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 (1 a–1c ) and trifluoromethylaryl (1 d–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 Brønsted superacid trifluoromethanesulfonic acid (CF 3 SO 3 H, TFSA) and in a mixture of TFSA with methylene chloride. Polymerizations of trifluoromethyl ketones ( 1c, 1 f–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. 1 H and 13 C NMR analyses of the polymers synthesized revealed their linear structure with para-substitution in the phenylene fragments of the main chain. The molecular weights ( M w ) of the polymers based on trifluoromethylalkyl ketones and aromatic are very high and reach 1 000 000, while the molecular weights of the polymers based on trifluoromethylaryl ketones and aromatic ranged from 30 000 to 300 000 g/mol. The polydispersity of the polymers is generally less than 2. The polymers also possess high thermostability. Mechanistic aspects of polymerization mechanism have been discussed, and a new approach for monomer design has been proposed.