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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. [ABSTRACT FROM AUTHOR]

Novel trisubstituted ethylenes, alkyl ring-substituted isopropyl 2-cyano-3-phenyl-2-propenoates, RPhCH = C(CN)CO2CH(CH3)2 (where R is H, 2-methyl, 3-methyl, 4-methyl, 4-ethyl, 4-propyl, 4-i-propyl, 4-butyl, 4-i-butyl, 4-t-butyl) were prepared and copolymerized with styrene. The ethylenes were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and isopropyl 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 FTIR, 1H and 13C NMR. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 250-500°C range with residue (2-5% wt.), which then decomposed in the 500-800°C range. [ABSTRACT FROM AUTHOR]

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 and13C-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 and13C-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. [ABSTRACT FROM PUBLISHER]

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- and13C-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 and13C-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. [ABSTRACT FROM AUTHOR]

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- and13C-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 and13C-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. [ABSTRACT FROM AUTHOR]

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- and13C-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 and13C-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. [ABSTRACT FROM AUTHOR]

Novel trisubstituted ethylenes, oxy ring-substituted propyl 2-cyano-3-phenyl-2-propenoates, RPhCH˭C(CN)CO2C3H7(where R is 2-methoxy, 3-methoxy, 4-methoxy, 2-ethoxy, 3-ethoxy, 4-ethoxy, 4-propoxy, 4-butoxy, 3-phenoxy, 4-phenoxy) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of oxy ring-substituted benzaldehydes and propyl cyanoacetate and characterized by CHN elemental analysis, IR,1H- and13C-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 and13C-NMR, GPC, DSC, and TGA. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (1.2–3.6% wt.), which then decomposed in the 500–800°C range. [ABSTRACT FROM AUTHOR]

Trisubstituted ethylenes, alkyl ring-substituted propyl 2-cyano-3-phenyl-2-propenoates, RPhCH˭C(CN)CO2C3H7(where R is H, 2-methyl, 3-methyl, 4-methyl, 4-ethyl, 4-propyl, 4-i-propyl, 4-butyl, 4-i-butyl, 4-t-butyl) 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 and13C-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 and13C-NMR. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 250–500°C range with residue (2–4% wt.), which then decomposed in the 500–800°C range. [ABSTRACT FROM AUTHOR]

Novel trisubstituted ethylenes, halogen ring-trisubstituted butyl 2-cyano-3-phenyl-2-propenoates, RPhCH ˭C(CN)CO2C4H9(where R is 3-bromo-4,5-dimethoxy, 5-bromo-2,4-dimethoxy, 2-bromo-3-hydroxy-4-methoxy, 3-chloro-2,6-difluoro, 4-chloro-2,6-difluoro, 2,3,5-trichloro, 2,3,6-trichloro, 2,4,5-trifluoro) 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 and13C-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 and13C-NMR. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (3–5% wt.), which then decomposed in the 500–800°C range. [ABSTRACT FROM PUBLISHER]

Novel electrophilic trisubstituted ethylenes, methyl and methoxy ring-trisubstituted butyl 2-cyano-3-phenyl-2-propenoates, RPhCH=C(CN)CO2C4H9where 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 and13C-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 and13C-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. [ABSTRACT FROM PUBLISHER]

Electrophilic trisubstituted ethylenes, halogen ring-disubstituted butyl 2-cyano-3-phenyl-2-propenoates, RPhCH˭C(CN)CO2C4H9where 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 and13C-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 and13C-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. [ABSTRACT FROM AUTHOR]

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 and13C-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 and13C-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. [ABSTRACT FROM AUTHOR]

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 and13C-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 and13C-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. [ABSTRACT FROM AUTHOR]

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 and13C-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 and13C-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. [ABSTRACT FROM PUBLISHER]

Novel trisubstituted ethylenes, methyl and methoxy ring-disubstituted butyl 2-cyano-3-phenyl-2-propenoates, RPhCH=C(CN)CO2C4H9(where R is 2,4-dimethyl, 2,5-dimethyl, 2,6-dimethyl, 3,5-dimethyl, 2,3-dimethoxy, 2,4-dimethoxy, 2,5-dimethoxy, 2,6-dimethoxy, 3,4-dimethoxy, and 3,5-dimethoxy) 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 and13C-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 and13C-NMR. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500ºC range with residue (0.7-4.0% wt.), which then decomposed in the 500-800ºC range. [ABSTRACT FROM AUTHOR]

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 and13C-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 and13C-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. [ABSTRACT FROM AUTHOR]

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 and13C-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 and13C‒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. [ABSTRACT FROM PUBLISHER]

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 and13C-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 and13C-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. [ABSTRACT FROM PUBLISHER]

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- and13C-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 and13C-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. [ABSTRACT FROM AUTHOR]

Novel trisubstituted ethylenes, alkyl ring-substituted butyl 2-cyano-3-phenyl-2-propenoates, RPhCH=C(CN)CO2C4H9(where R is 2-methyl, 3-methyl, 4-methyl, 2-ethyl, 4-ethyl, 4-butyl, 4-t-butyl, 4-i-butyl) 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 and13C-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 and13C-NMR. The order of relative reactivity (1/r1) for the monomers is 4-ethyl (4.69) > 3-methyl (4.18) > 4-t-butyl (2.98) > 2-ethyl (2.52) > 4-butyl (2.47) > 4-methyl (1.86) > 4-i-butyl (0.94) > 2-methyl (0.87). Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (3–8% wt), which then decomposed in the 500–800°C range. [ABSTRACT FROM AUTHOR]

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- and13C-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- and13C-NMR, GPC, DSC, and TGA. HighTgof 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. [ABSTRACT FROM AUTHOR]

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- and13C-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- and13C-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). HighTgof 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. [ABSTRACT FROM PUBLISHER]

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 and13C-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 and13C-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 highTgof 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. [ABSTRACT FROM AUTHOR]

Novel trisubstituted ethylenes, ring-substituted 2-cyano-3-phenyl-2-propenamides, RPhCH = C(CN)CONH2(where R is 3-bromo-4-methoxy, 5-bromo-2-methoxy, 3-fluoro-2-methyl, 3-fluoro-4-methoxy, 5-bromo-2,4-dimethoxy, and 6-bromo-3,4-dimethoxy) were synthesized by potassium hydroxide catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and cyanoacetamide prepared and characterized by CHN elemental analysis, IR,1H- and13C-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- and13C-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 CPA monomers is 5-Br-2,4-(CH3O)2(0.83) > 3-F-2-CH3(0.70) > 6-Br-3,4-(CH3O)2(0.57) > 3-Br-4-CH3O (0.35) > 5-Br-2-CH3O (0.33) > 3-F-4-CH3O (0.25). HighTgof 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 (3.2–5.7 wt%), which then decomposed in the 500-800°C range. [ABSTRACT FROM AUTHOR]

Novel trisubstituted ethylenes, ring substituted 2-cyano-3-phenyl-2-propenamides, RC6H4CH=C(CN)CONH2(where R is 4-carboxy, 2-cyano, 3-cyano, 4-cyano, 4-dimethylamino, and 4-diethylamino) were synthesized by potassium hydroxide catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and cyanoacetamide prepared and characterized by CHN elemental analysis, IR,1H‒ and13C‒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‒ and13C‒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 CPA monomers is 4-(C2H5)2N (0.40) > 4-CO2H (0.39) > 3-CN (0.36) > 4-CN (0.35) > 2-CN (0.34) > 4-(CH3)2N (0.33). HighTgof 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. [ABSTRACT FROM AUTHOR]

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 and13C-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 and13C-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 highTgof 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. [ABSTRACT FROM PUBLISHER]

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 and13C-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 and13C-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 highTgof 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. [ABSTRACT FROM AUTHOR]

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 and13C-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 and13C-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 highTgof 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. [ABSTRACT FROM AUTHOR]

Electrophilic trisubstituted ethylenes, oxy ring-substituted methyl 2-cyano-3-phenyl-2-propenoates, RPhCH = C(CN)CO2CH3(where R is 2-C2H5O, 3-C2H5O, 4-C6H11O, 4-C6H5O, 3-(3,4-Cl2-C6H5O), 3-(3,5-Cl2-C6H5O), 4-(2,4-Cl2-C6H5O), 2-C6H5CH2O,3-C6H5CH2O, 4-C6H5CH2O, and 4-CH3CO2) 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 and13C-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 and13C-NMR. The order of relative reactivity (1/r1) for the monomers is 3-(3,4-Cl2-C6H5O) (11.0) > 2-C6H5CH2O (7.8) > 4-(2,4-Cl2-C6H5O) (6.6) > 3-(3,5-Cl2-C6H5O) (4.6) > 3-C2H5O (1.5) > 2-C2H5O (1.3) > 4-CH3CO2(0.7) > 3-C6H5CH2O (0.4) > 4-C6H11O (0.3) > 4-C6H5CH2O (0.2) = 4-C6H5O (0.2). Relatively highTgof 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 (2–9% wt), which then decomposed in the 500–800°C range. [ABSTRACT FROM PUBLISHER]

Electrophilic trisubstituted ethylenes, ring-disubstituted methyl 2-cyano-3-phenyl-2-propenoates, RPhCH&dbnd;C(CN)CO2CH3(where R is 2,4-(CH3)2, 3,5-(CH3)2, 4-CH3O-2-CH3, 4-C2H5O-3-CH3O, 3,4-(C6H5CH2O)2, 3-C6H5CH2O-4-CH3O, 4-C6H5CH2O-3-CH3O, 2,3-(CH2)2O, 4-CH3-3-NO2) 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 and13C-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 and13C-NMR. The order of relative reactivity (1/r1) for the monomers is 4-CH3-3-NO2(0.31) > 2,3-(CH2)2O (0.26) > 3-C6H5CH2O-4-CH3O (0.20) > 2,4-(CH3)2(0.18) > 4-C6H5CH2O-3-CH3O (0.16) > 3,4-(C6H5CH2O)2(0.14) > 4-C2H5O-3-CH3O (0.13) > 4-CH3O-2-CH3(0.11) > 3,5-(CH3)2(0.08). Relatively highTgof 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 monomer unit. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200–500°C range with residue (2–33% wt), which then decomposed in the 500–800°C range. [ABSTRACT FROM PUBLISHER]

Electrophilic trisubstituted ethylenes, ring-substituted ethyl 2-cyano-1-oxo-3-phenyl-2-propenylcarbamates, RC6H4CH[dbnd]C(CN)CONHCO2[sbnd]C2H5 (where R is H, 2[sbnd]CH3, 3[sbnd]CH3, 4[sbnd]CH3, 2[sbnd]OCH3, 3[sbnd]OCH3, 4[sbnd]OCH3,4[sbnd]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[sbnd]NMR. The order of relative reactivity (1/r 1) for the monomers is 2[sbnd]CH3 (1.52) > H (1.20) = 3[sbnd]CH3 (1.20) > 2[sbnd]OCH3 (1.16) > 3[sbnd]OCH3 (0.88) > 4[sbnd]CH3 (0.48) = 4[sbnd]OC2H5 (0.48) > 4[sbnd]OCH3 (0.29). Higher Tg 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. [ABSTRACT FROM AUTHOR]