Ethylene-bridged Indenyl-fluorenyl Metallocene Complexes for Efficient Preparation of Allyl-terminated Propylene Oligomers and Polymers <italic style="font-style: italic">via</italic> Selective <italic style="font-style: italic">β</italic>-Methyl Transfer

Lei Zhang; Bin Zhang; Haiyan Ma

doi:10.1007/s10118-019-2224-1

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Ethylene-bridged Indenyl-fluorenyl Metallocene Complexes for Efficient Preparation of Allyl-terminated Propylene Oligomers and Polymers via Selective β-Methyl Transfer

ARTICLE | Updated：2021-02-18

- Ethylene-bridged Indenyl-fluorenyl Metallocene Complexes for Efficient Preparation of Allyl-terminated Propylene Oligomers and Polymers via Selective β-Methyl Transfer
- Ethylene-bridged Indenyl-fluorenyl Metallocene Complexes for Efficient Preparation of Allyl-terminated Propylene Oligomers and Polymers via Selective β-Methyl Transfer
- Chinese Journal of Polymer Science 2019年37卷第6期页码：578-590
- Affiliations：
  
  Shanghai Key Laboratory of Functional Materials Chemistry and Laboratory of Organometallic Chemistry, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China
- Author bio：
  
  haiyanma@ecust.edu.cn
- Funds：
  
  This work was financially supported by the National Natural Science Foundation of China (No. 21274041), the Key Project of Chinese Ministry of Education (No. 109064), and the Fundamental Research Funds for the Central Universities (No. WK1214048).
- DOI：10.1007/s10118-019-2224-1
  中图分类号：
- 收稿：2018-12-07，
  
  修回：2019-1-10，
  
  录用：2019-1-14，
  
  网络首发：2019-03-01，
  
  纸质出版：2019-06
- Accepted：
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Citation: Zhang, L.; Zhang, B.; Ma, H. Ethylene-bridged indenyl-fluorenyl metallocene complexes for efficient preparation of allyl-terminated propylene oligomers and polymers via selective β-methyl transfer. Chinese J. Polym. Sci. 2019, 37, 578–590

Lei Zhang, Bin Zhang, Haiyan Ma. Ethylene-bridged Indenyl-fluorenyl Metallocene Complexes for Efficient Preparation of Allyl-terminated Propylene Oligomers and Polymers via Selective β-Methyl Transfer[J]. Chinese Journal of Polymer Science, 2019, 37(6): 578-590. DOI: 10.1007/s10118-019-2224-1.
Citation: Zhang, L.; Zhang, B.; Ma, H. Ethylene-bridged indenyl-fluorenyl metallocene complexes for efficient preparation of allyl-terminated propylene oligomers and polymers via selective β-methyl transfer. Chinese J. Polym. Sci. 2019, 37, 578–590 DOI： 10.1007/s10118-019-2224-1.

Lei Zhang, Bin Zhang, Haiyan Ma. Ethylene-bridged Indenyl-fluorenyl Metallocene Complexes for Efficient Preparation of Allyl-terminated Propylene Oligomers and Polymers via Selective β-Methyl Transfer[J]. Chinese Journal of Polymer Science, 2019, 37(6): 578-590. DOI: 10.1007/s10118-019-2224-1. DOI：

摘要

Abstract

Four

-symmetric

ansa

-metallocene complexes

(Ind)(2

-Flu)ZrCl

(

)

(3-Bn-Ind)(2

-Flu)ZrCl

(

)

(3-Bn-Ind)(3

-Flu)ZrCl

(

)

and C

(3-Bn-Ind)(2

-Flu)HfCl

(

)

were synthesized and characterized. The structures of complexes

and

were further determined

via

X-ray diffraction studies. Upon activation with modified methylaluminoxane (MMAO) or Al

/[Ph

C][B(C

)

] (TIBA/TrB)

most of these complexes showed high efficiency in catalyzing propylene oligomerization/polymerization to afford products dominantly with allyl terminals

via

selective

-methyl transfer (

-Me transfer). The introduction of 3-benzyl group on the indenyl ring of the complexes was found to be crucial in enabling highly selective

-Me transfer during the polymerization process

leading to selectivities up to 89% obtained by zirconocene complexes

and

and up to 91% obtained by hafnocene complex

. Detailed chain-end analysis by

H-NMR

C-NMR

and MALDI-TOF mass spectroscopy revealed that the allyl chain-ends of the polymeric products resulted from a selective

-Me transfer process after two successively primary insertions of the monomer. Further studies concerning the dependence of chain release selectivity as well as the molecular weight of products on monomer concentration suggested that both

-Me transfer (major) and

-hydrogen transfer (

-H transfer) (minor) mediated by

/MMAO and

/MMAO systems may mainly operate in a bimolecular pathway.

关键词

Keywords

references

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Ethylene-bridged Indenyl-fluorenyl Metallocene Complexes for Efficient Preparation of Allyl-terminated Propylene Oligomers and Polymers via Selective β-Methyl Transfer

Ethylene-bridged Indenyl-fluorenyl Metallocene Complexes for Efficient Preparation of Allyl-terminated Propylene Oligomers and Polymers via Selective β-Methyl Transfer

DOI：10.1007/s10118-019-2224-1

摘要

Abstract

关键词

Keywords

references