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Platinum Metals Rev., 2000, 44, (4), 172

Silphenylenesiloxane Polymers

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Polysiloxanes are polymers with an alternating chain of silicon and oxygen atoms. Polysiloxanes have a range of very valuable properties which are utilised commercially: inertness, resistances to water and oxidation, and high thermal stabilities. However, little work has been done to develop dehydrocoupling polymerisation to give polysiloxanes. A team of scientists at the University of Cincinnati have now developed a general method of dehydrocoupling polymerisation to give alternating copolymers of silphenylenesiloxanes from bis-silanes and disilanols, under mild conditions, using Wilkinsonā€™s catalyst, RhCl(Ph3P)3, (R. Zhang, J. E. Mark and A. R. Pinhas, Macmmolecules, 2000, 33, (10), 3508ā€“3510).

Silphenylenesilane polymers with controllable microstructures and average molecular weight of 10,100 g molāˆ’1 were produced. The best polymerisation occurred between p -bis(dimethylsiryl)benzene and p -bis(dimethylhydroxysilyl)benzene. Among other alternating copolymers produced were poly-(tetramethyl-p -silphenylenesiloxane) (poly-TMPS) and a combination of tetramethyl-m -silphenylenesiloxane and TMPS. The rhodium catalyst was very efficient and robust under the reaction conditions.

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