共查询到20条相似文献,搜索用时 31 毫秒
1.
Gregory B. Kharas Emi Hanawa Benjamin L. Hill Katherine T. Flynn Emily Figueroa Anne M. Roubal 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(6):423-427
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 Tg 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. 相似文献
2.
Gregory B. Kharas Hui Feng Hemal S. Bhavsar Sara M. Rocus William S. Schjerven Ahlam Shahbain 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(2):90-94
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 Tg 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. 相似文献
3.
Gregory B. Kharas Benjamin L. Hill Jerry J. Frangello Agustin Orosquieta Annette Martin Christine Dittmann 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(3):192-196
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. 相似文献
4.
Gregory B. Kharas Eric S. Molina Brittany M. Fitzpatrick Mathew C. Francis Christopher Gallardo Jessica L. Gehle 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(4):370-374
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 Tg 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. 相似文献
5.
Caitlin E. Karver Eric S. Molina Erin T. Economos Jonathan C. Fuentes Socrates M. Kaitson Samuel Kogan 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(2):101-105
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. 相似文献
6.
Gregory B. Kharas Emi Hanawa Benjamin L. Hill Katherine T. Flynn Wilbert-John Alvarez Brigette A. Baronti 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(6):428-432
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 Tg 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. 相似文献
7.
Gregory B. Kharas Benjamin L. Hill Monica V. Garcia Walter J. Kinderman Kevin N. Kopack Jeffrey J. Kropp 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(5):331-335
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 Tg 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. 相似文献
8.
Gregory B. Kharas Katherine T. Flynn Benjamin L. Hill Mustafa R. Ishaq Darin A. Kopp Brittany G. Koroll 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(2):95-99
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 Tg 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. 相似文献
9.
Gregory B. Kharas Emi Hanawa Benjamin L. Hill Katherine T. Flynn Lauren N. Furlan Brandon Holtrup 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(2):91-94
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 Tg 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. 相似文献
10.
Gregory B. Kharas Sonia E. Chavez Alex C. Mast Mark Krzeszowiec Stan Mazo 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(6):451-454
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 Tg 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. 相似文献
11.
Gregory B. Kharas Benjamin L. Hill Vida M. Gaizutis Irma T. Garcia Lara Gutierrez Michelle E. Huddle 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(6):575-580
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-CH3?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 Tg 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. 相似文献
12.
Gregory B. Kharas Subha Ramnarayan Sonia E. Chavez Ramneek K. Mangat Benjamin Kanevsky Susan E. Averbeck 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(5):369-372
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 Tg 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. 相似文献
13.
Gregory B. Kharas Youya Gao Jihad Aburas Christina Chintanaphol Mallory L. Davis Hubert Dolubizno 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(8):593-598
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. 相似文献
14.
Justin J. Maresh Sonia E. Chavez Matthew J. Asciutto Nathan D. Brown Alexander A. Delgado Youya Gao 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(9):683-688
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 Tg 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. 相似文献
15.
Gregory B. Kharas Emi Hanawa Benjamin L. Hill Katherine T. Flynn Nikesh H. Bajaj Yousef Bittar 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(10):973-976
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. 相似文献
16.
Gregory B. Kharas Sonia E. Chavez Harrison S. Browning Jennifer A. Sepe Mario E. Romanelli Melissa K. Susnis 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(10):751-755
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 Tg 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. 相似文献
17.
Gregory B. Kharas Emi Hanawa Benjamin L. Hill Katherine T. Flynn Libby Lapson Amanda Mueller 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(11):1055-1058
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. 相似文献
18.
Gregory B. Kharas Lisa M. Gennett Yolondria L. Harvey Elizabeth R. Jennings Denny Petropoulos Ovie C. Smith 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(3):163-167
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 Tg 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. 相似文献
19.
Gregory B. Kharas Emi Hanawa Benjamin L. Hill Katherine Flynn Amy N. Addante Julio C. Argueta 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(3):197-201
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. 相似文献
20.
Salima Atlas Mustapha Raihane Gregory B. Kharas Peter G. Hendrickson Hamid Kaddami Mourad Arous 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(12):997-1010
Copolymerization of fluorine ring-substituted 2-phenyl-1,1-dicyanoethenes, RC6H3CH?C(CN)2 (R is 2,3-F,F, 2,4-F,F, 2,5-F,F, 2,6-F,F, and 4-CF3) with 4-fluorostyrene were prepared in the presence of a radical initiator (ABCN) at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the copolymers were characterized by IR, 1H and 13C-NMR, GPC, DSC, and TGA. The monomer reactivity ratios for 4-fluorostyrene (M1), r1 = 0.6 and 2-(2,4-difluorophenyl)-1,1-dicyanoethene (M2), r2 = 0 were determined from Fineman-Ross plot. The order of relative reactivity (1/r1) for difluoro-substituted monomers is 2,4-F,F (0.31) > 2,3-F,F (0.25) > 2,5-F,F (0.22) > 2,6-F,F (0.10). DSC curves showed that the copolymers were amorphous with high T g in comparison with that poly(4-fluorostyrene) indicating a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer units. From the thermogravimetric analysis, the copolymers began to degrade in the range 214–260°C. The copolymer of 4-fluorostyrene and 2-(2,4-difluorophenyl)-1,1-dicyanoethene and poly(4-fluorostyrene) were dielectrically characterized in the range 25–200°C. The dominating relaxation process detected in both materials was the α-relaxation, associated with the dynamic glass transition. The relationship polarity-permittivity was discussed. 相似文献