Comprehensive 2D NMR analysis: Acrylonitrile/ethyl methacrylate copolymers synthesized by ATRP at ambient temperature

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 (r_A = 0.68 and r_E = 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