Lyotropic Liquid Crystalline Property and Organized Structure in High Proton-Conductive Sulfonated Semialicyclic Oligoimide Thin Films.

Fully aromatic sulfonated polyimides with a rigid backbone can form lamellar structures under humidified conditions, thereby facilitating the transmission of protons in ionomers. Herein, we synthesized a new sulfonated semialicyclic oligoimide composed of 1,2,3,4-cyclopentanetetracarboxylic dianhydride (CPDA) and 3,3'-bis-(sulfopropoxy)-4,4'-diaminobiphenyl to investigate the influence of molecular organized structure and proton conductivity with lower molecular weight. The weight-average molecular weight ( M w ) determined by gel permeation chromatography was 9300. Humidity-controlled grazing incidence X-ray scattering revealed that one scattering was observed in the out-of-plane direction and showed that the scattering position shifted to a lower angle as the humidity increased. A loosely packed lamellar structure was formed by lyotropic liquid crystalline properties. Although the ch-pack aggregation of the present oligomer was reduced by substitution to the semialicyclic CPDA from the aromatic backbone, the formation of a distinct organized structure in the oligomeric form was observed because of the linear conformational backbone. This report is the first-time observation of the lamellar structure in such a low-molecular-weight oligoimide thin film. The thin film exhibited a high conductivity of 0.2 (±0.01) S cm -1 under 298 K and 95% relative humidity, which is the highest value compared to the other reported sulfonated polyimide thin films with comparable molecular weight.