Novel copolymers of styrene. 14. Halogen ring-trisubstituted butyl 2-cyano-3-phenyl-2-propenoates

Abstract

Novel trisubstituted ethylenes, halogen ring-trisubstituted butyl 2-cyano-3-phenyl-2-propenoates, RPhCH HC(CN)CO 2 C 4 H 9 (where R is 3-bromo-4,5-dimethoxy, 5-bromo-2,4-dimethoxy, 2-bromo-3-hydroxy-4-methoxy, 3-chloro-2,6-difluoro, 4-chloro-2,6-difluoro, 2,3,5-trichloro, 2,3,6-trichloro, 2,4,5-trifluoro) 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, 1 H and 13 C-NMR. All the ethylenes were copolymerized with styrene 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, 1 H and 13 C-NMR. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200-500 C range with residue (3-5% wt.), which then decomposed in the 500-800 C range.

Synthesis and styrene copolymerization of novel trisubstituted ethylenes: 11. Acetyl, methoxy, and halogen ring-substituted octyl phenylcyanoacrylates

“…The conversion of the copolymers was kept between 10 and 20% to minimize compositional drift (Table 1). Nitrogen elemental analysis showed that between 9.2 and 34.5 mol% of OPCA is present in the copolymers prepared at ST/ OPCA = 3 (mol), which is indicative of relatively high reactivity of the OPCA monomers towards ST radical which is typical of ring-substituted 12 OPCA [18][19][20][21][22][23][24][25][26]. Since OPCA monomers do not homopolymerize, the most likely structure of the copolymers would be isolated OPCA monomer units alternating with short ST sequences (Scheme 2).…”

“…Thus, copolymerization of electrophilic TSE monomers having double bonds substituted with halo, cyano, and carbonyl groups and electron-rich monosubstituted ethylenes such as styrene, N-vinylcarbazole, and vinyl acetate [16][17][18] show a tendency toward the formation of alternating copolymers -thus suggesting a way of functionalization of commercial polymers via introduction of isolated monomer units in copolymers. Earlier we have reported synthesis and styrene copolymerization of several ring-monosubstituted methyl [19][20][21], ethyl [22], propyl [23,24], isopropyl [25], butyl [26], isobutyl [27], and 2methoxyethyl [28] PCAs.…”

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.…”

Synthesis and vinyl benzene copolymerization of novel trisubstituted ethylenes: 15. Halogen and methoxy ring-substituted isopropyl 2-cyano-3-phenyl-2-propenoates

“…We continue to explore synthesis and copolymerization of CPP compounds; thus, we have prepared and copolymerized with vinyl benzene ring-trisubstituted methyl [15], ethyl [16], propyl [17,18], and butyl [19,20] esters of 2-cyano-3-phenyl-2-propenoic acid. Recently we have reported synthesis and vinyl benzene copolymerization of a number of novel chloro and methoxy [21] and dimethoxy [22] ring-disubstituted isopropyl esters of 2-cyano-3-phenyl-2-propenoic acid.…”