The chemistry of free radical polymerization
著者
書誌事項
The chemistry of free radical polymerization
Elsevier Science Ltd., c1995
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注記
Includes index
内容説明・目次
内容説明
In recent years, the study of radical polymerization has gone through something of a renaissance. This has seen significant changes in our understanding of the area and has led to major advances in our ability to control and predict the outcome of polymerization processes. Two major factors may be judged responsible for bringing this about and for spurring an intensified interest in all aspects of radical chemistry. Firstly, the realization that classical theories on radical reactivity and polymerization mechanism do not adequately explain the rate and specificity of simple radical reactions. Secondly, the development of new techniques which allow a more thorough characterization of both polymer microstructures and the kinetics and mechanism of polymerizations. This book critically evaluates the findings of the last few years. The overall aim is to provide a framework for greater understanding of free radical polymerization and create a definable link between synthesis conditions and polymer structure and properties. The end result should be polymers with predictable and reproducible properties. The book commences with a general introduction outlining the basic concepts.
This is followed by a chapter on the mechanisms of free radical reactions that is intended to lay the theoretical ground-work for the succeeding chapters which detail the chemistry of initiation, propagation and termination. Because of its importance, copolymerization is treated in a separate chapter. The authors then consider some of the implications of these chapters by discussing the prospects for controlling the polymerization process and structure-property relationships. Emphasis is placed on recent developments. Each chapter describes some of the techniques that have been employed to characterize polymers and polymerizations and which have led to breakthroughs in the understanding of radical polymerization.
目次
- Part 1 Free radical reactions: introduction
- addition to carbon-carbon double bonds
- steric factors
- polar factors
- bond strengths
- theoretical treatments
- hydrogen atom transfer
- polar factors
- stereoelectronic factors
- reaction conditions
- abstraction vs. addition
- summary radical-radical reactions
- pathways for combination
- pathways for disproportionation
- combination vs. disproportionation
- summary. Part 2 Initiation: introduction
- the initiation process
- reaction with monomer
- fragmentation
- reaction with solvents, additives or impurities
- effects of the reaction medium on radical reactivity
- reaction with oxygen
- initiator efficiency
- cage reaction and initiator-derived by-products
- primary radical termination
- transfer to initiator
- initiation in heterogeneous polymerization
- thermal initiation
- the radicals
- carbon-centred radicals
- oxygen-centred radicals. Part 3 Propagation: introduction
- stereosequence isomerism - tacticity
- monoene polymers
- conjugated diene polymers
- structural isomerism - rearrangement
- cyclopolymerization
- ring-opening polymerization
- intramolecular atom transfer
- propagation kinetics and thermodynamics. Part 4 Termination
- introduction
- radical-radical termination
- termination kinetics
- disproportionation vs. combination - general considerations
- disproportionation vs. combination - summary
- chain transfer
- mechanisms
- transfer agents
- transfer to monomer
- transfer to polymer
- inhibition and retardation
- "stable" radicals
- oxygen. Part 5 Copolymerization: introduction
- statistical copolymerization
- copolymerization mechanisms
- block and graft copolymerization
- end-functional polymers
- block and graft copolymer synthesis. Part 6 Controlling polymerization: introduction
- "defect structures" in polystyrene
- "defect structures" in poly(methyl methacrylate)
- controlling propagation
- solvent
- Lewis acids and inorganics
- template polymers
- compositional heterogeneity in copolymers
- agents for controlling termination
- organosulfur iniferters
- hexasubstituted ethanes and azo compounds
- alkoxyamines and related species.
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