Methyl methacrylate/N‐(o‐/m‐/p‐chlorophenyl) itaconimide copolymers: Microstructure determination by NMR spectroscopy

Abstract

AbstractHomopolymerization and copolymerization of N‐(o‐/m‐/p‐chlorophenyl) itaconimide with methyl methacrylate was carried out by taking varying mole fractions (0.1 to 0.5) of N‐aryl substituted itaconimide monomers in the initial feed using azobisisobutyronitrile as an initiator and tetrahydrofuran as the solvent. The copolymer composition was determined by 1H‐NMR spectroscopy using the ratio of proton resonance signal intensity attributed to OCH3 of MMA (δ = 3.5–3.8 ppm) and the aromatic protons (δ = 7.0–7.5 ppm) of N‐(o‐/m‐/p‐chlorophenyl) itaconimide. The comonomer reactivity ratios were determined using Kelen–Tüdos and nonlinear error in variable methods. The reactivity ratios obtained by nonlinear error in variable methods were r1 (PI) = 1.26/r2 (MMA) = 0.35; r1 (MI) = 1.21/r2 (MMA) = 0.34; and r1 (OI) = 0.78/r2 (MMA) = 0.34. The carbonyl carbon signals of MMA (M) as well as N‐aryl itaconimide (I) copolymers were used for the determination of the sequence distribution of M‐ and I‐centered triads. The sequence distribution of M‐ and I‐centered triads determined from 13C{1H}‐NMR spectra of the copolymers are in good agreement with the triad concentrations calculated using the Alfrey–Mayo statistical model and Monte Carlo simulation method. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2016–2027, 2004