Trichlorozirconium 2-Hydrazonides: Synthesis, Characterization and Their Catalytic Behavior toward Ethylene Polymerization

Citation: Xin-e Duan, Qi-feng Xing, Zhen-ming Dong, Jian-bin Chao, Sheng-di Bai, Dian-sheng Liu, Wen-hua Sun. Trichlorozirconium 2-Hydrazonides: Synthesis, Characterization and Their Catalytic Behavior toward Ethylene Polymerization[J]. Chinese Journal of Polymer Science, 2016, 34(3): 390-398. doi: 10.1007/s10118-016-1768-6 shu

Trichlorozirconium 2-Hydrazonides: Synthesis, Characterization and Their Catalytic Behavior toward Ethylene Polymerization

1.
1. Institute of Applied Chemistry, Shanxi University, Taiyuan 030006, China
2.
2. School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China
3.
3. Key Laboratory of Engineering Plastics and Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
4.
5.
Key Laboratory of Engineering Plastics and Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
6.
Institute of Applied Chemistry, Shanxi University, Taiyuan 030006, China
7.
School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China
基金项目:
This work was financially supported by the National Natural Science Foundation of China (Nos. 21272142 and U1362204) and the Natural Science Foundation of Shanxi Province (No. 2015011015).

摘要: The trichlorozirconium 2-hydrazonides (R=H, A; R=CH3, B) were synthesized through the finely controlled stoichiometrical reactions of anhydrous zirconium tetrachloride with the lithium salt of either 1-(furan-2-ylmethylene)-2-phenylhydrazonide or 1-(furan-2-ylethylidene)-2-phenyl hydrazonide in the solvent tetrahydrofuran (THF), respectively. These complexes were highly sensitive to air and moisture due to solely using less bulky ligand of hydrazonides. The molecular structures of the title complexes, determined by means of single crystal X-ray diffraction, were found to be the distorted pentagonal bipyramid geometry around zirconium atom, with three chlorides and the hydrazonato ligand acting as the 2-coordination mode as well as two incorporated THF molecules. Upon activation with either methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), both complexes A and B exhibited catalytic activities toward ethylene polymerization, producing polyethylenes with ultra-high molecular weights.

关键词:

Titanium complexes
/ Phenylhydrazonide
/ Ethylene polymerization
/ Ultra-high molecular weight polyethylene

English

Trichlorozirconium 2-Hydrazonides: Synthesis, Characterization and Their Catalytic Behavior toward Ethylene Polymerization

1.
1. Institute of Applied Chemistry, Shanxi University, Taiyuan 030006, China
2.
2. School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China
3.
3. Key Laboratory of Engineering Plastics and Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
4.
5.
Key Laboratory of Engineering Plastics and Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
6.
Institute of Applied Chemistry, Shanxi University, Taiyuan 030006, China
7.
School of Chemistry and Chemical Engineering, Shanxi University, Taiyuan 030006, China
Received Date: 21 November 2015
Revised Date: 21 December 2015
Available Online: 05 March 2016
Fund Project:
This work was financially supported by the National Natural Science Foundation of China (Nos. 21272142 and U1362204) and the Natural Science Foundation of Shanxi Province (No. 2015011015).

Abstract: The trichlorozirconium 2-hydrazonides (R=H, A; R=CH3, B) were synthesized through the finely controlled stoichiometrical reactions of anhydrous zirconium tetrachloride with the lithium salt of either 1-(furan-2-ylmethylene)-2-phenylhydrazonide or 1-(furan-2-ylethylidene)-2-phenyl hydrazonide in the solvent tetrahydrofuran (THF), respectively. These complexes were highly sensitive to air and moisture due to solely using less bulky ligand of hydrazonides. The molecular structures of the title complexes, determined by means of single crystal X-ray diffraction, were found to be the distorted pentagonal bipyramid geometry around zirconium atom, with three chlorides and the hydrazonato ligand acting as the 2-coordination mode as well as two incorporated THF molecules. Upon activation with either methylaluminoxane (MAO) or modified methylaluminoxane (MMAO), both complexes A and B exhibited catalytic activities toward ethylene polymerization, producing polyethylenes with ultra-high molecular weights.

Key words:

Titanium complexes
/ Phenylhydrazonide
/ Ethylene polymerization
/ Ultra-high molecular weight polyethylene

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沈阳化工大学材料科学与工程学院沈阳 110142

Trichlorozirconium 2-Hydrazonides: Synthesis, Characterization and Their Catalytic Behavior toward Ethylene Polymerization

English

Trichlorozirconium 2-Hydrazonides: Synthesis, Characterization and Their Catalytic Behavior toward Ethylene Polymerization

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Trichlorozirconium 2-Hydrazonides: Synthesis, Characterization and Their Catalytic Behavior toward Ethylene Polymerization

English

Trichlorozirconium 2-Hydrazonides: Synthesis, Characterization and Their Catalytic Behavior toward Ethylene Polymerization

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

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CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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