Phase transitions during membrane formation of polylactides. I. A morphological study of membranes obtained from the system polylactide-chloroform-methanol

The influence of solid-liquid demixing, liquid-liquid demixing and vitrification on the morphology of polylactide membranes has been investigated. To study the effects of crystallization of polylactides on the membrane and morphology, polylactides of varying stereoregularity were used. The polymers applied were poly--lactide (PLLA) and copolymers with different molar ratios of -lactide and -lactide [poly-L95/D5-lactide (PLA95), poly-L80/D20-lactide (PLA80) and poly-L50/D50-lactide (PDLLA)]. Solutions of polylactides in chloroform cast on a glass plate were immersed in methanol. From solutions containing the slowly crystallizing PLA80 or uncrystallizable PDLLA porous membranes were obtained if the phase separated system was removed from the nonsolvent bath within a few hours after immersion. After longer equilibration times in methanol the structure collapsed. The swelling in the nonsolvent methanol was too high to allow stabilization of the liquid-liquid demixed structure by vitrification. Stable membranes were easily obtained with more rapidly crystallizing polymers like PLLA. Casting solutions with low PLLA concentrations gave membranes with a cellular morphology due to liquid-liquid demixing by nucleation and growth of a polymer poor phase. Crystallization only played a role in the fixation of the liquid-liquid demixed structure. At increasing PLLA concentrations the demixing sequence gradually reversed to crystallization followed by liquid-liquid demixing. In these cases membranes with porous spherulites or spherulites surrounded with a cellular layer were obtained.