Influence of Molecular Weight on the Enzymatic Degradation of PLA Isomer Blends by a Langmuir System

Polylactides (PLAs) and lactide copolymers are biodegradable, compostable, and derived from renewable resources, offering a sustainable alternative to petroleum-based synthetic polymers owing to their advantages of comparable mechanical properties with commodity plastics and biodegradability. Their hydrolytic stability and thermal properties can affect their potential for long-lasting applications. However, stereocomplex crystallization is a robust method between isomer PLAs that allows significant amelioration in copolymer properties, such as thermal stability, mechanical properties, and biocompatibility, through substantial intermolecular interactions amid l-lactyl and d-lactyl sequences, which have been the key approach to initial degradation rate and further PLA applications. It was demonstrated that the essential parameters affecting stereocomplexation are the mixing ratio and the chain length of each unit sequence. This study deals with the molecular weight, one of the specific interactions between isomers of PLAs. A solution polymerization method was applied to control molecular weight and chain architecture. The stereocomplexation was monitored with DSC. It was confirmed that the lower molecular weight polymer showed a higher degradation rate, as a hydrolyzed fragment having a molecular weight below a certain length dissolves into the water. To systematically explore the critical contribution of molecular weights, the Langmuir system was used to observe the stereocomplexation effect and the overall degradation rate.