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| Contents | |
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| Index to Tables | |
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| Index to Figures | |
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| Preface to the First Edition | |
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| Preface to the Second Edition | |
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| Acknowledgments | |
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| Introduction | |
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| References | |
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| Radical Reactions | |
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| Introduction | |
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| Properties of Radicals | |
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| Structures of Radicals | |
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| Stabilities of Radicals | |
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| Detection of Radicals | |
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| Addition to Carbon-Carbon Double Bonds | |
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| Steric Factors | |
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| Polar Factors | |
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| Bond Strengths | |
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| Stereoelectronic Factors | |
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| Entropic Considerations | |
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| Reaction Conditions | |
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| Theoretical Treatments | |
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| Summary | |
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| Hydrogen Atom Transfer | |
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| Bond Dissociation Energies | |
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| Steric Factors | |
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| Polar Factors | |
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| Stereoelectronic Factors | |
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| Reaction Conditions | |
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| Abstraction vs Addition | |
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| Summary | |
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| Radical-Radical Reactions | |
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| Pathways for Combination | |
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| Pathways for Disproportionation | |
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| Combination vs Disproportionation | |
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| Summary | |
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| References | |
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| Initiation | |
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| Introduction | |
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| The Initiation Process | |
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| Reaction with Monomer | |
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| Fragmentation | |
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| Reaction with Solvents, Additives, or Impurities | |
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| Effects of Temperature and Reaction Medium on Radical Reactivity | |
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| Reaction with Oxygen | |
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| Initiator Efficiency in Thermal Initiation | |
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| Photoinitiation | |
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| Cage Reaction and Initiator-Derived Byproducts | |
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| Primary Radical Termination | |
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| Transfer to Initiator | |
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| Initiation in Heterogeneous Polymerization | |
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| The Initiators | |
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| Azo-Compounds | |
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| Peroxides | |
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| Multifunctional Initiators | |
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| Photochemical Initiators | |
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| Redox Initiators | |
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| Thermal Initiation | |
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| The Radicals | |
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| Carbon-Centered Radicals | |
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| Oxygen-Centered Radicals | |
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| Other Heteroatom-Centered Radicals | |
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| Techniques | |
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| Kinetic Studies | |
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| Radical Trapping | |
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| Direct Detection of End Groups | |
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| Labeling Techniques | |
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| References | |
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| Propagation | |
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| Introduction | |
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| Stereosequence Isomerism - Tacticity | |
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| Terminology and Mechanisms | |
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| Experimental Methods for Determining Tacticity | |
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| Tacticities of Polymers | |
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| Regiosequence Isomerism - Head vs Tail Addition | |
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| Monoene Polymers | |
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| Conjugated Diene Polymers | |
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| Structural Isomerism - Rearrangement | |
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| Cyclopolymerization | |
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| Ring-Opening Polymerization | |
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| Intramolecular Atom Transfer | |
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| Propagation Kinetics and Thermodynamics | |
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| Polymerization Thermodynamics | |
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| Measurement of Propagation Rate Constants | |
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| Dependence of Propagation Rate Constant on Monomer Structure | |
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| Chain Length Dependence of Propagation Rate Constants | |
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| References | |
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| Termination | |
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| Introduction | |
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| Radical-Radical Termination | |
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| Termination Kinetics | |
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| Disproportionation vs Combination | |
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| Inhibition and Retardation | |
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| 'Stable' Radicals | |
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| Oxygen | |
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| Monomers | |
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| Phenols | |
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| Quinones | |
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| Phenothiazine | |
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| Nitrones, Nitro- and Nitroso-Compounds | |
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| Transition Metal Salts | |
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| References | |
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| References | |
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| Chain Transfer | |
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| Introduction | |
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| Chain Transfer | |
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| Measurement of Transfer Constants | |
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| Homolytic Substitution Chain Transfer Agents | |
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| Addition-Fragmentation Chain Transfer Agents | |
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| Abstraction-Fragmentation Chain Transfer | |
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| Catalytic Chain Transfer | |
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| Transfer to Monomer | |
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| Transfer to Polymer | |
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| Transfer to Initiator | |
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| References | |
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| Copolymerization | |
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| Introduction | |
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| Copolymer Depiction | |
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| Propagation in Statistical Copolymerization | |
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| Propagation Mechanisms in Copolymerization | |
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| Chain Statistics | |
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| Estimation of Reactivity Ratios | |
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| Prediction of Reactivity Ratios | |
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| Termination in Statistical Copolymerization | |
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| Chemical Control Model | |
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| Diffusion Control Models | |
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| Combination and Disproportionation during Copolymerization | |
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| Functional and End-Functional Polymers | |
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| Functional Initiators | |
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| Functional Transfer Agents | |
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| Thiol-ene Polymerization | |
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| Functional Monomers | |
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| Functional Inhibitors | |
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| Compositional Heterogeneity in Functional Copolymers | |
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| Block & Graft Copolymerization | |
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| Polymeric and Multifunctional Initiators | |
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| Transformation Reactions | |
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| Radiation-Induced Grafting Processes | |
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| Radical-Induced Grafting Processes | |
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| Polymerization and Copolymerization of Macromonomers | |
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| References | |
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| Controlling Polymerization | |
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| Introduction | |
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| Controlling Structural Irregularities | |
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| "Defect Structures" in Polystyrene | |
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| "Defect Structures" in Poly(methyl methacrylate) | |
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| "Defect Structures" in Poly(vinyl chloride) | |
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| Controlling Propagation | |
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| Organic Solvents and Water | |
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| Supercritical Carbon Dioxide | |
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| Ionic liquids | |
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| Lewis Acids and Inorganics | |
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| Template Polymerization | |
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| Enzyme Mediated Polymerization | |
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| Topological Radical Polymerization | |
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| References | |
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| Living Radical Polymerization | |
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| Introduction | |
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| Living? Controlled? Mediated? | |
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| Tests for Living (Radical) Polymerization | |
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| Agents Providing Reversible Deactivation | |
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| Deactivation by Reversible Coupling and Unimolecular Activation | |
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| Kinetics and Mechanism | |
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| Sulfur-Centered Radical Mediated Polymerization | |
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| Selenium-Centered Radical Mediated Polymerization | |
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| Carbon-Centered Radical Mediated Polymerization | |
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| Reversible Addition-Fragmentation | |
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| Nitroxide Mediated Polymerization | |
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| Other Oxygen-Centered Radical Mediated Polymerization | |
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| Nitrogen-Centered Radical Mediated Polymerization | |
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| Metal Complex-Mediated Radical Polymerization | |
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| Atom Transfer Radical Polymerization | |
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| Initiators | |
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| Catalysts | |
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| Monomers and Reaction Conditions | |
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| Reversible Chain Transfer | |
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| Molecular Weights and Distributions | |
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| Macromonomer RAFT | |
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| Thiocarbonylthio RAFT | |
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| Iodine-Transfer Polymerization | |
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| Telluride-Mediated Polymerization | |
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| Stibine-Mediated Polymerization | |
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| Living Radical Copolymerization | |
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| Reactivity Ratios | |
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| Gradient Copolymers | |
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| NMP | |
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| ATRP | |
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| RAFT | |
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| End-Functional Polymers | |
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| NMP | |
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| ATRP | |
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| RAFT | |
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| Block Copolymers | |
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| Direct Diblock Synthesis | |
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| Transformation Reactions | |
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| Triblock Copolymers | |
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| Segmented Block Copolymers | |
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| Star Polymers | |
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| Core-first Star Synthesis | |
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| Arm-first Star Synthesis | |
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| Hyperbranched Polymers | |
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| Graft Copolymers/Polymer Brushes | |
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| Grafting Through - Copolymerization of Macromonomers | |
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| Grafting From - Surface Initiated Polymerization | |
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| Grafting To - Use of End-Functional Polymers | |
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| Outlook for Living Radical Polymerization | |
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| References | |
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| Abbreviations | |
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| Subject Index | |