Local Order and Dynamics of Nanoconstrained Ethylene-Butylene Chain Segments in SEBS

Subtle alterations in the mid-block of polystyrene-b-poly (ethylene-co-butylene)-b-polystyrene (SEBS) have a significant impact on the mechanical properties of the resulting microphase separated materials. In samples with high butylene content, the ethylene-co-butylene (EB) phase behaves as a rubber, as seen by differential scanning calorimetry (DSC), time domain (TD) and Magic Angle Spinning (MAS) NMR, X-ray scattering at small (SAXS), and wide (WAXS) angles. In samples where the butylene content is lower—but still sufficient to prevent crystallization in bulk EB—the DSC thermogram presents a broad endothermic transition upon heating from 221 to 300 K. TD NMR, supported by WAXS and dielectric spectroscopy measurements, probed the dynamic phenomena of EB during this transition. The results suggest the existence of a rotator phase for the EB block below room temperature, as a result of nanoconfinement.