2025年4月10日出版的《美国化学会杂志》发表了中国科学院大学汪洋研究组的最新成果，他们的最新研究探明了含动态配体的单催化剂合成烯烃嵌段共聚物。

介绍了一种以单一催化剂为主体合成OBCs的新方法。通过将该催化剂与调节剂偶联，该课题组一步合成了具有可调硬/软嵌段比和高熔融温度（~120°C）的OBCs。该方法具有操作简单、不需要连锁穿梭剂、单独添加单体、可调整反应条件等优点。机理研究表明，烷基链作为临时配体，动态影响催化剂的聚合行为。这一动态过程允许催化剂在高效和低效α-烯烃结合剂之间交替，从而促进OBCs的合成。

据介绍，烯烃嵌段共聚物（OBCs）是最先进的聚烯烃类别之一，作为每年约2亿吨聚烯烃产量的一部分，大量生产。然而，目前的OBCs制造依赖于一个复杂、昂贵的双催化剂过程，需要危险链穿梭剂。以单一催化剂为主题的更有效的合成OBCs的方法是非常理想的，但仍然具有很大的挑战性。传统的烯烃共聚催化剂通常生长单链聚合物，由于它们不能以必要的精度结合α-烯烃，因此无法产生嵌段结构。为了实现嵌段共聚，催化剂必须同时完成两个看似矛盾的任务，即高效和低效地将α-烯烃结合到聚合物链中。

附：英文原文

Title: Single Catalyst with Dynamic Ligands Enabled Synthesis of Olefin Block Copolymers

Author: Lanfei Lu, Yu Li, Chenxiaoning Meng, Kunyu Liu, Yue Yu, Hui Chen, Guoming Liu, Yang Wang

Issue&Volume: April 10, 2025

Abstract: Olefin block copolymers (OBCs) are among the most advanced classes of polyolefins, produced in large quantities as part of the approximately 200 million tons of polyolefins produced annually. However, current OBCs manufacturing relies on a complex, costly, two-catalyst process that requires hazardous chain shuttling agents. A more efficient approach using a single catalyst for the synthesis of the OBCs is highly desirable but remains significantly challenging. Traditional olefin copolymerization catalysts typically grow a single polymer chain and are incapable of generating block structures as they fail to incorporate α-olefins with the necessary precision. To achieve block copolymerization, the catalyst must simultaneously accomplish two seemingly contradictory tasks, efficiently and inefficiently incorporating α-olefins into the polymer chain. Here, we introduce a new approach for synthesizing OBCs using a single catalyst. By coupling this catalyst with a regulating agent, we enabled a one-step synthesis of OBCs with tunable hard/soft block ratios and high melting temperatures (～120 °C). This method offers significant advantages, featuring its operational simplicity, elimination of chain shuttling agents, separate comonomer addition, or adjustments in reaction conditions. Mechanistic studies suggest that alkyl chains act as temporary ligands, dynamically influencing the catalyst’s polymerization behavior. This dynamic process allows the catalyst to alternate between efficient and inefficient α-olefin incorporators, thereby facilitating the synthesis of OBCs.

DOI: 10.1021/jacs.4c18606

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.4c18606