Synthesis of poly(arylene)s copolymers containing pendant sulfonic acid groups bonded to naphthalene as proton exchange membrane materials

摘要

A new series of wholly aromatic poly(arylene ether ether ketone ketone)s containing pendant sulfonic acid groups (SPAEEKK) were conveniently prepared by potassium carbonate mediated nucleophilic polycondensation reactions of inexpensive commercially available monomers: 1,3-bis(4-fluorobenzoyl)benzene (BFBB), sodium 6,7-dihydroxy-2-naphthalenesulfonate (DHNS), and 4,4′-biphenol or hydroquinone in N-methyl-2-pyrrolidone (NMP) at 170° C. FT-IR and NMR were used to characterize the structures and the sulfonate or sulfonic acid contents (SC) of the polymers. Flexible membrane films were obtained by casting N,N-dimethylacetamide (DMAc) solutions of copolymers. Membrane films in acid form were then obtained by treating the sodium form membrane films in 2 N sulfuric acid at room temperature. Glass transition temperatures (T_gs) and decomposition temperatures (T_ds) of SPAEEKKs in both sodium and acid forms were determined. Water uptake and swelling ratio values increased with SCs and temperatures. The proton conductivities of acid form membrane films increased with SC value and temperature and reached 5.6×10⁻²S/cm at 100° C. for SPAEEKK-100.