复旦大学陈茂团队报道了利用光驱动有机催化控制自由基共聚制备定制化F/N杂化聚合物。相关研究成果于2024年6月24日发表在《德国应用化学》。

可控自由基共聚为获得具有复杂组成和序列的聚合物提供了有吸引力的途径。

该文中，研究人员首次报道了可见光驱动的氟烯烃和无环N-乙烯基酰胺的有机催化控制共聚的发展。该方法能够通过新型氟化硫代氨基甲酸酯按需合成广泛的酰胺官能化主链含氟聚合物，通过合理选择共聚单体对和比例，促进对化学组成和交替组分的调节。该方法能够通过外部光在时间上控制链生长，并保持高链末端保真度，从而促进了嵌段序列的制备。

值得注意的是，所获得的F/N杂化聚合物在水解时提供了自由氨基取代的氟聚合物，其适用于对各种官能团（例如酰胺、磺酰胺、氨基甲酰胺、硫代氨基甲酰胺）进行后修饰。研究人员进一步证明了在锂金属阳极上原位形成具有理想性能的聚合物网络作为保护层，为推进锂金属电池的发展提供了一条有前景的途径。

附：英文原文

Title: Controlled Radical Copolymerization toward Tailored F/N Hybrid Polymers by Using Light-Driven Organocatalysis

Author: Yufei Chen, Shantao Han, Kaixuan Chen, Xing Guo, Peng Wen, Mao Chen

Issue&Volume: 2024-06-24

Abstract: Controlled radical copolymerizations present attractive avenues to obtain polymers with complicated compositions and sequences. In this work, we report the development of a visible-light-driven organocatalyzed controlled copolymerization of fluoroalkenes and acyclic N-vinylamides for the first time. The approach enables the on-demand synthesis of a broad scope of amide-functionalized main-chain fluoropolymers via novel fluorinated thiocarbamates, facilitating regulations over chemical compositions and alternating fractions by rationally selecting comonomer pairs and ratios. This method allows temporally controlled chain-growth by external light, and maintains high chain-end fidelity that promotes facile preparation of block sequences. Notably, the obtained F/N hybrid polymers, upon hydrolysis, afford free amino-substituted fluoropolymers versatile for post modifications toward various functionalities (e.g., amide, sulfonamide, carbamide, thiocarbamide). We further demonstrate the in-situ formation of polymer networks with desirable properties as protective layers on lithium metal anodes, presenting a promising avenue for advancing lithium metal batteries.

DOI: 10.1002/anie.202408611

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202408611