Highly Isoselective Coordination Polymerization of ortho-Methoxystyrene with β-Diketiminato Rare-Earth-Metal Precursors

被引：136

作者：

Liu, Dongtao ^{[1
]}

Yao, Changguang ^{[1
]}

Wang, Rong ^{[2
]}

Wang, Meiyan ^{[1
,3
]}

Wang, Zichuan ^{[1
]}

Wu, Chunji ^{[1
]}

Lin, Fei ^{[1
]}

Li, Shihui ^{[1
]}

Wan, Xinhua ^{[2
]}

Cui, Dongmei ^{[1
]}

机构：

[1] Chinese Acad Sci, Changchun Inst Appl Chem, State Key Lab Polymer Phys & Chem, Changchun 130022, Peoples R China

[2] Peking Univ, Beijing Natl Lab Mol Sci, Key Lab Polymer Chem & Phys, Coll Chem & Mol Engn,Minist Educ, Beijing 100871, Peoples R China

[3] Jilin Univ, Inst Theoret Chem, Changchun 130022, Peoples R China

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2015年 / 54卷 / 17期

关键词：

beta-diketiminate ligand; density functional calculations; isoselective polymerization; ortho-methoxystyrene; rare-earth metal complex; SYNDIOTACTIC POLYSTYRENE; STYRENE POLYMERIZATION; ALPHA-OLEFINS; STEREOSPECIFIC POLYMERIZATION; INSERTION POLYMERIZATION; FUNCTIONALIZED OLEFINS; VINYL MONOMERS; COPOLYMERIZATION; COMPLEXES; CATALYSTS;

D O I：

10.1002/anie.201412166

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Stereoselective coordination/insertion polymerization of the polar ortho-methoxystyrene has been achieved for the first time by using the cationic beta-diketiminato rare-earth-metal species. High activity and excellent isoselectivity (mmmm>99%) were acheived. The unmasked Lewis-basic methoxy group does not poison the Lewis-acidic metal center, but instead activates the polymerization through sigma-pi chelation to the active species together with the vinyl group, thus lower the coordination and activation energies as compared with those of styrene derivatives lacking the methoxy group.

引用

页码：5205 / 5209

页数：5

共 46 条

[41] Syntheses of Well-Defined Functional Isotactic Polypropylenes via Efficient Copolymerization of Propylene with ω-Halo-α-alkenes by Post-metallocene Hafnium Catalyst [J].