Reactive extrusion fabrication of thermoplastic starch with Ca2+ heterodentate coordination structure for harvesting multiple-reusable PBAT/TPS films

Creating multiple-reusable PBAT/TPS (PT) films presents a novel solution to reduce carbon emissions from disposable packaging, addressing challenges like the high creep of PBAT and the glycerol migration of TPS. Consequently, adopting reactive extrusion to fabricate reversible cross-linking TPS with high shape memory performance, low migration, and homogeneous dispersion in PBAT matrix was a fascinating strategy. Herein, starch, glycerol and CaCl2 (calcium chloride) were extruded to fabricate TPS-Ca with Ca2+ heterodentate coordination structure and confirmed by XPS, 1H NMR and temperature-dependent FTIR. The results of DMA, dynamic rheology, flow activation energy and SEM revealed that TPS-Ca exhibited significant temperature-sensitive reversible properties and robust melt flow capability, enabling micro-nano scale dispersion in PBAT. Noteworthy, PBAT/TPS-Ca (PT-Ca) would recover 100 % length within 20 s by microwave heating after being loaded under the hygrothermal environment. Meanwhile, the migration weight of glycerol decreased from 2.5 % to 1.2 % for the heat-moisture-treated PBAT/TPS (HPT) and PBAT/TPS-Ca (HPTCa). Remarkably, the tensile strength and elongation at the break of HPT-Ca increased to 20.0 MPa and 924 %, respectively, due to reduced stress concentration sites in the phase interface. In summary, our study provides a streamlined strategy for fabricating multiple-reusable PT, offering a sustainable solution to eliminate carbon emissions linked to disposable plastic.