Computational Insights into Tunable Reversible Network Materials: Accelerated ReaxFF Kinetics of Furan-Maleimide Diels–Alder Reactions for Self-Healing and Recyclability

In this study, ReaxFF molecular dynamics simulations were benchmarked and used to study the relative kinetics of the retro Diels–Alder reaction between furan and N-methylmaleimide. This reaction is very important for the creation of polymer networks with self-healing and recyclable properties, since they can be used as reversible linkers in the network. So far, the reversible Diels–Alder reaction has not yet been studied by using reactive molecular dynamics simulations. This work is, thus, the first step in simulating a covalent adaptable network (CAN) using Diels–Alder reactions as reversible linkers. For both endo and exo, the bond breaking in 40 product molecules was simulated using the bond boost method and the endo/exo ratio was evaluated. This ratio was benchmarked against density functional theory (DFT) and experimental results for a changing set of bond boost parameters. Given their importance to understand how the CAN performs, the effect of the addition of a polymer backbone and the effect of temperature were successfully simulated using our newly parametrized reactive force field.