Design principles for vitrimers: Linking dynamic covalent chemistry, network architecture, and engineering performance

Abstract Vitrimers are commonly classified according to the dynamic covalent bonds that enable network topology rearrangement, but their practical performance is governed by more than exchange chemistry alone. Molecular structure, network architecture, chain mobility, and exchange kinetics collectively determine whether a vitrimer can maintain mechanical stability during use while retaining sufficient mobility for processing, repair, and reprocessing. This review examines vitrimer design by considering how molecular and network structures influence material properties. Particular attention is given to how factors such as catalyst concentration, reactive‐group stoichiometry, backbone structure, cross‐link density, molecular ordering, junction mobility, and network heterogeneity influence glass‐transition behavior, modulus, creep resistance, stress relaxation, and property recovery. These relationships are then considered in the context of emerging engineering applications, where the balance between service stability and processability is often more important than maximizing exchange rate alone. By connecting molecular and network design with rheological behavior and macroscopic performance, this Review provides a framework for the rational design and evaluation of vitrimer materials.