Type I main‐chain polyrotaxanes (PRs) with multiple wheels threaded onto the axle are widely employed to design slide‐ring materials. However, Type II main‐chain PRs with axles threading into the macrocycles on the polymer backbones have rarely been studied, although they feature special topological structures and dynamic characteristics. Herein, we report the design and preparation of Type II main‐chain PR‐based mechanically interlocked networks (PRMINs), based on which the relationship between microscopic motion of mechanical bonds on the PRs and macroscopic mechanical performance of materials has been revealed. The representative PRMIN‐2 exhibits a robust feature in tensile tests with high stretchability (1680%) and toughness (47.5 MJ/m3). Moreover, it also has good puncture performance with puncture energy of 22.0 mJ. Detailed rheological measurements and coarse‐grained molecular dynamics (CGMD) simulation reveal that the embedded multiple [2]rotaxane mechanical bonds on the PR backbones of PRMINs could undergo a synergistic long‐range sliding motion under external force, with the introduction of collective dangling chains into the network. As a result, the synchronized motions of coherent PR chains can be readily activated to accommodate network deformation and efficiently dissipate energy, thereby leading to enhanced mechanical performances of PRMINs.

中文翻译：

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具有多个主链机械键集体运动的机械连锁聚轮烷网络


具有多个螺纹连接在轴上的轮的 I 型主链聚轮烷（PR）被广泛用于设计滑环材料。然而，尽管具有特殊的拓扑结构和动态特性，但轴穿入聚合物主链上大环的II型主链PR却很少被研究。在此，我们报告了基于主链PR的机械联锁网络（PRMIN）的设计和制备，基于该网络揭示了PR上机械键的微观运动与材料的宏观力学性能之间的关系。代表性的 PRMIN-2 在拉伸测试中表现出强大的特性，具有高拉伸性 (1680%) 和韧性 (47.5 MJ/m3)。此外，它还具有良好的穿刺性能，穿刺能量为22.0 mJ。详细的流变测量和粗粒分子动力学（CGMD）模拟表明，PRMINs PR主链上嵌入的多个[2]轮烷机械键可以在外力作用下进行协同长程滑动运动，并引入集体悬挂链进入网络。因此，相干 PR 链的同步运动可以很容易地被激活，以适应网络变形并有效地耗散能量，从而增强 PRMIN 的机械性能。