Electroreductive Synthesis of Silicon Containing Polymers

摘要

The electroreduction of organochlorosilanes was carried out by using magnesium cathode and anode in a single compartment cell affording oligosilanes, polysilanes, and polycarbosilanes. The electroreductive coupling of orgnaochlorosilanes gave the corresponding disilanes in high yield. The cross-coupling of chloroorganosilanes with dichloroorganosilanes under the same reaction conditions produced various types of oilgosilanes such as trisilanes. tetrasilanes, and pentasilanes. This procedures was successfully applied to the stepwise elongation of silicon-silicon chains. The high efficiency of this electroreductive silicon-silicon bond formation reaction enabled the electroreductive synthesis of poly(alkylarylsilane)s having high molecular weight (Mn= 5200-31000, Mw/Mn=1.4-1.8). The electroreductive polymerization of the dichlorosilanes bearing various types of functional groups was also caaried out to afford the functionalized polysilanes. Moreover, the electroreductive polymerization of dichlorooligosilanes was successfully applied to the synthesis of sequence-ordered polysilanes. This electroreductive method was also applicable to the synthesis of poly-p-(disilanylene-phenylenes and silane-germane copolymers. The effects of electrode material, monomer concentration, amount of supplied electricity, and ultrasound were investigated in these reactions.