High-Pressure Reactivity of L,L-Lactide

L,L-Lactide, a dimer of L-lactic acid, is the typical monomer used for the catalytic synthesis of poly(L-lactic acid) (PLLA). We studied its phase diagram and reactivity at high pressure and high temperature by means of a diamond anvil cell. FTIR and Raman spectroscopy were employed to probe the changes occurring in the sample. An increase of temperature at pressure higher than 0.1 GPa revealed a solid-solid phase transition before the melting. A reaction was observed immediately after the melting with the almost complete transformation of the starting reactant to an amorphous poly(lactic acid) (PLA). The increase of pressure was found to accelerate the process, suggesting the reaction rate to be limited in the diffusion step. A steeper acceleration, likely due to multiphoton absorption processes of the 647.1 nm laser light by PLA, was observed in the Raman experiments.