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Amino-silicone bridge nitrogen-blending allyl zirconium catalyst and preparation method and application thereof

A technology of heteroallyl zirconium and heteroallyl lithium, which is applied in the field of ethylene polymerization IVB transition metal catalyst, can solve the problems of complicated preparation of raw materials, limited application and promotion, low catalytic activity, etc., and achieves simple and easy-to-obtain raw materials and high Catalytic activity, effect of simple preparation method

Inactive Publication Date: 2010-07-28
SHANXI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Among them, the reports of aziallyl metal compound catalysts are very rare, and there are disadvantages such as complex raw material preparation process, high price, low yield and low catalytic activity, which limit the development of this type of azaallyl metal compound catalysts. application promotion

Method used

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  • Amino-silicone bridge nitrogen-blending allyl zirconium catalyst and preparation method and application thereof
  • Amino-silicone bridge nitrogen-blending allyl zirconium catalyst and preparation method and application thereof
  • Amino-silicone bridge nitrogen-blending allyl zirconium catalyst and preparation method and application thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0020] (1) Preparation of lithium salt

[0021] Under the protection of nitrogen, under the acetone bath, lithium diisopropylamide (0.21g, 2mmol) was added to N-phenylethyl-2,6-diisopropylbenzimine (0.56g, 2mmol) In tetrahydrofuran solution, after reacting for 3 hours, cool down to -78°C again and add magnesium bromide (0.37g, 2mmol). When the solution naturally warms up to room temperature, keep stirring for 8 hours, vacuum dry, wash with n-hexane, and recrystallize The tetrahydrofuran complex A1 of 2,6-diisopropyl-N-styrylanilinomagnesium bromide is obtained. Under the protection of nitrogen, under the ice-water bath, dimethylaminodimethylsilyl chloride (0.3ml, 2mmol) was slowly added to the tetrahydrofuran solution of A1. After the solution was naturally warmed to room temperature, the reaction was kept stirring for 6 hours. Extraction with toluene gave N-(2-dimethylaminodimethylsilyl-1-styryl)-2,6-diisopropylaniline neutral compound B1 as an oil. Then under the protectio...

Embodiment 2

[0028] (1) The preparation of lithium salt is the same as in Example 1.

[0029] (2) Preparation of catalyst b1: the Schlenk bottle is evacuated and led to N 2 After three replacements, C1 (0.81g, 2mmol) and 25ml of tetrahydrofuran were added, and ZrCl was added at -78°C 4 (0.45g, 2mmol), return to room temperature under stirring and react for 24 hours, vacuum dry, add 50 ml of dichloromethane, filter, concentrate, wash with n-hexane, crystallize in tetrahydrofuran and dichloromethane (1:3), and obtain light yellow crystals Compound b1 1.03 g, yield: 87%. Decomposition temperature: 167-169°C. Elemental Analysis Theoretical Value C 24 h 35 Cl 3 N 2 SiZr: C, 49.89; H, 6.06; N, 4.85; Found: C, 49.87; H, 6.09; N, 4.83%. 1 H NMR (300MHz C 6 D. 6 )δ-0.02, 0.33(q, 6H, Si(CH 3 ) 2 ), 0.56, 0.93, 1.19-1.38, 1.67-1.73 (m, 12H, CH(CH 3 ) 2 ), 2.18-2.26(d, 6H, N(CH 3 ) 2 ), 3.79(m, 2H, CH(CH 3 ) 2 ), 4.54(s, 1H, CH), 6.84-6.99(m, 5H, Ph), 7.34-7.37(m, 3H, Aryl). 13 C NMR...

Embodiment 3

[0031] 1. The preparation of catalyst a1 is the same as in Example 1.

[0032] 2. Ethylene polymerization: Dry the 250ml polymerization bottle equipped with a magnetic stirrer at 130°C for 6 hours continuously, vacuumize it while it is hot and use N 2 Air replacement 3 times. Catalyst a1 (4.6 mg, 5 μmol) was added, followed by evacuation and replacement with ethylene twice. Inject a certain amount of toluene (26.6ml) with a syringe, then add methylaluminoxane (1.46mol / L, 3.4ml) to make Al / Zr=1000, at 50°C, keep the ethylene pressure of 1 atmosphere, stir vigorously for 30 minute. Add 5% hydrochloric acid ethanol solution to the reaction solution for neutralization, and a small amount of white solid precipitates out. After filtration it was vacuum dried for 3 hours. Obtained product 0.0075g, polymerization activity: 3.0×10 3 g mol(Zr) -1 h -1 , Melting point of the polymer: 134.4°C.

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Abstract

The invention provides an amino-silicone bridge nitrogen-blending allyl zirconium catalyst, relating to a vinyl-polymerization IVB transition metal catalyst, in particular to a nitrogen-blending allyl ligand zirconium catalyst with an N-C-C-Si-N skeleton. The preparation method of the catalyst comprises the following steps of: dehydrogenating ketimine containing a substituent group in the protection of nitrogen by using lithium diisopropylamide (LDA); adding equimolar magnesium bromide to obtain magnesium salts A and then adding equimolar silane compounds to prepare a compound B; dehydrogenating once again by using the LDA to prepare amino-silicone bridge nitrogen-blending allyl lithium C; and finally reacting with ZrC14 to obtain the amino-silicone bridge nitrogen-blending allyl zirconium catalyst. The preparation method has the advantages of simplicity, simple and easy obtainment of materials, low cost and higher yield; and the catalyst displays very high catalytic activities when used for vinyl polymerization.

Description

technical field [0001] The invention relates to ethylene polymerization IVB transition metal catalysts, in particular to a zirconium complex catalyst with an N-C-C-Si-N skeleton, more specifically to an amino-silicon-bridged azaallyl Zirconium-based catalyst and its preparation method and application. Background technique [0002] At present, industrial olefin polymerization catalysts include Ziegler-Natta catalysts, Phillips catalysts and metallocene catalysts. These catalysts can control the catalytic activity and polymer properties by adjusting the structure of the ligand. Among them, the reports of aziallyl metal compound catalysts are very rare, and there are disadvantages such as complex raw material preparation process, high price, low yield and low catalytic activity, which limit the development of this type of azaallyl metal compound catalysts. App promotion. Contents of the invention [0003] The object of the present invention is to provide an amino silicon-br...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/22C08F4/642C08F110/02
Inventor 袁世芳白生弟刘滇生童红波张文娟孙文华
Owner SHANXI UNIV
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