Simultaneous, Synergistic Control of Ion Exchange Capacity and Cross-Linking of Sterically-Protected Poly(benzimidazolium)s

The application of highly charged anion exchange membranes is often limited by strong water sorption leading to excessive swelling and eventual dissolution, especially at elevated temperatures. The cross-linking of polymers has been shown to be an excellent mitigation strategy but this often restricts membrane and ionomer processing methods. Here, we explore the reaction, stability, and utility of a cross-linking agent for the recently discovered class of cationic polymers: methylated, C2-protected poly(benzimidazolium)s. In situ reaction and formation of p-xylyl cross-linking groups is found to provide novel, highly functionalized, hydroxide-stable membranes and films with enhanced anion conductivities and superior mechanical properties compared to un-cross-linked polymers. The versatility of this strategy will be important in the design of polymers for the preparation of stable, hydroxide-conducting films, membranes, and ionomers.