Sequencing of methyl methacrylate/vinylidene chloride copolymers by NMR spectroscopy

Methyl methacrylate/vinylidene chloride (M/V) copolymers of different monomer concentrations were prepared by photopolymerization using the uranyl ion as photosensitizer. The copolymer composition was determined by chlorine estimation of the copolymers. The complete assignment of the ¹³C{¹H} NMR spectra of these copolymers is made by comparison with the spectra of poly(methyl methacrylate) and observing the changes in the intensities of the resonances with copolymer composition. The quaternary carbon of V- and M- center resonances were used for determining the sequence in terms of the distribution of V- and M- centered triads. The triad fractions thus obtained were compared with theoretically determined triad concentrations. The Monte Carlo simulation method was also used for estimating the copolymerization behavior. The variation of V- and M- centered triad concentrations was reported as a function of fractional conversions. The comonomer reactivity ratios, determined by both Kelen Tudos and nonlinear error in variables methods are r_V = 0.26 ± 0.04 and r_M = 2.88 ± 0.23. © 1998 John Wiley & Sons, Inc. J. Appl. Polym. Sci. 70: 373–381, 1998