Abstract
Polylactide (PLA) has become widely adopted across biomedical, packaging, and manufacturing sectors due to its biodegradability and renewable sourcing. However, the rapid growth in PLA consumption has created urgent challenges related to waste management and the cleaning of processing equipment. This study investigates glycolysis as a promising chemical depolymerization pathway for PLA recycling and in situ reactor cleaning. A systematic analysis of four glycolysis agents (GA) (ethylene glycol, diethylene glycol, propylene glycol, and glycerol) was performed across molar PLA:GA ratios from 1:0.125 to 1:4 at 220 °C, targeting the efficient conversion of high-molecular-weight PLA (Mn ≈ 165 kDa) into low-molecular-weight oligomers. Gel permeation chromatography (GPC) demonstrated that propylene glycol exhibited the highest depolymerization efficiency, yielding oligomers with Mn as low as 200 g·mol(-1) even at minimal glycolysis agent ratios, while glycerol produced hydroxyl-rich oligomers optimal for subsequent lactide synthesis. Hydroxyl value (HV) measurements showed excellent agreement with theoretical values (<5% deviation), allowing us to make an assumption about an approximate, close to near-quantitative con-version. Glycolysis products with Mw below 400 g·mol(-1) displayed excellent water solubility, making them particularly attractive for reactor cleaning applications. Using glycerol-derived (GL) oligomers (PLA:GL = 1:0.25), purified L-lactide with a melting point of 98.1 °C and high purity (>99%) was obtained through thermocatalytic depolymerization and five recrystallization cycles, as confirmed by (1)H nuclear magnetic resonance ((1)H NMR) and differential scanning calorimetry (DSC) analyses. The recovered lactide's high purity renders it suitable for ring-opening polymerization, enabling closed-loop PLA recycling schemes. Overall, glycolysis emerges as a highly promising chemical recycling route complementary to hydrolysis and pyrolysis: propylene glycol maximizes depolymerization efficiency for cleaning applications, while glycerol optimizes oligomer functionality for lactide recovery and advanced material synthesis. Our results provide practical guidelines for selecting glycolysis agents and conditions for cleaning and recycling applications.