Abstract
Abstract In order to clarify the effect of the substituents in a-substituted acrylonitriles and acrylic esters on their relative reactivities toward a polystyryl radical, the radical copolymerizations of diethyl methylenemalonate, ethyl a-chloroacrylate, ethyl a-bromoacrylate, a-chloroacrylonitrile, methyl a-methoxyacrylate, and a-methoxyacrylonitrile with styrene (M2) were investigated at 60°C. From the copolymerization parameters obtained in this study and those reported in the literature, it was confirmed that the a substituents additively contributed to the values of log Q and e of the monomers. Hence, the reactivities of a-substituted acrylonitriles and acrylic esters relative to unsubstituted acrylonitrile and methyl acrylate toward polystyryl radical, respectively, were expressed by the following equation: log (rel. react.) = δlog QX + 0.83 σp where δ log Qx and σp are the resonance and polar substituent constants of α substituents, respectively. The values of δ log Qx were determined for CH30, CH3...
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