Novel Ordered Crown Ether-Containing Polyimides for Ion Conduction

We report the synthesis and characterization of thermally-stable polyimides for use as battery and fuel cell electrolyte membranes. Dianhydrides used were 1,4,5,8- naphthalenetetracarboxylic dianhydride and/or 4,4'-(hexafluoroisopropylidene)diphthalic anhydride. Diamines used were anti-4,4-diaminodibenzo-l8-crown-6, 4,4'- diaminodibenzo-24-crown-8, 2,2-bis(4-aminophenyl)hexafluoropropane, and/or 2,5- diaminobenzenesulfonic acid. The polymers were characterized using electrochemical impedance spectroscopy (EIS), thermal analysis and X-ray diffraction. Polymers containing the hexafluoroisopropylidene (HFIP) group were soluble in common organic solvents, while polymers without the HFIP group were very poorly soluble. Sulfonation yields polymers that are sparingly soluble in aqueous base and/or methanol. Degree of sulfonation, determined by titration, was between one and three sulfonate groups per repeat unit. Proton conductivity was determined as a function of water content, with a maximum conductivity of l x 10(exp -2) per centimeter when fully hydrated. Crown ether-containing polymers exhibit a high degree of order that may be indicative of crown ether channel formation, which may facilitate Li(+) transport for use in battery membranes.