In recent years, disposing of large amounts of polymers has posed a serious environmental issue, driving the need for more durable materials. In particular, polymer materials incorporating reversible cross-linking formed between β-cyclodextrin (β-CD) as a ring-shaped host and adamantane (Ad) as a cage-shaped guest have demonstrated excellent toughness, owing to efficient energy dissipation through reversible complex dissociation under stress. Furthermore, the reversibility of the crosslinks has attracted attention for self-healing applications, with experimental studies underway.
In this study, all-atom molecular dynamics (MD) simulations were used to investigate polymers with β-CD/Ad reversible crosslinks. First, a local host–guest model confirmed that the complex formation is stable and matching experimental data. Next, PMMA‐based polymers incorporating the crosslinks were analyzed to study interfacial diffusion and layer thickness at temperatures above the glass transition temperature (Tg). The results successfully explained experimental trends without contradiction. Finally, tensile tests in MD revealed that β-CD/Ad complexation contributes significantly to the enhancement of mechanical properties, particularly toughness.