Effect of composition of added random copolymer on the phase behavior of block copolymer

Blends of styrene–butadiene diblock copolymer (S–B, 52 wt% styrene content) and styrene–butadiene random copolymer (SBR) of various styrene compositions were studied by small-angle X-ray scattering, light scattering, and transmission electron microscopy. The composition of random copolymer plays an important role in the solubilization of SBR in S–B. The order–disorder transition temperature, TODT, decreases linearly with the addition of SBR. TODT decreases as the symmetry in SBR composition increases and shows the highest value in the case of homopolymers. Asymmetric butadiene-rich SBR dissolves mostly into PB microdomain of S–B to increase lamella microdomain spacing, D, and its addition makes the overall microdomains of S and B in the mixture more asymmetrical. Symmetric SBR is localized into the interface of S–B microdomain to reduce unfavorable S–B contact at the interface. The phase diagram for S–B containing asymmetric SBR shows a succession of mixed mesophases of different morphologies from lamellae and cylinder to disordered liquid phases, whereas the phase diagram containing symmetric SBR shows two homogeneous phases and one region of two-phase coexistence, where macroscopically separated phases coexist together.