Anhydrous proton conducting membranes based on crosslinked graft copolymer electrolytes

A comb-like copolymer consisting of a poly(vinylidene fluoride-co-chlorotrifluoroethylene) backbone and poly(hydroxy ethyl acrylate) side chains, i.e. P(VDF-co-CTFE)-g-PHEA, was synthesized through atom transfer radical polymerization (ATRP) using CTFE units as a macroinitiator. Successful synthesis and a microphase-separated structure of the copolymer were confirmed by proton nuclear magnetic resonance (H-1 NMR), FT-IR spectroscopy, and transmission electron microscopy (TEM). This comb-like polymer was crosslinked with 4,5-imidazole dicarboxylic acid (IDA) via the esterification of the -OH groups of PHEA and the -COOH groups of IDA. Upon doping with phosphoric acid (H3PO4) to form imidazole-H3PO4 complexes, the proton conductivity of the membranes continuously increased with increasing H3PO4 content. A maximum proton conductivity of 0.015 S/cm was achieved at 120 degrees C under anhydrous conditions. In addition, these P(VDF-co-CTFE)-g-PHEA/IDA/H3PO4 membranes exhibited good mechanical properties (765 MPa of Young's modulus), and high thermal stability up to 250 degrees C, as determined by a universal testing machine (UTM) and thermal gravimetric analysis (TGA), respectively. (C) 2008 Elsevier B.V. All rights reserved.