POLYMERS FOR ADVANCED TECHNOLOGIES, vol.19, no.8, pp.1126-1132, 2008 (SCI-Expanded)
This paper describes our work on the synthesis of a series of sulfonated homo-/co-polyimides (SPI) which were obtained by post-sulfonation method over three steps. In the first step, 4,4′-oxydianiline (ODA) and 4,4′-diaminodiphenylsulfone (DDS) dissolved in N-methyl pyrrolidone (NMP) were reacted with benzophenonetetracarboxylic dianhydride (BTDA) in order to yield poly(amic acid) (PAA). Secondly, precipitated PAA was sulfonated via concentrated sulfuric acid (95–98%) at room temperature to give post-sulfonated PAA (PSPAA). Finally, PSPAA was converted into post-sulfonated PI (PSPI) by the thermal imidization method. PSPIs with ion exchange capacity (IEC) ranging from 0.20 to 0.67 meq/g were prepared. The thermal properties of the PSPIs were evaluated and high desulfonation temperature was found in the range of 190–350°C, suggesting the high stability of sulfonic acid groups. In water, PSPI-5 membrane displayed similar proton conductivity to Nafion®117, whereas this membrane showed poor conductivity in dry state. All PSPIs displayed good solubility in common polar aprotic solvents such as NMP and dimethylacetamide (DMAc). Furthermore, the effects of post-sulfonation reaction on chemical structure, thermal oxidative behavior, and physical properties of the PSPI membranes such as membrane quality/stability and water uptake were discussed.