Synthesis and characterization of poly(N-tert-alkylmaleimide)s

N-tert-Butylmaleimide (tBMI) polymerized readily in the presence of a radical initiator in spite of its bulky N-substituent to give a high molecular weight and less-flexible poly(substituted methylene). From kinetic investigation for the polymerization of tBMI with 2,2-azobisisobutyronitrile (AIBN) in benzene, it was revealed that the rate of polymerization (R _p) was expressed as R _p=k AIBN]^0.51tBMI]^1.4, and the overall activation energy was 99.6 kJ/mol. The high polymerization of tBMI was assumed to result from the decrease in the rate of bimolecular termination between rigid polymer radicals bearing a bulky substituent. The flexibility of the polymer chain was examined by the viscometric and light scattering methods, and the effect on the polymerization reactivity was discussed.