NMR SPECTROSCOPY AND STEREOREGULARITY OF POLYMERS Kei Matsuzaki, Toshiyuki Uryu, and Tetsuo Asakura with 148 Figures and 80 Tables JAPAN SCIENTIFIC SOCIETIES PRESS Tokyo KARGEH Basel-Freiburg-Paris-London-New York-New Delhi- Bangkok Singapore Tokyo Sydney
Contents PREFACE V ACKNOWLEDGEMENTS XV ABBREVIATIONS X\i I. NMR SPECTROSCOPY AND STEREOREGULARITY OF VINYL POLYMERS AND POLY(ALKYLENE OXIDE)S Chapter 1 Introduction 2 1.1 Configuration of Polymers 2 1.2 'H NMR Spectra of Vinyl Polymers 9 1.3 Deuteration of Monomers and Polymers 11 1.4 Opening Mode of Vinyl Double Bonds and Ditactic Polymers 12 1.5 Model Compounds 13 1.6 13 C NMR Spectra of Vinyl Polymers 13 1.7 13 C Side-Band Spectra.. 14 1.8 Conformation of Vinyl Polymers 18 1.9 Rate Processes Observed with NMR Spectroscopy... 21 Chapter 2 Polyolefins 25 2.1 Polyethylene 25
Vlll 2.2 Polypropylene. 26 2.3 Poly(l-butene) 32 2.4 Poly(l-pentene), Poly(l-hexene), Poly(l-heptene), Poly(loctene) andpoly(l-nonene) 37 2.5 Poly(3-methyl-l-butene) 38 Chapter 3 Polydienes 41 3.1 Polybutadiene 41 3.2 Polyisoprene 46 3.3 Polychloroprene 51 Chapter 4 Poly(methyl methacrylate) and Related Ester Derivatives 57 4.1 Synthesis of Stereoregular Polymethacrylates 57 4.2 'H and 13 C NMR Spectroscdpy of Poly(methyl methacrylate) 58 4.3 Stereoregularity of Related Ester Derivatives 63 4.4 Polymerization of Optically Active Monomers and the Stereoregularity of Polymers.. ; 67 4.5 Two Phase Polymerization of Poly(methyl methacrylate); Polymerization with Grignard Reagent as Catalyst... 69 4.6 Stereoregularity of Poly(methyl methacrylate) Obtained in Matrix Polymerization 71 4.7 Optically Active Derivatives with Helical Structure..., 74 Chapter 5 Poly(methyl acrylate) and Related Ester Derivatives 80 5.1 Synthesis of Stereoregular Polyacrylates 80 5.2 Stereoregularity of Polyacrylates Determined by 'H NMR Spectroscopy 80 5.3 13 C NMR Spectroscopy of Polyacrylates 84 5.4 Double Bond Opening Mode of Acrylates in Polymerization 87 5.5 Asymmetric Effects of Optically Active Side Groups in the Polymerization of Optically Active Acrylates 88
Contents ix 5.6 Conformation of Poly(methyl acrylate) 89 Chapter 6 Poly(a-chloroacrylate)s 94 6.1 Introduction 94 6.2 Synthesis of Stereoregular Poly(a-chloroacrylate)s... 94 6.3 'H NMR Spectroscopy of Poly(a-chloroacrylate)s... 95 6.4 Stereocomplex Formation of Poly(a-chloroacrylate)s.. 97 Chapter 7 Poly(vinyl ether)s 98 7.1 Introduction 98 7.2 Synthesis of Stereoregular Poly(vinyl ether)s 98 7.3 'H NMR Spectroscopy of Poly(vinyl ether)s 98 7.4 13 C NMR Spectroscopy of Poly(vinyl ether)s 102 7.5 Stereochemistry in the Cationic Polymerization of Vinyl Ethers 103 7.6 Optically Active Copolymers of Poly(vinyl ether)s... 108 Chapter 8 Poly(a-methyl vinyl ether)s 113 Chapter 9 Poly(vinyl ketone)s and Poly(isopropenyl ketone)s 118 9.1 'H and 13 C NMR Spectroscopy of Poly(vinyl ketone)s. 118 9.2 13 C NMR Spectroscopy of Poly(isopropenyl ketone)s.. 120 Chapter 10 Polyacrylonitrile 123 10.1 Synthesis of Polyacrylonitrile 123 10.2 'H NMR Spectroscopy of Polyacrylonitrile 123 10.3 13 C NMR Spectroscopy of Polyacrylonitrile 128 Chapter 11 Polymethacrylonitrile 131 11.1 Synthesis of Polymethacrylonitrile 131
X 11.2 'H NMR Spectroscopy and Stereoregularity of Polymethacrylonitrile 131 11.3 13 C NMR Spectroscopy of Polymethacrylonitrile... 132 Chapter 12 Polystyrene and Its Derivatives 137 12.1 Synthesis of Stereoregular Polystyrene 137 12.2 'H NMR Spectroscopy of Polystyrene 138 12.3 13 C NMR Spectroscopy of Polystyrene 139 12.4 Stereoregularity of Polystyrenes Obtained by Anionic Polymerization 141 12.5 Stereoregularity of Polystyrenes Obtained with Butyllithium-Water 145 12.6 Stereoregularity of Polystyrenes Obtained with Alfin Catalyst 146 12.7 Stereoregularity of Polystyrenes Obtained with Cationic Catalysts 147 12.8 Stereoregularity of Polystyrerfes Obtained by Radiation-Induced Polymerization 147 12.9 Synthesis and Stereoregularity of Poly(methylstyrene)s 149 12.10 Synthesis and Stereoregularity of Poly(methoxystyrene)s 152 Chapter 13 Poly(a-methylstyrene) 157 13.1 Synthesis of Poly(oe-methylstyrene) 157 13.2 ] H NMR Spectroscopy of Poly(a-methylstyrene).... 158 13.3 13 C NMR Spectroscopy of Poly(a-methylstyrene)... 158 13.4 Stereoregularity of Poly(a-methylstyrene) Obtained with Anionic Catalysts 158 13.5 Stereoregularity of Poly(oe-methylstyrene) Prepared with Cationic Catalysts. 161 Chapter 14 Poly(vinylpyridine)s 163 14.1 Synthesis of Poly(vinylpyridine)s 163 14.2 'H and 13 C NMR Spectroscopy of Poly(vinylpyridine)s. 163
Contents xi 14.3 Mechanism of Isotactic Polymerization of Poly(2- vinylpyridine) 168 Chapter 15 Poly(N-vinylcarbazole) 173 15.1 Synthesis of Poly(N-vinylcarbazole) 173 15.2 'H and 13 C NMR Spectroscopy of Poly(N-vinylcarbazole) 173 15.3 The Structure of Poly(N-vinylcarbazole) Obtained with Electron Acceptors as Catalysts 175 Chapter 16 Poly (vinyl acetate) 179 16.1 Synthesis of Poly(vinyl acetate) 179 16.2 'H and 13 C NMR Spectroscopy of Poly(vinyl acetate).. 179 Chapter 17 Poly(isopropenyl acetate) 182 17.1 Synthesis of Poly(isopropenyl acetate) 182 17.2 'H and 13 C NMR Spectroscopy of Poly(isopropenyl acetate) 182 Chapter 18 Polyethylene oxide) 185 18.1 Synthesis of Polyethylene oxide) 185 18.2 Conformation of Poly(ethylene oxide) Determined by 'H NMR spectroscopy. 185 18.3 Opening Mode in the Polymerization of Ethylene Oxide 193 Chapter 19 Poly(propylene oxide) 198 19.1 Synthesis of Poly(propylene oxide) 198 19.2 NMR Spectroscopy and Stereoregularity of Poly(propylene oxide) 199
xii Chapter 20 Poly(propenyl ether)s 203 20.1 Introduction 203 20.2 'H and 13 C NMR Spectroscopy of Poly(j3-substituted vinyl ether)s 204 20.3 Stereochemistry in the Process of Polymerization... 206 Chapter 21 Poly (vinyl alcohol) 212 21.1 Synthesis of Poly (vinyl alcohol) 212 21.2 'H and 13 C NMR Spectroscopy of Poly(vinyl alcohol). 212 Chapter 22 Poly (vinyl chloride) 216 22.1 Synthesis of Poly(vinyl chloride) 216 22.2 'H and 13 C NMR Spectroscopy of Poly(vinyl chloride). 216 Chapter 23 Factors Affecting Stereoregularity of Vinyl Polymers 221 23.1 Radical Polymerization 222 23.2 Cationic Polymerization 224 23.3 Anionic Polymerization 225 II. REACTIONS CORRELATED TO THE STEREOREGULARITY OF POLYMERS Chapter 24 Thermal Reaction and Hydrolysis of Polymethacrylates and Polyacrylates 228 24.1 Thermal Reaction and Anhydride Formation of Polymethacrylates 228 24.2 Hydrolysis and Anhydride Formation of Polymethacrylates 230 24.3 Hydrolysis and Anhydride Formation of Polyacrylates. 231
Contents xiii Chapter 25 Thermal Reaction of Poly(methyl vinyl ketone) and Poly(isopropenyl methyl ketone) 234 25.1 Thermal Reaction of Poly (methyl vinyl ketone)... 234 25.2 Thermal Reaction of Poly(isopropenyl methyl ketone). 235 Chapter 26 Racemization of Polyacrylonitrile 239 III. NMR SPECTROSCOPY OF LIVING POLYMERS AND QUANTUM CHEMICAL ANALYSIS Chapter 27 Living Polystyrene 242 27.1 NMR Spectroscopy of Polystyryl Anions and Their Model Compounds 242 27.2 NMR Spectroscopy of Polystyryllithium and Its Model Compounds 244 27.3 NMR Spectroscopy of Polystyrylpotassium and Its Model Compounds 245 27.4 Effect of Counter Cation on the Excess Charge Distribution 245 27.5 Effect of the Kind of Solvent on the Excess Charge Distribution 247 27.6 Rotation of Ca-Cl Bond of Polystyryllithium and Its Model Compounds 248 27.7 Quantum Chemical Treatment of Polystyryl Anions.. 248 27.8 Spin-Lattice Relaxation Times T x of Living Anion... 251 Chapter 28 Living Poly(a-methylstyrene) 253 28.1 'H and 13 C NMR Spectroscopy of Living Poly(amethylstyrene) 253 28.2 Quantum Chemical Calculation of Poly(a-methylstyryl) Anion 256 28.3 Rotation of Ca-C 1 Bond of Poly (a-methylstyryl) Lithium 257
xiv Chapter 29 Living Poly(methylstyrene)s 258 29.1 Introduction 258 29.2 NMR Spectroscopy of Living Poly(o-methylstyrene) and Its Model Compound 259 29.3 NMR Spectroscopy of Living Poly(m-methylstyrene) and Its Model Compound 261 29.4 NMR Spectroscopy of Living Poly(p-methylstyrene).. 263 Chapter 30 Living Poly(o-methoxystyrene) 265 SUBJECT INDEX 2 6 9 ABOUT THE AUTHORS 2 7 7