Next-Generation Vitrimers Design through Theoretical Understanding and Computational Simulations

Vitrimers are an innovative class of polymers that boast a remarkable fusion of mechanical and dynamic features, complemented by the added benefit of end-of-life recyclability. This extraordinary blend of properties makes them highly attractive for a variety of applications, such as the automotive sector, soft robotics, and the aerospace industry. At their core, vitrimer materials consist of crosslinked covalent networks that have the ability to dynamically reorganize in response to external factors, including temperature changes, pressure variations, or shifts in pH levels. In this review, the aim is to delve into the latest advancements in the theoretical understanding and computational design of vitrimers. The review begins by offering an overview of the fundamental principles that underlie the behavior of these materials, encompassing their structures, dynamic behavior, and reaction mechanisms. Subsequently, recent progress in the computational design of vitrimers is explored, with a focus on the employment of molecular dynamics (MD)/Monte Carlo (MC) simulations and density functional theory (DFT) calculations. Last, the existing challenges and prospective directions for this field are critically analyzed, emphasizing the necessity for additional theoretical and computational advancements, coupled with experimental validation. MD/MC simulations elucidate the intricate relationships among structure, dynamics, and properties, enhancing comprehension of how polymer chain behaviors impact relevant properties. They provide insights into tailoring vitrimer properties on a macro scale. Concurrently, DFT calculations delve deeper into chemical nuances, aiding in the design of bond exchange mechanisms and fine-tuning reaction kinetics.image