The article contains sections titled: 1. Introduction 2. Linear and Cyclic Polyorganosiloxanes 2.1. Production 2.1.1. Hydrolysis 2.1.2. Methanolysis 2.1.3. Cyclization 2.1.4. Polymerization 2.1.5. Polycondensation 2.1.6. Industrial Production of Linear Polysiloxanes 2.2. Polydimethylsiloxanes 2.3. Siloxane‐Based Copolymers 3. Silicone Fluids 3.1. Methylsilicone Fluids 3.2. Methylphenylsilicone Fluids 3.3. Other Types of Silicone Fluids 3.4. Properties 3.5. Formulation 3.6. Applications 4. Silicone Rubbers and Elastomers 4.1. General Properties 4.2. Rubber Compounds 4.3. Rheology 4.4. Curing Systems 4.4.1. Radical Curing with Peroxides 4.4.2. Hydrosilylation Curing 4.4.3. Condensation Curing 4.4.4. Radiation Curing 4.4.5. Oxidative Coupling 4.5. Peroxide‐Cured High‐Temperature Vulcanizing Silicone Rubbers 4.6. Liquid Silicone Rubbers 4.7. Room Temperature Curing Silicone Rubbers 4.7.1. Two‐Component RTV Systems 4.7.2. One‐Component RTV Systems 4.8. Paper and Textile Coatings 4.8.1. Paper Coating 4.8.2. Textile Coating 4.9. Properties of Silicone Elastomers 4.10. Applications 5. Silicone Resins 5.1. Structure and General Properties 5.2. Production 5.3. Curing 5.4. Properties 5.5. Applications 6. Block and Graft Copolymers 6.1. Polysiloxane ‐ Polyether Copolymers 6.2. Other Block Copolymers 6.3. Graft Copolymers 6.4. Applications of Block and Graft Copolymers 7. Analysis 8. Toxicology 9. Environmental Aspects 10. Economic Aspects
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Die partielle Ammonolyse you Siliciumtetrachlorid in Diäthyläther <−60° führt zu Hexachlordisilazan (I; 40% Ausbeute), Hexachlorcyclotrisilazan (II; 3–5%) und Polychlorsilazanen, vornehmlich [Ci2SiNH]x (III). Einen Überblick über die einzelnen Reaktionsschritte gibt Schema 2. Durch Spaltung von III mit HCl oder HBr in Benzol oder Äther bzw. mit SiCl4 unter erhöhten Temperaturen und Drücken entsteht weiteres I in bescheidenen und Oktachlortrisildiazan (IV) in sehr geringen Ausbeuten. I bildet mit Butyllithium Lithium‐bis‐(trichlorsilyl)amid (IX). Dieses reagiert mit Schwerem Wasser zu Deuterohexachlordisilazan (V) und zerfällt beim Erwärmen in LiCl und Dekachlor‐bis(silyl)‐cyclodisilazan (XIX). Physikalische Daten und Analysen dieser Verbindungen sind in Tab. 2 und 3 zusammengefaßt. Weitere Reaktionen von I. II und IX können aus Kap. 4a. b sowie Schema 3, 4 und 6 ersehen werden.
Kinetic Investigation of the Platinum‐catalysed Hydrosilylation of Vinylsiloxanes with Hydrogensiloxanes A kinetic investigation of the platinum‐catalysed hydrosilylation of monofunctional oligomeric vinylsiloxanes by monofunctional oligomeric hydrogensiloxanes was performed under stoichiometric conditions with use of quantitative 1H‐NMR spectrometry. The reaction rate up to 50% conversion can be expressed by v=k [Pt]. During further hydrosilylation the kinetic changed to second order. No induction period was observed. A hydrogensiloxane with a dimethylsilyl end group gives much higher rates than a siloxane with a methylsiloxy group. The main reactions of all hydrosilylations, determined by GC‐MS and 29Si‐NMR, are β‐additions. Less then 5% α‐products are obtained.
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