Late transition metal catalyst for ethylene oligomerization and preparation method thereof

A technology of transition metal and ethylene oligomerization, applied in the directions of physical/chemical process catalysts, catalysts, carbon compound catalysts, etc., can solve the problems of long synthesis steps, difficult industrial production, low total yield, etc., and achieves a simple and easy preparation method. Industrial production, the effect of high catalytic ethylene oligomerization activity

Active Publication Date: 2016-12-07
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the synthesis steps are long, and the catalyst ligands need to be purified, the overall yield is low, and it is difficult to realize industrial production

Method used

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  • Late transition metal catalyst for ethylene oligomerization and preparation method thereof
  • Late transition metal catalyst for ethylene oligomerization and preparation method thereof
  • Late transition metal catalyst for ethylene oligomerization and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0048] This embodiment provides a late transition metal catalyst for ethylene oligomerization, its structural formula is as shown in formula (1-1):

[0049]

[0050] This embodiment also provides a preparation method for the late transition metal catalyst for ethylene oligomerization described in formula (1-1), which comprises the following steps:

[0051] Step 1, under a nitrogen atmosphere, add 3g of anhydrous sodium sulfate, cyclohexylamine as a solution of ethanol (20mL) of 1.0G hyperbranched macromolecules (3.27g, 0.01mol) and salicylaldehyde (3.66 g, 0.03mol) of ethanol (20mL), stirred at room temperature for 30min, then warmed up to 78°C, reacted under ethanol reflux for 12h, and filtered to remove anhydrous sodium sulfate to obtain hyperbranched water with cyclohexylamine as the nucleus. Mixed solution of salicylaldimine ligand;

[0052] Step 2, under nitrogen atmosphere, NiCl 2 ·6H 2 The ethanol (20mL) solution of O (2.38g, 0.01mol) is slowly dripped into the hy...

Embodiment 2

[0058] This embodiment provides a late transition metal catalyst for ethylene oligomerization, the structural formula of which is shown in formula (2-1):

[0059]

[0060] This embodiment also provides a preparation method for the late transition metal catalyst for ethylene oligomerization described in formula (2-1), which comprises the following steps:

[0061] Step 1, under a nitrogen atmosphere, add 3g of anhydrous sodium sulfate, linear tetradecylamine as a solution of 1.0G hyperbranched macromolecules (4.30g, 0.01mol) in ethanol (20mL) and salicylaldehyde in a three-necked flask (6.11g, 0.05mol) in ethanol (20mL), stirred at room temperature for 30min, then heated to 80°C, reacted for 24h under ethanol reflux, and filtered to remove anhydrous sodium sulfate to obtain linear tetradecylamine as the nucleus The hyperbranched salicylaldimine ligand mixed solution;

[0062] Step 2, under nitrogen atmosphere, NiCl 2 ·6H 2 The ethanol (40mL) solution of O (4.76g, 0.02mol) ...

Embodiment 3

[0068] This embodiment provides a late transition metal catalyst for ethylene oligomerization, the structural formula of which is shown in formula (3-1):

[0069]

[0070] This embodiment also provides a preparation method for the late transition metal catalyst for ethylene oligomerization described in formula (3-1), which comprises the following steps:

[0071] Step 1, under a nitrogen atmosphere, add 3g of anhydrous sodium sulfate, straight-chain octadecylamine as a solution of 1.0G hyperbranched macromolecules (4.86g, 0.01mol) in ethanol (20mL) and salicylaldehyde in a three-necked flask (3.05g, 0.025mol) in ethanol (20mL), stirred at room temperature for 30min, then heated to 70°C, reacted under ethanol reflux for 18h, and filtered to remove anhydrous sodium sulfate to obtain linear octadecylamine as the nucleus. Hyperbranched salicylaldimine ligand mixed solution;

[0072] Step 2, under nitrogen atmosphere, the CoCl 2 ·6H 2 O (2.38g, 0.01mol) ethanol (20mL) solution...

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Abstract

The invention provides a late transition metal catalyst for ethylene oligomerization and a preparation method thereof. The preparation method comprises the following steps: by using hyperbranched molecules using low generation terminal group as amido group and salicylaldehyde or salicylaldehyde derivatives as the raw materials in combination with anhydrous sodium sulfate and ethanol, carrying out reflux reaction under nitrogen conditions, and filtering to obtain a salicylaldehyde-Schiff base mixture; under nitrogen conditions, slowly and dropwisely adding a crystalline-water-bearing late transition metal halide ethanol solution into the salicylaldehyde-Schiff base mixture to react; and filtering and washing to obtain the late transition metal catalyst for ethylene oligomerization. The preparation method of the late transition metal catalyst for ethylene oligomerization prepared by the one-pot process is simple, and avoids the complex process of purifying the ligand in the conventional late transition metal catalyst for ethylene oligomerization; and the catalyst yield is 80-90%. The catalyst has higher catalytic ethylene oligomerization activity, and can easily implement industrial production.

Description

technical field [0001] The invention belongs to the technical field of catalysts, and relates to a post-transition metal catalyst for ethylene oligomerization and a preparation method thereof. Background technique [0002] Late transition metal catalysts are a new generation of olefin polymerization catalysts that appeared in the 1990s with high activity for olefin polymerization. The catalyst can realize the catalytic polymerization of polar monomers and the copolymerization of polar monomers and non-polar monomers, and can also obtain high molecular weight polyethylene, poly alpha-olefins and alpha-olefins. Compared with metallocene catalysts, the catalytic activity of late transition metal catalysts is higher than that of metallocene catalysts. The molecular weight and branching degree of polymerization products can be adjusted and controlled. The catalyst is cheap, stable in performance, easy to prepare, and can simplify the production rate of the synthesis process. Hig...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/02C07F15/04C07F15/06B01J31/22C07C11/02C07C2/32
CPCY02P20/52C07F15/025B01J31/2243B01J2231/20B01J2531/0213B01J2531/0252B01J2531/842B01J2531/845B01J2531/847C07C2/32C07C2531/22C07F15/045C07F15/065C07C11/02
Inventor 李翠勤王俊施伟光李杰张志秋
Owner PETROCHINA CO LTD
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