美国康奈尔大学Fors, Brett P.团队近日研究了二氧化碳介导的可控阴离子聚合。2025年5月13日，《自然-化学》杂志发表了这一成果。

乙烯基单体的阴离子聚合是制造定义明确材料的强大合成平台。然而，这些反应对水分和氧气极其敏感，需要使用高纯度的试剂，必须在低温下进行，并使用危险且难以处理的烷基锂引发剂。这些缺点共同限制了这些聚合的实用性，并阻碍了它们的广泛使用。 在此基础上，开发一种用户友好的甲基丙烯酸酯阴离子聚合工艺是一个巨大的挑战。

研究组报告了一种由二氧化碳介导的甲基丙烯酸酯阴离子聚合，该聚合可以在高温下进行，并使用易于处理的固体引发剂。将CO₂可逆地添加到烯醇化物链末端有效地缓和了阴离子的反应性，使聚合物在高温下具有窄的摩尔质量分布和优异的分子量靶向性。这种可扩展且更用户友好的二氧化碳介导方法提高了阴离子聚合的可及性和安全性，并促进了各种聚合物材料的生产。

附：英文原文

Title: Controlled anionic polymerization mediated by carbon dioxide

Author: Jacky, Paige E., Easley, Alexandra D., Fors, Brett P.

Issue&Volume: 2025-05-13

Abstract: Anionic polymerizations of vinyl monomers are powerful synthetic platforms for making well-defined materials. However, these reactions are extremely sensitive to moisture and oxygen, require the use of highly purified reagents, must be run at low temperatures, and use hazardous and difficult-to-handle alkyl lithium initiators. Together, these drawbacks limit the practicality of these polymerizations and impede their widespread usage. On this basis, the development of a user-friendly anionic polymerization process for methacrylates is a grand challenge. Here we report an anionic polymerization of methacrylates mediated by CO2 that can be run at elevated temperatures and uses an easy-to-handle solid initiator. The reversible addition of CO2 to the enolate chain end efficiently tempers the reactivity of the anion, giving polymers with narrow molar mass distributions and excellent molecular weight targeting at elevated temperatures. Our scalable and more user-friendly CO2-mediated method improves the accessibility and safety of anionic polymerizations and facilitates the production of a variety of polymeric materials.

DOI: 10.1038/s41557-025-01819-7

Source: https://www.nature.com/articles/s41557-025-01819-7