1,3-Butadiene Polymerizations Catalyzed by Cobalt and Iron Dichloride Complexes Bearing Pyrazolylimine Ligands

Liang Fang; Wen-Peng Zhao; Chao Han; Chun-Yu Zhang; Heng Liu; Yan-Ming Hu; Xue-Quan Zhang

doi:10.1007/s10118-019-2198-z

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1,3-Butadiene Polymerizations Catalyzed by Cobalt and Iron Dichloride Complexes Bearing Pyrazolylimine Ligands

ARTICLE | Updated：2021-02-18

- 1,3-Butadiene Polymerizations Catalyzed by Cobalt and Iron Dichloride Complexes Bearing Pyrazolylimine Ligands
- 1,3-Butadiene Polymerizations Catalyzed by Cobalt and Iron Dichloride Complexes Bearing Pyrazolylimine Ligands
- Chinese Journal of Polymer Science 2019年37卷第5期页码：462-470
- Affiliations：
  
  a.CAS Key Laboratory of High-Performance Synthetic Rubber and its Composite Materials, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
  b.University of Chinese Academy of Sciences, Beijing 100049, China
  c.School of Materials Science and Engineering, Shenyang University of Chemical Technology, Shenyang 110142, China
- Author bio：
  
  cyzhang@ciac.ac.cn (C.Y.Z.)
  hengliu@ciac.ac.cn (H.L.)
- Funds：
  
  This work was financially supported by the National Basic Research Program of China (No. 2015CB654700 (2015CB654702)) and the National Natural Science Foundation of China (No. 21801236).
- DOI：10.1007/s10118-019-2198-z
  中图分类号：
- 收稿：2018-09-27，
  
  修回：2018-10-30，
  
  录用：2018-11-3，
  
  网络首发：2018-11-26，
  
  纸质出版：2019-05
- Accepted：
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Citation: Fang, L.; Zhao, W. P.; Han, C.; Zhang, C. Y.; Liu, H.; Hu, Y. M.; Zhang, X. Q. 1,3-Butadiene polymerizations catalyzed by cobalt and iron dichloride complexes bearing pyrazolylimine ligands. Chinese J. Polym. Sci. 2019, 37, 462–470

Liang Fang, Wen-Peng Zhao, Chao Han, et al. 1,3-Butadiene Polymerizations Catalyzed by Cobalt and Iron Dichloride Complexes Bearing Pyrazolylimine Ligands[J]. Chinese Journal of Polymer Science, 2019, 37(5): 462-470.
Citation: Fang, L.; Zhao, W. P.; Han, C.; Zhang, C. Y.; Liu, H.; Hu, Y. M.; Zhang, X. Q. 1,3-Butadiene polymerizations catalyzed by cobalt and iron dichloride complexes bearing pyrazolylimine ligands. Chinese J. Polym. Sci. 2019, 37, 462–470 DOI： 10.1007/s10118-019-2198-z.

Liang Fang, Wen-Peng Zhao, Chao Han, et al. 1,3-Butadiene Polymerizations Catalyzed by Cobalt and Iron Dichloride Complexes Bearing Pyrazolylimine Ligands[J]. Chinese Journal of Polymer Science, 2019, 37(5): 462-470. DOI： 10.1007/s10118-019-2198-z.

摘要

Abstract

A series of pyrazolylimine ligated Co(II) and Fe(II) complexes with general formula of (PhC＝N(C

)

-2

6)(C

)

-3

5)MtCl

= Me

= H

Mt = Co (

)

Fe (

); R

= Me

Mt = Co (

)

Fe (

); R

= H

Mt = Co (

)

Fe (

); R

= Me

Mt = Co (

)

Fe (

); R

= Ph

Mt = Co (

)

Fe (

)) were synthesized and thoroughly characterized. Determined by single crystal X-ray diffraction

complexes

and

revealed dimeric structures

in which distorted trigonal bipyramid geometries were adopted for each metal centers. In the presence of ethylaluminum sesquichloride (EASC)

all the cobalt complexes displayed high activities in 1

3-butadiene polymerization

affording polybutadienes with predominant

cis

-1

4 contents (up to 97.0%). Influences of ligand structure and polymerization parameters on catalytic performance were investigated systematically. For pyrazolylimine iron(II) dichloride complexes

the catalytic activities and microstructures of the resultant polybutadienes were highly dependent on ligand structures and polymerization conditions. For complex

changing cocatalyst from trialkyl aluminums to methyl aluminoxane (MAO) led to an shift of selectivity from high

cis

-1

4- to

trans

-1

4-/1

2- manner. Being activated by MAO

complexes

and

gave

trans

-1

4-/1

2- binary polybutadienes

while complexes

and

afforded

cis

-1

4- enriched polymers.

关键词

Keywords

references

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