Exploring the Adaptability of 4D Printed Shape Memory Polymer Featuring Dynamic Covalent Bonds.

4D printing (4DP) of high-performance shape memory polymers (SMPs), particularly using digital light processing (DLP), has garnered intense global attention due to its capability for rapid and high-precision fabrication of complex configurations, meeting diverse application requirements. However, the development of high-performance dynamic shape memory polymers (DSMPs) for DLP printing remains a significant challenge due to the inherent incompatibilities between the photopolymerization process and the curing/polymerization of high-strength polymers. Here, a mechanically robust DSMP compatible is developed with DLP printing, which incorporates dynamic covalent bonds of imine linking polyimide rigid segments, exhibiting remarkable mechanical performance (tensile strength ≈41.7 MPa, modulus ≈1.63 GPa) and thermal stability (Tg ∼ 113 °C, Td ∼ 208 °C). More importantly, benefiting from the solid-state plasticity conferred by dynamic covalent bonds, 4D printed structures demonstrate rapid network adaptiveness, enabling effortless realization of reconfiguration, self-healing, and recycling. Meanwhile, the extensive π-π conjugated structures bestow DSMP with an intrinsic photothermal effect, allowing controllable morphing of the 4D configuration through dual-mode triggering. This work not only greatly enriches the application scope of high-performance personalized configurations but also provides a reliable approach to addressing environmental pollution and energy crises.