Ultratough, Robustness, and Reprocessable Thermoset Epoxy Resins Synergistically Enhanced by Hierarchical Coordination Interactions and Dynamic Covalent Networks

Abstract Epoxy resins, ubiquitous and indispensable thermosetting material in various industries, suffer from the resistance to crack initiation, poor ductility, and irreparable permanent cross‐linked network, which hinder their utilization in high‐performance applications and are detrimental to the development of a sustainable economy. However, achieving the trade‐off between toughness, robustness, and reprocessability of epoxy resins remains a formidable challenge. Herein, an epoxy resin that combines ultratoughness, robustness, and reprocessability by incorporating a hierarchical crosslink structure embedded in a transesterification network is reported. The construction of hierarchical coordination structures facilitates formation of dense nano‐hard domains, enabling enhancement of both strength and toughness at multilength scales. As a result, the epoxy resin, integrating covalent adaptable networks with sacrificial non‐covalent networks, exhibits exceptional elongation at break (280%), modulus (1.8 GPa), stress at break (56.3 MPa), and tensile toughness (142 MJ m −3 ), showcasing its excellent endurance and ability to undergo multiple reprocessability. The application of this epoxy resin in carbon fiber‐reinforced polymer composites further underscores its potential as the resulting HCEV‐CFRPs exhibit unprecedented tensile properties and facilitate multiple non‐destructive recycling of high‐value carbon fiber under mild conditions. This research provides novel design principles for recyclable and high‐performance materials that combine strength and toughness.