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Ethylene oligomerization modification additive and homogeneous catalysis system thereof

A technology for ethylene oligomerization and homogeneous catalysis, which is applied in physical/chemical process catalysts, organic compound/hydride/coordination complex catalysts, organic chemistry, etc., and can solve the problems of high cost, high cocatalyst ash content, and product economy Lowering and other issues

Active Publication Date: 2022-07-29
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] In summary, the current field of ethylene oligomerization to prepare linear α-olefins has the following shortcomings in terms of catalysts: (1) The activity of the catalyst is low, resulting in more impurities and ash content in the product, which affects the quality of the final product; ( 2) The yield and selectivity of 1-hexene and 1-octene (that is, ethylene trimerization and tetramerization) are low; (3) The amount of co-catalyst is mostly expensive methyl aluminoxane or modified methyl aluminum Oxygen, and the amount is huge, resulting in high cost and high co-catalyst ash content in the product, and the economical efficiency of the product is reduced; (4) There are too many solid-phase products in the product, which will cause the reaction kettle to stick or the pipeline to be blocked

Method used

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  • Ethylene oligomerization modification additive and homogeneous catalysis system thereof
  • Ethylene oligomerization modification additive and homogeneous catalysis system thereof
  • Ethylene oligomerization modification additive and homogeneous catalysis system thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0059] The oligomerization modifier component D is shown on the left of the figure below, where M is Si, X=Y=Z=5, R 1 , R 2 , R 3 , R 4 , R5 , R 6 is isopropyl, R 7 , R 8 , R 9 It is n-butyl group; the ligand structure of the main catalyst component A is shown on the right side of the figure below, the central metal atom is Co(II), R 1 , R 2 , R 3 is isopropyl.

[0060]

[0061] Homogeneous catalytic system S configuration: Add 0.1 mmol of oligomerization modification assistant component D shown in the figure above to 1 L of toluene solution to form a homogeneous solution, and the homogeneous solution is kept under continuous stirring for at least 30 minutes. Then 5 mmol of main catalyst component A was added and dissolved, and the stirring was continued for at least 120 min. The above configuration operations were all performed in an inert gas environment, and the obtained homogeneous catalytic system S was reserved for oligomerization.

[0062] The 1L oligomeriz...

Embodiment 2

[0064] The oligomerization modifier component D is shown on the left of the figure below, where M is Si, X=Y=Z=12, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 is isopropyl, R 7 , R 8 , R 9 is isobutyl group; the ligand structure of main catalyst component A is shown on the right side of the figure below, the central metal atom is Cr(VI), and R is isopropyl group.

[0065]

[0066] Homogeneous catalytic system S configuration: add 50 mmol of oligomerization modification assistant component D shown in the figure above into 1 L of n-hexane solution to form a homogeneous solution, and the homogeneous solution is kept under continuous stirring for at least 30 min. Then 5 mmol of main catalyst component A was added and dissolved, and the stirring was continued for at least 120 min. The above configuration operations were all performed in an inert gas environment, and the obtained homogeneous catalytic system S was reserved for oligomerization.

[0067] The 1L oligomerization reacto...

Embodiment 3

[0069] The oligomerization modifier component D is shown on the left of the figure below, where R 1 , R 2 , R 3 , R 4 is hydroxyl, R 5 , R 6 , R 7 , R 8 is n-butyl group; the ligand structure of main catalyst component A is shown on the right of the figure below, the central metal atom is Fe(III), and R is isobutyl group.

[0070]

[0071] Homogeneous catalytic system S configuration: Add 80 mmol of oligomerization modification assistant component D shown in the figure above into 1 L of toluene solution to form a homogeneous solution. The homogeneous solution is kept under continuous stirring for at least 30 minutes. 500 mmol of the main catalyst component A was added and dissolved, and the stirring was continued for at least 120 min. The above configuration operations were all performed in an inert gas environment, and the obtained homogeneous catalytic system S was reserved for oligomerization.

[0072] The 1L oligomerization reactor was baked for at least 120min u...

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Abstract

The invention discloses an ethylene oligomerization modification auxiliary agent and an olefin oligomerization homogeneous catalytic system thereof. The catalytic system comprises a component A, a component B and a component C, wherein the component A is a main catalyst component; the component B is a cocatalyst component; the component C is a solvent component, and the component D is an oligomerization modification additive component. The oligomerization modification auxiliary agent component D and the main catalyst component A can exist in the form of coordination complexation or supramolecular assembly or covalent bonds. The oligomerization modification additive component D can significantly improve the polymerization activity and high-temperature stability of the catalytic system, improve the product selectivity and total yield of 1-hexene and 1-octylene, and reduce the content of solid-phase products represented by oligomerization products. In particular, the oligomerization modification aid component D can also significantly reduce the use amount of a cocatalyst, and has high technical economy.

Description

technical field [0001] The technology relates to the field of olefin polymerization and catalysts, in particular to an ethylene oligomerization modification assistant and a homogeneous catalyst system for olefin oligomerization. The catalytic system in the present invention is especially suitable for olefin oligomerization, has excellent polymerization activity in oligomerization, and can significantly improve the total yield of 1-hexene and 1-octene, and at the same time, the content of solid-phase products can also be obtained. The selectivity for 1-hexene and 1-octene is also improved. In particular, due to the addition of oligomerization modification aids, the amount of cocatalysts is also significantly reduced. Background technique [0002] Linear α-olefins refer to straight-chain olefins with double bonds at or above C4 at the end of the molecule, which are a class of important petrochemical raw materials in huge demand. Among them, C 4 ~C 24 The linear α-olefins a...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/02B01J31/06B01J31/18B01J31/24C07C2/32C07C2/36C07C11/02C07C11/107
CPCB01J31/0274B01J31/0275B01J31/063B01J31/06B01J31/1815B01J31/2409C07C2/32C07C2/36B01J2531/845B01J2531/842B01J2531/62B01J2531/847B01J2531/0241B01J2231/20C07C2531/18C07C2531/24C07C11/02C07C11/107Y02P20/52
Inventor 陈毓明历伟姚伟陶干张鑫鹏王靖岱阳永荣
Owner ZHEJIANG UNIV
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