Transition phenomena of polymers in mixed solvents in the vicinity of theta conditions: Effect of preferential adsorption

Viscosimetric measurements were obtained with the ternary systems polystyrene/dioxane/methanol, polystyrene/benzene/methanol and poly(methyl methacrylate)/dioxane/cyclohexane, changing the solvent mixture composition at constant temperature. The polystyrene and poly(methyl methacrylate) systems exhibit a transition phenomenon with solvent-mixture composition in which the polymer is just above the theta condition. In the case where two theta conditions occur ((θ-intra, θ-inter) the transition point is closely related to the intramolecular theta conditions. Moreover the intramolecular theta conditions vary with the molecular weight in the region of molecular weights where the preferential adsorption also varies. This variation induces a variation of the transition point with molecular weight which obeys a formula analogous to that giving the variation of the preferential adsorption with molecular weight.