Dynamic Enamine-one Bond Based Vitrimer via Amino-yne Click Reaction
Dynamic Enamine-one Bond Based Vitrimer via Amino-yne Click Reaction
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DOI：
10.1021/acsmacrolett.1c00550
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发表时间：
2021-09-16
影响因子：
7.015
通讯作者：
Lin, Yangju
中科院分区：
文献类型：
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作者：
Guo, Xinru;Gao, Fei;Lin, Yangju
在这里，我们报告了一个动态的制造烯胺一键为基础的vitrimer通过氨基炔点击化学。与胺-乙酰乙酸酯缩合相反，氨基-炔点击反应产生动态烯胺-一基序，其由顺式/反式（3：1）异构体组成，并且由于不存在甲基取代基而具有相对较低的活化能（35 +/-3 kJ/mol vs 59 +/-6 kJ/mol）。与胺-乙酰乙酸酯缩合法制备的玻璃态聚合物相比，所得玻璃态聚合物网络具有上级力学性能和更快的动态交换速度，这分别归因于较少的网络缺陷和较少的空间位阻交换反应。最后，有效的氨基-炔点击反应被证明是与仲胺底物相容的，仲胺底物对胺-乙酰乙酸酯缩合具有低反应性。高效且无副产物的氨基-炔反应为玻璃体制造提供了强有力的化学工具，并且对于密封和粘合应用是潜在期望的。
Here, we report the fabrication of a dynamic enamine-one bond based vitrimer through amino-yne click chemistry. In contrast to amine-acetoacetate condensation, the amino-yne click reaction yields a dynamic enamine-one motif that is composed of cis/trans (3:1) isomers and has a relatively lower activation energy (35 +/- 3 kJ/mol vs 59 +/- 6 kJ/mol), owing to the absence of a methyl substituent. The resulting vitrimer network has superior mechanical properties and faster dynamic exchange than that of a reference vitrimer derived from amine-acetoacetate condensation, and they are attributed to the fewer network defects and the less sterically hindered exchange reaction, respectively. Lastly, the efficient amino-yne click reaction is demonstrated to be compatible with the secondary-amine substrate, which has a low reactivity toward the amine-acetoacetate condensation. The efficient and side product-free amino-yne reaction offers a powerful chemical tool for vitrimer fabrication and is potentially desirable for sealing and adhesion applications.