Synthesis and characterization of methacrylic acid–ethyl acrylate copolymers

Copolymerization of methacrylic acid (MAA) and ethyl acrylate (EA) was performed in aqueous medium in the presence of an emulsifier with MAA as the major component (53.7–82.3 mol %). Emulsion stability was studied as a function of concentration and the nature of the emulsifier (ionic or nonionic). Copolymers were characterized using IR and ¹H-NMR spectroscopy. ¹³C-NMR spectra of MAA–EA copolymers have been discussed in terms of their triad monomer sequence distributions. Reactivity ratios of the MAA–EA pair were determined using a nonlinear least-square errors in variables method. Partition of the monomers in aqueous and organic phases was studied using a gas chromatographic technique. A two-loci polymerization mechanism was proposed on the basis of this partition behavior and the calculated composition of the oligomeric radicals formed in the initial stages of polymerization. © 1994 John Wiley & Sons, Inc.