Repeatedly Recyclable 3D Printing Catalyst‐Free Dynamic Thermosetting Photopolymers

Abstract Photo‐curing 3D printing technology has promoted the advanced manufacturing in various fields, but has exacerbated the environmental crisis by the demand for the chemically cross‐linked thermosetting photopolymers. Here, the authors report a generic strategy to develop catalyst‐free dynamic thermosetting photopolymers, based on photopolymerization and transesterification, that can enable users to realize repeatable 3D printing, providing a practical solution to the environmental challenges. That the β‐carbonyl group adjacent to the ester group greatly accelerates the rate of transesterification is demonstrated. The generated resins from the immobilization of the catalyst‐free reversible bonds into the photopolymers leads to a dynamic covalently crosslinked network structure upon UV based 3D printing, which exhibit controllable mechanical properties with elastomeric behaviors to thermadapt shape memory polymers. Furthermore, the resulting network can be reverted into an acrylate‐functioned photopolymer that is suitable for 3D printing again, presenting an on‐demand, repeatedly recyclable thermosetting photopolymer platform for sustainable 3D printing.