Tuning the polylactide hydrolysis rate by plasticizer architecture and hydrophilicity without introducing new migrants.

The possibility to tune the hydrolytic degradation rate of polylactide by plasticizer architecture and hydrophilicity without introduction of new degradation products was investigated by subjecting polylactide with cyclic oligolactide and linear oligolactic acid additives to hydrolytic degradation at 37 and 60 °C for up to 39 weeks. The more hydrophilic oligolactic acid plasticizer led to larger water uptake and rapid migration of plasticizer from the films into the aging water. This resulted in a porous material more susceptible to further hydrolysis. During hydrolysis at 37 °C the mass loss was generally 10-20% higher for the material containing linear oligolactic acid plasticizers. The hydrolysis accelerating effect of the linear oligolactic acid is probably counteracted by the higher degree of crystallinity in the films containing oligolactic acid additives. The degradation process was monitored by measurements of mass loss, water uptake, molar mass changes, material composition changes, surface changes, and thermal properties. The water-soluble degradation products were analyzed by following pH changes and identified by electrospray ionization-mass spectrometry (ESI-MS). The time frame for formation of water-soluble products was influenced by the architecture and hydrophilicity of the plasticizer. Furthermore, the advantage with oligolactide and oligolactic acid plasticizers was clearly demonstrated as they do not introduce any new migrants into the degradation product patterns.