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NRC Publications Archive Archives des publications du CNRCThis publication could be one of several versions: author's original, accepted manuscript or the publisher's version. / La version de cette publication peut être l'une des suivantes : la version prépublication de l'auteur, la version acceptée du manuscrit ou la version de l'éditeur. For the publisher's version, please access the DOI link below./ Pour consulter la version de l'éditeur, utilisez le lien DOI ci-dessous.http://dx.doi.org/10.1021/ma035739i Macromolecules, 37, 4, pp. 1403Macromolecules, 37, 4, pp. -1410Macromolecules, 37, 4, pp. , 2004 Preparation and characterization of polysulfones containing both hexafluoroisopropylidene and trimethylsilyl groups as gas separation membrane materials Dai, Y.; Guiver, Michael; Robertson, Gilles; Kang, Y.; Lee, Kunchan; Jho, J. Science and Technology, P.O. Box 131, Cheongryang, Seoul 130-650, Korea; and Hyperstructured Organic Materials Research Center and School of Chemical Engineering, Seoul National University, Seoul 151-744, Korea Received November 19, 2003; Revised Manuscript Received December 16, 2003 ABSTRACT: Trimethylsilylated derivatives of hexafluoropolysulfone (6FPSf) and tetramethylhexafluoropolysulfone (TM6FPSf) were prepared by reaction of lithiated polymer intermediates with halotrimethylsilane electrophiles for a membrane gas separation study to compare improvements in gas permeabilities with those of unmodified polymers. Ortho sulfone substituted 6FPSf and TM6FPSf having pendant trimethylsilyl (TMS) groups were obtained by a two-step process involving first direct lithiation of 6FPSf and TM6FPSf solutions with n-butyllithium to afford ortho sulfone dilithiated intermediates, followed by reaction with a TMS electrophile. The corresponding ortho ether 6FPSf derivative was obtained by lithiation of dibrominated 6FPSf at the bromine sites, followed by reaction with a TMS electrophile. The degree of substitution (DS) of the TMS groups was g2.0 and was dependent on the molar ratio of n-butyllithium and electrophile quantity, electrophile reactivity, and reaction conditions. Detailed structural characterization and DS of the modified polymers were obtained by nuclear magnetic resonance spectroscopy. The glass transition temperatures and thermal stabilities were determined by differential scanning calorimetry and thermogravimetric analysis, respectively. Polymer chain d-spacing was investigated using wide-angle X-ray diffraction. Polymer free volume was calculated from the polymer density and specific van der Waals volume. The polymer gas permeability coefficients (P) were measured for He, CO 2,O 2, and N2. Both CO2 and O2 permeabilities of modified 6FPSf increased by 8-9-fold (P(CO2) ) 110 barre...