Rapid Self‐Healing and Durable Adhesion of Imine‐Linked Dynamic Polymer and Its Thermally Conductive Composites

The development of dynamic covalent chemistry offers new opportunities to provide novel and functional thermal conductive materials. In this work, we demonstrate a flexible material with dynamic imine‐bonded crosslinking networks, which was synthesized from bio‐based vanillin (VAN), glycerol triglycidyl ether (GTE) and bis‐amino‐terminated polydimethylsiloxane (AT‐PDMS). The dynamic exchange property of imine bonds endows the material with rapid room‐temperature self‐healing ability and durable adhesion. Additionally, the composites were prepared by introducing boron nitride (BN) as a thermally conductive filler through blending, which achieved a significantly enhanced thermal conductivity of 2.891 W m −1 K −1 at a BN addition ratio of 50%. The composite demonstrated not only the maintenance of outstanding self‐healing properties and malleability but also exhibited excellent durable adhesive capability, which enabled the thermally conductive composite to better adapt to a variety of complex working conditions in practical applications, thereby improving heat dissipation efficiency as demonstrated. This study is expected to provide a new, efficient, and environmentally friendly solution to create high performance and sustainable polymer composites.