More than simply an up-to-date review of ionic polymerization, this book presents an in-depth and critical comparison of the anionic and cationic polymerization of vinyl monomers and heterocyclic compounds. These different modes of ionic polymerization are examined with regard to their capacity for producing living polymers. The concept of living polymers is re-examined and redefined in light of current knowledge of ionic polymerization and possible side reactions. Throughout, the authors offer perceptive insights into the basic concepts of polymerization chemistry and polymerization reaction mechanisms. The book begins with a review of ionic and radical polymerizations, the development of ionic polymerization, living and dormant polymers, and polymerizability. It goes on to consider important aspects of the structure and properties of ionic species; initiation and propagation of ionic polymerization; polymerization steps other than initiation or propagation, such as termination, isomerization, transfer, backbiting, and degraduation; and ionic copolymerization. Ionic Polymerization and Living Polymers is a much needed advanced text that will be widely read and referred to by polymer scientists, macromolecular chemists, and materials scientists.

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1. Introduction.- 1. Comparison of Ionic and Radical Polymerizations.- 2. Developments of Ionic Polymerization.- 3. Living and Dormant Polymers.- 4. Polymerizability and the Monomer-Living Polymer Equilibria.- 2. Ionic Species.- 1. Formation of Ions.- 2. Ionophores and Ionogens, Ion-Pairs, and Covalent Species.- 3. Free Ions and Ion-Pairs.- 4. Different Types of Ion-Pairs.- 5. Equilibria Between Free Ions and Ion-Pairs: Conductance Studies.- 6. Heat and Entropy of Dissociation of Ion-Pairs.- 7. Triple Ions.- 8. Higher Ionic Aggregates.- 9. Dynamics of Interconversions Between Ionic Species.- 3. Initiation and Propagation of Ionic Polymerization.- 1. General Remarks.- 2. Initiation and Propagation Induced by Salts.- 3. Initiation and Propagation Involving Lithium Alkyls.- 4. Initiation of Cationic Polymerization by Protonic Acids: Role of Esters (Including Halides).- 5. Initiation of Polymerization by Lewis Bases and Acids: Problem of Zwitterions.- 6. Initiation of Cationic Polymerization by Friedel-Crafts Reagents in Conjunction with Co-initiators.- 7. Initiation of Polymerization by Electron Transfer and Related Topics.- 8. Polymerization Initiated by High Energy Radiation.- 9. Initiators Involving Al, Fe, Zn, and Other Metallo-Organics.- 10. Activated Monomer Mechanism.- 4. Elementary Steps of Polymerization Other Than Initiation or Propagation.- 1. Termination.- 2. Intramolecular Proton or Hydride Ion Transfers and Other Isomerizations.- 3. "Wrong" Monomer Addition.- 4. Chain-Transfer.- 5. Proton Traps.- 6. Polymerization of Isobutene Initiated by Cumyl Chloride and Its Analogues.- 7. Ring-Chain Competitions.- 5. Ionic Copolymerization.- 1. General Schemes of Copolymerization and the Crossover Constants.- 2. Reactivity and Basicity of Monomers.- 3. ReactivityRatios: Composition of Copolymer and Feed.- 4. Copolymerization and Homopolymerization.- 5. System Li-Polystyryl and Li-Polybutadienyl in Hydrocarbon Solvents.- 6. Consequences of Equilibria Between Unreacted Aggregates and Reactive Nonassociated Polymers: Mixed Dimerizations.- 7. Reversible Copolymerization: System 2-Vinylnaphthalene-Styrene.- 8. Cationic Copolymerizations.