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Syntheses, Structures and Properties of Polycarbosilanes Formed Directly by Polymerization of Alkenylsilanes

Published online by Cambridge University Press:  25 February 2011

John Masnovi ,
Xin Y. Bu ,
Kassahun Beyene ,
Paula Heimann ,
Terrence Kacik ,
A. Harry Andrist  and
Frances I. Hurwitz
John Masnovi
Affiliation:
Cleveland State University, Cleveland, OH 44115
Xin Y. Bu
Affiliation:
Cleveland State University, Cleveland, OH 44115
Kassahun Beyene
Affiliation:
Cleveland State University, Cleveland, OH 44115
Paula Heimann
Affiliation:
Cleveland State University, Cleveland, OH 44115
Terrence Kacik
Affiliation:
Cleveland State University, Cleveland, OH 44115
A. Harry Andrist
Affiliation:
Cleveland State University, Cleveland, OH 44115
Frances I. Hurwitz
Affiliation:
NASA Lewis Research Center, Cleveland, OH 44135
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Abstract

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 substituent apparently activates a double bond to participate in a number of polymerization processes in this system, particularly hydrosilation. Isotopie 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 β-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.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 271: Symposium N – Better Ceramics Through Chemistry V , 1992 , 771
Copyright
Copyright © Materials Research Society 1992

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References

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