Synthesis and Characterization of Multiblock Copolymers Based on Hydrophilic Disulfonated Poly(arylene ether sulfone) and Hydrophobic Partially Fluorinated Poly(arylene ether ketone) for Fuel Cell Applications

Sulfonated fluorinated multiblock copolymers based on high performance polymers were synthesized and evaluated for use as proton exchange membranes (PEMs). The multi-block copolymers consist of fully disulfonated poly(arylene ether sulfone) and partially fluorinated poly(arylene ether ketone) as hydrophilic and hydrophobic segments, respectively. Synthesis of the multiblock copolymers was achieved by a condensation coupling reaction between controlled molecular weight hydrophilic and hydrophobic oligomers. The coupling reaction could be conducted at relatively low temperatures (e.g., 105 degrees C) by utilizing highly reactive hexafluorobenzene (HFB) as a linkage group. The low coupling reaction temperature could prevent a possible trans-etherification, which can randomize the hydrophilic-hydrophobic sequences. Tough ductile membranes were prepared by solution casting and their membrane properties were evaluated. With similar ion exchange capacities (IECs), proton conductivity and water uptake were strongly influenced by the hydrophilic and hydrophobic block sequence lengths. Conductivity and water uptake increased with increasing block length by developing nano-phase separated morphologies. Atomic force microscopy (AFM) and transmission electron microscopy (TEM) experiments revealed that the connectivity of the hydrophilic segments was enhanced by increasing the block length. The systematic synthesis and characterization of the copolymers are reported. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 214-222, 2010