Copolymers of Cyano Compounds with Captodative Monomers. Studies of Their Microstructures

Copolymers of vinylidene cyanide, methacrylonitrile, and acrylonitrile with various captodative monomers such as cyanovinyl acetate, methyl α-acetoxyacrylate or methyl 1-(methoxy carbonyl) vinyl carbonate were synthesized by radical copolymerization. The microstructures of these copolymers were studied by means of 13C NMR. The copolymers of vinylidene cyanide are rich in alternating structure, and the copolymers of methacrylonitrile and acrylonitrile are rather statistical than alternating. The measurements of reactivity ratios for three copolymerization reactions, vinylidene cyanide, methacrylonitrile, and acrylonitrile with methyl α-acetoxyacrylate, confirm these conclusions.