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A seawater triggered dynamic coordinate bond and its application for underwater self-healing and reclaiming of lipophilic polymer

机译:海水触发的动态配位键及其在亲脂性聚合物的水下自修复和再生中的应用

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In this work, water triggered dynamic catechol–Fe3+ coordinate bonds are revealed and studied at atomic, molecular and macroscopic levels using M?ssbauer spectroscopy, rheological analysis, etc. DOPA–iron complexation is found to be dynamic in the presence of water, and this dynamic manner is immobilized after removing water. Accordingly, a water saturated lipophilic polymer containing catechol–Fe3+ crosslinks, rather than the dry version, exhibits dynamic coordination–dissociation behavior. In addition, a migration of iron proves to be enabled in the catechol–Fe3+ crosslinked polymer immersed in seawater. Rearrangement of the dynamic catechol–Fe3+ coordinate bonds among different molecules is thus favored. Based on these results, we develop a bulk lipophilic polymer solid capable of repeated autonomic recovery of strength in seawater without manual intervention. When the polymer is damaged in seawater, reshuffling of the mobile hyperbranched polymer networks across the crack interface, owing to the dynamic catechol–Fe3+ crosslinkages activated by the alkaline circumstances, rebinds the damaged site. By taking advantage of the same mechanism, the polymer can be remolded with the help of seawater and this recycled polymer is still self-healable in seawater. Unlike in the case of conventional polymers where water would shield macromolecules from interacting, here, seawater is a necessary environmental assistant for the material interaction to take effect. The outcomes are beneficial for deepening the understanding of coordinate bonds, and the development of robust underwater self-healing lipophilic polymers.
机译:在这项工作中,揭示了水触发的动态儿茶酚-Fe 3 + 配位键,并使用Msssbauer光谱,流变分析, etc。发现在水存在下,DOPA-铁络合物是动态的,这种动态方式在除去水后被固定。因此,含有邻苯二酚-Fe 3 + 交联键而不是干式交联键的水饱和亲脂性聚合物表现出动态配位-离解行为。此外,浸入海水中的邻苯二酚-Fe 3 + 交联聚合物被证明可以迁移铁。因此有利于不同分子之间动态邻苯二酚-Fe 3 + 配位键的重排。基于这些结果,我们开发了一种块状亲脂性聚合物固体,无需人工干预即可在海水中反复自主恢复强度。当聚合物在海水中遭到破坏时,由于碱性条件下活化的儿茶酚-Fe 3 + 交联,在裂缝界面上流动的超支化聚合物网络发生了改组,重新绑定损坏的站点。通过利用相同的机理,可以在海水的帮助下将聚合物重塑,并且这种回收的聚合物在海水中仍然可以自愈。与常规聚合物的情况不同,在常规聚合物中,水会阻止大分子相互作用,而海水是使材料相互作用生效的必要环境助手。这些结果有助于加深对配位键的理解,并有助于开发强大的水下自修复亲脂性聚合物。

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