Plastics Materials 7E Episode 1 pps

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
EINEMANN
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
may
be reproduced in any material form (including
photocopying
or
storing in any medium by electronic
means and whether

or
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or
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to some other use
of
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of
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Designs and Patents Act 1988
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Applications
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to reproduce any part
of
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be
addressed
to the publisher

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
Preface
to
the First Edition
Acknowledgements for the Seventh Edition
Abbreviations for Plastics and Rubbers
1
The Historical Development of Plastics Materials
1.1 Natural Plastics
1.2 Parkesine and Celluloid
1.4
1.5 Developments since 1939
1.6 Raw Materials for Plastics
1.7 The Market for Plastics
1.8
The Future for Plastics
1.3 1900-1930
The Evolution
of
the Vinyl Plastics
2 The Chemical Nature
of
Plastics

2.1 Introduction
2.2 Thermoplastic and Thermosetting Behaviour
2.3
Further Consideration
of
Addition Polymerisation
2.3.1
2.3.2 Ionic polymerisation
2.3.3 Ziegler-Natta and metallocene polymerisation
Elementary kinetics of free-radical addition polymerisation
2.4 Condensation Polymerisation
3
States
of
Aggregation in Polymers
3.1 Introduction
3.2 Linear Amorphous Polymers
3.2.1
3.3 Crystalline Polymers
3.3.1 Orientation and crystallisation
3.3.2 Liquid crystal polymers
Orientation
in
linear amorphous polymers
3.4
Cross-linked Structures
3.5 Polyblends
3.6 Summary
xvii
xix

xxi
xxiii
1
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55
57
V

vi
Contents
4
Relation of Structure to Thermal and Mechanical Properties
4.1 Introduction
4.2 Factors Affecting the Glass Transition Temperature
4.3 Factors Affecting the Ability to Crystallise
4.4 Factors Affecting the Crystalline Melting Point
4.5 Some Individual Properties
4.5.1 Melt viscosity
4.5.2 Yield strength and modulus
4.5.3 Density
4.5.4 Impact strength
5
Relation of Structure to Chemical Properties
5.1
Introduction
5.2 Chemical Bonds
5.3 Polymer Solubility
5.3.1 Plasticisers
5.3.2 Extenders
5.3.3 Determination
of
solubility parameter
5.3.4 Thermodynamics and solubility
Effects
of
Thermal, Photochemical and High-energy Radiation
5.4 Chemical Reactivity
5.5

5.6 Aging and Weathering
5.7 Diffusion and Permeability
5.8 Toxicity
5.9 Fire and Plastics
6
Relation of Structure to Electrical and Optical Properties
6.1 Introduction
6.2
6.3
6.4 Electronic Applications of Polymers
6.5 Electrically Conductive Polymers
6.6 Optical Properties
Appendix-Electrical Testing
Dielectric Constant, Power Factor and Structure
Some Quantitative Relationships of Dielectrics
7 Additives for Plastics
7.1 Introduction
7.2 Fillers
7.2.1 Coupling agents
7.3 Plasticisers and Softeners
7.4 Lubricants and Flow Promoters
7.5 Anti-aging Additives
7.5.1 Antioxidants
7.5.2 Antiozonants
7.5.3 Stabilisers against dehydrochlorination
7.5.4
Ultraviolet absorbers and related materials
7.6 Flame Retarders
7.7 Colorants
7.8 Blowing Agents

7.9 Cross-linking Agents
7.10 Photodegradants
7.11 2-Oxazolines
59
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59
64
70
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74
74
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96
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103
1 04
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110
110

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128
131
132
134
134
143
143
143
145
149
150
153
154
155
Contents
vii
8
Principles
of
the Processing of Plastics
8.1 Introduction
8.2 Melt Processing of Thermoplastics

8.2.1 Hygroscopic behaviour
8.2.2 Granule characteristics
8.2.3
8.2.4 Thermal stability
8.2.5 Flow properties
8.2.5.1 Terminology
8.2.5.2 Effect of environmental and molecular factors
on
viscous flow properties
8.2.5.3 Flow in
an
injection mould
8.2.5.4 Elastic effects in polymer melts
8.2.6 Thermal properties affecting cooling
8.2.7 Crystallisation
8.2.8 Orientation and shrinkage
Melt Processing of Thermosetting Plastics
Processing
in
the Rubbery State
Solution, Suspension
and
Casting Processes
Thermal properties influencing polymer melting
8.3
8.4
8.5
8.6 Summary
9 Principles of Product Design
9.1 Introduction

9.2 Rigidity of Plastics Materials
9.2.1
The assessment of maximum service temperature
9.2.1.1 Assessment of thermal stability
9.2.1.2 Assessment of softening point
The assessment of impact strength
9.3 Toughness
9.3.1
9.4 Stress-Strain-Time Behaviour
9.4.1 The
WLF
equations
9.4.2 Creep curves
9.4.3
9.5 Recovery from Deformation
9.6 Distortion, Voids and Frozen-in Stress
9.7 Conclusions
Practical assessment
of
long-term behaviour
10 Polyethylene
10.1 Introduction
10.2 Preparation of Monomer
10.3 Polymerisation
10.3.1 High-pressure polymerisation
10.3.2 Ziegler processes
10.3.3 The Phillips process
10.3.4 Standard Oil Company (Indiana) process
10.3.5 Processes for making linear low-density polyethylene and
metallocene polyethylene

Structure
and
Properties
of
Polyethylene
10.5.1 Mechanical properties
10.5.2 Thermal properties
10.5.3 Chemical properties
10.5.4 Electrical properties
10.5.5
10.5.6 Properties of metallocene-catalysed polyethylenes
10.4
10.5 Properties of Polyethylene
Properties of LLDPE and VLDPE
158
158
159
159
159
161
163
163
164
167
170
171
174
17.5
175
176

179
181
182
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188
190
192
195
196
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200
20
1
202
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205
207
208
208
209
210
211
21
1
212

217
217
22 1
223
226
227
227
viii
Contents
10.6 Additives
10.7 Processing
10.8
10.9 Cross-linked Polyethylene
10.10 Chlorinated Polyethylene
10.11 Applications
Polyethylenes of
Low
and High Molecular Weight
11
Aliphatic Polyolefins other than Polyethylene, and Diene Rubbers
11.1 Polypropylene
11.1.1 Preparation of polypropylene
11.1.2
11.1.3 Properties of isotactic polypropylene
11.1.4 Additives for isotactic polypropylene
11.1.5 Processing characteristics
11.1.6 Applications
11.1.7 Atactic and syndiotactic polypropylene
11.1.8 Chlorinated polypropylene
11.2.1 Atactic polybut- 1-ene

Structure and properties of polypropylene
11.2 Polybut-1-ene
11.3 Polyisobutylene
11.4
Poly-(4-methylpent-l-ene)
11.4.1 Structure and properties
11.4.2 General properties
11.4.3 Processing
11.4.4 Applications
11.5 Other Aliphatic Olefin Homopolymers
11.6 Copolymers Containing Ethylene
1
1.6.1
1 1.6.2 Ethylene-cyclo-olefin copolymers
11.7 Diene Rubbers
Ethylene-carbon monoxide copolymers (ECO)
11.7.1 Natural rubber
11.7.2 Synthetic polyisoprene (IR)
11.7.3 Polybutadiene
11.7.4 Styrene-butadiene rubber(SBR)
11.7.4.1 ‘High styrene resins’
11.7.5 Nitrile rubber (NBR)
11.7.6 Chloroprene rubbers (CR)
11.7.7 Butadiene-pentadiene rubbers
11.8 Thermoplastic Diene Rubbers
11.9 Aliphatic Olefin Rubbers
11.10 Rubbery Cyclo-olefin (Cyclo-alkene) Polymers
11.9.1 Thermoplastic polyolefin rubbers
1
1.10.1 Aliphatic polyalkenamers

11.10.2 Polynorbomene
11.10.3 Chlorine-containing copolymers
11.11 1,2-Polybutadiene
11 .I2 Ethylene-styrene copolymers
11.13 Other elastomers
12 Vinyl Chloride Polymers
12.1 Introduction
12.2 Preparation
of
Vinyl Chloride
12.3 Polymerisation
12.4 Structure
of
Poly(viny1 chloride)
12.4.1 Characterisation
of
commercial polymers
228
232
238
239
240
24 1
247
247
248
25 1
253
260
262

265
267
268
268
269
269
270
270
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273
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273
275
278
280
280
285
289
290
29
1
294
294
295
296
296
299
302
304
304

306
307
307
308
309
311
311
313
315
317
320
12.5
12.6
12.7
12.8
12.9
Compounding Ingredients
12.5.1 Stabilisers
12.5.2 Plasticisers
12.5.3 Extenders
12.5.4 Lubricants
12.5.5 Fillers
12.5.6 Pigments
12.5.7
12.5.8 Miscellaneous additives
12.5.9 Formulations
Properties
of
PVC Compounds
Processing

12.7.1 Plasticised PVC
12.7.2 Unplasticised PVC
12.7.3 Pastes
12.7.4 Copolymers
12.7.5 Latices
Applications
Miscellaneous Products
12.9.1 Crystalline PVC
12.9.2 Chlorinated PVC
12.9.3 Graft polymers based on PVC
12.9.4 Vinyl chloride-propylene copolymers
12.9.5 Vinyl
chloride-N-cyclohexylmaleimide
copolymers
Polymeric impact modifiers and processing aids
13 Fluorine-containing Polymers
13.1 Introduction
13.2 Polytetrafluoroethylene
13.2.
I
Preparation
of
monomer
13.2.2 Polymerisation
13.2.3 Structure and properties
13.2.4 General properties
13.2.5 Processing
13.2.6 Additives
13.2.7 Applications
13.3

Tetrafluoroethylene-Hexafluoropropylene
Copolymers
1
3.4
Tetrafluoroethylene-Ethylene
Copolymers (ETFE)
13.5
Polychlorotrifluoroethylene
Polymers (PCTFE)
13.6 Poly(viny1 fluoride) (PVF)
13.7 Poly(viny1idene fluoride)
13.8
1
3.9
Hexafluoroisobutylene-Vinylidene
Fluoride Copolymers
13.10 Fluorine-containing Rubbers
13.11 Thermoplastic fluoroelastomers
13.12 Miscellaneous Fluoropolymers
Poly(viny1 acetate) and its Derivatives
14.1 Introduction
14.2 Poly(viny1 acetate)
and Copolymers with Ethylene (ECTFE)
Other Plastics Materials Containing Tetrafluoroethylene
14
14.2.1 Preparation
of
the monomer
1
4.2.2 Polymerisation

14.2.3 Properties and uses
14.3.1 Structure and properties
14.3.2 Applications
14.3 Poly(viny1 alcohol)
Contents
ix
325
325
330
336
336
337
338
338
342
342
345
346
347
349
350
354
355
355
359
359
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360

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37
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374
374
376
376
377
379
379
383
384
386
386
386
386
388
389
389
390
39 1

x
Contents
14.4 The Poly(viny1 acetals)
14.4.1 Poly(viny1 formal)
14.4.2 Poly(viny1 acetal)
14.4.3 Poly(viny1 butyral)
14.5 Ethylene-Vinyl Alcohol Copolymers
14.6 Poly(viny1 cinnamate)
14.7 Other Organic Vinyl Ester Polymers
15 Acrylic Plastics
15.i
15.2
15.3
15.4
15.5
15.6
15.7
15.8
15.9
15.10
15.11
Introduction
Poly(methy1 methacrylate)
15.2.1 Preparation of monomer
15.2.2 Polymerisation
15.2.3 Structure and properties
15.2.4
15.2.5 Additives
15.2.6 Processing
15.2.7 Applications

Methyl Methacrylate Polymers with Enhanced Impact
Resistance and Softening Point
Nitrile Resins
Acrylate Rubbers
Thermosetting Acrylic Polymers
Acrylic Adhesives
Hydrophilic Polymers
Poly(methacry1imide)
Miscellaneous Methacrylate and Chloroacrylate Polymers
and Copolymers
Other Acrylic Polymers
General properties
of
poly(methy1 methacrylate)
16 Plastics Based on Styrene
16.1
16.2
16.3
16.4
16.5
16.6
16.7
16.8
16.9
16.10
16.11
16.12
16.13
Introduction
Preparation of the Monomer

16.2.1 Laboratory preparation
16.2.2 Commercial preparation
Polymerisation
16.3.1 Mass polymerisation
16.3.2 Solution polymerisation
16.3.3 Suspension polymerisation
16.3.4 Emulsion polymerisation
16.3.5 Grades available
Properties and Structure of Polystyrene
General Properties
High-impact Polystyrenes (HIPS) (Toughened Polystyrenes (TPS))
Styrene-Acrylonitrile Copolymers
ABS Plastics
16.8.1 Production of ABS materials
16.8.2
Processing
of
ABS
materials
16.8.3
Miscellaneous Rubber-modified Styrene- Acrylonitrile
and Related Copolymers
Styrene-Maleic Anhydride Copolymers
Butadiene-Styrene Block Copolymers
Miscellaneous Polymers and Copolymers
Stereoregular Polystyrene
16.13.1 Syndiotactic polystyrene
Properties and applications of ABS plastics
39
1

392
393
393
394
395
397
398
398
400
400
40
1
405
405
409
409
41
I
413
415
417
418
419
420
420
42 1
423
425
425
426

426
427
429
429
43 1
43 1
432
432
433
434
437
44 1
441
442
447
447
448
450
450
452
454
454
Contents
xi
16.14 Processing
of
Polystyrene
16.15 Expanded Polystyrene
16.15.1 Structural foams
16.16 Oriented Polystyrene

16.17 Applications
17 Miscellaneous Vinyl Thermoplastics
17.1 Introduction
17.2
Vinylidene Chloride Polymers and Copolymers
17.2.1
17.2.2 Vinylidene chloride-acrylonitrile copolymers
Properties and applications
of
vinylidene chloride-vinyl
chloride copolymers
17.3 Coumarone-Indene resins
17.4 Poly(viny1 carbazole)
17.5 Poly(viny1 pyrrolidone)
17.6 Poly(viny1 ethers)
17.7 Other Vinyl Polymers
18 Polyamides and Polyimides
18.1
18.2
18.3
18.4
18.5
18.6
18.7
18.8
18.9
18.10
18.1
1
18.12

18.13
18.14
18.15
18.16
Polyamides: Introduction
Intermediates
for Aliphatic Polyamides
18.2.1 Adipic acid
18.2.2 Hexamethylenediamine
18.2.3
18.2.4 Caprolactam
18.2.5 w-Aminoundecanoic acid
18.2.6 w-Aminoenanthic acid
18.2.7 Dodecanelactam
Polymerisation of Aliphatic Polyamides
18.3.1
18.3.2 Nylon 6
18.3.3 Nylon 11
18.3.4 Nylon 12
18.3.5 Nylon 7
Structure and Properties
of
Aliphatic Polyamides
General Properties
of
the Nylons
Additives
Glass-filled Nylons
18.7.1
Processing

of
the Nylons
Applications
Polyamides of Enhanced Solubility
Other Aliphatic Polyamides
Aromatic Polyamides
18.12.1 Glass-clear polyamides
18.12.2 Crystalline aromatic polyamides
Sebacic acid and Azelaic acid
Nylons 46, 66, 69, 610 and 612
Comparison
of
nylons 6 and 66 in glass-filled compositions
18.12.2.1 Poly-rn-xylylene adipamide
18.12.2.2 Aromatic polyamide fibres
18.12.2.3 Polyphthalamide plastics
Polyimides
Modified Polyimides
18.14.1 Polyamide-imides
18.14.2 Polyetherimides
Elastomeric Polyamides
455
457
4.59
46 1
462
466
466
466
468

470
47 1
472
474
475
476
478
478
480
480
48 1
48 1
482
483
484
485
486
486
486
487
487
487
487
490
496
498
500
500
502
505

507
509
509
513
513
514
516
516
52 1
524
525
526
Polyesteramides- 528
xii
Contents
19
Polyacetals and Related Materials
19.1
Introduction
19.2
Preparation of Formaldehyde
19.3
Acetal Resins
19.3.1
Polymerisation of formaldehyde
19.3.2
19.3.3
Properties of acetal resins
19.3.4
Processing

19.3.5
Additives
19.3.6
Acetal-polyurethane alloys
19.3.7
Polyethers from Glycols and Alkylene Oxides
19.5.1 Elastomeric polyethers
Structure and properties of acetal resins
Applications of the acetal polymers and copolymers
19.4
Miscellaneous Aldehyde Polymers
19.5
19.6
Oxetane Polymers
19.7
Polysulphides
20.1
Introduction
20.2
Production
of
Intermediates
20.3
Polymer Preparation
20
Polycarbonates
20.3.1
Ester exchange
20.3.2
Phosgenation process

Relation
of
Structure and Properties
20.4.1
Variations in commercial grades
20.4
20.5
General Properties
20.6
Processing Characteristics
20.7
20.8
20.9
20.10
Miscellaneous Carbonic Ester Polymers
Other Thermoplastics Containing p-Phenylene Groups
Applications of Bis-phenol
A
Polycarbonates
Alloys based on Bis-phenol A Polycarbonates
Polyester Carbonates and Block Copolymers
2
1
21.1
21.2
21.3
21.4
21.5
21.6
21.7

21.8
21.9
21.10
Introduction
Polyphenylenes
Pol y-p-xylylene
Poly(pheny1ene oxides) and Halogenated Derivatives
Alkyl Substituted Poly(pheny1ene oxides) including PPO
21.5.1
Structure and properties of
21.5.2
21.5.3
21.5.4
Styrenic PPOs
21.5.5
Processing of styrenic PPOs
21.5.6
Polyamide PPOs
21 57
Poly(2,6-dibromo-l,4-phenylene
oxide)
Polyphenylene Sulphides
21.6.1
Amorphous polyarylene sulphides
Pol ysulphones
21.7.1
21.7.2
General properties of polysulphones
21.7.3
Processing

of
polysulphones
21.7.4
Applications
21.7.5
Blends based on polysulphones
Polyarylether Ketones
Phenoxy Resins
Linear Aromatic Polyesters
poly-(2,6-dimethyl-p-phenylene
oxide) (PPO)
Processing and application of PPO
Blends based in polyphenylene oxides
Properties and structure of polysulphones
531
53
1
532
533
533
536
538
542
543
544
544
546
546
547
549

55
1
556
556
557
558
558
560
56
1
564
567
573
575
578
579
580
584
584
584
586
586
586
587
589
589
590
59
1
592

592
593
596
596
599
600
60
1
60
1
602
602
607
607
Contents
xiii
21.11 Polyhydantoin Resins
21.12 Poly(parabanic acids)
21.13 Summary
22 Cellulose Plastics
22.1
22.2 Cellulose Esters
Nature and Occurrence
of
Cellulose
22.2.1 Cellulose nitrate
22.2.2 Cellulose acetate
22.2.3 Other cellulose esters
22.3.1 Ethyl cellulose
22.3.2 Miscellaneous ethers

22.3 Cellulose Ethers
22.4 Regenerated Cellulose
22.5 Vulcanised Fibre
609
610
611
613
613
616
616
62 1
627
629
629
632
632
634
23 Phenolic Resins 635
23.1 Introduction 635
23.2 Raw Materials 635
23.2.1 Phenol 636
23.2.2 Other phenols 638
23.2.3 Aldehydes 639
23.3 Chemical Aspects 639
23.3.1
Novolaks
639
23.3.2 Resols 64
1
23.4 Resin Manufacture 643

23.5 Moulding Powders 645
23.5.1 Compounding ingredients 646
23.5.2 Compounding
of
phenol-formaldehyde moulding compositions 648
23.5.3 Processing characteristics 649
23.5.4 Properties
of
phenolic mouldings 652
23.5.5 Applications 65 2
654
23.6.1 The properties
of
phenolic laminates 656
23.6.2 Applications of phenolic laminates 65 8
23.7 Miscellaneous Applications 659
23.8 Resorcinol-Formaldehyde Adhesives 662
662
23.9 Friedel-Crafts and Related Polymers
666
23.10 Phenolic Resin Fibres
23.11 Polybenzoxazines 666
24 Aminoplastics 668
668
24.1 Introduction
669
24.2 Urea-Formaldehyde Resins
669
24.2.1 Raw materials
24.2.2 Theories

of
resinification 670
24.2.3 U-F moulding materials 67
1
677
24.2.4 Adhesives and related uses
24.2.5 Foams and firelighters 679
24.2.6 Other applications 679
680
24.3.1 Melamine 680
682
24.3.2 Resinification
24.3.3 Moulding powders 684
24.3.4 Laminates containing melamine-formaldehyde resin 688
24.3.5 Miscellaneous applications 688
23.3.3 Hardening
641
23.6 Phenolic Laminates
24.3 Melamine-Formaldehyde Resins
xiv
Contents
24.4
Melamine-Phenolic Resins
24.5
Aniline-Formaldehyde Resins
24.6
Resins Containing Thiourea
25
Polyesters
25.i

25.2
25.3
25.4
25.5
25.6
25.7
25.8
25.9
25.10
25.11
25.12
25.13
Introduction
Unsaturated Polyester Laminating Resins
25.2.1
Selection of raw materials
25.2.2
Production of resins
25.2.3
Curing systems
25.2.4
Structure and properties
25.2.5
Polyester-glass fibre laminates
25.2.6
Water-extended polyesters
25.2.7
Allyl resins
Polyester Moulding Compositions
Fibre-forming and Film-forming Polyesters

Poly(ethy1ene terephthalate) Moulding Materials
25.5.1
Poly(ethy1ene naphthalate) (PEN)
Poly(buty1ene terephthalate)
Poly(trimethy1ene terephthalate)
Poly-(
1,4-~yclohexylenedimethyleneterephthalate)
(PCT)
25.8.1
Poly-(
1,4-~yclohexylenedimethyleneterephthalate-
co-isophthalate)
Highly Aromatic Linear Polyesters
25.9.1
Liquid crystal polyesters
Polyester Thermoplastic Elastomers
Poly(pivalo1actone)
Polycaprolactones
Surface Coatings, Plasticisers and Rubbers
26
Epoxide Resins
26.1
Introduction
26.2
26.3
Preparation of Resins from Bis-phenol A
Curing of Glycidyl Ether Resins
26.3.1
Amine hardening systems
26.3.2

Acid hardening systems
26.3.3
Miscelfaneous hardener systems
26.3.4
Comparison of hardening systems
26.4.1
Miscellaneous glycidyl ether resins
26.4.2
Non-glycidyl ether epoxides
Diluents, Flexibilisers and other Additives
Structure and Properties
of
Cured Resins
26.4
Miscellaneous Epoxide Resins
26.5
26.6
26.7
Applications
27.1
Introduction
27.2
Isocyanates
27.3
27.4
Rubbers
27
Polyurethanes and Polyisocyanurates
Fibres and Crystalline Moulding Compounds
27.4.1

Cast polyurethane rubbers
27.4.2
Millable gums
27.4.3
Properties and applications of cross-linked polyurethane
rubbers
27.4.4
Thermoplastic polyurethane rubbers and Spandex fibres
27.5
Flexible Foams
27.5.1
One-shot polyester foams
27.5.2
Polyether prepolymers
689
690
69
1
694
694
696
696
701
702
704
704
708
708
709
713

720
723
724
728
728
729
730
733
737
739
740
740
744
744
745
75
1
753
758
76
1
761
76
1
76
1
7 64
768
772
772

778
778
779
782
784
784
788
788
789
79
1
792
793
Contents
xv
27.5.3 Quasi-prepolymer polyether foams
27.5.4 Polyether one-shot foams
27.5.5
27.6.1
Properties and applications of flexible foams
Self-skinning foams and the RIM process
27.6 Rigid and Semi-rigid Foams
27.7 Coatings and Adhesives
27.8 Polyisocyanurates
27.9 Polycarbodi-imide Resins
27.10 Polyurethane-Acrylic Blends
27.1
1
Miscellaneous Isocyanate-Based Materials
28 Furan Resins

28.1 Introduction
28.2 Preparation of Intermediates
28.3 Resinification
28.4
28.5 Applications
Properties
of
the Cured Resins
29 Silicones and Other Heat-resisting Polymers
29.1 Introduction
29.1.1 Nomenclature
29.1.2
29.2.1 The Grignard method
29.2.2 The direct process
29.2.3 The olefin addition method
29.2.4 Sodium condensation method
29.2.5 Rearrangement
of
organochlorosilanes
General Methods of Preparation and Properties
of
Silicones
29.4.1 Preparation
29.4.2 General properties
29.4.3 Applications
29.5.1 Preparation
29.5.2 Properties
29.5.3 Applications
29.6.1 Dimethylsilicone rubbers
29.6.2 Modified polydimethylsiloxane rubbers

29.6.3 Compounding
29.6.4 Fabrication and cross-linking
29.6.5 Properties
and
applications
29.6.6 Liquid silicone rubbers
29.6.7
Polysiloxane-polyetherimide
copolymers
Polymers for use at High Temperatures
29.7.1 Fluorine-containing polymers
29.7.2 Inorganic polymers
29.7.3 Cross-linked organic polymers
29.7.4
29.7.5
29.7.6 Co-ordination polymers
29.7.7 Summary
Nature
of
chemical bonds containing silicon
29.2 Preparation
of
Intermediates
29.3
29.4 Silicone Fluids
29.5 Silicone Resins
29.6 Silicone Rubbers
29.7
Linear polymers with p-phenylene groups and
other ring structures

Ladder polymers and spiro polymers
794
794
799
800
803
805
805
807
808
808
810
810
810
811
812
812
814
814
815
816
817
818
818
820
820
820
82
1
823

823
824
826
828
828
828
829
832
832
832
836
837
838
839
840
84 1
84 1
842
846
847
848
850
85
1
xvi
Contents
30 Miscellaneous Plastics Materials
30.1 Introduction
30.2 Casein
30.2.1 Chemical nature

30.2.2 Isolation of casein from milk
30.2.3 Production of casein plastics
30.2.4 Properties
of
casein
30.2.5 Applications
30.3 Miscellaneous Protein Plastics
30.4 Derivatives of Natural Rubber
30.5
30.6 Shellac
Gutta Percha and Related Materials
30.6.1 Occurrence and preparation
30.6.2 Chemical composition
30.6.3 Properties
30.6.4 Applications
30.7.1 Composition and properties
30.7 Amber
30.8 Bituminous Plastics
3
1
Selected Functional Polymers
3
1.1
Introduction
3 1.2 Thermoplastic Elastomers
3 1.2.1
3 1.2.2
31.3.1
Polyhydroxybutyrate-valerate
copolymers (PHBV)

31.3.2
Intrinsically Electrically Conducting Polymers (ICPs)
Applications of thermoplastic elastomers
The future for thermoplastic elastomers
3 1.3 Degradable Plastics
The future for degradable plastics
3 1.4
32 Material Selection
32.1 Introduction
32.2 Establishing Operational Requirements
32.3
32.4 Material Data Sources
32.5
32.6
Economic Factors Affecting Material Choice
32.4.1 Computer-aided selection
A Simple Mechanistic Non-computer Selection System
A Simple Pathway-based Non-computer Selection System
853
853
853
854
855
856
858
859
860
860
865
867

867
868
868
869
870
870
87 1
874
874
874
878
880
880
883
886
886
890
890
89
1
89
1
892
894
895
895
Appendix
Index
898
899

Preface to the Seventh Edition
I
mentioned in the preface to the sixth edition that when
I
began preparation of
the first edition of this book in the early
1960s
world production
of
plastics
materials was of the order of
9
million tonnes per annum. In the late
1990s
it has
been estimated at 135 million tonnes per annum! In spite of this enormous
growth my prediction in the first edition that the likelihood of discovering new
important general purposes polymers was remote but that new special purpose
polymers would continue to be introduced has proved correct.
Since the last edition several new materials have been announced. Many of
these are based on metallocene catalyst technology. Besides the more obvious
materials such as metallocene-catalysed polyethylene and polypropylene these
also include syndiotactic polystyrenes, ethylene-styrene copolymers and cyclo-
olefin polymers. Developments also continue with condensation polymers with
several new polyester-type materials of interest for bottle-blowing and/or
degradable plastics. New phenolic-type resins have also been announced. As with
previous editions I have tried to explain the properties of these new materials in
terms of their structure and morphology involving the principles laid down in the
earlier chapters.
This new edition not only includes information on the newer materials but

attempts to explain in modifications to Chapter
2
the basis of metallocene
polymerisation. Since it is also becoming apparent that successful development
with these polymers involves consideration of molecular weight distributions an
appendix to Chapter
2
has been added trying to explain in simple terms such
concepts as number and molecular weight averages, molecular weight distribu-
tion and in particular concepts such as bi- and trimodal distributions which are
becoming of interest.
As
in previous editions
I
have tried to give some idea of the commercial
importance of the materials discussed. What has been difficult is to continue to
indicate major suppliers since there have been many mergers and transfers of
manufacturing rights. There has also been considerable growth in manufacturing
capacity
in
the Pacific Rim area and in Latin America. However this has tended
to coincide with the considerable economic turmoil in these areas particularly
during the period of preparation for this edition. For this reason most of the
xvii
xviii
figures
on
production and consumption is based
on
1997

data as this was felt to
be more representative than later, hopefully temporary, distortions.
In
a book which has in effect been written over a period of nearly
40
years the
author would request tolerance by the reader for some inconsistencies.
In
particular
I
am mindful about references.
In
the earlier editions these were
dominated by seminal references to fundamental papers
on
the discovery of new
materials, often by individuals, or classic papers that laid down the foundations
relating properties to structure.
In
more recent editions
I
have added few new
individual references since most announcements of new materials are the result
of work by large teams and made by companies. For this reason
I
have directed
the reader to reviews, particularly those by Rapra and those found in
Kunstoffe
for which translations in English are available.
I

am also aware that some of the
graphs from early editions do not show data in
SI
units. Since
in
many cases the
diagram is there to emphasise a relationship rather than to give absolute values
and because changing data provided by other authors is something not to be
undertaken lightly
I
would again request tolerance by the reader.
Preface to the Seventh Edition
J.
A.
B
Brent Eleigh
Suffolk,
1999
Preface
to
the
First Edition
There are at the present time many thousands of grades of commercial plastics
materials offered for sale throughout the world. Only rarely are the properties of
any two of these grades identical, for although the number of chemically distinct
species (e.g. polyethylenes, polystyrenes) is limited, there are many variations
within each group. Such variations can arise through differences in molecular
structure, differences in physical form, the presence of impurities and also in the
nature and amount of additives which may have been incorporated into the base
polymer. One of the aims of this book is to show how the many different

materials arise, to discuss their properties and to show how these properties can
to a large extent be explained by consideration of the composition of a plastics
material and in particular the molecular structure of the base polymer
employed.
After a brief historical review in Chapter
1
the following five chapters provide
a short summary of the general methods of preparation of plastics materials and
follow
on
by showing how properties are related to chemical structure. These
particular chapters are largely qualitative in nature and are aimed not
so
much at
the theoretical physical chemist but rather at the polymer technologist and the
organic chemist who will require this knowledge in the practice of polymer and
compound formulation.
Subsequent chapters deal with individual classes of plastics.
In
each case a
review is given
of
the preparation, structure and properties of the material.
In
order to prevent the book from becoming too large
I
have omitted detailed
discussion of processing techniques. Instead, with each major class of material an
indication is given of the main processing characteristics. The applications of the
various materials are considered in the light

of
the merits and the demerits of the
material.
The title
of
the book requires that a definition
of
plastics materials be given.
This is however very difficult. For the purpose of this book
I
eventually used as
a working definition ‘Those materials which are considered to be plastics
materials by common acceptance’. Not a positive definition but one which is
probably less capable
of
being criticised than any other definition
I
have seen.
Perhaps a rather more useful definition but one which requires clarification is
xix
xx
Preface to the First Edition
‘Plastics materials are processable compositions based on macromolecules’. In
most cases (certainly with all synthetic materials) the macromolecules are
polymers, large molecules made by the joining together of many smaller ones.
Such a definition does however include rubbers, surface coatings, fibres and
glasses and these, largely for historical reasons, are not generally regarded as
plastics. While we may arbitrarily exclude the above four classes of material the
borderlines remain undefined. How should we classify the flexible polyurethane
foams-as rubbers or as plastics? What about nylon tennis racquet filament?-

or polyethylene dip coatings? Without being tied by definition I have for
convenience included such materials in this book but have given only brief
mention to coatings, fibres and glasses generally. The rubbers
I
have treated as
rather a special case considering them as plastics materials that show reversible
high elasticity. For this reason I have briefly reviewed the range of elastomeric
materials commercially available.
I
hope that this book will prove to be of value to technical staff who are
involved in the development and use of plastics materials and who wish to obtain
a broader picture of those products than they could normally obtain in their
everyday work. Problems that are encountered in technical work can generally be
classified into three groups; problems which have already been solved elsewhere,
problems whose solutions are suggested by a knowledge of the way in which
similar problems have been tackled elsewhere and finally completely novel
problems. In practice most industrial problems fall into the first two categories
so
that the technologist who has a good background knowledge to his subject and
who knows where to look for details of original work has an enhanced value to
industry. It is hoped that in a small way the text of this
book
will help to provide
some of the background knowledge required and that the references, particularly
to more detailed monographs, given at the end of each chapter will provide
signposts along the pathways of the ever thickening jungle of technical
literature.
1965
J.
A.

B.
Acknowledgements
for
the Seventh
Edition
As
I
have said in previous editions the information provided in this volume is a
distillation of the work of very many scientists, technologists, engineers,
economists and journalists without which
this
book could not have existed.
Over the years with the different editions
I
have received help from very many
companies concerned with the production
of
plastics materials and from very
many individuals. For this edition
I
should specifically like to thank Susan
Davey, Academic Information Services Manager of the University of North
London, Rebecca Dolbey and Ray Gill of Rapra Technology Ltd, Peter Lewis of
the Open University, Simon Robinson of European Plastics News, Christopher
Sutcliffe of Crystal Polymers Ltd and Graham Bonner of BP Chemicals.
Once again
I
should acknowledge that
I
have drawn heavily from the journals

European Plastics News, Kunstoffe, Modern Plastics International
and
Plastics
and Rubber Weekly
for data
on
production and consumption statistics.
My thanks also go to the publishers Butterworth-Heinemann and particularly
Rebecca Hammersley for their tolerance and help.
Once again
1
must also express my thanks to Wendy, my wife, who has had to
tolerate me writing, at intervals, editions of this book for much of our married
life.
xxi
Preface to the Seventh Edition
I
mentioned in the preface to the sixth edition that when
I
began preparation of
the first edition of this book in the early
1960s
world production
of
plastics
materials was of the order of
9
million tonnes per annum. In the late
1990s
it has

been estimated at 135 million tonnes per annum! In spite of this enormous
growth my prediction in the first edition that the likelihood of discovering new
important general purposes polymers was remote but that new special purpose
polymers would continue to be introduced has proved correct.
Since the last edition several new materials have been announced. Many of
these are based on metallocene catalyst technology. Besides the more obvious
materials such as metallocene-catalysed polyethylene and polypropylene these
also include syndiotactic polystyrenes, ethylene-styrene copolymers and cyclo-
olefin polymers. Developments also continue with condensation polymers with
several new polyester-type materials of interest for bottle-blowing and/or
degradable plastics. New phenolic-type resins have also been announced. As with
previous editions I have tried to explain the properties of these new materials in
terms of their structure and morphology involving the principles laid down in the
earlier chapters.
This new edition not only includes information on the newer materials but
attempts to explain in modifications to Chapter
2
the basis of metallocene
polymerisation. Since it is also becoming apparent that successful development
with these polymers involves consideration of molecular weight distributions an
appendix to Chapter
2
has been added trying to explain in simple terms such
concepts as number and molecular weight averages, molecular weight distribu-
tion and in particular concepts such as bi- and trimodal distributions which are
becoming of interest.
As
in previous editions
I
have tried to give some idea of the commercial

importance of the materials discussed. What has been difficult is to continue to
indicate major suppliers since there have been many mergers and transfers of
manufacturing rights. There has also been considerable growth in manufacturing
capacity
in
the Pacific Rim area and in Latin America. However this has tended
to coincide with the considerable economic turmoil in these areas particularly
during the period of preparation for this edition. For this reason most of the
xvii
xviii
figures
on
production and consumption is based
on
1997
data as this was felt to
be more representative than later, hopefully temporary, distortions.
In
a book which has in effect been written over a period of nearly
40
years the
author would request tolerance by the reader for some inconsistencies.
In
particular
I
am mindful about references.
In
the earlier editions these were
dominated by seminal references to fundamental papers
on

the discovery of new
materials, often by individuals, or classic papers that laid down the foundations
relating properties to structure.
In
more recent editions
I
have added few new
individual references since most announcements of new materials are the result
of work by large teams and made by companies. For this reason
I
have directed
the reader to reviews, particularly those by Rapra and those found in
Kunstoffe
for which translations in English are available.
I
am also aware that some of the
graphs from early editions do not show data in
SI
units. Since
in
many cases the
diagram is there to emphasise a relationship rather than to give absolute values
and because changing data provided by other authors is something not to be
undertaken lightly
I
would again request tolerance by the reader.
Preface to the Seventh Edition
J.
A.
B

Brent Eleigh
Suffolk,
1999
Preface
to
the
First Edition
There are at the present time many thousands of grades of commercial plastics
materials offered for sale throughout the world. Only rarely are the properties of
any two of these grades identical, for although the number of chemically distinct
species (e.g. polyethylenes, polystyrenes) is limited, there are many variations
within each group. Such variations can arise through differences in molecular
structure, differences in physical form, the presence of impurities and also in the
nature and amount of additives which may have been incorporated into the base
polymer. One of the aims of this book is to show how the many different
materials arise, to discuss their properties and to show how these properties can
to a large extent be explained by consideration of the composition of a plastics
material and in particular the molecular structure of the base polymer
employed.
After a brief historical review in Chapter
1
the following five chapters provide
a short summary of the general methods of preparation of plastics materials and
follow
on
by showing how properties are related to chemical structure. These
particular chapters are largely qualitative in nature and are aimed not
so
much at
the theoretical physical chemist but rather at the polymer technologist and the

organic chemist who will require this knowledge in the practice of polymer and
compound formulation.
Subsequent chapters deal with individual classes of plastics.
In
each case a
review is given
of
the preparation, structure and properties of the material.
In
order to prevent the book from becoming too large
I
have omitted detailed
discussion of processing techniques. Instead, with each major class of material an
indication is given of the main processing characteristics. The applications of the
various materials are considered in the light
of
the merits and the demerits of the
material.
The title
of
the book requires that a definition
of
plastics materials be given.
This is however very difficult. For the purpose of this book
I
eventually used as
a working definition ‘Those materials which are considered to be plastics
materials by common acceptance’. Not a positive definition but one which is
probably less capable
of

being criticised than any other definition
I
have seen.
Perhaps a rather more useful definition but one which requires clarification is
xix
xx
Preface to the First Edition
‘Plastics materials are processable compositions based on macromolecules’. In
most cases (certainly with all synthetic materials) the macromolecules are
polymers, large molecules made by the joining together of many smaller ones.
Such a definition does however include rubbers, surface coatings, fibres and
glasses and these, largely for historical reasons, are not generally regarded as
plastics. While we may arbitrarily exclude the above four classes of material the
borderlines remain undefined. How should we classify the flexible polyurethane
foams-as rubbers or as plastics? What about nylon tennis racquet filament?-
or polyethylene dip coatings? Without being tied by definition I have for
convenience included such materials in this book but have given only brief
mention to coatings, fibres and glasses generally. The rubbers
I
have treated as
rather a special case considering them as plastics materials that show reversible
high elasticity. For this reason I have briefly reviewed the range of elastomeric
materials commercially available.
I
hope that this book will prove to be of value to technical staff who are
involved in the development and use of plastics materials and who wish to obtain
a broader picture of those products than they could normally obtain in their
everyday work. Problems that are encountered in technical work can generally be
classified into three groups; problems which have already been solved elsewhere,
problems whose solutions are suggested by a knowledge of the way in which

similar problems have been tackled elsewhere and finally completely novel
problems. In practice most industrial problems fall into the first two categories
so
that the technologist who has a good background knowledge to his subject and
who knows where to look for details of original work has an enhanced value to
industry. It is hoped that in a small way the text of this
book
will help to provide
some of the background knowledge required and that the references, particularly
to more detailed monographs, given at the end of each chapter will provide
signposts along the pathways of the ever thickening jungle of technical
literature.
1965
J.
A.
B.
Acknowledgements
for
the Seventh
Edition
As
I
have said in previous editions the information provided in this volume is a
distillation of the work of very many scientists, technologists, engineers,
economists and journalists without which
this
book could not have existed.
Over the years with the different editions
I
have received help from very many

companies concerned with the production
of
plastics materials and from very
many individuals. For this edition
I
should specifically like to thank Susan
Davey, Academic Information Services Manager of the University of North
London, Rebecca Dolbey and Ray Gill of Rapra Technology Ltd, Peter Lewis of
the Open University, Simon Robinson of European Plastics News, Christopher
Sutcliffe of Crystal Polymers Ltd and Graham Bonner of BP Chemicals.
Once again
I
should acknowledge that
I
have drawn heavily from the journals
European Plastics News, Kunstoffe, Modern Plastics International
and
Plastics
and Rubber Weekly
for data
on
production and consumption statistics.
My thanks also go to the publishers Butterworth-Heinemann and particularly
Rebecca Hammersley for their tolerance and help.
Once again
1
must also express my thanks to Wendy, my wife, who has had to
tolerate me writing, at intervals, editions of this book for much of our married
life.
xxi

Preface to the Seventh Edition
I
mentioned in the preface to the sixth edition that when
I
began preparation of
the first edition of this book in the early
1960s
world production
of
plastics
materials was of the order of
9
million tonnes per annum. In the late
1990s
it has
been estimated at 135 million tonnes per annum! In spite of this enormous
growth my prediction in the first edition that the likelihood of discovering new
important general purposes polymers was remote but that new special purpose
polymers would continue to be introduced has proved correct.
Since the last edition several new materials have been announced. Many of
these are based on metallocene catalyst technology. Besides the more obvious
materials such as metallocene-catalysed polyethylene and polypropylene these
also include syndiotactic polystyrenes, ethylene-styrene copolymers and cyclo-
olefin polymers. Developments also continue with condensation polymers with
several new polyester-type materials of interest for bottle-blowing and/or
degradable plastics. New phenolic-type resins have also been announced. As with
previous editions I have tried to explain the properties of these new materials in
terms of their structure and morphology involving the principles laid down in the
earlier chapters.
This new edition not only includes information on the newer materials but

attempts to explain in modifications to Chapter
2
the basis of metallocene
polymerisation. Since it is also becoming apparent that successful development
with these polymers involves consideration of molecular weight distributions an
appendix to Chapter
2
has been added trying to explain in simple terms such
concepts as number and molecular weight averages, molecular weight distribu-
tion and in particular concepts such as bi- and trimodal distributions which are
becoming of interest.
As
in previous editions
I
have tried to give some idea of the commercial
importance of the materials discussed. What has been difficult is to continue to
indicate major suppliers since there have been many mergers and transfers of
manufacturing rights. There has also been considerable growth in manufacturing
capacity
in
the Pacific Rim area and in Latin America. However this has tended
to coincide with the considerable economic turmoil in these areas particularly
during the period of preparation for this edition. For this reason most of the
xvii