Advanced Vitrimer with Spiropyran Beads: A Multi‐Responsive, Shape Memory, Self‐Healing, and Reprocessable Smart Material

Abstract Thermosetting materials have limitations in terms of reshaping and recycling due to their irreversible bond structures, leading to significant plastic waste issues. Recently, epoxy vitrimers based on dynamic covalent bond exchange have been introduced as promising alternatives to traditional thermosets. Particularly, they demonstrate significant potential applications in the field of multi‐responsive materials. In this research, a self‐healable and mechano‐responsive vitrimer (EB‐V) is successfully prepared, incorporating epoxide spiropyran beads (ESP beads) derived from citric acid and epoxy derivatives. To enable self‐reporting of cracks through color changes, ESP beads are covalently bonded to the vitrimer via an epoxy‐carboxylic acid reaction. The photochromic properties of EB‐V are demonstrated by color and fluorescence changes, and its tensile strength increased from 2.0 to 6.8 MPa compared to the control sample. Dynamic mechanical analysis confirmed the covalent exchange reaction of the vitrimer, revealing its reconfigurable behavior and stress relaxation at elevated temperatures. Furthermore, EB‐V exhibited exceptional properties, including self‐healing and reprocessability. As a smart material, it holds great promise for a wide range of applications, such as sensors, actuators, 4D printing, and industrial safety diagnostics.