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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Contents

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

5

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

j

8


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

9

10


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.


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.)

11

12


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


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

14


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


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


002

EGA thermogram

Averaged mass spectrum 41 69

55

100

200

300

400

500

600

700 ºC


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

16


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

n

C15 C9 C12

C’13 C13

C18

C21

C’16

10

C3 C5

TIC

0

10


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


003

EGA thermogram


69 55 100

200

300

400

500

600

700 ºC


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


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


41

43 55

126 111

97

55

69

69

29

83

83 111 97

125 132

125

97 168


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


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


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.


19


004

EGA thermogram


69

100

200

300

400

500

600

700 ºC


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


69

69

43

55

55 85

84

111

112 97

29

125 132

168


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


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


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


21


005

EGA thermogram

Averaged mass spectrum 55 41 100

200

300

400

500

600

700 ºC


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


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


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


23


006

EGA thermogram


100

200

300

400

500

600

700 ºC


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


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


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


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


25


007

EGA thermogram


100

200

300

400

500

600

700 ºC


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


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


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


008

EGA thermogram

Averaged mass spectrum 41 55 69 100

200

300

400

500

600

700 ºC


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


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


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


009

EGA thermogram


41

69 100

200

300

400

500

600

700 ºC


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


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


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


010

EGA thermogram


69

200

300

400

500

600

700 ºC


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


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


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


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


011

EGA thermogram


200

300

400

500

600

700 ºC


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


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



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


012

EGA thermogram


69

200

300

400

500

600

700 ºC


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


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


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


013

EGA thermogram


83

200

300

400

500

600

700 ºC


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


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


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


014

EGA thermogram


100

200

300

400

500

600

700 ºC


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


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



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


015

EGA thermogram


69

200

300

400

500

600

700 ºC


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


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


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



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


016

EGA thermogram


91 78

100

200

300

400

500

39

600

700 ºC


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


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


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


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


017

EGA thermogram


100

200

300

400

500

600

700 ºC


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


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


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


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


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


018

EGA thermogram


78

300

400

500

600

700 ºC


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


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


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


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


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.


49


019

EGA thermogram


78

100

103

39

200

300

400

500

600

700 ºC


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


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


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


117 3951

6577

129

178

194 207 221

297312

39 51

190

77

204

158172 217

277

50


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


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.


51


020

EGA thermogram


78

100

103

39

200

300

400

500

600

700 ºC


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


115

O

O

O O 176

91 39

51

32

65

144

89

161

32

39

51

115

65

145 158

176 190


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


117 44 32 51 6977

129

165178 194

281

190 204 158172

277

52


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


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


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

395 710 766 835 866 892 983 1668 1736 2482


53


021

EGA thermogram


100

200

300

400

500

69

600

700 ºC


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


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


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



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


022

EGA thermogram


104

78

100

39

65

300

400

500

170

700 ºC

150

261 255

210 220

182 193 100

600


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


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


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.


57


023

EGA thermogram


91

78

100

200

300

400

500

144

51

600

700 ºC


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


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



65

91

N

117 117

39 51 63

77

128

157

182

65 77 39 51

210


156169

91

N

115 77

65 205

220233

261

N 170

115 118

91

118

195


144

39 51 65

128

260

39 51

77

105

156 142 246261

58


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


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


* 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


59


024

EGA thermogram


91

78

100

200

300

400

500

600

700 ºC


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


SA : 4-phenylpent-4-enenitrile 115

N

N

157

39

51

77

39

157

115 128 140

129 142

63

32

SA' : 4-phenylpentanenitrile


103

91

N 169

77 39

103

77

51 65

154 115

51

141

63

128

39 51


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


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


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



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


61


025

EGA thermogram


91 78

100

200

300

400

500

600

700 ºC


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


104

103

78 51 39

39

63


51

65

157

77

115 128 140


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


144

91

N

N 115 118

91

77

208

104 117


39 51 65

165 178 193



115 130

65 77

105

115 118

170 156

77 65 170

203

220 233

260

39 51

142 246261

62


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


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


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


026

EGA thermogram


104

78 100

200

300

400

500

117

39

65

144 129

50

156

100

600

700 ºC


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



N

115

N

157

91 103

77

130

51 39

51

65 77

157

128

104


142

63

39

AAS : 2-methylene-4-phenethylpentanedinitrile

91

91

N

N

105 39 51

65

104115 130

77

39

208 180 193


65 77

51

91

91

66

128

157168 182

210

39 51


182

209

N

65 77

128

169

91

N

N 115 118

91

105

115 104

65

77 220233

261


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


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


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


027

EGA thermogram


78

100

200

300

400

500

39

600

700 ºC


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


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


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


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

91

145 156

102

196

152

178190

208

39 51

6577

129

194207 221

297312

66


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


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


67


028

EGA thermogram


91 100

200

300

400

500

600

700 ºC


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


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


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


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


029

EGA thermogram


78

51

200

300

400

500

39

600

700 ºC


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


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


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


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


030

EGA thermogram


100

39

51

77

63

300

400

500

600

700 ºC


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


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


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.


73


031

EGA thermogram


103

100

200

300

400

500

600

700 ºC


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


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


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


032

EGA thermogram


100

200

300

400

500

91

600

700 ºC


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


033 Poly(2-vinylpyridine) CH2CH(C5H4N)

n

VV

V

IP

VVV

c b d

a

e

10

TIC

20

MP

0

10

Peak Notation


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


811 933 1023 1613 1832 1921 1935 1988 2101 2619


* 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


033

EGA thermogram


100

93

200

300

210

65

144 154

50

500

600

700 ºC


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


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


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


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.


79


034

EGA thermogram


200

300

400

500

600

77 75

51

700 ºC


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


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


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


81


035

EGA thermogram


105117

100

200

300

400

500

600

700 ºC


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


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

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

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

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