Table of contents for Polymers : chemistry and physics of modern materials.

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Contents
PREFACE
CHAPTER 1 INTRODUCTION
1.1	Birth of a concept									1
1.2	Some basic definitions								4
1.3	Synthesis of polymers									6
1.4	Nomenclature										7
1.5	Average molar masses and distributions						9
1.6	Size and shape										12
1.7	Configuration										16
1.8	The glass transition temperature Tg¬ and the melting temperature Tm			17
1.9	Elastomers, fibres and plastics							19
1.10	Fibre-forming polymers								20
1.11	Plastics										22
1.12	Thermosetting polymers								23
1.13	Elastomers										25
CHAPTER 2 STEP-GROWTH POLYMERIZATION
2.1 	General reactions									45
2.2 	Reactivity of functional groups							47
2.3 	Carothers equation							47
2.4 	Control of the molar mass							49
2.5 	Stoichiometric control of Mn							52
2.6 	Kinetics							54
2.7 	Molar mass distribution in linear systems						56
2.8 	Average molar masses							58
2.9 	Characteristics of step-growth polymerization					59
2.10 	Typical step-growth reactions							60
2.11 	Ring formation							62
2.12 	Non-linear step-growth reactions							63
2.13 	Statistical derivation							65
2.14 	Comparison with experiment							67
2.15 	Polyurethanes							68
2.16 	Thermosetting polymers							73
CHAPTER 3 FREE RADICAL ADDITION POLYMERIZATION
3.1 	Addition polymerization							91
3.2 	Choice of initiators							91
3.3 	Free radical polymerization							93
3.4 	Initiators							93
	3.4.1 Initiator efficiency							96
3.5 	Chain growth							97
3.6 	Termination							98
3.7 	Steady-state kinetics							99
3.8 	High-conversion bulk polymerizations							102
3.9 	Chain transfer							105
	3.9.1 Consequences of chain transfer							109
3.10 	Inhibitors and retarders							110
3.11	Activations energies and the effect of temperature					111
3.12	Thermodynamics of free-radical polymerization					112
3.13	Heats of polymerization							116
3.14	Polymerization processes							117
3.15	Features of the free radical polymerization						122
3.16	Controlled radical polymerization							123
3.17	Nitroxide mediated polymerizations							125
3.18	Atom transfer radical polymerization (ATRP)					128
3.19	Reverse ATRP							128
3.20	Degenerative chain transfer reaction (DT)						130
3.21	Reversible addition fragmentation chain transfer (RAFT)				131
3.22	CRP of vinyl chloride							134
3.23	The kinetics of CRP processes							135
3.24	Application to experimental data							138
CHAPTER 4 IONIC POLYMERIZATION
4.1	General characteristics							153
4.2	Cationic polymerization							154
4.3 	Propagation by cationic chain carriers							156
4.4 	Termination							158
4.5 	General kinetic scheme							159
4.6 	Energetics of cationic polymerization							159
4.7	Telechelic polymers via cationic polymerization					160
4.8	Cationic ring opening polymerization							161
4.9	Stable carbocations							164
4.10	Anionic polymerization							166
4.11	¿Living¿ polymers							167
4.12	Kinetics and molar mass distribution in ¿living¿ anionic systems			169
4.13 	Metal alkyl initiators	 						172
4.13 	Metal alkyl initiators	 						172
4.14 	Solvent and gegen-ion effects	 						173
4.15 	Anionic ring opening polymerization	 						174
CHAPTER 5 LINEAR COPOLYMERS AND OTHER ARCHITECTURES
5.1	General characteristics							185
5.2	Composition drift							187
5.3	The copolymer equation							188
5.4	Monomer reactivity ratios							189
5.5 	Reactivity ratios and copolymer structure						191
5.6 	Monomer reactivities and chain initiation						193
5.7 	Influence of structural effects on monomer reactivity ratios				194
5.8 	The Q-e scheme							197
5.9 	Alternating copolymers							199
5.10 	Block copolymer synthesis							202
	5.10.1 Transformation reactions							204
	5.10.2 Coupling reactions							211
	5.10.3 Use of CRP methods							214
5.11 	Block copolymer synthesis							218
5.12 	Statistical / gradient copolymers							222
5.13 	Complex molecular architectures							224
5.14 	Dendrimers							227
	5.14.1 Divergent growth 								227
	5.14.2 Convergent growth								229
	5.14.2 Dendrimer molecular weight							231
5.14.4 Properties of dendrimers							234
CHAPTER 6 POLYMER STEREOCHEMISTRY
6.1	Architecture							244
6.2	Orientation							245
6.3	Configuration							246
	6.3.1 Monotactic polymers							248
	6.3.2 Ditactic polymers							249
	6.3.3 Polyethers							250
6.4	Geometric isomerism							250
6.5	Conformation of stereoregular polymers							252
6.6 	Factors influencing stereoregulationReactivity ratios and copolymer structure	254	
6.7 	Homogeneous stereospecific cationic polymerizations				257
6.8 	Homogeneous stereoselective anionic polymerizations				259
6.9 	Homogeneous diene polymerization							262
6.10 	Summary							264
CHAPTER 7 POLYMERIZATION REACTIONS INITIATED by 
	METAL CATALYSTS and TRANSFER REACTIONS
7.1 	Polymerization using Ziegler-Natta catalysts						270
7.2 	Nature of the catalyst							272
7.3 	Nature of active centres							273
7.4 	Bimetallic mechanism							274
7.5 	Monometallic mechanism							275
7.6 	Stereoregulation							277
7.7 	Ring opening metathesis polymerizations (ROMP) 					278
7.8	Monocyclic monomers							279
7.9 	Bicyclo- and tricyclo-monomers							281
7.10 	Copolyalkenamers							283
7.11 	Living systems							283
7.12 	Group transfer polymerization (GTP) 							285
7.13 	Aldol group transfer polymerization							289
7.14 	Metallocene Catalysts							290
	7.14.1 Metallocene/aluminoxane Catalysts						291
	7.14.2 Stereoregulation							292
	7.14.3 Cationic Metallocenes							296
	7.14.4 Mechanism of stereoregulation							296
7.15	Concluding remarks							298
CHAPTER 8 POLYMERS IN SOLUTION 
8.1 	Thermodynamics of polymer solutions							303
8.2 	Ideal mixtures of small molecules							304
8.3 	Non-ideal solutions							306
8.4 	Flory-Huggins theory: Entropy of Mixing						307
8.5	Enthalpy change on mixing							312
8.6 	Free energy of mixing							314
8.7 	Limitations of the Flory-Huggins theory							315
8.8 	Phase equilibria							316
8.9 	Flory-Krigbaum theory							320
8.10 	Location of the theta temperature							322
8.11 	Lower critical solution temperatures							324
8.12 	Solubility and the cohesive energy density						328
8.13 	Polymer-polymer mixtures							332
8.14 	Kinetics of Phase Separation							337
CHAPTER 9 POLYMER CHARACTERIZATION ¿ MOLAR MASSES 
9.1 	Introduction							351
9.2 	Molar masses, molecular weights, and SI units					351
9.3	Number average molar mass Mn							352
9.4	End-group assay							352
9.5 	Colligative properties of solutions							353
9.6 	Osmotic pressure							354
9.7 	Light scattering							357
	9.7.1 Scattering from large particles							361
9.8 	Dynamic light scattering							364
9.9 	Viscosity							365
	9.9 Viscosity average molecular weight							367
9.10 	Gel permeation chromatography							368
9.11 	MALDI							372
CHAPTER 10 POLYMER CHARACTERIZATION ¿ 
	CHAIN DIMENSIONS, STRUCTURES AND MORPHOLOGY 
10.1 	Average chain dimensions							385
10.2 	Freely-jointed chain model							386
10.3 	Short range effects							388
10.4 	Chain stiffness							388
10.5 	Treatment of dilute solution data							389
	10.5.1 The second virial coefficient							390
	10.5.2 Expansion factor ?							391
	10.5.3 Flory-Fox theory							392
	10.5.4 Indirect estimates of 		394
	10.5.5 Influence of tacticity on chain dimensions					395
10.6 	Nuclear Magnetic Resonance (NMR)							395
10.7 	Infrared spectroscopy							398
10.8 	Thermal analysis							400
10.9 	Wide angle and small angle scattering							402
	10.9.1 Wide angle X-ray scattering							404
	10.9.2 Small angle X-ray scattering (SAXS) 					405
	10.9.3 Small angle neutron scattering (SANS) 					407
10.10 Microscopy							411
	10.10.1 Optical microscopy							411
	10.10.2 Scanning electron microscopy							413
	10.10.3 Transmission electron microscopy						414
	10.10.4 Atomic force microscopy (AFM) and 
	 Scanning tunneling microscopy (STM)					415
	
CHAPTER 11 POLYMER CHARACTERIZATION ¿ 
	CHAIN DIMENSIONS, STRUCTURES AND MORPHOLOGY 
11.1 	Introduction							423
11.2 	Mechanism of crystallization							424
11.3 	Temperature and growth rate							426
11.4 	Melting							427
11.5 	Thermodynamic parameters							429
11.6 	Crystalline arrangement of polymers							431
	11.6.1 Factors affecting crystallinity and Tm						431
11.7 	Morphology and kinetics							435
11.8 	Morphology							435
11.9	Kinetics of crystallization							443
11.10	Block Copolymers							446
11.11 Historical development of Polymer Liquid Crystals					448
11.12 Liquid crystalline phases							450
11.13 	Identification of the mesophases							453
11.14 Lyotropic main chain liquid crystalline polymers					455
11.15 Thermotropic main chain liquid crystal polymers					458
11.16 Side chain liquid crystalline polymers						464
11.17 Chiral nematic liquid crystal polymers						467
CHAPTER 12 THE GLASSY STATE AND GLASS TRANSITION
12.1 	The amorphous state							483
12.2 	The glassy state							483
12.3	Relaxation processes in the glassy state							484
12.4	Glass transition region							486
12.4.1 The glass transition temperature, Tg						487
	12.4.2 Experimental demonstration of Tg							488
12.4 	Factors affecting Tg							492
12.5 	Theoretical treatments							495
12.5.1 The free volume theory							495
12.5.2 Gibbs-Di Marzio thermodynamic theory					500
12.5.3 Adam-Gibbs theory								502
12.6 Dependence of Tg on molar mass							504
12.7 	Structural Relaxation and Physical Ageing						506
CHAPTER 13 RHEOLOGY AND MECHANCAL PROPERTIES
13.1 	Introduction to Rheology							518
13.2 	The five regions of viscoelastic behaviour						519
13.3 	The viscous region							522
	13.3.1 Shear dependence of viscosity							525
	13.3.2 Kinetic units in polymer chains							526	13.3.3 Effect of chain length							527
	13.3.4 Temperature dependence of ?							529
	13.3.5 Concentration dependence of viscosity					529
	13.3.6 Time dependent behaviour							531
13.4 Mechanical properties							532
	13.4.1 Interrelation of moduli							533
13.5	Mechanical models describing viscoelasticity					534
13.6 	Linear viscoelastic behaviour of amorphous polymers				538
	13.6.1 Creep							539
	13.6.2 Stress-strain measurements							542
	13.6.3 Effect of temperature on stress-strain response				543
	13.6.4 Boltzmann superposition principle						544
	13.6.5 Stress-relaxation							544
13.7 	Dynamic mechanical and dielectric thermal analysis					546
	13.7.1 Dynamic mechanical thermal analysis (DMTA) 				547
	13.7.2 Dielectric thermal analysis (DETA) 						550
	13.7.3 Comparison between DMTA and DETA					553
13.8	Time-temperature superposition principle						556
13.9 	Dynamic viscosity							559
13.10 A molecular theory for viscoelasticity							561
13.11 The reptation model							565
CHAPTER 14 THE ELASTOMERIC STATE
14.1 	General introduction							578
	14.1.1 Natural rubber							579
14.2 	Experimental vulcanization							581
14.3 	Properties of elastomers							583
14.4 	Thermodynamic aspects of rubber-like elasticity					583
14.5 	Non-ideal elastomers							586
14.6 	Distribution function for polymer conformation					588
14.7 	Statistical approach							590
	14.7.1 Experimental stress-strain results							591
14.8 	Swelling of elastomeric networks							593
14.9 	Network defects							594
14.10	Resilience of elastomers							596
CHAPTER 15 STRUCTUR	E PROPERTY RELATIONS
15.1 	General considerations							607
15.2 	Control of Tm and Tg							608
	15.2.1 Chain stiffness							609
	15.2.2 Intermolecular bonding							610
15.3 	Relation between Tm and Tg							611
15.4 	Random copolymers							612
15.5 	Dependence of Tm and Tg on copolymer composition				614
15.6 	Block copolymers							617
15.7	Plasticizers							619
15.8 	Crystallinity and mechanical response							620
15.9 	Application to fibres, elastomers and plastics						624
15.10 Fibres							624
	15.10.1 Chemical requirements							626
	15.10.2 Mechanical requirements for fibres						629
15.11 Aromatic polyamides							634
15.12 Polyethylene							638
15.13 Elastomers and crosslinked networks							640
15.14 Plastics							642
15.15 High temperature speciality polymers							647
CHAPTER 16 POLYMERS FOR THE ELECTRONICS INDUSTRY
16.1 	Introduction							680
16.2	Polymer resists for integrated circuit fabrication					681
16.3 	The lithographic process							681
16.4 	Polymer resists							683
	16.4.1 Sensitivity							684
	16.4.2 Resolution							684
16.5 	Photolithography							685
	16.5.1 Positive photoresists								685
	16.5.2 Negative photoresists								687
16.6 	Electron beam sensitive resists							689
	16.6.1 Positive resists							690
	16.6.2 Negative resists							691
16.7 	X-ray and ion sensitive resists							692
16.8 	Electroactive polymers							692
16.9 	Conduction mechanisms							694
16.10 Preparation of conductive polymers							695
16.11 Polyacetylene							697
16.12 Poly(p-phenylene) 							701
16.13 Polyheterocyclic systems							703
	16.13.1 Polypyrrole							704
	16.13.2 Sulphur compounds								706
16.14 Polyaniline							706
16.15 Poly(phenylene sulphide) 							707
16.16 Poly(1,6-heptadiyne) 							707
16.17 Applications							707
16.18 Photonic applications							708
16.19 Light emitting polymers							709
	16.19.1 Applications							710
16.20 Non-linear optics							712
16.21 Langmuir-Blodgett films							716
16.22 Optical information storage							718
16.23 Thermorecording on liquid crystalline polymers					721
Preface
Preface
When the first edition of this book appeared in 1973 it was meant to serve two major functions; the first was to provide a broadly based text on polymer science at an introductory level which would illustrate the interdisciplinary nature of the subject, and the second was to create a high information, inexpensive text that students would be able to afford. The response to the book over the intervening years has been both surprising and gratifying, and seems to indicate that the stated aims have been achieved.
The same principles are still applied, in this, the 3rd edition and I have simply attempted to keep abreast of the recent advances in various areas of the subject. While the basics of polymer science remain unchanged, significant discoveries have been made in the area of control over molecular weight, macromolecular structure and architecture and the consequent ability to prepare materials with specific properties. To account for this the relevant chapters have been expanded to include controlled radical polymerizations, metallocene chemistry and the preparation of block and graft copolymers, multiarmed and dendritic structures. Work has also moved steadily into extending the areas where polymeric materials can be used in electronic, biological and medical applications, and examples of this are included. The chapter on characterization has also been modified to reflect the current approaches, where newer techniques have tended to replace or improve on the older methods. Perhaps the most noticeable change is in the addition of a series of problems at the end of each chapter. These are designed to test whether the reader has understood the various points raised in each chapter, and in some cases to expand on that knowledge. This feature has been introduced in response to comments from several lecturers who use the book as a text for their courses in polymer science and I hope this will prove useful to them and their students.
In preparing this 3rd edition I have been ably assisted by Dr Valeria Arrighi, who, among other things, has been largely responsible for compiling all the problems and exercises, and restructuring one or two of the chapters.
The addition of new material has inevitably meant that some sections, present in previous editions, have been omitted, if no longer deemed to be in common use or have been superseded by modern techniques. However, I hope that the revisions will be acceptable to those who use the text and that it will continue to satisfy the educational needs it was originally designed to meet.
Finally, I would like to dedicate this 3rd edition to my family Ann, Graeme and Christian and grandchildren Emma and Lauren. 

Library of Congress Subject Headings for this publication:

Polymers -- Textbooks.
Polymerization -- Textbooks.