Reaction of electrochemically produced radical cations with organic monomers

The reactivity of free radical cations, produced by anodic oxidation of 9, 10-diphenylanthracene (and perylene), with polymerizable organic monomers has been investigated by amperometry.It results that the radical cations, which are relatively stable in acetonitrile and nitrobenzene, decay with the monomer substrate by either an addition reaction or an electron transfer process. The cationic species of the monomer thus produced by catalyze the cationic polymerization of the substrate.The cationic polymerization initiated in this way has been investigated in the case of styrene: this reaction shows some similarity with the process initiated by perchloric acid, but carbonium ion carriers seem to give the main contribution to the propagation stage.