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RESEARCH PRODUCT

Cellulose/Water:  Liquid/Gas and Liquid/Liquid Phase Equilibria and Their Consistent Modeling

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Liquid/liquid and liquid/gas equilibria were measured for the water/cellulose system at 80 °C using three different polymer samples. For these experiments we prepared cellulose films of approximately 20−25 μm in thickness and determined their equilibrium swelling in water. Thereafter the polymer concentration in the mixed phase was increased by means of a stepwise removal of the volatile component, and the equilibrium vapor pressures were measured using an automated combination of head space sampling and gas chromatography. Contrary to the usual behavior of polymers, the swelling of cellulose increases as its molar mass becomes larger. The Flory−Huggins interaction parameters calculated from the measured vapor pressures pass a pronounced minimum as a function of composition; for high cellulose contents they are negative, whereas they become positive for water-rich mixtures. All experimental findings are consistently interpreted by means of an approach accounting explicitly for the effects of chain connect...