Silicon in Polymer Synthesis

1 Polymerization of Si-Containing Vinyl Monomers and Acetylenes.- 1.1 Si-Containing Styrenes.- 1.1.1 Radical Polymerizations.- 1.1.2 Anionic Polymerizations.- 1.2 Various Vinyl Monomers.- 1.2.1 Vinyl Silanes.- 1.2.2 Allyl Silanes.- 1.2.3 Methacrylates and Fumarates.- 1.2.4 Vinyl Ethers.- 1.2.5 1,3-Dienes.- 1.3 Polymerizations of Si-Containing Acetylenes.- 1.4 Silylated Acetylenes in Condensation Reactions.- 1.4.1 Stepwise Syntheses of Oligomers.- 1.4.2 Acetylene-Terminated Oligomers.- 1.4.3 Polycondensations.- 1.5 Silicon-Containing Initiators and Catalysts.- 1.5.1 Initiators of Radical Polymerizations.- 1.5.2 Initiators of Cationic Polymerizations.- 1.5.3 Ziegler-Natta Catalysts and Related Systems.- 1.5.4 Polymerizations on Silica or Silicate Surfaces.- 1.6 References.- 2 Group Transfer Polymerization.- 2.1 The GTP Process.- 2.2 Mechanism.- 2.3 Catalysis.- 2.3.1 Nucleophilic Anions.- 2.3.2 Lewis Bases.- 2.3.3 Lewis Acids.- 2.3.4 Zeolytes.- 2.3.5 Mercuric Iodide.- 2.3.6 High Pressure.- 2.4 Initiators.- 2.4.1 Functional Initiators.- 2.4.2 Difunctional Initiators.- 2.4.3 Other -Silyl Ketene Acetal Initiators.- 2.4.4 Macroinitiators.- 2.4.5 Other Silicon-Containing Initiators.- 2.5 Monomers.- 2.5.1 ?, ?-Unsaturated Esters.- 2.5.2 Monomers with Protected Functional Groups.- 2.5.3 Other Monomers.- 2.5.4 Difunctional Monomers.- 2.5.5 Macromonomers.- 2.6 Termination.- 2.7 Aldol-GTP.- 2.8 Conclusions.- 2.9 References.- 3 Polysiloxanes and Polymers Containing Siloxane Groups.- 3.1 Polysiloxanes.- 3.1.1 Definition.- 3.1.2 Synthesis of Polydiorganosiloxanes.- 3.1.3 Chemical Properties of Polydiorganosiloxanes.- 3.1.4 Physical Properties of Polydiorganosiloxanes.- 3.1.5 Polydimethylsiloxanes with Functional Groups.- 3.2 Polysiloxane Copolymers.- 3.2.1 Fundamental Principles.- 3.2.2 Siloxane-Alkylene Oxide Copolymers.- 3.2.3 Polysiloxane-Polyester Copolymers.- 3.2.4 Polysiloxane-Polysulfone Block Copolymers.- 3.2.5 Polysiloxane-Polyimide, -Polyamide, -Polyurea and Polyurethane Copolymers.- 3.2.6 Polysiloxane-Polyalkene Copolymers.- 3.2.7 Polysiloxane-Polyalkine Copolymers.- 3.2.8 Polysiloxane-Silylarylene Copolymers.- 3.2.9 Polydimethylsiloxane-Polydiphenylsiloxane and Polymethylphenylsiloxane Copolymers.- 3.3 Polysiloxanes Forming Mesophases.- 3.3.1 Mesomorphic Polysiloxanes with Alkyl and Aryl Substituents.- 3.3.2 LC-Polysiloxanes Containing Mesogens-Syntheses.- 3.3.3 LC-Polysiloxanes Containing Mesogen-Modifications.- 3.3.4 LC-Main Chain Polymers.- 3.3.5 LC-Polysiloxanes with Pendant Mesogens.- 3.3.6 Liquid Crystalline Siloxanes Networks.- 3.3.7 Complex Structures.- 3.4 References.- 4 Poly(organosilanes), Poly(carbosilanes), Poly(organosilazanes).- 4.1 Poly(organosilanes).- 4.1.1 Preparation of the Raw Materials.- 4.1.2 Preparation of Poly(organosilanes).- 4.1.3 Chemical Properties of Poly(organosilanes).- 4.1.4 Physical Properties of Poly(organosilanes).- 4.1.5 Applications of Poly(organosilanes).- 4.1.6 Toxicological Properties of Poly(organosilanes).- 4.2 Poly(carbosilanes).- 4.2.1 Preparation of Poly(carbosilanes) with Alternating Silicon and Carbon Atoms.- 4.2.2 Reactions of Poly(carbosilanes).- 4.2.3 Poly(carbosilanes) with Longer Carbon Chains.- 4.2.4 Poly(carbosilanes) with Acetylene Groups in the Chain.- 4.2.5 Silane Dendrimers.- 4.2.6 Poly(carbosilanes) with Phenyl Groups in the Chain.- 4.3 Poly(organosilazanes).- 4.3.1 Preparation of Cyclic, Low-Molecular Weight Poly(organosilazanes) as Starting Material for the Preparation of Polymeric Poly(organosilazanes) by the Ammonolysis of Dichlorodiorganosilanes.- 4.3.2 Ring-Opening Polymerization of Cyclic Poly(organosilazanes)..- 4.3.3 Deaminization/Condensation Reaction Through the Thermolysis of Silylamines.- 4.3.4 Preparation of Poly(organosilazanes) by the Equilibration Reaction of ?Si—Cl— with Compounds Containing ?Si—N=.- 4.3.5 Preparation of Poly(organosilazanes) by Polycondensation of ?SiH— and = N—H-Containing Oligomeric Poly(organosilazanes).- 4.3.6 Chemical Properties of Poly(organosilazanes).- 4.4 Poly(carbosilazanes).- 4.5 References.- 5 Polycondensation of Silylated Monomers.- 5.1 Introduction.- 5.2 Polyureas and Related Polymers.- 5.3 Polyamides.- 5.4 Polyimides.- 5.5 Polybenzoxazoles.- 5.6 Aromatic Polyethers.- 5.7 Polyesters.- 5.8 Polyanhydrides.- 5.9 Phosphorus Containing Polymers.- 5.10 Miscellaneous Polymers.- 5.11 References.- 6 Miscellaneous Applications of Silicon Reagents.- 6.1 Difunctional Isocyanates and Isothiocyanates.- 6.1.1 Introduction.- 6.1.2 Difunctional Isocyanates via Trimethylsilylazide.- 6.1.3 Synthesis and Reactions of Isocyanato-and Isothiocyanato Carboxylic Acid Chlorides.- 6.2 Syntheses of N Carboxyanhydrides, Polypeptides and Polyamides.- 6.3 Silicon in Ring-Opening Polymerization.- 6.3.1 Silicon-Containing Monomers.- 6.3.2 Silicon-Containing Initiators.- 6.3.3 Si-Containing Terminators.- 6.4 Various Polymerizations and Polymers.- 6.5 References.- 7 Chemical Modification of Polymers and Surfaces.- 7.1 Coupling Agents-Introduction and Syntheses.- 7.1.1 Introduction.- 7.1.2 Syntheses of Coupling Agents.- 7.2 Application of Coupling Agents in Composites.- 7.2.1 Aqueous Solutions of Coupling Agents.- 7.2.2 Structure of the Interlayer and Performance of Composites.- 7.3 Coupling Agents for Chromatography, Immobilization of Metal Ions and Enzymes.- 7.3.1 Charge Transfer and Ligand-Exchange Chromatography.- 7.3.2 Binding of Metal Ions.- 7.3.3 Immobilization of Enzymes and Other Proteins.- 7.4 Surfactants and Analysis of Silanized Surfaces.- 7.4.1 Surfactants.- 7.4.2 Analysis of Silanized Surfaces.- 7.5 Miscellaneous Modification.- 7.5.1 Silylation of Polysaccharides.- 7.5.2 Chemical Modification of Poly-enes and Poly-ynes.- 7.5.3 Chemical Modification of Various Polymers.- 7.6 References.- Appendix A.- Silicon-Based Thermoset Resins.- Appendix B.- Silylation and Silylating Agents.