妨 Contents 7.9 Thermodynamics of Free Radical Polymerization.......... 172 7.9.1 Monomer Reactivity.....,.................. 173 7.9.2 Ceiling Temperature.··················· 175 7.9.3 Characteristics of AS Values of Free Radical Polymerization.......······ 176 7.l0 Molecular Weight Distribution at Low Conversion.···.···· 176 7.11 Synthesis of Commercial Polymers.................... 178 7.ll.1 Polyethylene......·.················· 178 7.l12 Polystyrene....·.······· 179 7.ll.3 Polyvinyl Chloride.........·.···· 180 7.ll.4 Polyvinyl Acetate......··..·.··..·.······· 180 7.11.5 Polyvinylidene Chloride .................... 180 7.11.6 Acryl Polymer.·.,···.·…············ 180 7.l1.7 Fluoropolymers....·················· 181 7.11.8 Cost of Common Polymers.........·.....···. 182 712 Problems.··················· 182 References......。t。。···+· 183 8 Ionic Chain Polymerization..·.....····················· 185 8.1 Characteristics of Ionic Chain Polymerization............ 187 8.2 Cationic Polymerization....·............·.······· 189 8.2.1 Initiators of Cationic Polymerization............. 189 8.2.2 Reaction Mechanisms of Cationic Polymerization .. 190 8.2.3 Kinetics of Cationic Polymerization............. 196 8.2.4 Commercial Cationic Polymerization............ 200 8.3 Anionic Polymerization.··.························ 201 8.3.1 Reaction Mechanisms of Anionic Polymerization.... 201 8.3.2 Kinetics of Anionic Polymerization with Termination..············ 204 8.4 Group Transfer Polymerization....................... 209 8.5 Chain Polymerization of Carbonyl Monomer............. 213 8.5.1 Anionic Polymerization of Carbonyl Monomer 213 8.5.2 Cationic Polymerization of Carbonyl Monomer..... 215 8.5.3 Radical Polymerization of Carbonyl Monomer...... 215 8.5.4 End-Capping Polymerization.................. 216 86 Problems..….·。,···…······…··…···· 217 References...,,·.。········· 218 9 Coordination Polymerization.,·..·.····················· 219 g.1 Heterogeneous Ziegler--Natta Polymerization......·..···. 219 9.l.1 Catalysts........········· 219 9.l.2 Reaction Mechanisms...··.················· 222 9.2 Homogeneous Ziegler-Natta Polymerization............. 225 9.3 Ziegler--Natta Copolymerization.···.················· 2297.9 Thermodynamics of Free Radical Polymerization . . . . . . . . . . 172 7.9.1 Monomer Reactivity . . . . . . . . . . . . . . . . . . . . . . . . 173 7.9.2 Ceiling Temperature . . . . . . . . . . . . . . . . . . . . . . . . 175 7.9.3 Characteristics of DS Values of Free Radical Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176 7.10 Molecular Weight Distribution at Low Conversion . . . . . . . . . 176 7.11 Synthesis of Commercial Polymers. . . . . . . . . . . . . . . . . . . . 178 7.11.1 Polyethylene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178 7.11.2 Polystyrene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179 7.11.3 Polyvinyl Chloride . . . . . . . . . . . . . . . . . . . . . . . . . 180 7.11.4 Polyvinyl Acetate . . . . . . . . . . . . . . . . . . . . . . . . . . 180 7.11.5 Polyvinylidene Chloride . . . . . . . . . . . . . . . . . . . . . 180 7.11.6 Acryl Polymer . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180 7.11.7 Fluoropolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . 181 7.11.8 Cost of Common Polymers . . . . . . . . . . . . . . . . . . . 182 7.12 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 182 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183 8 Ionic Chain Polymerization. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185 8.1 Characteristics of Ionic Chain Polymerization . . . . . . . . . . . . 187 8.2 Cationic Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . 189 8.2.1 Initiators of Cationic Polymerization. . . . . . . . . . . . . 189 8.2.2 Reaction Mechanisms of Cationic Polymerization . . . 190 8.2.3 Kinetics of Cationic Polymerization . . . . . . . . . . . . . 196 8.2.4 Commercial Cationic Polymerization . . . . . . . . . . . . 200 8.3 Anionic Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201 8.3.1 Reaction Mechanisms of Anionic Polymerization . . . . 201 8.3.2 Kinetics of Anionic Polymerization with Termination . . . . . . . . . . . . . . . . . . . . . . . . . . 204 8.4 Group Transfer Polymerization. . . . . . . . . . . . . . . . . . . . . . . 209 8.5 Chain Polymerization of Carbonyl Monomer . . . . . . . . . . . . . 213 8.5.1 Anionic Polymerization of Carbonyl Monomer . . . . . 213 8.5.2 Cationic Polymerization of Carbonyl Monomer . . . . . 215 8.5.3 Radical Polymerization of Carbonyl Monomer. . . . . . 215 8.5.4 End-Capping Polymerization . . . . . . . . . . . . . . . . . . 216 8.6 Problems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218 9 Coordination Polymerization. . . . . . . . . . . . . . . . . . . . . . . . . . . . 219 9.1 Heterogeneous Ziegler–Natta Polymerization . . . . . . . . . . . . . 219 9.1.1 Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219 9.1.2 Reaction Mechanisms . . . . . . . . . . . . . . . . . . . . . . . 222 9.2 Homogeneous Ziegler–Natta Polymerization . . . . . . . . . . . . . 225 9.3 Ziegler–Natta Copolymerization . . . . . . . . . . . . . . . . . . . . . . 229 xii Contents