In Situ Self‐Polymerization Strategy Toward Intrinsic Autonomous Self‐Healing Materials

Achieving spontaneous contact of damaged interfaces under stimulus‐free conditions is a prerequisite and major challenge for intrinsic autonomous self‐healing polymers. This study presents an intrinsic self‐healing polymer system based on polythioctic acid. Under alkaline conditions, its segments transition from an opaque semicrystalline state to a transparent elastomer with high mobility, enabling spontaneous contact and repair of fractured scratch surfaces. When subjected to damage, the material demonstrates self‐healing anticorrosion performance, with the impedance magnitude of the scratched coating at 0.01 Hz increasing from 2.3 × 10 5 Ω·cm 2 at 0 h to 1.4 × 10 7 Ω·cm 2 after 120 h of exposure to 3.5 wt% NaCl without any external stimulus. Furthermore, the material demonstrates outstanding sustainability in terms of recyclability under mild conditions after its service life. This smart polymer design strategy provides a feasible approach for developing intrinsic self‐healing polymer systems requiring no external intervention.