Soft‐Rigid Construction of Mechanically Robust, Thermally Stable, and Self‐Healing Polyimine Networks with Strongly Recyclable Adhesion

Abstract Reversible and recyclable thermosets have garnered increasing attention for their smart functionality and sustainability. However, they still face challenges in balancing comprehensive performance and dynamic features. Herein, silicon (Si)─oxygen (O) and imidazole units covalent bonds are coupled to generate a new class of bio‐polyimines (Bio‐Si‐PABZs), to endow them with high performance and excellent reprocessing capability and acid‐degradability. By tailoring the molar content of diamines, this Bio‐Si‐PABZs displayed both a markedly high glass transition temperature (162 °C) and a high char yield at 800 °C in an oxygen atmosphere (73.1%). These Bio‐Si‐PABZs with their favorable properties outperformed various previously reported polyimines and competed effectively with commercial fossil‐based polycarbonate. Moreover, the scratch (≈10 µ m) on the surface of samples can be self‐healing within only 2 min, and an effective “ Bird Nest ”‐to‐“ Torch ” recycling can also be achieved through free amines solution. Most importantly, a bio‐based siloxane adhesive derived from the intermediate Bio‐Si‐PABZ‐1 by acidic degradation demonstrated broad and robust adhesion in various substrates, with values reaching up to ≈3.5 MPa. For the first time, this study lays the scientific groundwork for designing robust and recyclable polyimine thermosets with Si─O and imidazole units, as well as converting plastic wastes into thermal‐reversibility and renewable adhesives.