Type I‐B Main‐Chain Polyrotaxane Network

Polyrotaxanes (PRs) are recognized for their outstanding conformational flexibility, making them ideal candidates for the design of high‐performance mechanically interlocked materials. However, Type I‐B main‐chain PRs, featuring multiple wheels and stoppers along the polymer backbone, remain underexplored due to the challenges in their design and synthesis. Herein, we introduce a facile “host−guest recognition followed by click polymerization” strategy for the synthesis of Type I‐B main‐chain PR, which is subsequently employed to prepare the first‐ever Type I‐B main‐chain PR network (PRN). Compared to the control whose wheels are nonslidable under applied force, the distinctive dynamic behaviors of Type I‐B main‐chain PR impart extraordinary mechanical enhancements to PRN, with fracture strain, toughness, and puncture resistance all surging by more than 27‐fold. Moreover, the combination of the host−guest recognition and multiple stoppers endows the PRN with great self‐recovery capability due to the restriction of the motion range of mechanical bonds. This work not only presents a novel strategy for designing and synthesizing Type I‐B main‐chain PR networks but also highlights the pivotal role of Type I‐B main‐chain PRs in enhancing material performance, offering valuable insights for advancing the development of dynamic polymer materials.