| Abstract: | Radical homopolymerization and copolymerizations of ring-methoxy substituted α-cyanostyrenes were studied using benzoyl peroxide and dimethyl 2,2′-azobisisobutylate at 60°C. It was found that the cyanostyrenes containing 2-methoxy cyanostyrene gave homopolymer in moderate yield and they were also copolymerized with vinyl monomers such as styrene and vinyl acetate. The relative reactivity of the cyanostyrenes towards a polystyryl radical (1/r2) in the copolymerization of cyanostyrenes (M1) and styrene (M2) was correlated with the Hammett and Taft substituent constants of the methoxy groups and the 13C NMR chemical shift of the β-carbon of the cyanostyrenes. The enhancement of the radical polymerization reactivity by introducing a nitrile group in the captodative α-position of styrene was considered to be due to the suppression of the termination reaction and the activation of the propagation reaction. In addition, thermal properties such as glass transition and degradation temperatures of the cyanostyrene polymers obtained were also examined. |
