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

Abstract

<p>Novel ring-disubstituted isobutyl phenylcyanoacrylates, RPhCH=C(CN)CO<sub>2</sub>CH<sub>2</sub>CH(CH<sub>3</sub>)<sub>2</sub> (where R is 2,3-difluoro, 2,4-difluoro, 2,6-difluoro, 3,4-difluoro, 3,5-difluoro, 2-chloro-4-fluoro, 2-chloro-6-fluoro, 3-chloro-2-fluoro, 3-chloro-4-fluoro, 4-chloro-3-fluoro) were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-disubstituted benzaldehydes and isobutyl cyanoacetate and characterized by CHN analysis, IR, <sup>1</sup>H and <sup>13</sup>C NMR. The acrylates were copolymerized with styrene in solution with radical initiation (ABCN) at 70C. The compositions of the copolymers were calculated from nitrogen analysis.</p>

Synthesis and styrene copolymerization of novel trisubstituted ethylenes: 9. Ring-disubstituted 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 18.1 and 35.9 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 ring-substituted phenylcyanoacrylates [18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35]. 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 halogen ring-disubstituted PCAs, such esters as methyl [18][19][20][21], ethyl [22], propyl [23][24][25][26], isopropyl [27][28][29], butyl [30][31][32], and isobutyl [33][34][35].…”

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 trisubstituted ethylenes: 9. Halogen, methyl, methoxy and nitro 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 halogen, methyl, methoxy and nitro ring-substituted methyl [19][20][21], ethyl [22], propyl [23,24], isopropyl [25,26], butyl [27], isobutyl [29,30], and 2-methoxyethyl [31,32] PCAs.…”