Volume 33, Issue 4
FULL PAPER

Controlled isoprene polymerization mediated by iminopyridine‐iron (II) acetylacetonate pre‐catalysts

Mengmeng Zhao

Key Laboratory of Biobased Materials, Qingdao Institute of Biomass Energy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, 266000 China

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Liang Wang

Key Laboratory of Biobased Materials, Qingdao Institute of Biomass Energy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, 266000 China

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Qaiser Mahmood

Key Laboratory of Biobased Materials, Qingdao Institute of Biomass Energy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, 266000 China

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Chuyang Jing

Key Laboratory of Biobased Materials, Qingdao Institute of Biomass Energy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, 266000 China

Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, 100049 China

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Guangqian Zhu

Key Laboratory of Biobased Materials, Qingdao Institute of Biomass Energy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, 266000 China

Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, 100049 China

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Xianhui Zhang

Key Laboratory of Biobased Materials, Qingdao Institute of Biomass Energy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, 266000 China

Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing, 100049 China

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Xiaowu Wang

Corresponding Author

Key Laboratory of Biobased Materials, Qingdao Institute of Biomass Energy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, 266000 China

Correspondence

Qinggang Wang and Xiaowu Wang, Key Laboratory of Biobased Materials, Qingdao Institute of Biomass Energy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266000, China.

Email: wangqg@qibebt.ac.cn; wangxw@qibebt.ac.cn

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Qinggang Wang

Corresponding Author

Key Laboratory of Biobased Materials, Qingdao Institute of Biomass Energy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao, 266000 China

Correspondence

Qinggang Wang and Xiaowu Wang, Key Laboratory of Biobased Materials, Qingdao Institute of Biomass Energy and Bioprocess Technology, Chinese Academy of Sciences, Qingdao 266000, China.

Email: wangqg@qibebt.ac.cn; wangxw@qibebt.ac.cn

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First published: 01 February 2019
Citations: 6

Abstract

A ligand controlled stereoselective polymerization of isoprene has been developed. A series of (aryl/alkyl)‐iminopyridine iron (II) acetylacetonate complexes: (aryl = Ph Fe1; alkyl = CH2Ph Fe2, CH (Ph)2 Fe3, CH (Me)2 Fe4, C (Me)3 Fe5, C (Me)2CH2C(Me)3 Fe6), has been prepared in which steric and electronic substituents systematically modified to investigate their influences for isoprene polymerization. The molecular structure of representative complex Fe2 was confirmed by single crystal X‐ray diffraction and, revealed a distorted octahedral geometry at iron center. On treatment with methylaluminoxane (MAO), Fe1Fe6 displayed low (Fe5 & Fe6) to high activities (Fe1Fe4) with quantitative monomer conversion (>99%) for isoprene polymerization producing polyisoprene of high molecular weight (up to 2.0 × 105 g/mol) and unimodal molecular weight distribution (1.4–3.3). Specifically, complex Fe2 (alkyl = CH2Ph) displayed the highest activity of 7.0 × 106 g (mol of Fe)−1 h−1 with 85% conversion of monomer over run time of 10 min at 25 °C. While, Fe6 catalyzed polyisoprene possessed high content of trans‐1,4 unit (up to 87%). Furthermore, the influence of the reaction parameters and the nature of the ligands on the catalytic activities and microstructural properties of the polymer were investigated in detail.

Number of times cited according to CrossRef: 6

  • Synthesis of characteristic polyisoprenes using rationally designed iminopyridyl metal (Fe and Co) precatalysts: investigation of co-catalysts and steric influence on their catalytic activity, New Journal of Chemistry, 10.1039/D0NJ00942C, (2020).
  • An unsymmetrical binuclear iminopyridine-iron complex and its catalytic isoprene polymerization, Chemical Communications, 10.1039/D0CC04122J, (2020).
  • Highly active and thermo‐stable iminopyridyl vanadium oxychloride catalyzed isoprene polymerization, Journal of Polymer Science, 10.1002/pol.20200291, 58, 19, (2708-2717), (2020).
  • Synthesis and characterization of aminopyridine iron( ii ) chloride catalysts for isoprene polymerization: sterically controlled monomer enchainment , Dalton Transactions, 10.1039/C9DT00452A, (2019).
  • Isoprene Polymerization: Catalytic Performance of Iminopyridine Vanadium(III) Chloride versus Vanadium(III) Chloride, Polymers, 10.3390/polym11071122, 11, 7, (1122), (2019).
  • Highly Active Iminopyridyl Iron-Based Catalysts for the Polymerization of Isoprene, Molecules, 10.3390/molecules24173024, 24, 17, (3024), (2019).

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