Novel Copolymers of 4-Fluorostyrene. 8. Some Ring-Trisubstituted 2-Phenyl-1,1-dicyanoethylenes

Abstract

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, 1 H and 13 C-NMR. The order of relative reactivity (1/r 1 ) for the monomers is 3,4,5-(CH 3 O) 3 (10.6) > 2,4,6-(CH 3 O) 3 (9.3) > 2,4,5-(CH 3 O) 3 (5.4) > 2,3,4-(CH 3 O) 3 (4.4) > 6-Br-3,4-(CH 3 O) 2 (3.2) > 2,3,5-Cl 3 (1.5) > 2,3,6-Cl 3 (1.0) > 2,4-(CH 3 O) 2 -3-CH 3 (0.7). 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 200-400 • C range with residue, which then decomposed in the 400-800 • C range.

Novel Copolymers of Styrene and Ring-trisubstituted 2-Phenyl-1,1-dicyanoethylenes

“…Benzene rings of both monomers show ring stretching bands in 1495-1450 cm −1 region, as well as a doublet in 780-660 cm −1 region associated with C-H out-of-plane deformations. These bands were found also in copolymers of 2-phenyl-1,1-dicyanoethylene with vinyl acetate (15) and 4-fluorostyrene (16). 1 H-NMR spectra of the ST-TSE copolymers show a broad double peak in a 5.8-7.5 ppm region corresponding to phenyl ring protons.…”

Synthesis and Styrene Copolymerization of Novel Chloro and Fluoro Ring-Trisubstituted Propyl Cyanophenylpropenoates

“…ring-substituted TSE monomers, 3-phenyl-2-dicyanoethenes (Kharas 2011) and butyl 3-phenyl-2-cyano-2-propenoates (Kharas 2016) were copolymerized with 4-flourostyrene and styrene, respectively. With the objective to design novel structures, that could serve as a spring board for further development of novel materials with new properties and applications, and in continuation of our studies of the monomer structure-reactivity correlation in the radical copolymerization of TSE monomers we have prepared ring-trisubstituted propyl 2-cyano-3-phenyl-2-propenoates (PCPP), RPhCH=C(CN)CO 2 C 3 H 7 , where R is 2, 3,6-trichloro, 2,3,4-trifluoro, 2,3,5-trifluoro, 2,4,5-trifluoro, 2,4,6-trifluoro, 3,4,5-trifluoro, and explore the feasibility of their copolymerization with styrene.…”