Effect of the Hydrophilic Component in Aromatic Ionomers: Simple Structure Provides Improved Properties as Fuel Cell Membranes.

To elucidate the effect of the hydrophilic component on the properties of aromatic ionomers, we have designed for the first time one of the simplest possible structures, the sulfo-1,4-phenylene unit, as the hydrophilic component. A modified Ni-mediated coupling polymerization produced the title aromatic ionomers composed of sulfonated -phenylene groups and oligo(arylene ether sulfone ketone)s, as high-molecular-weight polymers ( = 202-240 kDa), resulting in the formation of tough, flexible membranes. The aromatic ionomer membranes showed well-developed hydrophilic/hydrophobic phase separation. Comparison with our previous aromatic ionomer membrane containing sulfonated benzophenone groups as a hydrophilic component revealed that the simple sulfophenylene structure (i.e., no polar groups such as ether, ketone, or sulfone groups in the hydrophilic component) was effective for the improvement of the membrane properties, i.e., reduced water uptake and excellent mechanical stability under humidified conditions. Furthermore, because of the high local ion exchange capacity (IEC), the simple structure led to high proton conductivity, especially at low humidity (reaching up to ca. 7.3 mS/cm at 80 °C and 20% RH), which is one of the highest values reported thus far. The improved properties of the membranes were also confirmed in an operating fuel cell.