Abstract
A 220-MHz NMR investigation was carried out on the random and alternating copolymers of methyl methacrylate (MMA) with butadiene (BD) or isoprene (IP) and their partially deuterated analogues. An absorption by the α-methyl protons of MMA units in the MMA—BD random copolymer splits into several overlapping peaks. The triad sequence distributions centered at the MMA unit were roughly estimated and compared with those calculated from the first-order Markov chain model, providing that the monomer reactivity ratios were rMMA=0.18 and rBD=0.62. The observed and calculated sequence distribution for the random copolymer are in fair agreement. From the resonance mode of the α-methyl proton of MMA—Bd-d4 alternating copolymer, an isotactic configuration with flanking BD units was suggested. The alternating copolymer contains more than 95% of the alternating MMA—BD triad.Almost the same spectrum was observed for the MMA—IP alternating copolymer, and the chain structure was established to be composed of a linkage between the α-position of MMA and the 1-position of IP. To determine the monomer sequence distribution of MMA—IP random copolymers, the lanthanide NMR shift reagent was used to separate the overlapped peaks. The monomer sequence distribution of the random copolymer obeys the first-order Markov chain model, providing that the monomer reactivity ratios are rMMA=0.26 and rIP=0.625. The alternating copolymer contains more than 97% of the MMA—IP alternating triad.
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Suzuki, T., Mitani, K., Takegami, Y. et al. 220-MHz NMR Spectra of Methyl Methacrylate—1,3-Diolefin Alternating and Random Copolymers. Polym J 6, 496–505 (1974). https://doi.org/10.1295/polymj.6.496
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DOI: https://doi.org/10.1295/polymj.6.496