Vitrimeric Polylactide by Two-step Alcoholysis and Transesterification during Reactive Processing for Enhanced Melt Strength

Because of its rather low melt strength, polylactide (PLA) has yet to fulfill its promise as advanced biobased and biodegradable foams to replace fossil-based polymer foams. In this work, PLA vitrimers were prepared by two-step reactive processing from commercial PLA thermoplastics, glycerol, and diphenylmethane diisocyanate (MDI) using Zn­(II)-catalyzed addition and transesterification chemistry. The transesterification reaction of PLA and glycerol occurs with zinc acetate as the catalyst, and chain scission will take place due to the alcoholysis of the PLA chains by the free hydroxyl groups from the glycerol. Long-chain PLA with hydroxyl groups can be obtained and then cross-linked with MDI. Rheological analysis shows that the formed cross-linked network can significantly improve melt strength and promote strain hardening under extensional flow. PLA vitrimers still maintain the ability of thermoplastic processing via extrusion and compression. The enhanced melt strength and the rearrangement of network topology facilitate the foaming processing. An expansion ratio as large as 49.2-fold and microcellular foam with a uniform cell morphology can be obtained for PLA vitrimers with a gel fraction of 51.8% through a supercritical carbon dioxide foaming technique. This work provides a new way with the scale-up possibility to enhance the melt strength of PLA, and the broadened range of PLA applicability brought by PLA vitrimers is truly valuable in terms of the realization of a sustainable society.