Electro-initiated cationic polymerizations—VII: The use of perchlorates and of complex anions containing salts for the electropolymerization of oxyheterocyclic compounds

Electropolymerizations of some oxyheterocyclic monomers have been carried out under amperostatic conditions at Pt electrodes in both 1,2-dichloroethane and acetonitrile solution with various electrolytes. The experiments in 1,2-dichloroethane confirmed results previously obtained for vinylic compounds. The results in acetonitrile in the presence of perchlorates needed an investigation of the electrolysis in the absence of monomer. Both amperostatic and potentiostatic electrolyses showed that the acidity responsible for the polymerization is only one of the various products formed by the reaction between anodically produced chlorine dioxide and the solvent, so that the polymerization cannot be controlled. Cyclic voltammetries carried out on various lactones and on oxirane showed the impossibility of performing direct electropolymerization via anodic monomer oxidation. Hence, some reported electropolymerizations of such monomers under similar conditions must be attributed to the mixture of acids formed by secondary reactions in the anolyte.