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 4-Fluorostyrene. 7. Halogen Ring-Disubstituted 2-Phenyl-1,1-dicyanoethylenes

Novel copolymers of trisubstituted ethylene monomers, halogen ring-disubstituted 2-phenyl-1,1-dicyanoethylenes, RC₆H₃CH= C(CN)₂ (where R is 2,3-Cl₂, 2,4-Cl₂, 2,6-Cl₂, 3,4-Cl₂, 3,5-Cl₂, 2-Cl-4-F, 2-Cl-6-F, 3-Cl-4-F) and 4-fluorostyrene 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. The order of relative reactivity (1/r ₁) for the monomers is 2-Cl-4-F (2.42) > 3,4-Cl₂(2.40) > 2,4-Cl₂(1.97) > 2-Cl-6-F (1.86) > 3-Cl-4-F (1.68) > 2,3-Cl₂ (0.89) > 3,5-Cl₂ (0.70) > 2,6-Cl₂ (0.47). High T_g of the copolymers, in comparison with that of poly(4-fluorostyrene) indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. Softening of the copolymers started in 194–216°C range. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 290–400°C range with residue, which then decomposed in 400–800°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 styrene. 12. Halogen ring-disubstituted butyl 2-cyano-3-phenyl-2-propenoates

Electrophilic trisubstituted ethylenes, halogen ring-disubstituted butyl 2-cyano-3-phenyl-2-propenoates, RPhCH?C(CN)CO₂C₄H₉ where R is 2-chloro-4-fluoro, 2-chloro-6-fluoro, 3-chloro-2-fluoro, 3-chloro-4-fluoro, 4-chloro-3-fluoro, 2-fluoro-5-iodo, 3-(3,4-dichlorophenoxy), 4-(2,4-dichlorophenoxy) 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 (1.7–6.8% wt), which then decomposed in the 500–800°C range.     

Novel Copolymers of Styrene. 18. Halogen Ring-Trisubstituted Methyl 2-Cyano-3-Phenyl-2-Propenoates

Novel trisubstituted ethylene monomers, halogen ring-trisubstituted methyl 2-cyano-3-phenyl-2-propenoates, RPhCH=C(CN)CO₂CH₃, where R is 4-bromo-2,6-difluoro, 3-chloro-2,6-difluoro, 4-chloro-2,6-difluoro, 2,3,5-trichloro, 2,3,6-trichloro, and 2,4,5-trifluoro, were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of halogen 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 3-Cl-2,6-F₂ (4.2) > 4-Cl-2,6-F₂ (3.9) > 4-Br-2,6-F₂ (1.8) > 2,3,5-Cl₃ (1.1) > 2,4,5-F₃ (0.9) > 2,3,6-Cl₃ (0.5). 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 (3.1–3.9% wt), which then decomposed in the 500–800°C range.     

Novel copolymers of styrene. 10. Bromo and chloro ring-disubstituted propyl 2-cyano-3-phenyl-2-propenoates

Novel trisubstituted ethylenes, ring-disubstituted propyl 2-cyano-3-phenyl-2-propenoates, RPhCH = C(CN)CO₂C₃H₇ (where R is 2-bromo-4-methyl, 2-chloro-6-methyl, 3-chloro-4-methyl, 2,5-dibromo, 3,5-dibromo, 2,3-dichloro, and 2,4-dichloro) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and propyl cyanoacetate and characterized by CHN elemental analysis, IR, ¹H and ¹³C-NMR. All the ethylenes were copolymerized with styrene 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. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200-500°C range with residue (7-12% 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 styrene. 9. Chloro and fluoro ring-disubstituted propyl 2-cyano-3-phenyl-2-propenoates

Novel trisubstituted ethylenes, ring-disubstituted propyl 2-cyano-3-phenyl-2-propenoates, RPhCH = C(CN)CO₂C₃H₇ (where R is 2,5-dichloro, 2,6-dichloro, 3,4-dichloro, 2,3-difluoro, 2,4-difluoro, 2,5-difluoro, 2,6-difluoro) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and propyl 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. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (1.2–3.1% wt.), which then decomposed in the 500–800°C range.     

Novel copolymers of styrene. 7. Some ring-disubstituted butyl 2-cyano-3-phenyl-2-propenoates

Novel trisubstituted ethylenes, ring-disubstituted butyl 2-cyano-3-phenyl-2-propenoates, RPhCH?C(CN)CO₂C₄H₉ (where R is 2-bromo-5-methoxy, 3-bromo-4-methoxy, 5-bromo-2-methoxy, 2-chloro-3-methoxy, 3-chloro-4-methoxy, 2-chloro-6-methyl, 3-chloro-4-methyl, 2-fluoro-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 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 200-500ºC range with residue (1-6% wt.), which then decomposed in the 500–800ºC range.     

Novel Copolymers of 4-Fluorostyrene. 10. Some Ring-substituted 2-Phenyl-1,1-dicyanoethylenes

Novel copolymers of trisubstituted ethylene monomers, ring-substituted 2-phenyl-1,1-dicyanoethylenes, RC₆H₂CH=C(CN)₂ (where R is 4-C₆H₅O, 2-C₆H₅CH₂O, 3,4-(C₆H₅CH₂O)₂, 2-C₆H₅CH₂O-3-CH₃O, 3-C₆H₅CH₂O-4-CH₃O, 2-Cl-6-NO₂, 4-Cl-3-NO₂, 5-Cl-2-NO₂) and 4-fluorostyrene 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. The order of relative reactivity (1/r ₁) for the monomers is 3,4-(C₆H₅CH₂O)₂(31.0) > 2-C₆H₅CH₂O-3-CH₃O (24.8) > 3-C₆H₅CH₂O-4-CH₃O (15.2) > 4-C₆H₅O (3.1) > 4-Cl-3-NO₂ (1.9) > 2-Cl-6-NO₂ (1.6) > 5-Cl-2-NO₂ (1.5) > 2-C₆H₅CH₂O (1.4). High T_g of the copolymers, in comparison with that of poly(4-fluorostyrene) 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 270-400°C range with residue, which then decomposition in 400–800°C range.     

Novel Copolymers of Styrene. 4. Halogen Ring-Substituted Butyl 2-Cyano-3-Phenyl-2-Propenoates

Novel trisubstituted ethylenes, halogen ring-substituted butyl 2-cyano-3-phenyl-2-propenoates, RPhCH ? C(CN)CO₂C₄H₉ (where R 2-Br, 3-Br, 4-Br, 2-Cl, 3-Cl, 4-Cl, 2-F, 3-F, 4-F) 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 3-F (22.97) > 3-Br (6.05) > 2-Cl (4.32) > 4-F (3.19) > 4-Br (2.47) > 4-Cl (1.92) > 2-F (1.74) > 3-Cl (1.10) > 2-Br (1.07). Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (2.3–5.9% wt.), which then decomposed in the 500–800°C range.     

Novel copolymers of styrene. 7. Some ring-disubstituted propyl 2-cyano-3-phenyl-2-propenoates

Novel trisubstituted ethylenes, ring-disubstituted propyl 2-cyano-3-phenyl-2-propenoates, RPhCH = C(CN)CO₂C₃H₇ (where R is 2-bromo-5-methoxy, 3-bromo-4-methoxy, 5-bromo-2-methoxy, 2-chloro-3-methoxy, 3-chloro-4-methoxy, 2-fluoro-3-methoxy, 2-fluoro-4-methoxy, 3-fluoro-4-methyl, 4-fluoro-3-phenoxy) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and propyl 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. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (3–7% wt.), which then decomposed in the 500–800°C range.     

Novel copolymers of styrene. 10. halogen ring-disubstituted butyl 2-cyano-3-phenyl-2-propenoates

Novel trisubstituted ethylenes, halogen ring-disubstituted butyl 2-cyano-3-phenyl-2-propenoates, RPhCH?C(CN)CO₂C₄H₉ (where R is 2,5-diBr, 3,5-diBr, 2,3-diCl, 2,4-diCl, 2,5-diCl, 2,6-diCl, 3,4-diCl, 3,5-diCl) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-disubstituted 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.     

Novel copolymers of styrene. 9. Fluoro ring-disubstituted butyl 2-cyano-3-phenyl-2-propenoates

Electrophilic trisubstituted ethylenes, ring-disubstituted butyl 2-cyano-3-phenyl-2-propenoates, RPhCH?C(CN)CO₂C₄H₉ (where R is 2-fluoro-5-methoxy, 2-fluoro-6-methoxy, 3-fluoro-4-methoxy, 4-fluoro-3-methoxy, 5-fluoro-2-methoxy, 3-fluoro-2-methyl, 3-fluoro-4-methyl, 4-fluoro-2-methyl, 4-fluoro-3-methyl, 5-fluoro-2-methyl were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-disubstituted benzaldehydes and butyl cyanoacetate, and characterized by CHN analysis, IR, ¹H and ¹³C-NMR. All the ethylenes were copoly-merized 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 (1.2–3.5% wt.), which then decomposed in the 500–800°C range.     

Synthesis and styrene copolymerization of novel trisubstituted ethylenes: 11. Halogen ring-substituted propyl 2-cyano-3-phenyl-2-propenoates

Abstract

Novel trisubstituted ethylenes, ring-substituted propyl 2-cyano-3-phenyl-2-propenoates, RPhCH=C(CN)CO₂C₃H₇ (where R is 4-chloro-3-fluoro, 2-fluoro-5-iodo, 2-fluoro-6-iodo, 2-trifluoromethyl, 3-trifluoromethyl, 4-trifluoromethyl, 2-trifluoromethoxy, 3-trifluoromethoxy, and 4-trifluoromethoxy) were prepared and copolymerized with styrene. The ethylenes were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and propyl cyanoacetate and characterized by CHN analysis, FTIR, ¹H and ¹³C NMR. All the ethylenes were copolymerized with styrene 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 FTIR, ¹H and ¹³C NMR. Decomposition of the copolymers in nitrogen (TGA) occurred in two steps, first in the 250–500?°C range with residue (0.5–3.1% wt.), which then decomposed in the 500–700?°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. 4. Halogen ring-substituted propyl 2-cyano-3-phenyl-2-propenoates

Novel trisubstituted ethylenes, halogen ring-substituted propyl 2-cyano-3-phenyl-2-propenoates, RPhCH ? C(CN)CO₂C₃H₇ (where R is 2-Br, 3-Br, 4-Br, 2-Cl, 3-Cl, 4-Cl, 2-F, 3-F, 4-F were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and propyl 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 (0.9–4.7% 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. 6. Some oxy ring-disubstituted propyl 2-cyano-3-phenyl-2-propenoates

Novel trisubstituted ethylenes, oxy ring-disubstituted propyl 2-cyano-3-phenyl-2-propenoates, RPhCH = C(CN)CO₂C₃H₇ (where R is 4-methoxy-2-methyl, 4-methoxy-3-methyl, 3-ethoxy-4-methoxy, 3,4-dibenzyloxy, 3-benzyloxy-4-methoxy, 4-benzyloxy-3-methoxy) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and propyl 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. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (3–22% wt.), which then decomposed in the 500–800°C range.