Abstract
Electrophilic trisubstituted ethylenes, ring-substituted ethyl 2-cyano-1-oxo-3-phenyl-2-propenylcarbamates, RC6H3CH = C(CN)CONHCO2C2H5(where R is 2-CN, 3-CN, 4-CN, 3-Br- 4-CH3O, 5-Br-2-CH3O, 5-Br-2,3-(CH3O)2, 5-Br-2,4-(CH3O)2), 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 70°C. 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/r 1) for the monomers is 5-Br-2-CH3O (3.4) > 5-Br-2,3-(CH3O)2 (1.7) > 3-Br- 4-CH3O (1.4) > 5-Br-2,4-(CH3O)2 (0.7) > 4-CN (0.4) > 3-CN (0.4) > 2-CN (0.3). High T g 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 two steps, first in 250–420°C with residue (5–15% wt), which then decomposed in the 420–650°C range.
Acknowledgments
We thank the National Science Foundation Polymer Program (DMR-0710520) for support. We are grateful to acknowledge that the project is partly supported by the Coatings Industry Education Foundation (CIEF), Chicago Society of Coatings Technology and Office of Sponsored Programs and Research of DePaul University. B.L. Hill was partly supported by a CIEF graduate fellowship.
Notes
a Polymerization time was 5 h.
b T g transition was observed by DSC.