Morphologically controlled proton-conducting membranes using graft polymers possessing block copolymer graft chains

Ionic graft membranes comprising macromonomeric poly( styrene-block-styrene sulfonic acid) grafted polystyrene [PS-g-mac(PS-b-PSSA)] polymers were prepared by copolymerization of styrene and poly(styrene-block-sodium styrene sulfonate) (PS-b-PSSNa) macromonomers followed by ion-exchange. The latter were prepared with controlled molecular weight by stable free radical polymerization. Membranes exhibit varying degrees of phase separation. Membranes of low ion content are comprised of isolated ionic domains and exhibit low ionic conductivity. Increasing the number density of ionic graft chains in the polymer results in a network of nanochannels and a dramatic increase in ion conductivity. In comparison to analogous macromonomeric poly( styrene sulfonic acid) grafted polystyrene (PS-g-macPSSA) membranes, of similar ion exchange capacity (IEC) and PSSA chain length, dehydrated PS-g-mac(PS-b-PSSA) membranes consist of smaller, more densely connected ionic domains; however, water sorption and ionic conductivity are similar.