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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/ma801000uMacromolecules, 41, 20, pp. 7411-7417, 2008 Linear high molecular weight ladder polymers by optimized polycondensation of tetrahydroxytetramethylspirobisindane and 1,4-dicyanotetrafluorobenzene Song, Jingshe; Du, Naiying; Dai, Ying; Robertson, Gilles; Guiver, Michael; Thomas, Sylvie; Pinnau, Ingo ABSTRACT: A study on the optimization of conditions for polycondensation of 3,3,3′,3′-tetramethyl-1,1′-spirobisindane-5,5′,6,6′-tetrol, TTSBI, with 1,4-dicyanotetrafluorobenzene (DCTB) in dimethylformamide (DMF) at 50-70°C is reported. A linear PIM-1 polymer (PIM ) polymer with intrinsic microporosity) with high molecular weight was obtained by optimized reaction conditions. Of the solvents tested, DMF was the preferred solvent for this reaction. The optimized molar ratio TTSBI/DCTB/K 2 CO 3 was 1/1/2.04. The mechanism of PIM-1 crosslinking during polymerization was studied, and gel-free, high molecular weight PIM-1 polymer was prepared. The physical properties of anhydrous K 2 CO 3 significantly affected the reaction rate. Flexible tough polymer films were cast from PIM-1 solution in chloroform, and pure permeability data are reported for several gases.