Abstract
AbstractUsing a self‐constructed light scattering apparatus, the pressure dependence of the demixing temperature of solutions of PVC 20 000, PVC 37 000 and PVC 70 000 in THE/water was determined up to 1 000 bar for different compositions of the mixed solvent. (The numbers in the codes of the PVC specimens are their approximate molecular weights.) In contrast to the thetasolvents o‐xylene and phenetole, the solubility decreases with increasing pressure for all molecular weights and compositions under investigation typically by about 1 K/100 bar. The evaluation of the experimental findings demonstrates that the volume fraction of the nonsolvent in the mixed solvent, φ, is the variable that governs phase separation: For the present region of p and T, a given polymer solution demixes at a characteristic constant value of φ, no matter how it is reached. This fact allows the prediction of pressure influences from known pVT data of the pure components and measurements at atmospheric pressure. A qualitative theoretical understanding of the observed influences of p and T can be reached on the basis of the solubility parameter theory.
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