4.3.4Special Characteristics of Classical Cationic Polymerizations80

4.4KINETICS OF IONIC POLYMERIZATION80

4.4.1Anionic Polymerization81

4.4.2Cationic Polymerization87

Exercises4 91



Chapter 5 STEP POLYMERIZATION93

5.1INTRODUCTION93

5.1.1Types of Condensation Reactions94

5.1.2Requirements for High Molecular Weight95

5.2SPECIFIC CONDENSATION POLYMERIZATIONS95

5.2.1Linear Polyesters95

5.2.2Branched and Crosslinked Polyesters96

5.2.3Polycarbonates97

5.2.4Polyamides(nylons)98

5.3KINETICS OF STEP POLYMERIZATION99

5.3.1Equal Reactivity of Functional Groups99

5.3.2Rate of Polymerization Reactions99

5.3.3Kinetics of Polyesterification100

5.4TIME DEPENDENCE OF THE AVERAGE DEGREE OF POLYMERIZATION103

5.5MOLECULAR WEIGHT DISTRIBUTIONS105

5.6EFFECT OF NONSTOICHIOMETRIC REACTANT RATIOS108

5.7BRANCHED AND CROSSLINKED CONDENSATION POLYMERS111

5.8THE METHOD OF STEP POLYMERIZATION114

5.8.1Melt Condensation Polymerization115

5.8.2Solution Polymerization116

5.8.3Interfacial Polycondensation116

5.8.4Solid Phase Polycondensation117

5.9RANDOM PREPOLYMERS AND STRUCTURE PREPOLYMERS118

5.9.1Random Performed Polymers118

5.9.2Structure Prepolymers119

Exercises5 122



Chapter 6 RING-OPENING POLYMERIZATION126

6.1INTRODUCTION126

6.2CHARACTERISTICS OF RING-OPENING POLYMERIZATION 126

6.3POLYMERIZATION ABILITY OF CYCLIC MONOMERS127

6.4THERMODYNAMICS OF RING-OPENING POLYMERIZATION OF CYCLOALKANES127

6.5THERMODYNAMIC AND KINETIC CHARACTERISTICS OF CYCLOALKANE POLYMERIZATION128

6.6IMPORTANT RING-OPENING POLYMERIZATION IN INDUSTRY130

6.6.1Cyclic Ether130

6.6.2Cationic Ring-opening Polymerization of Carbonyl Compounds and Acetals133

6.6.3Ring-opening Polymerization of Cyclic Amides134

6.6.4Cyclosiloxane137

Exercises6 138



Chapter 7 REACTIONS OF SYNTHETIC POLYMERS139

7.1REACTIONS INVOLVING THE MAIN CHAIN139

7.1.1Addition Reactions139

7.1.2Reactions that Generate Skeletal Unsaturation140

7.1.3Hydrolytic Chain Cleavage140

7.1.4Enzymatic Degradation of Synthetic Polymers141

7.1.5Oxidation Reactions142

7.1.6High Temperature Degradation Reactions143

7.1.7Electron Beam Depolymerization147

7.2REACTIONS INVOLVING THE SIDE GROUPS147

7.2.1Principles of Polymer Reactivity147

7.2.2Hydrolysis of Side Group Structures148

7.2.3Chloromethylation of Polystyrene150

7.3GRAFT POLYMER FORMATION151

7.4CROSS-LINKING REACTION152

7.5SURFACE REACTIONS OF POLYMERS153

7.5.1Surface Fluorination153

7.5.2Surface Nitrification and Sulfonation154

7.5.3Surface Oxidation154

Exercises7 155



Chapter 8 METHODS OF POLYMERIZATION156

8.1BULK (MASS) POLYMERIZATION156

8.2SOLUTION POLYMERIZATION157

8.3SUSPENSION POLYMERIZATION157

8.4EMULSION POLYMERIZATION159

8.4.1Description of Process160

8.4.2Quantitative Aspects168

8.4.3Other Characteristics of Emulsion Polymerization176

8.4.4Soap-Free Emulsion Polymerization179

8.4.5Inverse Emulsion Polymerization180

8.4.6Miniemulsion Polymerization181

8.4.7Microemulsion Polymerization181

8.4.8Seed Emulsion Polymerization181

8.4.9Core-shell Emulsion Polymerization182

8.4.10Dispersion Polymerization182

8.4.11Living Radical Polymerization182

Exercises8 184



REFERENCE185

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