Novel Copolymers of Styrene. 5. Oxy Ring-Substituted Ethyl 2-Cyano-3-Phenyl-2-Propenoates

作者：Kharas Gregory B^*; Delgado Alexander A; Gange Nicole; Hartzell Matthew C; Hawley Nicholas W; Kupczyk Kathryn A; Lam Emily K; Lyngaas Stephanie S; Mohammad Fahad B; Montgomery Mary E; Ryan Adelin J; Wright Vanessa M

来源：Journal of Macromolecular Science Part A-Pure and Applied Chemistry, 2013, 50(3): 271-275.

DOI：10.1080/10601325.2013.755375

• Trisubstituted ethylenes
• radical copolymerization
• styrene copolymers

Electrophilic trisubstituted ethylenes, oxy ring-substituted ethyl 2-cyano-3-phenyl-2-propenoates, RPhCHC(CN)CO2C2H5, (where R is 3-ethoxy, 4-ethoxy, 4-propoxy, 4-butoxy, 4-hexyloxy, 3-phenoxy, 4-phenoxy, 3-(4-chlorophenoxy), 2-benzyloxy, 3-benzyloxy) 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, H-1 and C-13-NMR. All the ethylenes were copolymerized with styrene (M-1) in solution with radical initiation (ABCN) at 70 degrees C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, H-1 and C-13-NMR. The order of relative reactivity (1/r(1)) for the monomers is 3-(4-chlorophenoxy) (1.82) > 3-phenoxy (1.14) > 4-phenoxy (0.91) > 3-ethoxy (0.66) > 2-benzyloxy (0.65) > 4-hexyloxy (0.42) > 4-propoxy (0.34) > 4-ethoxy (0.25) > 4-butoxy (0.20) > 3-benzyloxy (0.15). 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 250500 degrees C range with residue (38% wt), which then decomposed in the 500800 degrees C range.

• 出版日期2013-1-1