Bio‐Based Covalent Adaptable Oligorotaxane Networks

ABSTRACT The construction of high‐performance polymers from sustainable resources represents a forefront direction in materials science. Dynamic covalent chemistry can introduce recyclability into bio‐based cross‐linked polymers, yet a trade‐off between their mechanical robustness and reprocessability often persists. Herein, we report a synergistic integration of biomass feedstocks, dynamic covalent bonds, and mechanically interlocked architectures to create bio‐based covalent adaptable oligorotaxane networks ( OR BCANs), seamlessly combining mechanical robustness, biomass‐derived sustainability, and circular reprocessability. These networks form through catalyst‐free reactions between epoxidized soybean oil and the topologically engineered polyrotaxane. Benefiting from unique force‐responsive behaviors of the polyrotaxanes, representative OR BCAN‐ 3 exhibits exceptional mechanical properties with significantly enhanced Young's modulus (42 vs. 7.0 MPa), maximum stress (8.6 vs. 2.3 MPa), fracture strain (234% vs. 89%), and toughness (12.6 vs. 1.2 MJ/m 3 ) compared to control whose wheels are nonslidable under applied force. Furthermore, the incorporated β ‐hydroxy ester linkages enable dynamic transesterification under mild conditions, allowing the material to be efficiently reprocessed multiple times at 110°C while completely retaining its structural integrity and mechanical performance. This strategy bridges biomass‐derived platforms and mechanically interlocked architectures, opening a pathway to sustainable polymers with robust mechanical properties, extended durability, and end‐of‐life recyclability.