Novel Copolymers of Trisubstituted Ethylenes and Styrene. 3. Alkyl and Alkoxy Ring-Substituted Ethyl 2-Cyano-1-oxo-3-phenyl-2-propenylcarbamates

Abstract

5 O), were prepared and copolymerized with styrene. The monomers were synthesized by the piperidine catalyzed Knoevenagel condensation of ring-substituted benzaldehydes and N-cyanoacetylurethane, and characterized by CHN analysis, IR, 1 H-and 13 C-NMR. All the ethylenes were copolymerized with styrene (M 1 ) 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 IR, 1 H-and 13 C-NMR. The order of relative reactivity (1/r 1 ) for the monomers is 3-C 2 H 5 O (2.1) > 4-CH 3 (CH 2 ) 3 (1.7) > 2-C 2 H 5 O (1.5) ≈ 4-CH 3 CH 2 (1.5) > 4-CH 3 (CH 2 ) 2 O (0.9) > 2,5-(CH 3 ) 2 (0.5) ≈ 4-CH 3 (CH 2 ) 3 O (0.5) > 2,4-(CH 3 ) 2 (0.4) > 4-CH 3 (CH 2 ) 4 O (0.3) ≈ 4-(CH 3 ) 2 CH (0.3). High T g of the copolymers, in comparison with that of polystyrene, indicates decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene structural unit. Decomposition of the copolymers in nitrogen occurred in two steps, first in 270-420 • C with a residue (3-10% wt), which then decomposed in the 550-700 • C range.

Novel Copolymers of Trisubstituted Ethylenes and Styrene. 8. Fluoro Ring-Substituted Ethyl 2-Cyano-1-oxo-3-phenyl-2-propenylcarbamates

“…Benzene rings of both monomers show ring stretching bands at 1440-1495 and 1520-1596 cm −1 as well as a doublet 735-759, 695-710 cm −1 , associated with out of plane C H bending motions. These bands can be readily identified in ST copolymers with TSE monomers containing cyano and carbonyl groups (10)(11)(12)(13). The broadening of the NMR signals in the spectra of the copolymers is apparently associated with head-to-tail and head-to-head structures, which formed through the attack of a styrene-ended radical on both sides of TSE monomer (15).…”

“…In continuation of our studies of the monomer structurereactivity correlation in the radical copolymerization of TSE monomers with carbamate group (11)(12)(13) we have prepared novel fluoro ring-substituted ethyl 2-cyano-1-oxo-3-phenyl-2-propenylcarbamates, RC 6 H 3 CH=C(CN) CONHCO 2 C 2 H 5 (where R is 4-F-3-CH 3 , 2-CF 3 , 4-CF 3 , 2,4-diF, 2,5-diF, 2,6-diF, 3,4-diF, and 3,5-diF, and explore the feasibility of their copolymerization with styrene.…”

Preparation of poly(styrene‐co‐isobornyl methacrylate) beads having controlled glass transition temperature by suspension polymerization

“…It is difficult to prepare high‐molecular weight styrene and α‐methylstyrene copolymers which are incorporated high enough fraction of α‐methylstyrene unit by a standard industrial EPS production process. Recently, Kharas et al19–25 investigated a series of trisubstituted styrenes with strong electrophilic groups on the α‐position. These polymer products showed a considerable high T g compared to the polystyrene homopolymer.…”