Rheological behavior of oligomeric ionomers

The rheological behavior of the alkali metal salts of oligomeric sulfonated polystyrene (PS) ionomers was characterized using dynamic and steady shear measurements. The starting PS had a weight average molecular weight of 4000 g/mol and a narrow molecular weight distribution (1.06). Two sulfonation levels were examined, 2.5 and 4.8 mol %, which corresponded, respectively, to one and two sulfonate groups per chain on average. The ionomers exhibited nanophase separation of an ion-rich phase, and as a consequence, time-temperature superposition failed for all samples. Sulfonation increased the melt viscosity of the ionomers, as much as seven orders of magnitude. The zero shear viscosity scaled as cq/a, where c was the concentration of the ionic groups, q was the charge of the cation, and a was the cation radius, and although the molecular weight of the parent polystyrene was much lower than the entanglement molecular weight, the ionomer melts exhibited strong elastic behavior. The flow activation energy of the ionomers was similar to that of high molecular weight PS and the calculated molecular weight between entanglements of the ionomers was the same as for PS.