SYNTHESIS AND RADICAL COPOLYMERIZATION OF TRISUBSTITUTED ETHYLENES WITH STYRENE. 6. ALKOXY,PHENOXY, AND CYANO RING-SUBSTITUTED METHYL-2-CYANO-3-PHENYL-2-PROPENOATES

Electrophilic trisubstituted ethylene monomers, ring-substituted methyl 2-cyano-3-phenyl-2-propenoates, RC₆H₄CH?C(CN) CO₂CH₃ (where R is 4-C₂H₅O, 4-C₃H₇O, 4-C₄H₉O, 3-C₆H₅O, and 3-CN), 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 elemental analysis, IR, ¹H- and ¹³C-NMR. All the propenoates 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/r₁ ) for the monomers is 3-CN (1.21) > 3-C₆H₅O (1.16) > 4-C₂H₅O (0.94) > 4-C₃H₇O (0.8305) > 4-C₄H₉O (0.616). The high T _g's of the copolymers (> 130°C) in comparison with that of polystyrene indicate a substantial decrease in the chain mobility of the copolymers due to the high dipolar character of the trisubstituted monomer unit. Gravimetric analysis indicated that the copolymers decompose in the range 300–400°C.     

Novel Copolymers of Alkyl and Alkoxy Ring‐Substituted Ethyl 2‐Cyano‐3‐phenyl‐2‐propenoates and Styrene

Abstract

Electrophilic trisubstituted ethylenes, ring‐substituted ethyl 2‐cyano‐3‐phenyl‐2‐propenoates, RC₆H₄CH?C(CN)CO₂C₂H₅ (where R is 2‐CH₃, 3‐CH₃, 4‐CH₃, 2‐OCH₃, 3‐OCH₃, and 4‐OCH₃) were prepared and copolymerized with styrene (ST). The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring‐substituted benzaldehydes and ethyl cyanoacetate, 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 3‐OCH₃ (0.88)?>?4‐CH₃ (0.71)?>?2‐OCH₃ (0.68)?>?3‐CH₃ (0.55)?>?2‐CH₃ (0.47)?>?4‐OCH₃ (0.40). Higher 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 TSE structural unit. Gravimetric analysis indicated that the copolymers decompose in the 257–287°C range.     

Novel Copolymers of 4-Fluorostyrene. 2. Alkoxy Ring-Substituted 2-Phenyl-1,1-dicyanoethylenes

Novel copolymers of trisubstituted ethylene monomers, alkoxy ring-substituted 2-phenyl-1,1-dicyanoethylenes, RC₆H₄CH = C(CN)₂ (where R is 2-methoxy, 3-methoxy, 4-methoxy, 2-ethoxy, 3-ethoxy, 4-ethoxy, 4-propoxy, 4-buthoxy, 4-hexyloxy) 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-methoxy (1.5) > 4-ethoxy (1.0) > 4-methoxy (0.8) > 3-ethoxy (0.7) = 3-methoxy (0.7) > 4-hexyloxy (0.6) = 2-ethoxy (0.6) > 4-butoxy (0.5) = 4-propoxy (0.5). 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 284–500°C range with residue (5–9% wt), which then decomposed in the 500–800°C range.     

Novel Copolymers of Styrene. Alkyl and Alkoxy Ring-Substituted 2-Phenyl-1,1-dicyanoethylenes

Novel copolymers of trisubstituted ethylene monomers, alkyl and alkoxy ring-substituted 2-phenyl-1,1-dicyanoethylenes, RC₆H₄CH=C(CN)₂ (where R is 2-ethyl, 4-i-propyl, 4-butyl, 4-i-butyl, 4-t-butyl, 2-ethoxy, and 4-hexyloxy) 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. The order of relative reactivity (1/r ₁) for the monomers is 4-t-butyl (1.45) > 4-i-propyl (1.38) > 2-ethyl (1.37) > 4-hexyloxy (1.33) > 4-i-butyl (1.24) > 2-ethoxy (1.13) > 4-butyl (1.04). 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 (1–10% wt.), which then decomposed in the 500–800°C range.     

Novel Copolymers of 4-Fluorostyrene. 8. Some Ring-Trisubstituted 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 2,4-(CH₃O)₂-3-CH₃, 2,3,4-(CH₃O)₃, 2,4,5-(CH₃O)₃, 2,4,6-(CH₃O)₃, 3,4,5-(CH₃O)₃, 6-Br-3,4-(CH₃O)₂), 2,3,5-Cl₃, 2,3,6-Cl₃ 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 3,4,5-(CH₃O)₃(10.6) > 2,4,6-(CH₃O)₃(9.3) > 2,4,5-(CH₃O)₃ (5.4) > 2,3,4-(CH₃O)₃ (4.4) > 6-Br-3,4-(CH₃O)₂ (3.2) > 2,3,5-Cl₃ (1.5) > 2,3,6-Cl₃ (1.0) > 2,4-(CH₃O)₂-3-CH₃ (0.7). 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 200–400°C range with residue, which then decomposed in the 400–800°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 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 4-Fluorostyrene. 6. Dialkoxy 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 2,3-(CH₃O)₂, 2,4-(CH₃O)₂, 2,5-(CH₃O)₂, 2,6-(CH₃O)₂, 3,4-(CH₃O)₂, and 3,5-(CH₃O)₂ 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 2,6-(CH₃O)₂(2.8) > 2,5-(CH₃O)₂(2.5) > 2,3-(CH₃O)₂ (2.1) > 3,5-(CH₃O)₂ (1.8) > 3,4-(CH₃O)₂ (0.9) > 2,4-(CH₃O)₂ (0.7). 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 250–400°C range with residue, which then decomposition in 400–800°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 4-Fluorostyrene. 3. 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 4-dimethylamino, 4-diethylamino, 3-phenoxy, 3-benzyloxy, 4-benzyloxy, 4-acetoxy, 2-cyano, 3-cyano, and 4-cyano) 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-benzyloxy (2.9) > 4-cyano (2.7) > 3-phenoxy (1.9) > 4-acetoxy (1.8) > 3-cyano (1.7) > 2-cyano (1.6) > 4-benzyloxy (0.6) > 4-dimethylamino (0.4) = 4-diethylamino (0.4). 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 290–400°C range with residue, which then decomposition in 400–800°C range.     

Novel Copolymers of 4-Fluorostyrene. 1. Alkyl Ring-Substituted 2-Phenyl-1,1-dicyanoethylenes

Novel copolymers of trisubstituted ethylene monomers, alkyl ring-substituted 2-phenyl-1,1-dicyanoethylenes, RC₆H₄CH = C(CN)₂ (where R is 2-methyl, 3-methyl, 4-methyl, 4-ethyl, 4-i-propyl, 4-butyl, 4-i-butyl, and 4-t-butyl) 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 4-ethyl (42.6) > 4-butyl (29.4) > 4-t-butyl (26.7) > 4-i-butyl (1.6) > 4-i-propyl (1.29) > 3-methyl (1.26) > 2-methyl (0.8) > 4-methyl (0.4). 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 183–500°C range with residue (5–30% wt.), which then decomposed in the 500–800°C range.     

Novel Copolymers of 4-Fluorostyrene. 9. Some Ring-Disubstituted 2-Phenyl-1,1-dicyanoethylenes

Novel copolymers of trisubstituted ethylene monomers, ring-disubstituted 2-phenyl-1,1-dicyanoethylenes, RC₆H₃CH=C(CN)₂ (where R = 3-Br-4-CH₃O, 5-Br-2-CH₃O, 2-F-5-CH₃, 2-F-6-CH₃, 3-F-2-CH₃, 3-F-4-CH₃, 4-F-2-CH₃, 4-F-3-CH₃) 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-F-4-CH₃(1.64) > 5-Br-2-CH₃O (1.62) > 3-Br-4-CH₃O (1.36) > 4-F-2-CH₃(1.3) > 4-F-3-CH₃(1.26) > 3-F-2-CH₃(1.11) > 2-F-5-CH₃ (0.98) > 2-F-6-CH₃ (0.97). 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 290–400°C range with residue, which then decomposed in 400–800°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 4-Fluorostyrene. 11. Some Ring-substituted 1,1-dicyano-2-(1-naphthyl)ethylenes

Novel copolymers of trisubstituted ethylene monomers, ring-substituted 1,1-dicyano-2-(1-naphthyl)ethylenes, RC₁₀H₆CH?C(CN)₂ (where R is H, 2-OCH₃, 4-OCH₃) and 4-fluorostyrene 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 (5.86) > 2-CH₃O (4.28) > 4-CH₃O (2.87). Relatively high T_g of the copolymers in comparison with that of poly(4-fluorostyrene) 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 (7.3–7.7% wt.), which then decomposed in the 500–800°C range.     

Radical Copolymerization of Fluorine Ring-Substituted 2-Phenyl-1,1-dicyanoethylenes with 4-Fluorostyrene: Synthesis and Characterization

Novel copolymers of trisubstituted ethylene monomers, fluorine ring-substituted 2-phenyl-1,1-dicyanoethenes, RC₆H₄CH[dbnd]C(CN)₂ (where R is 2-F, 3-F, and 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. 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. The gravimetric analysis indicated that the copolymers decomposed in two stages in the range 210–600°C.     

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. 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. 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. 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. 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.