Revisiting Properties of Vitrimers: Special Rheological and Chemical Characteristics and Reconsidered Concepts

ABSTRACT Vitrimers offer higher sustainability for traditional polymers through enhanced recyclability, healability and better properties. Therefore, their rheological and viscoelastic profiles and chemical behavior require a deeper understanding to valorize these properties. In this review, we discuss tuning of stress relaxation of vitrimers and reconsider their viscosity profiles. In addition, we highlight application opportunities of their dynamic rheology and redefine their characteristic temperatures, shape memory and chemical behaviors. Master curves were found to demonstrate special purpose for vitrimers with their complex structure, which shows variations in rheological behavior through different time scales. In addition, calculation methods of the temperature at the topology freezing transition ( T v ) were discussed and compared. Moreover, the difference between T v and other characteristic temperatures like malleability temperature ( T malleability ) and solid‐to‐liquid transformation temperature was established, which are sometimes mistakenly considered the same. Finally, special chemical behavior of vitrimers was presented, including other uses of the swelling phenomenon. This review promotes a constructive dialogue using competing interpretations about the rheological properties of vitrimers. It provides more understanding of vitrimers' characteristics and offers wider theoretical frameworks for developing new vitrimers. Additionally, it highlights the common question of how to accurately describe and harness the rheological and chemical behavior of these emerging polymer networks.