Novel copolymers of styrene. 11. Fluoro ring-substituted butyl 2-cyano-3-phenyl-2-propenoates

Novel trisubstituted ethylenes, fluorine ring-substituted butyl 2-cyano-3-phenyl-2-propenoates, RPhCHC?(CN)CO₂C₄H₉ (where R is 2,3-diF, 2,4-diF, 2,5-diF, 2,6-diF, 3,4-diF, 3,5-diF, and 2,4,5-triF) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and butyl cyanoacetate, 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. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200-500°C range with residue (1.5–2.3% wt.), which then decomposed in the 500–800°C range.