Electroinitiated cationic polymerization by anodic dissolution

The polymerization of several monomers, such as styrene, α‐methylstyrene, lactones, isobutyl vinyl ether, and hexamethylcyclotrisiloxane, was carried out in H‐shaped cells equipped with sacrificial anodes. The solvents, dichloromethane or nitromethane, contained tetrabutylammonium perchlorate playing the role of supporting electrolyte. Among the different metals tested (Cu, Ag, Hg, Al, Pb, Sn), only mercury and aluminium anodes gave initiation. The conditions of the electrolysis, the nature of the monomers, and the results of special experiments carried out in the presence of a hindered pyridine demonstrate that the polymerization involves the electrophilic addition of the active species to the monomer followed by cationic chain growth.