A topological polymer network with Cu(II)-coordinated reversible imidazole-urea locked unit constructs an ultra-strong self-healing elastomer

It is exceedingly desired, but difficult to construct self-healing materials with both excellent mechanical properties and healing efficiency, which are usually realized by using mutually exclusive methods. Here, we reconcile this contradiction by utilizing copper-bis-(imidazole-2-yl)-methane-urea (Cu-BIMU) locked units based on novel designed dynamic imidazole-urea bonds with coupled multiple noncovalent bonds (coordination bonds, π−π stacking bonds, and hydrogen bonds). The coordination of Cu(II) greatly reduces the electron-cloud density of imidazole, which lowers the free energy barrier of imidazole-urea bonds and promotes their reversible dissociation, as demonstrated by the density functional theory and small-molecule model reaction. The topological design of Cu-BIMU polyurethane (Cu-BIMU-PU), which concentrates multiple crosslinking-in-one locked unit to avoid the formation of excessive crosslinking sites to ensure high chain mobility, facilitates self-healing. Accumulative extensive intermolecular interactions endowed excellent mechanical properties to the resulting Cu-BIMU-PU elastomer with a tensile strength of 65.3 MPa, among the highest ever-reported value. This work provides a novel molecular design principle for fabricating high-performance dynamic polymers.