Abstract: | 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. © 1996 John Wiley & Sons, Inc. |