Novel fluorinated polymers by radical polyaddition of bis(α-trifluoromethyl-β-difluorovinyl) dicarboxylate with ether

To develop the radical polyaddition reaction of bis(alpha-trifluoromethyl-beta-difluorovinyl) terephthalate (BFP) with 1,4-dioxane, bis(alpha-trifluoromethyl-beta-difluorovinyl) cyclohexane-1,4-dicarboxylate (FDFC) and bis(alpha-trifluoromethyl-beta-difluorovinyl) adipate (FDFA) were prepared and polyadditions with 1,4-dioxane, diethyl ether, and 1,2-dimethoxyethane were examined in the presence of benzoyl peroxide (BPO). The molecular weight of the polymer obtained from FDFC with dioxane was 2.9 x 10(3). A polymer with a molecular weight of 4.5 x 10(3) was obtained by the reaction of FDFA with 1,4-dioxane initiated with BPO. Polyaddition reactions of FDFC or FDFA with 1,2-dimethoxyethane or diethyl ether were found to produce linear polymers which are soluble in common organic solvents. These: results suggested that 1,4-dioxane, diethyl ether and 1,3-dimethoxyethane work as monomers in this reaction system. Postpolymerization of the polymer obtained from BFP with 1,4-dioxane was also examined to yield a polymer of higher molecular weight compared to that of the starting polymer. A postulated polymerization mechanism of BFP with 1,4-dioxane is briefly discussed.