Olefin Metathesis for Effective Polymer Healing via Dynamic Exchange of Strong Carbon-Carbon Double Bonds

In this article, we demonstrate transition-metal-catalyzed olefin metathesis as a simple, effective method for healing polymers via dynamic exchange of strong carbon-carbon double bonds. Upon introducing a very low level of the Grubbs' second-generation Ru metathesis catalyst into cross-linked polybutadiene (PBD) network, the material self-heals effectively at various conditions under moderate pressures. In sharp contrast, catalyst-free control samples with identical network topology and cross-linking density show minimal healing. The healing efficiency of the materials was carefully investigated under different concentrations of the Ru catalyst, compression pressures, and temperatures. It is demonstrated for the first time that a bulk polymer could effectively heal via dynamic covalent bond formation at sub-ambient temperature. The Ru-loaded PBD samples not only heal well with themselves but also with control samples without any catalyst. Furthermore, a completely Ru-free PBD network can heal effectively upon simply applying a very small amount of Ru catalyst only at the fracture surface. The simplicity and effectiveness of this self-healing approach make it potentially applicable to a wide range of olefin-containing polymers.