Novel Copolymers of Trisubstituted Ethylenes with Styrene. II. Halogen Ring-Substituted Methyl 2-Cyano-3-Phenyl-2-Propenoates

Abstract

Electrophilic trisubstituted ethylene monomers, ring-substituted methyl 2-cyano-3-phenyl-2-propenoates, RC6H4CH = C(CNC02CH, (where R is 0-C1, m-C1, p-C1, p-Br, and p-F) were prepared and copolymerized in solution with styrene at equimolar monomer feed composition in the presence of a radical initiator, AIBN at 80°C. The order of reactivity (lh,) for the trisubstituted ethylene monomers was p-C1 (3.0) > m-CI (2.9) > p-Br (2.3) > 0-C1 (2.0) > p-F (1.4). High Tg's of the copolymers in comparison with that of polystyrene indicates substantial decrease in chain mobility of the copolymer due to high dipolar character of the trisubstituted monomer units.

Novel co-polymers of vinyl acetate and halogen ring-substituted methyl 2-cyano-3-phenyl-2-propenoates

“…The preparation procedure and characterization of the TSE monomers was described earlier [9,10]. The condensation reaction proceeded smoothly, yielding crystalline products, which were purified by conventional techniques.…”

Synthesis and styrene copolymerization of novel trisubstituted ethylenes: 5. Halogen 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 17.2 and 29.6 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 phenoxy ring-substituted phenylcyanoacrylates [18][19][20][21][22][23][24]. 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-substituted PCAs, such esters as methyl [18][19], ethyl [20], propyl [21], isopropyl [22], butyl [23], and isobutyl [24]. Our objectives in exploration of novel 2methoxyethyl phenylcyanoacrylates (MEPA) were twofold: (1) to utilize Knoevenagel condensation for synthesis of MEPA compounds with a variety of potentially reactive functional groups and (2) to explore feasibility of radical copolymerization with a commercial monomer styrene.…”

Synthesis and styrene copolymerization of novel trisubstituted ethylenes: 4. Halogen ring-substituted octyl phenylcyanoacrylates

“…The conversion of the copolymers was kept between 10 and 20% to minimize compositional drift (Table 1). Nitrogen elemental analysis showed that between 23.3 and 41.1 mol% of OPCA is present in the copolymers prepared at ST/ OPCA = 3 (mol), which is indicative of relatively high reactivity of the OPCA monomers towards ST radical which is typical of halogen ring-substituted OPCA [18][19][20][21][22][23][24][25][26][27]. Since OPCA monomers do not homopolymerize, the most likely structure of the copolymers would be isolated OPCA monomer units alternating with short ST sequences (Scheme 2).…”

“…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 ring-substituted methyl [19][20][21], ethyl [22], propyl [23], isopropyl [24], butyl [25], isobutyl [26], and 2methoxyethyl [27] PCAs.…”