Regio- and Stereoselective Polymerization of Bio-based Ocimene by Rare-Earth Metal Catalysts

Qi-Yuan Wang; Li-Peng Sang; Zhen Zhang; Yang Jiang; Hui Tian; Xia Zhao; Xiang Guo; Shi-Hui Li

doi:10.1007/s10118-023-3047-7

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Regio- and Stereoselective Polymerization of Bio-based Ocimene by Rare-Earth Metal Catalysts

RESEARCH ARTICLE | Updated：2024-01-12

- Regio- and Stereoselective Polymerization of Bio-based Ocimene by Rare-Earth Metal Catalysts
- Regio- and Stereoselective Polymerization of Bio-based Ocimene by Rare-Earth Metal Catalysts
- 高分子科学（英文版） 2024年42卷第2期页码：223-229
- Affiliations：
  
  a.State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
  b.School of Applied Chemistry and Engineering, University of Science and Technology of China, Hefei 230026, China
  c.Science and Technology on Aerospace Chemical Power Laboratory, Hubei Institute of Aerospace Chemotechonology, Xiangyang 441003, China
  d.Shanxi Coal Chemical Industry Technology Research Institute, Xi’an 710000, China
  e.Hubei Institute of Aerospace Chemotechonology, Xiangyang 441003, China
- Author bio：
  
  guoxcasc@163.com (X.G.)
  shihui-li@ciac.ac.cn (S.H.L.)
- Funds：
  
  This work was financially supported by the open research fund program of Science and Technology on Aerospace Chemical Power Laboratory (No. STACPL120221B03) and the National Natural Science Foundation of China (Nos. s22175059, 52073275 and U21A20279).;Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-023-3047-7.
- DOI：10.1007/s10118-023-3047-7
  中图分类号： M
- 收稿：2023-07-11，
  
  修回：2023-8-21，
  
  录用：2023-8-21，
  
  网络首发：2023-09-20，
  
  纸质出版：2024-02-01
- Accepted：
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Wang, Q. Y.; Sang, L. P.; Zhang, Z.; Jiang, Y.; Tian, H.; Zhao, X.; Guo, X.; Li, S. H. Regio- and stereoselective polymerization of bio-based ocimene by rare-earth metal catalysts. Chinese J. Polym. Sci. 2024, 42, 223–229

Qi-Yuan Wang, Li-Peng Sang, Zhen Zhang, et al. Regio- and Stereoselective Polymerization of Bio-based Ocimene by Rare-Earth Metal Catalysts[J]. Chinese Journal of Polymer Science, 2024, 42(2): 223-229.
Wang, Q. Y.; Sang, L. P.; Zhang, Z.; Jiang, Y.; Tian, H.; Zhao, X.; Guo, X.; Li, S. H. Regio- and stereoselective polymerization of bio-based ocimene by rare-earth metal catalysts. Chinese J. Polym. Sci. 2024, 42, 223–229 DOI： 10.1007/s10118-023-3047-7.

Qi-Yuan Wang, Li-Peng Sang, Zhen Zhang, et al. Regio- and Stereoselective Polymerization of Bio-based Ocimene by Rare-Earth Metal Catalysts[J]. Chinese Journal of Polymer Science, 2024, 42(2): 223-229. DOI： 10.1007/s10118-023-3047-7.

摘要

A new type of isotactic cis-1

4-polyocimene is synthesized by coordination polymerization of renewable

-ocimene using complex

which is readily transformed into epoxidized and hydroxylated products. The excellent isotactic

trans

-1

2-polyocimene is produced by complex

Cis

-1

4-PIP-b-

cis

-1

4-POc and

cis

-1

4-PBD-b-

cis

-1

4-POc is obtained in one-pot reactions of

-ocimene with isoprene and butadiene.

Abstract

Coordination polymerization of renewable

-ocimene has been investigated using asymmetric diiminophosphinate lutetium complex

-diketiminate yttrium complex

bis(phosphino)carbazolide yttrium complex

half-sandwich benzyl fluorenyl scandium complex

and pyridyl-methylene-fluorenyl rare-metal complexes

–

. Complexes

and

–

show

trans

-1

2-regioselectivities and high activities

of which

exhibits excellent isoselectivity (

mmmm

99%). Conversely

complexes

and

promote

-ocimene polymerization to produce isotactic

cis

-1

4-polyocimenes (

cis

-1

99%

95%). Diblock copolymers

cis

-1

4-PIP-block-

cis

-1

4-POc and

cis

-1

4-PBD-block-

cis

-1

4-POc are obtained in one-pot reactions of

-ocimene with isoprene and butadiene using complex

. Epoxidation and hydroxylation of polyocimene afford functionalized polyolefins with enhanced

(from −20 °C to 79 °C and 74 °C) and hydrophilicity.

关键词

Keywords

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