Solution free radical copolymerizations of hydroxyethyl acrylate/methacrylic acid (HEA/MAA) and ethyl acrylate/hydroxyethyl acrylate (EA/HEA) have been conducted in m-xylene (60 wt% solvent level) over the temperature range of 70 -1308C using tert-butyl peroxybenzoate as initiator. High resolution magic angle spinning spectroscopy (HR-MAS) and 2D-NMR have been utilized to characterize the copolymer gel for copolymer composition. The reactivity ratio values have been determined from low conversion copolymer composition data using the computer software package RREVM, which is based on the error in variables model (EVM) method. Also, Arrhenius-type reactivity ratio expressions have been developed that describe how reactivity ratios vary with temperature.
Styrene/ethyl acrylate (Sty/EA) free-radical copolymerizations have been conducted in bulk with and without initiator and in solution using p-xylene and m-xylene (30 wt% and 60 wt% solvent level) at 100• C and 130• C. The monomer reactivity ratio values and their temperature dependence have been determined from low conversion copolymer composition data using the computer software package RREVM, which is based on the error in variables model (EVM) method. Copolymer composition data at low conversion confirmed the MayoLewis model at both temperatures. The reactivity ratio values of the Sty/EA system do not seem to change with dilution by nonpolar solvents at low concentration from the reactivity ratio values obtained in bulk with and without initiator. However, xylene isomers were found to have a slight effect on the reactivity ratio value of ethyl acrylate when high solvent concentration was utilized.
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