Abstract: | Copolymerization of acrylonitrile and ethyl methacrylate using atom transfer radical polymerization (ATRP) at ambient temperature was carried out under optimized reaction conditions using 2‐bromopropionitrile as initiator and CuBr/2,2′‐bipyridine as the catalyst system. The copolymer composition, obtained from 1H NMR spectra, were used to determine the monomer reactivity ratios (rA = 0.68 and rE = 1.75) involved in ATRP. Two‐dimensional NMR (heteronuclear single quantum correlation and total correlated spectroscopy) experiments were employed to resolve the highly overlapping and complex 1H and 13C{1H} NMR spectra of copolymers. The complete spectral assignments of the quaternary carbons viz. carbonyl and nitrile carbons were done with the help of heteronuclear multiple bond correlation spectra. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2955–2971, 2006 |