Copolymerization of polar vinyl monomers with butadiene in the presence of Lewis acids

Abstract

The copolymerization of acrylonitrile (AN), methacrylonitrile (MAN), methyl acrylate (MA), and methyl methacrylate (MMA) with butadiene (BD) in the presence of ethylaluminium dichloride, zinc chloride, and stannic chloride was investigated. The reactivity of polar monomers in the copolymerization was found to decrease in the following order: AN>MAN>MMA>MA. It was also found that AN and MAN form with BD copolymers of essentially 1 : 1 composition; MMA, and particularly MA were found, however, to form with BD copolymers of a composition different from 1 : I.In competition with the copolymerization, a Diels-Alder reaction was shown to occur in the investigated systems. The reactivity of polar monomers in the Diels-Alder reaction was found to increase in the following order: MAN < AN < MMA < MA. In the presence