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Chemistry of Radical Polymerization

ISBN-10: 0080442862
ISBN-13: 9780080442860
Edition: 2nd 2005 (Revised)
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Description: This book commences with a general introduction outlining the basic concepts of radical polymerization. This is followed by a chapter on radical reactions that is intended to lay the theoretical ground-work for the succeeding chapters on initiation,  More...

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Book details

Edition: 2nd
Copyright year: 2005
Publisher: Elsevier Science & Technology Books
Publication date: 1/11/2006
Binding: Hardcover
Pages: 666
Size: 6.50" wide x 9.25" long x 1.00" tall
Weight: 2.640
Language: English

This book commences with a general introduction outlining the basic concepts of radical polymerization. This is followed by a chapter on radical reactions that is intended to lay the theoretical ground-work for the succeeding chapters on initiation, propagation and termination.

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

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