Bioinspired Synergistic Dynamic Bonding Enables Robust and Rapid Self‐Healing Elastomers for Intelligent Human–Machine Interfaces

A molecular design strategy for polydimethylsiloxane‐polyurea (PDMSPU) elastomers is developed by tailoring hard‐segment architectures to balance weak hydrogen bonds and aromatic disulfide bonds. Weak hydrogen bonds confer enhanced dynamicity, while aromatic disulfide moieties leverage phenyl rings for network reinforcement and dynamic disulfide bonds promote chain mobility by disrupting π–π stacking. The optimized elastomer (6PDMS‐7IU‐DDS) achieves 92.8% self‐healing at room temperature within 6 h, skin‐like mechanical properties, and conformal epidermal contact. Utilizing a solvent‐assisted strategy mimicking skin's intercellular looseness regulation, the elastomer achieves rapid room‐temperature healing (98.1%, 1.5 h) and even complete healing at −30°C. This strategy further enables room‐temperature transfer of laser‐induced graphene (LIG) circuits to PDMSPU and self‐encapsulation of electrodes. The resulting LIG‐PDMSPU strain sensors feature a wide sensing range (0%–320%), high sensitivity (15.8–381.3), and excellent stability (>20,000 cycles), which enables precise physiological monitoring, gesture recognition, and human‐machine interaction even at −17°C. This work establishes a rational design paradigm for robust, room‐temperature self‐healing elastomers for multifunctional flexible electronics.