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Fluorene-based poly(arylene ether sulfone)s containing clustered flexible pendant sulfonic acids as proton exchange membranes

NRC Institute for Chemical Process and Environmental Technology; National Research Council Canada
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Clean Energy Technologies; Technologies pour l'énergie propre
ECAT - Electrocatalysis; ECAT - Électrocatalyse
Clean Energy Technologies Program; Programme des technologies pour l'énergie propre
A new bisphenol monomer, 9,9-bis(3,5-dimethoxy-4-hydroxyphenyl) fluorene, was synthesized and polymerized to form fluorene-based poly(arylene ether sulfone) copolymers containing tetra-methoxy groups (MPAES). After converting the methoxy group to the reactive hydroxyl group, the respective side-chain type sulfonated copolymers (SPAES) were obtained by sulfobutylation. The polymers were characterized by 1H NMR, thermogravimetric analysis (TGA), water uptake, and proton and methanol transport for fuel cell applications. These SPAES copolymers had good overall properties as polymer electrolyte membrane (PEM) materials, having high proton conductivity in the range of 0.061-0.209 and 0.146- 0.365 S/cm at 30 and 80C (under hydrated conditions), respectively. SPAES-39 (IEC = 1.93 mequiv/g) showed higher or comparable proton conductivity than that of Nafion 117 at 50-95% RH (relative humidity). The methanol permeabilities of these membranes were in the range of 3.22 to 13.1 x 10-7 cm2/s, which is lower than Nafion (15.5 x 10-7 cm2/s). In comparison with some reported sulfonated poly(arylene ether sulfone)s containing pendent sulfophenyl groups, the present fluorene-based SPAES containing clustered flexible pendent aliphatic sulfonic acid groups displayed better properties, such as lower water uptake and higher proton conductivities. A combination of high proton conductivities, low water uptake, and low methanol permeabilities for selected SPAES indicates that they are good candidate proton exchange membrane materials for evaluation in fuel cell applications.
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