Radical Polymerization and Copolymerization of Methyl α-(Fluoroalkoxymethyl)acrylates and Characterization of Their Polymers

Representatives of a new type of fluorine-containing monomer, methyl α-(fluoroalkoxymethyl)acrylates (MCFMA's), were prepared. The fluoroalkoxy groups introduced were OCH2CF3, OCH2CF2CF2H, and OCH(CF3)2. All the monomers synthesized readily polymerized to number-average molecular weights of 55,000 to 110,000 at a 2 mol/L monomer concentration in dioxane using 5 × 10−3 mol/L of 2,2′-azobisisobutyronitrile at 60°C. The polymerization rate tended to decrease slightly with an increase in the size of the alkoxy group. Copoly-merization of MCFMA's with styrene revealed that the fluoroalkoxy-methyl group functions as an electron-attracting group depending on the number of fluorine atoms. According to thermogravimetric analysis, poly(MCFMA)'s were thermally less stable than poly(methyl methacrylate). Greater contact angles of the polymers from MCFMA's with water than poly(methyl methacrylate) were observed.