Synergistic Covalently and Mechanically Interlocked Polymer

Abstract Integrating different polymer types into a unified system in a thoughtful manner leverages their complementary advantages, providing a promising strategy for developing high‐performance materials. Mechanically interlocked polymers (MIPs), characterized by their unique spatial entanglement, exhibit distinctive performance advantages, yet their potential to expand material properties through rational integration with other polymer architectures presents substantial opportunities for continued investigation. Herein, we report a coherent integration of covalent polymers (CPs) and mechanically interlocked polymers through sequential orthogonal polymerizations, developing a novel synergistic covalently and mechanically interlocked polymer (CMIP) featuring both structural stability and force‐induced dynamics. Compared to its structurally similar but noninterlocked control sample, CMIP demonstrates markedly enhanced thermomechanical stability and performance recovery, achieving a 93.4% recovery efficiency at 100% strain after just 5 min of rest, in contrast to 59.7% for the control. This remarkable stability and recovery result from the synergistic interplay between the covalent polymer framework and the interlocked structure, which work in tandem to preserve network integrity and enable rapid host−guest reformation. Notably, despite this significant improvement, CMIP retains a comparable damping capacity (91% versus 87%) and material toughness (14.8 versus 15.1 MJ m −3 ), owing to the efficient energy dissipation mechanisms enabled by host−guest dissociation and subsequent sliding motion. This strategy imparts CMIP with unique characteristics, offering a prospective pathway for the development of a diverse array of advanced synergistic materials with enhanced, multifaceted properties.