Song Silin, Wang Shuo, Wang Ziqiang, Sun Hao, Wang Xianjin, Zhu Chen
Frontiers Science Center for Transformative Molecules, Zhangjiang Institute for Advanced Study, and Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, China.
Angew Chem Int Ed Engl. 2025 Feb 3;64(6):e202418350. doi: 10.1002/anie.202418350. Epub 2024 Dec 13.
Introducing polar groups into non-polar polyolefins can significantly enhance the important properties of materials. However, producing polyolefin backbones consisting of polar blocks remains elusive, due to the substantial difference of reactivity ratios between polar and non-polar olefin monomers in radical polymerization or the poisoning of transition-metal catalysts by polar groups in coordination polymerization. Herein we present a practical way for the preparation of polyethylene-based polymers with distinct polar groups by radical polymerization of α-olefins. A strategy of switchable remote hydrogen atom or group transfer is devised, leading to a diverse range of AAB or ABC sequence-defined carbon-chain polyolefins. The utility of these polymers is demonstrated by using poly(ethyl 2-cyanohept-6-enoate) (P2) as an interphase layer material in anode-free Li metal battery, which effectively improves the cycling stability of the battery and indicates its potential in energy storage applications.
将极性基团引入非极性聚烯烃中可显著增强材料的重要性能。然而，由于自由基聚合中极性和非极性烯烃单体的反应活性比存在显著差异，或者配位聚合中极性基团会使过渡金属催化剂中毒，因此制备由极性嵌段组成的聚烯烃主链仍然难以实现。在此，我们提出了一种通过α-烯烃的自由基聚合制备具有不同极性基团的聚乙烯基聚合物的实用方法。设计了一种可切换的远程氢原子或基团转移策略，从而得到了多种AAB或ABC序列定义的碳链聚烯烃。以聚（2-氰基庚-6-烯酸乙酯）（P2）作为无阳极锂金属电池的界面层材料，证明了这些聚合物的实用性，它有效地提高了电池的循环稳定性，并显示出其在储能应用中的潜力。
