Rare-Earth Aryloxide/Ylide-Functionalized Phosphine Frustrated Lewis Pairs for the Polymerization of 4-Vinylpyridine and Its Derivatives
Yujie Su1, Yanan Zhao2, Hongyue Zhang1, Yi Luo2,3,*（罗毅）, and Xin Xu1,*（徐信）
1 Soochow Univ, Coll Chem Chem Engn & Mat Sci, Key Lab Organ Synth Jiangsu Prov, Suzhou, Peoples R China
2 Dalian Univ Technol, Sch Chem Engn, State Key Lab Fine Chem, Dalian 116024, Peoples R China
3 PetroChina Petrochem Res Inst, Beijing 102206, Peoples R China
Macromolecules 2021, 54, 17, 7724--7731
This work reports the efficient polymerization of 4-vinylpyridine (4VP) using Lewis pairs composed of homoleptic rare-earth (RE) aryloxides and ylide-functionalized phosphines (YPhos). The resultant P4VP was readily quaternized by the addition of 1-bromododecane. Polymerization of 4VP derivatives (2-methoxy-4-vinylpyridine, 4-vinylquinoline, and 2,6-dimethyl-4-vinylpyridine) also occurred under identical reaction conditions. The RE/YPhos Lewis pair polymerization system effectively copolymerized 4VP with methyl methacrylate, which resulted in copolymers with gradient architectures and narrow molecular weight distributions. A combined experimental and computational study provided critical insights into the polymerization mechanism. Density functional theory calculations also revealed that the use of YPhos as a Lewis base greatly facilitated both the initiation and subsequent monomer insertion in comparison with PEt3.
链接：https://pubs.acs.org/doi/10.1021/acs.macromol.1c01339
