Methyl acrylate (A)/methyl methacrylate (B) copolymers of different compositions were synthesized in bulk at 50 degrees C and the compositions were determined from H-1 NMR spectra. Reactivity ratios were optimized using the least square methodology. Compositional and configurational assignments were done using two-dimensional (2D) Heteronuclear Single Quantum Correlation (HSQC) and Total Correlation Spectroscopy (TOCSY) experiments. Methylene proton and carbon resonances were assigned for compositional and configurational sensitivity at tetrad level. Carbon resonances of methine group of methyl acrylate were assigned for compositional sensitivity up to triad level with the help of 2D HSQC spectra. alpha-Methyl group of methyl methacrylate was assigned up to triad level of compositional and configurational placements for carbon and proton resonances by 2D HSQC spectroscopy. (c) 2005 Wiley Periodicals, Inc.