Phase behavior of polylactides in solvent-nonsolvent mixtures

P. van de Witte, P.J. Dijkstra, J.W.A. van den Berg, J. Feijen

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Isothermal phase diagrams for the semicrystalline poly-L-lactide (PLLA) and the amorphous poly-DL-lactide (PDLLA) in combination with several solvent-nonsolvent combinations (dioxane/water, dioxane/methanol, chloroform/methanol, and NMP/water) have been determined. The locations of the liquid-liquid miscibility gap, the solid-liquid miscibility gap and the vitrification boundary in the isothermal phase diagrams at 25°C were identified. The liquid-liquid miscibility gap for the systems with PLLA was located in the same composition range as the corresponding systems with PDLLA. For the systems containing PLLA solid-liquid demixing was thermodynamically preferred over liquid-liquid demixing. Attempts were made to correlate the experimental findings with predictions on the basis of the Flory-Huggins theory for ternary solutions using interaction parameters derived from independent experiments. Qualitative agreement was found between the theoretical predictions and the experimentally obtained liquid-liquid miscibility gap. No good agreement was found for the solid-liquid miscibility gap.
Original languageEnglish
Pages (from-to)2553-2568
Number of pages16
JournalJournal of polymer science. Part B: Polymer physics
Issue number34
Publication statusPublished - 1996


  • METIS-105385
  • IR-71258
  • demixing
  • Ternary phase diagrams
  • polylactides
  • Membranes
  • Flory-Huggins

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