Synthesis and Styrene Copolymerization of Novel Ring-Disubstituted Isopropyl Cyanoarylacrylates

Abstract

<p>Novel oxy ring-substituted isopropyl 2-cyano-3-arylacrylates, RPhCH=C(CN)CO<sub>2</sub>CH(CH<sub>3</sub>)<sub>2</sub><sub> </sub>(where R is 3,4-dibenzyloxy, 3-benzyloxy-4-methoxy, 4-benzyloxy-3-methoxy, 2,3-methylenedioxy, 3-iodo-4-methoxy, 5-iodo-2-methoxy, 3,4-difluoro, 3,5-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, FTIR, <sup>1</sup>H and <sup>13</sup>C-NMR. All the acrylates were copolymerized with styrene in solution with radical initiation (ABCN) at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by FTIR, <sup>1</sup>H and <sup>13</sup>C-NMR. Thermal properties of the copolymers are characterized by DSC and TGA. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 200-500ºC range with a residue, which then decomposed in the 500-800ºC range.</p>

Synthesis and styrene copolymerization of novel trisubstituted ethylenes: 6. Methyl, halogen and oxy ring-disubstituted 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 methyl, halogen, and oxy ring-disubstituted methyl [19][20][21], ethyl [22][23][24], propyl [25][26][27], isopropyl [28][29][30], butyl [31,32], isobutyl [33,34], and 2-methoxyethyl [35] PCAs.…”

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].…”