Continuous fractionation and solution properties of PVC, 2. Scrutiny of solvents, intrinsic viscosity

Investigations with ca. 100 organic liquids in a temperature range from −20°C to 90°C result in a survey of the solubility behaviour of PVC. The experimental results were compared with the predictions of the solubility parameter theory: Accepting δ = 9,75 (cal/cm3)1/2 as the solubility parameter for PVC, all solvents (except ketones in which PVC is soluble independent of their solubility parameters) are located within the range of δPVC ± 0,75. Only three of the 100 liquids examined turned out to be (endothermal) theta-solvents, namely the aromatic solvents o-xylene, phenetole and dimethyl phthalate. The theta-temperatures in o-xylene and phenetole were determined viscometrically by means of the temperature dependence of the Mark-Houwink exponent to be 84 and 88°C, respectively. Viscosity measurements were also performed in the temperature range of 25 to 60°C with solutions of PVC 75 000 in 10 thermodynamically good solvents used for rheological investigations. In all cases the intrinsic viscosities decrease slightly with increasing temperature, i.e., all solutions are weakly exothermal. The binary cluster integral, β, was determined (taking the monomeric unit as the statistical segment) and the polar contribution, βe, was calculated from Yamakawa's theory. The correlations between the non-polar part of (βn = β – βe) and the solubility parameter of the solvent, found by Utracki, were tested and found to be valid for the present systems, too.