An Bang, Yue Chaowei, Liu Shuai, Sun Lixing, Sun Tingting, Liu Jian-Biao, Li Yifan
School of Physical Science and Technology, ShanghaiTech University, 201210, Shanghai, China.
College of Chemistry, Chemical Engineering and Materials Science, Shandong Normal University, 250014, Jinan, China.
Angew Chem Int Ed Engl. 2024 Nov 11;63(46):e202408487. doi: 10.1002/anie.202408487. Epub 2024 Oct 8.
Non-activated linear α-olefins are valuable building blocks for organic transformation or olefin (co)polymerization, but they are recognized as textbook knowledge for non-homopolymerizable monomers under radical conditions. In this article, we disclose our effort to achieve an unprecedented library of all carbon-bonded sequence-regulated polymers via radical isomerization homopolymerization of α-olefin derivatives. The success of this distinctive polymerization is attributed to the remarkable efficiency and selectivity exhibited during the cyano group migration or hydrogen atom transfer, which is greatly enhanced by the precise engineering of their monomer structures. This polymerization process enables the elongation of polymer chains by five, six, or seven carbon atoms at each propagation step. These polymers, obtained through the cyano group migration or hydrogen atom transfer involved radical isomerization polymerization processes, emerge as promising candidates resembling polyethylene or polyacrylonitrile copolymers.
未活化的线性α-烯烃是有机转化或烯烃（共）聚合的重要基础原料，但在自由基条件下，它们被认为是不可均聚的单体，这是教科书上的知识。在本文中，我们展示了通过α-烯烃衍生物的自由基异构化均聚反应来构建前所未有的全碳键序列规整聚合物库的研究成果。这种独特聚合反应的成功归因于氰基迁移或氢原子转移过程中所表现出的显著效率和选择性，而单体结构的精确设计极大地提高了这些效率和选择性。该聚合过程能够在每个增长步骤使聚合物链延长五个、六个或七个碳原子。这些通过涉及氰基迁移或氢原子转移的自由基异构化聚合过程得到的聚合物，有望成为类似聚乙烯或聚丙烯腈共聚物的候选材料。
