Computational Insights\ninto Tunable Reversible Network\nMaterials: Accelerated ReaxFF Kinetics of Furan-Maleimide Diels–Alder\nReactions for Self-Healing and Recyclability

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