Mechanically Robust and UV‐Curable Shape‐Memory Polymers for Digital Light Processing Based 4D Printing

4D printing is an emerging fabrication technology that enables 3D printed structures to change configuration over “time” in response to an environmental stimulus. Compared with other soft active materials used for 4D printing, shape‐memory polymers (SMPs) have higher stiffness, and are compatible with various 3D printing technologies. Among them, ultraviolet (UV)‐curable SMPs are compatible with Digital Light Processing (DLP)‐based 3D printing to fabricate SMP‐based structures with complex geometry and high‐resolution. However, UV‐curable SMPs have limitations in terms of mechanical performance, which significantly constrains their application ranges. Here, a mechanically robust and UV‐curable SMP system is reported, which is highly deformable, fatigue resistant, and compatible with DLP‐based 3D printing, to fabricate high‐resolution (up to 2 µm), highly complex 3D structures that exhibit large shape change (up to 1240%) upon heating. More importantly, the developed SMP system exhibits excellent fatigue resistance and can be repeatedly loaded more than 10 000 times. The development of the mechanically robust and UV‐curable SMPs significantly improves the mechanical performance of the SMP‐based 4D printing structures, which allows them to be applied to engineering applications such as aerospace, smart furniture, and soft robots. A mechanically robust and UV‐curable shape‐memory polymer (SMP) system can be stretched by up to 1240% of its original length and is compatible with Digital Light Processing (DLP)‐based high‐resolution 3D printing technology (up to 2 µm). The high deformability and fatigue resistance (more than 10 000 cycles loading–unloading) make the SMP an ideal 4D printing material for engineering applications.