ELECTROREDUCTIVE POLYMERIZATION OF MIXTURES OF CHLOROMONOSILANES

For improving the yield of oxygen-free polysilanes in the electroreductive polymerization of organodichloromonosilanes, particularly dimethyldichlorosilane which gives poly(dimethylsilane) preferable as a precursor of silicon carbide ceramics, the polymerization of mixtures of chloromonosilanes were examined. Oxygen-free polysilanes could be obtained in a high yield of 78%, when a 1:1 mixture of Me2SiCl2 and Ph3SiCl was electrolysed at 4.5 mA cm-2 current density at a Pt cathode in 0.4 M Bu4NBF4/DME at room temperature. This result seems to be much better than that achieved previously (26% yield) in the polymerization of pure Me2SiCl2.