Reversible addition−fragmentation chain-transfer polymerization

About: Reversible addition−fragmentation chain-transfer polymerization is a research topic. Over the lifetime, 7964 publications have been published within this topic receiving 301066 citations.

Principles of polymerization

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.

Living free-radical polymerization by reversible addition - Fragmentation chain transfer: The RAFT process

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