Microwave-assisted chemical recycling of polylactide (PLA) by alcoholysis with various diols

A process for the chemical recycling of degradable polylactide (PLA) has been developed, to convert its disposable wastes into small-sized products for further use as value-added starting materials for specialty products. A microwave-assisted alcoholysis reaction, using diols and tetrabutyl orthotitanate (TBT) catalyst, was employed. The effects of the types of diols and PLA/diol feeding ratios on the structures and properties of the resulting alcoholized products were examined by using ethylene glycol (EG), propane-1,3-diol (PDO), and butane-1,4-diol (BDO). The PLA/diol ratios were varied from 1:1 to 4:1 wt/wt. The products were characterized by ATR-FTIR, 1H NMR, and 2D-NMR HMQC and HMBC spectroscopy. The products compost to diol-capped lactate sequences with different lengths, i.e., lactate, lactyllactate, and poly-lactate. The yield of the shortest lactate was about 65% for the LBDOT11 system, and 90% for the LEGT11 and LPDOT11 systems, when a feeding ratio of 1:1 wt/wt was employed. The yield decreased with an increase in the ratios, from 1:1 to 4:1 wt/wt. In contrast, the yields of longer lactyllactate and poly-lactate increased with an increase in the ratios. In terms of OH-endcapping efficiency, the products have two structures: (A) LA-O-(CH2)x-OH and (B) LA-O-(CH2)x-O-LA. The contents depend on diol types and the PLA/diol feeding ratio. The alcoholized products were then used as starting polyols in the preparation of lactide-based polyurethanes (PUs) by reacting with 1,6-diisocyanatohexane (HDI) and BDO chain extender. The resulting PUs exhibit promising mechanical and thermal properties. These PUs are suitable for use as either single-component materials, e.g., 3D-printing filaments and degradable adhesives, or as toughness-enhancing agents for brittle polymers, especially PLA.