Journal of Polymer Science Part B: Polymer Physics, Vol.34, No.1, 181-192, 1996
Study of Mixed-Solvent Quality in a Polystyrene Dioctyl Phthalate Polystyrene System
Polymer solvent interactions in the ternary system high molecular weight polystyrene (HMPS), low molecular weight polystyrene (LMPS), and dioctyl phthalate (DOP) have been characterized by means of intrinsic viscometry (IV), dynamic light scattering (DLS), and static light scattering (SLS). Excluded volume exponents have been extracted from the scaling of intrinsic viscosity and translational diffusivity with polymer molecular weight for a mixed solvent of 13 wt % LMPS/87 wt % DOP. The value of the excluded volume exponent, nu = 0.45, indicates that HMPS in the mixed solvent DOP/LMPS has apparently assumed a reduced conformation relative to the theta condition. However, SLS measures of the second virial coefficient (A(2)) confirm that DOP is a theta solvent at our experimental temperature of 22 degrees C and indicate that the addition of LMPS increases A(2). SLS also suggests that neither solvent component is strongly preferentially adsorped into the HMPS coil. Our system then is a mixture of a theta solvent and a good solvent that exhibits poor solvent scaling behavior. We believe this to be the first demonstration of such behavior in a system that does not exhibit appreciable preferential adsorption. We conclude by examining our observations in the context of current descriptions of mixed solvent thermodynamics.
Keywords:LIGHT-SCATTERING;CONCENTRATION FLUCTUATIONS;POLYMER-SOLUTIONS;CHAIN;COLLAPSE;MIXTURES;DYNAMICS;TOLUENE;COIL