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

Electrophilic trisubstituted ethylenes, ring-substituted ethyl 2-cyano-3-phenyl-2-propenoates, RPhCH˭C(CN)CO 2 C 2 H 5 (where R is 2-Cl, 3-Cl, 4-Cl, 2-Br, 3-Br, 4-Br, 2-F, 3-F, 4-F, 2-Cl-4-F, 2-Cl-6-F, 3-Cl-4-F) were prepared and copolymerized with styrene. The monomers were synthesized by the piper...

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Published in:Journal of macromolecular science. Part A, Pure and applied chemistry Pure and applied chemistry, 2013-01, Vol.50 (2), p.139-143
Main Authors: Kharas, Gregory B., Molina, Eric S., Abma, Kathleen E., Ali, Roshan A., Bairaktaris, Kiki D., Biasiello, Fred P., Cygan, Eva A., Gibson, Jami, Haq, Syed, Hoag, Dawn E., Johnson, Kasandra, Jordan, Shenik I., Mathews, Michael B., Shadduck, Caitlyn A., Tuzik, Nora
Format: Article
Language:English
Subjects:
Applied sciences
Copolymerization
Copolymers
Decomposition
Ethylene
Exact sciences and technology
Halogens
Infrared radiation
Monomers
Organic polymers
Physicochemistry of polymers
Preparation, kinetics, thermodynamics, mechanism and catalysts
radical copolymerization
styrene copolymers
Styrenes
Trisubstituted ethylenes
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Summary:Electrophilic trisubstituted ethylenes, ring-substituted ethyl 2-cyano-3-phenyl-2-propenoates, RPhCH˭C(CN)CO 2 C 2 H 5 (where R is 2-Cl, 3-Cl, 4-Cl, 2-Br, 3-Br, 4-Br, 2-F, 3-F, 4-F, 2-Cl-4-F, 2-Cl-6-F, 3-Cl-4-F) were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and ethyl cyanoacetate, and characterized by CHN analysis, IR, 1 H and 13 C-NMR. All the ethylenes were copolymerized with styrene (M 1 ) 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, 1 H and 13 C-NMR. The order of relative reactivity (1/r 1 ) for the monomers is 4-Br (7.74) > 2-Br (1.62) > 3-Cl (1.56) > 3-Br (1.39) > 4-F (0.97) > 3-F (0.86) = 4-Cl (0.86) > 2-Cl-6-F (0.57) > 3-Cl-4-F (0.51) > 2-Cl (0.49) > 2-F (0.42) > 2-Cl-4-F (0.37). 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 (1-7% wt), which then decomposed in the 500-800°C range.
ISSN:1060-1325
1520-5738
DOI:10.1080/10601325.2013.741408