Dilute-solution properties of arborescent polystyrenes: further evidence for perturbed-hard-sphere behavior

Toward improved understanding of the dilute-solution properties of arborescent polystyrenes, new measurements are reported for osmotic second virial coefficients and for intrinsic viscosities in three common organic solvents. As observed for other branched polymers, branching decreases the second virial coefficient in good solvents and lowers the theta temperature for a polymer–solvent system. For generation-zero arborescent polystyrene in methylcyclohexane, the theta temperature is 36±2°C. espondence between intrinsic viscosity and second virial coefficient, valid for hard-spheres solutions, holds in good solvents; this correspondence improves with decreasing branch molecular weight. motic-pressure data are interpreted with a colloid-like thermodynamic framework using a van der Waals-type equation of state. The reference state is the hard sphere and the perturbation is given by an attraction decaying with the sixth power of the center-to-center distance between polymers. The hard-sphere diameter is obtained from intrinsic-viscosity data. Predicted and observed osmotic pressures are in good agreement.