In this study, we have explored the first use of the siliceous MCM-41 molecular sieve as an additive to enhance the gas permeability characteristics of a high-performance polysulfone. For all gases tested (N 2 , O 2 , CO 2 , CH 4 ), the permeability increased in proportion to the weight percent of MCM-41 present in the film. At the same time, calculated ideal selectivities remained almost constant irrespective of MCM-41 loading. ATR-FTIR spectroscopy, supported by molecular mechanics calculations, revealed hydrogen-bonding interactions between polysulfone and MCM-41. The increase in permeability, without a loss in selectivity, which is not observed with dense silica or zeolites, suggests that using a mesoporous molecular sieve as the adsorbent additive enhances contact and penetration of the polymer.

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 Brønsted superacid trifluoromethanesulfonic acid (CF 3 SO 3 H, 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. 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.

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Novel, linear, high-molecular-weight single-strand heteroaromatic polymers and copolymers containing 9H-xanthene moieties in the backbone were synthesized by metal-free superacid-catalyzed stoichiometric and nonstoichiometric step-growth polymerizations of carbonyl compounds bearing electron-withdrawing substituents with bisphenols. The electrophilic aromatic substitution reactions of ketones with phenol fragments occur exclusively in ortho-positions to the hydroxy phenol group and followed by highly efficient cyclodehydration reaction of hydroxyl-containing intermediates to give corresponding substituted 9H-xanthene-2,7-diyl polymers. 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 and nitrobenzene.