Self-Assembled Entanglements in Elastomers for Superior Toughness and Fatigue Resistance

To address the long-standing trade-off between modulus, toughness, and fatigue resistance in elastomers, in this study, we propose an innovative strategy based on self-assembled chain entanglements. Unlike conventional strategies, the proposed entanglement-driven composite combines rigid, self-assembled entangled particles with a soft matrix enabled by strong interfacial adhesion. This system synergizes rigid entangled particles (with molecular segment entanglement topology) and the soft matrix to enable energy dissipation across molecular segments, polymer chains, and rigid entangled particles, ultimately achieving simultaneous enhancement of fracture toughness (∼0.043 MJ/m2), fatigue threshold (∼300 J/m2), and elastic modulus. Implemented via a one-step in situ self-assembly method, this strategy provides novel insights into designing high-performance elastomers.