Syntheses, structures and properties of polycarbosilanes formed directly by polymerization of Alkenylsilanes

Vinylsilane polymerizes to form predominantly a carbosilane polymer using dimethyltitanocene catalyst. This is in contrast to alkylsilanes, which afford polysilanes under the same conditions. The mechanism of polymerization of alkenylsilanes has been shown to be fundamentally different from that for the polymerization of alkylsilanes. The silyl substitute apparently activates a double bond to participate in a number of polymerization processes in this system, particularly hydrosilation. Isotopic labeling indicates the involvement of silametallocyclic intermediates, accompanied by extensive nuclear rearrangement. Polymers and copolymers derived from alkenylsilanes have relatively high char yields even for conditions which afford low molecular weight distributions. Formation of crystalline beta-SiC is optimum for a copolymer of an alkylsilane and an alkenylsilane having a silane/carbosilane backbone ratio of 85/15 and a C/Si ratio of 1.3/1.