Living/controlled polymerization of vinylpyridines into sequence-regulated copolymers by Lewis pair  

作　　者：Qiankun Ding Wuchao Zhao Fukuan Li Jianghua He Yuetao Zhang 

机构地区：[1]Department of State Key Laboratory of Supramolecular Structure and Materials,College of Chemistry,Jilin University,Changchun 130012,China

出　　处：《Science China Chemistry》2024年第8期2737-2746,共10页中国科学（化学英文版）

基　　金：supported by the National Natural Science Foundation of China (22225104, 92356302 and 22071077);China Postdoctoral Science Foundation (2022TQ0115 and 2022M711297)。

摘　　要：The poly(vinylpyridine)(PVP) based(co)polymers are of particular interest in materials science, due to their multifunctionality and diverse applications. So far, there is no report on the sequence-regulated copolymerization of vinylpyridines(VPs) and methacrylate monomer in one-step manner yet. Here we designed and synthesized a series of guanidine phosphines as Lewis base(LB), which is combined with bulky organoaluminium to construct Lewis pairs(LPs) for polymerization of VPs. The living/controlled polymerization of 4-vinylpyridine(4-VP) or 2-vinylpyridine(2-VP) can be accomplished with remarkable efficiency by such Lewis pair polymerization(LPP), furnishing polymers with high molecular weight(up to 288 kg/mol) and narrow molecular weight distribution(as low as 1.17). Mechanistic studies reveal the interaction of LPs and formation of zwitterionic intermediates, providing solid evidences to support the proposed polymerization mechanism. More importantly, by simply adjusting the LA dosage, this LPP strategy realizes the unprecedented control over the sequence regulation of 2-VP-based copolymers from gradient to block in one-step manner, regardless of the monomer ratio, which greatly expands the versatility of the LPP.

关 键 词：guanidine phosphine Lewis pair polymerization living/controlled polymerization vinyl pyridine sequence regulation 

分 类 号：TQ317[化学工程—高聚物工业]