Synthesis and characterization of perfluorinated acrylatemethyl methacrylate copolymers

A novel perfluorinated acrylic monomer 3,5-bis(perfluorobenzyloxy)benzyl acrylate (FM) with perfluorinated aromatic units was synthesized with 3,5-bis(perfluorobenzyl)oxybenzyl alcohol, acryloyl chloride, and triethylamine. Copolymers of FM monomer with methyl methacrylate (MMA) were prepared via free-radical polymerization at 80 degrees C in toluene with 2,2-azobisisobutyronitrile as the initiator. The obtained copolymers were characterized by 1H-NMR and gel permeation chromatography. The monomer reactivity ratios for the monomer pair were calculated with the extended KelenTudos method. The reactivity ratios were found to be r1 = 0.38 for FM, r2 = 1.11 for MMA, and r1r2 < 1 for the pair FMMMA. This shows that the system proceeded as random copolymerization. The thermal behavior of the copolymers was investigated by thermogravimetric analysis and differential scanning calorimetry (DSC). The copolymers had only one glass-transition temperature, which changed from 46 to 78 degrees C depending on the copolymer composition. Melting endotherms were not observed in the DSC traces; this indicated that all of the copolymers were completely amorphous. Copolymer films were prepared by spin coating, and contact angle measurements of water and ethylene glycol on the films indicated a high degree of hydrophobicity. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013