Structure and properties of oil extended styrene butadiene block copolymers

Abstract The relationships between mechanical properties and structure of rapidly spin cast styrene‐butadiene‐styrene (SBS) block copolymers diluted with two different types of mineral oil are discussed. Small angle X‐ray scattering (SAXS) measurements indicate that both oils go mainly into the rubbery polybutadiene phase. While during rapid spin casting the paraffinic oil improves the phase separation of polystyrene (PS) and polybutadiene (PB), the opposite is true for the aromatic oil. The measurements also suggest that the oils cause a preferential swelling of the superstructure along the longitudinal direction of the cylindrical PS domains. From this, it can be concluded that a larger number of interconnecting PB chains is present in the cross direction than in the longitudinal one. With increasing oil content, a further decrease of interconnecting chains in the latter direction may be the reason for the decrease of the tensile modulus. Furthermore, above a critical value of dilution (33 wt percent for paraffinic oil, 50 wt percent for the aromatic one), more and more spherical domains are formed instead of the cylindrical ones. This morphological transition explains the step present in the double logarithmic plot of the large strain tensile modulus as a function of oil dilution.