Table Of ContentSpecialty Polymers
SPECIALTY POLYMERS
Edited by
R.W. DYSON
Senior Lecturer in Polymer Technology
London School of Polymer Technology
Polytechnic of North London
Blackie
Glasgow and London
Published in the USA by
Chapman and Hall
New York
Blackie & Son Limited,
Bishopbriggs, Glasgow G64 2NZ
7 Leicester Place
London WC2H 7BP
Published in the USA by
Chapman and Hall
in association with Methuen, Inc.
29 West 35th Street, New York, NY 10001-2291
© 1987 Blackie & Son Ltd
First published 1987
All rights reserved.
No part of this publication may be reproduced,
stored in a retrieval system, or transmitted,
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British Library Cataloguing in Publication Data
Specialty polymers.
1. Polymers and polymerization
I. Dyson, R.W.
547.7 QD381
ISBN-13: 978-0-216-92248-8 e-ISBN-13: 978-1-4615-7894-9
DOl: 10.1007/978-1-4615-7894-9
Library of Congress Cataloging-in-Publication Data
Specialty polymers.
Bibliography: p.
Includes index.
1. Polymers and polymerization. I. Dyson, R.W.
(Robert William), 1942-
QD381.S634 1987 668.9 87-6673
Phototypesetting by Thomson Press (India) Ltd, New Delhi
Contents
Abbreviations ix
Trade names xi
Introduction 1
1 Polymer structures and general properties 3
R.W. DYSON
1.1 Introduction 3
1.2 Polymer structures 3
1.3 Morphology and softening behaviour 5
1.4 Amorphous polymers and softening behaviour 8
1.5 Semi-crystalline polymers and softening behaviour 9
1.6 Molecular weight 10
1.7 Copolymers 12
1.8 Chemical behaviour 14
1.9 Solubility 16
1.10 Electrical properties 18
1.11 Conclusion 19
Further reading 19
2 Polymerization 20
R.W. DYSON
2.1 Introduction 20
2.2 Addition polymerization 20
2.2.1 Monomers 20
2.2.2 Free radical polymerization 21
2.2.3 Ionic polymerization 23
2.2.4 Catalytic surface polymerization 24
2.3 Step-growth polymerization 24
2.4 Copolymer formation 26
2.4.1 Step growth polymerization 27
2.4.2 Random copolymers 27
2.4.3 Block copolymers 30
2.4.4 Graft copolymers 32
2.5 Chemical conversion 35
2.6 Polyblends 35
2.7 Conclusion 37
3 High-temperature and fire-resistant polymers 38
M.S.M. ALGER
3.1 Introduction 38
3.2 The need for thermally resistant polymers 40
3.3 Improving low-performance polymers for high-temperature use 40
3.4 The need for fire-resistant polymers 42
3.5 Polymers for low fire hazards 45
VI CONTENTS
3.6 Polymers for high temperature resistance 46
3.6.1 Fluoropolymers 48
3.6.2 Aromatic polymers 49
3.6.3 Hydrocarbon polymers 51
3.6.4 Polyethers 52
3.6.5 Polyphenyl sulphide 53
3.6.6 Polysulphones 53
3.6.7 Polyesters 55
3.6.8 Polyamides 57
3.6.9 Polyketones 59
3.7 Heterocyclic polymers 60
3.7.1 Polyimides 60
3.7.2 Other polymers 63
Further reading 64
4 Hydrophilic polymers 65
CA. FINCH
4.1 Introduction 65
4.2 Natural polymers 67
4.2.1 Carbohydrates 67
4.2.2 Proteins 71
4.3 Semi-synthetic polymers 72
4.4 Synthetic polymers 75
4.4.1 Hydrogel 75
4.4.2 Polyacrylamide hydrophilic polymers 79
4.4.3 Polyvinyl alcohol 81
4.4.4 Polyvinyl pyrrolidone 81
Further reading 82
5 Polymers with electrical and electromeric properties 83
M. GOOSEY
5.1 Introduction 83
5.2 Conducting polymers 83
5.2.1 Introduction 83
5.2.2 Conduction mechanisms 84
5.2.3 Polyacetylene 86
5.2.4 Polyparaphenylenes (PPP) 88
5.2.5 Polypyrrole 89
5.2.6 Other important conducting polymers 90
5.2.7 Organometallic polymers 91
5.2.8 Applications for conducting polymers 92
5.3 Photoconducting polymers 92
5.4 Polymers in non-linear optics 94
5.5 Polymers with piezoelectric, pyroelectric and ferroelectric properties 95
5.5.1 Introduction 95
5.5.2 Polyvinylidene l1uoride (CH2 CF 2) 96
5.5.3 Polyvinylidene l1uoride-tril1uoroethylene copolymers (PVDF- TrF) 98
5.5.4 Other materials 98
5.s.5 Applications 99
5.6 Photoresists for semiconductor fabrication 100
5.6.1 Introduction 100
5.6.2 Negative photoresists 103
5.6.3 Positive photoresists 104
5.6.4 Electron beam lithography 105
5.6.5 Plasma developable photoresists 106
References 108
CONTENTS vii
no
6 Ionic polymers
B.N. HENDY
6.1 Introduction 110
6.2 Classification 110
6.2.1 Type of bound ion 110
6.2.2 Position of the bound ion 111
6.2.3 Amount of bound ion 111
6.2.4 Type of counter-ion 111
6.2.5 The backbone 112
6.3 Synthesis 112
6.4 Physical properties and applications 114
6.4.1 Ionic cross-linking 114
6.4.2 Ion-exchange 117
6.4.3 Hydrophilicity 121
6.5 Ionomers based on polyethylene 123
6.6 Elastomeric ionomers 126
6.7 Ionomers based on polystyrene 130
6.8 Ionomers based on polytetralluoroethylene 134
6.9 Ionomers with polyaromatic backbones 136
6.10 Polyelectrolytes for ion-exchange 137
6.11 Polyelectrolytes based on carboxylates 141
6.12 Polymers with integral ions 142
6.12.1 Halato-telechelic polymers (HTPs) 142
6.12.2 Ionenes 143
6.12.3 Polyethylenimine (PEl) 144
6.13 Polyelectrolyte complexes 144
6.14 Blends of polymers and salts 145
6.15 Biological and inorganic ionic polymers 146
6.16 Conclusions 148
References 148
7 Polyurethanes 150
R.G. PEARSON
7.1 Introduction 150
7.2 Chemical aspects 150
7.2.1 Reactions 150
7.2.2 Molecular structures 154
7.2.3 Component materials 157
7.3 Product types 160
7.3.1 Foams 160
7.3.2 RIM and RRIM 168
7.3.3 Thermoplastic polyurethanes 172
7.3.4 Rubbers 176
7.3.5 Fibres, coatings and adhesives 179
7.4 Conclusion 180
References and further reading 180
Index 181
Contributors
M.S.M. Alger London School of Polymer Technology,
The Polytechnic of North London,
Holloway, London N7 8DB, UK
R.W. Dyson London School of Polymer Technology,
The Polytechnic of North London,
Holloway, London N7 8DB, UK
C.A. Finch Pentafin Associates, Weston Turville,
Aylesbury, Bucks HP22 5TT, UK
M. Goosey Plessey Research, Allen Clark Research
Centre, Caswell, Towcester, Northants
MN12 8EQ, UK
B.N. Hendy New Science Group, ICI pIc, PO Box 90,
Wilton, Middlesbrough, Cleveland TS6 8JE
R.G. Pearson London School of Polymer Technology,
The Polytechnic of North London,
Holloway, London N7 8DB, UK
Abbreviations
ABS acrylonitrile-butadiene-styrene
AMPS 2-acrylamido-2-methylpropane sulphonic acid
C-PS carboxylated polystyrene
DSC differential scanning calorimeter (calorimetry)
DVB di-vinyl benzene
ENB ethylene norbornene
EPDM ethylene-propylene-diene monomer terpolymer
EPR ethylene-propylene rubber
HEMA hydroxyethyl methacrylate
HDT heat distortion temperature
HTP halato-telechelic polymer
IPN interpenetrating network
LCP liquid crystal polymer
LOI limiting oxygen index
MDI 4,4 diphenylmethane diisocyanate
MOCA 4,4 methylene-bis-2-chloroaniline
MOSFET metal oxide semiconductor field effect transistor
NBR nitrile rubber (acrylonitrile-butadiene copolymer)
NDI naphthalene diisocyanate
PA polyamide (nylons)
PAQR poly (acene-quinone radical) polymer
PBI polybenzimidazole
PBT polybutylene terephthalate
PC polycarbonate
PEC polyelectrolyte complex
PEEK polyether-etherketone
PEl polyethylenimine
PEK polyether ketone
PES polyether sulphone (victrex type)
PESujPSu polyether sulphone (udel type)
PET polyethylene terephthalate
PF phenol formaldehyde resin
PMMA polymethylmethacrylate
POM polyoxy-methylene (acetals)
POSFET piezoelectric oxide semiconductor field effect transistor
PPE polyphenylene ether
PPO poly dimethyl-phenylene oxide
x
ABBREVIATIONS
PPP polyparaphenylene
PPS polyphenylene sulphide
PPSe polyphenylene selenide
PPTS poly pyrrole toluene sulphonate
PPV poly-p-phenylene vinylene
PS polystyrene
PTFE polytetrafluoroethylene
PTrFE polytrifluoroethylene
PU polyurethane
PYA polyvinyl alcohol
PVC polyvinyl chloride
PVDF polyvivnylidene fluoride
PVK poly-n-vinyl carbazole
PVP polyvinyl pyrrolidone
RIM reaction injection moulding
RRIM reinforced reaction injection moulding
SAXS small angle X-ray scattering
SBR styryne butadiene rubber
SCMC sodium carboxy-methyl cellulose
SIN simultaneously inter-penetrating network
S-PS sulphonated polystyrene
TDI tolylene (or toluene) diisocyanate
TLV threshold limit value
TNF trinitrofluorenone
TrFE trifluoro ethylene
Note: this list includes standard abbreviations for polymers mentioned in
the text, even though the abbreviation itself is not mentioned.
Trade names
Aclar fluoropolymer Du Pont
Adiprene polyurethane Uniroyal
Algoflon fluoropolymer Montedison
Amberlite ion exchange resins Rohm and Haas
Amberlyst polyelectrolyte Rohm and Haas
Arcton fluorotrichloromethane ICI
Ardel aromatic polyester Union Carbide
Arylef aromatic polyester Solvay
Arylon aromatic polyester Du Pont
Astrel polyether sui phone 3M
Carbopol acrylic polyelectrolyte BF Goodrich
Carboset acrylic polyelectrolyte BF Goodrich
Dowex aminated styrene copolymer Dow Chemical
Duolite polyelectrolyte Rohm and Haas
Ekkcel aromatic polyester Carborundum
Ekonol aromatic polyester Carborundum
Flemion carboxylated fluoropolymer Asahi Glass
Fluon fluoropolymer ICI
Fluorel fluoropolymer 3M
Fluothane fluoropolymer USI
Freon fluorotrichloromethane Du Pont
Gantrez AN polyelectrolyte GAF
Grilamid TR aromatic polyamide Emser
Halon fluoropolymer Du Pont
H resin aromatic hydrocarbon Hercules
Hostaflon fluoropolymer Hoechst
Hostaflor C fluoropolymer Hoechst
Hostatec polyether ketone Hoechst
Hycar polycarboxyllic acid BF Goodrich
Hypalon chi oro-sulphonated polyethylene Du Pont
Ixef aromatic polyamide Solvay
Kalrez fluoropolymer Du Pont
Kapton polyimide Du Pont
Kelf fluoropolymer 3M
Kerimid polybismaleimide Rhone-Poulenc
Kevlar aromatic polyamide Du Pont
Kinel polybismaleimide Rhone-Poulenc
Krynac carboxylated nitrile rubber Doverstrand
Luranyl polyphenylene oxide (blend) BASF
