Mechanisms of Ionic Polymerization

1: Characteristics of Ionic Polymerization Processes.- 1.1. Anionic Systems.- 1.2. Cationic Systems.- 1.3. Systems Based on Transition Metals.- 1.3.1. Ziegler-Natta Catalysts.- 1.3.2. ?-Allyl Complexes.- References.- 2: The Informativeness of Research Methods into Ionic Active Sites.- 2.1. Electrochemical Studies.- 2.1.1. Anionic Systems.- 2.1.2. Cationic Systems.- 2.2. Spectroscopic Studies.- 2.2.1. UV Spectroscopy.- 2.2.2. IR Spectroscopy.- 2.2.3. NMR Spectroscopy.- 2.2.3.1. Allyl Compounds.- 2.2.3.2. Derivatives of Unsaturated Monomers and Their Models.- 2.2.3.3. Ziegler-Natta Catalysts.- 2.3. Quantum-Chemical Studies.- 2.3.1. The Problem of Modelling in the Study of Ionic Systems Using Quantum-Chemical Methods.- 2.3.2. The Basic Approaches and Examples of Their Application.- 2.3.2.1. Series of Compounds.- 2.3.2.2. Individual Compounds.- 2.3.2.3. Multicomponent Systems.- 2.3.3. Summary.- References.- 3: General Questions on the Problem of Multicenteredness.- 3.1. Types of Multicentered Systems and Forms of Their Corresponding Active Sites.- 3.1.1. Dissociation of Aggregates.- 3.1.2. Ionic Dissociation.- 3.1.3. Intermolecular Complex Formation.- 3.1.4. Intramolecular Complex Formation.- 3.1.5. Isomerization of Active Sites.- 3.2. Overall and Individual Effects.- 3.2.1. Kinetic Features of Polymerization Reactions.- 3.2.2. Molecular Mass Distribution in Polymers.- 3.2.3. Structural Features of Macromolecules.- 3.3. The Role of Multicenteredness in Real Processes.- 3.4. Multicenteredness in Copolymerization Processes.- 3.4.1. The Aggregated State of Active Sites.- 3.4.2. Ion Pairs and Free Ions.- 3.4.3. Complex Formation with External Reagents.- 3.4.4. Intramolecular Effects.- 3.4.5. Isomerization.- References.- 4: The Reactivity of Active Sites and Monomers in Homogeneous Ionic Systems.- 4.1. The Relative Reactivity of Growing Chains.- 4.1.1. The Role of the State and the Environment of Growing Mn*Y Chains.- 4.1.1.1. Organolithium Growing Chains and Their Associates.- 4.1.1.2. Complexes of Organolithium Active Sites in the Polymerization of Nonpolar Monomers.- 4.1.1.3. Anionic Chains in the Polymerization of Polar Monomers.- 4.1.1.4. The Activating Effect of Electron Donors on Organolithium Associates.- 4.1.1.5. The Activating Effect of Electron Acceptors on the Polymerization of Cationic Growing Chains.- 4.1.1.6. Influence of the Nature of the Reaction Medium.- 4.1.2. The Role of the Nature of the Y Component in the Growing Mn*Y Chains.- 4.1.2.1. The Influence of the Nature of the Central Atom of the Counterion.- 4.1.2.2. The Total Effect of the Central Atom and Ligands of the Y Component.- 4.1.3. The Role of the Nature of the Mn* Component in Growing Mn*Y Chains.- 4.1.4. Concluding Remarks.- 4.2. Reactivity of the Monomers.- 4.2.1. Unsaturated Monomers.- 4.2.1.1. The Principles of Selection and the Indices of Reactivity.- 4.2.1.2. Nonterminating Copolymerization Processes.- 4.2.1.3. Copolymerization in Processes with Termination.- References.- 5: The Problem of Stereospecificity.- 5.1. The Polymerization of Vinyl and Vinylidene Monomers.- 5.1.1. Nonpolar Monomers.- 5.1.1.1. Propylene.- 5.1.1.2. Styrene Monomers.- 5.1.2. Polar Monomers.- 5.1.2.1. Methacrylates and Related Monomers.- 5.1.2.2. Vinylpyridines.- 5.1.2.3. Alkenyl Ethers.- 5.2. Diene Monomers.- 5.2.1. Polymerization in Cationic Systems.- 5.2.2. Polymerization in Anionic Systems.- 5.2.2.1. Butadiene and Isoprene.- 5.2.2.2. Diene Phenyl Derivatives.- 5.2.3. Polymerization in Systems with Transition Metals.- References.- 6: Conclusion.- References.