Effect of Substituents on the Radical Copolymerization of Ring-Substituted Methyl 2-Cyano-3-Phenyl-2-Propenoates with Styrene

Abstract

Copolymerizations of ring-substituted methyl 2-cyano-3-phenyl-2-propenoates, RC,H,CH=C(CN)CO,CH, (R = CtH5, CH30, C1, Br, F) with styrene (M,) were studied in solution in the presence of a radical initiator. Terminal and penultimate kinetic models were applied for best prediction of the copolymer composition. The Alfrey-Price Q and e parameters calculated for the monomers correlate well with the relative reactivity ( l/rl). The relative reactivity showed a tendency to increase with increasing Hammett constant 6, cyclic voltammetric reduction potential, Ep, caIculated atomic charge, and I3C-NMR chemical shift on the olefinic a-carbon of the ring-substituted monomers. 627 Copyright 0 1997 by Marcel Dekker, Inc.

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 alkoxy ring-substituted isobutyl phenylcyanoacrylates

“…Earlier we have reported synthesis and styrene copolymerization a number of alkoxy ringsubstituted PCAs, such esters as methyl [12], ethyl [13], propyl [14], isopropyl [15], butyl [16], and tert-butyl [17].…”

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].…”