Factors influencing the electroreductive polymerization of di‐n‐hexyldichlorosilane

This paper reports the study of the effects of solvent, support electrolyte and the nature of the electrodes on the electroreduction of di‐n‐hexyldichlorosilane. The work performed involved the use of different types of sacrificial anode (magnesium, aluminium and zinc) and cathode (magnesium, aluminium, zinc, stainless steel, nickel, carbon and palladium) in tetrahydrofuran containing lithium perchlorate (LiClO₄). Monomodal poly(di‐n‐hexyldichlorosilane) was obtained with Al/Al and Mg/Mg electrode pairs, but the polymer yield was about ten times higher with Al/Al (11%) than with Mg/Mg (1%). From the solvents and co‐solvents used (tetrahydrofuran, hexamethylphosphorotriamide, acetone, hexane, toluene, 1,1,3,3‐tetramethylurea, tris(3,6‐dioxaheptyl)amine, 1,2‐dimethoxyethane, N,N‐dimethylacetamide and dimethylformamide) with LiClO₄, only the system tetrahydrofuran + hexamethylphosphorotriamide, tetrahydrofuran + N,N‐dimethylacetamide and tetrahydrofuran + toluene have given monomodal poly(di‐n‐hexyldichlorosilane) using an aluminium anode and stainless‐steel cathode. Copyright © 2001 John Wiley & Sons, Ltd.