Segmental dynamics of disordered styrene–isoprene tetrablock copolymers

Abstract

The local segmental dynamics of four styrene-b-isoprene-b-styrene-b-isoprene (SISI) tetrablock copolymers with different styrene composition fs and constant total degree of polymerization N≈120 has been studied in the disordered state in the nano-picosecond time scale, by incoherent quasielastic neutron (QENS), and Brillouin (BS) and depolarized Rayleigh (DRS) light scattering. Far above the glass transition temperature, all three techniques demonstrate the presence of two distinct time scales from which the fast segmental relaxation was quantitatively resolved. This process is associated with the mobility of the polyisoprene (PI) component, and is moderately slower and possesses a broader distribution of relaxation times than in bulk PI. The comparison between the correlation times of DRS and the characteristic times of QENS suggest that segment (hydrogen nucleus) diffusion over a distance of ≈0.8 nm suffices for the loss of local orientation correlations. The faster times of the BS experiment correspond to shorter displacements, ≈0.3 nm. These results demonstrate that the segmental dynamics of the PI are much faster than would be inferred from the monomeric friction factor of PI previously extracted by diffusion and viscosity measurements in the same tetrablock matrices. This, in turn, indicates a substantial local spatial heterogeneity in the segmental dynamics. The slow process is due to the PS segments, which do not relax, appreciably on the time scales accessible here.