Hydrodynamic radius and intrinsic viscosity of polystyrene in the crossover region from θ to good‐solvent conditions

Abstract

AbstractThe radius of gyration Rg, the hydrodynamic radius Rh, and the intrinsic viscosity [η] have been measured for polystyrene in cyclohexane (at the θ temperature and 44.5°C), 2‐butanone (at 30°C), and toluene (at 30°C) in the molecular weight range 2.38 × 105 ≤ Mw ≤ 5.47 × 106 to elucidate the excluded‐volume effects on dynamical behavior in dilute polymer solutions in the crossover region from θ to good‐solvent conditions. The results are compared with theoretical predictions of current thermal blob theories and the Pade approximant theory of Tanaka. It is found that the ratio of Rh/Rg decreases with an increase in the excluded‐volume effect, following the prediction of the simple blob theory, but that its magnitude is about 15% higher than the theoretical value. Experimental variation of [η] with Rh and/or Rg lies in between predictions of the scaling law and the Pade approximant. The concentration dependence of the diffusion coefficient is also compared with predictions of current theories.