Influence of polymer molecular weight on selected thermodynamic properties of polymer/solvent systems and the application of the UNIFAC theory

The intrinsic viscosities of eleven narrow molecular weight distribution polystyrene samples ranging from number-average molecular weight 1820 to 1 292 000 have been determined in pure solvents of tetrahydrofuran and chloroform with a Ubbelohde No. 1 viscometer at 25°C. By combining the original and modified Fox-Flory viscosity treatments, respectively, with the Flory-Huggins Lattice theory, the interaction parameters were calculated. With the aid of original and modified UNIFAC methods the solvent activity, clustering function of the solvent, and the interaction parameter were computed and compared with the experimental data. It was established that the influence imposed by the polymer molecular weight on the activity of the solvent, the clustering function of solvent, and interaction parameter is insignificant. The modified UNIFAC method satisfactorily predicted the solvent activity as illustrated by previous investigators. However, both UNIFAC methods failed to predict the interaction parameter.