Third Edition FUNDAMENTAL PRINCIPLES OF POLYMERIC MATERIALS CHRISTOPHER S.BRAZEL STEPHEN L.ROSEN Linear Branched Crosslinked ③WILEY
CONTENTS PREFACE xiii PREFACE TO THE SECOND EDITION XV ACKNOWLEDGMENTS xvii 1 INTRODUCTION 1 Problems 7 References 7 PART I.POLYMER FUNDAMENTALS 9 2 TYPES OF POLYMERS 11 2.1 Reaction to Temperature 11 2.2 Chemistry of Synthesis 12 2.3 Structure 19 2.4 Conclusions 30 Problems 30 Reference 34 3 MOLECULAR STRUCTURE OF POLYMERS 35 3.1 Types of Bonds 35 3.2 Bond Distances and Strengths 35 3.3 Bonding and Response to Temperature 37 3.4 Action of Solvents 38
vi CONTENTS 3.5 Bonding and Molecular Structure 39 3.6 Stereoisomerism in Vinyl Polymers 40 3.7 Stereoisomerism in Diene Polymers 42 3.8 Summary 44 Problems 44 References 45 4 POLYMER MORPHOLOGY 46 4.1 Amorphous and Crystalline Polymers 47 4.2 The Effect of Polymer Structure,Temperature,and Solvent on Crystallinity 48 4.3 The Effect of Crystallinity on Polymer Density 49 4.4 The Effect of Crystallinity on Mechanical Properties 50 4.5 The Effect of Crystallinity on Optical Properties 51 4.6 Models for the Crystalline Structure of Polymers 53 4.7 Extended Chain Crystals 56 4.8 Liquid Crystal Polymers 57 Problems 59 References 60 5 CHARACTERIZATION OF MOLECULAR WEIGHT 61 5.1 Introduction 61 5.2 Average Molecular Weights 62 5.3 Determination of Average Molecular Weights 66 5.4 Molecular Weight Distributions 75 5.5 Gel Permeation (or Size-Exclusion)Chromatography (GPC,SEC) 79 5.6 Summary 85 Problems 86 References 89 6 THERMAL TRANSITIONS IN POLYMERS 91 6.1 Introduction 91 6.2 The Glass Transition 91 6.3 Molecular Motions in an Amorphous Polymer 92 6.4 Determination of Te 92 6.5 Factors that Influence T 95 6.6 The Effect of Copolymerization on T 97 6.7 The Thermodynamics of Melting 97 6.8 The Metastable Amorphous State 100 6.9 The Influence of Copolymerization on Thermal Properties 101 6.10 Effect of Additives on Thermal Properties 102
CONTENTS vii 6.11 General Observations about Te and Tm 103 6.12 Effects of Crosslinking 103 6.13 Thermal Degradation of Polymers 103 6.14 Other Thermal Transitions 104 Problems 104 References 106 7 POLYMER SOLUBILITY AND SOLUTIONS 107 7.1 Introduction 107 7.2 General Rules for Polymer Solubility 107 7.3 Typical Phase Behavior in Polymer-Solvent Systems 109 7.4 The Thermodynamic Basis of Polymer Solubility 110 7.5 The Solubility Parameter 112 7.6 Hansen's Three-Dimensional Solubility Parameter 114 7.7 The Flory-Huggins Theory 116 7.8 Properties of Dilute Solutions 118 7.9 Polymer-Polmyer-Common Solvent Systems 121 7.10 Polymer Solutions,Suspensions,and Emulsions 121 7.11 Concentrated Solutions:Plasticizers 122 Problems 124 References 126 PART II.POLYMER SYNTHESIS 129 8 STEP-GROWTH(CONDENSATION)POLYMERIZATION 131 8.1 Introduction 131 8.2 Statistics of Linear Step-Growth Polymerization 132 8.3 Number-Average Chain Lengths 133 8.4 Chain Lengths on a Weight Basis 136 8.5 Gel Formation 137 8.6 Kinetics of Polycondensation 142 Problems 143 References 145 9 FREE-RADICAL ADDITION(CHAIN-GROWTH) POLYMERIZATION 146 9.1 Introduction 146 9.2 Mechanism of Polymerization 147 9.3 Gelation in Addition Polymerization 148 9.4 Kinetics of Homogeneous Polymerization 149 9.5 Instantaneous Average Chain Lengths 153
viii CONTENTS 9.6 Temperature Dependence of Rate and Chain Length 155 9.7 Chain Transfer and Reaction Inhibitors 157 9.8 Instantaneous Distributions in Free-Radical Addition Polymerization 160 9.9 Instantaneous Quantities 165 9.10 Cumulative Quantities 166 9.11 Relations Between Instantaneous and Cumulative Average Chain Lengths for a Batch Reactor 169 9.12 Emulsion Polymerization 173 9.13 Kinetics of Emulsion Polymerization in Stage II,Case 2 176 9.14 Summary 180 Problems 180 References 183 10 ADVANCED POLYMERIZATION METHODS 185 10.1 Introduction 185 10.2 Cationic Polymerization 185 10.3 Anionic Polymerization 186 10.4 Kinetics of Anionic Polymerization 192 10.5 Group-Transfer Polymerization 194 10.6 Atom Transfer Radical Polymerization 195 10.7 Heterogeneous Stereospecific Polymerization 196 10.8 Grafted Polymer Surfaces 202 10.9 Summary 203 Problems 203 References 205 11 COPOLYMERIZATION 207 11.1 Introduction 207 11.2 Mechanism 207 11.3 Significance of Reactivity Ratios 209 11.4 Variation of Composition with Conversion 210 11.5 Copolymerization Kinetics 216 11.6 Penultimate Effects and Charge-Transfer Complexes 216 11.7 Summary 217 Problems 217 References 219 12 POLYMERIZATION PRACTICE 220 12.1 Introduction 220 12.2 Bulk Polymerization 220