Kinetics of the radical copolymerization of 2,2,2‐trifluoroethyl methacrylate with tert ‐butyl α‐trifluoromethacrylate

The radical copolymerization of two different methacrylate monomers, 2,2,2‐trifluoroethyl methacrylate (TFEMA) and tert ‐butyl α‐trifluoromethacrylate (TBTFMA) in solution was investigated. The resulting statistic poly(TFEMA‐ co ‐TBTFMA) copolymers were characterized by NMR spectroscopy to assess their compositions. The kinetics of copolymerization enabled one to determine the reactivity ratios of both comonomers according to the methods of Fineman‐Ross, Kelen‐Tüdos, and extended Kelen‐Tüdos. Excellent correlations were found between these methods leading to the following reactivity ratios: r TFEMA = 4.87 ± 1.50 and r TBTFMA = 0.10 ± 0.02 at 74 °C. These values indicated that the structure of the copolymers was composed of poly(TFEMA) micro‐blocks separated by one TBTFMA unit. Both yields and molecular weights (ranging between 1,000 and 12,000 g/mol) increased with the TFEMA content. The thermal stability of these (co)polymers showed that the decomposition temperature at 10% weight loss increased both with TFEMA content and increasing molecular weights of the poly(TFEMA‐ co ‐TBTFMA) copolymers. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1029–1037, 2010