Stereoselective Copolymerization of Unprotected Polar and Nonpolar Stryenes by an Yttrium Precursor:Control of Polar-Group Distribution and Mechanism

被引：94

作者：

Liu, Dongtao ^{[1
]}

Wang, Meiyan ^{[2
]}

Wang, Zichuan ^{[1
]}

Wu, Chunji ^{[1
]}

Pan, Yupeng ^{[1
]}

Cui, Dongmei ^{[1
]}

机构：

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

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

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2017年 / 56卷 / 10期

关键词：

polar monomers; sequence regulation; styrene; syndioselective copolymerization; yttrium; PALLADIUM-CATALYZED COPOLYMERIZATION; EARTH-METAL PRECURSORS; SYNDIOTACTIC POLYSTYRENE; COORDINATION POLYMERIZATION; FUNCTIONALIZED OLEFINS; SUBSTITUTED STYRENES; METHYL ACRYLATE; NICKEL-CATALYST; ETHYLENE; MONOMERS;

D O I：

10.1002/anie.201611066

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Styrene underwent unprecedented coordinationinsertion copolymerization with naked polar monomers (ortho-/ meta-/ para-methoxystyrene) in the presence of a pyridyl methylene fluorenyl yttrium catalyst. High activity (1.26 X 10(6) gmol(Y)(- 1)h (-1)) and excellent syndioselectivity were observed, and high-molecular-weight copolymers (24.6 X 10(4) gmol (-1)) were obtained. The insertion rate of the polar monomers could be adjusted in the full range of 0-100% simply by changing the loading of the polar styrene monomer. Strikingly, the copolymers had tapered, gradient, and even random sequence distributions, depending on the position of the polar methoxy group on the phenyl ring and thus on its mode of coordination to the active metal center, as shown by tracking the polymerization process and DFT calculations.

引用

页码：2714 / 2719

页数：6

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