Catalyst‐Free Dynamic Covalent Polyureas: From Structural Design to Functional Applications

ABSTRACT Catalyst‐free dynamic covalent polyureas (DCPUs) have emerged as a promising class of environmentally friendly and sustainable materials that combine the mechanical robustness of traditional polyureas with the stimuli‐responsive properties of dynamic urea bonds (DUBs). This review elaborates on the general concepts that have guided important developments of the recent advances in catalyst‐free DUBs and DCPUs, focusing on the dynamic mechanisms of well‐designed urea bonds, structure‐property relationships, and diverse applications. The rational design of DUBs is discussed, highlighting their unique features in terms of DUBs' reversibility and kinetics. Furthermore, the mechanical properties, self‐healing efficiency, thermal stability, reprocessability, and recyclability of DCPUs are analyzed, along with their potential applications in self‐healing coatings, recyclable composites, shape‐memory materials, 3D printing, and so on. Finally, the current challenges and future perspectives in this fast‐growing field of DUBs and DCPUs are discussed.