Synthesis and styrene copolymerization of novel trisubstituted ethylenes: 3. Alkoxy ring-substituted isopropyl 2-cyano-3-phenyl-2-propenoates

Abstract

Novel trisubstituted ethylenes, alkoxy ring-substituted isopropyl 2-cyano-3-phenyl-2-propenoates, RPhCH = C(CN)CO2CH(CH3)2 (where R is 2-methoxy, 3-methoxy, 4-methoxy, 2-ethoxy, 3-ethoxy, 4-ethoxy, 4-propoxy, 4-butoxy, 4-hexyloxy) were prepared and copolymerized with styrene. The ethylenes were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and isopropyl cyanoacetate, and characterized by CHN analysis, FTIR, 1H and 13C 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 FTIR, 1H and 13C NMR. Decomposition of the copolymers in nitrogen occurred in two steps, first in the 250-500ºC range with residue (2.6–3.9% wt.), which then decomposed in the 500-800ºC range.

Synthesis and Styrene Copolymerization of Novel Trisubstituted Ethylenes: 2. Alkoxy Ring-substituted 2-Methoxyethyl Phenylcyanoacrylates

“…The conversion of the copolymers was kept between 10 and 20% to minimize compositional drift (Table 1). Nitrogen elemental analysis showed that between 19.4 and 30.0 mol% of MEPA is present in the copolymers prepared at ST/MEPA = 3 (mol), which is indicative of relatively high reactivity of the MEPA monomers towards ST radical which is typical of alkoxy ring-substituted phenylcyanoacrylates [18][19][20][21][22]. Since MEPA monomers do not homopolymerize, the most likely structure of the copolymers would be isolated MEPA monomer units alternating with short ST sequences (Scheme 2).…”

“…Earlier we have reported synthesis and styrene copolymerization a number of alkoxy ring-substituted PCAs, such esters as methyl [18], ethyl [19], propyl [20], isopropyl [21], and butyl [22].…”

Synthesis and Styrene Copolymerization of Novel Halogen, Alkoxy, and Alkyl Ring-Disubstituted Isopropyl 2-Cyano-3-Phenyl-2-Propenoates

“…Yield 91%; mp 95.4°C, 1 H-NMR  8.6 (s, 1H, CH=), 7.8-6.9 (m, 3H, Ph), 5.2 (m, 1H, CH), 3.9 (s, 3H, OCH3), 1.4 (d, 6H, CH3); 13…”

“…Copolymerization of TSE having double bonds substituted with halo, cyano, and carbonyl groups and electron-rich monosubstituted ethylenes such as styrene, Nvinylcarbazole, and vinyl acetate (7)(8)(9) show a tendency toward the formation of alternating copolymers. Thus, some ring-substituted MCPP and ECPP monomers were copolymerized with styrene (10, 11) and vinyl acetate (12,13). Recently we have reported synthesis and styrene copolymerization of a number of novel isopropyl 2-cyano-3-phenyl-2-propenoates (14,15).…”

Synthesis and styrene copolymerization of novel fluoro-iodo, trifluoromethyl, and trifluoromethoxy ring-substituted 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 [13][14][15] 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 alkoxy ring-substituted PCAs, such esters as methyl [16], ethyl [17], propyl [18], isopropyl [19], and butyl [20].…”