Synthesis and properties of novel sulfonated polyimides containing binaphthyl groups as proton-exchange membranes for fuel cells

A novel sulfonated diamine monomer, 2,2'-bis(p-aminophenoxy)-1,1'-binaphthyl-6,6'-disulfonic acid (BNDADS), was synthesized. A series of sulfonated polyimide copolymers containing 30-80 mol % BNDADS as a hydrophilic component were prepared. The copolymers showed excellent solubility and good film-forming capability. Atomic force microscopy phase images clearly showed hydrophilic/hydrophobic microphase separation. The relationship between the proton conductivity and degree of sulfonation was examined. The sulfonated polyimide copolymer with 60 mol % BNDADS showed higher proton conductivity (0.0945-0.161 S/cm) at 20-80 degrees C in liquid water. The membranes exhibited methanol permeability from 9 x 10(-8) to 5 X 10(-7) cm(2)/s at 20 degrees C, which was much lower than that of Nafion (2 x 10(-6) cm(2)/s). The copolymers were thermally stable up to 300 degrees C. The sulfonated polyimide copolymers with 30-60 mol % BNDADS showed reasonable mechanical strength; for example, the maximum tensile strength at break of the sulfonated polyimide copolymer with 40 mol % BNDADS was 80.6 MPa under high moisture conditions. The optimum concentration of BNDADS was found to be 60 mol % from the viewpoint of proton conductivity, methanol permeability, and membrane stability.