Novel Copolymers of Styrene. 7. Chlorine Ring-Substituted 2-Cyano-3-phenyl-2-propenamides

Novel trisubstituted ethylenes, chlorine ring-substituted 2-cyano-3-phenyl-2-propenamides, RC₆H₃CH?C(CN)CONH₂ (where R is 2,3-dichloro, 2,4-dichloro, 2,6-dichloro, 3,4-dichloro, 2-chloro-5-nitro, 4-chloro-3-nitro, 5-chloro-2-nitro) 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 in the presence of a radical initiation (AIBN) 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. Thus, the order of relative reactivity (1/r1) and the tendency toward alternation of monomer units in the copolymer for the monomers is 2-Cl-5-NO₂ (3.09) > 5-Cl-2-NO₂ (1.88) > 4-Cl-3-NO₂ (0.97) > 2,6-Cl₂ (0.93) > 3,4-Cl₂ (0.31) > 2,4-Cl₂ (0.30) > 2,3-Cl₂ (0.22). 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 (3.5–5.0 wt%), which then decomposed in the 500–800°C range.     

Novel Copolymers of Styrene. 8. Ring-Trisubstituted 2-Cyano-3-phenyl-2-propenamides

Novel trisubstituted ethylenes, ring-trisubstituted 2-cyano-3-phenyl-2-propenamides, RC₆H₂CH?C(CN)CONH₂ (where R is 2,4,6-trimethyl, 2,3-dimethyl-4-methoxy, 2,3,4-trimethoxy, 2,4,5-trimethoxy, 2,4,6-trimethoxy, and 3,4,5-trimethoxy) were synthesized by potassium hydroxide catalyzed Knoevenagel condensation of ring-trisubstituted 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 in the presence of a radical initiation (AIBN) 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. Thus, the order of relative reactivity (1/r1) and the tendency toward alternation of monomer units in the copolymer for the monomers is 2,4,6-(CH₃)₃ (0.71) > 2,3-(CH₃)₂-4-CH₃O (0.52) > 2,3,4-(CH₃O)₃ (0.34) > 2,4,5-(CH₃O)₃ (0.30) > 3,4,5-(CH₃O)₃ (0.15) > 2,4,6-(CH₃O)₃ (0.12). 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 (2.9–9.9 wt%), which then decomposed in the 500–800°C range.     

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

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.     

Novel Copolymers of Trisubstituted Ethylenes and Styrene. 7. Dihalogen Ring-Substituted Ethyl 2-Cyano-1-oxo-3-phenyl-2-propenylcarbamates

Electrophilic trisubstituted ethylenes, dihalogen ring-substituted ethyl 2-cyano-1-oxo-3-phenyl-2-propenylcarbamates, RC₆H₃ CH = C(CN)CONHCO₂C₂H₅(where R is 2,3-diCl, 2,4-diCl, 2,6-diCl, 3,4-diCl, 3,5-diCl, and 2-Cl-6-F, 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 2,4-diCl (4.4) > 2,6-diCl (3.6) > 2,3-diCl (3.4) = 3,4-diCl (3.4) > 2-Cl-6-F (2.7) > 3,5-diCl (2.0). 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 270–420°C with residue (5–13% wt), which then decomposed in the 420–650°C range.     

Novel Copolymers of Trisubstituted Ethylenes and Styrene. 9. Some Ring-Substituted Ethyl 2-Cyano-1-oxo-3-phenyl-2-propenylcarbamates

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.     

Novel Copolymers of Styrene. 4. Halophenoxy Ring-Substituted 2-Cyano-3-phenyl-2-propenamides

Novel electrophilic trisubstituted ethylenes, halophenoxy ring substituted 2-cyano-3-phenyl-2-propenamides, RC₆H₄CH?C(CN)CONH₂,where R is 4-(4-bromophenoxy), 2-(4-chlorophenoxy), 3-(4-chlorophenoxy), 4-(3-chlorophenoxy), 4-(4-chlorophenoxy), and 4-(4-fluorophenoxy) 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 in the presence of a radical initiator, 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, GPC, DSC, and TGA. Thus, the order of relative reactivity (1/r₁) is 4-(4-ClC₆H₄O) (2.01) > 4-(4-FC₆H₄O) (0.89) > 4-(4-BrC₆H₄O) (0.73) > 3-(4-ClC₆H₄O) (0.65) > 2-(4-ClC₆H₄O) (0.24) > 4-(3-ClC₆H₄O) (0.22). 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 (10.4–15.0 wt%), which then decomposed in the 500-800°C range.     

Novel Copolymers of Styrene. 10. Halo Ring-Substituted 2-Cyano-3-phenyl-2-propenamides

Novel electrophilic trisubstituted ethylene monomers, halo ring-substituted 2-cyano-3-phenyl-2-propenamides, RPhCH ? C(CN)CONH₂, where R is 2-bromo, 3-bromo, 2-fluoro, 3-fluoro, 2-iodo, 3-iodo, and 4-iodo 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 (7-19 wt%), which then decomposed in the 500–800°C range.     

Novel Copolymers of Styrene. 8. Some Ring-Disubstituted Ethyl 2-Cyano-3-Phenyl-2-Propenoates

Electrophilic trisubstituted ethylenes, ring-disubstituted ethyl 2-cyano-3-phenyl-2-propenoates, RPhCH?C(CN)CO₂C₂H₅ (where R is 3-Br-4-CH₃O, 5-Br-2-CH₃O, 3-F-2- CH₃, 3-F-4-CH₃, 4-F-2-CH₃, 4-F-3-CH₃, 5-F-2-CH₃, 2-Cl-5-NO₂, 2-Cl-6-NO₂, 4-Cl-3- NO₂) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-disubstituted benzaldehydes and ethyl 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 composition of the copolymers was 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 (1.02) > 4-Cl-3-NO₂ (0.93) > 3-F-4-CH₃ (0.81) > 2-Cl-6-NO₂ (0.77) > 2-Cl-5-NO₂ (0.71) > 3-Br-4-CH₃O (0.66) > 4-F-3-CH₃ (0.60) > 3-F-2-CH₃ (0.38) > 4-F-2-CH₃ (0.31) > 5-F-2-CH₃ (0.16). 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 250–500°C range with residue (2–26% wt.), which then decomposed in the 500–800°C range.     

Novel Copolymers of Trisubstituted Ethylenes and Styrene. 8. Fluoro Ring-Substituted Ethyl 2-Cyano-1-oxo-3-phenyl-2-propenylcarbamates

Electrophilic trisubstituted ethylenes, fluoro ring-substituted ethyl 2-cyano-1-oxo-3-phenyl-2-propenylcarbamates, RC₆H₃CH = C(CN)CONHCO₂C₂H₅(where R is 4-F-3-CH₃, 2-CF₃, 4-CF₃, 2,4-diF, 2,5-diF, 2,6-diF, 3,4-diF, and 3,5-diF), 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 4-CF₃ (5.4) > 2,6-diF (2.0) > 2,4-diF (1.7) > 2,5-diF (1.0) > 2-CF₃ (0.8) > 3,4-diF (0.5) > 3,5-diF (0.4) > 4-F-3-CH₃ (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 270–420°C with residue (5–13% wt), which then decomposed in the 420–650°C range.     

Novel Copolymers of Styrene. 3. Some Ring-Substituted Butyl 2-Cyano-3-Phenyl-2-Propenoates

Novel trisubstituted ethylenes, ring-substituted butyl 2-cyano-3-phenyl-2-propenoates, RPhCH=C(CN)CO₂C₄H₉ (where R is 2-C₆H₅CH₂O, 3-C₆H₅CH₂O, 4-C₆H₅CH₂O, 4-CH₃COO, 3-CH₃CO, 4-CH₃CO, 4-CH₃CONH, 2-CN, 3-CN, 4-CN, 4-(CH₃)₂N, 4-(C₂H₅)₂N) 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. The order of relative reactivity (1/r₁) for the monomers is 4-C₆H₅CH₂O (6.39) > 2-C₆H₅CH₂O (2.06) > 3-CH₃CO (1.86) > 3-C₆H₅CH₂O (1.78) > 4-CH₃COO (1.58) > 3-CN (1.47) > 4-CN (1.21) > 4-(C₂H₅)₂N (1.19) > 4-(CH₃)₂N (1.18) > 2-CN (1.04) > 4-CH₃CO (0.71) > 4-CH₃CONH (0.63). Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (3.6–9.5% wt), which then decomposed in the 500–800°C range.     

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

Novel electrophilic trisubstituted ethylene monomers, oxy ring substituted 2-cyano-3-phenyl-2-propenamides, RC₆H₄CH? C(CN)CONH₂ (where R is 2-CH₃O, 3-CH₃O, 4-CH₃O, 2-C₂H₅O, 3-C₂H₅O, 4-C₂H₅O, 4-C₃H₇O, 4-C₄H₉O, 4-C₆H₁₃O, 3-C₆H₅O, 4-C₆H₅O, 3-C₆H₅CH₂O, 4-C₆H₅CH₂O), 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, AIBN 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 (0.2–1.2 wt%), which then decomposed in the 500–800°C range.     

Novel Copolymers of Styrene. 17. Ring-Trisubstituted Methyl 2-Cyano-3-Phenyl-2-Propenoates

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.     

Novel Copolymers of Styrene. 3. Oxy Ring-disubstituted 2-cyano-3-phenyl-2-propenamides

Novel electrophilic trisubstituted ethylene monomers, oxy ring-disubstituted 2-cyano-3-phenyl-2-propenamides, RC₆H₃CH? C(CN)CONH₂ (where R is 2,3-(CH₃O)₂, 2,4-(CH₃O)₂, 2,5-(CH₃O)₂, 2,6-(CH₃O)₂, 3,4-(CH₃O)₂, 3,5-(CH₃O)₂, 3-CH_3?4-CH₃O, 3-C₂H₅O-4-CH₃O, 3,4-(C₆H₅CH₂O)₂, 2-C₆H₅CH₂O-3-CH₃O, 3-C₆H₅CH₂O-4-CH₃O, 4-C₆H₅CH₂O-3-CH₃O) were synthesized by potassium hydroxide catalyzed Knoevenagel condensation of ring-disubstituted benzaldehydes and cyanoacetamide, and characterized by CHN 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, AIBN at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H- and ¹³C-NMR. 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 300–500°C range with residue (2–9% wt), which then decomposed in the 500–800°C range.     

Novel Copolymers of Styrene. 2. Oxy Ring-Substituted Butyl 2-Cyano-3-Phenyl-2-Propenoates

Novel trisubstituted ethylenes, oxy ring-substituted butyl 2-cyano-3-phenyl-2-propenoates, RPhCH=C(CN)CO₂C₄H₉ (where R is 2-methoxy, 3-methoxy, 4-methoxy, 2-ethoxy, 3-ethoxy, 4-ethoxy, 4-propoxy, 4-butoxy, 4-hexyloxy, 3-phenoxy) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of oxy ring-substituted benzaldehydes and butyl cyanoacetate and characterized by CHN elemental analysis, IR, ¹H- and ¹³C-NMR. All the ethylenes were copolymerized with styrene (M₁) in solution with radical initiation (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. The order of relative reactivity (1/r₁) for the monomers is 4-methoxy (6.56) > 3-methoxy (2.97) > 2-methoxy (2.72) > 4-butoxy (2.20) > 3-ethoxy (2.18) > 4-propoxy (2.15) > 4-hexyloxy (1.78) > 4-ethoxy (1.66) > 2-ethoxy (1.48) > 3-phenoxy (1.29). Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200-500°C range with residue (0.8–3.6% wt.), which then decomposed in the 500–800°C range.     

Novel Copolymers of Styrene and Some Ring-substituted 2-Phenyl-1,1-dicyanoethylenes

Novel copolymers of trisubstituted ethylene monomers, ring-substituted 2-phenyl-1,1-dicyanoethylenes, RC₆H₄CH = C(CN)2 (where R is 2-F, 2-CN, 3-CN, 4-CN, 3-C₆H₅O, 4-C₆H₅O, 2-C₆H₅CH₂O, 3-C₆H₅CH₂O, 4-C₆H₅CH₂O, 4-CH₃CO₂, 4-CH₃CONH, 4-(CH₃)₂N) and styrene were prepared 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. The order of relative reactivity (1/r ₁) for the monomers is 4-(CH₃)₂N (3.35) > 4-C₆H₅CH₂O (3.1) > 2-C₆H₅CH₂O (1.77) > 3-C₆H₅CH₂O (1.72) > 4-C₆H₅O (1.70) > 4-CH₃CO₂ (1.58) > 2-F (1.11) > 3-C₆H₅O (0.90) > 3-CN (0.88) > 2-CN (0.86) > 4-CH₃CONH (0.84) > 4-CN (0.76). 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 200–500°C range with residue (1–10% wt), which then decomposed in the 500–800°C range.     

Novel Copolymers of Styrene. 6. Some Oxy Ring-Disubstituted Butyl 2-Cyano-3-Phenyl-2-Propenoates

Novel trisubstituted ethylenes, oxy ring-disubstituted butyl 2-cyano-3-phenyl-2-propenoates, RPhCH=C(CN)CO₂C₄H₉ (where R is 4-methoxy-2-methyl, 4-methoxy-3-methyl, 3-ethoxy-4-methoxy, 4-ethoxy-3-methoxy, 3,4-dibenzyloxy, 2-benzyloxy-3-methoxy, and 3-benzyloxy-4-methoxy) 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 (2-17 % wt.), which then decomposed in the 500-800°C range.     

Novel Copolymers of Styrene and Some Halogen Ring-substituted 2-Phenyl-1,1-dicyanoethylenes

Novel copolymers of trisubstituted ethylene monomers, ring-substituted 2-phenyl-1,1-dicyanoethylenes, RC₆H₃CH═C(CN)₂ (where R is 2-bromo,3-bromo, 3-chloro, 2,3-dichloro, 2-chloro-6-fluoro, 2,6-difluoro, 3,4-difluoro, and 3,5-difluoro) and styrene were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator (AIBN) 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. The gravimetric analysis indicated that the copolymers decompose in the 200–800°C range.     

Novel Copolymers of Styrene. 12. Halogen Ring-Substituted Methyl 2-Cyano-3-Phenyl-2-Propenoates

Electrophilic trisubstituted ethylenes, halogen ring-substituted methyl 2-cyano-3-phenyl-2-propenoates, RPhCH=C(CN)CO₂CH₃ (where R is 3-Br-4-CH₃O, 5-Br-2-CH₃O, 2-F-5-CH₃, 2-F-6-CH₃, 4-F-3-CH₃, 4-F-3-PhO, 2-F-5-I, 2-F-6-I, 2-F₃C, 4-F₃C) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted 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/r ₁) for the monomers is 2-F-5-CH₃ (6.4) > 4-F-3-PhO (5.6) > 4-F₃C (4.8) > 3-Br-4-CH₃O (3.7) > 2-F-5-I (3.6) > 2-F₃C (2.2) > 2-F-6-I (2.1) > 5-Br-2-CH₃O (1.9) > 4-F-3-CH₃ (1.8) > 2-F-6-CH₃ (1.2). 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 200-500°C range with residue (2–21% wt), which then decomposed in the 500–800°C range.     

Novel Copolymers of Styrene. 15. Phenoxy Ring-Substituted Methyl 2-Cyano-3-Phenyl-2-Propenoates

Electrophilic trisubstituted ethylenes, phenoxy ring-substituted methyl 2-cyano-3-phenyl-2-propenoates, RPhCH=C(CN)CO₂CH₃, where R is 4-(4-BrC₆H₅O), 2-(4-ClC₆H₅O), 3-(4-ClC₆H₅O), 4-(3-ClC₆H₅O), 4-(4-ClC₆H₅O), 4-(4-FC₆H₅O), 2-(3-CH₃OC₆H₅O), 2-(4-CH₃OC₆H₅O), 3-(4-CH₃OC₆H₅O), 4-(4-CH₃OC₆H₅O), 3-(4-CH₃C₆H₅O) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of phenoxy ring-substituted 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 4-(4-CH₃OC₆H₅O) (6.07) > 3-(4-ClC₆H₅O) (3.38) > 3-(4-CH₃OC₆H₅O) (2.78) > 4-(3-ClC₆H₅O) (2.77) > 2-(4-ClC₆H₅O) (2.29) > 3-(4-CH₃C₆H₅O) (1.98) > 4-(4-FC₆H₅O) (1.92) > 4-(4-ClC₆H₅O) (1.89) > 2-(3-CH₃OC₆H₅O) (1.39) > 2-(4-CH₃OC₆H₅O) (0.90) > 4-(4-BrC₆H₅O) (0.77). 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 200-500°C range with residue (2.5-8.0% wt), which then decomposed in the 500-800°C range.     

Novel Copolymers of Styrene. 16. Halogen Ring-Disubstituted Methyl 2-Cyano-3-Phenyl-2-Propenoates

Electrophilic trisubstituted ethylenes, ring-disubstituted methyl 2-cyano-3-phenyl-2-propenoates, RPhCH?C(CN)CO₂CH₃, where R is 2,5-dichloro, 3,5-dichloro, 2,3-difluoro, 3-chloro-2-fluoro, 3-chloro-4-fluoro, 4-chloro-3-fluoro, 2-chloro-5-nitro, and 2-chloro-6-nitro were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-disubstituted 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 4-Cl-3-F (4.87) > 2,3-F₂ (4.49) > 3-Cl-4-F (3.50) > 3-Cl-2-F (2.96) > 2-Cl-5-NO₂ (2.02) > 2,5-Cl₂ (1.54) > 2-Cl-6-NO₂ (1.00) > 3,5-Cl₂ (0.41). 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 (1.5–34.5% wt), which then decomposed in the 500-800ºC range.