Synthesis and characterization of postsulfonated poly(arylene ether sulfone) diblock copolymers for proton exchange membranes

Sulfonated poly(arylene ether sulfone) diblock copolymers were studied through the postsulfonation process. Two kinds of hydrophobic oligomers with a molecular weight of 20 kDa were prepared in advance as block sequences and then coupled together to obtain diblock copolymers. One oligomer was synthesized from bis(4‐hydroxyphenyl) sulfone (BHPS) and 4,4′‐difluorodiphenyl sulfone (DFDPS), which was thought to be incapable of postsulfonation. The other oligomer was synthesized from hydroquinone (HQ) and 4,4′‐dichlorodiphenyl sulfone (DCDPS), which successfully proceeded to a hydrophilic sequence as a result of sulfonation onto the HQ moiety after the coupling reaction. Consequently, a diblock copolymer with high molecular weight was obtained; although its intrinsic viscosity was too low to form a tough membrane because of its high rigidity and high crystallinity. Therefore, the use of decafluorobiphenyl (10F) as a termination reagent was investigated with the aim of achieving higher coupling reactivity and a kinky property. As a result, a sulfonated diblock copolymer was successfully obtained with sufficient molecular weight and intrinsic viscosity to form the membrane, as well as with adequate thermal properties. It was observed that proton conductivity, water uptake, and the water diffusion coefficient increased with higher ion exchange capacity. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 700–712, 2009