Electroinitiated cationic polymerization in the presence of diaryliodonium salts

Rapid and efficient electrochemical initiation of cationic polymerization takes place at low potentials in the presence of diaryliodonium salts bearing non-nucleophilic anions. The mechanism of this polymerization was investigated using cyclic voltammetry and by the analysis of the products of electrolysis. A mechanism involving reduction of the diaryliodonium salts by free radical species formed by electrolysis of trace amounts of water present in the reaction mixture is postulated. The electroinitiated cationic polymerization of typical vinyl and heterocyclic monomers was investigated.