Polymers Chemistry and Physics of Modern Materials, Fourth Edition

Dedication
Preface to the Third Edition
Preface to the Fourth Edition
Acknowledgements
List of Abbreviations

CHAPTER 1 INTRODUCTION
Abstract
1.1 Birth of a concept
1.2 Some basic definitions
1.3 Classification based on source of origin
1.4 Synthesis of polymers
1.4.1 Polycondensation and polyaddition
1.4.2 Chain Polymerization
1.5 Nomenclature
1.6 Average molar masses and distributions
1.7 Size and shape
1.8 Configuration
1.9 Chemical Structure and Intermolecular Interactions
1.10 The glass transition temperature Tg¬ and the melting temperature Tm
1.11 Elastomers, fibers and plastics
1.11.1 Fiber-forming polymers
1.11.2 Plastics
1.11.3 Thermosetting polymers
1.11.4 Elastomers
1.12 Biorelated Polymers
1.13 Supramolecular Polymers
1.14 Summary

CHAPTER 2 POLYCONDENSATION AND POLYADDITION
Abstract
2.1 Terminology
2.2 General Reactions
2.3 Reactivity of functional groups
2.4 Carothers equation
2.5 Control of the molar mass
2.6 Stoichiometric control of Mn
2.7 Kinetics
2.8 Molar mass distribution in linear systems
2.9 Average molar masses
2.10 Characteristics of step-growth polymerization
2.11 Typical step-growth reactions
2.12 Ring formation
2.13 Non-linear reactions
2.14 Statistical derivation
2.16 Comparison with experiment
2.16 Polyurethanes
2.17 Thermosetting polymers
2.18 Summary

CHAPTER 3 CHAIN POLYMERIZATION
Abstract
3.1 General Aspects of Chain Polymerization
3.2 Choice of initiators
3.3 Free radical chain polymerization
3.3.1 Initiators
3.3.2 Initiator efficiency
3.3.3 Chain growth
3.3.4 Termination
3.3.5 Steady-state kinetics
3.3.6 High-conversion bulk polymerizations
3.3.7 Chain transfer
3.3.8 Consequences of chain transfer
3.3.9 Inhibitors and retarders
3.3.10 Activations energies and the effect of temperature
3.3.11 Thermodynamics of free-radical polymerization
3.3.12 Heats of polymerization
3.3.13 Polymerization processes
3.3.14 Features of the free radical polymerization
3.4 Reversible-deactivation radical polymerization
3.4.1 Nitroxide mediated polymerizations
3.4.2 Atom transfer radical polymerization (ATRP)
3.4.3 Degenerative chain transfer reaction (DT)
3.4.4 Reversible addition fragmentation chain transfer (RAFT)
3.4.5 CRP of vinyl chloride
3.4.6 The kinetics of CRP processes
3.4.7 Application to experimental data
3.5 Summary

CHAPTER 4 IONIC POLYMERIZATION
Abstract
4.1 General characteristics
4.2 Cationic polymerization
4.2.1 Propagation by cationic chain carriers
4.2.2 Termination
4.2.3 General kinetic scheme
4.2.4 Energetics of cationic polymerization
4.2.5 Telechelic polymers via cationic polymerization
4.2.6 Cationic ring opening polymerization
4.2.7 Stable carbocations
4.3 Anionic polymerization
4.3.1 ”Living” polymers
4.3.2 Kinetics and molar mass distribution in “living” anionic systems
4.3.3 Metal alkyl initiators
4.3.4 Solvent and gegen-ion effects
4.3.5 Anionic ring opening polymerization
4.4 Summary

CHAPTER 5 LINEAR COPOLYMERS AND OTHER ARCHITECTURES
Abstract
5.1 General characteristics
5.2 Composition drift
5.3 The copolymer equation
5.4 Monomer reactivity ratios
5.5 Reactivity ratios and copolymer structure
5.6 Monomer reactivities and chain initiation
5.7 Influence of structural effects on monomer reactivity ratios
5.7.1 Resonance Effects
5.7.2 Polar Effects
5.10.3 Use of CRP methods
5.8 The Q-e scheme
5.9 Alternating copolymers
5.10 Block copolymer synthesis
5.10.1 Transformation reactions
5.10.2 Coupling reactions
5.10.3 Use of CRP methods
5.11 Block copolymer synthesis
5.12 Statistical / gradient copolymers
5.13 Complex molecular architectures
5.14 Dendrimers
5.14.1 Divergent growth
5.14.2 Convergent growth
5.14.2 Dendrimer molecular weight
5.14.4 Properties of dendrimers
5.15 Summary

CHAPTER 6 POLYMER STEREOCHEMISTRY
Abstract
6.1 General Aspects
6.2 Architecture
6.3 Orientation
6.4 Configuration
6.4.1 Monotactic polymers
6.4.2 Ditactic polymers
6.4.3 Polyethers
6.5 Geometric isomerism
6.6 Conformation of stereoregular polymers
6.7 Factors influencing stereoregulation
6.8 Homogeneous stereospecific cationic polymerizations
6.9 Homogeneous stereoselective anionic polymerizations
6.10 Homogeneous diene polymerization
6.11 Summary

CHAPTER 7 POLYMERIZATION REACTIONS INITIATED by
METAL CATALYSTS and TRANSFER REACTIONS
Abstract
7.1 Polymerization using Ziegler-Natta catalysts
7.1.1 Nature of the catalyst
7.1.2 Nature of active centres
7.1.3 Bimetallic mechanism
7.1.4 Monometallic mechanism
7.1.5 Stereoregulation
7.2 Ring opening metathesis polymerizations (ROMP)
7.2.1 Monocyclic monomers
7.2.2 Bicyclo- and tricyclo-monomers
7.2.3 Copolyalkenamers
7.3 Living systems
7.4 Group transfer polymerization (GTP)
7.5 Aldol group transfer polymerization
7.6 Metallocene Catalysts
7.6.1 Metallocene/aluminoxane Catalysts
7.6.2 Stereoregulation
7.6.3 Cationic Metallocenes
7.6.4 Mechanism of stereoregulation
7.7 Summary

CHAPTER 8 POLYMERS IN SOLUTION

Abstract 91
8.1 Thermodynamics of polymer solutions
8.2 Ideal mixtures of small molecules
8.3 Non-ideal solutions
8.4 Flory-Huggins theory: Entropy of Mixing
8.5 Enthalpy change on mixing
8.6 Free energy of mixing
8.7 Limitations of the Flory-Huggins theory
8.8 Phase equilibria
8.9 Flory-Krigbaum theory
8.10 Location of the theta temperature
8.11 Lower critical solution temperatures
8.12 Solubility and the cohesive energy density
8.12.1 Group Contributions
8.12.2 Computational Methods
8.13 Polymer-polymer mixtures
8.14 Kinetics of Phase Separation
8.15 Summary

CHAPTER 9 POLYMER CHARACTERIZATION – MOLAR MASSES
Abstract
9.1 Introduction
9.2 Molar masses, molecular weights, and SI units
9.3 Determination of the average molar mass
9.4 End-group assay
9.5 Colligative properties of solutions
9.5.1 Osmotic pressure
9.6  Light scattering
9.6.1 Scattering from large particles
9.7  Dynamic light scattering
9.8  Viscosity
9.8.1 Viscosity average molecular weight
9.9  Gel permeation chromatography
9.10  MALDI
9.11  Summary

CHAPTER 10 POLYMER CHARACTERIZATION –
CHAIN DIMENSIONS, STRUCTURES AND MORPHOLOGY
Abstract
10.1 Average chain dimensions
10.2 Freely-jointed chain model
10.3 Short range effects
10.4 Chain stiffness
10.5 Treatment of dilute solution data
10.5.1 The second virial coefficient
10.5.2 Expansion factor 
10.5.3 Flory-Fox theory
10.5.4 Indirect estimates of
10.5.5 Influence of tacticity on chain dimensions 395
10.6 Nuclear Magnetic Resonance (NMR)
10.7  Infrared spectroscopy
10.8  Thermal analysis
10.9  Wide angle and small angle scattering
10.9.1 Wide angle X-ray scattering
10.9.2 Small angle X-ray scattering (SAXS)
10.9.3 Small angle neutron scattering (SANS)
10.10 Microscopy
10.10.1 Optical microscopy
10.10.2 Scanning electron microscopy
10.10.3 Transmission electron microscopy
10.10.4 Atomic force microscopy (AFM) and
Scanning tunneling microscopy (STM
10.11 Summary

CHAPTER 11 POLYMER CHARACTERIZATION –
CHAIN DIMENSIONS, STRUCTURES AND MORPHOLOGY
Abstract
11.1 Introduction
11.2 Mechanism of crystallization
11.3 Temperature and growth rate
11.4 Melting
11.4.1 Effect of Crystallite Size on Melting
11.5  Thermodynamic parameters
11.6  Factors affecting crystallinity and Tm
11.6.1 Symmetry
11.6.2 Intermolecular Bonding
11.6.3 Tacticity
11.6.4 Branching and Molar Mass
11.7  Morphology
11.7.1 Crystallites
11.7.2 Single Crystals
11.7.3 Hedrites
11.7.4 Crystallization from the Melt
11.7.5 Spherulites
11.8 Kinetics of Crystallization
11.8.1 Isothermal Crystallization
11.8.2 The Avrami Equation
11.8.3 Deviations from Avrami Equation
11.9 Block Copolymers
11.10 Polymer Liquid Crystals
11.10.1 Liquid crystalline phases
11.10.2 Identification of the mesophases
11.10.3 Lyotropic main chain liquid crystalline polymers
11.10.4 Thermotropic main chain liquid crystal polymers
11.10.5 Side chain liquid crystalline polymers
11.10.6 Chiral nematic liquid crystal polymers
11.11 Summary

CHAPTER 12 THE GLASSY STATE AND GLASS TRANSITION
Abstract
12.1 The amorphous state
12.2 The glassy state
12.2.1 Relaxation processes in the glassy state
12.3 Glass transition region
12.3.1 The glass transition temperature
12.3.2 Experimental demonstration of Tg
12.3.3 Measurements of Tg from V-T curves
12.3.4 Thermal methods
12.4  Factors affecting the glass transition region
12.4.1 Chain flexibility
12.4.2 Steric Effects
12.4.3 Steric Effects
12.4.4 Effect of cross-links on Tg
12.5  Theoretical treatments
12.5.1 The free volume theory
12.5.2 Gibbs-Di Marzio thermodynamic theory
12.5.3 Adam-Gibbs theory
12.6 Dependence of Tg on molar mass
12.7 Structural Relaxation and Physical Ageing
12.8 Summary

CHAPTER 13 RHEOLOGY AND MECHANICAL PROPERTIES
Abstract
13.1  Introduction to Rheology
13.2  The five regions of viscoelastic behaviour
13.3  The viscous region
13.3.1 Shear dependence of viscosity
13.3.2 Kinetic units in polymer chains
13.3.3 Effect of chain length
13.3.4 Temperature dependence of 
13.3.5 Concentration dependence of viscosity
13.3.6 Time dependent behavior
13.4 Mechanical properties
13.4.1 Interrelation of moduli
13.5 Mechanical models describing viscoelasticity
13.6 Linear viscoelastic behavior of amorphous polymers
13.6.1 Creep
13.6.2 Stress-strain measurements
13.6.3 Effect of temperature on stress-strain response
13.6.4 Boltzmann superposition principle
13.6.5 Stress-relaxation
13.7  Dynamic mechanical and dielectric thermal analysis
13.7.1 Dynamic mechanical thermal analysis (DMTA)
13.7.2 Dielectric thermal analysis (DETA)
13.7.3 Comparison between DMTA and DETA
13.8 Time-temperature superposition principle
13.9 Dynamic viscosity
13.10 A molecular theory for viscoelasticity
13.11 The reptation model
13.12 Summary

CHAPTER 14 THE ELASTOMERIC STATE
Abstract
14.1  General introduction
14.1.1 Natural rubber
14.2  Experimental vulcanization
14.3  Properties of elastomers
14.4  Thermodynamic aspects of rubber-like elasticity
14.5  Nonideal elastomers
14.6  Distribution function for polymer conformation
14.7  Statistical approach
14.7.1 Experimental stress-strain results
14.7.1.1 Simple Extension
14.7.1.2 Simple Compression
14.7.1.3 Pure Shear
14.7.1.3 Large Elastic Deformation
14.8  Swelling of elastomeric networks
14.9  Network defects
14.10 Resilience of elastomers
14.11 Conclusion

CHAPTER 15 STRUCTUR E PROPERTY RELATIONS
Abstract
15.1  General considerations
15.2  Control of Tm and Tg
15.2.1 Chain stiffness
15.2.2 Intermolecular bonding
15.2.3 Relation between Tm and Tg
15.3  Random copolymers
15.3.1 Dependence of Tm and Tg on copolymer composition
15.4  Block copolymers
15.4.1 Thermomechanical Properties of Block Copolymers
15.4.2 Microphase-Separation
15.5 Plasticizers
15.6  Crystallinity and mechanical response
15.7  Application to fibers, elastomers and plastics
15.8 Fibers
15.8.1 Chemical requirements
15.8.1.1 Linear Polyesters
15.8.2 Mechanical requirements for fibers
15.8.2.1 Spinning Techniques
15.8.2.2 Drawing, Orientation and Crystallinity
15.8.2.3 Modulus and Chain Stiffness
15.8.2.4 Other Factors
15.9 Aromatic polyamides
15.10 Polyethylene
15.11 Elastomers and crosslinked networks
15.11.1 Cross-linking
15.11.2 Creep in Cross-linked Polymers
15.11.3 Additives in Cross-linked Polymers
15.12 Plastics
15.12.1 Additives in Plastics
15.12.2 Medical Applications
15.13 Engineering and High Temperature Speciality Polymers
15.14 Polymer Composites and Nanocomposites
15.15 Polymers with Electrical Properties
15.15.1 Conduction Mechanism
15.15.2 Polyacetylene
15.15.3 Conduction Mechanism of poly(p-phenylene)
15.15.4 Common Electrically Conductive Polymers
15.16 Computational Approaches
15.17 Summary

CHAPTER 16 SUSTAINABLE POLYMERS AND CIRCULARITY
Abstract
16.1  Introduction
16.2  Recycling and Recovery of Polymers
16.2.1 Historical aspects
16.2.2 Reasons for recycling
16.2.3 Recycling options
16.2.4 Mechanical recycling
16.2.5 Solvent-based recycling
16.2.6 Chemical recycling
16.2.6.1 Thermal depolymerization
16.2.6.2 Chemical depolymerization
16.2.7 Energy recovery
16.3  Sustainable and Biorelated Polymers
16.3.1 Bio-based Polymers
16.3.2 Biodegradable Polymers
16.3.3 Incorporating Carbon Dioxide into Polymers
16.4  Life Cycle Assessment
16.5  Design for Circularity
16.6  Legislation
16.7 Summary

Biography

Valeria Arrighi (VA) is Associate Professor at Heriot-Watt University, Edinburgh and Acting Head of Materials Chemistry. She graduated in Pure Chemistry in Italy and after teaching Chemistry for a year and spending a short period in industry, she returned to academia. She was awarded a PhD in Polymer Science in 1992 from Imperial College and continued working there as an RA before joining Heriot-Watt University in 1996, as Lecturer. Her main interest is in the study of the properties of polymers including mechanical, aging but also structure, dynamics and order. For some of these, her group is making extensive use of large scale neutron scattering facilities. Currently, main activities are in polymer nanocomposites and membranes for water purification. She is a Fellow of the Royal Society of Chemistry and co-author of the polymer textbook: Polymers: Chemistry and Physics of Modern Materials (J.M.G. Cowie and V. Arrighi, 3rd edition, CRC Press, 2007).