Poly(isobornyl methacrylate‐co‐methyl acrylate): Synthesis and stereosequence distribution analysis by NMR spectroscopy

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 °C. The copolymer compositions determined from ¹H NMR spectra are used to determine reactivity ratios of the monomers. The reactivity ratio determined from linear Kelen–Tudos method and non‐linear error‐in‐variable method, are r_I = 1.25 ± 0.10, r_M = 0.84 ± 0.08 and r_I = 1.20, r_M = 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 β‐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. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012