Sustainable Waterborne Polylactide Coatings Enabled by Hydrophobic Deep Eutectic Solvents Plasticization

This work presents an approach to water-dispersible polylactide (PLA) particle fabrication and their application in low-temperature film formation using a combination of mechanical dispersion and ultrasonication techniques. Stable PLA dispersions were obtained after removal of surfactant and allowed for thin-film preparation, exhibiting a significantly reduced minimum film formation temperature (MFFT) from 128 °C to 80 °C after reducing the characteristic particle size from ~2.2 µm to ~140 nm. To tailor the interfacial behavior and mechanical flexibility of the resulting coatings, a set of conventional and bio-based plasticizers was evaluated, including epoxidized fatty acids, PEG-400, and several hydrophobic deep eutectic solvents (HDESs) synthesized from menthol and carboxylic acids. Compatibility between PLA and each plasticizer was predicted using Hansen solubility parameters. The efficiency of plasticization was assessed through glass transition temperature suppression in solvent-cast films. The combination of submicron PLA particles and selected plasticizers enabled film formation at temperatures as low as 48 °C, confirming the potential of these systems for energy-efficient coating technologies. Furthermore, composite coatings incorporating micro-sized cellulose fibers (L/D ≈ 10.5-11.5) regenerated from agricultural residues were successfully obtained, demonstrating the feasibility of integrating bio-derived fillers into waterborne PLA formulations. In this study, the use of water-insoluble deep eutectic solvents type plasticizers for PLA coatings from water dispersions was reported for the first time. This establishes a foundation for developing sustainable, low-VOC, and low film formation temperature PLA-based coating materials.