Effect of solvents on closed-loop phase behavior of block copolymers

We studied the effect of solvent selectivity on the closed-loop phase behavior of a polystyrene-block-poly(n-pentyl methacrylate) copolymer. It was found that the lower disorder-to-order transition temperature (LDOT) and upper order-to-disorder transition temperature (UODT) consisting of the closed-loop were very sensitive to the selectivity of the solvent. With the addition of very small amounts of non-selective solvents such as di-n-octyl phthalate and dimethyl phthalate, the LDOT increased rapidly, whereas the UODT decreased dramatically; thus, the immiscibility loop was shrunk greatly. On the other hand, both the LDOT and UODT decreased with increasing amount of dodecanol, a highly selective solvent to poly(n-pentyl methacrylate) block. However, the decrease in the LDOT was greater than that of the UODT, leading to an increased immiscibility loop.