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Very rapid crystallization behaviors of poly(L-lactic acid) (PLLA) are observed at room temperature when it is precipitated from a chloroform solution into a large amount of alcohols (non-solvents). The resulting crystalline phase contains both a highly ordered (α) and less ordered (α′) modifications, and the fraction of these phases depends on the alcohols used as the non-solvents: methanol tends to produce the highly ordered phase. The degree of crystallinity tends to be high for lower alcohols. When the precipitation occurs in  n -hexane, almost no crystalline phase is formed, but a mesomorphic phase is formed as a precursor to the crystalline phase. The results suggest that the hydroxyl group of alcohols tends to promote the crystallization of PLLA. However, it is found that the precipitation in methanol at lower temperatures, such as 0°C, does not yield any crystalline phase. It is suggested that the present rapid crystallization during precipitation originates from the enhanced mobility of PLLA molecules in a metastable (non-equilibrium) liquid state.

Rapid crystallization and mesophase formation of poly(L-lactic acid) during precipitation from a solution