Novel Copolymers of Styrene. 11. Ring-Substituted 2-Cyano-3-phenyl-2-propenamides

Abstract

Novel electrophilic trisubstituted ethylene monomers, halo ring-disubstituted 2-cyano-3-phenyl-2-propenamides, RPhCH = C(CN)CONH₂, where R is 2,3-difluoro, 2,4-difluoro, 2,5-difluoro, 2,6-difluoro, 3,4-difluoro, 3,5-difluoro, 2-chloro-4-fluoro, 3-chloro-2-fluoro, 3-chloro-4-fluoro were prepared and copolymerized with styrene. The monomers were synthesized by potassium hydroxide catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and cyanoacetamide, and characterized by CHN elemental analysis, IR, ¹H- and ¹³C-NMR. Novel copolymers of the ethylenes and styrene were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator, ABCN at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H- and ¹³C-NMR, GPC, DSC, and TGA. High T_g of the copolymers in comparison with that of polystyrene indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (10–14 wt%), which then decomposed in the 500–800°C range.

Keywords:

• Trisubstituted ethylenes
• radical copolymerization
• styrene copolymers

Funding

The authors 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 Research Services of DePaul University.