Plastics Materials

954 Pages·1999·47.982 MB·English

by  J A Brydson

PLASTICS
MATERIALS
SEVENTH EDITION
J. A. Brydson
Former Head of the Department of Physical Sciences
and Technology,
Polytechnic of North London (now known as the University of North London)
f
E I N E M A N N
OXFORD AUCKLAND BOSTON JOHANNESBURG MELBOURNE NEW DELHI
Butterworth-Heinemann
Linacre House, Jordan Hill, Oxford OX2 8DP
225 Wildwood Avenue, Wobum, MA 01801-2041
A division of Reed Educational and Professional Publishing Ltd
A member of the Reed Elsevier plc group
First published by Iliffe Books Ltd 1966
Second edition 1969
Reprinted 1970
Third edition 1975
Reprinted with revisions 1977
Reprinted 1979
Fourth edition published by Butterworth-Heinemann 1982
Reprinted 1985
Fifth edition 1989
Reprinted 1991, 1993
Sixth edition 1995
Reprinted 1995, 1996, 1998
Seventh edition 1999
0 J. A. Brydson 1995, 1999
All rights reserved. No part of this publication
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British Library Cataloguing in Publication Data
Brydson, J. A. (John Andrew), 1932-
Plastics materials. - 7th ed.
1. Plastics
I. Title
668.4
ISBN 0 7506 4132 0
Library of Congress Cataloguing in Publication Data
Brydson, J. A.
Plastics materia1slJ.A. Brydson. - 7th ed.
p. cm.
Includes bibliographical references and index.
ISBN 0 7506 4132 0 (hbk.)
1. Plastics. I. Title.
TP1120 B7 99-30623
668.4-dc21 CIP
Composition by Genesis Typesetting, Laser Quay, Rochester, Kent
Printed and bound in Great Britain by Biddles Lt4 Guildford and King’s Lynn
Contents
Preface to the Seventh Edition xvii
Preface to the First Edition xix
Acknowledgements for the Seventh Edition xxi
Abbreviations for Plastics and Rubbers xxiii
1 The Historical Development of Plastics Materials 1
1.1 Natural Plastics 1
1.2 Parkesine and Celluloid 3
1.3 1900-1930 4
1.4 The Evolution of the Vinyl Plastics 6
1.5 Developments since 1939 7
1.6 Raw Materials for Plastics 9
1.7 The Market for Plastics 11
1.8 The Future for Plastics 15
2 The Chemical Nature of Plastics 19
2.1 Introduction 19
2.2 Thermoplastic and Thermosetting Behaviour 23
2.3 Further Consideration of Addition Polymerisation 24
2.3.1 Elementary kinetics of free-radical addition polymerisation 29
2.3.2 Ionic polymerisation 33
2.3.3 Ziegler-Natta and metallocene polymerisation 37
2.4 Condensation Polymerisation 39
3 States of Aggregation in Polymers 43
3.1 Introduction 43
3.2 Linear Amorphous Polymers 43
3.2.1 Orientation in linear amorphous polymers 47
3.3 Crystalline Polymers 49
3.3.1 Orientation and crystallisation 52
3.3.2 Liquid crystal polymers 53
3.4 Cross-linked Structures 53
3.5 Polyblends 55
3.6 Summary 57
V
vi Contents
4 Relation of Structure to Thermal and Mechanical Properties 59
4.1 Introduction 59
4.2 Factors Affecting the Glass Transition Temperature 59
4.3 Factors Affecting the Ability to Crystallise 64
4.4 Factors Affecting the Crystalline Melting Point 70
4.5 Some Individual Properties 73
4.5.1 Melt viscosity 73
4.5.2 Yield strength and modulus 74
4.5.3 Density 74
4.5.4 Impact strength 74
5 Relation of Structure to Chemical Properties 76
5.1 Introduction 76
5.2 Chemical Bonds 76
5.3 Polymer Solubility 80
5.3.1 Plasticisers 87
5.3.2 Extenders 89
5.3.3 Determination of solubility parameter 89
5.3.4 Thermodynamics and solubility 93
5.4 Chemical Reactivity 95
5.5 Effects of Thermal, Photochemical and High-energy Radiation 96
5.6 Aging and Weathering 99
5.7 Diffusion and Permeability 100
5.8 Toxicity 103
5.9 Fire and Plastics 10 4
6 Relation of Structure to Electrical and Optical Properties 110
6.1 Introduction 110
6.2 Dielectric Constant, Power Factor and Structure 110
6.3 Some Quantitative Relationships of Dielectrics 117
6.4 Electronic Applications of Polymers 119
6.5 Electrically Conductive Polymers 120
6.6 Optical Properties 120
Appendix-Electrical Testing 122
7 Additives for Plastics 124
7.1 Introduction 124
7.2 Fillers 126
7.2.1 Coupling agents 128
7.3 Plasticisers and Softeners 131
7.4 Lubricants and Flow Promoters 132
7.5 Anti-aging Additives 134
7.5.1 Antioxidants 134
7.5.2 Antiozonants 143
7.5.3 Stabilisers against dehydrochlorination 143
7.5.4 Ultraviolet absorbers and related materials 143
7.6 Flame Retarders 145
7.7 Colorants 149
7.8 Blowing Agents 150
7.9 Cross-linking Agents 153
7.10 Photodegradants 154
7.11 2-Oxazolines 155
Contents vii
8 Principles of the Processing of Plastics 158
8.1 Introduction 158
8.2 Melt Processing of Thermoplastics 159
8.2.1 Hygroscopic behaviour 159
8.2.2 Granule characteristics 159
8.2.3 Thermal properties influencing polymer melting 161
8.2.4 Thermal stability 163
8.2.5 Flow properties 163
8.2.5.1 Terminology 164
8.2.5.2 Effect of environmental and molecular factors
on viscous flow properties 167
8.2.5.3 Flow in an injection mould 170
8.2.5.4 Elastic effects in polymer melts 171
8.2.6 Thermal properties affecting cooling 174
8.2.7 Crystallisation 17.5
8.2.8 Orientation and shrinkage 175
8.3 Melt Processing of Thermosetting Plastics 176
8.4 Processing in the Rubbery State 179
8.5 Solution, Suspension and Casting Processes 181
8.6 Summary 182
9 Principles of Product Design 184
9.1 Introduction 184
9.2 Rigidity of Plastics Materials 184
9.2.1 The assessment of maximum service temperature 186
9.2.1.1 Assessment of thermal stability 186
9.2.1.2 Assessment of softening point 188
9.3 Toughness 190
9.3.1 The assessment of impact strength 192
9.4 Stress-Strain-Time Behaviour 195
9.4.1 The WLF equations 196
9.4.2 Creep curves 198
9.4.3 Practical assessment of long-term behaviour 200
9.5 Recovery from Deformation 20 1
9.6 Distortion, Voids and Frozen-in Stress 202
9.7 Conclusions 204
10 Polyethylene 205
10.1 Introduction 205
10.2 Preparation of Monomer 207
10.3 Polymerisation 208
10.3.1 High-pressure polymerisation 208
10.3.2 Ziegler processes 209
10.3.3 The Phillips process 210
10.3.4 Standard Oil Company (Indiana) process 211
10.3.5 Processes for making linear low-density polyethylene and
metallocene polyethylene 21 1
10.4 Structure and Properties of Polyethylene 212
10.5 Properties of Polyethylene 217
10.5.1 Mechanical properties 217
10.5.2 Thermal properties 22 1
10.5.3 Chemical properties 223
10.5.4 Electrical properties 226
10.5.5 Properties of LLDPE and VLDPE 227
10.5.6 Properties of metallocene-catalysed polyethylenes 227
viii Contents
10.6 Additives 228
10.7 Processing 232
10.8 Polyethylenes of Low and High Molecular Weight 238
10.9 Cross-linked Polyethylene 239
10.10 Chlorinated Polyethylene 240
10.11 Applications 24 1
11 Aliphatic Polyolefins other than Polyethylene, and Diene Rubbers 247
11.1 Polypropylene 247
11.1.1 Preparation of polypropylene 248
11.1.2 Structure and properties of polypropylene 25 1
11.1.3 Properties of isotactic polypropylene 253
11.1.4 Additives for isotactic polypropylene 260
11.1.5 Processing characteristics 262
11.1.6 Applications 265
11.1.7 Atactic and syndiotactic polypropylene 267
11.1.8 Chlorinated polypropylene 268
11.2 Polybut-1-ene 268
11.2.1 Atactic polybut- 1-ene 269
11.3 Polyisobutylene 269
11.4 Poly-(4-methylpent-l-ene) 270
11.4.1 Structure and properties 270
11.4.2 General properties 272
11.4.3 Processing 273
11.4.4 Applications 273
11.5 Other Aliphatic Olefin Homopolymers 273
11.6 Copolymers Containing Ethylene 275
1 1.6.1 Ethylene-carbon monoxide copolymers (ECO) 278
11 .6.2 Ethylene-cyclo-olefin copolymers 280
11.7 Diene Rubbers 280
11.7.1 Natural rubber 285
11.7.2 Synthetic polyisoprene (IR) 289
11.7.3 Polybutadiene 290
11.7.4 Styrene-butadiene rubber(SBR) 29 1
11.7.4.1 ‘High styrene resins’ 294
11.7.5 Nitrile rubber (NBR) 294
11.7.6 Chloroprene rubbers (CR) 295
11.7.7 Butadiene-pentadiene rubbers 296
11.8 Thermoplastic Diene Rubbers 296
11.9 Aliphatic Olefin Rubbers 299
11.9.1 Thermoplastic polyolefin rubbers 302
11.10 Rubbery Cyclo-olefin (Cyclo-alkene) Polymers 304
1 1.10.1 Aliphatic polyalkenamers 304
11.10.2 Polynorbomene 306
11.10.3 Chlorine-containing copolymers 307
11.11 1,2-Polybutadiene 307
11. I2 Ethylene-styrene copolymers 308
11.13 Other elastomers 309
12 Vinyl Chloride Polymers 311
12.1 Introduction 311
12.2 Preparation of Vinyl Chloride 313
12.3 Polymerisation 315
12.4 Structure of Poly(viny1 chloride) 317
12.4.1 Characterisation of commercial polymers 320
Contents ix
12.5 Compounding Ingredients 325
12.5.1 Stabilisers 325
12.5.2 Plasticisers 330
12.5.3 Extenders 336
12.5.4 Lubricants 336
12.5.5 Fillers 337
12.5.6 Pigments 338
12.5.7 Polymeric impact modifiers and processing aids 338
12.5.8 Miscellaneous additives 342
12.5.9 Formulations 342
12.6 Properties of PVC Compounds 345
12.7 Processing 346
12.7.1 Plasticised PVC 347
12.7.2 Unplasticised PVC 349
12.7.3 Pastes 350
12.7.4 Copolymers 354
12.7.5 Latices 355
12.8 Applications 355
12.9 Miscellaneous Products 359
12.9.1 Crystalline PVC 359
12.9.2 Chlorinated PVC 359
12.9.3 Graft polymers based on PVC 360
12.9.4 Vinyl chloride-propylene copolymers 360
12.9.5 Vinyl chloride-N-cyclohexylmaleimide copolymers 360
13 Fluorine-containing Polymers 363
13.1 Introduction 363
13.2 Polytetrafluoroethylene 364
13.2.I Preparation of monomer 364
13.2.2 Polymerisation 364
13.2.3 Structure and properties 365
13.2.4 General properties 361
13.2.5 Processing 369
13.2.6 Additives 37 1
13.2.7 Applications 372
13.3 Tetrafluoroethylene-Hexafluoropropylene Copolymers 373
1 3.4 Tetrafluoroethylene-Ethylene Copolymers (ETFE) 374
13.5 Polychlorotrifluoroethylene Polymers (PCTFE)
and Copolymers with Ethylene (ECTFE) 374
13.6 Poly(viny1 fluoride) (PVF) 376
13.7 Poly(viny1idene fluoride) 376
13.8 Other Plastics Materials Containing Tetrafluoroethylene 377
13 .9 Hexafluoroisobutylene-Vinylidene Fluoride Copolymers 379
13.10 Fluorine-containing Rubbers 379
13.11 Thermoplastic fluoroelastomers 383
13.12 Miscellaneous Fluoropolymers 384
14 Poly(viny1 acetate) and its Derivatives 386
14.1 Introduction 386
14.2 Poly(viny1 acetate) 386
14.2.1 Preparation of the monomer 386
14 .2.2 Polymerisation 388
14.2.3 Properties and uses 389
14.3 Poly(viny1 alcohol) 389
14.3.1 Structure and properties 390
14.3.2 Applications 39 1
x Contents
14.4 The Poly(viny1 acetals) 39 1
14.4.1 Poly(viny1 formal) 392
14.4.2 Poly(viny1 acetal) 393
14.4.3 Poly(viny1 butyral) 393
14.5 Ethylene-Vinyl Alcohol Copolymers 394
14.6 Poly(viny1 cinnamate) 395
14.7 Other Organic Vinyl Ester Polymers 397
15 Acrylic Plastics 398
15.i Introduction 398
15.2 Poly(methy1 methacrylate) 400
15.2.1 Preparation of monomer 400
15.2.2 Polymerisation 40 1
15.2.3 Structure and properties 405
15.2.4 General properties of poly(methy1 methacrylate) 405
15.2.5 Additives 409
15.2.6 Processing 409
15.2.7 Applications 41 I
15.3 Methyl Methacrylate Polymers with Enhanced Impact
Resistance and Softening Point 413
15.4 Nitrile Resins 415
15.5 Acrylate Rubbers 417
15.6 Thermosetting Acrylic Polymers 418
15.7 Acrylic Adhesives 419
15.8 Hydrophilic Polymers 420
15.9 Poly(methacry1imide) 420
15.10 Miscellaneous Methacrylate and Chloroacrylate Polymers
and Copolymers 42 1
15.11 Other Acrylic Polymers 423
16 Plastics Based on Styrene 425
16.1 Introduction 425
16.2 Preparation of the Monomer 426
16.2.1 Laboratory preparation 426
16.2.2 Commercial preparation 427
16.3 Polymerisation 429
16.3.1 Mass polymerisation 429
16.3.2 Solution polymerisation 43 1
16.3.3 Suspension polymerisation 43 1
16.3.4 Emulsion polymerisation 432
16.3.5 Grades available 432
16.4 Properties and Structure of Polystyrene 433
16.5 General Properties 434
16.6 High-impact Polystyrenes (HIPS) (Toughened Polystyrenes (TPS)) 437
16.7 Styrene-Acrylonitrile Copolymers 44 1
16.8 ABS Plastics 441
16.8.1 Production of ABS materials 442
16.8.2 Processing of ABS materials 447
16.8.3 Properties and applications of ABS plastics 447
16.9 Miscellaneous Rubber-modified Styrene- Acrylonitrile
and Related Copolymers 448
16.10 Styrene-Maleic Anhydride Copolymers 450
16.11 Butadiene-Styrene Block Copolymers 450
16.12 Miscellaneous Polymers and Copolymers 452
16.13 Stereoregular Polystyrene 454
16.13.1 Syndiotactic polystyrene 454
Contents xi
16.14 Processing of Polystyrene 455
16.15 Expanded Polystyrene 457
16.15.1 Structural foams 4.59
16.16 Oriented Polystyrene 46 1
16.17 Applications 462
17 Miscellaneous Vinyl Thermoplastics 466
17.1 Introduction 466
17.2 Vinylidene Chloride Polymers and Copolymers 466
17.2.1 Properties and applications of vinylidene chloride-vinyl
chloride copolymers 468
17.2.2 Vinylidene chloride-acrylonitrile copolymers 470
17.3 Coumarone-Indene resins 47 1
17.4 Poly(viny1 carbazole) 472
17.5 Poly(viny1 pyrrolidone) 474
17.6 Poly(viny1 ethers) 475
17.7 Other Vinyl Polymers 476
18 Polyamides and Polyimides 478
18.1 Polyamides: Introduction 478
18.2 Intermediates for Aliphatic Polyamides 480
18.2.1 Adipic acid 480
18.2.2 Hexamethylenediamine 48 1
18.2.3 Sebacic acid and Azelaic acid 48 1
18.2.4 Caprolactam 482
18.2.5 w-Aminoundecanoic acid 483
18.2.6 w-Aminoenanthic acid 484
18.2.7 Dodecanelactam 485
18.3 Polymerisation of Aliphatic Polyamides 486
18.3.1 Nylons 46, 66, 69, 610 and 612 486
18.3.2 Nylon 6 486
18.3.3 Nylon 11 487
18.3.4 Nylon 12 487
18.3.5 Nylon 7 487
18.4 Structure and Properties of Aliphatic Polyamides 487
18.5 General Properties of the Nylons 490
18.6 Additives 496
18.7 Glass-filled Nylons 498
18.7.1 Comparison of nylons 6 and 66 in glass-filled compositions 500
18.8 Processing of the Nylons 500
18.9 Applications 502
18.10 Polyamides of Enhanced Solubility 505
18.1 1 Other Aliphatic Polyamides 507
18.12 Aromatic Polyamides 509
18.12.1 Glass-clear polyamides 509
18.12.2 Crystalline aromatic polyamides 513
18.12.2.1 Poly-rn-xylylene adipamide 513
18.12.2.2 Aromatic polyamide fibres 514
18.12.2.3 Polyphthalamide plastics 516
18.13 Polyimides 516
18.14 Modified Polyimides 52 1
18.14.1 Polyamide-imides 524
18.14.2 Polyetherimides 525
18.15 Elastomeric Polyamides 526
18.16 Polyesteramides- 528
xii Contents
19 Polyacetals and Related Materials 531
19.1 Introduction 53 1
19.2 Preparation of Formaldehyde 532
19.3 Acetal Resins 533
19.3.1 Polymerisation of formaldehyde 533
19.3.2 Structure and properties of acetal resins 536
19.3.3 Properties of acetal resins 538
19.3.4 Processing 542
19.3.5 Additives 543
19.3.6 Acetal-polyurethane alloys 544
19.3.7 Applications of the acetal polymers and copolymers 544
19.4 Miscellaneous Aldehyde Polymers 546
19.5 Polyethers from Glycols and Alkylene Oxides 546
19.5.1 Elastomeric polyethers 547
19.6 Oxetane Polymers 549
19.7 Polysulphides 55 1
20 Polycarbonates 556
20.1 Introduction 556
20.2 Production of Intermediates 557
20.3 Polymer Preparation 558
20.3.1 Ester exchange 558
20.3.2 Phosgenation process 560
20.4 Relation of Structure and Properties 56 1
20.4.1 Variations in commercial grades 564
20.5 General Properties 567
20.6 Processing Characteristics 573
20.7 Applications of Bis-phenol A Polycarbonates 575
20.8 Alloys based on Bis-phenol A Polycarbonates 578
20.9 Polyester Carbonates and Block Copolymers 579
20.10 Miscellaneous Carbonic Ester Polymers 580
2 1 Other Thermoplastics Containing p-Phenylene Groups 584
21.1 Introduction 584
21.2 Polyphenylenes 584
21.3 Pol y-p-xylylene 586
21.4 Poly(pheny1ene oxides) and Halogenated Derivatives 586
21.5 Alkyl Substituted Poly(pheny1ene oxides) including PPO 586
21.5.1 Structure and properties of
poly-(2,6-dimethyl-p-phenyleneo xide) (PPO) 587
21.5.2 Processing and application of PPO 589
21.5.3 Blends based in polyphenylene oxides 589
21.5.4 Styrenic PPOs 590
21.5.5 Processing of styrenic PPOs 59 1
21.5.6 Polyamide PPOs 592
21 57 Poly(2,6-dibromo-l,4-phenyleneo xide) 592
21.6 Polyphenylene Sulphides 593
21.6.1 Amorphous polyarylene sulphides 596
21.7 Pol ysulphones 596
21.7.1 Properties and structure of polysulphones 599
21.7.2 General properties of polysulphones 600
21.7.3 Processing of polysulphones 601
21.7.4 Applications 60 1
21.7.5 Blends based on polysulphones 602
21.8 Polyarylether Ketones 602
21.9 Phenoxy Resins 607
21.10 Linear Aromatic Polyesters 607