Abstract
Abstract Radical copolymerizations of N-(4-substituted phenyl)-α-chloromaleimide (RPhClMI: 1, R = H; 2, R = Cl; 3, R = OCH3; 4, R = CH3; 5, R = COOC2H5) (M1) with styrene (ST) (M2) or methyl methacrylate (MMA) (M2) in tetra-hydrofuran at 60°C were performed with azobisisobutyronitrile as initiator. This report explores the polymerization behavior of RPhClMI and the substituent effects in copolymerizations. The following reactivity ratios were determined: r 1 = 0.008–0.02, r 2 = 0.056–0.11 in the RPhClMI-ST system and r 1 = 0.021-0.11, r 2 = 0.55–0.63 in the RPhClMI-MMA system. It was found that the relative reactivities (1/r 2) of RPhClMI toward a polystyryl radical was not correlated to the resonance-substituent constant (ER ), but it was correlated to the polar-substituent constant ([sgrave]) in the modified Hammett equation (log (1/r 2) = ρσ + γER ). The M n in the RPhClMI-ST copolymer was 6 000 to 49 000; that of the RPhClMI-MMA copolymer was 2 100 to 9700.
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