日本名古屋大学Kamigaito Masami研究团队报道了以C-H键为休眠态物种的质子转移阴离子聚合。相关研究成果于2024年7月4日发表在国际顶尖学术期刊《自然—化学》。

活性阴离子聚合是最常见和历史最长的活性聚合，通常需要严格的无水条件和每个聚合物链一种金属引发剂。

该文中，研究人员介绍了甲基丙烯酸酯的质子转移阴离子聚合，使用酸性C–H键作为被碱催化剂活化的休眠物种。聚合机理涉及生长的烯醇化物物种的可逆链转移或终止。弱酸性化合物，如异丁酸烷基酯，在大量的钾碱催化剂存在下用作引发剂或链转移剂，以产生聚合物链，从而降低金属化合物/链的比例。

添加的酒精可以作为可逆的终止剂来抑制繁殖。末端官能化的星形、嵌段和接枝聚合物，很容易从具有C–H键的化合物中获得。

附：英文原文

Title: Proton transfer anionic polymerization with C–H bond as the dormant species

Author: Uchiyama, Mineto, Ohira, Natsumi, Yamashita, Konomi, Sagawa, Katsutoshi, Kamigaito, Masami

Issue&Volume: 2024-07-04

Abstract: Living anionic polymerization—the most common living polymerization and the one with the longest history—generally requires stringent, water-free conditions and one metal initiator per polymer chain. Here we present the proton transfer anionic polymerization of methacrylates using acidic C–H bonds as the dormant species that are activated by base catalysts. The polymerization mechanism involves reversible chain transfer or termination of the growing enolate species. A weakly acidic compound, such as an alkyl isobutyrate, serves as the initiator or chain-transfer agent in the presence of a bulky potassium base catalyst to produce a polymer chain and, thereby, diminishes the metal compound per chain ratio. An added alcohol serves as a reversible terminator to tame the propagation. End-functionalized, star, block and graft polymers are easily accessible from compounds with C–H bonds.

DOI: 10.1038/s41557-024-01572-3

Source: https://www.nature.com/articles/s41557-024-01572-3