Determination of thermodynamic properties of isotactic poly(1-butene) at infinite dilution using density and inverse gas chromatography

Abstract

The partial molar volumes, V 1 M , and the molar volume of isotactic crystalline low-molecular-weight poly(1-butene), iPBu-1, V 1, have been calculated from the measured density of {iPBu-1 + solvent ( n-hexane, n-heptane, n-nonane, n-decane, p-xylene, cyclohexane and chloroform)} systems. Some of the thermodynamic quantities were also obtained for the iPBu-1 with eight hydrocarbons ( n-octane, n-decane, n-undecane, n-dodecane, n-tridecane, o-xylene, m-xylene, p-xylene) by the method of inverse gas chromatography at various temperatures. The weight fraction activity coefficients of the solvent at infinite dilution, Ω 2 ∞ , and the Flory-Huggins thermodynamic interaction parameters, χ 21 ∞ , between polymer and solvents were determined. The partial molar free energy, Δ G 2 ∞ , the partial molar heat of mixing, Δ H 2 ∞ , at infinite dilution and the polymer solubility parameter, δ 1, were calculated. Additionally, the (solid + liquid) binary mixtures equilibria, SLE, of iPBu-1 with three hydrocarbons ( n-octane, n-decane and m-xylene) were studied by a dynamic method. By performing these experiments over a large concentration range, the T– x phase diagrams of the polymer–solvent systems were constructed. The excess Gibbs energy models were used to describe the nonideal behaviour of the liquid phase. The Ω 2 ∞ were determined from the solubility measurements and were predicted by using the UNIFAC FV model.