Hydrolysis of Polylactic Acid (PLA) and Polycaprolactone (PCL) in Aqueous Acetonitrile Solutions: Autocatalysis

Polylactic acid (PLA) is a hydrolytically degradable aliphatic polyester. The rate of polymer hydrolysis increases with time, and that has been attributed to the high reactivity of the terminal ester and the kinetics of autocatalysis. Hydrolysis is carried out in an acetonitrile/water solution to eliminate any solid-state contributions such as diffusion and crystallinity to the degradation process. A kinetic equation is derived to describe the autocatalytic effect of the increasing carboxylic acid end-group concentration. The results of solution hydrolysis are examined and found to fit the derived equation. Hydrolysis was also carried out with polycaprolactone (PCL) in acetonitrile, where reaction kinetics were found to differ from those of PLA. The PCL polymer required external acid catalysis by the addition of HCl, whereas hydrolysis of PLA was selfcatalyzed by the carboxylic acid end-groups.