Linear versus Three-Arm Star Polybutadiene: Effects of Polymer Architecture on the Thermodynamic Solution Behavior

The interaction of linear and of three-arm star polybutadiene (PB) with THF was studied in the temperature range between 25 and 55 °C. Information for dilute solution rests on light scattering experiments; Flory–Huggins interaction parameter χ stem from vapor pressure measurements as a function of φ, the volume fraction of polymer. Despite the minute divergence in the architecture, the second osmotic virial coefficients of the two PBs differ noticeably. The present work demonstrates that these disparities become much more pronounced as φ increases and that they depend strongly on temperature. These findings are interpreted on the basis of an approach accounting for the effects of chain conn…