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.