NIR-light-induced thermoset shape memory polyurethane composites with self-healing and recyclable functionalities

To endow thermoset shape memory polymers with self-healing and recyclable functionalities is highly desirable. In this study, we fabricated Diels-Alder crosslinked polyurethane/functionalized reduced graphene oxide composites (DAPU-FRGOs) through in situ polymerization. The incorporated FRGO with urethane chains could achieve good compatibility with the DAPU matrix, forming physical and chemical crosslinking structures in the composite. And the most effective improvements of mechanical, thermal stability, crystallization-triggered, and photothermal effect were achieved for the DAPU/FRGO2 composite with 2 wt% FRGO. Owing to the outstanding crystallization-induced and photo-thermal effects of FRGO and the thermal reversible behavior of Diels-Alder bonds, the DAPU-FRGO2 composite showed rapid shape memory (<10 s, shape-fixity and recovery ratios were 92.3% and 94.1%, respectively) and self-healing (<120 s, healing efficiencies for tensile strength and elongation at break were 89.3% and 90.4%, respectively) under near-infrared light. Meanwhile, the DAPU-FRGO2 composite exhibited good repeatability of self-healing and shape-memory functionalities, and its shape memory parameters and healing efficiencies were maintained above 92% and 85% after three-cycles, respectively. Further recycling test demonstrated that the mechanical properties of the recycled DAPU-FRGO2 composite could be recovered to more than 82% of the original sample. This work provides a heuristic perspective for designing durable light-responsive thermoset shape memory composite materials.