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

Abstract

<p>Novel trisubstituted ethylenes, alkyl ring-substituted 2-methoxyethyl phenylcyanoacrylates, RPhCH=C(CN)CO<sub>2</sub>CH<sub>2</sub>CH<sub>2</sub>OCH<sub>3</sub><sub> </sub>(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 2-methoxyethyl cyanoacetate, and characterized by CHN analysis, IR, <sup>1</sup>H and <sup>13</sup>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.</p>

Synthesis and styrene copolymerization of novel alkoxy ring-substituted tert-butyl phenylcyanoacrylates

“…The conversion of the copolymers was kept between 10 and 20% to minimize compositional drift (Table 1). Nitrogen elemental analysis showed that between 10.6 and 31.2 mol% of APCA is present in the copolymers prepared at ST/ APCA = 3 (mol), which is indicative of relatively high reactivity of the APCA monomers towards ST radical which is typical of alkoxy ring-substituted APCA [13][14][15][16][17][18][19][20][21][22][23]. Since APCA monomers do not homopolymerize, the most likely structure of the copolymers would be isolated APCA monomer units alternating with short ST sequences (Scheme 2).…”

“…Earlier we have reported synthesis and styrene copolymerization of a number of alkoxy ring-substituted methyl [13][14][15], ethyl [16,17], propyl [18], isopropyl [19], butyl [20], isobutyl [21], 2-methoxyethyl [22], and octyl [23] phenylcyanoacrylates.…”

Synthesis and styrene copolymerization of novel trisubstituted ethylenes: 2. Alkoxy 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 alkoxy ring-substituted methoxy [19][20][21], ethyl [22,23], propyl [24], isopropyl [25], butyl [26], isobutyl [27], 2methoxyethyl [28] PCAs.…”