Synthesis and Styrene Copolymerization of Novel Dihalogen Ring-Substituted Isopropyl Cyanophenylacrylates

Abstract

<p>Novel dihalogen ring-substituted isopropyl 3-phenyl-2-cyanoacrylates, RPhCH=C(CN)CO<sub>2</sub>CH(CH<sub>3</sub>)<sub>2</sub> (where R is 2,5-dibromo, 3,5-dibromo, 2,3-dichloro, 2,4-dichloro, 2,5-dichloro, 2,6-dichloro, 3,4-dichloro, 3,5-dichloro, 2,4-difluoro, 2,5-difluoro, 2,6-difluoro) were prepared and copolymerized with styrene. The acrylates were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-disubstituted benzaldehydes and isopropyl cyanoacetate and characterized by CHN elemental analysis, IR, 1H- and 13C-NMR. All the acrylates were copolymerized with styrene in solution with radical initiation (ABCN) at 70C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, 1H and 13C-NMR, GPC, DSC, and TGA. </p>

Synthesis and styrene copolymerization of novel dibromo and dichloro ring-disubstituted isobutyl phenylcyanoacrylates

“…The conversion of the copolymers was kept between 10 and 20% to minimize compositional drift (Table 1). Nitrogen elemental analysis showed that between 11.8 and 30.4 mol% of IPCA is present in the copolymers, which is indicative of relatively high reactivity of the IPCA monomers towards ST radical which is typical of halogen ring-substituted different esters PCA [17][18][19][20][21][22][23][24][25]. Since IPCA monomers do not homopolymerize, the most likely structure of the copolymers would be isolated IPCA monomer (y = 1) units alternating with short ST The copolymers prepared in the present work are all soluble in ethyl acetate, THF, DMF and CHCl3 and insoluble in methanol, ethyl ether, and petroleum ether.…”

“…Thus, copolymerization of electrophylic 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 [15][16][17] 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 a number of methyl and oxy ringsubstituted PCAs, such esters as methyl [18,19], ethyl [20], propyl [21][22][23], propyl [24], and butyl [25].…”

Synthesis and styrene copolymerization of novel trisubstituted ethylenes: 8. Dichloro and difluoro ring-substituted octyl phenylcyanoacrylates

“…Thus, copolymerization of electrophylic 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 a number of dichloro and difluoro ringsubstituted methyl [19][20][21], ethyl [22], propyl [23][24][25], isopropyl [26,27], butyl [28,29], isobutyl [30,31], and 2-methoxyethyl [32] PCAs.…”

Synthesis and styrene copolymerization of novel fluoro and chloro ring-disubstituted isobutyl phenylcyanoacrylates

“…Thus, copolymerization of electrophylic 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 [15][16][17] 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 a number of methyl and oxy ringsubstituted PCAs, such esters as methyl [18][19][20], ethyl [21], propyl [22][23][24], isopropyl [25][26][27], and butyl [28][29].…”