以磷酰亚胺脒（PADIs）作为双功能布朗斯特酸催化剂的ε-己内酯的有机催化开环聚合反应
Organocatalytic Ring-Opening Polymerization of ϵ-Caprolactone with Phosphoramidimidates (PADIs) as a Bifunctional Brønsted Acid Catalyst.
作者信息
Zhang Xun, Sun Pan, Jiang Yu, Liao Saihu
机构信息
Key Laboratory of Molecule Synthesis and Function Discovery (Fujian Province University) College of Chemistry, Fuzhou University, Fuzhou, 350116, P. R. China.
Department State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry Chinese Academy of Sciences, Lingling Lu, Shanghai, 200032, P. R. China.
出版信息
Chem Asian J. 2023 Jan 17;18(2):e202201127. doi: 10.1002/asia.202201127. Epub 2022 Dec 12.
In this study, an organocatalytic ring-opening polymerization (ROP) of ϵ-caprolactone (ϵ-CL) has been developed by employing PADIs as a novel and efficient acid/base bifunctional organocatalyst, which could afford metal-free poly(ϵ-caprolactone) with predictable molecular weight and narrow dispersity at a low catalyst loading under mild conditions. NMR and kinetic studies indicate that the ring-opening polymerizations of lactones catalyzed by PADIs proceed in a living and well controlled manner. Moreover, this organic Brønsted acid catalytic system could allow the synthesis of PCL with molecular weight above 60 kg/mol, as well as well-defined star polymers.
在本研究中，通过使用PADIs作为新型高效的酸碱双功能有机催化剂，开发了一种ε-己内酯（ε-CL）的有机催化开环聚合（ROP）方法，该方法能够在温和条件下以低催化剂负载量提供具有可预测分子量和窄分散度的无金属聚（ε-己内酯）。核磁共振（NMR）和动力学研究表明，PADIs催化的内酯开环聚合以活性和良好控制的方式进行。此外，这种有机布朗斯特酸催化体系能够合成分子量高于60 kg/mol的聚己内酯以及结构明确的星形聚合物。
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