A 4D Printable Shape Memory Vitrimer with Repairability and Recyclability through Network Architecture Tailoring from Commercial Poly(ε‐caprolactone)

Vitrimers have shown advantages over conventional thermosets via capabilities of dynamic network rearrangement to endow repairability as well as recyclability. Based on such characteristics, vitrimers have been studied and have shown promises as a 3D printing ink material that can be recycled with the purpose of waste reduction. However, despite the brilliant approaches, there still remain limitations regarding requirement of new reagents for recycling the materials or reprintability issues. Here, a new class of a 4D printable vitrimer that is translated from a commercial poly(ε‐caprolactone) (PCL) resin is reported to exhibit self‐healability, weldability, reprocessability, as well as reprintability. Thus, formed 3D‐printed vitrimer products show superior heat resistance in comparison to commercial PCL prints, and can be repeatedly reprocessed or reprinted via filament extrusion and a handheld fused deposition modeling (FDM)‐based 3D printing method. Furthermore, incorporation of semicrystalline PCL renders capabilities of shape memory for 4D printing applications, and as far as it is known, such demonstration of FDM 3D‐printed shape memory vitrimers has not been realized yet. It is envisioned that this work can fuel advancement in 4D printing industries by suggesting a new material candidate with all‐rounded capabilities with minimized environmental challenges.