Contents xi 4 Controlled Polymerization..........117 4.1 Introduction.. .117 4.2 Poisson Distribution for an Ideal Living Polymerization...............18 4.2.1 Kinetic Scheme............. .119 4.2.2 Breadth of the Poisson Distribution..... .122 4.3 Anionic Polymerization........... 126 4.4 Block Copolymers,End-Functional Polymers,and Branched Polymers by Anionic Polymerization......... .129 4.4.1 Block Copolymers... 129 4.4.2 End-Functional Polymers........ 133 4.4.3 Regular Branched Architectures.135 4.5 Cationic polymerization137 4.5.1 Aspects of Cationic Polymerization..138 4.5.2 Living Cationic Polymerization.140 4.6 Controlled Radical Polymerization142 4.6.1 General Principles of Controlled Radical Polymerization.........................142 4.6.2 Particular Realizations of Controlled Radical Polymerization.....................144 4.6.2.1 Atom Transfer Radical Polymerization (ATRP).......................144 4.6.2.2 Stable Free-Radical Polymerization (SFRP)............................145 4.6.2.3 Reversible Addition-Fragmentation Transfer(RAFT) Polymerization... .146 4.7 Polymerization Equilibrium.. .147 4.8 Ring-Opening Polymerization (ROP)............................ .150 4.8.1 General Aspects .150 4.8.2 Specific Examples of Living Ring-Opening Polymerizations.....................152 4.8.2.1 Poly(ethylene oxide)....152 4.8.2.2 Polylactide.... 153 4.8.2.3 Poly(dimethylsiloxane)......... .154 4.8.2.4 Ring-Opening Metathesis Polymerization(ROMP) .155 4.9 Dendrimers............ .156 4.10 Chapter Summary. .160 Problems .... .161 References.... .163 Further Readings...... .163 5 Copolymers,Microstructure,and Stereoregularity...........................165 5.1 Introduction. .165 5.2 Copolymer Composition...... …166 5.2.1 Rate Laws ..166 5.2.2 Composition versus Feedstock.............. .168 5.3 Reactivity Ratios............... .170 5.3.1 Effects of r Values..... ..171 5.3.2 Relation of Reactivity Ratios to Chemical Structure.. .173 5.4 Resonance and Reactivity............ ..175 5.5 A Closer Look at Microstructure ............ …179 5.5.1 Sequence Distributions.......... .180 5.5.2 Terminal and Penultimate Models.... .1834 Controlled Polymerization .......................................................................117 4.1 Introduction................................................................................................................ 117 4.2 Poisson Distribution for an Ideal Living Polymerization ......................................... 118 4.2.1 Kinetic Scheme ..............................................................................................119 4.2.2 Breadth of the Poisson Distribution ..............................................................122 4.3 Anionic Polymerization ............................................................................................. 126 4.4 Block Copolymers, End-Functional Polymers, and Branched Polymers by Anionic Polymerization........................................................................ 129 4.4.1 Block Copolymers .........................................................................................129 4.4.2 End-Functional Polymers ..............................................................................133 4.4.3 Regular Branched Architectures....................................................................135 4.5 Cationic Polymerization ............................................................................................ 137 4.5.1 Aspects of Cationic Polymerization..............................................................138 4.5.2 Living Cationic Polymerization ....................................................................140 4.6 Controlled Radical Polymerization ........................................................................... 142 4.6.1 General Principles of Controlled Radical Polymerization............................142 4.6.2 Particular Realizations of Controlled Radical Polymerization.....................144 4.6.2.1 Atom Transfer Radical Polymerization (ATRP)...........................144 4.6.2.2 Stable Free-Radical Polymerization (SFRP).................................145 4.6.2.3 Reversible Addition-Fragmentation Transfer (RAFT) Polymerization ...............................................................................146 4.7 Polymerization Equilibrium....................................................................................... 147 4.8 Ring-Opening Polymerization (ROP) ....................................................................... 150 4.8.1 General Aspects .............................................................................................150 4.8.2 Specific Examples of Living Ring-Opening Polymerizations......................152 4.8.2.1 Poly(ethylene oxide)......................................................................152 4.8.2.2 Polylactide......................................................................................153 4.8.2.3 Poly(dimethylsiloxane) ..................................................................154 4.8.2.4 Ring-Opening Metathesis Polymerization (ROMP) .....................155 4.9 Dendrimers................................................................................................................. 156 4.10 Chapter Summary ...................................................................................................... 160 Problems ................................................................................................................................ 161 References.............................................................................................................................. 163 Further Readings.................................................................................................................... 163 5 Copolymers, Microstructure, and Stereoregularity................................165 5.1 Introduction................................................................................................................ 165 5.2 Copolymer Composition............................................................................................ 166 5.2.1 Rate Laws ......................................................................................................166 5.2.2 Composition versus Feedstock ......................................................................168 5.3 Reactivity Ratios........................................................................................................ 170 5.3.1 Effects of r Values.........................................................................................171 5.3.2 Relation of Reactivity Ratios to Chemical Structure....................................173 5.4 Resonance and Reactivity.......................................................................................... 175 5.5 A Closer Look at Microstructure .............................................................................. 179 5.5.1 Sequence Distributions ..................................................................................180 5.5.2 Terminal and Penultimate Models ................................................................183 Hiemenz/ Polymer Chemistry, 2nd Edition DK4670_C000 Final Proof page xi 5.11.2007 8:20pm Compositor Name: JGanesan Contents xi