Macromolecules, Vol.35, No.17, 6707-6713, 2002
Novel sulfonated polyimides as polyelectrolytes for fuel cell application. 2. Synthesis and proton conductivity, of polyimides from 9,9-bis(4-aminophenyl)fluorene-2,7-disulfonic acid
A new sulfonated diamine monomer., 9,9-bis(4-aminophenyl)fluorene-2,7-disulfonic acid (BAPFDS), was synthesized by direct sulfonation of the parent diamine, 9,9-bis(4-aminophenyl)fluorene (BAPF), using fuming sulfuric acid as the sulfonating reagent. A series of sulfonated polyimides with different sulfonation degrees were prepared from 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA), BAPFDS, and common nonsulfonated diamines. The resulting sulfonated polyimides generally showed good solubility in m-cresol and DMSO. Proton conductivities of these polyimide membranes were measured as the functions of relative humidity and temperature. The resulting homopolyimide, NTDA-BAPFDS, displayed proton conductivities quite similar to those of Nafion 117 in the whole humidity range. (RH < 100%). At 100% relative humidity, all the BAPFDS-based polyimide membranes showed proton conductivities similar to or higher than those of Nafion 117. In addition, BAPFDS-based polyimide membranes exhibited much better water stability than those derived from, a widely used sulfonated diamine, 2,2'-benzidinedisulfonic acid (BDSA), with similar IEC. This is probably because of the higher basicity of BAPFDS, which is favorable for maintaining the stability of imido rings.