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基于硒鎓盐转烷基化反应的热响应性含硒化物材料

Thermally Responsive Selenide-containing Materials Based on Transalkylation of Selenonium Salts.

作者信息

Chen Sisi, Scholiers Vincent, Zhang Mengyao, Zhang Jiandong, Zhu Jian, Prez Filip E Du, Pan Xiangqiang

机构信息

State and Local Joint Engineering Laboratory for Novel Functional Department Polymeric Materials, Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application, Department of Polymer Science and Engineering, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China.

Polymer Chemistry Research group, Centre of Macromolecular Chemistry (CMaC), Department of Organic and Macromolecular Chemistry, Faculty of Sciences, Ghent University, Krijgslaan 281, S4-bis, 9000, Ghent, Belgium.

出版信息

Angew Chem Int Ed Engl. 2023 Dec 4;62(49):e202309652. doi: 10.1002/anie.202309652. Epub 2023 Oct 31.

Abstract

Covalent adaptable networks (CANs) possess unique properties as a result of their internal dynamic bonds, such as self-healing and reprocessing abilities. In this study, we report a thermally responsive C-Se dynamic covalent chemistry (DCC) that relies on the transalkylation exchange between selenonium salts and selenides, which undergo a fast transalkylation reaction in the absence of any catalyst. Additionally, we demonstrate the presence of a dissociative mechanism in the absence of selenide groups. After incorporation of this DCC into selenide-containing polymer materials, it was observed that the cross-linked networks display varying dynamic exchange rates when using different alkylation reagents, suggesting that the reprocessing capacity of selenide-containing materials can be regulated. Also, by incorporating selenonium salts into polymer materials, we observed that the materials exhibited good healing ability at elevated temperatures as well as excellent solvent resistance at ambient temperature. This novel dynamic covalent chemistry thus provides a straightforward method for the healing and reprocessing of selenide-containing materials.

摘要

共价自适应网络(CANs)由于其内部的动态键而具有独特的性质,如自我修复和再加工能力。在本研究中,我们报道了一种热响应性的C-Se动态共价化学(DCC),它依赖于硒鎓盐和硒化物之间的烷基转移交换,在没有任何催化剂的情况下能发生快速的烷基转移反应。此外,我们证明了在没有硒化物基团的情况下存在解离机制。将这种DCC引入含硒化物的聚合物材料后,观察到当使用不同的烷基化试剂时,交联网络显示出不同的动态交换速率,这表明含硒化物材料的再加工能力可以得到调节。而且,通过将硒鎓盐引入聚合物材料中,我们观察到这些材料在高温下表现出良好的愈合能力,在环境温度下具有优异的耐溶剂性。这种新型的动态共价化学因此为含硒化物材料的愈合和再加工提供了一种直接的方法。

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