ELECTROCHEMICALLY INITIATED POLYMERIZATION OF STYRENE WITH TETRAALKYL AND TETRAAYRL GROUP VA HALIDE SUPPORT ELECTROLYTES

In the reported experiments, the electrochemically initiated polymerization of styrene in methylene chloride solvent with the use of platinum electrodes and tetraalkyl and -aryl group VA halides (i. e. , quaternary ammonium, phosphonium, and arsonium compounds) as electrolyte has been investigated. The order of reactivity of the electrolytes with respect to polymerization rate and initiation efficiency was found to be: arsonium greater than phosphonium greater than ammonium. Mechanisms involving the electroreduction of the group VA quaternary halides to species capable of electroinitiating polymerization are postulated. The observed losses in solution conductivities during polymerization with the quarternary phosphonium and arsonium electrolytes indicate possible interaction between the initiating radical-ionic species and the supporting electrolyte. In an attempt to further elucidate the mechanism of initiation in these systems, a separate series of experiments, employing the nonpolymerizing monomer, 1,1-diphenylethylene, has been carried out.