Branched sulfonated poly(aryl ether ketone) copolymers (Br-SPAEKs) were synthesized based on 4,4'-(hexafluoroisopropylidene) diphenol (6F-BPA, A2monomer), 4,4'-difluorobenzophenone (DFBP, unsulfonated B2monomer), 3,3'-disodiumsulfonyl-4,4'-difluorobenzophenone (SDFBP, sulfonated B2monomer) and 2,4',6-trifluoro-benzophenone (TFBP, branched BB'2monomer). Structures of Br-SPAEKs were confirmed by FT-IR and NMR. Compared to linear sulfonated poly(aryl ether ketone) copolymer (L-SPAEK) membrane with similar ion exchange capacity (IEC), these Br-SPAEK membranes showed a higher proton conductivity and a lower methanol permeability. This synergistic effect on proton conductivity and methanol permeability was mainly due to the characteristics of large free volume and similar to cross-linking architecture arising from the introduction of the branched monomers. Moreover, the Br-SPAEK membrane containing 20mol% branched monomer possesses the best selectivity, and the value of selectivity is almost 3 times higher than that of L-SPAEK. Proton conductivities of Br-SPAEK membranes are higher than 10-2S/cm and increase gradually with increasing temperature. At 80°C, the proton conductivity of Br-20-SPAEK-40 (branched monomer of 20mol% and sulfonated monomer of 40mol%) membrane reaches 0.121Scm-1, compare to that of Nafion 117 (0.139Scm-1). Additionally, the methanol permeability of Br-20-SPAEK-40 is one order magnitude lower than that of Nafion 117. © 2013 Elsevier B.V.
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