Citation: Min Su, Meng-Qin Pu, Hang Xiao, Yu-Jiao Chen, Wen-Ming Wan. Super-Grignard reagents (R₂Mg·LiCl) mediated covalent-anionic-radical polymerization capable of low Đ and reactive hydrogen compatibility[J]. Chinese Chemical Letters, ;2023, 34(9): 108167. doi: 10.1016/j.cclet.2023.108167 shu

Super-Grignard reagents (R₂Mg·LiCl) mediated covalent-anionic-radical polymerization capable of low Đ and reactive hydrogen compatibility

Min Su ^{a, b} ,
Meng-Qin Pu ^a ,
Hang Xiao ^a ,
Yu-Jiao Chen ^a ,
Wen-Ming Wan ^{a, b, *,}

a.
Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, State Key Laboratory of Structural Chemistry, Center for Excellence in Molecular Synthesis, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China
b.
University of Chinese Academy of Sciences, Beijing 100049, China

wanwenming@fjirsm.ac.cn

Received Date: 23 October 2022
Revised Date: 10 November 2022
Accepted Date: 27 January 2023
Available Online: 3 February 2023

Figures(3)

The precise synthesis of polymer with narrow molecular weight distribution (Đ) and well-defined architectures is very essential to exploring the functions and properties of polymer materials. Here, a universal polymerization method capable of low Đ and reactive hydrogen compatibility is reported by introducing super-Grignard reagents (R₂Mg·LiCl) into polymer chemistry. Under mild conditions, various monomers, including nonpolar polystyrene and 4-methoxystyrene that cannot be initiated by Grignard reagents, and polar methacrylate, are successfully polymerized with full monomer conversion and low Đ. This approach is amenable to wide varieties of initiators, polymerization temperature, and feed ratio, which makes it attractive for applications in polymer synthesis. By adding methanol and water during the polymerization process, the reactive hydrogen compatibility of this method is confirmed, which makes this method avoid the rigorous restriction on polymerization conditions of anionic polymerization. Moreover, chain extension polymerization and block copolymerization are achieved and demonstrate the livingness of chain propagation, enabling the facile synthesis of well-defined macromolecular architectures. This work therefore expands the methodology libraries of living polymerization, which may cause inspirations to polymer science.
- R₂Mg·LiCl,
- Grignard reagent,
- Living polymerization,
- Covalent-anionic-radical polymerization,
- Block copolymerization
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Super-Grignard reagents (R2Mg·LiCl) mediated covalent-anionic-radical polymerization capable of low Đ and reactive hydrogen compatibility

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Super-Grignard reagents (R₂Mg·LiCl) mediated covalent-anionic-radical polymerization capable of low Đ and reactive hydrogen compatibility