The free-radical-initiated copolymerization of 2-(4-acetylphenoxy)-2-oxoethyl-2-methylacrylate (AOEMA) and 2-(4-benzoylphenoxy)-2-oxoethyl-2-methylacrylate (BOEMA) with 2-[(4-fluorophenyoxy]-2-oxoethyl-2-methylacrylate (FPEMA) were carried out in 1,4-dioxane solution at 65°C using 2,2′-azobisisobutyronitrile as an initiator with different monomer-to-monomer ratios in the feed. The monomers and copolymers were characterized by FTIR and 1H- and 13C-NMR spectral studies. 1H-NMR analysis was used to determine the molar fractions of AOEMA, BOEMA, and FPEMA in the copolymers. The reactivity ratios of the monomers were determined by the application of Fineman-Ross and Kelen-Tudos methods. The analysis of reactivity ratios revealed that BOEMA and AOEMA are less reactive than FPEMA, and copolymers formed are statistically in nature. The molecular weights (Mw and Mn) and polydispersity index of the polymers were determined using gel permeation chromatography. Thermogravimetric analysis of the polymers reveals that the thermal stability of the copolymers increases with an increase in the mole fraction of FPEMA in the copolymers. Glass transition temperatures of the copolymers were found to decrease with an increase in the mole fraction of FPEMA in the copolymers. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009
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