Synthesis of Precisely Structured Olefin Copolymers by Phenylseleno Oxidation Elimination
Synthesis of Precisely Structured Olefin Copolymers by Phenylseleno Oxidation Elimination
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DOI：
10.1002/macp.202100351
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发表时间：
2021-11
影响因子：
2.5
通讯作者：
Bin Xu;Shaoxiang Liu;Yingying Li;Jiandong Zhang;Xiangqiang Pan;Jian Zhu
中科院分区：
文献类型：
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作者：
Bin Xu;Shaoxiang Liu;Yingying Li;Jiandong Zhang;Xiangqiang Pan;Jian Zhu
含硒聚合物由于其独特的氧化还原响应性而引起了相当大的关注。在这里，苯基乙烯基硒化物（PVSe）作为功能性含硒单体与马来酰亚胺（MI）或其衍生物通过可逆加成-断裂链转移聚合进行聚合。所得聚合物通过基质辅助激光解吸/电离飞行时间质谱和质子核磁共振谱表征，其特别证明通过PVSe和MI或其衍生物的聚合获得交替聚合物。系统地研究了所得聚合物的性质，如玻璃化转变温度、热性能和折射率。此外，基于苯硒基氧化消除，交替聚合物通过30%H2O2氧化，形成精确结构的具有碳-碳（C-C）双键的烯烃共聚物。系统地研究了交替聚合物中双键的选择性生成。由于碳-硒（C-Se）键的低电负性和键能，这种氧化在温和条件下效率很高，这为制备具有MI或其衍生物的精确结构的烯烃共聚物提供了一种新方法。
Selenium‐containing polymers have attracted considerable attention due to their unique redox responsiveness. Here, phenyl vinyl selenide (PVSe), as a functional selenium‐containing monomer, is polymerized with maleimide (MI) or its derivatives by reversible addition–fragmentation chain transfer polymerization. The resulting polymers are characterized by matrix‐assisted laser desorption/ionization time‐of‐flight mass spectroscopy and proton nuclear magnetic resonance spectra, which particularly prove the obtaining of alternating polymers through the polymerization of PVSe and MI or its derivatives. Properties of the resulting polymers are systematically investigated, such as glass transition temperature, thermal performance, and refractive indices. What's more, based on phenylseleno oxidation elimination, the alternating polymers are oxidized through 30% H2O2to form precisely structured olefin copolymers with carboncarbon (CC) double bonds. The selective generation of double bonds in the alternating polymers is systematically studied. The efficiency of such oxidation is very high under mild conditions due to low electronegativity and bond energy of carbonselenium (CSe) bond, which provides a novel method to prepare precisely structured olefin copolymers with MI or its derivatives.