Copolymerization of isobornyl methacrylate and methyl acrylate (I/M) is performed by atom transfer radical polymerization using methyl-2-bromopropionate as an initiator and PMDETA/CuBr as catalyst under nitrogen atmosphere at 70 degrees C. The copolymer compositions determined from 1H NMR spectra are used to determine reactivity ratios of the monomers. The reactivity ratio determined from linear KelenTudos method and non-linear error-in-variable method, are rI = 1.25 +/- 0.10, rM = 0.84 +/- 0.08 and rI = 1.20, rM = 0.82, respectively. 1D, distortion less enhancement by polarization transfer and 2D, heteronuclear single quantum coherence, and total correlation spectroscopy NMR experiments are employed to resolve highly overlapped and complex 1H and 13C{1H} NMR spectra of the copolymers. The carbonyl carbon of I and M units and methyl carbon of I unit are assigned up to triad compositional and configurational sequences, whereas beta-methylene carbons are assigned up to tetrad compositional and configurational sequences. Similarly, methine carbon of I unit is assigned up to triad level. The couplings of carbonyl carbon and quaternary carbon resonances are studied in detail using 2D hetero nuclear multiple bond correlation spectra. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012