Polymerization of vinyl monomers by $KO_2$-charge transfer agent

Abstract

Polymerization of vinyl monomers such as nitroethylene acrolein, acrylonitrile, methyl methacrylate, and styrene by $KO_2$-charge transfer agent systems was carried out in anhydrous dimethylsulfoxide (DMSO) under nitrogen atmosphere. Anion radicals generated by one-electron transfer from $KO_2$ to charge transfer agents such as naphthalene, anthracene, benzoquinone, benzophenone, azobenzene, azoxybenzene, were effective in the polymerization of electron acceptor monomers like nitroethylene, acrolein, acrylonitrile. In these polymerizations, both conversion and molecular weight were high and the rate of polymerization was rapid. The polydispersity of the polymers obtained by $KO_2$-charge transfer agent systems were found to be narrow by means of gel permeation chromatography. Based on the observations, it is proposed that polymerization proceeds via an anionic mechanism through one electron transfer from anion radicals to an electron acceptor monomer. The study on the block copolymerization of nitroethylene with acrylonitrile or acrolein was also attempted.