Substituent Effects of Pyridyl-methylene Cyclopentadienyl Rare-earth Metal Complexes on Styrene Polymerization

Zhen Zhang; Zhong-Yi Cai; Yu-Peng Pan; Yan-Li Dou; Shi-Hui Li; Dong-Mei Cui

doi:10.1007/s10118-019-2209-0

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Substituent Effects of Pyridyl-methylene Cyclopentadienyl Rare-earth Metal Complexes on Styrene Polymerization

ARTICLE | Updated：2021-02-18

- Substituent Effects of Pyridyl-methylene Cyclopentadienyl Rare-earth Metal Complexes on Styrene Polymerization
- Substituent Effects of Pyridyl-methylene Cyclopentadienyl Rare-earth Metal Complexes on Styrene Polymerization
- Chinese Journal of Polymer Science 2019年37卷第6期页码：570-577
- Affiliations：
  
  a.Key Laboratory of Automobile Materials of Ministry of Education, Department of Materials Science and Engineering, Jilin University, Changchun 130022, China
  b.State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
- Author bio：
  
  douyl@jlu.edu.cn (Y.L.D.)
  Shihui-li@ciac.ac.cn (S.H.L.)
  dmcui@ciac.ac.cn (D.M.C.)
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (Nos. 51773193 and 21634007), department of science and technology of Jilin province (No. 20180101171JC), and the “973” project (No. 2015CB654702).
- DOI：10.1007/s10118-019-2209-0
  中图分类号：
- 收稿：2018-11-17，
  
  修回：2018-11-29，
  
  录用：2018-12-9，
  
  网络首发：2019-01-04，
  
  纸质出版：2019-06
- Accepted：
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Citation: Zhang, Z.; Cai, Z. Y.; Pan, Y. P.; Dou, Y. L.; Li, S. H.; Cui, D. M. Substituent effects of pyridyl-methylene cyclopentadienyl rare-earth metal complexes on styrene polymerization. Chinese J. Polym. Sci. 2019, 37, 570–577

Zhen Zhang, Zhong-Yi Cai, Yu-Peng Pan, et al. Substituent Effects of Pyridyl-methylene Cyclopentadienyl Rare-earth Metal Complexes on Styrene Polymerization[J]. Chinese Journal of Polymer Science, 2019, 37(6): 570-577.
Citation: Zhang, Z.; Cai, Z. Y.; Pan, Y. P.; Dou, Y. L.; Li, S. H.; Cui, D. M. Substituent effects of pyridyl-methylene cyclopentadienyl rare-earth metal complexes on styrene polymerization. Chinese J. Polym. Sci. 2019, 37, 570–577 DOI： 10.1007/s10118-019-2209-0.

Zhen Zhang, Zhong-Yi Cai, Yu-Peng Pan, et al. Substituent Effects of Pyridyl-methylene Cyclopentadienyl Rare-earth Metal Complexes on Styrene Polymerization[J]. Chinese Journal of Polymer Science, 2019, 37(6): 570-577. DOI： 10.1007/s10118-019-2209-0.

摘要

Abstract

Salt metathesis reactions between pyridyl-methylene-cyclopentadienyl lithium salt and LnCl

followed by the addition of two equivalents of LiCH

SiMe

afforded a series of constrained-geometry-configuration rare-earth metal bis(alkyl) complexes (Cp′CH

-Py)Ln(CH

SiMe

)

(THF)

(Py = C

Cp′ = C

(Cp)

Ln = Sc

= 0 (

); Cp′ = C

(Ind)

Ln = Sc

= 0 (

); Cp′ = 3-Me

Si-C

(3-Me

Si-Ind)

Ln = Sc

= 0 (

)

Ln = Lu (

)

Y (

)

= 1; Cp′ = 2

7-(

Bu)

7-(

Bu)

-Flu)

Ln = Sc (

)

= 0

Ln = Lu (

)

Y (

)

= 1) in moderate to good yields

which were characterized by NMR spectroscopy and single-crystal X-ray diffraction (for complex

). In the presence of [Ph

C][B(C

)

] and Al

these complexes displayed different performances towards styrene polymerization. Rare-earth metal bis(alkyl) precursors bearing Cp

Ind

and 3-Me

Si-Ind segments exhibited very low catalytic activity to afford syndiotactic polystyrene. All electron-donating

Bu substituted complexes

and

showed very high activity and perfect syndiotactivity (

rrrr

99%)

producing high molecular weight polystyrene (up to 54.1 × 10

) with relatively narrow molecular distribution (PDI = 1.28−2.49).

关键词

Keywords

references

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