Synthesis of proton-conducting block copolymer membranes composed of a fluorinated segment and a sulfonic acid segment

Diblock copolymer membranes having a fluorinated segment and a sulfonic acid segment were prepared by living radical polymerization, solution casting, and crosslinking, followed by heat treatment. Diblock copolymers of 2,3,4,5,6-penta-fluorostyrene (PFS)/4-(1-methylsilacyclobutyl)styrene (SBS) and neopentyl styrenesulfonate (SSPen) (poly(PFS-co-SBS)-b-polySSPen)s were synthesized by nitoroxy-mediated living radical polymerization. Self-standing crosslinked membranes were obtained by casting a THF solution of the block copolymer with Pt catalyst. Heat treatment of the membrane at 230 degrees C induced decomposition of the neopentyl sulfonate esters to provide block copolymer membranes having a fluorinated segment and a free sulfonic acid segment. It was confirmed that the block copolymer with a high sulfonic acid content exhibited high ion exchange capacity and high proton conductivity as well as high thermal stability. (c) 2008 Wiley Periodicals, Inc.