DMAO-activated Rare-earth Metal Catalysts for Styrene and Its Derivative Polymerization

Zhen Zhang; Yang Jiang; Kai Zhang; Zhong-Yi Cai; Shi-Hui Li; Dong-Mei Cui

doi:10.1007/s10118-021-2583-2

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DMAO-activated Rare-earth Metal Catalysts for Styrene and Its Derivative Polymerization

ARTICLE | Updated：2021-06-02

- DMAO-activated Rare-earth Metal Catalysts for Styrene and Its Derivative Polymerization
- Chinese Journal of Polymer Science Vol. 39, Issue 9, Pages: 1185-1190(2021)
- Affiliations：
  
  a.College of Materials Science and Engineering, Jilin University, Changchun 130025, China
  b.State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
- Author bio：
  
  caizy@jlu.edu.cn (Z.Y.C.)
  shihui-li@ciac.ac.cn (S.H.L.)
- Funds：
- DOI：10.1007/s10118-021-2583-2
  CLC：
- Received：20 February 2021，
  
  Revised：2021-3-15，
  
  Accepted：19 March 2021，
  
  Online First：02 June 2021，
  
  Published：18 July 2021
- Accepted：
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Zhang, Z.; Jiang, Y.; Zhang, K.; Cai, Z. Y.; Li, S. H.; Cui, D. M. DMAO-activated rare-earth metal catalysts for styrene and its derivative polymerization. Chinese J. Polym. Sci. 2021, 39, 1185–1190

Zhen Zhang, Yang Jiang, Kai Zhang, et al. DMAO-activated Rare-earth Metal Catalysts for Styrene and Its Derivative Polymerization[J]. Chinese Journal of Polymer Science, 2021, 39(9): 1185-1190.
Zhang, Z.; Jiang, Y.; Zhang, K.; Cai, Z. Y.; Li, S. H.; Cui, D. M. DMAO-activated rare-earth metal catalysts for styrene and its derivative polymerization. Chinese J. Polym. Sci. 2021, 39, 1185–1190 DOI： 10.1007/s10118-021-2583-2.

Zhen Zhang, Yang Jiang, Kai Zhang, et al. DMAO-activated Rare-earth Metal Catalysts for Styrene and Its Derivative Polymerization[J]. Chinese Journal of Polymer Science, 2021, 39(9): 1185-1190. DOI： 10.1007/s10118-021-2583-2.

摘要

Abstract

The catalytic performance of rare-earth metal dialkyl complexes in combination with DMAO (dry methylaluminoxane) is explored. In the presence of 60 equivalents of DMAO

the half-sandwich complex (C

Ph)Sc(CH

SiMe

)

(THF) (

) is inert for styrene polymerization

but (C

Ph)Sc(CH

NMe

)

(

) converts 18% styrene into syndiotactic polystyrene. Under the same conditions

the constrained-geometry configuration sandium complex (C

Py)Sc(CH

SiMe

)

(

) displays extremely high catalytic activity (

6420 kg·mol

−1

·h

−1

) and perfect syndiospecific (

rrrr

99%) for styrene polymerization

while its lutetium (

) and yttrium (

) analogues are nearly inactive. Although the binary catalytic system

/DMAO exhibits very low activity for 4-methoxystyrene polymerization

it is an efficient catalyst for the syndioselective polymerization of other styrene derivatives such as 2-methoxystyrene

4-methylthiostyrene

4-fluorostyrene

4-dimethylhydrosilylstyrene

alkyne-susbstituted styrenes and 4-methylstyrene. In addition

the binary system

/DMAO can copolymerize ethylene and styrene to give alternating copolymers with a single glass transition at 80 °C and 0.4 MPa ethylene pressures. By increasing styrene feed amount from 20 mmol to 60 mmol

the styrene content slight increases from 48.2 mol% to 53.8 mol%

but the polymerization activity is obviously promoted from 240 kg·mol

–1

·h

–1

to 532 kg·mol

–1

·h

–1

关键词

Keywords

references

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