中国科学院长春应用化学研究所陈学思报道了通过切换催化，一锅法精密合成AB、ABA和ABC嵌段共聚物。相关研究成果于2022年1月17日发表在《德国应用化学》。

首次开发了使用商用salenMn催化剂的可切换催化，并将其应用于酸酐、环氧化物、CO₂和ε-己内酯（ε-CL）混合物的一锅选择性共聚，以精确合成AB、ABA和新型ABC嵌段共聚物。通过理论计算，对所观察到的由三个不同聚合循环组成的独特双开关过程进行了解释。令人惊讶的是，第一个嵌段被证明是一种有效的大分子引发剂，用于将碳酸盐键连续引入共聚物中，尽管仅使用催化剂即可实现主要的环化。

此外，通过对不同环氧化合物的选择性反应，实现了多达五种单体的可切换共聚，得到结构多样性和功能性良好的多嵌段共聚物。

附：英文原文

Title: One-pot Precision Synthesis of AB, ABA and ABC Block Copolymers via Switchable Catalysis

Author: Zhenjie Yang, Chenyang Hu, Fengchao Cui, Xuan Pang, Yuezhou Huang, Yanchuan Zhou, Xuesi Chen

Issue&Volume: 2022-01-17

Abstract: The switchable catalysis using a commercial salenMn catalyst was firstly developed and applied in the one-pot selective copolymerization from anhydrides, epoxides, CO  2  and ε-caprolactone (ε-CL) mixtures for the precise synthesis of AB, ABA and novel ABC block copolymers. The observed unique double switch process comprising three different polymerization cycles was rationalized by theoretical calculations. Surprisingly, the first block turned out to be an efficient macromolecular initiator for the consecutive introduction of carbonate linkages into copolymers, albeit with dominant cyclization with the catalyst alone. Further, through the selective reaction on different epoxides, the switchable copolymerization of up to five monomers was achieved yielding well-defined multi-block copolymers with structural diversity and functionality.

DOI: 10.1002/anie.202117533

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202117533