Novel Copolymers of Styrene. 6. Alkoxy Ring-Substituted Ethyl 2-Cyano-3-Phenyl-2-Propenoates

作者：Kharas Gregory B^*; Delgado Alexander A; Anderson Nathan E; Bajor Agnieszka; Colbert Acheera C; Coleman Adrienne; Gregory Carine E; Hayes John; Lantin Jason; Malecki Joseph M; Murphy Timothy C; Oprescu Anda; Rydzon Brett F; Timoshevskaya Irina

来源：Journal of Macromolecular Science Part A-Pure and Applied Chemistry, 2013, 50(3): 276-280.

DOI：10.1080/10601325.2013.755409

• Trisubstituted ethylenes
• radical copolymerization
• styrene copolymers

Electrophilic trisubstituted ethylenes, alkoxy ring-substituted ethyl 2-cyano-3-phenyl-2-propenoates, RPhCHC(CN)CO2C2H5, (where 2,3-dimethoxy, 2,4-dimethoxy, 2,5-dimethoxy, 2,6-dimethoxy, 3,4-dimethoxy, 3,5-dimethoxy, 3-methyl-4-methoxy, 3-ethoxy-4-methoxy, 4-ethoxy-3-methoxy, 2,3,4-trimethyl, 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-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 3,4,5-trimethoxy (0.42) > 2,3-dimethoxy (0.37) > 3-ethoxy-4-methoxy (0.36) > 2,4,5-trimethoxy (0.35) > 3,5-dimethoxy (0.25) > 3-methyl-4-methoxy (0.24) > 4-ethoxy-3-methoxy (0.23) > 2,4,6-trimethoxy (0.22) > 2,5-dimethoxy (0.19) = 3,4-dimethoxy (0.19) > 2,6-dimethoxy (0.18) > 2,4-dimethoxy (0.17) > 2,3,4-trimethyl (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 270500 degrees C range with residue (35% wt), which then decomposed in the 500800 degrees C range.

• 出版日期2013-1-1