Sulfonated poly(fluorene-co-sulfone)ether membranes containing perfluorocyclobutane groups for fuel cell applications

A new class of sulfonated poly(fluorene-co-sulfone)ether membranes containing perfluorocyclobutane (PFCB) groups were synthesized and characterized in terms of their electrochemical properties as proton exchange membranes for fuel cells. Two monomers, 9,9-bis(4-trifluorovinyloxyphenyl)fluorene and 4,4′-sulfonyl-bis(trifluorovinyloxy)biphenyl were synthesized and statistically copolymerized by thermal [2π + 2π] cycloaddition to yield a series of polymers containing 0–60 mol% of fluorenyl content (PFS-X). The copolymers were then sulfonated using chlorosulfonic acid to afford five kinds of ionomers with different sulfonation levels (SPFS-X), which were cast into membranes and analyzed in terms of electrochemical properties. It was found that the ion exchange capacity (IEC), water uptake, proton conductivity and methanol permeability values of SPFS-X increased with the increment of the sulfonated fluorenyl content. The proton conductivities of SPFS-50 and -60 with high IECs and water uptake values were higher than those of Nafion-115 between 25 and 80 °C. The methanol permeability of SPFS-X was considerably lower than that of Nafion-115.