NOVEL COPOLYMERS OF TRISUBSTITUTED ETHYLENES AND STYRENE. I. ALKYL AND ALKOXY RING-SUBSTITUTED ETHYL 2-CYANO-1-OXO-3-PHENYL-2-PROPENYLCARBAMATES

• Published in: Journal of macromolecular science. Part A, Pure and applied chemistry Pure and applied chemistry, 2002-01, Vol.39 (12), p.1383-1391
• Main Authors: Kharas, Gregory B., Fuerst, Antonia M., Scola, Anthony, Bavirsha, Daniel J., Bernau, Bradley M., Brown, Santkileo K., Ece, Pasa, Dabrowski, Anna N., De Angelo, Penny, Fatemi, Farrah R., Watson, Kenneth
• Format: Article
• Language: English
• Subjects: Applied sciences; Copolymerization; Exact sciences and technology; Organic polymers; Physicochemistry of polymers; Preparation, kinetics, thermodynamics, mechanism and catalysts; Radical copolymerization; Styrene copolymers; Trisubstituted ethylenes
• ISSN: 1060-1325; 1520-5738
• DOI: 10.1081/MA-120016042

Electrophilic trisubstituted ethylenes, ring-substituted ethyl 2-cyano-1-oxo-3-phenyl-2-propenylcarbamates, RC 6 H 4 CH˭C(CN)CONHCO 2 ‒C 2 H 5 (where R is H, 2‒CH 3 , 3‒CH 3 , 4‒CH 3 , 2‒OCH 3 , 3‒OCH 3 , 4‒OCH 3 ,4‒OC 2 H 5 ) 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 (AIBN) 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 2‒CH 3 (1.52) > H (1.20) = 3‒CH 3 (1.20) > 2‒OCH 3 (1.16) >  3‒OCH 3 (0.88) > 4‒CH 3 (0.48) = 4‒OC 2 H 5 (0.48) > 4‒OCH 3 (0.29). Higher 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 TSE structural unit. Gravimetric analysis indicated that the copolymers decompose in the range 200-355°C.