 77 91 29 39 51 65

165 141152

117

179 194

179 194 29 39 51 65

D2 : C18H22

77 91

117

141152

165

D3 : C19H24 223

252 238

118

237

146 132 118

179 194 209

193 208 77 29 41 51 65

91

117

178 152 165

29 39 51 65

D4 : C20H26

77 91 117

145

223

165 282

B : 4,4'-oxybis(methylene)bis(1,3-dimethylbenzene) 254

236

O

119

223 118 221 91 31

65

77

148 117

135

193 208 178 165

236 45 266

298

29

77

91 117

146

178

207

266

298 300

216

Tsuge, Ohtani and Watanabe

104 Unsaturated polyester; UP CH2 CH(C6H5)

CHCHCOOCH2CH2 OCO

COOCH2CH2 OCO

n

S

PA

SS PO

BA

T TIC

MS

S

a

b

SSS c

B

0

10

Peak Notation PO B T S S BA PA a MS SS b SSS c

Assignment of Main Peaks

30 [min]

20

Molecular Retention Weight Index

propylene oxide benzene toluene styrene -methylstyrene benzoic acid C6H5COOH phthalic anhydride C6H4COOCO 2-hydroxyethyl benzoate styrene-maleic anhydride (hybrid dimer) CH2=C(C6H5)CH2CH2C6H5 (styrene dimer) unidentified CH2=C(C6H5)CH2CH(C6H5)CH2CH2C6H5 (styrene trimer) unidentified * C6H5 represents phenyl group

[ Related References ] 1) Ravey, M. J. Polym. Sci., Polym. Chem. Ed. 1983, 21, 1. 2) Vijayakumar, C. T.; Fink, J. K.; Lederer, K. Eur. Polym. J. 1987, 23, 861. 3) Hiltz, J. A. J. Anal. Appl. Pyrolysis 1991, 22, 113. 4) Evans, S. J.; Haines, P. J.; Skinner, G. A. J. Anal. Appl. Pyrolysis 2000, 55, 13.

58 78 92 104 118 122 148 166 202 208 312 -

410 652 765 895 983 1180 1334 1396 1637 1738 1871 2445 2516

Relative Intensity 10.3 2.3 7.5 71.9 6.5 3.9 100.0 3.5 5.6 7.4 4.8 6.4 4.2

217

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

104

EGA thermogram

Averaged mass spectrum 104

100

76

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

50 103

74

31 39

131 132

50

100

149 162

179

193 202

150

250 [m/z]

200

( m/z range : 29 - 600 amu )

T : toluene

B : benzene 78

52

39

29

91

39

74

S : styrene

51

65

89

S : -methylstyrene 118

104

117 78

103

103 78

51 39

63

39

BA : benzoic acid O

51

63

PA : phthalic anhydride 105

OH

104

O

122 76 77

O 50

148 O

51 74 74

38

94

29

MS : styrene-maleic anhydride (hybrid dimer)

38

SS : but-3-ene-1,3-diyldibenzene (dimer)

202

91

129 115 39

51

64 77 91

174 145

104

156 173

39 51

196

SSS : 5-hexene-1,3,5-triyltribenzene (trimer) 91

117 77 39 51 65

118 143

194 179

207 221 242

297

312

65 77

208 130 165 180

193

218

Tsuge, Ohtani and Watanabe

105 Epoxy resin; EP CH2CH(OH)CH2O

C(CH3)2

OCH2CH(OH)CH2N

CH2

N

n

BA d f e IP’ P

g

h

c

a

AC TIC

IP

LB AA

b

OC

0

10

Peak Notation

Assignment of Main Peaks

LB AC AA P OC IP IP’

ethylene oxide etc. acetaldehyde allyl alcohol phenol + aniline o-cresol p-isopropylphenol p-isopropenylphenol C

HO

C

C C C

OH

C

O

44 58 94, 93 108 136 134

349 408 564 981 1055 1200 1305

2.7 7.3 0.4 12.9 3.9 6.0 16.3

212

1844

11.2

226

1944

5.5

242

2107

15.4

228

2192

100.0

242

2214

24.4

212

2219

19.2

226

2236

19.8

C C

C

BA

Relative Intensity

OH

C C

b c

Molecular Retention Weight Index

C

a

30 [min]

20

bisphenol A

C

HO

OH

C C

C

d

HO

C

OH

C

e

C N

C

f

C C

C

g

C N C

C

N

C

240

2325

18.1

h

C C

C

N

C C

254

2342

20.9

N

N

NH2

NH2

* bonding hydrogen is omitted

[ Related References ] 1) Nakagawa, H.; Tsuge, S.; Koyama, T. J. Anal. Appl. Pyrolysis 1987, 12, 97. 2) Nakagawa, H.; Wakatsuka, S.; Tsuge, S.; Koyama,T. Polym. J. 1988, 20, 9. 3) Plage, B.; Schulten, H.-R. Macromolecules 1988, 21, 2018. 4) Bradna, P.; Zima, J. J. Anal. Appl. Pyrolysis 1992, 24, 75. 5) Nakagawa, H. ; Wakatsuka, S. ; Ohtani, H. ; Tsuge, S. ; Koyama, T. Polymer 1992, 33, 3556. 6) Fuchslueger, U.; Grether, H.-J.; Grassercauer, M. Fresenius J. Anal. Chem. 1994, 349, 283.

219

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

105

EGA thermogram

Averaged mass spectrum 213 119

91

100

134

65 77

39

200

300

400

500

600

51 152 100

228237

165

254

181 197

31 50

700 ºC

programming rate: 20ºC/min

107

150

269 279290

200

250

300

400 [m/z]

350

( m/z range : 29 - 600 amu )

AC : acetaldehyde

P : phenol (+ aniline)

29

94

NH2

OH

44

O

+ 66 39 55

29

56

IP' : p-isopropenylphenol

79

a : p-hydroxy-2,2-diphenylpropane 134

OH

197

OH

119

212

91 39

29

65

51

77

105

39 51 65

146

c : 2-(4'-hydroxyphenyl)-2-(4'-methoxyphenyl)propane

103 119 135 152 165 182 115

77

BA : bisphenol A

227

HO

213

HO

O

OH

228 242 119 133 152165 183 197 212 39 51 65 77 91 106

119 29 39

244

d : 4-(2-(4-hydroxyphenyl)propan-2-yl)-2-methylphenol

55 65 77

91

107

135 152 165 181 197

e : 4-(4-aminobenzyl)-N-methylaniline 212

227

HO

230

OH

NH2

N H 242 106

29

55

77 91 107 119 133

244

210

g : N,N-dimethyl-4-(4-(methylamino)benzyl)aniline

30 42 52

7078

120 168 140 154

98

182 196

h : 4,4'-methylenebis(N,N-dimethylaniline) 254

240

120 134 42

65

91 112

N

N

N H

N

196 152

180

223 268

42

65

91 104

134 126

210 165 152

194

237 223

266

220

Tsuge, Ohtani and Watanabe

106 Brominated epoxy resin Br CH2 CHCH2 O O

Br C(CH3)2

Br

Br

Br OCH2CHCH2 O

Br

OH

n

C(CH3)2 Br

OCH2CH CH2 O

Br

H

J I G BM A

P BP

E

D

B

TIC

TP

T

C

0

10

F

30 [min]

20

Peak Notation

Assignment of Main Peaks

BM A

bromomethane CH3Br acetone

B

BrCH2CCH3

T P BP C D TP

toluene phenol 2-bromophenol 2,4-dibromophenol 2,6-dibromophenol 2,4,6-tribromophenol

O

Molecular Retention Weight Index

Relative Intensity

94 58

465

7.5 7.0

136

760

4.9

92 94 172 250 250 328

767 983 1077 1397 1397 1668

1.5 14.9 13.9 3.0 11.8 5.0

290

1715

16.1

384

2344

6.6

446

2479

22.8

462

2798

100.0

524

2869

32.9

540

3109

97.7

Br O

E

C H3 Br Br

F

HO

Br

G

HO

Br C(C H3 )2

Br Br

H

OH

C(CH 3) 2 Br

HO

Br C(C H3)2

OH

Br Br

I

HO

Br C (C H3 )2

Br

Br

Br

J

HO

Br OH

C (C H 3 ) 2 Br

Br

221

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

106

EGA thermogram

Averaged mass spectrum 43 82

100

200

300

400

500

600

529 63 53

29

0

152 181 91105 118133 165 196

50

100

150

277 293 212217 252 265

200

250

300

449 464 505 468489 513

371 369 386 409 350

400

450

700 ºC

programming rate: 20ºC/min

544 550 [m/z]

500

( m/z range : 29 - 600 amu )

B : 1-bromo-2-propanone

A : acetone 43

43

O

O Br

58 29

29

80

P : phenol

79

53

136

93

121

D : 2,6-dibromophenol OH

94

OH

Br

63

66 39 55

29

252

Br

79

E : 5,7-dibromo-2-methyl-2,3-dihydrobenzofuran O

197

223

F : 4,4'-(propane-2,2-diyl)bis(2-bromophenol)

292

Br

143 146

92

29

Br

291

Br

HO

OH

132

Br

277 29

39

51 66 77

103 104

131

196

252 265

211

29

G : 2-(3-bromophenyl)-

propan-2-yl)phenol Br

371

Br

Br

449

OH

HO

HO 369

Br 29

Br 386

63

89

118

152 181

152 181 213

29

J : 4,4'-(propane-2,2'-diyl)bis(2,6-dibromophenol)

propan-2-yl)phenol Br

468 105

211

I : 2,6-dibromo-4-(2-(3,5-dibromophenyl)

Br

513

Br

Br

HO

Br

Br

Br 163

293 272

528 353

432

529

OH

HO

41

308 277

H : 2,6-dibromo-4-(2-(3-bromo-4-hydroxyphenyl)

2-(3,5-dibromo-4-hydroxyphenyl)propane Br

197 212

119

51

152 53 76 112144 29

Br 217

293 277

544 448

222

Tsuge, Ohtani and Watanabe

2.2.13 Polyimide and polyamide-type engineering plastics 107 Bismaleimide triazine resin; BT resin O

C(CH3)2

N

O

CO N

N

CO

CH2

N

CO CO

N N

O n

O

BA

IP’

P

IP TIC

LB AL

PC

a

0

d

b

10

30 [min]

20

Peak Notation

Assignment of Main Peaks

LB AL P PC IP IP’

propylene etc. acrolein ? phenol + aniline p-cresol p-isopropylphenol p-isopropenylphenol

Molecular Weight

Retention Index

Relative Intensity

56 94; 93 108 136 134

295 498 985 1077 1231 1308

8.4 5.4 44.0 3.5 10.2 27.9

212

1758

2.4

226

1882

4.7

228

2212

100.0

242

2252

7.0

C C

a

OH

C C

C

b

C

OH

C

BA

C

bisphenol A C

d

HO

C

HO

C

OH

C

C OH

C

* bonding hydrogen is omitted

223

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

107

EGA thermogram

Averaged mass spectrum 94

66

100

44

200

300

600

700 ºC

134 152

30 50

500

213

107

77

51

400

programming rate: 20ºC/min

119

100

165

183

228

197

150

250 [m/z]

200

( m/z range : 29 - 600 amu )

PC : p-cresol

P : phenol (+ aniline) NH2

OH

94

107

OH

+ 66 77

39 55

29

79

29

39

51

133 90

63

IP' : p-isopropenylphenol

IP : p-isopropylphenol OH

121

134

OH 119

136 77 29

39

51

91

91

65

39

107

29

a : p-hydroxy-2,2-diphenylpropane

51

65

77

105

b : 2-methyl-4-(2-phenylpropan-2-yl)phenol 197

210

OH

OH

195 77 91 39 51 65

115 119

212 77 39 51 65

165 181 141152

103 119 135 152 165 182 115

d : 4-(2-(4-hydroxyphenyl)propan-2-yl)-2-methylphenol

BA : bisphenol A 213

HO

227

OH

HO

OH

228 242

119 29 39

55 65 77

91

107

135 152 165 181 197

230

119 91 106 133 149 165 181 197 213 29 39 5565 77

252

224

Tsuge, Ohtani and Watanabe

108 Polyetherimide; PEI CO O

C(CH3)2

CO N

O

CO

N CO

n

ID

P AI

c

PC

d DA

CB TIC

DE IP’ MD EP CP VP b

0

PA

10

Peak Notation

Assignment of Main Peaks

P CB PC EP VP DA IP’ CP b DE

phenol + aniline cyanobenzene + phenol p-cresol p-ethylphenol p-vinylphenol m-phenylenediamine p-isopropenylphenol m-cyanophenol p-cyanophenol diphenyl ether

MD

4-methyl(diphenyl ether)

30 [min]

20

Molecular Weight

O

C

Retention Index

Relative Intensity

94; 93 103; 94 108 122 120 108 134 119 119 170

985 1007 1078 1170 1220 1304 1306 1364 1406 1419

100.0 3.9 28.7 5.3 3.6 9.4 4.0 4.4 2.6 1.8

184

1532

7.0

210

1759

52.5

212

1882

5.4

238

2488

30.2

-

2935 3498

67.2 38.4

C

ID

4-isopropenyl(diphenyl ether) C

PA

O

C C

C OH

C H2 N

AI c d

N

CO CO

unidentified unidentified * bonding hydrogen is omitted [ Related References ] 1) Huang, F.; Wang, X.; Li, S. Polym. Degrad. Stab. 1987, 18, 247. 2) Carroccio, S.; Puglisi, C.; Montaudo, G. Macromol. Chem. Phys. 1999, 200, 2345. 3) Perng, L.-H. J. Polym. Res. 2000, 7, 185. 4) Perng, L.-H. J. Appl. Polym. Sci. 2001, 79, 1151.

225

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

108

EGA thermogram

Averaged mass spectrum 44

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

94 66

51

77

107

50

119

141

100

152

165

210

195

183

150

238 250 [m/z]

200

( m/z range : 29 - 600 amu )

CB : cyanobenzene (+ phenol)

P : phenol (+ aniline) 94

NH2

OH

N

94

OH

+

+

117

44

39

76

51

55

29

118

66

66 29

79

EP : p-ethylphenol

PC : p-cresol 107

OH

107

OH

122

77 29

39

51

77

90

63

120

OH

65

91

108

NH2

91

29

51

DA : m-phenylenediamine

VP : p-vinylphenol

39

39

29

80

NH2

65

51

89

105

53

39

30

134

119

91

65

CP : m-cyanophenol

IP' : p-isopropenylphenol 108

OH

134

119

N

119 80 91 39

53

OH

91

64

65 39

29

29

MD : 4-methyl(diphenyl ether)

76

108

AI : 2-(3-aminophenyl)isoindoline-1,3-dione 184

O

52

H2N

238

O N

91 O 39

51

65

77

141 155 115 128 169

76 39 50 65

91 104 119 134

154 167 181

194

210

226

Tsuge, Ohtani and Watanabe

109 Polypyromellitimide; PI CO

CO

CO

CO

N

O

N n

OI

AP

EA

a

PI

c AN b

I P CB

TIC

DE BF

0

d

10

30 [min]

20

Peak Notation

Assignment of Main Peaks

I P CB AP DE

phenyl isocyanate phenol + aniline cyanobenzene p-aminophenol diphenyl ether

PI

phthalimide

Molecular Weight

Retention Relative Index Intensity

119 94; 93 103 109 170

977 991 1014 1263 1419

1.5 50.8 2.4 100.0 3.9

147

1469

33.6

168

1545

5.0

185

1774

35.5

223

2081

16.6

CO NH CO O

BF EA

dibenzofuran O

NH2 CO

AN

N

phthalanil

CO

CO N

OH

OI

CO

239

2439

77.6

a b

unidentified unidentified

-

2687 2977

27.5 10.9

CO N

O

NH2

c

CO

330

3409

40.5

d

unidentified

-

3623

6.1

227

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

109

EGA thermogram

Averaged mass spectrum 44

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

94 66

51

77

107

50

119

141

100

152

165

210

195

183

150

238

20 0

[m/z]

250

( m/z range : 29 - 600 amu )

P : phenol (+ aniline)

CB : cyanobenzene 94

NH2

OH

93

N

66 39

67

+

39

79

51 107

50 76

32

121

136

119

AP : p-aminophenol

DE : diphenyl ether 109

OH

170

O

141

80 51

NH2 30

77

39

53 39

63

91

115

65

119

131

BF : dibenzofuran

PI : phthalimide 76

O

147

NH

168

O

104

139

103 50 74

O

39

38

EA : p-phenoxyaniline

113

84

159

129

AN : phthalanil 185

108

O

55 62

179

O

NH 2

223

N 76 80

O

51 32

50

156

65

39

129

92

39

169

139

N

52 39

195

92 75

330

O 108

OH

N

O

NH 2

O

O 104

139 152 167 130

102

239

O

104

c : 2-(4-(4-aminophenoxy)phenyl)isoindoline -1,3-dione

OI : 2-(4-hydroxyphenyl)isoindoline-1,3-dione

76

64

76 167

130140 154

182

210

39 50

65 90

130 154 183 210 238 266

301

356

228

Tsuge, Ohtani and Watanabe

110 Polyaminobismaleimide; PABM CH2

CO

CH

CO

N

CH2

N

CO

CH2

CO

CH NH

CH2

NH n

DA MI

AN TL b

MA,TI TIC

a

LB

I

0

10

Peak Notation

Assignment of Main Peaks

LB I AN

CO2 phenyl isocyanate aniline

TL

p-toluidine

MA

NH2

CH2

TI

CH3

N

DA

diaminodiphenylmethane

a b

unidentified unidentified

MI

CH2 CO CH2 CO

N

Molecular Weight

NH2

CH3

Retention Index

Relative Intensity

44 119 93

150 963 984

10.2 1.3 24.9

107

1081

15.5

183

1799

189

1795

198

2169

53.3

-

2185 2613

4.2 8.6

280

2982

100.0

7.3

CO CH2 CO CH2

CH2

30 [min]

20

NH2

CH2

NH2

NH2

[ Related Reference ] 1) Crossland, B.; Knight, G. J.; Wright, W. W. Br. Polym. J. 1987, 19, 291.

229

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

110

EGA thermogram

Averaged mass spectrum 93

106 44

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

66 77

51

119

30 50

133

100

152

198

182

167

208

150

250 [m/z]

200

( m/z range : 29 - 600 amu )

LB : carbon dioxide O

C

I : phenyl isocyanate O

44

O

119

C N 91 64 29

31

38

51

76

TL : p-toluidine

AN : aniline

106

93

NH2

NH2

66 77

39

52

30

O

91

189

183

106

N

183

O

189

106

H2N

133

55 39

63

MA : 4-benzylaniline

TI : 1-p-tolylpyrrolidine-2,5-dione

30

52

30 39

78

77

91

146

65

118

165

30 39

DA : diaminodiphenylmethane

55 65

133

77 91 118

146

165 203

a : unidentified 208

198

NH 2

H 2N

106 106

30 39 52 65

77

99

182 77 90 30 39 51 63

130 143152 168

b : unidentified

190 127 140 152 165 180

232

MI : 1-(4-(4-aminobenzyl)phenyl)pyrrolidine-2,5-dione 280

240

O 197

43

77 51 65

93

NH2 O

106

30

N

182 120

143152 168

212 224

3039

55 77 90 65

106

182 130

165

197

223

251 264

306

230

Tsuge, Ohtani and Watanabe

111 Polyamideimide; PAI CO

CO

N

O

NH

CO

CO

CO N

NH n

CO

b AI

AA

TIC

P CB I

LB

DA PI DN DE BF

0

EA

AN

10

OI

a

30 [min]

20

Peak Notation

Assignment of Main Peaks

Molecular Weight

Retention Index

Relative Intensity

LB I P CB DN DA DE

CO2 phenyl isocyanate phenol + aniline cyanobenzene p-aminophenol + dicyanobenzene m-phenylenediamine diphenyl ether

44 119 94; 93 103 109; 128 108 170

150 967 983 991 1271 1304 1419

18.4 0.3 9.4 10.9 6.6 7.7 1.9

PI

phthalimide

147

1474

4.4

BF

dibenzofuran

168

1547

0.5

EA

O

185

1776

4.6

223

2081

3.8

200

2140

14.3

CO NH CO O

NH2 CO

AN AA

phthalanil

N CO

H2 N

O

NH2

CO

OI AI a

N

OH

239

2443

17.6

N

NH2

238

2490

35.1

-

2971

5.9

330

3414

100.0

CO CO CO

unidentified CO

b

N CO

O

NH2

231

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

111

EGA thermogram

Averaged mass spectrum 94 66 44 100

200

300

400

500

48

600

700 ºC

programming rate: 20ºC/min

80 108

128 147 141

30 50

100

185

170

223

200

150

238 250 [m/z]

200

( m/z range : 29 - 600 amu )

DN : p-aminophenol (+dicyanobenzene)

P : phenol (+ aniline) 94

NH2

OH

109 H2 N

OH

+

+

66

80

N

39

53

55

29

N

77

29

119

DA : m-phenylenediamine

39

63

128

101

PI : phthalimide O

147

108

NH2

76

NH

104

80

NH2

91

65

74

29 38

EA : p-phenoxyaniline

218

AN : phthalanil 185

O

O

103

50 53

30 39

223

O

NH 2 179

N

108

O 51

39

80

65

129139

92

156 39

169

AA : p,p'-diamino(diphenyl ether) O

75

104 91

130 139

239

O

NH2 N

65

80 93

195 76

171 202 130 144156

39 50

182

AI : 2-(3-aminophenyl)isoindoline-1,3-dione H 2N

OH

O

108 39 53

152 166

OI : 2-(4-hydroxyphenyl)isoindoline-1,3-dione 200

H2N

76

50

75

167 182

210

330

O H2 N

N

130 140 154

b : 2-(4-(4-aminophenoxy)phenyl)isoindoline-1,3-dione 238

O

92 104

N O O

O 76 39 50 65

108

91 104 119 134

154 167 181

194

210

39

6576 92

130

165 183

210

238

273

301

232

Tsuge, Ohtani and Watanabe

112 Poly(p-phenylene terephthalamide); Kevlar CO

CONH

NH n

AB

CA

DA

NA

BN

AN CB

TIC

TN

DP

0

10

Peak Notation

Assignment of Main Peaks

AN

aniline + cyanobenzene

TN

p-tolunitrile

CH3

CN NC

DA

H2 N

DP

diphenyl

NA

p-cyanoaniline

BN

benzanilide

AB

4'-aminobenzanilide

CA

4-cyano-4'-aminobenzanilide

CONH

NC

Retention Index

Relative Intensity

93; 103

989

89.2

117

1117

2.7

128; 108

1269

58.3

154

1397

1.2

118

1457

19.6

197

1985

14.8

212

2390

100.0

237

2724

63.0

NH2

NH2

CONH

Molecular Weight

CN

+

p-dicyanobenzene + p-phenylenediamin

NC

30 [min]

20

NH2

CONH

NH2

[ Related References ] 1) Brown, J. R.; Power, A. J. Polym. Degrad. Stab. 1982, 4, 379. 2) Schulten, H. -R.; Plage, B.; Ohtani, H.; Tsuge, S. Angew. Makromol. Chem. 1987, 155, 1.

233

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

112

EGA thermogram

Averaged mass spectrum 103 108 44

100

200

300

400

500

80 50

600

700 ºC

programming rate: 20ºC/min

66

118 134

30 50

100

154

166

178

191

150

250 [m/z]

200

( m/z range : 29 - 600 amu )

AN : aniline (+ cyanobenzene)

TN : p-tolunitrile 117

93

N

N

NH 2

+

66 39

76

50

39

104

30

DA : p-dicyanobenzene (+ p-phenylendiamin)

90 89

63

50

32

118

DP : diphenyl

108

H2N

154

NH2 128

+ N

N

80

53 29

101

75

39

3239 51 63

NA : p-cyanoaniline

76

108 102

128 139

199

BN : benzanilide 118

105

O

N

NH 2

220

N H 77

197

91 64

52

41

76

117

39

65

92

139 152 167 184

105

107

212

NH2

NH 2

O

237

N H

N H

218

CA : 4-cyano-4'-aminobenzanilide

AB : 4'-aminobenzanilide O

51

77 N 80 102

51 39

65

90

128134

154 167 182

222

39

53

75

130 134 153

179

207

263

234

Tsuge, Ohtani and Watanabe

113 Poly(m-phenylene isophthalamide); Nomex CO

CONH

NH n

AB

DA

CA CB AN

TIC LB

B

TN

BN

BA DN DP

0

PD

10

30 [min]

20

Peak Notation

Assignment of Main Peaks

LB B AN CB

CO2 benzene aniline cyanobenzene

TN

m-tolunitrile

BA

benzoic acid

COOH

DN

m-dicyanobenzene

NC

Molecular Weight

Retention Index

Relative Intensity

44 78 93 103

150 661 983 990

30.2 7.4 8.7 21.9

117

1099

1.4

122

1181

17.9

128

1273

2.3

108

1307

46.5

154

1398

1.6

197

1986

6.1

212

2377

100.0

237

2695

18.3

CN CH3

DA

m-phenylenediamine

DP

diphenyl

BN

benzanilide

AB

3'-aminobenzanilide

CA

CN

H2 N

NH2

CONH

CONH

NH2

NC

CONH

3-cyano-3'-aminobenzanilide

NH2

[ Related References ] 1) Brown, J. R.; Power, A. J. Polym. Degrad. Stab. 1982, 4, 379. 2) Schulten, H. -R.; Plage, B.; Ohtani, H.; Tsuge, S. Angew. Makromol. Chem. 1987, 155, 1.

235

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

113

EGA thermogram

Averaged mass spectrum 108 80

44

100

103

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

51

122 66

139 147

30 50

100

169 179

194

150

212 250 [m/z]

200

( m/z range : 29 - 600 amu )

AN : aniline

CB : cyanobenzene 93

NH 2

103

N

66 39

76

52

30

39

78

50

104

75

DN : m-dicyanobenzene

BA : benzoic acid

128

105

O

OH

N

N

122 77

51 29

101 74

39

32

94

DA : m-phenylenediamine

37

50

76 75

108

DP : diphenyl 108

NH2

154

80

NH2 53

30 39

32

91

65

44 51 63

76

102 108

128 139

AB : 3'-aminobenzanilide

BN : benzanilide 105

105

O

O

212 N H

N H 77

39

51

77

197

65

92

139 152

167

39

184

51

92

134 128

237 N H

H N

NH 2 O

102

39 53

80 75

109

154 167 184 193

105

130

O

65

PD : N,N'-dibenzoyl-p-phenylenediamine

CA : 3-cyano-3'-aminobenzanilide N

NH2

77

134

208 164 182192

220

39

51

75

133

167 195 211

316 N H

O

287

236

Tsuge, Ohtani and Watanabe

114 Poly(p-phenylene/3,4-diphenylene ether terephthalamide) OC

CONH

NH

CONH

OC

O

NH n

C

G

PD AN

A

CB

E B

PC

D

F H

AP

TIC

0

10

Peak Notation

Assignment of Main Peaks

AN CB PC PD AP

aniline cyanobenzene benzoic acid p-phenylenediamine 3-aminophenol

A

O

B

CONH

30 [min]

20

NH 2

Molecular Weight

Retention Index

Relative Intensity

93 103 122 108 109

983 990 1182 1277 1291

20.6 43.4 50.3 58.9 11.6

185

1777

21.8

197

1987

13.2

200

2152

80.8

212

2394

100.0

237

2721

28.2

304

3230

54.0

304

3300

63.7

316

3551

50.9

NH2

C

H2N

D E F G H

O

CONH

CN

CONH

H2N

H2N

NH2

O

O

CONH

NH2 NHCO

NHCO

NHCO

237

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

114

EGA thermogram

Averaged mass spectrum 105

44

77

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

51

200

122

103

65

154 171 185

134

29 50

100

150

212 228 239 252 269

200

289 304 317 332

250

350 [m/z]

300

( m/z range : 29 - 600 amu )

PD : p-phenylenediamine

PC : benzoic acid O

105

OH

108 122

H2N

NH2

77 80 51 74

39

29

53 94

A : p-phenoxyaniline

91

63

128 136

B : benzanilide 185

O

41

30

105

O

N H2 N H 197

77 156

108 65

51

39

80

169

92

130 141

51

39

C : m,p'-diaminodiphenyl ether

65

167

139

D : 4'-aminobenzanilide 200

NH2

105

212

N H2

O

H2 N

92

O N H 108 80

65 30

39 53

93

202

130 144156

51

183

30 39

80 102 75

304

O H 2N

77 130 145

225

260

310 295

39 51 65

91

127

154

199

226

298

H : N,N'-dibenzoyl-p-phenylenediamine 105

H 2N

304

O

H N

O

316

N H

O

127 154

202

N H

77

77 92

H N

O

105

65

154 167 182

105

G : N-(4-(3-aminophenoxy)phenyl)benzamide

3951

128134

237

N

53

90

NH 2

O N H

2941

65

F : N-(3-(4-aminophenoxy)phenyl)benzamide

E : 4-cyano-4'-aminobenzanilide 107

77

171

276

328

361

51 39 75 102

130

225

O

301

356

403

238

Tsuge, Ohtani and Watanabe

2.2.14 Polyesters 115 Poly(ethylene terephthalate); PET COOCH2CH2OCO n

F G

D C

LB

A PE2

BA

AC TIC

DP

B 0

PA

PB

E

PE1

10

Peak Notation

Assignment of Main Peaks

LB AC B A BA DP C D PA PB E F PE1 PE2 G H I

CO2 acetaldehyde benzene vinyl benzoate benzoic acid diphenyl divinyl terephthalate CH2=CHOCOC6H4COOCH=CH2 CH2=CHOCOC6H4COOH C6H5-C6H4COOCH=CH2 C6H5-C6H4COOH C6H5COOCH2CH2OCOC6H5 C6H5COOCH2CH2OCOC6H4COOCH=CH2 C6H5-C6H4COOCH2CH2OCOC6H5 HOCOC6H4COOCH2CH2OCOC6H4COOCH=CH2 CH2=CHOCOC6H4COOCH2CH2OCOC6H4COOCH=CH2 C6H5COOCH2CH2OCOC6H4COOCH2CH2OCOC6H5 C6H5(COOCH2CH2OCOC6H4)2COOCH=CH2

H

I 30 [min]

20

Molecular Weight 44 44 78 148 122 154 218 192 224 198 270 340 346 384 410 462 532

Retention Index 150 408 654 1143 1186 1398 1577 1622 1889 1914 2178 2636 3050 3052 3089 3753 4180

* C6H5 represents phenyl group ; C6H4 represents p-phenylene group [ Related References ] 1) Sugimura, Y.; Tsuge, S. J. Chromatogr. Sci. 1979, 17, 269. 2) Bednas, M. E.; Day, M.; Ho, K.; Sander, R.; Wiles, D. M. J. Appl. Polym. Sci. 1981, 26, 277. 3) Adams, E. R. J. Polym. Sci., Polym. Chem. Ed. 1982, 20, 119. 4) Vijayakumar, C. T.; Fink, J. K. Thermochim. Acta 1982, 59, 51. 5) Ohtani, H.; Kimura, T.; Tsuge, S. Anal. Sci. 1986, 2, 179. 6) Montaudo, G.; Puglisi, C.; Samperi, F. Polym. Degrad. Stab. 1993, 42, 13.

Relative Intensity 25.2 8.8 3.0 14.0 44.7 1.8 25.7 100.0 3.9 6.0 7.1 39.9 1.5 3.3 42.8 11.9 17.9

239

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

115

EGA thermogram

Averaged mass spectrum 149

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

65 44

105

77

50

121

103 50

166175

135

100

150

193 200

300 [m/z]

250

( m/z range : 29 - 600 amu )

AC : acetaldehyde

B : benzene 29

78

44

O

51

44

A : vinyl benzoate O

74

C : divinyl terephthalate 105

O

175

77

O

O

O

O 104 76

51 74

39

148

91

42

50

66

91

149

OH

O

O

105

93 104

O

77 175

132

192

O

297

51

75

O

O

O

39

118

148

227

178

G : ethan-1,2-diyl divinyl diterephthalate

F : 2-(benzoyloxy)ethyl vinyl terephthalate

367

O

O

O

O

O

O

121 76

218

O

65 39 50

132 147

E : ethan-1,2-diyldibenzoate

D : 4-(vinyloxycarbonyl) benzoic acid O

119

O

O

O

O

O

O 105 77 103 132 39 51 75 121

325

149 175 191

267

300

297

268

296 337

370

O

O O

77 51 75 103

105

O

O

191 219

vinyl terephthalate

O

105

162

I : 2-(4-((2-(benzoyloxy)ethoxy)carbonyl)benzoyloxy)ethyl

H : bis(2-(benzoyloxy)ethyl) terephthalate O

104 76 132 50 75 103 39

O

O

O

O

O

O O

O

O

O

O

149 132

207

300 342

419

462

77103 5175

149

489 240 269 297

367

459

240

Tsuge, Ohtani and Watanabe

116 Poly(butylene terephthalate); PBT COOCH2CH2CH2CH2OCO

n

C

D

C4

A

F

H

BA

TIC

DP 0

E

10

Peak Notation C4 BA A DP D C E F G H

G 30 [min]

20

Assignment of Main Peaks 1,3-butadiene benzoic acid C6H5COOH C6H5COOCH2CH2CH=CH2 diphenyl C6H5-C6H5 CH2=CHCH2CH2OCOC6H4COOH CH2=CHCH2CH2OCOC6H4COOCH2CH2CH=CH2 C6H5COO(CH2)4OCOC6H5 C6H5COO(CH2)4OCOC6H4COOCH2CH2CH=CH2 CH2=CHCH2CH2OCOC6H4COO(CH2)4OCOC6H4COOH CH2=CHCH2CH2OCOC6H4COO(CH2)4OCOC6H4COOCH2CH2CH=CH2

Molecular Weight 54 122 176 154 220 274 298 396 440 494

* C6H5 represents phenyl group ; C6H4 represents p-phenylene group [ Related References ] 1) Sugimura, Y.; Tsuge, S. J. Chromatogr. Sci. 1979, 17, 269. 2) Lum, B. M. J. Polym. Sci., Polym. Chem. Ed. 1979, 17, 203 3) Adams, E. R. J. Polym. Sci., Polym. Chem. Ed. 1982, 20, 119. 4) Vijayakumar, C. T.; Fink, J. K. Thermochim. Acta 1982, 59, 51. 5) Ohtani, H.; Kimura, T.; Tsuge, S. Anal. Sci. 1986, 2, 179. 6) Montaudo, G.; Puglisi, C.; Samperi, F. Polym. Degrad. Stab. 1993, 42, 13. 7) Sato, H. ; Kondo, K. ; Tsuge, S. ; Ohtani. H. ; Sato, N. Polym. Degrad. Stab. 1998, 62, 41. 8) Koshiduka, T.; Ohkawa, T.; Takeda, K. Polym. Degrad. Stab. 2003, 79, 1.

Retention Index 395 1185 1362 1396 1848 2045 2441 3154 3649 3838

Relative Intensity 21.0 21.0 9.3 0.6 100.0 41.1 1.2 12.0 3.0 33.3

241

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

116

EGA thermogram

Averaged mass spectrum 149

100

54

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

65 39

203

121

76

104

93 50

132

167174

100

150

200

250

300

[m/z]

( m/z range : 29 - 600 amu )

BA : benzoic acid

C4 : 1,3-butadiene 54

O

39

105

OH

122 77

51 29

A : but-3-enyl benzoate

74

39

29

94

DP : diphenyl 105

O

154

O 77

54 29 39

122 135

74

105 102

128139

220

C : dibut-3-enyl terephthalate

D : 4-((but-3-enyloxy)carbonyl)benzoic acid O

76

39 51 63

176

203

O

149 O

O

O

OH

149 54

O 65

29

39

54 121

76

93 104

166 179

O

O

274

O O

325 O

O

O

O 105

O

54 149 203 77 71 103 121 176 132 162 193 220

54 71

176 193 149 122 135 166 203 223

93

256

298

G : 4-((4-(4-((but-3-enyloxy)carbonyl)benzoyloxy)butoxy) O

39 29

369 O

7176 121 180 103 162

O

O

O

O

149 O

O

OH

54

324 370

149

O

203

440 238

O

O

O

104

396

369

O

O

O

342

H : dibut-3-enyl'-butane-1,4-diyl diterephthalate

carbonyl)benzoic acid

29 41

220

F : 4-(benzoyloxy)butyl but-3-enyl terephthalate

77

132

167175

O

105

54

104 121 93 132

65 76

29 39

203 220

E : butane-1,4-diyl dibenzoate

29 41

O

542

29

108 176 132 162 201 39 65 93

370 353

423 494

242

Tsuge, Ohtani and Watanabe

117 Poly(ethylene naphthalate); PEN CH2CH2OCO COO n

BN

A

CN N

B LB AC

C

D E

TIC

0

10

Peak Notation

Assignment of Main Peaks

LB AC N

CO2 acetaldehyde naphthalene

BN CN A B C D E

30 [min]

20

Molecular Weight

Retention Index

Relative Intensity

44 44 128

150 408 1200

24.0 15.1 21.2

COOCH CH2

198

1708

30.4

COOH

172

1741

100.0

268

2178

32.4

254 254

2542 2702

10.1 9.3

370

3468

16.7

440

3926

21.3

H2C CHOCO COOCH CH2

1,1‘-binaphthalene 2,2‘-binaphthalene COOCH2CH2OCO

COOCH2CH2OCO COOCH CH2

243

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

117

EGA thermogram

Averaged mass spectrum

44

100

127

155

29 63

51

77

101

50

115

142

100

300

400

500

600

700 ºC

programming rate: 20ºC/min

242 254

225

185 150

200

199

172

200

300 [m/z]

250

( m/z range : 29 - 600 amu )

N : naphthalene

AC : acetaldehyde 29

128

O 44

51

39

BN : vinyl-2-naphthoate

64

102

77

CN : 2-naphthalenecarboxylic acid 155

O

172

O

127

O

OH

77 75

42 51

198

101 115

63 4551

141

A : divinyl naphthalene-2,6-dicarboxylate

127

77

101 115

155

144

174

B : 1,1'-binaphthalene

225

254

O O O 154

O 126 63 42 50

126

77 91 115

140

169182 197

268

39 51

C : 2,2'-binaphthalene

113 75 87 101

139

163

187

239

213

D : ethan-1,2-diyl di-2-naphthoate 254

155

O O

127

O O

199

51

113 75 88 101

126 139150 163

51 7577 101115

187 200 213 226 239

E : 2-(2-(2-naphthoyloxy)ethyl) 6-vinylnaphthalene -2,6-dicarboxylate 397

O O

O O

O O

127 155 199 225 252 281 51 77 91 115 140 171

325

367

398

440

172 185

370

252 281

351

244

Tsuge, Ohtani and Watanabe

118 Poly(p-hydroxybenzoic acid); type A O

O

CO

CO

O

CO n

BP

DB

PP BF PB

P TIC

BA

B

XO

DP

0

10

30 [min]

20

Peak Notation

Assignment of Main Peaks

B P

benzene phenol

BA

benzoic acid

DP

diphenyl

Molecular Weight

COOH

Retention Index

Relative Intensity

78 94

655 984

6.2 34.0

122

1172

6.8

154

1398

1.8

168

1546

0.7

198

1678

1.8

170

1731

11.9

196

1901

1.8

186

2061

100.0

290

2891

46.8

O

BF

dibenzofuran

PB

phenyl benzoate

PP

p-phenylphenol

COO

OH CO

XO

xanthone O

BP DB

diphenol COO

HO

OH

OH

[ Related References ] 1) Crossland, B.; Knight, G. J.; Wright, W. W. Br. Polym. J. 1986, 18, 371. 2) Sueoka, K.; Nagata, M.; Ohtani, H.; Nagai, N.; Tsuge, S. J. Polym. Sci. Part A 1991, 29, 1903. 3) Ohtani, H.; Fujii, R.; Tsuge, S. J. High Res. Chromatogr. 1991, 14, 388. 4) Ishida, Y.; Ohtani, H.; Tsuge, S. J. Anal. Appl. Pyrolysis. 1995, 33, 167.

245

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

118

EGA thermogram

Averaged mass spectrum 186 94

44

100

200

300

400

500

121

51

700 ºC

157 139

31 50

600

programming rate: 20ºC/min

105

66 77

170

100

196 212 225

150

200

290

246 262 250

350 [m/z]

300

( m/z range : 29 - 600 amu )

P : phenol

BA : benzoic acid

OH

94

O

OH

105 122 77

66

51

39 55

29

74

39

77

DP : diphenyl

94

BF : dibenzofuran 154

168

O

139 39

51 63

76

102 115 128 139

39

51

69

84

113 121

93

159

PP : p-phenylphenol

PB : phenyl benzoate 105

170

OH

O O

77

39

51

65

94

121

198

139

XO : xanthone

39

127

152

186

196 HO

OH

168

O

139

44 50

63

84 92

114 121

121 184

DB : 4'-hydroxybiphenyl-4-yl benzoate 105

O O

OH 290

77

39

102

BP : diphenol

O

51

141

115

85

51 63

75 102

128 157 185 139

65 77 29 39 51

157

93 115

139

169

188

214

246

Tsuge, Ohtani and Watanabe

119 Poly(p-hydroxybenzoic acid); type B O CO

O

CO n

P

HP

NO

HP’

a

A NP XO

HA DE

TIC

0

10

Peak Notation

Assignment of Main Peaks

P HA DE

phenol p-hydroxybenzaldehyde diphenyl ether

A

p-hydroxybenzoic acid

NO

30 [min]

20

HO

Molecular Weight

COOH

(monomer)

Relative Intensity

94 122 170

983 1364 1419

100.0 6.8 4.1

138

1518

44.8

144

1537

50.6

196

1901

4.7

220

2011

3.5

214

2061

63.4

214 ? 264 264

2155 2703 2718

26.3 22.8 19.4

OH

β -naphthol CO

XO

Retention Index

xanthone O

NP

2-naphthyl phenyl ether

HP

(p-hydroxyphenyl)benzoic acid

HP’

unidentified (C13H10O3?) Phenyl-1-hydroxy-2-naphthoate Phenyl-1-hydroxy-4-naphthoate

a

O

HO

COO

[ Related Reference ] 1) Ohtani, H.; Fujii, R.; Tsuge, S. J. High Res. Chromatogr. 1991, 14, 388.

247

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

119

EGA thermogram

Averaged mass spectrum 94

66

121

44

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

144

115 50

77

31

157 170

50

100

186 197

150

220

200

300 [m/z]

250

( m/z range : 29 - 600 amu )

HA : p-hydroxybenzaldehyde

P : phenol OH

94

121

O

39

OH 55

29

93

65

66 39

50

79

76

A : p-hydroxybenzoic acid

DE : diphenyl ether 170

O

121

O HO

138

OH

141 77

51 39

65

94

115

53

31

NO : β-naphthol

93

65

39 155

128

81

110

149

XO : xanthone 144

OH

O

196

115 168

O 39

89 90

63 57

126

84 92

63

39 50

170

146

139 114

184

129

HP : (p-hydroxyphenyl)benzoic acid

NP : 2-naphthyl phenyl ether 220

121

O HO

O

O 191

77 39 51 63

101

115 127 144152

165

204

39

178

121

157

186

214

65

171

O

214

53

93 77

a : phenyl-1-hydroxy-2-naphthoate

HP' : unidentified

39

65 51

O HO 143

93 77

107

197 139 157168 185

216

39 51 65

89 94

115 126

264 245

248

Tsuge, Ohtani and Watanabe

120 Polyarylate; PAR O

C(CH3)2

OCO

BA

TP

CO n

IP’

P ID

PC

VP EP IP BP DP A

TIC

PB

IB

MB TE

PA

B 0

10

30 [min]

20

Peak Notation

Assignment of Main Peaks

B P PC EP A VP IP BP IP’

benzene phenol p-cresol p-ethylphenol benzoic acid p-vinylphenol p-isopropylphenol p-tert-butylphenol p-isopropenylphenol

DP

diphenyl

PB

phenyl benzoate

Molecular Weight

Retention Index

Relative Intensity

78 94 108 122 122 120 136 150 134

664 985 1078 1169 1176 1220 1231 1298 1307

10.2 49.3 21.1 16.8 9.9 14.3 11.5 7.0 57.1

154

1398

6.5

198

1678

15.1

210

1759

26.1

212

1799

6.6

212

1881

6.4

238

2030

18.5

228

2202

71.8

C

332 ?

3043

100.0

OCO

436

3891

24.7

COOH

COO C

ID

4-isopropenyl(diphenyl ether)

O

C C

MB

p-tolyl benzoate

COO

C

C

PA IB

C

OH

C

C

COO

C C

C

BA

C

HO

bisphenol A

OH

C

TP

OCO

COO C

TE

COO

C C

* bonding hydrogen is omitted

249

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

120

EGA thermogram

Averaged mass spectrum 77

105 119

94

213

65

39

100

134

51

300

400

500

600

700 ºC

programming rate: 20ºC/min

152165 183195

31 0

200

50

100

150

200

228 238

332 250

300

350

[m/z]

400

( m/z range : 29 - 600 amu )

PC : p-cresol

P : phenol OH

94

OH

107

66

77

39 55

29

51

39

79

90

63

VP : p-vinylphenol

EP : p-ethylphenol 107

OH

OH

120

91

122 77 39

51

39

91

65

IP : p-isopropylphenol

65

51

89

105

PB : phenyl benzoate 121

OH

105

O 77

136 91

77 39

51

65

O

51

39

107

65

93

198

141

IB : 4-(prop-1-en-2-yl)phenyl benzoate

ID : 4-isopropenyl(diphenyl ether) 210

105

O

O

O 195 77 91 39 51 65

115 119

77

165 181 141152

39

51

238 63

103

119 133

165 181

TP : phenyl p-tolyl terephthalate

BA : bisphenol A

105

213

HO

O

OH

O

O 228 55 65 77

91 107

135 152 165 181 198

230

39

51 65 91 119

O 317 332

77

119 39

210

213 228

436

250

Tsuge, Ohtani and Watanabe

121 Poly(1,4-cyclohexanedimethylene terephthalate) H2C

CH2 OOC

COO

n

f

DM b a e c X BA LB TIC

B

d

T

0

10

Peak Notation

Assignment of Main Peaks

LB B T

CO2 benzene toluene

30 [min]

20

Molecular Weight

a CH 2

Retention Index

Relative Intensity

44 78 92

150 662 768

30.1 13.4 5.3

108

813

47.6

108

855

58.3

DM

H2C

X

p-xylene

106

873

33.2

BA

HOOC

122

1199

100.0

b c d e f

unidentified unidentified unidentified unidentified unidentified

-

1851 1877 2290 3138 3165

42.5 25.4 3.3 45.6 87.8

( including the form of

CH2

CH2

)

251

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

121

EGA thermogram

Averaged mass spectrum 93 108 100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

149

79

65 29 39

121

51 50

166

100

257

150

200

300 [m/z]

250

( m/z range : 29 - 600 amu )

DM : 1,4-dimethylenecyclohexane

a : bicyclo[2.2.2]octane

93

93 108

79

108 77

39 39

67

53

65

51

29

29

X : p-xylene

BA : benzoic acid 91

O

105

OH

122 77

106 51 39

51

65

77 29

b : unidentified

74

39

94

c : unidentified 105

93

93

108

77 77

29

41

51

67

51 29 41

123

67

123

f : unidentified

e : unidentified 108

108 93

93 149

79

257 149

79 29 41 55

67

230

121 132

167 189

229

258

67 29 41 55

121 132

257 189

229

258

252

Tsuge, Ohtani and Watanabe

122 Poly(lactic acid); PLA CH3 OCHCO

n

AA

TIC

PD

L2 L1

Acr

0

10

Peak Notation

Assignment of Main Peaks

AA PD Acr

acetaldehyde 2,3-pentadione acrylic acid

30 [min]

20

Molecular Weight

Retention Index

Relative Intensity

44 100 72

411 689 714

100.0 1.3 1.8

(meso-form)

144

1133

1.2

(DL-form)

144

1172

6.1

O

L1

* O

O

* O O

L2

* O

O

* O

[ Related References ] 1) Kopinke, F.-D.; Remmler, M.; Mackenzie, K. Moeder, M.; Wachsen, O. Polym. Degrad. Stab. 1996, 53, 329. 2) Kopinke, F.-D.; Mackenzie, K. J. Anal. Appl. Pyrolysis 1997, 40-41, 43. 3) Khabbaz, F.; Karlsson, S.; Albertsson, A.-C. J. Appl. Polym. Sic. 2000, 78, 2369. 4) Aoyagi, Y.; Yamashita, K.; Doi, Y. Polym. Degrad. Stab. 2002, 76, 53. 5) Fan, Y.; Nishida, H.; Hoshihara, S.; Shirai, Y.; Tokiwa, Y.; Endo, T. Polym. Degrad. Stab. 2003, 79, 547. 6) Fan, Y.; Nishida, H.; Shirai, Y.; Endo, T. Polym. Degrad. Stab. 2003, 80, 503. 7) Nishida, H.; Mori, T.; Hoshihara, S.; Fan, Y.; Shirai, Y.; Endo, T. Polym. Degrad. Stab. 2003, 81, 515. 8) Fan, Y.; Nishida, H.; Shirai, Y.; Tokiwa, Y.; Endo, T. Polym. Degrad. Stab. 2004, 86, 197. 9) Abe, H.; Takahashi, N.; Kim, K. J.; Mochizuki, M.; Doi, Y. Biomacromolecules 2004, 5, 1606. 10) Fan, Y.; Nishida, H.; Mori, T.; Shirai, Y.; Endo, T. Polymer 2004, 45, 1197. 11) Abe, H. Macromol. Biosci. 2006, 6, 469.

253

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

122

EGA thermogram

Averaged mass spectrum 56

100

200

300

400

500

45

600

700 ºC

programming rate: 20ºC/min

29 128 73 83 100 111 144 154 0

50

100

200

150

272

200

250

344 300

350

450 [m/z]

400

( m/z range : 29 - 600 amu )

AA : acetaldehyde

PD : 2,3-pentadione 29

44

29

43

O

O 57

O 100

74

L1 : 3,6-dimethyl-1,4-dioxane-2,5-dion (meso form)

Acr : acrylic acid 72

OH

O

55

56

O

*

O

45

*

O 45

29 29

L2 : 3,6-dimethyl-1,4-dioxane-2,5-dion (DL form) 56

O O

*

*

O

45

O

29 70

1 44

O

254

Tsuge, Ohtani and Watanabe

123 Poly( -caprolactone); PCL (CH2)5COO

n

CL1

F CL2 TIC

A

B

C

D

E0

CL3 E1

E2 CL4

0

10

Peak Notation

Assignment of Main Peaks

A B C D

pentene unidentified cyclopentanone CH2=CH(CH2)3COOH

CL1

ε-caprolactone

E0 F CL2 E1 CL3 E2 CL4

30 [min]

20

Retention Index

Relative Intensity

70 96 84 114

493 699 788 998

1.8 3.5 4.6 16.7

(CH2)5COO

114

1160

100.0

CH2=CH(CH2)2COO(CH2)4CH3 CH2=CH(CH2)3COO(CH2)5COOH

170 228

1278 1742

3.8 23.0

228

1788

7.2

270

2053

5.1

342

2602

8.2

370

2825

5.9

456

3401

5.8

(CH2)5COO

2

CH2=CH(CH2)2COO(CH2)4COO(CH2)4CH3

(CH2)5COO

3

CH2=CH(CH2)2COO[(CH2)4COO]2(CH2)4CH3

(CH2)5COO

4

Molecular Weight

[ Related References ] 1) Aoyagi, Y.; Yamashita, K.; Doi, Y. Polym. Degrad. Stab. 2002, 76, 53. 2) Abe, H.; Takahashi, N.; Kim, K. J.; Mochizuki, M.; Doi, Y. Biomacromolecules 2004, 5, 1480. 3) Abe, H. Macromol. Biosci. 2006, 6, 469.

255

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

123

EGA thermogram

Averaged mass spectrum 55

42

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

84

29

115

70

97

50

229

100

150

250 [m/z]

200

( m/z range : 29 - 600 amu )

C : cyclopentanone

D : 5-hexenoic acid 60

55

O

O OH

41 84

41

68 29

29

69

96

95

CL1 : ε -caprolactone

114

81

E0 : pentyl pent-4-enoate

55

43

O

42

O 55

O

O

84 29

114

97

68 29 114

70

81

97

CL2 : 1,8-dioxacyclotetradecane-2,9-dione (ε -caprolactone dimer)

F : 6-(5-hexenoyloxy)hexanoic acid 69

115 97

41 55

O

OH

O

55

O 41 29

128 133

81

O

O

115

O 97

69

29 156 174

O

84

210

128 141 156 169

210

CL3 : trimer of ε -caprolactone

E1 : 5-oxo-5-(pentyloxy)pentyl pent-4-enoate 115

115 O

O O

O O

O

41 55 69 41 29

81

128 142 156 169

185

O

O

97 55

E2 : 5-oxo-5-(5-oxo-5-(pentyloxy)pentyloxy)

97

69

29

203

O O

84

128

156

185 210 230

324

CL4 : tetramer of ε-caprolactone

pentyl pent-4-enoate

115

115

O O O

O

O

O

O O

O

O

O

97 41 55 69 29

84

128

169

185

55 69 41 211

244

283

324

29

O O

97 84

O

128

169

229

283

324

438

256

Tsuge, Ohtani and Watanabe

124 Poly(butylene succinate / adipate); PBSA O(CH2 )4OCO(CH2 )2 CO

O(CH2)4OCO(CH2 )4CO

n

S4

THF S3 SS2 B

CP BD

TIC

SA2 SS1 SA1

A4 H

San

P1

S1 S2 P2

0

A3

S5

A1 V2 A2

PS

A5

10

Peak Notation

Assignment of Main Peaks

B THF CP P1 BD

1,3-butadiene tetrahydrofuran cyclopentanone CH3CH2COO(CH2)2CH=CH2 1,4-butanediol O

O

S2 V2 H S3 A1 A2

Molecular Weight

Retention Index

Relative Intensity

54 72 84 128 90

395 621 788 890 947

64.9 97.9 45.9 6.6 35.1

100

1034

33.7

146 172

1174 1340

10.0 24.9

172

1354

12.5

174 168 226 200

1360 1370 1526 1531

4.5 19.6 46.4 12.7

200

1566

4.6

254 244 272 262 318 290

1733 1817 2026 2114 2320 2330

20.4 100.0 42.3 28.5 9.7 8.2

344

2580

26.8

O

San P2 S1

30 [min]

20

CH3CH2COO(CH2)4OH HOOC(CH2)2COO(CH2)2CH=CH2 OCO(CH2)2COO(CH2)4 CH3(CH2)3COO(CH2)4OH OCN(CH2)6NCO CH2=CH(CH2)2OOC(CH2)2COO(CH2)2CH=CH2 HOOC(CH2)4COO(CH2)2CH=CH2 OCO(CH2)4COO(CH2)4

SS1

CH2=CH(CH2)2OCO(CH2)4COO(CH2)2CH=CH2 CH2=CH(CH2)2OCO(CH2)2COO(CH2)4OH CH2=CH(CH2)2OCO(CH2)4COO(CH2)4OH HO(CH2)4OCO(CH2)2COO(CH2)4OH CH3CH2COO(CH2)4OCO(CH2)2COO(CH2)4OH HO(CH2)4OCO(CH2)4COO(CH2)4OH OCO(CH2)2COO(CH2)4OCO(CH2)2COO(CH2)4

SS2

CH2=CH(CH2)2OCO(CH2)2COO(CH2)4OCO(CH2)2COO(CH2)2CH=CH2

398

OCO(CH2)2COO(CH2)4OCO(CH2)4COO(CH2)4

372

2656 2862

26.0

CH2=CH(CH2)2OCO(CH2)2COO(CH2)4OCO(CH2)4COO(CH2)2CH=CH2

426

2966

42.8

A3 S4 A4 S5 PS A5

SA1 SA2

[ Related References ] 1) Plage, B.; Schulten, H.-R. J. Anal. Appl. Pyrolysis 1989, 15, 197 2) Plage, B.; Schulten, H.-R. Macromolecules 1990, 23, 2642. 3) Sato, H.; Furuhashi, M.; Yang, D.; Ohtani, H.; Tsuge, S.; Okada, M.; Tsunoda, K.; Aoi, K. Polym. Degrad. Stab. 2001, 73, 327.

42.6

257

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

124

EGA thermogram

Averaged mass spectrum 55

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

42

101

73

29

129

111

84 50

142

100

155 150

173 183

201

227

255

200

300 [m/z]

250

( m/z range : 29 - 600 amu )

B : 1,3-butadiene

THF : tetrahydrofuran 42

54

39

O 72

29 29

53

CP : cyclopentanone

S3 : 3-dibutenyl succinate 55

55

O

O O

O

84

O 41

101

29

29 39

69

S4 : 3-butenyl 4-hydroxybutyl succinate

101

125

O

55

O

O

O

OH

O

73

155

108

A4 : 3-butenyl 4-hydroxybutyl adipate

O

55

73 80

OH

129 O

O 111

183 71

155

29 43

89

119

173 174

142

213

S5 : bis(4-hydroxybuthyl) succinate 73

55 O

O

71

20 173

119 31 43 87

42

55

O

O O

101 29 39

73 80

108 119

55

O

O

288

326

O

O O

O

73

227

101 155173 227

173 174

254

O

O O

O

155

226

butyl adipate

O

O

214

SA2 : 3-butenyl 4-(4-(3-butenyloxy)-4-oxobutanoyloxy)

O

O

O

O

154 114 142

87

214 231

SS2 : dibut-3-enyl '-butane-1,4-diyl disuccinate

O

128

29

142 160 146

116

O

O

O

55

241

O

101

OH

O 101

201 202

141 154 170

SS1 : 1,6,11,16-tetraoxacycloicosane-2,5,12,15-tetraone

O HO

101

83

29 43

213

327

29 42

80

119 108 142

174 214

273

327 345

385

258

Tsuge, Ohtani and Watanabe

125 Poly(3-hydroxybutylic acid); PHB H

OCHCH2C CH3

O

OH n

LB

D F C B

TIC

A 0

10

Peak Notation

Assignment of Main Peaks

LB F A B C D

CO2, propylene etc. furan acetic acid CH2=C(CH3)COOH CH3CH=CHCOOH (cis) CH3CH=CHCOOH (trans)

30 [min]

20

Molecular Weight

Retention Index

44, 42 68 60 86 86 86

295 555 605 792 853 927

Relative Intensity 23.0 8.6 0.6 16.5 18.1 100.0

[ Related References ] 1) Watt, B. E.; Morgen, S. L. J. Anal. Appl. Pyrolysis 1991, 19, 237. 2) Lehrle, R. S.; Williams, R. J. Macromolecules 1994, 27, 3782. 3) Lehrle, R.; Williams, R.; French, C.; Hammond, T. Macromolecules 1995, 28, 4408. 4) Kopinke, F.-D.; Remmler, M.; Mackenzie, K. Polym. Degrad. Stab. 1996, 52, 25 5) Kopinke, F.-D.; Mackenzie, K. J. Anal. Appl. Pyrolysis 1997, 40-41, 43. 6) Aoyagi, Y.; Yamashita, K.; Doi, Y. Polym. Degrad. Stab. 2002, 76, 53. 7) Li, S.-D.; He, J.-D.; Yu, P. H.; Cheung, M. K. J. Appl. Polym. Sci. 2003, 89, 1530. 8) Gonzalez, A.; Irusta, L.; Fernandez-Berridi, M. J.; Iriarte, M.; Iruin, J. J. Polym. Degrad. Stab. 2005, 87, 347. 9) Abe, H. Macromol. Biosci. 2006, 6, 469.

259

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

125

EGA thermogram

Averaged mass spectrum 69

100

41

200

300

400

500

103

29

600

700 ºC

programming rate: 20ºC/min

86

57

154

113

50

100

171

150

200

[m/z]

( m/z range : 29 - 600 amu )

LB : propylene

F : furan 41

39

O

50

29

29

68

B : methacrylic acid

A : acetic acid 43

O

41

OH

60

86

OH

58

O 29 67

69

29

82

C : 2-butenoic acid (cis)

95

D : 2-butenoic acid (trans) 86

OH 39

O

68

86

O OH

39 68

29

57

29

57

260

Tsuge, Ohtani and Watanabe

126 Poly(butylene succinate / carbonate); PEC O(CH2)4OCO(CH2)2CO

O(CH2)4

OCO

n

S4 SS2 S3

B LB

SA2 S5

THF BO BD San

TIC

0

10

Peak Notation

Assignment of Main Peaks

LB B THF BO BD

CO2 1,3-butadiene tetrahydrofuran CH2=CH(CH2)2OH 1,4-butanediol O

O

Molecular Weight

Retention Index

Relative Intensity

44 54 72 72 90

150 395 617 625 947

36.6 39.2 55.3 39.1 30.2

100

1021

39.6

226 244 262 398 426

1516 1818 2116 2657 2969

50.2 100.0 41.0 62.6 75.3

O

San S3 S4 S5 SS2 SA2

30 [min]

20

CH2=CH(CH2)2OOC(CH2)2COO(CH2)2CH=CH2 CH2=CH(CH2)2OCO(CH2)2COO(CH2)4OH HO(CH2)4OCO(CH2)2COO(CH2)4OH CH2=CH(CH2)2OCO(CH2)2COO(CH2)4OCO(CH2)2COO(CH2)2CH=CH2 CH2=CH(CH2)2OCO(CH2)2COO(CH2)4OCO(CH2)4COO(CH2)2CH=CH2

261

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

126

EGA thermogram

Averaged mass spectrum 55

100

73

42

200

300

400

500

101

29 108 119

89 50

600

700 ºC

programming rate: 20ºC/min

142

100

155

174

227

150

250 [m/z]

200

( m/z range : 29 - 600 amu )

THF : tetrahydrofuran

B : 1,3-butadiene

42

54

39

O 72

29 29

53

BO : 3-buten-1-ol

BD : 1,4-butanediol 42

42

OH

OH

HO

31 31

71

57 57

72

S3 : 3-dibutenyl succinate

San : succinic anhydride 56

O

55

O

O

O

O

O O 101 29

42

29 39

100

S4 : 3-butenyl 4-hydroxybutyl succinate

73 80

73 O

73

89

119

119 31 43 87

213

SS2 : dibut-3-enyl '-butane-1,4-diyl disuccinate 55

O O

101

29 39

73 80

108 119

55

O

73

O

O O

O

227

101 155

173 227

173 174

214 231

191

O

O O

O

155

142 160 146

-4-oxobutanoyloxy)butyl adipate

O

O

116

SA2 : 3-butenyl 4-(4-(3-butenyloxy)

O

O O

OH

O

55

173 174

142

O

O

101

O

155 29 43

O HO

OH

O

101

125

S5 : bis(4-hydroxybutyl) succinate

O

55

155

108

213

243

273

327

29 42

80

119 108 142

174

214

245 273

345

385

262

Tsuge, Ohtani and Watanabe

2.2.15 The other engineering plastics with phenylene skeletons 127 Polycarbonate(melt method); MM-PC H

O

C(CH3)2

OCO

n

BA

PC

TIC

P

VP EP IP

PA ID

IP’

0

MA

10

30 [min]

20

Peak Notation

Assignment of Main Peaks

Molecular Weight

P PC EP VP IP IP’

phenol p-cresol p-ethylphenol p-vinylphenol p-isopropylphenol p-isopropenylphenol

ID

4-isopropenyl(diphenyl ether)

Retention Index

Relative Intensity

94 108 122 120 136 134

982 1077 1169 1220 1230 1305

6.3 14.0 7.0 5.8 1.5 5.7

210

1758

0.3

212

1881

4.0

226

1981

3.3

228

2200

100.0

C O

C

PA MA

C

C C C C

OH C OH C

C

BA

bisphenol A

C

HO

C

OH

C

* bonding hydrogen is omitted [ Related References ] 1) Lee, L. –H. J. Polym. Sci., Part A 1961, 2, 2859. 2) Tsuge, S.; Okumoto, T.; Sugimura, Y.; Takeuchi, T. J. Chromatogr. Sci. 1969, 7, 253. 3) Foti, S.; Giuffrida, M.; Maravigna, P.; Montaudo, G. J. Polym. Sci., Polym. Chem. Ed. 1983, 21, 1567. 4) Ito, Y.; Ogasawara, H.; Ishida, Y.; Tsuge, S.; Ohtani, H.; Polym. J. 1996, 28, 1090.

263

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

127

EGA thermogram

Averaged mass spectrum

100

200

300

400

500

213 65

39

91

77

51

31

700 ºC

119

107

134

50

600

programming rate: 20ºC/min

100

152

169

228

197

183

15 0

200

250 [m/z]

( m/z range : 29 - 600 amu )

PC : p-cresol

P : phenol 94

OH

107

OH

66

77

39 55

39

76

EP : p-ethylphenol

51

90

63

VP : p-vinylphenol 107

OH

120

OH

91

122 77 39

51

39

91

65

IP : p-isopropylphenol

51

65 89

105

IP' : p-isopropenylphenol 121

OH

134

OH 119

136 39

51

65

77

91

91 39

107

51

65

77

107

PA : p-hydroxy-2,2-diphenylpropane

ID : 4-isopropenyl(diphenyl ether) 210

197

O

OH

212

195 77 91 39 51 65

115

77 39 51 65

128 141152 165 182

MA : p-hydroxy-3-methyl-2,2-diphenylpropane

103 107119 135 152 165 182

BA : bisphenol A

211

213

OH

HO OH

228

226 91 39 51 65 77

119 135 152 165 181 196

39

119 91 107 135 152 165 181 197 55 65 77

264

Tsuge, Ohtani and Watanabe

128 Polycarbonate(solvent method); SM-PC (CH3)3C

OCO

O

C(CH3)2

OCO

O

n

C(CH3)3

BA

PC TIC

P

EP IP’ VP

BP IP

0

ID

PA MA

10

30 [min]

20

Peak Notation

Assignment of Main Peaks

P PC EP VP IP BP IP’

phenol p-cresol p-ethylphenol p-vinylphenol p-isopropylphenol p-tert-butylphenol p-isopropenylphenol

ID

4-isopropenyl(diphenyl ether)

Molecular Weight

Retention Index

Relative Intensity

94 108 122 120 136 150 134

985 1079 1169 1219 1229 1299 1307

7.6 19.7 10.7 7.9 2.4 6.8 8.6

210

1761

0.4

212

1885

5.2

226

1985

3.7

228

2207

100.0

C O

C

PA MA

C

C C C C

OH C OH C

C

BA

bisphenol A

C

HO

C

OH

C

* bonding hydrogen is omitted [ Related References ] 1) Lee, L. –H. J. Polym. Sci., Part A 1961, 2, 2859. 2) Tsuge, S.; Okumoto, T.; Sugimura, Y.; Takeuchi, T. J. Chromatogr. Sci. 1969, 7, 253. 3) Foti, S.; Giuffrida, M.; Maravigna, P.; Montaudo, G. J. Polym. Sci., Polym. Chem. Ed. 1983, 21, 1567. 4) Ito, Y.; Ogasawara, H.; Ishida, Y.; Tsuge, S.; Ohtani, H.; Polym. J. 1996, 28, 1090.

265

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

128

EGA thermogram

Averaged mass spectrum 213

100

91 65 77

39

300

400

500

600

700 ºC

programming rate: 20ºC/min

228

51

134

50

200

107 119

100

152 169183197 150

200

250

300

400 [m/z]

350

( m/z range : 29 - 600 amu )

PC : p-cresol

P : phenol 94

OH

107

OH

66

77

39 55

29

29

79

EP : p-ethylphenol

51

39

90

63

VP : p-vinylphenol 107

OH

120

OH

91 122 77 29

39

51

OH

51

89

105

BP : p-tert-butylphenol 121

29

51

29

IP : p-isopropylphenol

39

65

39

91

65

65

77

135

OH

107

136

91

150 41 51 29

107

65 77

95

119

PA : p-hydroxy-2,2-diphenylpropane

IP' : p-isopropenylphenol 134

OH

197

OH

119

91 29

39

51

65

77

212 105

77 39 51 65

MA : p-hydroxy-3-methyl-2,2-diphenylpropane

103 119 135 152 165 182 115

BA : bisphenol A 213

211

HO

OH

OH

226 29 39 51 65 77

91

119 135 152 165 181 196

29 39

119 91 107 135 152 165 181 197 55 65 77

228 230

266

Tsuge, Ohtani and Watanabe

129 Bisphenol Z polycarbonate O

OCO n

E

MP B EP A

VP PP CP CP’

Ph

C D

TIC

X 0

10

Peak Notation

Assignment of Main Peaks

X Ph MP EP VP CP PP CP’

p-xylene phenol p-cresol p-ethylphenol p-vinylphenol p-cyclohexylphenol p-phenylphenol p-cyclohexenylphenol

A

HO

B

HO

30 [min]

20

Molecular Weight

Retention Index

Relative Intensity

106 94 108 122 120 176 170 174

879 984 1079 1170 1221 1650 1730 1736

1.3 35.4 100.0 67.6 40.6 12.9 33.9 14.3

CH2

OH

200

2085

48.9

CH

OH

214

2143

80.7

OH

212

2191

24.8

OH

228

2207

19.1

OH

268

2654

95.7

CH 3

C

HO

C CH 2 CH 3

D

HO

C CH 3

E

HO

267

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

129

EGA thermogram

Averaged mass spectrum 107

100

200

300

400

500

77 51

91

133

65

170 183

148

29 0

600

700 ºC

programming rate: 20ºC/min

44

50

100

150

199 262 209 225 236 246 274 289 303 200

250

333 348 350 [m/z]

300

( m/z range : 29 - 600 amu )

X : p-xylene

Ph : phenol 91

94

OH

106 44

66 51

32

65

39

77

55

29

79

EP : p-ethylphenol

MP : p-cresol 107

OH

107

OH

122 77 29

51

39

77

90

63

29

VP : p-vinylphenol

39

51

91

65

PP : p-phenylphenol 120

OH

170

OH 91

29

51

141

115

65

39

105

89

39

85

51 63

102

152

127

B : 4,4'-ethylidenediphenol

A : 4,4'-methylenediphenol 200

199

OH 107

HO

OH

HO

214 77 94 29 39 55 65

183 152 165 128 141

254

210

29 39

55 65 77 91

115121

181 141152 169

216

E : 4,4'-(cyclohexane-1,1-diyl)diphenol

C : 4,4'-(ethene-1,1-diyl)diphenol

225

212 197

268

OH

HO

HO 65 82 91 29 39 51

165 152 181 118 139

OH 107 131

224

268 286

77 91 39 29 55 65

199 165 185 152

212

251 239

290

342

268

Tsuge, Ohtani and Watanabe

130 Polycarbonate (thermally stabilized) O

(CH3)3CCH2 C(CH3 )2

COO

C(CH3 )2

O

COO

O

COO

C(CH3 )2 CH2C(CH3)3

n

H3C

CH3 CH3

BA

D

MP

MA

P

EP VP

TIC

OP PP

0

B A

C

10

Peak Notation

Assignment of Main Peaks

P MP EP VP PP MA

phenol p-cresol p-ethylphenol p-vinylphenol p-isopropylphenol p-isopropenylphenol

OP

HO

A

HO

B

HO

C

HO

BA

bisphenol A

D

HO

Molecular Weight

C(CH3)2CH2C(CH3)3 C H2 C(CH3)2 OH

HO

C(CH3)2 OH

H3C

30 [min]

20

OH

Retention Index

Relative Intensity

94 108 122 120 136 134

983 1078 1169 1220 1231 1306

15.9 16.4 7.1 5.4 5.2 13.0

206

1620

7.8

184

1834

4.5

212

1881

7.5

214

2142

8.7

228

2207

100.0

310

2723

32.3

CH3

CH 3

[ Related Reference ] 1) Ishida, Y.; Kawaguchi, S.; Ito, Y.; Tsuge, S.; Ohtani, H. J. Anal. Appl. Pyrolysis 1997, 40-41, 321.

269

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

130

EGA thermogram

Averaged mass spectrum 213

107

100

44

300

400

500

119 135

29 50

600

700 ºC

programming rate: 20ºC/min

77

55 65

0

200

91 152 165 183

100

197

150

200

228 239

253

317 329 347 362

289

250

300

400 [m/z]

350

( m/z range : 29 - 600 amu )

MP : p-cresol

P : phenol 94

OH

107

OH

66

77

39 55

29

79

29

51

39

90

63

VP : p-vinylphenol

EP : p-ethylphenol 107

OH

120

OH

91

122 77 29

39

51

65

91

29

MA : p-isopropenylphenol

39

65

51

89

105

OP : 4-(1,1,3,3-tetramethylbutyl) phenol 134

OH

135

119

HO 91 29

39

51

65

77

105

29 41

B : p-hydroxy-2,2-diphenylpropane

57 65 77 91

107 119

206

149

C : 4,4'-ethylidenediphenol 197

199

OH OH

HO

214

212 29 39 51 65

103

77

119 135 152 165 179 115

29 39

BA : bisphenol A

55 65 77 91

115121

181 141152 169

216

D : 4,4'-(3,3,5-trimethylcyclohexane-1,1-diyl)diphenol 239

213

HO

OH 310 228

HO

119 29 39

55 65 77

91

107

135 152 165 181 197

230

29 41 55 6577 91

OH 253 107 121 145159 185197212 165 225

295

270

Tsuge, Ohtani and Watanabe

131 Brominated polycarbonate; Br-PC Br Br

Br OCO

C(CH3 )2 Br

Br

Br

Br

O

OCO

O

C(CH3 )2

OCO

O n

Br

Br Br

E

C LB

P A

TIC

BB

0

B

D 10

Peak Notation

Assignment of Main Peaks

LB BB P A B C D E

CO2, hydrogen bromide etc. bromobenzene phenol o-bromophenol p-bromophenol 2,6-dibromophenol 2,4-dibromophenol 2,4,6-tribromophenol

30 [min]

20

Molecular Weight 156 94 172 172 250 250 328

[ Related Reference ] 1) Sato, H.; Kondo, K.; Tsuge, S.; Ohtani. H.; Sato, N. Polym. Degrad. Stab. 1998, 62, 41.

Retention Index 150 937 983 1078 1292 1365 1397 1669

Relative Intensity 100.0 6.4 29.2 17.7 10.3 49.3 6.8 98.8

271

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

131

EGA thermogram

Averaged mass spectrum 82

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

44 94

63 29

143

119 50

100

174

150

196

252

222

200

330

275

250

350 [m/z]

300

( m/z range : 29 - 600 amu )

LB : hydrogen bromide

BB : bromobenzene 80

H

77

Br

Br

156

51 29

74

38

39

106

129 141

A : o-bromophenol

P : phenol 94

OH

172 174

OH Br 65

66 39

39

55

29

79

B : p-bromophenol

93 87

53

32

117119

143146

C : 2,6-dibromophenol 172

OH

252

OH

174

Br

Br 65 63

Br

93

39 50

32

86

117 119

143 146

29 38

86

143 92 117 126 146 172174 197

252

OH

330

OH Br

Br

Br

63

Br 62

Br 143 172 92 86 117 126 146 174

223

E : 2,4,6-tribromophenol

D : 2,4-dibromophenol

53 29 38

61

197

223

29

37

61

141 91 111 118 81

222 170 152 175 197

250

301

272

Tsuge, Ohtani and Watanabe

132 Polysulfone; PSF O

C(CH3)2

O

SO2 n

P

MD b

MB,VD

TIC

DE

PC

ED

LB

0

a

ID DT

F 10

Peak Notation

Assignment of Main Peaks

LB P PC DE

SO2 phenol p-cresol diphenyl ether

MD

4-methyl(diphenyl ether)

F

fluorene

ED

4-ethyl(diphenyl ether)

DT

di-p-tolyl ether

C

30 [min]

20

Molecular Weight

O

C

O

O

C

C

C

Retention Index

Relative Intensity

64 94 108 170

985 1078 1419

43.5 100.0 11.2 11.2

184

1532

32.8

166

1614

2.1

198

1639

10.9

198

1644

3.5

1665

13.2

210

1758

10.1

-

2707 3218

12.3 37.9

O

182

MB

C

VD

4-vinyl(diphenyl ether)

ID

4-isopropenyl(diphenyl ether)

O

C

196

C C

O

C C

a b

unidentified unidentified * bonding hydrogen is omitted [ Related References ]

1) Crossland, B.; Knight, G. J.; Wright, W. W. Br. Polym. J. 1986, 18, 156. 2) Almen, P.; Ericsson, I. Polym. Degrad. Stab. 1995, 50, 223. 3) Perng, L. -H. J. Polym. Sci., Part A Polym. Chem. 2000, 38, 583. 4) Ohtani, H. ; Ishida, Y. ; Ushiba, M. ; Tsuge, S. J. Anal. Appl. Pyrolysis 2001, 61, 35.

273

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

132

EGA thermogram

Averaged mass spectrum 94 66 39

100

200

300

400

500

48

600

700 ºC

programming rate: 20ºC/min

77 107

32

128 50

141 184 152 165 195 210 228 242 260 276 289 304

100

150

200

250

365

300

350

[m/z]

400

( m/z range : 29 - 600 amu )

PC : p-cresol

P : phenol 94

OH

107

OH

66

77

39 55

31

51

39

79

DE : diphenyl ether

90

63

MD : 4-methyl(diphenyl ether) 170

184

O

O 141 51 39

91

77 65

115

94

128

39

155

ED : 4-ethyl(diphenyl ether)

51

77

65

115 128

141 155 169

DT : di-p-tolyl ether 183

198

O

O 198

91 77 51

39

91 105

65

65 128 141 155 169

39 51

MB, VD : 2-methyldibenzo[b,d]furan +

77

107

128 141

155

169 183

ID : 4-isopropenyl(diphenyl ether)

4-vinyl(diphenyl ether) O

196

210

O

+ 182

O

195 39

51

77 65

152

91 115

120

167

141

a : unidentified

77 91 39 51 65

115 119 141152 165 181

b : unidentified 365

289

380

304 39 51 65

77 91 119 144 165181 195 152 115

39 5165

77

165183 195 115 152

271

274

Tsuge, Ohtani and Watanabe

133 Poly(phenylene oxide); PPO CH3 O n

CH3

X1 TP X2 OC D4 D3

D6 D5

T4 T3 T6 T2 T5

D2 D1 TIC

X3

PC

0

T1

10

Peak Notation

Assignment of Main Peaks

OC PC X1 X2 X3 TP

o-cresol p-cresol 2,6-xylenol (monomer) 2,4-xylenol 3,5-xylenol 2,4,6-trimethylphenol

D1

HO

C

C C

C

D2 HO

C

O C

C

C C HO C

1058 1077 1113 1153 1172 1213

72.9 7.2 100.0 74.7 9.0 72.5

242

1996

15.6

256

2038

21.3

228

2139

31.4

242

2185

49.6

242

2221

28.3

256

2263

40.8

362

2810

9.6

376

2843

15.3

350 ?

2991

22.7

364 ?

3019

31.8

364 ?

3057

16.4

378 ?

3086

28.7

HO

D5

C

C C

D6 C HO

O

C

HO

HO

C

C

C

C

C

C

O C

C

C

T2

HO C HO

C O

HO C

T4

O

C O

C

C

C

C

HO C

C

C C

O C

HO

108 108 122 122 122 136

(dimer group)

C

C

C

C HO

D4

T5

Relative Intensity

C

HO

D3

T3

Retention Index

C

HO C

T1

Molecular Weight

C O

HO

30 [min]

20

C O

O

C

C

C

C

HO C

C

O C

O

HO C

T6

HO

(*bonding hydrogen is omitted)

O C

(trimer group)

C

O C

HO C

[ Related References ] 1) Jachowicz, J.; Kryszewski, M.; Kowalski, P. J. Appl. Polym. Sci. 1978, 22, 2891. 2) Chandra, R. Prog. Polym. Sci. 1982, 8, 469. 3) Usami, T.; Keitoku, F.; Ohtani, H.; Tsuge, S. Polymer 1992, 33, 3024. 4) Takayama, S.; Matsubara, N.; Arai, T.; Takeda, K. Polym. Degrad. Stab. 1995, 50, 277.

275

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates 133

EGA thermogram

Averaged mass spectrum 107 122 77

100

91

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

39

51

135

65

152 165 181 197 211 228

31 50

100

150

200

242 258 250

300

400 [m/z]

350

( m/z range : 29 - 600 amu )

X1 : 2,6-xylenol

OC : o-cresol 108

OH

OH

77

77

91

90 51

39

29

63

122

107

39

29

51

65

TP : 2,4,6-trimethylphenol

X2 : 2,4-xylenol 107

OH

121

122

OH

77 39

29

51

136

91

91

65

39

29

D2 : 2,4-dimethyl-3-hydroxy-2',4',6'-trimethyldiphenol

121

HO

O

HO

228

108

135 122 77 29 41 53 65

91 107

181 195 211 226

241

29 39 51 65

258

D4 : 4-(2-hydroxy-3-methylbenzyl)-2,6-dimethylphenol

77 91

165 181 141152

199 213 230

D6 : 4-(2-hydroxy-3,5-dimethylbenzyl)-2,6-dimethylphenol

122

HO

117

D3 : 4,6'-methylenebis(2-methylphenol)

256

HO

77

65

51

135 242

HO

HO

HO 256 122

77 29 39 51 65

91 107

135 152165 181 195 211

227

77 29 39 53 65

244

T2 : 4-(4-(mesityloxy)-2,6-dimethylphenoxy)

91

107

152165 179197

-2,6-dimethylphenoxy)-2,6-dimethylphenol 376

O

362 HO

O

O

O HO

41 53 65

7791 119 135

258

T4 : 4-(4-(2-hydroxy-3-methylphenoxy)

-2,6-dimethylphenol HO

211225 241

188

239 223 255

361

242

195 225 77 91 122 107 137 165 181 209 41 53 65

244

347

276

Tsuge, Ohtani and Watanabe

134 Modified poly(phenylene oxide); Modified PPO CH3 CH2CH(C6H5)

m

O

+

n

CH3 D4 D3 S

D1

SS

T

10

toluene ethylbenzene styrene (S monomer) α -methylstyrene o-cresol 2,6-xylenol (PO monomer) 2,4-xylenol 2,4,6-trimethylphenol Ph-C-C-C-Ph C=C(Ph)-C-C-Ph (S dimer)

D1

HO

C C

C

C

C

C O

C

HO

HO

C

C

C

C

O

O

C

C

C

C HO

HO

C

C

C

(PO trimer group)

HO

C

C C

C

C C

O C

C

HO

C

HO

242

1996

6.4

256

2038

8.6

228

2139

13.3

242

2185

242

2221

22.9 14.5

256

2263

19.7

312

2487

18.8

362

2810

2.2

376

2843

4.7

348

2991

2.8

362

3019

5.9

362

3057

2.8

376

3085

7.7

362

3227

6.9

376

3288

6.7

C

HO

C

T6

O C

C

HO C

C

C

O C

C C

HO

13.6 7.6 100.0 9.1 16.0 35.7 24.4 34.5 8.5 3.2

C

C

HO

C

HO

769 866 894 987 1059 1114 1153 1213 1674 1734

C

C

O C

T4

T8

C

C

C

HO

T2

T7

(PO dimer group)

C

C=C(Ph)-C-C(Ph)C-C-Ph (S trimer)

SSS

92 106 104 118 108 122 122 136 196 208

C HO

C

HO

D6

T5

C C

HO C

HO

C O

C

C

D5

Relative Intensity

C HO C

D4

C HO

C HO

D3

Retention Index

C O

D2

T3

Molecular Weight

Assignment of Main Peaks

C

30 [min]

20

T EB S αS OC X1 X2 TP SS’ SS

T1

20

OC

0

Peak Notation

T4 T6 T7 T8 T5 T3

15

10

αS

EB

T2 T1

TP

X1 TIC

SSS D5

D2

SS’ X2

D6

C

HO

C

O C

C C

C HO C

C

C HO

HO

HO

C

C

C C C

(*bonding hydrogen is omitted) (*Ph represents C6H5 (phenyl group))

[ Related References ] 1) Jachowicz, J.; Kryszewski, M.; Kowalski, P. J. Appl. Polym. Sci. 1978, 22, 2891. 2) Mukherji, A. K.; Butler, M. A.; Evans, D. L. J. Appl. Polym. Sci. 1980, 25, 1145. 3) Wandelt, B.; Kryszewski, M.; Kowalski, P. Polymer 1981, 22, 1236. 4) Chandra, R. Prog. Polym. Sci. 1982, 8, 469. 5) Jachowicz, J.; Kryszwski, M.; Mucha, M. Macromolecules 1984, 17, 1315. 6) Usami, T.; Keitoku, F.; Ohtani, H.; Tsuge, S. Polymer 1992, 33, 3024.

277

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates 134

EGA thermogram

Averaged mass spectrum 91 104

77

121 100

39

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

51

135

65

242 152 165 178 196 213 228 258 50

100

150

200

306

250

362 376

300

400 [m/z]

350

( m/z range : 29 - 600 amu )

OC : o-cresol

S : styrene 104

108

OH

103

78

77 90

51 39

X2 : 2,4-xylenol

OH

107

77 29

63

29

X1 : 2,6-xylenol

39

51

39

63

51

122

107

OH

77

91

65

39

29

51

122

91

65

SS' : 1,3-diphenylpropane

TP : 2,4,6-trimethylphenol 121

OH

92 136 196 105

91 29

39

51

65

77

117

51

39

D4 : 4-(2-hydroxy-3-methylbenzyl)-2,6-dimethylphenol

65 77 118

D6 : 4-(2-hydroxy-3,5-dimethylbenzyl)-2,6-dimethylphenol

122

HO

139 152 165 178

135 242

HO

HO

HO 256 122

29 39 51 65

77 91 107

135 152 165 181 195 211

227 244

SSS : 5-hexene-1,3,5-triyltribenzene (styrene trimer)

77 29 39 53 65

91

165 241 152 179 197211225

107

258

T2 : 4-(4-(mesityloxy)-2,6-dimethylphenoxy) -2,6-dimethylphenol 376

91

HO

O

O

117 39 51 6577

194 118143 165 179

207 221

312 297

415365 77

91 119 117 135

188 181

239 255

361

278

Tsuge, Ohtani and Watanabe

135 Polyethersulfone; PESF SO2

O n

b PD

DE

a

PP

P BF TIC

LB

15

20

25

DP

0

10

Peak Notation

Assignment of Main Peaks

LB P DP DE BF PP PD a b

SO2 phenol diphenyl diphenyl ether dibenzofuran O OH p-phenylphenol 4-phenyl(diphenyl ether) 1-phenoxy-4-(phenylsulfonyl)benzene 4,4'-sulfonylbis(phenoxybenzene)

30 [min]

20

Molecular Weight

O

64 94 154 170 168 170 246 310 402

Retention Index 985 1398 1420 1546 1730 2230 2806 3659

[ Related References ] 1) Crossland, B.; Knight, G. J.; Wright, W. W. Br. Polym. J. 1986, 18, 156. 2) Almen, P.; Ericsson, I. Polym. Degrad. Stab. 1995, 50, 223. 3) Botvay, A.; Mathe, A.; Poppl, L.; Rohonczy, J.; Kubatovics, F. J. Appl. Polym. Sci. 1999, 74, 1. 4) Perng, L. -H. J. Polym. Sci., Part A Polym. Chem. 2000, 38, 583. 5) Ohtani, H. ; Ishida, Y. ; Ushiba, M. ; Tsuge, S. J. Anal. Appl. Pyrolysis 2001, 61, 35.

Relative Intensity 99.81 100.00 4.31 68.53 18.90 3.10 16.83 12.90 64.29

279

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

135

EGA thermogram

Averaged mass spectrum 64

48

94 100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

39

170

141

77

32

115 128

50

100

184 202 217 231 246 262

152 150

200

338

310

250

350 [m/z]

300

( m/z range : 29 - 600 amu )

LB : sulfur dioxide

P : phenol 64

S

94

OH

O

O

48 66 44

39

32

55

29

84

79

DE : diphenyl ether

DP : diphenyl 154

170

O 141

39

51

76

51 63

77

39

102 115 128 139

115

65

94

128

155

PP : p-phenylphenol

BF : dibenzofuran 168

O

170

OH

139 39

51

69

84

141

115 98

113

39

PD : 4-phenyl(diphenyl ether)

85

55 63

102

127

a : 1-phenoxy-4-(phenylsulfonyl)benzene 246

310

O O

S O

O 77

39 51 63 77

115 141152 169 102 126

202 217 230 189

51 262

b : 4,4'-sulfonylbis(phenoxybenzene) O

402

O S O

O

217 77 51 39 63

185 115 141 201 92 129 168 215 233 261

152

309 338 370

39

63

185 217 115 141 129 152169 189 97 215 233

280

Tsuge, Ohtani and Watanabe

136 Poly(ether ether ketone); PEEK O

O

CO n

P

OD c PP OF OB BF PD XO DE BO a PF PB DP F

TIC

0

10

b

30 [min]

20

Peak Notation

Assignment of Main Peaks

P

phenol

DP

Molecular Weight

Retention Index

Relative Intensity

94

987

100.0

diphenyl

154

1402

0.1

DE

diphenyl ether

170

1422

1.2

BF

dibenzofuran

168

1551

2.4

166

1620

0.4

182

1658

0.2

170 170

1726 1735

0.2 0.3

186

1748

6.6

184

1893

1.5

196

1909

0.1

198

2041

3.1

-

2193 2197

0.6 0.6

262

2233

0.5

268

2387

0.3

274

2510

0.4

-

2915 3076

3.8 6.9

O

F

fluorene

BO

benzophenone

CO OH

PP

OD

m-phenylphenol p-phenylphenol O

OH

OH OH

OF

O O

XO

xanthone C O

OB

CO

OH

a

9-phenylfluorene 2-hydroxy-9-fluorenone

PD

1,4-diphenoxybenzene

PF PB b c

O O O

CO

unidentified unidentified

O

O

281

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

136

EGA thermogram

Averaged mass spectrum 94

66

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

39 55

31

77

129 141

110

50

100

157 170 150

186

262 200

250

300

[m/z]

( m/z range : 29 - 600 amu )

DE : diphenyl ether

P : phenol 94

OH

170

O 141 51 39

65

39

55

29

77

BF : dibenzofuran

115

94

65

32

79

154

OD : 4-phenoxyphenol 168

O

186

OH

O

139 32 39

51

84

69

98

39

113

OF : 2-dibenzofuranol

51

109

77 65

157

129

93

141

169

188

OB : 4-hydroxybenzophenone 184

OH

121

O

O OH 128 39

92

51 63

77

139

113

155

168

39 51 65

196

a : 9-phenylfluorene

77

93

198

105 141 152 169181

a : 2-hydroxy-9-fluorenone 242

196

O OH 139

32 44 51 65

119 94 113

165 139

32 39 51

215 226

b : unidentified

69 84

168

94 113 121

242

c : unidentified 121

197 121

195

290

288

139

39 51

65 77 93 115

141 168 185 157

213

261 273

29

39

65 51

93 113 89

167 150

176

231 202 229

271 272

282

Tsuge, Ohtani and Watanabe

137 Poly(phenylene sulfide); PPS S n

TM

TE

M DM

TIC

0

DS DT PM 10

Assignment of Main Peaks

M

phenyl mercaptan

DM

HS

DT

diphenyl thioether

DS

PT

ST 30 [min]

20

Peak Notation

Molecular Weight

SH

SH

S

SH

PM

T

SM

diphenylene sulfide

Retention Index

Relative Intensity

110

973

38.7

142

1301

7.5

186

1617

2.4

186

1757

3.4

184

1788

1.2

218

1974

41.4

216

2177

7.4

294

2664

2.5

292

2884

1.4

326

3070

13.1

432

3943

100.0

S

TM SM PT ST T

S

SH SH

S S

S S

S S

S S

TE

SH S

SH

S

[ Related References ] 1) Ehlers, G. F. L.; Fisch, K. R.; Powell, W. R. J. Polym. Sci., Part A Polym. Chem. 1969, 7, 2955. 2) Montaudo, G.; Puglisi, C.; Scamporrino, E.; Vitalini, D. Macromolecules 1986, 19, 2157. 3) Montaudo, G.; Puglisi, C.; Samperi, F. J. Polymer. Sci., Part A Polym. Chem. 1994, 32, 1807. 4) Perng, L. -H. Polym. Degrad. Stab. 2000, 69, 323.

283

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

137

EGA thermogram

Averaged mass spectrum 110 218 100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

185 45

51 69 84 97

33 0

50

128

152 142

100

188

171

150

215

250

200

250

294

326

300

350

450 [m/z]

400

( m/z range : 29 - 600 amu )

M : phenyl mercaptan

DT : diphenyl thioether 110

SH

186

S

66

51 84

51

39

PM : diphenyl mercaptan

92

65 77

39

95

33

109 121

141

152

171

188

DS : diphenylene sulfide 186

184

SH

S 152 39

51 63

93

76

115

126 139

171

188

TM : 4-(phenylthio)benzenethiol

44 51 63

79

139

92

152

113 126

SM : dibenzo[b,d]thiophene-2-thiol 218

216

SH

SH

S

S

184

184 109 51 65 77 45

92

140

171

154 171

128

45

190 203

PT : 1,4-bis(phenylthio)benzene

51

69

108

85 95

127

139

215 152

190

ST : 2-(phenylthio)dibenzo[b,d]thiophene 292

294

S

S

S 185 145

S 51 77 45 65

152 109 139 171 95 129

51 69 77 93 32 44

217 215 230 245 260

115

129 146

247

phenylthio)benzenethiol SH

326

S

260 214 216

TE : 4-(4-(dibenzo[b,d]thiophen-2-ylthio)

T : (4-(4-(phenylthio)phenylthio)benzenethiol S

171 184

432

SH S S

184 217 51 65 77 97108 45

152 171 141

215

260

293

328

S 108 45 69 96

184 171 139 215 152

258 290

322 355

397

284

Tsuge, Ohtani and Watanabe

138 Poly(arylether nitrile); PEN CN O

O n

D

F E

BD CP

TIC

P 0

10

Peak Notation

Assignment of Main Peaks

P BD CP D

phenol 1,3-benzenediol p-cyanophenol unidentified

E

HO

F

unidentified

30 [min]

20

Molecular Weight

Retention Index

Relative Intensity

94 110 119 228

986 1281 1364 2086

10.0 15.1 8.8 100.0

227

2318

15.0

283

3148

49.9

CN O

OH

285

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

138

EGA thermogram

Averaged mass spectrum 228 100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

63 29 44 51 0

89

100 115 126

50

200 144154 171182

100

150

212 200

230 253

312

283

250

300

400 [m/z]

350

( m/z range : 29 - 600 amu )

P : phenol

BD : 1,3-benzenediol

OH

94

110

OH

OH

66 39 55

29

29

79

CP : p-cyanophenol

39

53

82 69

95

D : unidentified 119

HO

228

N

91

64 29

39

52

76

63 29 39 51

110

E : 2-hydroxy-6-(3-hydroxyphenoxy)benzonitrile HO

CN

OH

89

100 115 126 144 154 171182

200 202

F : unidentified

227

283

O

39 52 63

85 99 115126 143 154 170182 199

199 225 254 100 128141 150 174 202 230 39 51 74 87 113

286 310

230

286

Tsuge, Ohtani and Watanabe

2.2.16 Silicone polymers 139 Polydimethylsiloxane; PDMS Si(CH3)2

O

n

D9

D3

D4 D10

D6

D11

D5

D7

D13

D15 D17 D19

D8

D21

15

25

20

TIC

0

10

Peak Notation

Assignment of Main Peaks

30 [min]

20

Molecular Retention Weight Index

D3

S i(CH3 ) 2 O

3

222

D4

Si(CH3 ) 2 O

4

D5

Si(CH3 ) 2 O

D6

Si(CH3 ) 2 O

D7

Si(CH3 ) 2 O

D8

Si(CH3 ) 2 O

D9

S i(CH3 ) 2 O

D10

Si(CH3 ) 2 O

D11

S i(CH3 ) 2 O

D13

S i(CH3 ) 2 O

D15

S i(CH3 ) 2 O

D17

Si(CH3 ) 2 O

D19

Si(CH3 ) 2 O

19

Si(CH3 ) 2 O

21

D21

Relative Intensity

825

100.0

296

996

36.5

5

370

1152

18.2

6

444

1324

24.3

7

518

1497

17.7

8

592

1668

6.7

9

666

1828

2.2

10

740

1984

1.1

11

814

2135

0.8

13

962

2425

0.7

15

1110

2705

0.7

17

1258

2981

0.6

1406

3245

0.4

1554

3509

0.3

[ Related References ] 1) Grassie, N.; MacFarlane, I. G. Eur. Polym. J. 1978, 14, 875. 2) Ballistreri, A.; Garozzo, D.; Montaudo, G. Macromolecules 1984, 17, 1312. 3) Fujimoto, S.; Ohtani, H.; Tsuge, S. Fresenius Z. Anal. Chem. 1988, 331, 342. 4) Fujimoto, S.; Ohtani, H.; Yamagiwa, K.; Tsuge, S. J. High Res. Chromatogr. 1990, 13, 397. 5) Radhakrishnan, T. S. J. Appl. Polym. Sci. 1999, 73, 441.

287

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

139

EGA thermogram

Averaged mass spectrum 207 73 100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

281 133 147 191 96 119 341 355 177 237 267 163 89 115 221 251 295 325 356

45 59 50

100

150

200

250

300

429 399 415

350

503

400

450

550 [m/z]

500

( m/z range : 29 - 600 amu )

D4 : octamethylcyclotetrasiloxane

D3 : hexamethylcyclotrisiloxane 207

O

281 O

Si

Si

O

Si

O

Si

O

Si

O

29

Si

Si

45

96 191 119 133 147 163 177 61 75 89 115

O 133 193 207 249 265 103 125 147 163177 235

45 59 73

D5 : decamethylcyclopentasiloxane

D6 : dodecamethylcyclohexasiloxane 73

73 Si

341

Si

O

O

355

267 Si

Si O

Si

O

O

Si O

Si

Si

Si

O

O

Si

Si

O

O O

429

147

325

356 45 59

251

193

133 154

87

342 45 59

339

D7 : tetradecamethylcycloheptasiloxane O

O

Si

Si

Si

O

Si

O

O

O

O

O

Si

O

Si

Si

O

147

Si

503 487

45 59 87

D9 : octadeamethylcyclononasiloxane 73

O

O

O Si

Si

Si

O

O

O

O

O

Si

207 191

133

Si

O

O

Si

355

Si O

281 267 295 249

356 401 385 415

327 328

457 489

73

O

Si Si

413

D10 : eicosamethylcyclodecasiloxane

Si

147

Si

221

341 415 399 311 342

207 221 265 191

O

Si

327 133

311

73

O

Si

281 Si

45 59 87

251

D8 : hexadecamethylcyclooctasiloxane

73 147

207

133 163

87

Si

O

147

Si

O

Si

Si

Si

Si

Si O

O

O

O

O

Si

Si

Si

Si

O Si O

O

281 221 45 59 87

133

429 355 281 341 356 401 267 295 325 459

207 191

221

D11 : docosamethylcycloundecasiloxane O

73 147

O

Si

Si

Si

O

O

O

Si

Si

O

Si

O

O

Si

Si

133

73

O

Si

221 45 59 87

133

O

O

O

O

503

533

O

Si

Si

Si

Si

Si

Si

O

O

O

O

O

O

Si

Si

221

Si

281

281 341 267 295327

429 461 415

Si

147 O

355

207 191

355 341 267 295 327 356

D13 : hexacosamethylcyclotridecasiloxane

O

O

Si

45 59 87

489

207 191

207

356 429 461

503 535

59

96

145

191

Si

Si

Si

O Si

355 429

267 295

341

356 370

415

461

503

288

Tsuge, Ohtani and Watanabe

140 Polymethylphenylsiloxane; PMPS Si(CH3)(C6H5)

O

P3

n

P5

DP B P4 BC

TIC

T

0

10

Peak Notation B T DP P3

P4

benzene toluene diphenyl O O

3

Si (CH3)(C 6H5 )

O

4

Si (CH3)(C 6H5 )

O

4

Si (CH3)(C 6H5 )

O

4

S i (CH3)(C 6H5 )

O

4

S i (CH3)(C 6H5 )

O

5

S i (CH3)(C 6H5 )

O

5

Si (CH3)(C 6H5 )

O

5

Si (CH3)(C 6H5 ) C H3

O

Si(CH3)(C6H5)

Relative Intensity 100.0 6.0 10.8

(cis form)

408

2336

4.6

(trans form)

408

2357

12.8

(c-c-c-c)

544

2826

0.9

(c-c-t-t)

544

2924

6.6

(c-t-c-t)

544

2944

2.9

(t-t-t-t)

544

2973

1.9

(c-c-c-c-c)

680

3427

2.9

(c-c-c-t-t)

680

3519

23.4

(c-c-t-c-t)

680

3543

25.9

(c-t-t-t-t)

680

3583

31.9

694

3689

15.3

3

Si (CH3)(C 6H5 )

P5

BC

Molecular Retention Weight Index 651 78 767 92 1402 154

Assignment of Main Peaks

Si (CH3)(C 6H5 )

30 [min]

20

5

O

4

S i(CH3 )2

C6H5

(stereoisomer)

[ Related References ] 1) Grassie, N.; MacFarlane, I. G.; Francey, K. F. Eur. Polym. J. 1979, 15, 415. 2) Fujimoto, S.; Ohtani, H.; Tsuge, S. Fresenius Z. Anal. Chem. 1988, 331, 342. 3) Fujimoto, S.; Ohtani, H.; Yamagiwa, K.; Tsuge, S. J. High Res. Chromatogr. 1990, 13, 397.

289

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

140

EGA thermogram

Averaged mass spectrum 197 78 135 315

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

91 51 39

73

50

105119

165 150 179

100

150

259 218 253 209 239 200

285

250

313 329 345 300

373

393 408 432 451

350

400

529

450

550 [m/z]

500

( m/z range : 29 - 600 amu )

P3 : 2,4,6-Trimethyl-2,4,6-triphenyl-

DP : diphenyl

1,3,5,2,4,6-trioxatrisilinane(cis) 154

315 Si O

O Si

Si O

393 150 91 165 195 45 65 77 105 137 209

76 51 63

39

102 115 128 139

253 258

tetraoxatetrasilocane (c-c-t-t)

1,3,5,2,4,6-trioxatrisilinane(trans) 315

451 218

O Si Si

Si O

O Si

179 156

393 91 377 408

329

45 6577 105 135

P4 : 2,4,6,8-Tetramethyl-2,4,6,8-tetraphenyl-1,3,5,7,2,4,6,8-

315 389 435 165 195 253 209 239 267299 329359 469 421

218

P4 : 2,4,6,8-Tetramethyl-2,4,6,8-tetraphenyl-1,3,5,7,2,4,6,8218

451

O Si

451

O Si O

373

529

Si

Si

O

O

Si O

373

195 91 315 389 253 165 77 435 135 209239 267299 329 359 43 65 105 421 468

513 544

P5 : 2,4,6,8,10-Pentamethyl-2,4,6,8,10-pentaphenyl-

179

315 195 91 253 313 389 135 165 210 267 45 77 105 239 285 329 359

468

1,3,5,7,9,2,4,6,8,10-pentaoxapentasilecane (c-c-t-c-t)

197

197 O

Si

Si

O Si

O

10

O

135

Si

Si

O

Si

O O Si

259 313

Si

Si

259 247

O

10

O

135

O

Si

453 375 391 437

525

P5 : 2,4,6,8,10-Pentamethyl-2,4,6,8,10-pentaphenyl-

247

43 73 91 119 159181

375 359 391

313

453 454

525

BC : 2,4,6,8,10-pentamethyl-3,5,7,9-tetraoxa-2,4,6,8,10-

1,3,5,7,9,2,4,6,8,10-pentaoxapentasilecane (c-t-t-t-t)

pentaphenyl-2,4,6,8,10-pentasilaundecane (stereoisomer) 135

197 O

247

375 391

Si O

Si O

Si O

197

Si O

O

313

Si O

O

10

Si

259

Si

Si

Si O

135

43 73 91 119 155181 208

435

P5 : 2,4,6,8,10-Pentamethyl-2,4,6,8,10-pentaphenyl-

1,3,5,7,9,2,4,6,8,10- pentaoxapentasilecane (c-c-c-t-t)

181

529

Si Si O

156 179

91 119

513 544

tetraoxatetrasilocane (t-t-t-t)

tetraoxatetrasilocane (c-t-c-t)

43

529

Si Si O

O

O

373

O

O

165 253 195 77 91 119 150 180 209 239 285 45 65

Si

408

P4 : 2,4,6,8-Tetramethyl-2,4,6,8-tetraphenyl-1,3,5,7,2,4,6,8-

P3 : 2,4,6-Trimethyl-2,4,6-triphenyl-

Si

377

329

Si

453 437

73 525

43 57

209 121 147183

271 255 283

345 403 465 511 542 333 395 451

290

Tsuge, Ohtani and Watanabe

141 Dimethylsiloxane-methylphenylsiloxane copolymer Si(CH3)2

O

Si(CH3)(C6H5)

O

n

D2P

DP2 D3P

B

D3P2

D2P2

DP3

D4P

TIC

D3

P3

D4

0

10

Peak Notation B

Molecular Retention Weight Index 78 655 222 824

Assignment of Main Peaks benzene

D3

Si (CH3)2 O

D4

Si (CH3)2 O

D2P

Si(CH3)2 O

2

Si(CH3 )(C6H5)

D3P

Si(CH3)2 O

3

Si(CH3 )(C6H5)

Si(CH3)2 O

4

Si(CH3 )(C6H5)

O

D4P

S i(CH3)(C6H5) S i(CH3)(C6H5)

Si(CH3) 2 O Si(CH3) 2

2

D3P2 +

P3

DP3

2.2

O

284

1304

33.0

O

358

1447

7.8

O

Si(CH3)(C6 H5) O

O

O

2

Si (C H3) (C6H5) O

Si(CH3) (C 6H 5)

S i(CH3)(C 6H5)

O

S i(CH3)(C 6H5)

O

3

Si(CH3)(C6 H5)

O

3

Si(CH3)(C6 H5)

O

Si(CH3)(C6 H5)

O

2

2

O

3

O

2

S i(CH3)(C6H5)

2

O

432

1620

5.4

(cis form)

346

1789

8.2

(trans form)

346

1833

7.8

(cis form)

420

1911

3.4

(cis form)

420

1921

1.5

(trans form)

420

1938

5.0

(trans form)

420

1947

1.7

(cis form)

556

2047

1.7

2076

4.2

2

2

S i(CH3)(C6H5)

2

O

2

Si(C H3)(C6H 5) O

2

Si(CH3)2

S i(CH3)2

997

O

Si(CH3)(C6 H5) O

Si(CH3)2 O S i(CH3)2

296

Si(C H3)(C6H 5 ) O

O

Si(CH3 )2 O Si(CH3) 2

100.0 6.9

4

S i(CH3) 2 O

D2P2

Relative Intensity

3

S i(CH3) 2 O

DP2

30 [min]

20

2

3

Si(CH3 )2 O

3

Si(CH3 )2 O

3

Si(CH3 )2 O

(cis form)

494

(trans form)

556

(trans form)

S i (C H3 )2 O O

3

Si(CH3)2

O

494

2092

2.0

(cis form)

408

2266

0.7

(trans form)

408

2355

2.1

(c-c)

482

2371

0.8

(c-t)

482

2430

2.1

(t-t)

482

2444

1.1

[ Related References ] 1) Grassie, N.; Francey, K.F. Polym. Degrad . Stab. 1980, 2, 53. 2) Fujimoto, S.; Ohtani, H.; Tsuge, S. Fresenius Z. Anal. Chem. 1988, 331, 342. 3) Fujimoto, S.; Ohtani, H.; Yamagiwa, K.; Tsuge, S. J. High Res. Chromatogr. 1990, 13, 397.

291

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

141

EGA thermogram

Averaged mass spectrum 207 78 73

253 269

135 91

51 45 32

119 147 105

50

100

200

300

400

500

100

165 177

700 ºC

327 343

281 223 239

150

600

programming rate: 20ºC/min

193

200

313

250

300

405 389 417

357 350

400

447

463 477

450

537539 550 [m/z]

500

( m/z range : 29 - 600 amu )

D3P : 2,2,4,4,6,6,8-heptamethyl-8-phenyl-1,3,5,7,2,4,6,8 D2P : 2,2,4,4,6-pentamethyl-6-phenyl-1,3,5,2,4,6-trioxasilinane

-tetraoxatetrasilecane

269

343

Si

Si

O

O

O

Si

Si

253

O 91

45

O Si Si

127 133 147 163177 195207 223 239

105

Si O O

164 191 135156 125 179 205

73 91

32 45

286

327 253 265 281

313

D4P : 2,2,4,4,6,8,8,10-nonamethyl-10-phenylDP2 : 2,2,4,6-tetramethyl-4,6-diphenyl-1,3,5,2,4,6-trioxatrisilinane (cis)

1,3,5,7,9,2,4,6,8,10-pentaoxapentasilecane 166

253 O Si

Si

O

82 98 115

O

Si

Si

331

O

O

Si 3951 69

O

O

10

O

Si

Si

Si

139

32 51 65 77

327

91

119 149165 195 181 105 133

156

156 O

Si O

O

327

195 179

253 239 267

313 343

389

420

D3P2 : 2,2,4,4,6,8,8,10-octamethyl-6,10-diphenyl1,3,5,7,9,2,4,6,8,10-pentaoxapentasilecane (trans)

3245

O

389 253 328 269 195 91 135 165 205 311 343 373 239 79 105 297

P3 : 2,4,6-trimethyl-2,4,6-triphenylcyclotrisiloxane (cis)

135

315 O

Si

Si

O

10

O

Si

Si

Si

O O

Si

197 73 43

91 121 165 149 177

329 313 358

401

463

-tetraoxatetratrisilocane (c-t) 187 389

Si

Si

O

O

Si

467

Si O

91 32 51 78

156 253 135 164 195221 267

311 373 328 359 405

468 451

O

O

Si

Si O

479 267

DP3 : 2,2,4,6,8-pentamethyl-4,6,8-triphenyl-1,3,5,7,2,4,6,8

O

405

Si Si

328

327 O

O

405

O

135 73 91 119

2943

Si

Si

Si Si

346

-tetraoxatetrasilocane (trans)

1,3,5,7,2,4,6,8-tetraoxatetrasilocane (cis) O

315

267 285

D2P2 : 2,2,4,4,6,8-hexamethyl-6,8-diphenyl-1,3,5,7,2,4,6,8

D2P2 : 2,2,4,4,6,8-hexamethyl-6,8-diphenyl-

Si

239 223

73

91

135

165 195 180 209 253 270

393 408

540

292

Tsuge, Ohtani and Watanabe

142 Polymethylsilsesquioxane; PMSQ CH3 Si

O

O Si

T6

O

n

CH3

iT8

T8 T7

Et

T10

iT10 iT10’

TIC

0

10

30 [min]

20

Peak Notation

Assignment of Main Peaks

Molecular Retention Weight Index

Et T6

ethanol hexamethyl-T6

46 402

T7

heptamethyl-ethoxy-T7

506

T8 iT8 T10 iT10 iT10’

octamethyl-T8 isooctamethyl-T8 decamethyl-T10 isodecamethyl-T10 isodecamethyl-T10'

536 536 670 670 670

465 1321 1448 1467 1517 1544 1732 1738 1758

Relative Intensity 100.0 69.1 32.5 42.6 50.6 72.2 4.1 8.1 7.2

293

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

142

EGA thermogram

Averaged mass spectrum 31

45

100

200

300

400

224 253 283 320 195 209 238 261 313 329

73 0

50

100

150

200

250

300

389 405 350

400

600

700 ºC

521 491

447 433

500

programming rate: 20ºC/min

463

450

524 539 581597 567

507

500

600 [m/z]

550

( m/z range : 29 - 600 amu )

T6 : hexamethyl-T6

Et : ethanol

387

31

OH

Si

O

Si

O O

45 O Si O 186 193

142

T7-1 :heptamethyl-ethoxy-T7

O Si O

Si O

O Si 299

253

225

327

357 371

401

T7-2 : heptamethyl-ethoxy-T7 491

O

Si

O

O

491

Si O SiO

O

O

O

Si O O OSi O O Si O Si

387

238

447 431

Si O SiO

Si O O OSi O O Si O Si

461

223

144 172

29

Si

496

223

461 447 431

215

144

29

iT8 : isooctamethyl-iT8

T8 : octamethyl-T8 521 Si O

253

O

521 Si

Si O

O

Si

OO

Si

O

O

Si OO

Si

O Si

253

Si

505 524 417 447 475491

T10 : decamethyl-T10

223

159

S i O Si O O Si O O Si O O Si

32

Si

O

208 246 283 297 224

355 389 419

507 463 491 539

320 O

32

128

Si O Si

O

Si Si

Si

O O O

O

312

Si

208

417 447

505 524 491 538

283

507

549

32

320

Si O

O O

312

iT10‘ : isodecamethyl-iT10' Si O O Si Si O O O O Si Si O O O Si

O

O Si

96

Si

O O O Si O Si O O Si O O Si Si 299 373

iT10 : isodecamethyl-iT10 320

O Si O Si O O O O Si Si O O Si

O

Si O

O

O O

223

158

496

OO Si O S i O Si O

Si

312

O Si

91

183

208 246

283

507

547

294

Tsuge, Ohtani and Watanabe

143 Poly(methyl-phenyl) silsesquioxane; PMPSQ R Si

O

O Si R

B

Et

O

n

R=CH3(20 %), C6H5(80 %)

BP

EB St

TIC

0

10

Peak Notation

Assignment of Main Peaks

Et B EB St BP

ethanol benzene ethylbenzene styrene diphenyl

30 [min]

20

Molecular Retention Weight Index 46 78 106 104 154

466 656 872 895 1398

Relative Intensity 3.2 100.0 0.2 0.5 2.5

295

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

143

EGA thermogram

Averaged mass spectrum 78

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

51 39

74

154

50

100

200 [m/z]

150

( m/z range : 29 - 600 amu )

Et : ethanol

B : benzene 31

78

OH 45

39

EB : ethylbenzene

52 74

St : styrene 78

104 78 91

103 51

106

51 39

63

32

32 39

BP : diphenyl 154

39

51 63

76

102 115 128 139

63

296

Tsuge, Ohtani and Watanabe

2.2.17 Polyurethanes 144 TDI-Polyester polyurethane; PU CONHC6H3(CH3)NHCO(O(CH2)4OCO(CH2)4CO)mO(CH2)4O

n

CP A6

T

THF

A7 LB

A10

A4

B

A2 A3

BD TIC

VA

0

A11 A5

A1 AA 10

Peak Notation LB B THF CP VA BD A1 AA T A2 A3 A4 A5 A6 A7 A8 A9 A10 A11

Assignment of Main Peaks

A8

A9 30 [min]

20

Molecular Retention Weight Index

CO2 etc. 1,3-butadiene tetrahydrofuran cyclopentanone pentanoic acid CH3(CH2)3COOH 1,4-butanediol CH3(CH2)3COO(CH2)2CH=CH2 unidentified 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate OCNC6H3(CH3)NCO CH2=CH(CH2)2OCO(CH2)4COOH (CH2)4OCO(CH2)4COO CH2=CH(CH2)2OCO(CH2)4COO(CH2)2CH=CH2 HO(CH2)4OCO(CH2)4COOH CH2=CH(CH2)2OCO(CH2)4COO(CH2)4OH HO(CH2)4OCO(CH2)4COO(CH2)4OH CH2=CH(CH2)2OCO(CH2)4COO(CH2)4OCO(CH2)3CH3 HO(CH2)4OCO(CH2)4COO(CH2)4OCO(CH2)3CH3 COO(CH2)4OCO(CH2)4COO(CH2)4OCO(CH2)4 CH2=CH(CH2)2OCO(CH2)4COO(CH2)4OCO(CH2)4COO(CH2)2CH=CH2

54 72 84 102 90 156 128 174 200 200 254 218 272 290 356 374 400 454

150 395 618 790 819 952 1077 1183 1370 1535 1571 1735 1824 2034 2342 2418 2723 3003 3080

[ Related References ] 1) Ohtani, H.; Kimura, T.; Okamoto, K.; Tsuge, S.; Nagataki, Y.; Miyata, K. J. Anal. Appl. Pyrolysis 1987, 12, 115. 2) Lattimer, R. P.; Muenster, H.; Budzikiewicz, H. J. Anal. Appl. Pyrolysis 1990, 17, 237.

Relative Intensity 53.2 13.9 55.0 100.0 1.4 31.5 1.4 1.4 50.4 15.8 6.8 11.5 2.5 43.0 46.8 2.1 3.6 18.1 8.7

297

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

144

EGA thermogram

Averaged mass spectrum 55

100

41 31

71

200

300

400

500

600

84

700 ºC

programming rate: 20ºC/min

129 111 145 146

101 50

100

174 173

201 202

150

250 [m/z]

200

( m/z range : 29 - 600 amu )

B : 1,3-butadiene

THF : tetrahydrofuran 39

42

54

O

72 29

29

53

CP : cyclopentanone

BD : 1,4-butanediol 55

O

42

OH HO

31 84 41

71

57 29

69

AA : unidentified

A2 : adipic acid, 4-butenyl ester 55

54

OH

O 129

O

O

111 41 83

29 39

84

29

101

73

67

A4 : dibut-3-enyl adipate

141

A6 : 3-butenyl 4-hydroxybutyl adipate

55

55

O

O

O

O

129

O HO

O

O 129

71

183 29 43

101

83

141 155 165

A11 : dibut-3-enyl'-butane-1,4-diyl diadipate 55

O

O O

O

O

O O

O

129 111

29 41

101 7183

183

141 165

201 202

O

111

111 29 39

182

255 311

384

71

83

183

101 141 154 170

201 202

241

298

Tsuge, Ohtani and Watanabe

145 TDI-Polyether polyurethane; PU CONHC6H3(CH3)NHCO(O(CH2)4O)m

E3

T

n

E4 C

E2

B5

O2

B4 B3

O3

E5

A BA THF TIC

P LB

B

10

DF BO

0

B1

10

Peak Notation LB P B BA THF DF BO B1 E1 O1 T E2 O2 A B3 E3 O3 B4 E4 B5 E5 C

20

E1 O1

Assignment of Main Peaks CO2 propane n-butane butylaldehyde tetrahydrofuran O 2,3-dihydrofuran 1-butanol dibutyl ether CH3(CH2)3O(CH2)3CH3 CH3CH2O(CH2)4OCH=CH2 CH3(CH2)3O(CH2)4OH 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate OCNC6H3(CH3)NCO CH3CH2O[(CH2)4O]2CH=CH2 CH3(CH2)3O[(CH2)4O]2H unidentified CH3(CH2)3O[(CH2)4O]2(CH2)3CH3 CH3CH2O[(CH2)4O]3CH=CH2 CH3(CH2)3O[(CH2)4O]3H CH3(CH2)3O[(CH2)4O]3(CH2)3CH3 CH3CH2O[(CH2)4O]4CH=CH2 CH3(CH2)3O[(CH2)4O]4(CH2)3CH3 CH3CH2O[(CH2)4O]5CH=CH2 unidentified

30 [min]

20

Molecular Retention Weight Index

Relative Intensity

44 44 58 72 72 70 74 130 144 146 174

150 300 400 608 620 651 655 885 1074 1141 1371

6.3 25.2 22.5 10.1 42.7 11.9 4.7 2.2 7.8 5.3 100.0

216 218 274 288 290 346 360 418 432 -

1552 1618 1694 1821 2028 2095 2245 2501 2725 2794 2973

8.5 6.5 1.6 2.2 11.2 3.3 5.5 15.3 7.4 0.8 14.7

299

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

145

EGA thermogram

Averaged mass spectrum 71

100

55

41

200

300

400

29

85 91

106

50

500

600

700 ºC

programming rate: 20ºC/min

145 148

174

129

173

100

200 [m/z]

150

( m/z range : 29 - 600 amu )

E1 : vinyl-4-ethoxy butylether

BA : butylaldehyde 44

57

O 29

O

O

41 29

100

71

72

85

57 116

T : 2,4-tolylene diisocyanate

E2 : 1-ethoxy-4-(4-vinyloxy)butoxy)butane 71

174 O

O C

C N

O

O

145

O

N 146 39

51

91

64 76

43 173

85

98

129 111

147

E3 : 3,8,13,18-tetraoxaicos-1-ene

O2 : 4-(4-butoxybutoxy)butan-1-ol 55

57

29

118 117

71

71

O

O

O

O

OH

O

O

43 29

85

43 55

100 116 129

145 146

85

29

129

100

174

145

111

174

E4 : 3,8,13,18,23-pentaoxapentacos-1-ene

B4 : 5,10,15,20-tetraoxatetracosane 71

71 O

O

O

O

43

43

55

85

29

98

111 124

143 148

174

O

O

O

O

O

129

55 85 100

29

143 147

116

217

C : unidentified

B5 : 5,10,15,20,25-pentaoxanonacosane

71

71 O

O

O

O

O

129 55

43 29

55

85 98

124 114

143 147

43 173

215

29

85 100 115

143 147

173

217

300

Tsuge, Ohtani and Watanabe

146 MDI-Polylactone polyurethane; PU CONHC6H4CH2C6H4NHCO(O(CH2)5CO)mO(CH2)4O

n

M

CL

TIC

LB HF

CP

HA

0

D’ D

A

T

C

10

Peak Notation

30 [min]

20

Molecular Retention Weight Index

Assignment of Main Peaks

Relative Intensity

LB

propylene etc.

-

295

0.4

HF

tetrahydrofuran

72

613

0.2

CP

cyclopentanone

84

789

1.9

HA

5-hexenoic acid

114

994

2.6

CL

ε -caprolactone

114

1157

24.3

O

CH2=CH(CH2)3COOH

O O C

A

CH3(CH2)4OCO(CH2)5OH

202

1408

1.3

D’

CH2=CH(CH2)3COO(CH2)5COOH

228

1735

4.4

228

1785

1.6

250

2139

100.0

342

2598

1.5

410

2645

3.2

D M T C

(CH2)5COO(CH2)5COO

(CL dimer)

diphenylmethane diisocyanate

OCNC6H4CH2C6H4NCO

(CH2)5COO(CH2)5COO(CH2)5COO

(CL trimer)

CH2=CH(CH2)3COO(CH2)5COO(CH2)5COO(CH2)3CH=CH2

301

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

146

EGA thermogram

Averaged mass spectrum 55 42 100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

29

84

115

70

97

50

132 128

152 165

100

150

250

208 221

180 193

200

300 [m/z]

250

( m/z range : 29 - 600 amu )

CP : cyclopentanone

HF : tetrahydrofuran 42

55

O

O

84

72 41 29 29

CL : ε -caprolactone

HA : 5-hexenoic acid 60

39

67

55

O

O

42

OH

68

O 84

29

96

29

114

87

114 97

D' : 6-(5-hexenoyloxy)hexanoic acid

A : pentyl-6-hydroxyhexanoate 41

70

O

69

69

O

56

OH

97

97

55

O

OH

O

41

115

O

114 31 29

87

128137 152

D : 1,8-dioxacyclotetradecane-2,9-dione (ε -caprolactone dimer) O O

55

O

41

C

N

N

250 C O

O

69

97 84

210

M : diphenylmethane diisocyanate

115

29

128 133 156

81

169

208

O 128 141 156 169

221 39 51 63

210

77

132 90 104 125

165180 152 190

231

T : 1,8,15-trioxacyclohenicosane-2,9,16-trione (CL trimer) C : 6-oxo-6-(6-oxo-6-(pent-4-enyloxy)hexyloxy)hexylhex-5-enoate 115

115

69

O

O

O

29

O

O O

O

55 41

O O

O

97 41 55

183

O

69 97 84

O

128

229250 281

324

401

29

81

128 141

169 201

297 250 281

430

302

Tsuge, Ohtani and Watanabe

147 Urethane rubber; U CONHC6H4CH2C6H4NHCO(O(CH2)2OCO(CH2)4CO)mO(CH2)2O

n

CP MI

LB

D

A E M EG

TIC

B C

0

O1

F O3

O 2’ O2

O4

10

Peak Notation

30 [min]

20

Assignment of Main Peaks

Molecular Retention Weight Index

Relative Intensity

LB A EG CP B C O1

CO2 acetaldehyde ? ethylene glycol cyclopentanone 1,4-butanediol unidentified CH3(CH2)3COO(CH2)2OH

44 44 62 84 90 124 146

150 409 705 790 947 1024 1129

58.2 20.3 12.4 100.0 6.5 0.9 3.6

M O2 O2’ E F O3 MI O4

(CH2)2OCO(CH2)4COO CH2=CHOCO(CH2)4COO(CH2)2OH CH3CH2OCO(CH2)4COO(CH2)2OH CH3(CH2)3COO(CH2)2OCO(CH2)3CH3 unidentified HO(CH2)2OCO(CH2)4COO(CH2)2OH diphenylmethane diisocyanate OCNC6H4CH2C6H4NCO CH3(CH2)3COO(CH2)2OCO(CH2)4COO(CH2)2OH

172 216 218 230 234 250 318

1350 1531 1592 1748 1803 1867 2137 2262

9.3 1.1 2.2 4.4 4.2 6.2 39.6 3.8

344

2543

33.0

D

( CH 2) 2O C O (CH2)4C OO

2

303

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

147

EGA thermogram

Averaged mass spectrum 55

98

100

200

300

400

500

600

84

700 ºC

programming rate: 20ºC/min

41

173

111

31

154 129 142

69 50

100

174 188

150

213 200

250

350 [m/z]

300

( m/z range : 29 - 600 amu )

A : acetaldehyde

EG : ethylene glycol

29

31

HO

44

O

OH

43

62 61

58

CP : cyclopentanone

B : 1,4-butanediol 42

55

O

OH HO

31 84 41

57 29

84

O1 : 2-hydroxyethyl pentanoate

M : 1,4-dioxecane-5,10-dione

85

O

57

142

10

84 41

41

103 104

73

O

O2' : ethyl 2-hydroxyethyl adipate

29

O

O

111

O

154

OH

O O

54 101

69

129 142

N

N

68

31

137

173

D : 1,4,11,14-tetraoxacycloicosane-5,10,15,20-tetraone O

173 99

C 55

165180 152 193

86 41

231

29

68

20

O

113

221

132

O

O 208

103 104 125

109

82

250 O

77

126

41

174

MI : diphenylmethane diisocyanate

29

98

O

155

83

31

39 51 63

99

O

173

45

129

68

E : ethane-1,2-diyl dipentanoate O

55

C

112

O O

O

55

O

OH

O

29

71

69

155 126 142

174

217

O O

O O 285

344

304

Tsuge, Ohtani and Watanabe

2.2.18 Cellulose-type polymers 148 Cellulose CH2OH H

O

O

H OH

H

H

OH

H n

M

PA LB P

TIC

AO

LO G L’

MF FO FA

L

0

10

Peak Notation

Assignment of Main Peaks

LB PA M AO

CO2 pyruvic aldehyde CH3COCHO hydroxyacetaldehyde etc. acetone alcohol CH3COCH2OH O

FA FO MF

Molecular Retention Weight Index

O

O

5-methyl-2-furfural O

O

O

H3C

C H O

LO L’ L

3,6-dianhydro-α-glucopyranose ?

O

O O

150 650 654 651

18.7 23.2 58.9 8.8

96

833

7.5

98

924

6.9

110

963

6.8

110

998

17.6

O OH

144 ?

1190

8.9

126

1229

20.8

144

1309

18.7

162

1483

100.0

O

O

O

O

levoglucosan

O

O

levoglucosenone OH

44 72 74

C H2 O H

P G

Relative Intensity

C H O

2-furfural H3 C

30 [min]

20

OH OH

O OH

[ Related References ] 1) Schulten, H. -R.; Toertz, W. Anal. Chem. 1978, 50, 428. 2) Schulten, H. -R.; Bahr, U.; Goertz, W. J. Anal. Appl. Pyrolysis 1981, 3, 137. 3) Shafizadeh, F. J. Anal. Appl. Pyrolysis 1982, 3, 283. 4) Shafizadeh, F. J. Appl. Polym. Sci., Appl. Polym. Symp. 1983, 37, 723. 5) van der Kaaden, A. V.; Haverkamp, J.; Boon, J. J.; de Leeuw, J. W.; J. Anal. Appl. Pyrolysis 1983, 5, 199. 6) Evans, R. J.; Milne, T. A.; Soltys, M. N.; Schulten, H. –R. J. Anal. Appl. Pyrolysis 1984, 6, 273. 7) Piskorz, J.; Radlein, D.; Scott, D. S. J. Anal. Appl. Pyrolysis 1986, 9, 121. 8) Funazukuri, T.; Hudgins, R. R.; Silveston, P. L. Ind. Eng. Process Des. Dev. 1986, 25, 172. 9) Richards, G. N. J. Anal. Appl. Pyrolysis 1987, 10, 251. 10) Pouwels, A.; Eijkel, G. B.; Boon, J. J J. Anal. Appl. Pyrolysis 1989, 14, 237. 11) Yano, T.; Ohtani, H.; Tsuge, S.; Obokata, T. Tappi J. 1991, 74, 197. 12) Kelly, J.; Mackey, M.; Helleur, R. J. J. Anal. Appl. Pyrolysis 1991, 19, 105. 13) Yano, T.; Ohtani, H.; Tsuge, S.; Obokata, T. Analyst, 1992, 117, 849. 14) Ishida, Y. ; Ohtani, H. ; Tsuge, S. ; Yano, T. Anal. Chem. 1994, 66, 1444.

305

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

148

EGA thermogram

Averaged mass spectrum 29 43 100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

60 70

98

85

50

114

126

138

152

100

164 200 [m/z]

150

( m/z range : 29 - 600 amu )

PA : pyruvic aldehyde

M : hydroxyacetaldehyde

43

31

O

HO O

O 29 56

60

42

72

72

FA : 2-furfural

AO : acetone alcohol 43

96

O

O OH

O 39

31

74

29

53

55

FO : 5-methylfuran-2(3H)-one

P : 5-(hydroxymethyl)dihydro-2(3H)-furanone 98

H3C

O

82

67

114

O

O

O

OH 58

55 42

29 69

29

84

110

42

128

G : 3,6-dianhydro-α -glucopyranose 43

97

O O OH

69

85

LO : 5-(hydroxymethyl)-2-furfural O

57

29

68

126

41

O

O

85

69 96

OH

116 128

29

L' : 2-hydroxy-6,8-dioxabicyclo[3.2.1]octan-4-one

81

29

109

60

O

O

O HO

97

O

OH 43

140

L : levoglucosan

O 144 87

53

142

OH

57 73

69 113

29 126 146

43 89

98

115 126 144

167 182

OH

205 220

306

Tsuge, Ohtani and Watanabe

149 Methylcellulose; MC CH2OR H

B

O

O

H OR

H

H

OR

H n

R=H , CH3

A LB

IP TIC

0

10

Peak Notation LB A IP B

Assignment of Main Peaks CO2 + acetaldehyde methanol isopentane O

O

30 [min]

20

Molecular Retention Weight Index 44; 44 32 72 74

[ Related Reference ] 1) Schwarzinger, C.; Tanczos, I.; Schmidt, H. J. Anal. Appl. Pyrolysis 2002, 62, 179.

150 320 454 580

Relative Intensity 80.3 100.0 19.5 94.5

307

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

149

EGA thermogram

Averaged mass spectrum 45 29 100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

55

71

87

50

97

111

127

141

100

155

173

205

150

250 [m/z]

200

( m/z range : 29 - 600 amu )

A : methanol

B : methoxyacetaldehyde 31

45

H H

O

O H

H 29

44

58

55

74

O

308

Tsuge, Ohtani and Watanabe

150 Ethylcellulose CH2 OC2H5 H

O H OC2H5 H

O H

B

OC2 H5

H

n

C F

EO

D

K

HI G

J

E LB

A 10

20

TIC

0

10

Peak Notation

Assignment of Main Peaks

LB EO A B C D E F G H I J K

propylene etc. ethanol unidentified unidentified unidentified unidentified unidentified unidentified unidentified unidentified unidentified unidentified unidentified

30 [min]

20

Molecular Retention Weight Index 295 465 46 654 82 ? 1175 156 1199 150 1270 172 ? 1293 1490 200 1611 198 1724 262 1775 290 2438 246 2752 318

Relative Intensity 65.5 100.0 53.5 29.2 25.0 7.1 16.1 21.3 16.9 18.6 17.4 16.5 24.3

309

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

150

EGA thermogram

Averaged mass spectrum 31 59 43 97

71

100

200

300

400

500

85

600

700 ºC

programming rate: 20ºC/min

113

125 141 155 169 183

50

100

150

201 202

229

246

200

300 [m/z]

250

( m/z range : 29 - 600 amu )

A : unidentified

EO : ethanol 31

59

31

OH 45

45 69

B : unidentified

C : unidentified 83

83 156

43 29

78

111

43 55

99

111

29

71

55

127

71

E : unidentified

156

99 127

F : unidentified 97

113 141

59

171

85

29 59

31

69

41

125

85

115

143

41

200 97

69

125

155

H : unidentified

156

170

202 217

I : unidentified

59

59

141

101 73 85

129

43

86

29

116

29

159 145 174 173

43

73

262 199 216

101

117 129 157171 187 199 216

244

244

290

K : unidentified

J : unidentified

116

125

116 59 29

73 43

201

81 101 139155

183

202

247 259

301

333

59 85 172 217 2943 73 101 129 155 201 245

319 291

361

405

508

310

Tsuge, Ohtani and Watanabe

151 Cellulose acetate; CA CH2OCOCH3 H

O H OCOCH3 H

O

H

OCOCH3

H

G

LB

n

I F A

B

C D 5

H

JK

E

10

20

15

AA

TIC

0

10

Peak Notation

Assignment of Main Peaks

LB A AA B C D

CO2, ketene H2C=CO, etc. acetic acid acetic anhydride 2-hydroxyethyl acetate unidentified (acetic ester) unidentified

E F G H I J K

O

O

unidentified unidentified unidentified unidentified unidentified unidentified

(acetic ester)

30 [min]

20

Molecular Retention Weight Index

Relative Intensity

60 102 104 110 110

150 623 721 766 846 984

40.6 100.0 0.4 15.2 2.8 0.8

124

1288

0.9

186

1328

3.3

158 170 186 184 228

1344 1371 1505 1556 1599

6.1 2.8 4.1 2.8 2.6

311

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

151

EGA thermogram

Averaged mass spectrum 43

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

60

29

97

81

69 50

110

126

139

100

157 200 [m/z]

150

( m/z range : 29 - 600 amu )

AA : acetic anhydride

A : acetic acid 45

43

O

O

O

60

OH

O

29

94

60 65

62

B : 2-hydroxyethyl acetate

C : unidentified

43

53

O

81

HO O 29

73

60

43

E : 4,6-dimethyl-2H-pyran-2-one

63

95

F : unidentified

96

O

31

91

43

124

53 43

O 81

114 109

67

57

29

G : unidentified

73

156

43

82

82 54 71

98 110 125

142

184

54

29

99

71

113 125

142

184

J : unidentified

I : unidentified

43

43

70 82 31

126 141

H : unidentified

43

29

86 98

54

69 100 112 124

142 157 171 185

29

54

82

100 112 126

142 171 185

312

Tsuge, Ohtani and Watanabe

152 Cellulose acetate-propionate; CAP CH2 OR H

O

O

H OR

H

H

OR

R=COCH3 or COC2H5

H n

DB

LB AP BP D

AC TIC

A

P

0

PA

B

E F G

C

H

10

BS 30 [min]

20

Peak Notation

Assignment of Main Peaks

LB AC A P AP PA B C D E F G H DB BP BS

CO2 , propylene etc. acrolein acetic acid propionic acid hydroxy-2-butanone ? propionic anhydride unidentified unidentified unidentified unidentified unidentified unidentified C O O C 4H 9 unidentified dibutyl phthalate (plasticizer) C O O C 4H9 butyl palmitate CH3(CH2)14COO(CH2)3CH3 (plasticizer) butyl stearate CH3(CH2)16COO(CH2)3CH3 (plasticizer)

Molecular Retention Weight Index 56 60 74 88 130 130 180 182 222 ? 206 ? 212 256 278 312 340

150 490 607 773 868 937 985 1335 1528 1607 1624 1686 1782 1981 2150 2350

Relative Intensity 37.5 8.1 3.9 100.0 23.6 2.2 1.1 2.6 5.2 3.8 4.4 4.7 5.9 73.4 12.5 3.8

313

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

152

EGA thermogram

Averaged mass spectrum 57

149

29

100

200

300

400

500

74

45

600

700 ºC

programming rate: 20ºC/min

81

97104

50

126135

177

100

150

205

223

2 00

300 [m/z]

250

( m/z range : 29 - 600 amu )

A : acetic acid

AC : acrolein 56

43

O

O OH 60

29

44 29

72

P : propionic acid

AP : hydroxy-2-butanone

29

O

82

57

O

74

45

29

OH

HO

57 87

42

84

D : unidentified

PA : propionic anhydride 57

O

57

O

29

O 29 82 43

72

83

95

39

110

E : unidentified

75

131139 156

99 110

F : 4-(1,1,3,3-tetramethylbutyl) phenol 149

O O O

212

135

O HO

29

39

57 65 76

177 93 105 121132

166

195

222

29

41

57 95

65 77

107 119

149

206

H : unidentified

G : unidentified

57

57

29

29 41

69 82

98 113 98 110 126 138 156 171 185

213

39

68

85

126

139

154 170

182 200

314

Tsuge, Ohtani and Watanabe

153 Cellulose acetate-butyrate; CAB CH2OR H

O

O

H OR

H

H

OR

R=COCH3 or COC3H7

H n

LB

C AB

A MB B

F G

TIC

0

10

Peak Notation

Assignment of Main Peaks

LB MB A C B AB F G

CO2 methylbutene acetic acid 2-hydroxyethyl acetate butanoic acid CH3CH2CH2COOCOCH3 unidentified unidentified

30 [min]

20

Molecular Retention Weight Index 44 70 60 88 130 -

150 480 608 766 829 955 1328 1344

Relative Intensity 27.8 7.4 100.0 22.5 79.8 14.6 4.1 5.2

315

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

153

EGA thermogram

Averaged mass spectrum 43

100

200

300

400

500

60

600

700 ºC

programming rate: 20ºC/min

29

71

81

97

50

109

126

100

200 [m/z]

150

( m/z range : 29 - 600 amu )

MB : methylbutene

A : acetic acid 45

55

O

70

60

OH 39

29

29

82

62

B : n-butanoic acid

C : 2-hydroxyethyl acetate 43

60

O

O

HO OH

O 73

41 29

29

73

60

88

91

112

F : unidentified

AB : acetic butyric anhydride 43

43

O

O 71

O 114 29

87

55

101

29

110

G : unidentified 43

82 29

54 72

99

125

142

184

57 70

86 98

126135

156

316

Tsuge, Ohtani and Watanabe

154 Hydroxyethylcellulose; HEC CH2OR H

O H OR

H

H

OR

O H

n

R=H , or(CH2)2OH

LB C E D

A B

AA

F ED TIC

G

HA

0

10

Peak Notation LB AA HA ED A

Assignment of Main Peaks CO2 acetaldehyde hydroxyacetaldehyde ethylene glycol O

O OH

B C D E F G

diethylene glycol HO(CH2CH2O)3H HO(CH2CH2O)3CH2CHO HO(CH2CH2O)4H HO(CH2CH2O)4CH2CHO HO(CH2CH2O)5H [ Related Reference ] 1) Arisz, P. W.; Boon, J. J. J. Anal. Appl. Pyrolysis 1993, 25, 371.

30 [min]

20

Molecular Retention Weight Index

Relative Intensity

44 44 60 62

150 403 650 706

104

906

66.4

110 150 192 194 236 238

982 1239 1470 1514 1745 1796

100.0 84.0 44.9 43.0 19.2 14.7

94.9 35.3 14.5 89.4

317

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

154

EGA thermogram

Averaged mass spectrum 45

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

31 58

89 90

75

112 119

50

133

100

200 [m/z]

150

( m/z range : 29 - 600 amu )

AA : acetaldehyde

HA : hydroxyacetaldehyde 31

29

HO

O

O 44

58

42

60

72

A : 1,4-dioxan-2-ol

ED : ethylene glycol 31

45

HO

O

OH

O

58 29

OH 74 43

62 61

87

86

C : triethylene glycol

B : diethylene glycol 45

45

O HO

OH

58

D : 2-(2-(2-hydroxyethoxy)ethoxy)ethoxy)

HO

O

O

O

45

O

58

31

163

F : 14-hydroxy-3,6,9,12-tetraoxatetradecan-1-al

75

45 O

O

O

O

O

O

OH

119 133

163

O

O

O

OH

89

58 73

90

O

HO

O

87 31

119

G : pentaethylene glycol

45 HO

105

OH

89 119 103 117 133

75

O

HO

87 58

89 90

75

O

E : tetraethylene glycol

acetaldehyde 45

58

31

110

96

O

HO

75 76

31

31

104 103

103 117 119 133 147

163 175

31

58

73

119 133 103 115

151 163

195

318

Tsuge, Ohtani and Watanabe

155 Carboxymethyl cellulose; CMC CH2OR H

LB

AA TIC

O H OR

H

H

OR

O H n

R=H , or CH2COOH Degree of etheration 0.8~1.0

BD

HA AO

A

0

10

Peak Notation

Assignment of Main Peaks

LB AA HA BD AO

CO2 acetaldehyde hydroxyacetaldehyde 2,3-butanedione acetone alcohol

30 [min]

20

Molecular Retention Weight Index

Relative Intensity

44 44 60 86 74

150 403 653 690 707

100.0 6.8 4.4 3.2 8.5

126

1061

2.0

O

A

OH

319

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

155

EGA thermogram

Averaged mass spectrum 44

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

29

57

85

69

50

91 150 [m/z]

100

( m/z range : 29 - 600 amu )

AA : acetaldehyde

HA : hydroxyacetaldehyde 31

29

HO

O

O

43

58

44

60

72

AO : acetone alcohol

BD : 2,3-butanedione 43

O

43

O

OH O 86

60

31

70

55

A : 2-hydroxy-3,4-dimethyl-2-cyclopenten-1-one 126

O OH 41 111

56 69 31

83 97

31 74

320

Tsuge, Ohtani and Watanabe

2.2.19 The other natural polymers, etc 156 Glue

LB

G H

B C

A TIC

E F

D 0

10

Peak Notation

30 [min]

20

Assignment of Main Peaks

Molecular Retention Weight Index

Relative Intensity

LB

CO2

44

150

A

acetaldehyde

44

408

5.4

B

pyrrole

67

755

15.3

C

toluene

92

766

6.4

D

1-ethylpyrrole

95

814

1.1

E

2-methylpyrrole

81

844

3.3

F

phenol

94

985

2.7

154

1781

45.5

210

2221

13.0

N

G

O

N

N

H N

O

N

100.0

O

H

N N O

OH

321

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

156

EGA thermogram

Averaged mass spectrum 44

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

55

70

29

84

94 111

50

124 134

100

154

170

186 192

150

210 250 [m/z]

200

( m/z range : 29 - 600 amu )

A : acetaldehyde

B : pyrrole

29

O

67

H N

44

41

64

33

81

52

52

D : 1-ethylpyrrole

C : toluene 91

95

80

N 44 29 39

65

51

53

67

89

F : phenol

E : 2-methylpyrrole 80

H N

94

OH

53 39

41

29

G : hexahydropyrrolo[1,2-a]pyrazine-1,4-dione N N

O N

41

86 70 98

55 126 135

166

186

29

N

124

41

55 30

107

70 154

83

O

81

H : 2-hydroxyoctahydrodipyrrolo[1,2-a:1',2'-d]pyrazine-5,10-dio

111

O

65 55

29

93

66

OH 210

O 96 112

138

154 165 182193

223

322

Tsuge, Ohtani and Watanabe

157 Shellac CH2OH (CH2)5 CHOH CH (CH2)7 O O

H

n

O O

R R

D E

FG

LB B

TIC

A

C

0

10

Peak Notation LB A B C D E F G H

Assignment of Main Peaks CO2 unidentified CH3(CH2)5CHO (CH3)2C=CH(CH2)2CH=C(CH3)2 unidentified unidentified unidentified unidentified unidentified

30 [min]

20

Molecular Retention Weight Index 44 114 138 -

[ Related Reference ] 1) Wang, L.; Ishida, Y.; Ohtani, H.; Tsuge, S.; Nakayama, T. Anal. Chem. 1999, 71, 1316.

150 842 902 995 1181 1485 1912 1961 2256

Relative Intensity 54.1 4.3 7.4 5.9 56.7 88.1 25.3 38.3 100.0

323

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

157

EGA thermogram

Averaged mass spectrum 55

41 67

81

91

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

131

29

105

50

135 148

100

150

203

217

171 187189

232

244

200

300 [m/z]

250

( m/z range : 29 - 600 amu )

B : heptanal

A : unidentified 67

96

70

41

O

55

39 53

29

81

81

29

96 108

110

128

D : unidentified

C : 2,7-dimethyl-2,6-octadiene

69

69 55

41 41

84

29 82

55

29

95

107

123

E : unidentified 55

97

138

112

F : unidentified 189

73 83

41

111 204 91

29

98

129 144

107

77

154 162174

41 55 67 213

G : unidentified

133 131

159 171 175

29

H : unidentified 113

173 91

55 41 29

216 234

73

117

131 145

77

85 102

131 141 148

41

216 234 256

29

55

67

155 174

246 189

202

218

324

Tsuge, Ohtani and Watanabe

158 Chitin CH2OH H

LB

O

O

H OH

H

H

NHCOCH3

H n

C D

B HA A TIC

AAc

AAm

Pr Pd

0

10

Peak Notation LB A HA AAc Pd Pr AAm B C D

Assignment of Main Peaks CO2 etc. acetaldehyde hydroxyacetaldehyde acetic acid pyridine pyrrole acetamide C6H7NO2 ? C7H7NO2 ? unidentified

30 [min]

20

Molecular Retention Weight Index 44 60 60 79 67 59 125 137 185

? ? ?

150 408 651 607 748 757 782 1010 1224 1894

Relative Intensity 65.7 13.6 12.6 56.9 3.7 3.6 33.4 33.7 25.0 100.0

[ Related References ] 1) van der Kaaden, A.; Boon, J. J.; de Leeuw, J. W.; de Lange, F.; Schuyl, P. J. W. Anal. Chem. 1984, 56, 2160. 2) Lal, G. S.; Hayes, E. R. J. Anal. Appl. Pyrolysis 1984, 6, 183. 3) Franich, R. A.; Goodin, S. J. J. Anal. Appl. Pyrolysis 1984, 7, 91. 4) Davies, D. H.; Hayes, E. R.; Lal, G. S. R. A. A. Muzzarelli, C. Jeuniaux, G. W. Gooday (Eds.), Chitin in Nature and Technology, Plenum Press, New York 1986, 365. 5) Sato, H. ; Tsuge, S. ; Ohtani, H. ; Aoi, K. ; Takasu, A. ; Okada, M. Macromolecules 1997, 30, 4030. 6) Sato, H. ; Mizutani, S. ; Tsuge, S. ; Ohtani, H. ; Aoi, K. ; Takasu, A. ; Okada, M. ; Kobayashi, S. ; Kiyosato, T.; Shoda, S. Anal. Chem. 1998, 70, 7. 7) Sato, H. ; Ohtani, H. ; Tsuge, S. ; Aoi, K. ; Takasu, A. ; Okada, M. Macromolecules 2000, 33, 357.

325

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

158

EGA thermogram

Averaged mass spectrum 44

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

59

29

84 91

69

105

50

125

139

152

100

167 200 [m/z]

150

( m/z range : 29 - 600 amu )

A : acetaldehyde

HA : hydroxyacetaldehyde 31

44

29

HO

O

O

60

42

56

72

62

78

Pd : pyridine

AAc : acetic acid 43

79

N

O 60

52

OH

29

44

31

82

62

Pr : pyrrole

97

69

AAm : acetamide 67

H N

59

O

44

NH 2 39

55

29

79

31

B : C6H7NO2

C : C7H7NO2 43

109

30

73 39 68 86

58

95

109

29

125

D : C7H9NO2 59

43 101 114 72 29

85

130139

160

185

54

81

137

95

122

326

Tsuge, Ohtani and Watanabe

159 Chitosan CH2OH H

LB

O

O

H OH

H

H

NH2

H n

HA D A TIC

AP

AA P

0

10

Peak Notation LB A HA AA P AP D

Assignment of Main Peaks CO2 acetaldehyde hydroxyacetaldehyde ? acetic acid pyrazine acetylpyrazine C7H9NO2 ?

30 [min]

20

Molecular Retention Weight Index 44 44 60 60 80 122 139

150 408 ? 656 602 732 1025 ? 1869

Relative Intensity 100.0 31.0 38.0 23.0 20.6 15.4 35.3

[ Related References ] 1) Mattai, J.; Hayes, E. R. J. Anal. Appl. Pyrolysis 1982, 3, 327. 2) Lal, G. S.; Hayes, E. R. J. Anal. Appl. Pyrolysis 1984, 6, 183. 3) Sato, H. ; Mizutani, S. ; Tsuge, S. ; Ohtani, H. ; Aoi, K. ; Takasu, A. ; Okada, M. ; Kobayashi, S. ; Kiyosato, T. ; Shoda, S. Anal. Chem. 1998, 70, 7.

327

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

159

EGA thermogram

Averaged mass spectrum 44

29

100

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

55

80

67

94 109

50

131132

146

100

160 200 [m/z]

150

( m/z range : 29 - 600 amu )

A : acetaldehyde

HA : hydroxyacetaldehyde 31

44

29

HO

O

O

60

42

58

AA : acetic acid

72

79

P : pyrazine 43

60

80

N

O OH

N 53

29 70

79

38

D : C7H9NO2

AP : acetylpyrazine O

29

122

43

N

59

80 52

94

N

43 101 114

29

67

107

72 29

84

130139

158

185

328

Tsuge, Ohtani and Watanabe

160 Ivory

LB

D

P AN TIC

C CP

MP

0

10

Peak Notation LB AN CP P MP C

Assignment of Main Peaks CO2 acetonitrile 1-vinylaziridine pyrrole 1-methylpyrrole 2-methylpyrrole p-cresol N

D O

N

O

30 [min]

20

Molecular Retention Weight Index

Relative Intensity

44 41 69 67 81 81 108

150 470 681 757 842 852 1078

100.0 22.4 20.0 33.8 8.3 5.4 16.6

154

1772

82.1

329

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

160

EGA thermogram

Averaged mass spectrum 44

100

55

200

300

400

500

70

83

29

111

50

600

700 ºC

programming rate: 20ºC/min

94 124 136

100

154

164

186192

150

210 250 [m/z]

200

( m/z range : 29 - 600 amu )

AN : acetonitrile

CP : 1-vinylaziridine 41

N

41

N

29

57

69

64

56

29

P : pyrrole

84

99

MP : 1-methylpyrrole 67

H N

80

N 41 53 33

52

79

41

29

68

C : p-cresol

MP : 2-methylpyrrole 80

H N

107

OH 42

42

53 93

29

111

D : hexahydropyrrolo[1,2-a]pyrazine-1,4-dione N O

83

O

111

154

70

N 41 55 30

97

55 67

29

93

98 126 143

186

77 68 125 138

153

330

Tsuge, Ohtani and Watanabe

161 Synthetic lignin; DHP

F

H

C

D

B A

TIC

E

0

10

Peak Notation A

30 [min]

20

Assignment of Main Peaks H 3CO

Molecular Retention Weight Index

Relative Intensity

124

1095

8.6

CH 3

138

1200

22.7

CH=CH2

150

1325

27.2

164

1462

27.2

180

1685

2.0

178

1756

100.0

358

3263 3272

95.8

HO

B

H 3CO HO

C

H 3 CO HO

D

H 3 CO

CH=CHCH3

HO

E

H3CO HO

F

CH2OH

H 3CO C HO HO

H

O

H3CO HO

OH O OCH3

331

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

161

EGA thermogram

Averaged mass spectrum 137

100

29 39

51

200

300

400

500

151

123 77

600

700 ºC

programming rate: 20ºC/min

91

65

109

50

164 178

100

298 312 326 340 358 199205 216 241 255 260 284

150

200

250

300

400 [m/z]

350

( m/z range : 29 - 600 amu )

B : 2-methoxy-4-methylphenol

A : 2-methoxyphenol 109

HO O

138

123

O

124

HO

81

95 53 29

39

65

67

55

39

95

77

110

29

D : (E)-2-methoxy-4-(1-propenyl)-phenol

C : 2-methoxy-4-vinylphenol 150

O

O

HO

HO

164

135

149

77 107

77

51 39 63 91 118 29

341

429

29

39

55

103

65

104

131 133

E : 4-((1E)-3-hydroxy-1-propenyl)-2-methoxyphenol F : 4-hydroxy-2-methoxycinnamaldehyde 137

O

178

O

OH

O

180

HO

124

HO

135

91 29 39

55 65

77

190

161

29 39

206 219

H1 : 4,4'-(hexahydrofuro[3,4-c]furan1,4-diyl)bis(2-methoxyphenol) 151

107

77

151

109

161 192

H2 : 4,4'-(hexahydrofuro[3,4-c]furan -1,4-diyl)bis(2-methoxyphenol) O

O

151

O

O

147

124

91

51 63

OH

OH HO

HO O 137 131 29

55 81 103

137

358

131 163 205 180 221 259

327

403

O

O

O

542

29

39

55

77 65

109

358 163 205 189 221

259

299

327 343

332

Tsuge, Ohtani and Watanabe

162 Wood powder

LB

tE cE Va Eu

VS a

S

cP

VG HAa

tP

MG

SA AS

Fa

G

TIC

tS

cS

0

10

Peak Notation LB HAa

Molecular Retention Weight Index

Assignment of Main Peaks CO2 etc. hydroxyacetaldehyde O

30 [min]

20

Relative Intensity

-

150

30.6

60

652

4.1

96

835

3.5

124

1095

2.1

CHO

Fa

furfural

G

guaiacol

MG

4-methylguaiacol

138

1200

5.2

VG

4-vinylguaiacol

150

1325

6.0

S

syringol

154

1360

4.0

Eu

eugenol

164

1368

0.5

152

1411

0.8

164

1420

0.2

164

1462

2.0

162

1475

100.0

180

1576

10.3

194

1663

1.2

194

1713

7.8

196

1748

1.4

210

1929

0.3

208

1999

3.2

210

2005

2.0

HO CH3O

CH 3O HO CH 3O

HO

CH2CH=CH2

HO CH 3O

CHO

Va

vanillin

cE

cis-isoeugenol

HO

tE

trans-isoeugenol

CH3O

a

levoglucosan

VS

vinylsyringol

cP

cis-propenylsyringol

CH3O

CH=CHCH3

OCH3 OCH=CH2 CH 3O

OCH3

tP

trans-propenylsyringol

AS

acetosyringon

cS

cis-sinapylalcohol

C H3O

CH 3COO

HO CH 3O

O C

C H3

CH3O

trans-sinapaldehyde HO

tS

trans-sinapylalcohol

CH3O

CH3O HO

CH3O

SA

CH=CHCH3

CH =CHCH2OH

CH3O CH=CHCHO CH3O HO CH3O

CH=CHCH2OH

[ Related References ] 1) Genuit, W.; Boon, J. J.; Faix, O. Anal. Chem. 1987, 59, 508. 2) Faix, O.; Meier, D.; Fortmann, I. Holz als Roh- und Werstoff 1990, 48, 281 3) Kleen, M.; Gellerstedt, G. J. Anal. Appl. Pyrolysis 1991, 19, 139. 2) Kuroda, K.; Yamaguchi, A. J. Anal. Appl. Pyrolysis 1995, 33, 51. 5) Rodrigues, J.; Meier, D.; Faix, O.; Pereira, H. J. Anal. Appl. Pyrolysis 1999, 48, 121. 6) Yokoi, H. ; Ishida, Y. ; Ohtani, H. ; Tsuge, S. ; Sonoda, T. ; Ona, T. Analyst 1999, 124, 669. 7) del Rio, J. C.; Gutierrez, A.; Martinez, M. J.; Martinez, A. T. J. Anal. Appl. Pyrolysis 2001, 58-59, 441. 8) Martinez, A. T.; Camarero, S.; Gutierrez, A.; Bocchini, P.; Galletti, G. C. J. Anal. Appl. Pyrolysis 2001, 5859, 401.

333

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

162

EGA thermogram

Averaged mass spectrum 60

29

100

43

200

300

400

500

600

700 ºC

programming rate: 20ºC/min

73 97

85 50

114 126

144 150 167 180 196 213 216

100

150

302

200

250

350 [m/z]

300

( m/z range : 29 - 600 amu )

HAa : hydroxyacetaldehyde

Fa : furfural

31

96

O

HO O

O 39

42

60

29

72

G : guaiacol

67

50

82

108

MG : 4-methylguaiacol 109

HO

110

HO 124

138

123

O

O

81

64 29

53

39

55

39

65

92

VG : 4-vinylguaiacol

95 77

29

144

151

S : syringol 150

O

154

OH

135

O

O

HO 139 107

77 29

39

51 63

91

118

29

a : levoglucosan

51

65

96 79

125

166

VS : vinylsyringol

60

180

O O HO OH

73

O O

O

OH

165 137

29 43 89

98

115 131 144 160

205

tP : trans-propenylsyringol

29 39

220

51

65

77

91

105

122 151

AS : acetosyringon

O

181

OH

194

HO O

39

111

O

O 196

O 65 29 39 53

77

91 105

119

167 179 133 151

204

29

43

53 67

82 93 108 123 138

153 167

219 234

334

Tsuge, Ohtani and Watanabe

163 Gluten

b LB

PA

C

T

0

10

Peak Notation

c

Gl a

P

TIC

Assignment of Main Peaks

LB T P C GI

CO2 etc. toluene phenol p-cresol glutamic acid

a

HN

O

30 [min]

20

Molecular Retention Weight Index

Relative Intensity

92 94 108 147

150 767 983 1078 1688

98.3 23.7 5.4 21.8 58.6

154

1767

8.4

208

2292

100.0

244

2410

15.9

N O

b

unidentified O

c

HN N O

335

Pyrograms and Thermograms of 163 High Polymers, and MS Data of the Major Pyrolyzates

163

EGA thermogram

Averaged mass spectrum 44 84 70 55 100

200

300

400

500

91

29

600

700 ºC

programming rate: 20ºC/min

107

50

154

125

138

100

208 165

180

228 239 244

199

150

250 [m/z]

200

( m/z range : 29 - 600 amu )

T : toluene

P : phenol 91

94

OH

66 39

51

39

65

89

55

29

C : p-cresol

79

110

Gl : glutamic acid 84

107

OH

O

O OH

HO NH2 77 41

51

95

41

68

30

66

98

113 128 140 150 165

b : unidentified

a : 1,4-diazabicyclo[4.3.0]nonane-2,5-dione 83

56

29

70

111 154

O

208

70

HN

41

N

55

98

30

41

126 135

O

175 199 216

343

c : hexahydro-3-(phenylmethyl) pyrrolo[1,2-a]pyrazine-1,4-dione 125

O HN N O 70 41 29

55

77

244 91

153 104

132

174

201

242

29

96 55

84 111

124

152 138

166

180

189

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PART 3

Pyrograms for 33 Condensation Polymers and MS Data of the Major Pyrolyzates Obtained in the Presence of Organic Alkaline 3.1. EXPERIMENTAL CONDITIONS FOR MEASURING PYROGRAMS AND MS DATA OF THE MAJOR PYROLYZATES FOR THE CONDENSATION POLYMERS BY MEANS OF REACTIVE PYROLYSISGC/MS IN THE PRESENCE OF ORGANIC ALKALINE 3.1.1. Polymer samples In the following data acquisition, 33 condensation polymer samples selected from the 163 samples used in Part 2 for conventional pyrolysis were subjected to analysis like in the former edition.*

3.1.2. Measuring conditions for the pyrograms of the polymers and the MS data of the major peaks on each pyrogram by use of reactive pyrolysis in the presence of organic alkaline Figure 3.1 illustrates the schematic flow diagrams of the measuring systems of the reactive Py-GC/MS in the presence of organic alkaline, tetramethylammonium hydroxide [(CH3)4NOH, TMAH].** A methanol solution (25 wt%) of TMAH supplied by Aldrich (Steinheim, Germany) was used as the organic alkaline reagent. About 2 ml of the reagent solution was added to powdered polymer sample (ca. 50 mg) weighed into the same deactivated stainless steel sample cup used in Chapter 2.1.2 before mounting the cup into the pyrolyzer of which temperature was maintained at 420 C to promote specific hydrolysis followed by methylation suppressing the contribution of conventional thermal decomposition. Basically the same Py-GC/MS measuring system shown in Figure 2.1 was used under the same conditions except for this sampling technique and the lower reaction temperature (420 C) setting. The products formed through the specific reactions for a given condensation polymer were separated by a stainless steel capillary column (Frontier Lab. Ultra ALLOY-5) * Tsuge S, Ohtani H, Watanabe C. “Pyrolysis-GC/MS of high polymers - fundamentals and pyrogram compilations”. Techno System Co., Tokyo, 2006. ** Challinor J. M. J Anal Appl Pyrol 1989, 16, 323–333.

Pyrolysis-GC/MS Data Book of Synthetic Polymers/Tsuge ISBN 978-0-444-53892-5, Doi:10.1016/B978-0-444-53892-5.10003-3

Ó 2011 Elsevier B.V. All rights reserved.

337

j

338

Tsuge, Ohtani and Watanabe

Pyrolyzer He TMAH solution

sample cup

powder sample

vent

separation column GC/MS adaptor

GC Oven

Q-MS

Figure 3.1 Schematic ﬂow diagram of Py-GC/MS system (from the upper to the lower ﬂow). (a) Carrier gas: 100 ml/min of He ﬂow at the pyrolyzer, 1 ml/min at the separation column through a splitter (1/100); (b) pyrolyzer: a micro-furnace pyrolyzer (Frontier Lab., PY-2020iD) at 420 C; (c) Pyrolyzer/GC interface temperature: 320 C; (d) GC injection temp.: 320 C; (e) sample size: ca. 50 mg weighed into a sample cup (ECO CUP-L: (o.d. 4.2 i.d. 4.0 8 mm height, deactivated stainless steel cup); (f) GC separation column: Ultra ALLOY-5 (0.25 mm 30 m; 0.25 mm of 5%diphenyl–95%dimethylpolysiloxane ﬁlm), temp. programmed from 40 C (2 min hold) – (20 C/min) – 320 C (13 min hold); (g) GC/MS interface temp.: 320 C; (h) EI source (70 eV) temp.: 230 C; (i) MS scan range: 29–600 (m/z) at 2000 amu/sec.

coated with 5%diphenyl–95%dimethylpolysiloxane liquid phase under a programming temperature condition; 40 C (2 min hold) – (20 C/min) – 320 C (13 min hold). Thus, obtained mass spectrometric data for all the peaks on the pyrograms stored as the total ion chromatogram (TIC), and the selected mass spectra of the top 6 major peaks at most were compiled on this data book, together with the retention index (RI) data of the main peaks on the pyrograms. Typical reaction passes for condensation linkages in the presence of TMAH are as follows. O R1 C

O O R2

(CH3)4NOH

R1 C O

CH3

H3C O R2

O R3

O C O R4

(CH3)4NOH

R3 O

CH3

H3C O R4

CO2

Pyrograms for 33 Condensation Polymers and MS Data of the Major Pyrolyzates Obtained in the Presence of Organic Alkaline

3.1.3. Data descriptions for the reaction pyrograms and the MS data of the major peaks on the pyrograms for 33 condensation polymer samples In the following Chapter 3.2, one page was allocated for the most condensation polymers. For example, the observed data for poly(acrylic acid) is given in page 340. At the top of the page, you can find the following statements:

R01 [042] Poly(acrylic acid); PAA CH 2CH(COOH)

n

where the sample number, R01 (042) is followed by the full name with its abbreviation and chemical structure. Here, “R01” designates the No. 01 for the series of Reaction Pyrolysis Data, and the following number in the parenthesis, (042) corresponds to that in Chapter 2.2 for the conventional pyrolysis data number. The upper display is its reaction pyrogram at 420 C, where most of the prominent components are formed through reactive pyrolysis in the presence of TMAH. Under the pyrogram, you can see the peak assignment table for the pyrogram together with molecular weight (MW), retention index (RI), and relative peak intensity data. At the bottom of the page, the selected mass spectra for up to the top 6 major peaks are compiled. On the other hand, facing two pages were allocated for some of the condensation polymers yielding more than 6 well-assigned mass spectra for their pyrolyzates. For example, as shown in the facing two pages (pp. 344–345), at the top of the associated first page, you can find the statements for unsaturated polyester as follows:

R04 [104] Unsaturated polyester; UP CH2CH(C6H5)

CHCHCOOCH2CH2OCO

COOCH2CH2OCO

n

where the sample number, R04 (104) is followed by the full name with its abbreviation and chemical structure. The upper display is its reaction pyrogram at 420 C, followed by the peak assignment table for the pyrogram together with MW, RI, and relative peak intensity data. As the footnote, the related references in which the concerned pyrolysis information is reported were listed. At the right hand page, its selected mass spectra for up to 12 major peaks are compiled.

339

340

Tsuge, Ohtani and Watanabe

3.2 DATA COMPILATION OF PYROGRAMS OF 33 CONDENSATION POLYMERS THROUGH REACTIVE PYROLYSIS R01 [042] Poly(acrylic acid; isotactic); PAA CH 2CH(COOH)

n

M3

M5

M2

M4

M6

M2 ’

2

10

Peak Notation M2’ M2 M3 M4 M5 M6

Assignment of Main Peaks C(COOC)-C-C-COOC C=C(COOC)-C-C-COOC (dimer) C=C(COOC)-C-C(COOC)-C-C-COOC (trimer) C=C(COOC) C-C(COOC) 2C-C-COOC (meso (m)) C=C(COOC) C-C(COOC) 2C-C-COOC (racemic (r)) C=C(COOC) C-C(COOC) 3C-C-COOC(pentamer) C=C(COOC) C-C(COOC) 3C-C-COOC (hexamer) *bonding hydrogen is omitted

25 [min]

20

Molecular Retention Index Weight 160 172 258 (tetramer) 344 430 516

1150 1211 1691 2127 2138 2556 2966

Relative Intensity 19.9 31.4 100.0 26.5 25.2 77.9 47.8

Pyrograms for 33 Condensation Polymers and MS Data of the Major Pyrolyzates Obtained in the Presence of Organic Alkaline

R01 [042]

M2' : dimethyl glutarate O

O O

M2 : dimethyl 2-methylenepentanedioate 112

59 O

O

100

O

O 140

129 42

59

O 39

87

29

81 97

29

74

121

M4 : tetramethyl oct-7-ene-1,3,5,7-tetracarboxylate (meso form)(tetramer)

M3 : trimethyl hex-5-ene-1,3,5-tricarboxylate O

O

O

O

O

O

59

O

133

194

161

59 106 79 167

227

O O

O O

O

192 220

105

252

313 280

153

29

M5 : pentamethyl dec-9-ene-1,3,5,7,9-pentacarboxylate (pentamer)

100 79 112 41 67

91

41

125

41 29

59

O O

134

79

314

M6 : hexamethyl dodec-11-ene-1,3,5,7,9,11hexacarboxylate(hexamer)

O

187

O

O

O

O

247 275

O

O

O

O

59

O

O

79

306 334

399 366

100

O

172 153

41 31

O

O

O

O

O

O

O

O

O

O

227 361 325

420

485

341

342

Tsuge, Ohtani and Watanabe

R02 [099] Diallyl phthalate resin; DAP CH2CHCH2OCO

COOCH2CHCH2

n

BD

PA

MB

M

2

10

25 [min]

20

Peak Notation

Assignment of Main Peaks

MB

methyl benzoate

Molecular Weight COOCH 3

Retention Index

Relative Intensity

136

1102

1.4

148

1328

6.6

194

1470

100.0

246

1761

0.3

O

PA

phthalic anhydride

O

COOCH 3

O

BD COOCH 3

C OOCH2CH=CH 2

M

(monomer)

COOCH 2CH=CH2

MB : methyl benzoate

PA : phthalic anhydride O

105

O

104 76

O

O

77

O

136

50

51

74 74

29

148

38

91

BD : dimethyl phthalate

M : diallyl phthalate (monomer) 163

O

41

149

O O

O

O

O O

O

76

77 50

92

104

120 133

194

50 29

104 98

132

189 172

Pyrograms for 33 Condensation Polymers and MS Data of the Major Pyrolyzates Obtained in the Presence of Organic Alkaline

R03 [100] Poly(ethylene glycol bisallyl carbonate); CR-39 CH2 CHCH2 OCOOCH2 CH2 OCH2OCOOCH2 CHCH2

n

B

A MB MC 2

10

25 [min]

20

Peak Notation

Assignment of Main Peaks

Molecular Retention Relative Weight Index Intensity

MC A B

CH3OCOOCH3 CH3OCH2CH2OCH2CH2OH CH3OCH2CH2OCH2CH2OCH3

90 120 134

613 944 954

3.2 51.5 100.0

MB

methyl benzoate

136

1102

16.0

COOCH 3

MC : dimethyl carbonate

A : diethylene glycol monomethyl ether

45

45

O

O

O

59

29

O

HO

59

O 29 62

B : diethylene glycol dimethyl ether 59

O

75

90

O

MB : methyl benzoate O

105

O O

29

89 90

77 136

45 51

89 75

102

29

39

74

92

343

344

Tsuge, Ohtani and Watanabe

R04 [104] Unsaturated polyester; UP CH2 CH(C6H5)

CHCHCOOCH2 CH2 OCO

COOCH2 CH2 OCO

n

BD

PA PB’ SS PB

S ME

BO MBBA

2

SSS DOP

10

Peak Notation

Assignment of Main Peaks

ME S BO MB BA PA

CH3OCH2CH2OCH3 styrene CH3OCOCH=CHCOOCH3 methyl benzoate benzoic acid phthalic anhydride

25 [min]

20

Molecular Retention Relative Weight Intensity Index 90 104 144 136 122 148

652 899 1023 1102 1168 1334

2.8 100.0 4.3 6.3 6.0 56.4

194

1146

97.3

196 194 208 312 390

1677 1697 1746 2493 2563

10.0 6.6 9.0 28.1 11.2

COOCH 3

BD COOCH 3

PB PB’ SS SSS DOP

CH2(C6H5)CH2CH2(C6H5) CH(C6H5)=CHCH2(C6H5) CH2=C(C6H5)CH2CH2(C6H5) (styrene dimer) CH2=C(C6H5)CH2CH2(C6H5) CH2CH2(C6H5) (styrene trimer) dioctyl phthalate

[ Related Reference ] 1) Challinor, J. M. J. Anal. Appl. Pyrolysis 1989, 16, 323.

Pyrograms for 33 Condensation Polymers and MS Data of the Major Pyrolyzates Obtained in the Presence of Organic Alkaline

R04 [104]

ME : ethylene dimethyl ether

S : styrene 104

45

O O 78

103

51

29 60

39

90

BO : dimethyl fumarate

63

MB : methyl benzoate

O

105

113

O O

O

O

85

77

O

136 59

29

41

51 100

69

144

BA : benzoic acid

29

74

39

PA : phthalic anhydride 105

O

104

O 122

77

O

OH 51

31

O 74

38

76

50 74

94

29

BD : dimethyl phthalate

148

38

PB : 1,3-diphenylpropane 163

92

O O 105

O O 29 39

65

77 50

74

92 104

120 133

39

194

149

PB' : 1-propene-1,3-diyldibenzene

196

77

51

148

118

30

179

SS : 3-butene-1,3-diyldibenzene (styrene dimer) 162

91

104

76 50 29 41

74

132 92

121

51 29 39

149

SSS : 5-hexene-1,3,5-triyltribenzene

65

104

208

130

77

165 180 193

DOP : dioctyl phthalate

(styrene trimer)

149

91

O OC8H17 OC8H17

117 3951 65

77

194 207 129 152165 178 221234

167

O

57 312

29

43

71

83 93104 121132

279 178

202

231

260

345

346

Tsuge, Ohtani and Watanabe

R05 [105] Epoxy resin; EP CH2CH(OH)CH2O

C(CH3)2

OCH2CH(OH)CH2N

CH2

N

n

b

IP’

DM BA

P

IP

a

AD DA c

OC 2

10

Peak Notation

Assignment of Main Peaks

P OC IP IP’

phenol o-cresol p-isopropylphenol p-isopropenylphenol

a

H3CO

b

HO

DM

H 2N

C(CH3) 2

C(CH3)2

CH2

25 [min]

20

Molecular Retention Weight Index

OCH3

OCH3

NH 2 HO

C(CH3)2

OH

Relative Intensity

94 108 136 134

982 1059 1228 1304

31.6 9.6 21.6 100.0

256

2088

13.2

242

2144

94.0

198

2161

39.3

228

2197

29.9

226

2270

14.1

BA

bisphenol A

AD

H2N

DA

H3CH N

CH 2

N(CH 3) 2

240

2360

3.0

c

(H3C) 2N

CH2

N(CH 3) 2

254

2378

11.6

CH 2

N(CH 3) 2

[ Related Reference ] 1) Challinor, J. M. J. Anal. Appl. Pyrolysis 1989, 16, 323.

Pyrograms for 33 Condensation Polymers and MS Data of the Major Pyrolyzates Obtained in the Presence of Organic Alkaline

R05 [105]

OC : o-cresol

P : phenol 94

108

OH

OH

77 66 39

90

51 39

55

29

79

63

30

IP : p-isopropylphenol

IP' : p-isopropenylphenol 134

121

OH

OH 119

91

136 91

77 29

39

39

65

51

29

107

a : 2,2-bis(4'-methoxyphenyl)propane

65

51

77

105

b : 2-(4'-hydroxyphenyl)-2-(4'-methoxyphenyl)propane 227

241 O

O

HO

242

256

133 152 165183195 211226 121

29 41 51 63 77 91

O

119 133 152 165 183 197 212

91 29 39 51 65 77

DM : diaminodiphenylmethane

BA : bisphenol A 198

213

HO

OH

NH 2

H 2N 106

182 65 77 30 39 52

93

130 143152

39 5565 77

91

119 107 135 152

228 181 198

DA : N,N-dimethyl-4-(4-(methylamino)benzyl)aniline

AD : 4-(4-aminobenzyl)-N,N-dimethylaniline 226

77 90 32 42 51 63

106118

120134

182

134 152 165

210 77 91 111 32 4251 65

196

c : 4,4'-methylenebis(N,N-dimethylaniline) 254

N

N

42

96

134 126 117

N H

N

NH2

N H

240

210 166

237 224

196 152165180

210 223

347

348

Tsuge, Ohtani and Watanabe

R06 [107] Bismaleimide triazine resin; BT resin O C(CH3 )2

N

O

CO N

N

CH2

CO

N

CO CO

N N

O

n

O

b

c d a

2

f h e g

10

25 [min]

20

Peak Notation

Assignment of Main Peaks

a

unidentified

b

H3CO

c

HO

d

H 2N

CH2

e

H2 N

f

H2N

g

H3 C H N

CH 2

h

H3CH N

CH 2

Molecular Retention Weight Index

Relative Intensity

171

1394

8.4

256

2105

100.0

242

2150

1.1

NH 2

198

2166

1.3

CH 2

NHCH 3

212

2260

6.1

CH 2

N(CH 3) 2

226

2279

2.9

NHCH 3

226

2353

7.0

N(CH 3) 2

240

2371

4.1

C(CH3) 2

C(CH3)2

OCH3

OCH3

Pyrograms for 33 Condensation Polymers and MS Data of the Major Pyrolyzates Obtained in the Presence of Organic Alkaline

R06 [107]

a : unidentified

b : 2,2-bis(4'-methoxyphenyl)propane 171

241 O

58

O

143 256 29

70 42

85

99

113

39 51 63 77 91

156

133 121

165

195 211

c : 2-(4'-hydroxyphenyl)-2-(4'-methoxyphenyl)propane d : diaminodiphenylmethane 198

227

HO

O NH 2

H2N 106

182

242 119 133

39 51 65 77 91

152 165 181 197 212

30 39 52

e : 4-(4-aminobenzyl)-N-methylaniline

65 77

93

130 143152 168

f : 4-(4-aminobenzyl)-N,N-dimethylaniline 226

212

H2 N

NH2

N H

106 120 77 91 30 39 51 65

182 196

N

106

152 168

77 91 30 42 51 65

182

134 118

152 165

210 194

h : N,N-dimethyl-4-(4-(methylamino)benzyl)aniline

g : 4,4'-methylenebis(N-methylaniline) 226

N H

N H

240

N H

N 120 196

77 91 30 39 51 65

112

152 165 180

120 134 211

91 30 42 51 65 77

112

196 152 165 180

210 223

349

350

Tsuge, Ohtani and Watanabe

R07 [108] Polyetherimide; PEI CO O

C(CH3)2

CO N

O

N

CO

CO

n

c

h

b a

f d

HA

ID 2

g

e

i

BA

10

20

Peak Notation

Assignment of Main Peaks

HA

p-hydroxybenzaldehyde COOCH 3

a

Molecular Retention Index Weight

Relative Intensity

122

1396

1.9

194

1464

4.8

136

1481

51.0

150

1500

100.0

164

1507

2.2

210

1759

10.6

256

2093

1.7

242

2147

30.8

228

2203

1.5

238

2492

1.7

-

2714 3228

8.6 4.0

COOCH 3

b

H3CHN

c

H3CHN

d

(H3 C)2N

NHCH 3

N(CH3)2

N(CH3)2 CH2

ID

O

CCH3

e

H3CO

f

HO

C(CH3)2

HO

C(CH3) 2

BA

C(CH3) 2

OCH3

OCH3

OH

H2N

g h i

N

CO CO

unidentified unidentified

Pyrograms for 33 Condensation Polymers and MS Data of the Major Pyrolyzates Obtained in the Presence of Organic Alkaline

R07 [108]

HA : p-hydroxybenzaldehyde

a : dimethyl phthalate 122

OH

163

O O 29

O

93 O 29 O

65 39

80

53

39

51

66 76

104 94

194 120

135

c : N,N,N'-trimethyl-1,3-phenylenediamine

b : N1,N3-dimethylbenzene-1,3-diamine

150

136

N H

N H

N H

106

N 106

67 51

30 39

94

77

150

120

29

d : N,N,N',N'-tetramethyl-1,3-benzenediamine

121

74

42 51

135

91

ID : 4-isopropenyl diphenyl ether

164

N

210

O

N 120 77 73

42 30

53

135 195

149 91

104

77 91 39 51 65

115 119 141152 165

f : 2-(4'-hydroxyphenyl)-2-(4'-methoxyphenyl)propane

e : 2,2-bis(4'-methoxyphenyl)propane

227

241 O

O

HO

O

242

256 77 91 29 41 51 63

115

133 152 165 183

91 107119 134 29 39 51 65 77

211226

BA : bisphenol A

153165 183 197 212

g : 2-(3-aminophenyl)isoindoline-1,3-dione 213

HO

H2N

238

O

OH N O 39 55 65 77

91

119 107 135

228

76 39 50 65

169

h : unidentified

91 104 119 134

154 167 181

210

i : unidentified 365

289

380

304 77 91 39 51 65

194

119 144 165181 195

39 5165

77

165183 195 115 152

271

351

352

Tsuge, Ohtani and Watanabe

R08 [109] Polypyromellitimide; PI O

CO

CO

CO

CO

N

N n

i e a d b

h f g

2

j 14

8

10

Peak Notation a

Assignment of Main Peaks H3CO

25 [min]

20

NHCH3

Molecular Retention Relative Index Weight Intensity 137

1309

3.4

194

1512

0.1

252

1855

1.4

310

2164

4.7

COOCH 3

b

COOCH 3 H3 COCO

and its isomers COOCH 3

c COOCH 3 H3 COCO

COOCH3

H3 COCO

COOCH3

d

e

H2 N

O

NHCH 3

214

2238

29.8

f

H2N

O

N(CH3 ) 2

228

2249

7.3

H3 C H N

O

NHCH3

228

2330

40.4

h

H3CH N

O

N(CH 3) 2

242

2344

100.0

i

(H3C) 2N

O

256

2354

10.5

g

N(CH 3)2

Pyrograms for 33 Condensation Polymers and MS Data of the Major Pyrolyzates Obtained in the Presence of Organic Alkaline

R08 [109]

a : p-methoxy-N-methylaniline

b : dimethyl phthalate 122

163

O

NH

O

O 137

30

40

52

90

66

77 74

29 39 50

77

c : 1,2,4-benzenetricarboxylic acid, trimethyl ester O

O O

194

d : 1,2,4,5-benzenetetracarboxylic acid, tetramethyl ester

221

O

279 O

O

92 104

O

O O

O

O

O O

29 39

59

103 119135

75

O O

162

29 43 59 75

252

193

O 233

162

105 124

310

251

f : 4-(4-aminophenoxy)-N,N-dimethylaniline

e: 4-(4-aminophenoxy)-N-methylaniline

228

214 H2N

O

NH

H 2N

O

N

136

122 53 29 39

65

80 93 108

171

108

185 31

39 53 65 79

120

156

199

213

h : N,N-dimethyl-4-(4-(methylamino)phenoxy)aniline

g : 4,4'-oxybis(N-methylaniline) 228 HN

O

242 HN

NH

O

N

122

30 39 52

65 77

94 106

134

170

185

122

199 213

i : 4,4'-oxybis(N,N-dimethylaniline) 256 N

O

N

136 4251 65 77 92104

127

168 184

226 241 213

65 77 30 4251

94104

136 154 170

199 213 227

353

354

Tsuge, Ohtani and Watanabe

R09 [110] Polyaminobismaleimide; PABM CH2

CO

CH

CO

N

CH2

CO

CH2

CO

CH

N

NH

CH2

NH n

DA

e

b d

a

MD

c 2

10

25 [min]

20

Peak Notation

Assignment of Main Peaks

DA

H 2N

CH2

NH 2

198

2164

100.0

a

H2 N

CH 2

NHCH 3

212

2255

17.0

b

H2N

CH 2

N(CH 3) 2

226

2274

4.6

c

H3 C H N

CH 2

NHCH 3

226

2348

6.7

d

H3CH N

CH 2

N(CH 3) 2

240

2366

4.5

MD

(H3C) 2N

CH2

N(CH 3) 2

254

2384

0.7

e

CO H2C N H2C CO

294

2974

85.0

CH2

NHCH3

Molecular Retention Weight Index

Relative Intensity

Pyrograms for 33 Condensation Polymers and MS Data of the Major Pyrolyzates Obtained in the Presence of Organic Alkaline

R09 [110]

DA : diaminodiphenylmethane

a : 4-(4-aminobenzyl)-N-methylaniline 212

198

NH2

N H

NH 2

H 2N 106

182 65 77 30 39 52

98

130

106 120

182 196

77 91 30 39 51 65

152 168

b : 4-(4-aminobenzyl)-N,N-dimethylaniline

152 168

c : 4,4'-methylenebis(N-methylaniline) 226

H2 N

226

N H

N

N H 120

77 91 30 42 51 65

106

118

196

182

134

210

152 165

77 91 30 39 51 65

195

d : N,N-dimethyl-4-(4-(methylamino)benzyl)aniline

112

211

139 152 165 180

MD : 4,4'-methylenebis(N,N-dimethylaniline) 254

240

120 134 91 30 42 51 65 77

196 152 165 180

112

280

O

55 2939

N H

106

O

182 77 90

132

167

197

223 235

265

210

134 210 223

e : 1-(4-(4-(methylamino)benzyl)phenyl)pyrrolidine -2,5- dione

N

N

N

N H

N

294

118 29 42 51 65

91 104

165 152

237 194

223

355

356

Tsuge, Ohtani and Watanabe

R10 [115] Poly(ethylene terephthalate); PET COOCH2CH2OCO n

c

a

b

2

10

Peak Notation

Assignment of Main Peaks

a b

CH3OCH2CH2OH CH3OCH2CH2OCH3

c

H3COCO

25 [min]

20

Relative Intensity

Molecular Retention Index Weight

COOCH3

76 90

627 645

1.2 15.5

194

1516

100.0

[ Related Reference ] 1) Challinor, J. M. J. Anal. Appl. Pyrolysis 1989, 16, 323.

a : methoxyethanol

b : ethylene dimethyl ether 45

45

O

O O

HO 29 29

60

76

c : dimethyl terephthalate 163

O

O

O

O

29 39

50

76 75

103 104 120

194

135 179

90

Pyrograms for 33 Condensation Polymers and MS Data of the Major Pyrolyzates Obtained in the Presence of Organic Alkaline

R11 [116] Poly(butylene terephthalate); PBT COOCH2CH2CH2CH2OCO

n

c

a b 2

10

Peak Notation

Assignment of Main Peaks

a b

CH3O(CH2)4OCH3 CH3O(CH2)4OH

c

H3COCO

25 [min]

20

Molecular Retention Index Weight

COOCH3

a : 1,4-dimethoxybutane

Relative Intensity

118 104

851 882

18.0 6.1

194

1516

100.0

b : butylene glycol methyl ether

45

45 58

O

O

O

HO 58

29

71

86

31

103 104

c : dimethyl terephthalate 163

O

O

O

O

29 39

50

76 75

194

135

103 120

149

179

71

89 90

357

358

Tsuge, Ohtani and Watanabe

R12 [117] Poly(ethylene naphthalate); PEN CH2CH 2OCO COO n

DN

ME DE

2

10

25 [min]

20

Peak Notation

Assignment of Main Peaks

ME DE

CH3OCH2CH2OH CH3OCH2CH2OCH3

DN

H3COCO

Molecular Retention Index Weight

COOCH3

ME : methoxyethanol

Relative Intensity

76 90

626 645

1.1 8.5

244

2118

100.0

DE : ethylene dimethyl ether 45

45

O

O O

HO 29 29 76

58

DN : dimethyl-2,6-naphthalene dicarboxylate 213 O

244

O O O

185

126 154

29 39

63 77 91

114

142

170

199

229

60

90

Pyrograms for 33 Condensation Polymers and MS Data of the Major Pyrolyzates Obtained in the Presence of Organic Alkaline

R13 [118] Poly(p-hydroxybenzoic acid); type A O

O

CO

CO

O

CO n

c a

b

2

10

Peak Notation

Molecular Retention Index Weight

Assignment of Main Peaks

a

H3CO

b

H3COCO

c

H3CO

25 [min]

20

COOCH3

COOCH3

OCH3

Relative Intensity

166

1387

96.4

194

1512

50.7

214

1965

100.0

[ Related References ] 1) Ohtani, H. ; Fujii, R. ; Tsuge, S. J. High Resolut. Chromatogr. 1991, 14, 388. 2) Ishida, Y. ; Ohtani, H. ; Tsuge, S. J. Anal. Appl. Pyrolysis 1995, 33, 167.

a : methyl 4-methoxybenzoate

b : dimethyl terephthalate 135

163

O

O

O

O O 166 77 29 38

50

92

63

123

199 O

171 128 29 39 51 63 76

102

139 156 115

O

29 39

c : 4,4'-dimethoxy-1,1'-biphenyl O

O

107

214

50

76

103 104 120

194

135 149

179

359

360

Tsuge, Ohtani and Watanabe

R14 [119] Poly(p-hydroxybenzoic acid); type B O CO

O

CO n

b c

a 2

10

Peak Notation

Molecular Retention Index Weight

Assignment of Main Peaks

a

H3CO

b

H3CO

COOCH3

H3CO

c

25 [min]

20

108

920

0.6

166

1396

100.0

216

1974

78.1

COOCH3

[ Related References ] 1) Ohtani, H. ; Fujii, R. ; Tsuge, S. J. High Resolut. Chromatogr. 1991, 14, 388. 2) Oba, K. ; Ishida, Y. ; Ohtani, H. ; Tsuge, S. Polym. Degrad. Stab. 2002, 76, 85.

a : anisole

b : methyl 4-methoxybenzoate 135

108 O 65

O

78

O

O 166 39 51

77

93 29 38

29

c : methyl 6-methoxy-2-naphthoate 185

216

O O

O 157

114 142 29 39 50

63

88

127

173

201

50

63

Relative Intensity

92

107 123

Pyrograms for 33 Condensation Polymers and MS Data of the Major Pyrolyzates Obtained in the Presence of Organic Alkaline

R15 [120] Polyarylate; PAR O

C(CH3)2

OCO

CO

n

d

b c

a 2

10

Peak Notation

Assignment of Main Peaks

a

H3CO

b

Molecular Retention Weight Index

C(CH3) 3

H3COCO

c

H3COCO

d

H3CO

25 [min]

20

COOCH3

COOCH3

C(CH3) 2

OCH3

a : p-methoxy-tert-butylbenzene

Relative Intensity

164

1251

1.0

194

1517

21.2

194

1530

23.0

256

2107

100.0

b : dimethyl terephthalate 163

149

O

O

O

O 121 41 51

65

77

91

109

O

164 134

39

c : dimethyl m-phthalate

50

103 104 120

76

194

135 179

d : 2,2-bis(4'-methoxyphenyl)propane 241

163 O O

O

O O 135

O 39

50

76

103

120

194 149

179

256 121133 152 165183 39 51 63 77 91 113

211226

361

362

Tsuge, Ohtani and Watanabe

R16 [121] Poly(1,4-cyclohexane dimethylene terephthalate) H2C

CH2 OOC

COO

n

DP

H1 H2 H3 H4

2

10

Peak Notation

Molecular Retention Weight Index

Assignment of Main Peaks

H1 H3COH2C

CH 2OCH3

H2 H3 H3COH2C

H4

CH 2OH

H3COCO

DP

172

1246

28.6

cis form

172

1253

12.2

trans form

158

1300

7.9

cis form

158

1311

3.4

194

1516

100.0

COOCH3

H2 : 1,4-bis(methoxymethyl)cyclohexane (cis)

95

45 108

45

Relative Intensity

trans form

H1 : 1,4-bis(methoxymethyl)cyclohexane (trans) O

25 [min]

20

O

95

O

108 O

67 67

29

79

79

140

55 127

55

29

140

125

H3 : (4-(methoxymethyl)cyclohexyl)methanol (trans)

H4 : (4-(methoxymethyl)cyclohexyl)methanol (cis)

95

95 O

O

45

OH

67

45

79

67 79

108

108

55

29

OH

55

126

31

126 140

DP : dimethyl terephthalate 163

O

O

O

O

29 39

50

76

194

135

103 120

149

179

Pyrograms for 33 Condensation Polymers and MS Data of the Major Pyrolyzates Obtained in the Presence of Organic Alkaline

R17 [122] Poly(lactic acid); PLA CH 3 OCHCO

n

B

A

DB MB

DS DA

2

10

Peak Notation

20

Molecular Retention Relative Weight Index Intensity

Assignment of Main Peaks CH3

A

OHCHCOOCH3 CH3

B

CH3OCHCOOCH3 CH3O(CH2)4OCH3 CH3O(CH2)4OH CH3OCO(CH2)2COOCH3 CH3OCO(CH2)4COOCH3

DB MB DS DA

104

749

38.1

118

799

100.0

118 104 146 174

856 886 1033 1242

4.8 3.8 8.1 1.7

[ Related Reference ] 1) Urakami, K.; Higashi, A.; Umemoto, K.; Godo, M.; Watanabe, C.; Hashimoto, K. Chem. Pharm. Bull. 2001, 49, 203.

A : methyl 2-hydroxypropanoate

B : methyl 2-methoxypropanoate

45

59 O

OH

O

O O

O 29

29

43

61

DB : 1,4-dimethoxybutane

88

75

89

103

MB : butylene glycol methyl ether 45

45 58

O

O

O

HO 58

29

71

86

31

103 104

71

76

89

DA : dimethyl hexanedioate

DS : dimethyl succinate 115

O

O

59

O

114

O

O O

O

O 55

74 41 29

87 29

45

101

72

101

83

143

363

364

Tsuge, Ohtani and Watanabe

R18 [123] Poly(ε -caprolactone); PCL (CH2)5COO

n

A

C 2

10

25 [min]

20

Peak Notation

Assignment of Main Peaks

A B

CH3O(CH2)5COOCH3 CH3O [ (CH2)5COO ] CH3

Molecular Retention Weight Index 160 274

2

1150 1926

Relative Intensity 100.0 0.2

[ Related Reference ] 1) Sato, H. ; Kiyono, Y. ; Ohtani, H. ; Tsuge, S. ; Aoi, H. ; Aoi, K. J. Anal. Appl. Pyrolysis 2003, 68, 37.

B : 6-methoxy-6-oxohexyl 6-methoxyhexanoate

A : methyl 6-methoxyhexanoate 45

129

69

O

O

O

45 O

87 55 29

74

O

O

55

O

O

97

87 98

113 128

29

145 160

115

143

188

Pyrograms for 33 Condensation Polymers and MS Data of the Major Pyrolyzates Obtained in the Presence of Organic Alkaline

R19 [124] Poly(butylene succinate / adipate); PBSA O(CH2 )4OCO(CH2 )2 CO

O(CH2 )4OCO(CH2 )4CO

n

DS

DB

MB DA

2

10

25 [min]

20

Peak Notation

Assignment of Main Peaks

DB MB DS DA

CH3O(CH2)4OCH3 CH3O(CH2)4OH CH3OCO (CH2)2COOCH3 CH3OCO (CH2)4COOCH3

Molecular Retention Relative Weight Index Intensity 118 104 146 174

856 886 1033 1241

45.0 46.2 100.0 26.8

MB : butylene glycol methyl ether

DB : 1,4-dimethoxybutane 45

45 58

O

O

O HO

58

29

71

86

29

103

DS : dimethyl succinate

71

89

DA : dimethyl hexanedioate 115

O

O

59

O

114

O

O O

O O

55 41 87

29

45

101

143

74

72

83

29 101

123

365

366

Tsuge, Ohtani and Watanabe

R20 [125] Poly(3-hydroxybutylic acid); PHB H

OCHCH2C CH3

O

OH n

B3

A M

B2 B1

2

10

Peak Notation

Assignment of Main Peaks

A B1 B2 B3

methyl acetate CH2=CHCH2COOCH3 CH3CH=CHCOOCH3 (cis form) CH3CH=CHCOOCH3 (trans form)

Molecular Retention Relative Weight Index Intensity

CH3

M

25 [min]

20

CH3OCHCH2COOCH3

74 100 100 100

487 718 735 765

6.1 10.7 25.3 100.0

132

886

19.6

[ Related Reference ] 1) Sato, H. ; Hoshino, M. ; Aoi, H. ; Seino, T. ; Ishida, Y. ; Aoi, K. ; Ohtani, H. J. Anal. Appl. Pyrolysis 2005, 74, 193.

A : methyl acetate

B1 : methyl 3-butenoate 41

43

O

O O 59

O 74

59

29

100

69 29

B2 : methyl 2-butenoate (cis)

B3 : methyl 2-butenoate (trans)

69

69

O

O

O 39

O

100 41 85 100

29

59

29

85

M : methyl 3-methoxybutanoae 59

O

O

O

75 29

43

85

102

117

59

Pyrograms for 33 Condensation Polymers and MS Data of the Major Pyrolyzates Obtained in the Presence of Organic Alkaline

R21 [126] Poly(butylene succinate / carbonate); PEC O(CH2)4OCO(CH2)2CO

O(CH2)4

OCO

n

S

B1 B2

2

10

25 [min]

20

Peak Notation

Assignment of Main Peaks

B1 B2 S

CH3O(CH2)4OCH3 CH3O(CH2)4OH CH3OCO(CH2)2COOCH3

Molecular Retention Relative Weight Intensity Index 118 104 146

B1 : 1,4-dimethoxybutane

855 886 1034

37.7 47.0 100.0

B2 : butylene glycol methyl ether

45

45 58

O

O HO

O 58

29

71

86

29

103

71

S : dimethyl succinate 115

O O O O

55 87

29

45

72

101

89

367

368

Tsuge, Ohtani and Watanabe

R22 [127] Polycarbonate (melt method); MM-PC H

O

C(CH3)2

OCO n

b

a 2

10

Peak Notation

Molecular Retention Weight Index

Assignment of Main Peaks

a

H3CO

b

H3CO

C(CH3) 2

25 [min]

20

OCH3

108

922

0.2

256

2103

100.0

[ Related References ] 1) Ito, Y. ; Ogasawara, H. ; Ishida, Y. ; Ohtani, H. ; Tsuge, S. Polym. J. 1996, 28, 1090. 2) Oba, K. ; Ishida, Y. ; Ito, Y. ; Ohtani, H. ; Tsuge, S. Macromolecules 2000, 33, 8173. 3) Hayashida, K. ; Ohtani, H. ; Tsuge, S. ; Nakanishi, K. Polym. Bull. 2002, 48, 483.

a : anisole

b : 2,2-bis(4'-methoxyphenyl)propane 108

241

O 65

29

O

O

78

39 50

256

93 39 51 63 77 91

Relative Intensity

133 121

165183

211226

Pyrograms for 33 Condensation Polymers and MS Data of the Major Pyrolyzates Obtained in the Presence of Organic Alkaline

R23 [128] Polycarbonate (solvent method); SM-PC (CH3)3C

OCO

O

C(CH3)2

OCO

O

C(CH3)3

n

b

a 2

10

25 [min]

20

Peak Notation

Assignment of Main Peaks

a

H3CO

C(CH3)3

b

H3CO

C(CH3)2

Molecular Retention Index Weight

OCH3

164

1252

1.5

256

2103

100.0

[ Related References ] 1) Ito, Y. ; Ogasawara, H. ; Ishida, Y. ; Ohtani, H. ; Tsuge, S. Polym. J. 1996, 28, 1090. 2) Oba, K. ; Ishida, Y. ; Ito, Y. ; Ohtani, H. ; Tsuge, S. Macromolecules 2000, 33, 8173. 3) Oba, K. : Ohtani, H. ; Tsuge, S. Polym. Degrad. Stab. 2001, 74, 171. 4) Hayashida, K. ; Ohtani, H. ; Tsuge, S. ; Nakanishi, K. Polym. Bull. 2002, 48, 483.

a : p-methoxy-tert-butylbenzene

b : 2,2-bis(4'-methoxyphenyl)propane 149

241

O

O

121 29 41 51

65 77

91

O

164

256

109 133

51

77 91

Relative Intensity

133 121

165 183

211 226

369

370

Tsuge, Ohtani and Watanabe

R24 [129]

Bisphenol Z polycarbonate O

OCO n MM

2

10

Peak Notation

Assignment of Main Peaks

MM

H3 CO

Molecular Retention Weight Index 296

OCH3

MM : 1-(2-methoxyphenyl)-1-(4-methoxyphenyl)cyclohexane 253 O

296

O

121 29 41 55 65 77 91

115

145

227

153165 178 199 210

25 [min]

20

265

2536

Relative Intensity 100.0

Pyrograms for 33 Condensation Polymers and MS Data of the Major Pyrolyzates Obtained in the Presence of Organic Alkaline

R25 [130] Polycarbonate (thermally stabilized) O

(CH3)3CCH2 C(CH3 )2

COO

C(CH3 )2

O

COO

O

COO

C(CH3 )2 CH2C(CH3 )3

n

CH3

H3 C CH3

B C

A 2

10

25 [min]

20

Peak Notation

Assignment of Main Peaks

A

H3CO

B

H3CO

C

H3CO

Molecular Retention Weight Index

C(CH3)2CH2C(CH3)3

C(CH3)2

OCH3 OCH 3

220

1564

2.1

256

2101

100.0

338

3584

75.1

CH3

H3C

CH 3

[ Related Reference ] 1) Ishida, Y.; Kawaguchi, S.; Ito, Y.; Tsuge, S.; Ohtani, H. J. Anal. Appl. Pyrolysis 1997, 40-41, 321.

A : 1-methoxy-4-(2,4,4-trimethylpentan-2-yl)benzene B : 2,2-bis(4'-methoxyphenyl)propane 241

149

O

O

O

29 41

57 65 77 91 109

121 133

133 121 152165 183 195 211226 29 39 51 63 77 91 115

220

163

C : 4,4'-(3,3,5-trimethylcyclohexane-1,1-diyl) bis(methoxybenzene) 267

O

O

338

29 41

55

121 159 7791 115 135 165

209 225 199

281 307 323

Relative Intensity

256

371

372

Tsuge, Ohtani and Watanabe

R26 [132] Polysulfone; PSF O

C(CH3)2

O

SO2 n

a

b

MM

A 2

c

10

25 [min]

20

Peak Notation

Assignment of Main Peaks

A

H3CO

MM

H3 CSO2

a

H3 CO

C(CH3) 2

b

H3 CO

SO2

c

unidentified

Molecular Retention Weight Index

OCH3 OCH3 OCH3

Relative Intensity

108

922

1.3

186

1699

2.4

256

2103

92.8

278

2607

100.0

380

3232

1.2

[ Related Reference ] 1) Ohtani, H. ; Ishida, Y. ; Ushiba, M. ; Tsuge, S. J. Anal. Appl. Pyrolysis 2001, 61, 35.

A : anisole

MM : methyl 4-methoxyphenyl sulfone 108

171 O

O 65

O

78

S

186

77 107

O 92 63

39 51

93 31 38

32

a : 2,2-bis(4'-methoxyphenyl)propane

O

O

O

133 121

77 91

64 29 41 50

211 226

c : unidentified 365

380 77 3951

102

141

165179195

257

139

155

O S O

256 165 183

50

155

b : 4,4'-sulfonylbis(methoxybenzene)

241

39 51

123

O

278

123

77 92 107 139

199 171 214 183

Pyrograms for 33 Condensation Polymers and MS Data of the Major Pyrolyzates Obtained in the Presence of Organic Alkaline

R27 [135] Polyethersulfone; PESF SO2

O n

b

a 2

10

Peak Notation

Assignment of Main Peaks

a

H3CO

b

H3 CO

SO2

25 [min]

20

Molecular Retention Weight Index

OCH3

Relative Intensity

108

108

1.5

278

278

100.0

[ Related Reference ] 1) Ohtani, H. ; Ishida, Y. ; Ushiba, M. ; Tsuge, S. J. Anal. Appl. Pyrolysis 2001, 61, 35.

a : anisole

b : 4,4'-sulfonylbis(methoxybenzene) 108 O

O

65

78

39 51 31

155

O S O

64

93 29 41 50

O

278 123

77 92 107

171

199

214

246

373

374

Tsuge, Ohtani and Watanabe

R28 [136] Poly(ether ether ketone); PEEK O

O

CO n

b

a

c

2

10

Peak Notation

Assignment of Main Peaks

a

H3CO

b

H3CO

CO

OCH3

c

H3CO

CO

O

Molecular Retention Index Weight

OCH3

OCH3

a : p-methoxyanisole

Relative Intensity

138

1170

27.2

242

2285

100.0

334

3140

33.7

b : 4,4'-dimethoxybenzophenone 123

O

25 [min]

20

135 O

O 138 O

95 41 29

52

63

80

108

29

c : (4-(4-methoxyphenoxy)phenyl)(4-methoxyphenyl) methanone 334 O

O

O

O

135

227

77 92 39 50

64

107 128

O

242

77 92

156171184

211 255

303319

50

64

211 107

128

156 171

199

227

Pyrograms for 33 Condensation Polymers and MS Data of the Major Pyrolyzates Obtained in the Presence of Organic Alkaline

R29 [151] Cellulose acetate; CA CH 2OCOCH3 H

O H OCOCH3 H H

MA

O

H n

OCOCH3

DF

MA’

2

10

25 [min]

20

Peak Notation

Assignment of Main Peaks

DF MA MA’

dimethyl formal methyl acetate methoxyacetaldehyde

Molecular Retention Weight Index 76 74 74

471 487 584

[ Related Reference ] 1) Schwarzinger, C.; Tanczos, I.; Schmidt, H. J. Anal. Appl. Pyrolysis 2002, 62, 179.

DF : dimethyl formal O

O

MA : methyl acetate 45

43

O 75

O 29 74 29 76

MA' : methoxyacetaldehyde 45

O O

29

56

74

59

Relative Intensity 100.0 1.7 5.7

375

376

Tsuge, Ohtani and Watanabe

R30 [152] Cellulose acetate-propionate; CAP CH2 OR H

MPr

O

O

H OR

H

H

OR

R=COCH3 or COC2H5

H n

DP

MA DC

B a b

2

MP BP P MS

10

Peak Notation

Assignment of Main Peaks

MA DC MPr B DP a b MP BP MS P

methoxyacetaldehyde dimethyl carbonate methyl propionate n-butanol dimethyl phthalate unidentified unidentified palmitic acid, methyl ester dibutyl phthalate stearic acid, methyl ester palmitic acid, butyl ester

25 [min]

20

Molecular Retention Index Weight

(plasticizer)

(plasticizer) (plasticizer) (plasticizer) (plasticizer)

74 90 88 74 194 270 278 298 312

584 613 623 654 1464 1560 1728 1923 1971 2125 2143

Relative Intensity 8.4 1.6 100.0 6.3 61.5 4.4 0.7 9.4 7.3 2.5 1.5

Pyrograms for 33 Condensation Polymers and MS Data of the Major Pyrolyzates Obtained in the Presence of Organic Alkaline

R30 [152]

MA : methoxyacetaldehyde

DC : dimethyl carbonate

45

45

O

O

O

O

29

59

31

O

62

74

56

MPr : methyl propionate

90

B : 1-butanol 56

57

O

OH

41

O

31

29 88

45

74

DP : dimethyl phthalate

a : unidentified 163

149

O O O O

77 92

50

29

104

120 133

194

149

b : unidentified

29 41

57

77 91

109

121 133

220

163

MP : palmitic acid, methyl ester 74

163

O 87

O

149 43 55 76

29 41 50

92 104

181

135

29

97

143 129

171185199

227 239

270

MS : stearic acid, methyl ester

BP : dibutyl phthalate 149

74 O O

87

O O 43

O

55 143

O 29 41

76

104 121

29

205 223

P : palmitic acid, butyl ester 57

O O 257 41 29

239 71

83 97 116

157

185

213

312

97

129

199 185

255 267

298

377

378

Tsuge, Ohtani and Watanabe

R31 [153] Cellulose acetate-butyrate; CAB CH2OR H

MB

O

O

H OR

H

H

OR

R=COCH3 or COC3H7

H n

MA DF

e a

b

c

d

2

10

Assignment of Main Peaks DF MA MB a b c d e

dimethyl formal methyl acetate methyl butanoate unidentified unidentified unidentified unidentified unidentified

25 [min]

20

Molecular Retention Index Weight 76 74 102 100 128 158 154 205

471 487 724 800 1040 1225 1256 2277

Relative Intensity 10.6 52.2 100.0 31.3 4.3 7.4 4.0 12.8

Pyrograms for 33 Condensation Polymers and MS Data of the Major Pyrolyzates Obtained in the Presence of Organic Alkaline

R31 [153]

DF : dimethyl formal

MA : methyl acetate 45

O

43

O

O 75

O

29

74 29

59

57

MB : methyl butanoate

a : unidentified

43

100

74

O 29

O

41

56 70

87

59 29

85

102

b : unidentified

c : unidentified 127

97

158

128 39

53

111 67

82 113

32

d : unidentified

45 53

29

69 81

53

111

83

45 111

68

81

125

173

139

95 29

143

e : unidentified 154

39

97

29

59

71

101 125 141 157

205

379

380

Tsuge, Ohtani and Watanabe

R32 [157] Shellac CH

2

O H

(C H

2

)5

CHOH CH (C H

2

f

)7 n

O

O

O O

R

R

e a

2

b c

d

g

h i

j

k

10

25 [min]

20

Molecular Retention Index Weight

Peak Notation

Assignment of Main Peaks

a

CH3O(CH2)12COOCH3 OCH3

242

1725

0.5

b

CH3(CH2)7CH(CH2)4COOCH3

272

1861

7.1

c

hexadecenoic acid, methyl ester

268

1917

0.5

322

2131

9.2

336

2221

21.1

360

2384

100.0

346

2447

12.6

410 438 466

2522 3029 3231 3429

0.5 3.1 1.7 1.0

d

H 3CO H 3COC

H 3CO H 3COC

Relative Intensity

COOCH3

CH 2OH COOCH3

e CH 2O CH3

OCH3 f

CH3O(CH2)6CHCH(CH2)7COOCH3 OCH3 OCH3

g

CH3O(CH2)6CHCH(CH2)7COOCH3 OH

h i j k

unidentified 1-octacosanol 1-triacontanol 1-pentacontanol [ Related Reference ]

1) Wang, L. ; Ishida, Y. ; Ohtani, H. ; Tsuge, S. ; Nakayama, T. Anal. Chem. 1999, 71, 1316.

381

Pyrograms for 33 Condensation Polymers and MS Data of the Major Pyrolyzates Obtained in the Presence of Organic Alkaline

R32 [157]

a : methyl tetradecanoate

b : methyl 6-methoxytetradecanoate

74

127

O O

87

41 55

43 55 29

143

129

101

199 211 185

157

242

c : hexadecenoic acid, methyl ester 87

O O

O

83 95

29

109

241 257

191

d : C18H26O5 45

O

113

159

69

O

55

67

81

O

O

O

O

95 145

41 55 67 29

95

127

166

185

227

e : C19H28O5

HO 262 217234

275

307 322

f : methyl 9,10,16-trimethoxyhexadecanoate 291

O

45

109 135 121 185 153 167

29

O

O

75 129 115 155

91 59

O

272

181

O

197213 227

71

95

201

304

O

O

O O

O

159

45

259

137

336

257

55 29

109

81

169185

126

329

265

g : methyl 10-hydroxy-9,16-dimethoxyhexadecanoate h : unidentified 95

71

O

O

45

145155

55

O

187201

4555

119

169

251

187

125

251

320

j : 1-triacontanol 57 83 97

HO

43

111

125

139 153 181 210 236 264 292 323

29

HO 71 111

125 364

392

29

k : 1-dotriacontanol 57 8397 HO 43 69 111

29

95 67 87 109

29

315

i : 1-octacosanol 57 83 97 45 69

145

109

81

29

155

O

OH

125 139 181 195 222 249 281 153

344

405

448

139 153 181 196 223 250

315

392

420

382

Tsuge, Ohtani and Watanabe

R33 [161] Synthetic lignin; DHP

b

d a MV

DS

E

2

c

MI

10

Peak Notation DS

Assignment of Main Peaks H3CO

25 [min]

20

CH=CH 2

Molecular Retention Weight Index

Relative Intensity

164

1371

0.2

182

1454

6.0

166

1487

6.0

178

1502

0.2

208

1749

34.5

270

1805

72.4

370

3222

37.5

386

3297

100.0

H3CO H 3CO

CH 2OCH3

E H 3CO H 3CO

CHO

MV H 3CO H3CO

CH=CHCH3

MI H3CO

a

H 3CO

CH=CHCH2OCH3

H 3CO

b

H 3CO

CH(OCH 3)CH(OCH3)CH 2OCH3

H 3CO H3CO

CH

CH

CH=CHCH 2OCH3

c H3CO

H 3CO OCH 2

d

H 3CO

OCH 3

CHCHCHCH

OCH 3

OCH 2 H 3CO

OCH 3

[ Related References ] 1) Mckinney, D. E.; Carson, D. M.; Clifford, D. J.; Minard, R. D.; Hatcher, P. G. J. Anal. Appl. Pyrolysis 1995, 34, 41. 2) del Rio, J. C.; Martin, F.; Gonzalez-Vila, F. J. Trends Anal. Chem. 1996, 15, 70. 3) Vane, C. H.; Abbott, G. D.; Head, I. M. J. Anal. Appl. Pyrolysis 2001, 60, 69. 4) Kuroda, K.; Nakagawa-Izumi, A. J. Agric. Food Chem. 2005, 53, 8859. 5) Kuroda, K.; Nakagawa-Izumi, A. Org. Geochem. 2005, 36, 53. 6) Klingberg, A.; Odermatt, J.; Meier, D. J. Anal. Appl. Pyrolysis 2005, 74, 104. 7) Kuroda, K.; Nakagawa-izumi, A. J. Anal. Appl. Pyrolysis 2006, 75, 104.

Pyrograms for 33 Condensation Polymers and MS Data of the Major Pyrolyzates Obtained in the Presence of Organic Alkaline

R33 [161]

DS : 3,4-dimethoxystyrene

E : 1,2-dimethoxy-4-(methoxymethyl)benzene 164

O

151 O

O 77

29

43

O 149

182

O

91 121

51 63

29 39

MV : 3,4-dimethoxybenzaldehyde

65 77

51

107

91

124 139

166

MI : 1,2-dimethoxy-4-(prop-1-enyl)benzene 178

166 O

O O O

O 107

95 51 29 41

65

163

91

77 107 119

41

151

137

31

63

51

79 131

a : 1,2-dimethoxy-4-(3-methoxy-1-propenyl)benzene b : 1,2-dimethoxy-4-(1,2,3-trimethoxypropyl)benzene 181

177 O

O

208

O

O O O

51 65

29

77

91 115

131

O

O

146 161

193

45

c : 1-(3,4-dimethoxystyryl)-2,3-dimethoxy-5-

77 91

137

270

d : 1,4-bis(3,4-dimethoxyphenyl)hexahydrofuro 165

370

O O

O 151 177

O

O

166

[3,4-c]furan

(3-methoxyprop-1-enyl)benzene O

151

O

O O

O 386 O

45

71

89 115

151 165 181

339 355

55

77 95

138 115

189 219 235

355

383

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APPENDIX

Monographs and Reviews for Pyrolysis-GC of Polymers

Monographs M-1 Stevens MP. Characterization and analysis of polymers by gas chromatography. New York: Marcel Dekker; 1969. M-2 May RW, Pearson EF, Scothern D. Pyrolysis-gas chromatography (Anal. Sci. Monograph, No. 3) The Chemical Society. London: Burlington Howe; 1977. M-3 Berezkin VG, Alishoyev VR, Nemiraskaya IB. Gas chromatography of polymers ( J. Chromatogr. Library vol. 10). Amsterdam: Elsevier; 1977. M-4 Jones CE, Cramers CA, editors. Analytical pyrolysis (Proceedings of 3rd international symposium on analytical and applied pyrolysis, Amsterdam 1976). Amsterdam: Elsevier; 1976. M-5 Voorhees KJ, editor. Analytical pyrolysis. London: Butterworths; 1984. M-6 Liebman SA, Levy EJ, editors. Pyrolysis and GC in polymer analysis (Chromatographic Science Series, vol. 29). New York: Marcel Dekker, Inc.; 1985. M-7 Ohtani H, Tsuge S. Polymer characterization by high-resolution pyrolysis-gas chromatography. In: Mitchell Jr, II-H J, editor. Applied polymer analysis and characterization. Munich: Hanser Publisher; 1987. M-8 Hammond T, Lehrle RS. Pyrolysis GLC. In: Booth C, Price C, editors. Comprehensive Polymer Science, vol. 1. Oxford: Pergamon Press; 1989. Chapter 27. M-9 Irwin WJ. Pyrolysis technique. In: Winefordner JD, editor. Treatise on analytical chemistry, part I thermal methods. 2nd ed. vol. 13. New York: John Wiley & Sons; 1993. M-10 Smith CG, et al., editors. Pyrolysis gas chromatography (CRC handbook of chromatography polymers vol. 2, I.4, III.3, and IV.3). Boca Raton: CRC Press; 1994. M-11 Wampler TP, editor. Applied pyrolysis handbook. New York: Marcel Dekker; 1995. M-12 Irwin WJ. Gas chromatography: pyrolysis gas chromatography (Encyclopedia of analytical science). Academic Press; 1995. M-13 Moldoveanu SC. Analytical pyrolysis of natural organic polymers. Amsterdam: Elsevier; 1998. M-14 Ohtani H, Tsuge S. Pyrolysis gas chromatography/mass spectrometry (Py-GC/MS). In: Montaudo G, Lattimer RP, editors. Mass spectrometry of polymer. CRC Press; 2002. Chapter 3. M-15 Moldoveanu SC. Analytical pyrolysis of synthetic organic polymers. Amsterdam: Elsevier; 2005. M-16 Kusch P, Knuppf G, Morrisson A. Analysis of synthetic polymers and copolymers by pyrolysis-gas chromatography/mass spectrometry. In: Bregg RK, editor. Horizons in polymer research. New York: Nova Science; 2005. Chapter 5. M-17 Wampler TP, editor. Applied pyrolysis handbook. 2nd ed. Boca Raton: CRC Press; 2007.

Reviews R-1 Irwin WJ, Slack JA. Analytical pyrolysis in biomedical studies. Analyst 1978;103:673–704. R-2 Irwin WJ. Analytical pyrolysis - an overview. J Anal Appl Pyrol 1979;1:3–25. R-3 Wolf CJ, Grayson MA, Fanter DL. Pyrolysis gas chromatography of polymers. Anal Chem 1980;52:348A–58A. R-4 Wheals BB. Analytical pyrolysis techniques in forensic science. J Anal Appl Pyrol 1981;2:277–92. R-5 Hu JC-A. Chromatography for polymer characterization. Anal Chem 1981;53:311A–8A.

385

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Monographs and Reviews for Pyrolysis-GC of Polymers

R-6 Tsuge S. Structural characterization of polymers by pyrolysis-gas chromatography. Tr Anal Chem 1981;1:87–90. R-7 Liebman SA, Levy EJ. Advances in pyrolysis GC systems: applications to modern trace organic analysis. J Chromatogr Sci 1983;21:1–10. R-8 Liebman SA, Wampler TP, Levy EJ. Developments in pyrolysis capillary GC. J High Res Chromatogr, Chromatogr Commun 1984;7:172–84. R-9 Jones ST. Application of pyrolysis gas chromatography in an industrial research laboratory. Analyst 1984;109:823–8. R-10 Hu JC-A. Chromatopyrography. Adv Chromatogr 1984;23:149–97. R-11 Hummel DO, Du¨ssel H-J, Czybulka G, Wenzel N, Holl G. Analytical pyrolysis of copolymers. Spectrochim Acta 1985;41:279–90. R-12 Levy EJ, Wampler TP. Identification and differentiation of synthetic polymers by pyrolysis capillary gas chromatography. J Chem Educ 1986;63:A64–8. R-13 Tsuge S. Characterization of polymers by high-resolution pyrolysis-gas chromatography with fusedsilica capillary columns. Chromatography Forum 1986;1:44–51. R-14 Tsuge S, Ohtani H, Matsubara H, Ohsawa M. Some empirical consideration on the pyrolysis-gas chromatographic conditions required to obtain characteristic and reliable high-resolution pyrograms for polymer samples. J Anal Appl Pyrol 1987;11:181–94. R-15 Hammond T, Lehrle RS. Pyrolysis-GLC Applied to composition analysis, general characterization and the detailed specification of polymers. Br Polym J 1989;21:23–30. R-16 Tsuge S, Ohtani H. Structural characterization of polymeric materials by pyrolysis-GC/MS. Polym Degrad Stab 1997;58:109–30. R-17 Haken JK. Pyrolysis gas chromatography of synthetic polymers - a bibliography. J Chromatogr A 1998;825:171–87. R-18 Wampler TP. Introduction to pyrolysis-capillary gas chromatography. J Chromatogr A 1999;842:207–20. R-19 Wang FC-Y. Polymer analysis by pyrolysis gas chromatography. J Chromatogr A 1999;843:413–23. R-20 Moldoveanu SC. Pyrolysis GC/MS, present and future (recent past and present needs). J Microcolumn Sep 2001;13:102–25. R-21 Challinor JM. Review: the development and applications of thermally assisted hydrolysis and methylation reaction. J Anal Appl Pyrol 2001;61:3–34. R-22 Watanabe C, Hosaka A, Kawahara Y, Tobias P, Ohtani H, Tsuge S. GC-MS analysis of heart-cut fractions during evolved gas analysis of polymeric materials. LC GC N Am 2002;20:374–8. R-23 R-23 Watanabe C, Sato K, Hosaka A, Ohtani H, Tsuge S. Development of a multifunctional pyrolyzer for evolved gas analysis, thermal desorption, and/or pyrolysis-GC of polymeric materials. Am Lab News 2002;10:14–5. R-24 Tsuge S, Ohtani H, Watanabe C, Kawahara Y. Application of a multifunctional pyrolyzer for evolved gas analysis and pyrolysis-GC of various synthetic and natural materials. Am Lab 2003;35(1):32–7. R-25 Tsuge S, Ohtani H, Watanabe C, Kawahara Y. Application of a multifunctional pyrolyzer for evolved gas analysis and pyrolysis-GC of various synthetic and natural materials; part 2. Am Lab 2003;35(3):48–52. R-26 Tsuge S, Ohtani H, Watanabe C. Application of a multifunctional pyrolyzer for evolved gas analysis and pyrolysis-GC of various synthetic and natural materials: part 3. Am Lab 2003;35(12):16–8. R-27 Tsuge S, Ohtani H, Watanabe C. Application of a multifunctional pyrolyzer for evolved gas analysis and pyrolysis-GC of various synthetic and natural materials: part 4. Am Lab 2004;36(2):22–6. R-28 Sobeih KL, Baron M, Gonzalez-Rodriquez J. Recent trends and developments in pyrolysis-gas chromatography. J Chromatogr A 2008;1186:51–66. R-29 Rial-Otero R, Galesio M, Capelo J-L, Simal-Gandara J. A review of synthetic polymer characterization by pyrolysis-GC-MS. Chromatographia 2009;70:339–48. R-30 Shadkami F, Helleur R. Recent applications in analytical thermochemolysis. J Anal Appl Pyrol 2010;89:2–16.

INDEX A AAS [Acrylonitrile-acrylate-styrene copolymer], 60 ABS [Acrylonitrile-butadiene-styrene copolymer], 58 ACM [Acrylic rubber], 100 Acrylic rubber, 100 Acrylonitrile-acrylate-styrene copolymer, 60 Acrylonitrile-styrene copolymer, 54 Acrylonitrile-butadiene rubber, 160 Acrylonitrile-butadiene-styrene copolymer, 58 Acrylonitrile-p-chlorostyrene copolymer, 78 Acrylonitrile-EPDM-styrene copolymer, 62 Acrylonitrile-methyl acrylate copolymer, 104 Acrylonitrile-styrene alternating copolymer, 56 Acrylonitrile-vinyl chloride alternating copolymer, 124 Acrylonitrile-vinyl chloride copolymer, 122 AES [Acrylonitrile-EPDM-styrene copolymer], 62 AS [Acrylonitrile-styrene copolymer], 54

B Bismaleimide triazine resin, 222, 348 Bisphenol Z polycarbonate, 266, 370 BR [High cis-butadiene rubber], 150 Brominated polycarbonate, 270 Brominated epoxy resin, 220 Br-PC [Brominated polycarbonate], 270 BT resin [Bismaleimide triazine resin], 222, 348

C CA [Cellulose acetate], 310, 375 CAB [Cellulose acetate-butyrate], 314, 378 CAP [Cellulose acetate-propionate], 312, 376 Caproamide-hexamethylene adipamide copolymer, 186 Carboxymethyl cellulose, 318 Cellulose, 304 Cellulose acetate, 310, 375 Cellulose acetate-butyrate, 314, 378 Cellulose acetate-propionate, 312, 376 CHC [Epichlorohydrin-ethylene oxide rubber], 198

Chitin, 324 Chitosan, 326 Chlorinated poly(vinyl chloride), 114 Chlorinated polyethylene, 116 Chloromethylated styrene-divinylbenzene copolymer, 80 Chloroprene rubber, 156 Chlorosulfonated polyethylene, 120 CHR [Epichlorohydrin rubber], 196 CM [Chlorinated polyethylene], 116 CMC [Carboxylmethyl cellulose], 318 CPVC [Chlorinated poly(vinyl chloride)], 114 CR [Chloroprene rubber], 156 CR-39 [Poly(ethylene glycol bisallyl carbonate)], 208, 343 Cresol formaldehyde resin (novolak), 204 CSM [Chlorosulfonated polyethylene], 120

D DAP [Diallyl phthalate resin], 206, 342 DHP [Synthetic lignin], 330, 382 Diallyl phthalate resin, 206, 342 Dimethylsiloxane-methylphenylsiloxane copolymer, 290

E EP [Epoxy resin], 218, 346 EPDM [Ethylene-propylene-diene rubber], 28 Epichlorohydrin rubber, 196 Epichlorohydrin-ethylene oxide rubber, 198 Epoxy resin, 218, 346 Ethylcellulose, 308 Ethylene-acrylic acid copolymer, 32 Ethylene-ethyl acrylate copolymer, 36 Ethylene-methyl methacrylate copolymer, 30 Ethylene-propylene copolymer, 26 Ethylene-propylene-diene rubber, 28 Ethylene-vinyl acetate copolymer, 34 Ethylene-vinyl alcohol copolymer, 38 EVA [Ethylene-vinyl acetate copolymer], 34

F FEP [Tetrafluoroethylene-hexafluoropropylene copolymer], 131

387

j

388

Index

G Glue, 320 Gluten, 334

H HEC [Hydroxyethylcellulose], 316 High cis-butadiene rubber, 150 Higher methacrylate copolymer, 98 Hydrogenated acrylonitrile-butadiene rubber, 162 Hydrogenated natural rubber, 158 Hydroxyethylcellulose, 316

Nylon-12 [Polylauroamide], 176 Nylon-12,6 [Poly(dodecamethylene adipamide)], 184 Nylon-4,6 [Poly(tetramethylene adipamide)], 178 Nylon-6 [Polycaproamide], 172 Nylon-6,10 [Poly(hexamethylene sebacamide)], 182 Nylon-6,6 [Poly(hexamethylene adipamide)], 180 Nylon-6/66 [Caproamide-hexamethylene adipamide copolymer], 186 Nylon-MXD6 [Poly(m-xylene adipamide)], 188

P I IIR [Isobutylene-isoprene rubber], 24 IO [Polyethylene ionomer], 40 Isobutylene-isoprene rubber, 24 Ivory, 328

K Kevlar, 232

M MBS [Methyl methacrylate-butadiene-styrene copolymer], 52 MC [Methylcellulose], 306 MDI-polylactone polyurethane, 300 Melamine formaldehyde resin, 212 Methyl acrylate-vinyl chloride alternating copolymer, 128 Methyl acrylate-vinyl chloride copolymer, 126 Methylcellulose, 306 Methyl methacrylate-butadiene-styrene copolymer, 52 Methyl methacrylate-methyl acrylate copolymer, 96 MF [Melamine formaldehyde resin], 212 MM-PC [Polycarbonate (melt method)], 262, 368 Modified poly(phenylene oxide), 276 Modified PPO [Modified poly(phenylene oxide)], 276

N Natural rubber, 154 NBR [Acrylonitrile-butadiene rubber], 160 Nomex [Poly(m-phenylene isophthalamide)], 234 NR [Natural rubber ], 154 Nylon-11 [Polyundecanoamide], 174

PAA [Poly(acrylic acid; isotactic)], 94, 340 PAAm [Polyacrylamide], 106 PABM [Polyaminobismaleimide], 228, 354 PAI [Polyamideimide], 230 PAN [Polyacrylonitrile], 102 P(AN-VC) [Acrylonitrile-vinyl chloride copolymer], 122 PAR [Polyarylate], 248, 361 PBA [Poly(butyl acrylate)], 92 PBMA [Poly(n-butyl methacrylate)], 84 PBT [Poly(butylene terephthalate)], 240, 357 PBSA [Poly(butylene succinate/adipate)], 256, 365 PCL [Poly(3-caprolactone)], 254, 364 PCTFE [Polychlorotrifluoroethylene], 132 PDMS [Polydimethylsiloxane], 286 PDVB [Polydivinylbenzene], 70 PE (HDPE) [Polyethylene (high density)], 12 PEA [Poly(ethyl acrylate)], 90 P(E-AA) [Ethylene-acrylic acid copolymer], 32 PEC [Poly(butylene succinate/carbonate)], 260, 367 P(E-EA) [Ethylene-ethyl acrylate copolymer], 36 PEEK [Poly(ether ether ketone)], 280, 374 PEI [Polyetherimide], 224, 350 P(E-MMA) [Ethylene-methyl methacrylate copolymer], 30 PEN [Poly(arylether nitrile)], 284 PEN [Poly(ethylene naphthalate)], 242, 358 P(E-P) [Ethylene-propylene copolymer], 26 PESF [Polyethersulfone], 278, 373 PET [Poly(ethylene terephthalate)], 238, 356 P(E-VA) [Ethylene-vinyl alcohol copolymer], 38 PF [Phenol formaldehyde resin (novolak)], 200 PHB [Poly(3-hydroxybutylic acid)], 258, 366 PHEMA [Poly(2-hydroxyethyl methacrylate)], 86

389

Index

Phenol formaldehyde resin (novolak), 200 Phenol formaldehyde resin (resol), 202 PI [Polypyromellitimide], 226, 352 PLA [Poly(lactic acid)], 252, 363 PMA [Poly(methyl acrylate)], 88 PMAH [Poly(maleic anhydride)], 108 P(MA-VC) [Methyl acrylate-vinyl chloride copolymer], 126 PMMA [Poly(methyl methacrylate)], 82 P(MMA-MA) [Methyl methacrylate-methyl acrylate copolymer], 96 PMP [Poly(4-methyl-1-pentene)], 22 PMPS [Polymethylphenylsiloxane], 288 PMPSQ [Poly(methyl-phenyl)silsesquioxane], 294 PMS [Poly(p-methylstyrene)], 74 P-a-MS [Poly(a-methylstyrene)], 68 PMSQ [Polymethylsilsesquioxane], 292 Polyamideimide, 230 Polyaminobismaleimide, 228, 354 Polyacrylamide, 106 Polyarylate, 248, 361 Poly(acrylic acid; isotactic), 94, 340 Polyacrylonitrile, 102 Poly(arylether nitrile), 284 Poly(1,2-butadiene), 152 Polybutene-1 (isotactic), 20 Poly(butyl acrylate), 92 Poly(butylene succinate/adipate), 256, 365 Poly(butylene succinate/carbonate), 260, 367 Poly(butylene terephthalate), 240, 357 Poly(n-butyl methacrylate), 84 Polycaproamide, 172 Poly(3-caprolactone), 254, 364 Polycarbonate(melt method), 262, 368 Polycarbonate(solvent method), 264, 369 Polycarbonate(thermally stabilized), 268, 371 Poly(p-chlorostyrene), 72 Polychlorotrifluoroethylene, 132 Poly(1,4-cyclohexane dimethylene terephthalate), 250, 362 Polydimethylsiloxane, 286 Polydivinylbenzene, 70 Poly(dodecamethylene adipamide), 184 Polyetherimide, 224, 350 Polyethersulfone, 278, 373 Poly(ethyl acrylate), 90 Polyethylene (high density), 12 Poly(ethylene glycol bisallyl carbonate), 208, 343

Polyethylene ionomer, 40 Poly(ethylene naphthalate), 242, 358 Poly(ethylene oxide), 194 Poly(ethylene terephthalate), 238, 356 Poly(ether ether ketone), 280, 374 Poly(hexamethylene adipamide), 180 Poly(hexamethylene sebacamide), 182 Poly(p-hydroxybenzoic acid) (type A), 244, 359 Poly(p-hydroxybenzoic acid) (type B), 246, 360 Poly(3-hydroxybutylic acid), 258, 366 Poly(2-hydroxyethyl methacrylate), 86 Poly(lactic acid), 252, 363 Polylauroamide, 176 Poly(maleic anhydride), 108 Poly(methyl acrylate), 88 Poly(methyl methacrylate), 82 Poly(4-methyl-1-pentene), 22 Polymethylphenylsiloxane, 288 Poly(methyl-phenyl)silsesquioxane, 294 Polymethylsilsesquioxane, 292 Poly(a-methylstyrene), 68 Poly(p-methylstyrene), 74 Polynorbornene, 164 Polyoxymethylene, 190 Polyoxymethylene(copolymer), 192 Poly(phenylene oxide), 274 Poly(phenylene sulfide), 282 Poly(p-phenylene/3,4-diphenylene ether terephthalamide), 236 Poly(m-phenylene isophthalamide), 234 Poly(p-phenylene terephthalamide), 232 Polypropylene(atactic), 16 Polypropylene(isotactic), 14 Polypropylene(syndiotactic), 18 Polypyromellitimide, 226, 352 P(S-DVB) [Styrene-divinylbenzene copolymer], 66 P(S-MA) [Styrene-methyl acrylate copolymer], 44 P(S-Mah) [Styrene-maleic anhydride copolymer], 64 P(S-MMA) [Styrene-methyl methacrylate copolymer], 48 Polystyrene, 42 Polysulfone, 272, 372 Polytetrafluoroethylene, 130 Poly(tetramethylene adipamide), 178 Polyundecanoamide, 174 Poly(vinyl acetate), 146

390

Index

Poly(vinyl alcohol), 142 Poly(vinyl butyral), 144 Poly(vinyl chloride), 110 Poly(vinyl fluoride), 134 Poly(vinylidene fluoride), 136 Poly(2-vinylpyridine), 76 Poly(vinyl pyrrolidone), 148 Poly(m-xylene adipamide), 188 POM [Polyoxymethylene], 190 at-PP [Polypropylene (atactic)], 16 iso-PP [Polypropylene (isotactic)], 14 syn-PP [Polypropylene (syndiotactic)], 18 PPO [Poly(phenylene oxide)], 274 PPS [Poly(phenylene sulfide)], 282 Propylene-tetrafluoroethylene rubber, 140 PS [Polystyrene], 42 PSF [Polysulfone], 272, 372 PTFE [Polytetrafluoroethylene], 130 PU [TDI-polyester polyuretane], 296 PU [TDI-polyether polyuretane], 298 PU [MDI-polylactone polyurethane], 300 PVA [Poly(vinyl alcohol)], 142 PVAc [Poly(vinyl acetate)], 146 PVB [Poly(vinyl butyral)], 144 PVC [Poly(vinyl chloride)], 110 P(VC-VAc) [Vinyl chloride-vinyl acetate copolymer], 118 P(VC-VdC) [Vinyl chloride-vinylidene chloride copolymer], 112 PVDF [Poly(vinylidene fluoride)], 136 PVF [Poly(vinyl fluoride)], 134 PVP [Poly(vinyl pyrrolidone)], 148

S SBR [Styrene-butadiene rubber], 166 SBS (TPS) [Styrene-butadiene-styrene block copolymer], 168 Shellac, 322, 380 SM-PC [Polycarbonate (solvent method)], 264, 369 Styrene-butadiene rubber, 166

Styrene-butadiene-styrene block copolymer, 168 Styrene-divinylbenzene copolymer, 66 Styrene-ethylene-butadiene-styrene block copolymer, 170 Styrene-maleic anhydride copolymer, 64 Styrene-methyl acrylate alternating copolymer, 46 Styrene-methyl acrylate copolymer, 44 Styrene-methyl methacrylate alternating copolymer, 50 Styrene-methyl methacrylate copolymer, 48 Synthetic lignin, 330, 382

T TDI-polyester polyuretane, 296 TDI-polyether polyuretane, 298 Tetrafluoroethylene-hexafluoropropylene copolymer, 131

U U [Urethane rubber], 302 UF [Urea formaldehyde resin], 210 Unsaturated polyester, 216, 344 UP [Unsaturated polyester], 216, 344 Urea formaldehyde resin, 210 Urethane rubber, 302

V Vinyl chloride-vinyl acetate copolymer, 118 Vinyl chloride-vinylidene chloride copolymer, 112 Vinylidene fluoride-hexafluoropropylene rubber, 138

W Wood powder, 332

X Xylene resin, 214