Synthese, Funktionalisierung und Vernetzung Siliciumorganischer Polymere mit Hilfe von Silyltriflat-Intermediaten

Abstract

The design and synthesis of new materials are two key steps in the advancement of technology. One of the most promising approaches of development of new materials that combine advantages of organic polymers with those of inorganic solids is to devise polymers that have a backbone of inorganic atoms to which are attached organic side groups. Among the best developed examples of „ inorganic organic polymers„ are organosilicon polymers. The synthesis of new organosilicon polymers using silyl triflate intermediates is reviewed in this article. Protodephenylation of phenylated polysilanes as well as poly(silylenemethylenes) by triflic acid gave new functionalized compounds 12—25, 27—39. Network polymers were obtained by reductive coupling of silyl triflates with potassium‐graphite. Novel poly(silylenealkynes) 51—67 and poly(silylenearylenes) 68—91 containing a regular alternating arrangement of silylene groups and organic units were prepared from α, ω‐bis[(trifluoromethyl)sulfonyloxysilyl]‐substituted compounds and dinucleophiles. Some of the polymers are potential organic precursor for ceramic materials. The correlation between structure and thermolytic behaviour is demonstrated on selected examples.

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“…Examples discussed include the dephenylation of phenylated polysilanes, the formation of network polymers by reductive coupling of silyl triflates and the synthesis of alternating copolymers by reaction of a,w-disilyltriflates with dinucleophiles. 9 Silicon-containing dendrimers have been reviewed. Carbosilane, siloxane, silane, silazane and silatrane dendrimers and hyperbranched polymers were discussed.…”

“…24 Analogous polymers have been reported this year by the co-condensation of (S),(S)-HO(Np)(Ph)SiCH 2 CH 2 SiMe 2 CH 2 CH 2 Si(Ph)(Np)OH (Np = naphthyl) and (Me 2 N) 2 SiMe 2 . 25 Dehydrocoupling polymerisation of disilanes (7) and disilanols (8) using Wilkinson's catalyst gives silylphenylene siloxane polymers (9). High molecular weight polymers are obtained with the phenylene spacer groups and polymerisation proceeds rapidly at room temperature in an open flask.…”