Ding Yi-Jie, Zhang Sheng-Ye, Li Ya-Ning, Yu Shu-Yang, Huang Kongchanghao, Zhang Yuchen, Li Jun-Fang, Wang Xiao-Yan, Tang Yong
The State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai, China.
School of Physical Science and Technology, ShanghaiTech University, Shanghai, China.
Nat Commun. 2025 Jul 28;16(1):6939. doi: 10.1038/s41467-025-62145-7.
Copolymerization of more activated methacrylates and less activated vinyl esters is challenging because of their large difference in reactivity ratio. This severely limits the development of high-performance materials. Herein, we design a side-armed bisoxazoline (SaBOX)/CoBr catalyst with sheltered coordination environment to achieve strong binding ability to propagating radicals in photoinduced cobalt-mediated radical polymerization (CMRP) of vinyl ester and methacrylate. This enables the efficient synthesis and structure regulation of methacrylate-vinyl ester copolymers. The catalytic system efficiently and directly produces di- and tri-block copolymers via in-situ chain extension. Moreover, homogeneous random copolymers of vinyl ester and methacrylate are also facilely synthesized. The mechanistic studies are consistent with the polymerization results, which validate the CMRP mechanism and our catalyst design concept.
由于活性差异较大，更具活性的甲基丙烯酸酯与活性较低的乙烯基酯的共聚具有挑战性。这严重限制了高性能材料的发展。在此，我们设计了一种具有屏蔽配位环境的侧臂双恶唑啉（SaBOX）/CoBr催化剂，以在乙烯基酯和甲基丙烯酸酯的光致钴介导自由基聚合（CMRP）中实现对增长自由基的强结合能力。这使得甲基丙烯酸酯-乙烯基酯共聚物能够高效合成并进行结构调控。该催化体系通过原位扩链高效直接地制备二嵌段和三嵌段共聚物。此外，乙烯基酯和甲基丙烯酸酯的均相无规共聚物也能轻松合成。机理研究与聚合结果一致，验证了CMRP机理和我们的催化剂设计理念。
