Surface morphology and Flory–Huggins interaction strength in UCST blend system comprising poly(4-methyl styrene) and isotactic polystyrene

Abstract

The surface morphology and polymer–polymer interaction parameter (χ12) of UCST blend systems comprising isotactic polystyrene and poly(4-methyl styrene) (P4MS) were investigated using atomic-force microscopy (AFM) and differential scanning calorimetry (DSC). From the measured glass transition temperature and the specific heat increments (ΔCp) at Tg, it was found that the P4MS dissolved more easily in the iPS rich-phase than did the iPS in the P4MS rich-phase. AFM result also supported that the compatibility increased more in the regions of P4MS-rich compositions than in the regions of PS-rich compositions of the PS/P4MS blends. From the measured Tg’s and apparent weight fractions of iPS and P4MS dissolved in each phase, the values of the Flory–Huggins interaction parameter (χ12) were determined to be 0.0163–0.0232 depending on the composition. These results indicate that the χ12 is quite dependend on the apparent volume fraction of the polymers dissolved in each phase. The values of χ12 calculated from this work (method based on Tg’s of phases) were lower than those estimated using an earlier method based on the UCST or clarity temperatures. All values of χ12 are greater than the values of interaction parameter at the critical point (χ12)c. This fact indicates that the iPS/P4MS blend are immiscible for all blend compositions. The surface of the phase-separated blend system was mostly covered with the P4MS rich-phase owing to its lower surface free energy in comparison with that of the neat iPS. The mechanism of surface phase separation for the P4MS blends with aPS or iPS is governed by two factors: (1) difference in the solubility of the two polymers in the solvent and (2) surface free energy.