Electrophilic trisubstituted ethylenes, ring-trisubstituted methyl 2-cyano-3-phenyl-2-propenoates, RPhCH = C(CN)CO₂CH₃ (where R is 2,4,6-trimethyl, 3,5-dimethoxy-4-hydroxy, 3,5-dimethyl-4-hydoxy, 3,4,5-trimethoxy, 2-bromo-3-hydroxy-4-methoxy, 5-bromo-2,3-dimethoxy, 5-bromo-2,4-dimethoxy, 6-bromo-3,4-dimethoxy were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-trisubstituted benzaldehydes and methyl 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. The order of relative reactivity (1/r₁) for the monomers is 5-bromo-2,3-dimethoxy (2.69) > 3,4,5-trimethoxy (1.86) > 6-bromo-3,4-dimethoxy (0.84) > 5-bromo-2,4-dimethoxy (0.39) > 4-hydoxy-3,5-dimethyl (0.31) = 2-bromo-3-hydroxy-4-methoxy (0.31) > 3,5-dimethoxy-4-hydroxy (0.24) > 2,4,6-trimethyl (0.22). Relatively high T_g of the copolymers in comparison with that of polystyrene indicates a 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 200–500ºC range with residue (1–6% wt), which then decomposed in the 500–800ºC range.

Electrophilic trisubstituted ethylenes (TSE), halogen ring‐substituted ethyl 2‐cyano‐1‐oxo‐3‐phenyl‐2‐propenylcarbamates, RC6H4CH˭C(CN)CONHCO2C2H5 (where R is 3‐Br, 4‐Br, 3‐Cl, 4‐Cl, 2‐F, 3‐F, and 4‐F) were prepared and copolymerized with styrene (ST). 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 ST (M1) in solution with radical initiation (AIBN) 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 2‐F (3.81) > 3‐Cl (1.36) > 4‐Br (1.31) > 3‐Br (1.13) > 4‐F (0.90) > 3‐F (0.63) > 4‐Cl (0.37). Higher 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 TSE str...

Electrophilic trisubstituted ethylenes, ring-substituted ethyl 2-cyano-1-oxo-3-phenyl-2-propenylcarbamates, RC₆H₄CH˭C(CN)CONHCO₂‒C₂H₅ (where R is H, 2‒CH₃, 3‒CH₃, 4‒CH₃, 2‒OCH₃, 3‒OCH₃, 4‒OCH₃,4‒OC₂H₅) 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 (AIBN) 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 2‒CH₃ (1.52) > H (1.20) = 3‒CH₃ (1.20) > 2‒OCH₃ (1.16) > 3‒OCH₃ (0.88) > 4‒CH₃ (0.48) = 4‒OC₂H₅ (0.48) > 4‒OCH₃ (0.29). Higher 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 TSE structural unit. Gravimetric analysis indicated that the copolymers decompose in the range 200–355°C.

Electrophilic trisubstituted ethylene monomers, ring-substituted N-(aminocarbonyl)-2-cyano-3-phenyl-2-propenamides, RC₆H₄CH C(CN)CONHCONH₂ (where R = H, 2-CH₃, 3-CH₃, 4-CH₃, 2-OCH₃, 3-OCH₃, 4-OCH₃, 4-Br, 2-Cl, 3-Cl and 4-Cl), were synthesized by the piperidine-catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and cyanoacetylurea, and characterized by CHN elemental analysis, IR, and ¹H- and ¹³C-NMR. All the propenamides were copolymerized with styrene (M₁) in solution with radical initiation (AIBN) at 70 °C. The compositions of the copolymers were calculated from nitrogen analysis and the structures were analyzed by IR and ¹H- and ¹³C-NMR. The order of relative reactivity (1/r ₁) for the monomers is 4-Br (0.27) > H (0.20) > 2-Cl (0.16) > 3-Cl (0.12) > 3-OCH₃ (0.11) > 3-CH₃ (0.10) > 4-Cl (0.08) > 2-CH₃ (0.06) > 4-OCH₃ (0.05) > 4-CH₃ (0.04) > 2-OCH₃ (0.04). The elevated glass transition temperatures of the copolymers in comparison with that of polystyrene indicate a decrease in the chain mobility of the copolymers due to the high dipolar character of the trisubstituted ethylene monomer unit. The gravimetric analysis indicated that the copolymers decompose in the 200–400 °C range.

Novel electrophilic trisubstituted ethylenes, methyl and methoxy ring-trisubstituted butyl 2-cyano-3-phenyl-2-propenoates, RPhCH=C(CN)CO₂C₄H₉ where R is 2,4,5-trimethyl, 2,4,6-trimethyl, 2,3-dimethyl-4-methoxy, 2,5-dimethyl-4-methoxy, 2,4-dimethoxy-3-methyl, 2,3,4-trimethoxy, 2,4,5-trimethoxy, 2,4,6-trimethoxy, 3,4,5-trimethoxy were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-trisubstituted 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 (2–5% wt), which then decomposed in the 500–800°C range.

Copolymerization of 2-phenyl-1,1-dicyanoethylene (PDE) with 4-fluorostyrene and pentafluorostyrene in solution with radical initiation (ABCN) at 70°C yielded random copolymers with PDE alternating units. The composition of the copolymers was calculated from nitrogen analysis and the structure was analyzed by IR, ¹H and ¹³C-NMR. The order of relative reactivity (1/r₁) and the tendency toward alternation of monomer units in the copolymer for these two monomers, is 4-fluorostyrene (1.96) > pentafluorostyrene (0.51). Higher glass transition temperature of the copolymers in comparison with that of homopolymers indicates a decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit.