Novel high molecular weight aromatic fluorinated polymers from one-pot, metal-free step polymerizations

A novel series of linear, high-molecular-weight polymers and copolymers was synthesized by one-pot, metal-free superacid-catalyzed reaction of trifluoromethylalkyl (1a–1c) and trifluoromethylaryl (1d–1h) ketones with the linear, nonactivated, multiring aromatic hydrocarbons biphenyl (A), p-terphenyl (B), and p-quaterphenyl (C).The polymerizations were performed at room temperature in the Bronsted superacid trifluoromethanesulfonic acid (CF3SO3H, TFSA) and in a mixture of TFSA with methylene chloride. Polymerizations of trifluoromethyl ketones (1c, 1f–1h) bearing functional groups gave polymers with reactive lateral groups such as bromomethyl, 4-(N,N-dimethylamino)phenyl-, 3-sulfophenyl-, and 2,3,4,5,6-pentafluorophenyl. The polymers obtained were soluble in most common organic solvents and flexible transparent films could be cast from the solutions. 1H and 13C NMR analyses of the polymers synthesized revealed their linear structure with para-substitution in the phenylene fragments of the main chain. The m...