Ketyl Radical Anion Mediated Radical Polymerization and Anionic Ring‐Opening Polymerization to Give Polymers with Low Molecular Weight Distribution

乙烯基 聚合 化学 离子聚合 自由基聚合 高分子化学 阳离子聚合 开环聚合 钴介导的自由基聚合 活性自由基聚合 光化学 一氧化氮介导的自由基聚合 动链长度 聚合物 链生长聚合 有机化学 二苯甲酮
作者
Yu‐Jiao Chen,Liang‐Tao Wu,Tai‐An Li,Meng‐Qin Pu,Xiaoli Sun,Hongli Bao,Wen‐Ming Wan
出处
期刊:Angewandte Chemie [Wiley]
卷期号:62 (31) 被引量:4
标识
DOI:10.1002/anie.202304033
摘要

The development of novel polymerization capable of yielding polymers with low molecular weight distribution (Đ) is essential and significant in polymer chemistry, where monofunctional initiator contains only one initiation site in these polymerizations generally. Here, ketyl radical anion species is introduced to develop a novel Ketyl Mediated Polymerization (KMP), which enables radical polymerization at carbon radical site and anionic ring-opening polymerization at oxygen anion site, respectively. Meanwhile, polymerization and corresponding organic synthesis generally couldn't be performed simultaneously in one pot. Through KMP, organic synthesis and polymerization are achieved in one pot, where small molecules (cyclopentane derivates) and polymers with low Đ are successfully prepared under mild condition simultaneously. At the initiation step, both organic synthesis and polymerization are initiated by single electron transfer reaction with ketyl radical anion formation. Cyclopentane derivates are synthesized through 3-3 coupling reaction and cyclization. Polystyrene and polycaprolactone with low Đ and a full monomer conversion are prepared by KMP via radical polymerization and anionic ring-opening polymerization, respectively. This work therefore enables both organic synthesis and two different polymerizations from same initiation system, which saves time, labour, resource and energy and expands the reaction mode and method libraries of organic chemistry and polymer chemistry.
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