Electroiniated cationic polymerization in the presence of addition-fragmentation agents

SummaryElectrochemical initiation of cationic polymerization of heterocyclic and vinyl monomers such as cyclohexene oxide (CHO) and butyl vinylether (BVE), respectively at low potentials in the presence of allylic salts namely, allyl-thiophenium (AT), allyl-triphenyl phosphonium (APP), allyl-isoquinolinium (AIQ), allyl-pyridinium (AP) and allyl-dimethyl anilinium salts, was investigated. The mechanism of this polymerization was studied using cyclic voltammetry and by electropolymerization experiments performed in undivided and H-type cells. A mechanism involving addition-fragmentation decomposition of allylic salts by free radical species formed by electrolysis of trace amounts of water present in the system is postulated.