Chen Yasu, Wang Shuo, Wang Tongkun, Wang Xianjin, Sun Hao, Zhu Chen
Frontiers Science Center for Transformative Molecules, School of Chemistry and Chemical Engineering, State Key Laboratory of Synergistic Chem-Bio Synthesis, and Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, China.
State Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Road, Shanghai, 200032, China.
Angew Chem Int Ed Engl. 2025 Jul 7;64(28):e202507557. doi: 10.1002/anie.202507557. Epub 2025 May 7.
Cyclic olefin polymers (COPs) are of high importance in optical and medical materials. These materials are typically synthesized via ring-opening metathesis polymerization of norbornene derivatives, using metallocene catalysts, followed by high-pressure hydrogenation catalyzed by noble metals. However, the complex synthetic processes, the continuous use of expensive catalysts, and the need to remove metal residues remain substantial barriers in COP production. In contrast, radical cyclopolymerization of dienes, which eliminates the need for metal catalysis and hydrogenation, offers a promising alternative for COP synthesis. Nevertheless, chain transfer reactions hinder the radical polymerization of non-conjugated dienes. To address these challenges, we present a novel strategy, group transfer radical cyclopolymerization (GTRCP), which effectively suppresses chain transfer and enables radical polymerization of dienes to yield COPs. This approach allows for the production of a broad range of sequence-regulated COPs with high molecular weights and low dispersity. Density functional theory calculations support the proposed GTRCP mechanism, highlighting its efficiency and selectivity, driven by substantial thermodynamic forces. The resulting COPs demonstrate great potential as the interphase layer materials in anode-free lithium metal batteries, significantly enhancing the cycling performance towards practical energy storage applications.
环状烯烃聚合物（COPs）在光学和医学材料中具有高度重要性。这些材料通常通过降冰片烯衍生物的开环易位聚合反应，使用金属茂催化剂合成，随后进行由贵金属催化的高压氢化反应。然而，复杂的合成过程、昂贵催化剂的持续使用以及去除金属残留物的需求仍然是COP生产中的重大障碍。相比之下，二烯烃的自由基环化聚合反应消除了对金属催化和氢化的需求，为COP合成提供了一种有前景的替代方法。然而，链转移反应阻碍了非共轭二烯烃的自由基聚合。为应对这些挑战，我们提出了一种新策略，即基团转移自由基环化聚合反应（GTRCP），它有效地抑制了链转移，并使二烯烃的自由基聚合能够生成COPs。这种方法允许生产具有高分子量和低分散性的多种序列规整的COPs。密度泛函理论计算支持所提出的GTRCP机理，突出了其由强大热力学力驱动的效率和选择性。所得的COPs作为无阳极锂金属电池的界面层材料显示出巨大潜力，显著提高了面向实际储能应用的循环性能。
