Novel Copolymers of Trisubstituted Ethylenes and Styrene. 6. Trialkoxy Ring-Substituted Ethyl 2-Cyano-1-oxo-3-phenyl-2-propenylcarbamates

摘要

Electrophilic trisubstituted ethylenes, trialkoxy ring-substituted ethyl 2-cyano-1-oxo-3-phenyl-2-propenylcarbamates, RC6H2CH C(CN)CONHCO2C2H5 (where R is 2,3,4-(CH3O)3, 2,4,5-(CH3O)3, 2,4,6-(CH3O)3, 3,4,5-(CH3O)3, 2,3-(CH3)2 and 4-CH3O), were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and N-cyanoacetylurethane, and characterized by CHN analysis, IR, 1H- and 13C-NMR. All the ethylenes were copolymerized with styrene (M1) in solution with radical initiation (ABCN) at 70C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR, 1H- and 13C-NMR. The order of relative reactivity (1/r1) for the monomers 2,4,5-(CH3O)3 (1.41) > 3,4,5-(CH3O)3(1.39) > 2,3,4-(CH3O)3 (0.9) > 2,4,6-(CH3O)3 (0.47) > 2,3-(CH3)2 and 4-CH3O (0.37).High Tg of the copolymers in comparison with that of polystyrene indicates decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene structural unit. Decomposition of the copolymers in nitrogen occurred in one step in the 270–450C range.