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Living polymerization

About: Living polymerization is a research topic. Over the lifetime, 5469 publications have been published within this topic receiving 183553 citations.

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01 Jan 1981
TL;DR: In this paper, the authors present an overview of the properties of polymers and their applications in the literature, including the following: 1.1 Types of Polymers and Polymerization. 2.3 Linear, Branched, and Crosslinked Polymers.
Abstract: Preface. 1. Introduction. 1.1 Types of Polymers and Polymerizations. 1.2 Nomenclature of Polymers. 1.3 Linear, Branched, and Crosslinked Polymers. 1.4 Molecular Weight. 1.5 Physical State. 1.6 Applications of Polymers. 2. Step Polymerization. 2.1 Reactivity of Functional Groups. 2.2 Kinetics of Step Polymerization. 2.3 Accessibility of Functional Groups. 2.4 Equilibrium Considerations. 2.5 Cyclization versus Linear Polymerization. 2.6 Molecular Weight Control in Linear Polymerization. 2.7 Molecular Weight Distribution in Linear Polymerization. 2.8 Process Condition. 2.9 Multichain Polymerization. 2.10 Crosslinking. 2.11 Molecular Weight Distributions in Nonlinear Polymerizations. 2.12 Crosslinking Technology. 2.13 Step Copolymerization. 2.14 High-Performance Polymers. 2.15 Inorganic and Organometallic Polymers. 2.16 Dendric (Highly Branched) Polymers. 3. Radical Chain Polymerization. 3.1 Nature and Radical Chain Polymerization. 3.2 Structural Arrangement of Monomer Units. 3.3 Rate of Radical Chain Polymerization. 3.4 Initiation. 3.5 Molecular Weight. 3.6 Chain Transfer. 3.7 Inhibition and Retardation. 3.8 Determination of Absolute Rate Constants. 3.9 Energetic Characteristics. 3.10 Autoacceleration. 3.11 Molecular Weight Distribution. 3.12 Effect of Pressure. 3.13 Process Conditions. 3.14 Specific Commercial Polymers. 3.15 Living Radical Polymerization. 3.16 Other Polymerizations. 4. Emulsion Polymerization. 4.1 Description of Process. 4.2 Quantitative Aspects. 4.3 Other Characteristics of Emulsion Polymerization. 5. Ionic Chain Polymerization. 5.1 Comparison of Radical and Ionic Polymerization. 5.2 Cationic Polymerization of the Carbon-Carbon Double Bond. 5.3 Anionic Polymerization of the Carbon-Carbon Double. 5.4 Block and Other Polymer Architecture. 5.5 Distinguishing Between Radical, Cationic, and Anionic Polymerizations. 5.6 Carbonyl Polymerization. 5.7 Miscellaneous Polymerizations. 6. Chain Copolymerization. 6.1 General Considerations. 6.2 Copolymer Composition. 6.3 Radical Copolymerization. 6.4 Ionic Copolymerization. 6.5 Deviations from Terminal Copolymerization Model. 6.6 Copolymerizations Involving Dienes. 6.7 Other Copolymerizations. 6.8 Applications of Copolymerizations. 7. Ring-Opening Polymerization. 7.1 General Characteristics. 7.2 Cyclic Ethers. 7.3 Lactams. 7.4 N-Carboxy-alphaAmino Acid Anhydrides. 7.5 Lactones. 7.6 Nitrogen Heterocyclics. 7.7 Sulfur Heterocyclics. 7.8 Cycloalkenes. 7.9 Miscellaneous Oxygen Heterocyclics. 7.10 Other Ring-Opening Polymerizations. 7.11 Inorganic and Partially Inorganic Polymers. 7.12 Copolymerization. 8. Stereochemistry of Polymerizaton. 8.1 Types of Stereoisomerism in Polymers. 8.2 Properties of Stereoregular Polymers. 8.3 Forces of Stereoregulation in Alkene Polymerization. 8.4 Traditional Ziegler-Natta Polymerization of Nonpolar Alkene Monomers. 8.5 Metallocene Polymerization of Nonpolar Alkene Monomers. 8.6 Other Hydrocarbon Monomers. 8.7 Copolymerization. 8.8 Postmetallocene: Chelate Initiators. 8.9 Living Polymerization. 8.10 Polymerization of 1,3-Dienes. 8.11 Commercial Applications. 8.12 Polymerization of Polar Vinyl Monomers. 8.13 Alehydes. 8.14 Optical Activity in Polymers. 8.15 Ring-Opening Polymerization. 8.16 Statistical Models of Propagation. 9. Reactions of Polymers. 9.1 Principles of Polymers Reactivity. 9.2 Crosslinking. 9.3 Reactions of Cellulose. 9.4 Reactions of Poly(vinyl) acetate). 9.5 Halogenation. 9.6 Aromatic Substitution. 9.7 Cyclization. 9.8 Other Reactions. 9.9 Graft Copolymers. 9.10 Block Copolymers. 9.11 Polymers as Carriers or Supports. 9.12 Polymer Reagents. 9.13 Polymer Catalysts. 9.14 Polymer Substrates. Index.

4,933 citations

Journal ArticleDOI
TL;DR: The authors proposed a reversible additive-fragmentation chain transfer (RAFT) method for living free-radical polymerization, which can be used with a wide range of monomers and reaction conditions and in each case it provides controlled molecular weight polymers with very narrow polydispersities.
Abstract: mechanism involves Reversible Addition-Fragmentation chain Transfer, and we have designated the process the RAFT polymerization. What distinguishes RAFT polymerization from all other methods of controlled/living free-radical polymerization is that it can be used with a wide range of monomers and reaction conditions and in each case it provides controlled molecular weight polymers with very narrow polydispersities (usually <1.2; sometimes <1.1). Living polymerization processes offer many benefits. These include the ability to control molecular weight and polydispersity and to prepare block copolymers and other polymers of complex architecturesmaterials which are not readily synthesized using other methodologies. Therefore, one can understand the current drive to develop a truly effective process which would combine the virtues of living polymerization with versatility and convenience of free-radical polymerization.2-4 However, existing processes described under the banner “living free-radical polymerization” suffer from a number of disadvantages. In particular, they may be applicable to only a limited range of monomers, require reagents that are expensive or difficult to remove, require special polymerization conditions (e.g. high reaction temperatures), and/or show sensitivity to acid or protic monomers. These factors have provided the impetus to search for new and better methods. There are three principal mechanisms that have been put forward to achieve living free-radical polymerization.2,5 The first is polymerization with reversible termination by coupling. Currently, the best example in this class is alkoxyamine-initiated or nitroxidemediated polymerization as first described by Rizzardo et al.6,7 and recently exploited by a number of groups in syntheses of narrow polydispersity polystyrene and related materials.4,8 The second mechanism is radical polymerization with reversible termination by ligand transfer to a metal complex (usually abbreviated as ATRP).9,10 This method has been successfully applied to the polymerization of various acrylic and styrenic monomers. The third mechanism for achieving living character is free-radical polymerization with reversible chain transfer (also termed degenerative chain transfer2). A simplified mechanism for this process is shown in

4,561 citations

Journal ArticleDOI
TL;DR: In this article, a review of recent mechanistic developments in the field of controlled/living radical polymerization (CRP) is presented, with particular emphasis on structure-reactivity correlations and "rules" for catalyst selection in ATRP, for chain transfer agent selection in reversible addition-fragmentation chain transfer (RAFT) polymerization, and for the selection of an appropriate mediating agent in stable free radical polymerisation (SFRP), including organic and transition metal persistent radicals.
Abstract: Recent mechanistic developments in the field of controlled/living radical polymerization (CRP) are reviewed. Particular emphasis is placed on structure–reactivity correlations and “rules” for catalyst selection in atom transfer radical polymerization (ATRP), for chain transfer agent selection in reversible addition-fragmentation chain transfer (RAFT) polymerization, and for the selection of an appropriate mediating agent in stable free radical polymerization (SFRP), including organic and transition metal persistent radicals. Novel methods of fine tuning initiation, activation, and deactivation processes for all techniques are discussed, including activators regenerated by electron transfer (ARGET) and initiators for continuous activator regeneration (ICAR) ATRP, whereby Cu catalyst concentrations in ATRP can be lowered to just 10 ppm. Progress made in each technique related to the synthesis of both high and low molecular weight polymers, end functional polymers, block copolymers, expanding the range of polymerizable monomers, synthesis of hybrid materials, environmental issues, and polymerization in aqueous media is thoroughly discussed and compared.

2,869 citations

01 Jan 1981
TL;DR: In this article, the authors discuss the history of polymers and their application in the field of chemical engineering, including the origins of polymer science and the Polymer Industry, as well as a discussion of the role of elastic deformation in polymers.
Abstract: CONCEPTS, NOMENCLATURE AND SYNTHESIS OF POLYMERS Concepts and Nomenclature The Origins of Polymer Science and the Polymer Industry Basic Definitions and Nomenclature Molar Mass and Degree of Polymerization Principles of Polymerization Introduction Classification of Polymerization Reactions Monomer Functionality and Polymer Skeletal Structure Functional Group Reactivity and Molecular Size: The Principle of Equal Reactivity Step Polymerization Introduction Linear Step Polymerization Non-Linear Step Polymerization Radical Polymerization Introduction to Radical Polymerization The Chemistry of Conventional Free-Radical Polymerization Kinetics of Conventional Free-Radical Polymerization Free-Radical Polymerization Processes Reversible-Deactivation ('Living') Radical Polymerizations Non-Linear Radical Polymerizations Ionic Polymerization Introduction to Ionic Polymerization Cationic Polymerization Anionic Polymerization Group-Transfer Polymerization Stereochemistry and Coordination Polymerization Introduction to Stereochemistry of Polymerization Tacticity of Polymers Geometric Isomerism in Polymers Prepared from Conjugated Dienes Ziegler-Natta Coordination Polymerization Metallocene Coordination Polymerization Ring-Opening Polymerization Introduction to Ring-Opening Polymerization Cationic Ring-Opening Polymerization Anionic Ring-Opening Polymerization Free-Radical Ring-Opening Polymerization Ring-Opening Metathesis Polymerization Specialized Methods of Polymer Synthesis Introduction Solid-State Topochemical Polymerization Polymerization by Oxidative Coupling Precursor Routes to Intractable Polymers Supramolecular Polymerization (Polyassociation) Copolymerization Introduction Step Copolymerization Chain Copolymerization Block Copolymer Synthesis Graft Copolymer Synthesis CHARACTERIZATION OF POLYMERS Theoretical Description of Polymers in Solution Introduction Thermodynamics of Polymer Solutions Chain Dimensions Frictional Properties of Polymer Molecules in Dilute Solution Number-Average Molar Mass Introduction to Measurements of Number-Average Molar Mass Membrane Osmometry Vapour Pressure Osmometry Ebulliometry and Cryoscopy End-Group Analysis Effects of Low Molar Mass Impurities upon Mn Scattering Methods Introduction Static Light Scattering Dynamic Light Scattering Small-Angle X-Ray and Neutron Scattering Frictional Properties of Polymers in Solution Introduction Dilute Solution Viscometry Ultracentrifugation Molar Mass Distribution Introduction Fractionation Gel Permeation Chromatography Field-Flow Fractionation Mass Spectroscopy Chemical Composition and Molecular Microstructure Introduction Principles of Spectroscopy Ultraviolet and Visible Light Absorption Spectroscopy Infrared Spectroscopy Raman Spectroscopy Nuclear Magnetic Resonance Spectroscopy Mass Spectroscopy PHASE STRUCTURE AND MORPHOLOGY OF BULK POLYMERS The Amorphous State Introduction The Glass Transition Factors Controlling the Tg Macromolecular Dynamics The Crystalline State Introduction Determination of Crystal Structure Polymer Single Crystals Semi-Crystalline Polymers Liquid Crystalline Polymers Defects in Crystalline Polymers Crystallization Melting Multicomponent Polymer Systems Introduction Polymer Blends Block Copolymers PROPERTIES OF BULK POLYMERS Elastic Deformation Introduction Elastic Deformation Elastic Deformation of Polymers Viscoelasticity Introduction Viscoelastic Mechanical Models Boltzmann Superposition Principle Dynamic Mechanical Testing Frequency Dependence of Viscoelastic Behaviour Transitions and Polymer Structure Time-Temperature Superposition Effect of Entanglements Non-Linear Viscoelasticity Elastomers Introduction Thermodynamics of Elastomer Deformation Statistical Theory of Elastomer Deformation Stress-Strain Behaviour of Elastomers Factors Affecting Mechanical Behaviour Yield and Crazing Introduction Phenomenology of Yield Yield Criteria Deformation Mechanisms Crazing Fracture and Toughening Introduction Fundamentals of Fracture Mechanics of Fracture Fracture Phenomena Toughened Polymers Polymer Composites Introduction to Composite Materials Matrix Materials Types of Reinforcement Composite Composition Particulate Reinforcement Fibre Reinforcement Nanocomposites Electrical Properties Introduction to Electrical Properties Dielectric Properties Conduction in Polymers Polymer Electronics Answers to Problems Index Problems and Further Reading appear at the end of each chapter.

1,348 citations

Reference BookDOI
15 Mar 1996
TL;DR: Anionic and living polymerization: Living polymerization - definitions, consequences and criteria general aspects of anionic polymerization are discussed in this paper, where anionic synthesis of polymers with well-defined structures is discussed.
Abstract: Part 1 Structure and bonding in carbanionic compounds: structure of carbanions and organometallic compounds stabilities of carbanionic species ion pairs, free ions and stereochemistry in carbanionic chemistry. Part 2 Introduction to anionic and living polymerization: living polymerization - definitions, consequences and criteria general aspects of anionic polymerization. Part 3 Kinetics and mechanism in anionic polymerization: initiation reactions in anionic polymerization - kinetics of addition of organolithium compounds to vinyl monomer propagation reactions - kinetics and mechanism for styrenes and dienes in hydrocarbon solvents with lithium as counterion termination and chain transfer reactions stereochemistry of polymerization copolymerization. Part 4 Anionic synthesis of polymers with well-defined structures: functionalized polymers and macromonomers block copolymers star polymers graft copolymers. Part 5 Commercial applications of anionically prepared polymers: commercial applications of anionically polymerized products - an overview polydiene rubbers styrene-diene rubbers styrenic thermoplastic elastomers applications of styrenic thermoplastic rubbers in plastics modifications, adhesives and footwear clear impact-resistant polystyrene nonfunctional telechelic prepolymers. Part 6 Polar monomers: anionic polymerization of methyl methacrylate and related polar monomers block polymers prepared via anionic ring-opening polymerization.

1,000 citations

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