Multiblock‐co‐polymers with different ion exchange capacities were synthesised by nucleophilic aromatic step‐growth polycondensation of hydrophilic and hydrophobic oligomers. The main focus of this work was to investigate the dependence of oligomer reactivity on molecular weight and how the reaction conditions need to be changed to obtain high‐molecular multiblock‐co‐polymers, consisting of long block segments. Multiblock‐co‐polymers composed of short oligomers could be synthesised under mild reaction conditions. The coupling of longer oligomers required more basic reaction conditions, because the reactive functional end‐groups were shielded by the long oligomeric main chain. The membranes were investigated further in terms of their properties relevant for use as polymer electrolyte membrane in direct methanol fuel cells (DMFCs). The mechanical stability of the acidic polymers was improved through ionical crosslinking with basic polybenzimidazole. A series of membranes was tested in a self‐ and in an air‐breathing DMFC.

This contribution comprises an overview in the development of ionomers/ionomer (blend) membranes for fuel cells. The topics include the development of novel sulfonated monomers and homoand copolymers; the preparation of ionically cross-linked membranes prepared by mixing these polymers with different polybenzimidazoles (PBI); the application of these membranes to PEFC and DMFC; development of novel base-excess PBI/sulfonated polymer/H 3 PO 4 blend membranes, and test of these membranes in fuel cells at intermediate fuel cell operation temperatures (170-200°C). These membranes have been tested in a DMFC. The i/U polarization curves of the membranes showed a better performance than Nafion ® . Acid-base blend membranes were also applied to the HyS electrolysis process, showing good stability and electrolysis performance. Phosphonated polymers and ternary blend membranes for the application in intermediate T fuel cells have been developed as well. These membranes showed good chemical stability rivalling that of pure PBI membranes.