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Catalyst system for ethylene selective oligomerization, reaction method and application of reaction method

A catalyst and selectivity technology, applied in catalytic reactions, catalysts, carbon compound catalysts, etc., can solve the problems of low total selectivity of α-olefins and high methylenecyclopentane content, and achieve high selectivity and total selectivity. High, high catalytic activity effect

Active Publication Date: 2021-06-25
TIANJIN UNIVERSITY OF SCIENCE AND TECHNOLOGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the content of by-products methylcyclopentane and methylenecyclopentane in this type of catalytic system is relatively high, and the total selectivity of C6~C8 linear α-olefins is low

Method used

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  • Catalyst system for ethylene selective oligomerization, reaction method and application of reaction method
  • Catalyst system for ethylene selective oligomerization, reaction method and application of reaction method
  • Catalyst system for ethylene selective oligomerization, reaction method and application of reaction method

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Effect test

preparation example Construction

[0051] In an embodiment of the present invention, the preparation method of ligand a may include the following steps:

[0052] (1) Preparation of Ph 2 PPhBr

[0053] Take a certain amount of 1,2-dibromobenzene, add a small amount of n-hexane and cool it in the refrigerator for 10-20 minutes for later use. Take a certain amount of n-BuLi, add a small amount of n-hexane and put it in the refrigerator to cool for 10-20 minutes, then take out the above two medicines, slowly add n-BuLi to the above standby solution, stir and react for about 30 minutes, add a small amount of n-hexane Ph after alkane dilution 2 PCl was added dropwise and stirred overnight. After the reaction is complete, use a sand core funnel to filter out the lithium salt, and the solution is distilled under reduced pressure to remove the solvent to obtain the colorless oily product Ph 2 PPhBr.

[0054] (2) Preparation of Ph 2 PPhP (NR 3 R 4 )(NR 5 R 6 )

[0055] Take a certain amount of Ph 2 Add approp...

Embodiment 1

[0067] 1. Preparation of N,N,N',N'-tetramethyl-1-(2-(methyl(phenyl)phosphino)phenyl)-phosphinediamine (L1):

[0068]

[0069] Take (2-bromophenyl)(methyl)(phenyl)phosphine (1.71g, 5mmol) and add an appropriate amount of n-hexane and put it in the refrigerator for later use. Take a certain amount of n-BuLi (0.32g, 5mmol), add a small amount of n-hexane Put the alkanes in the refrigerator to cool for 10-20 minutes, then take out the above two drugs, slowly add n-BuLi dropwise to the above standby solution, and stir for about 30 minutes. Take 1-chloro-N,N,N',N'-tetramethylphosphinediamine (0.77g, 5mmol) and add an appropriate amount of n-hexane into the refrigerator. After 15-20min, take out the above solution and put 1-chloro-N ,N,N',N'-Tetramethylphosphinediamine was slowly added to the above mixed solution, stirred overnight, then filtered and vacuum-dried to obtain a yellow oil, then added an appropriate amount of n-hexane and stirred, mixed thoroughly and put into the ref...

Embodiment 2

[0076] With embodiment 1. The difference is that R 3 , R 4 is ethyl, R 5 , R 6 For ethyl. The distribution of oligomerization products is shown in Table 1, and the experimental conditions and catalyst activity are shown in Table 2.

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Abstract

The invention provides a catalyst system for ethylene selective oligomerization, a reaction method and application of the reaction method, and belongs to the technical field of homogeneous catalysis. The catalyst system comprises: a ligand a; and a transition metal compound b, wherein the transition metal compound b is a metal compound of IVB to VIII groups. The structural general formula of the ligand a is as shown in formula (I): R1 and R2 can be the same or different and are respectively and independently selected from alkyl, aryl or aryl derivatives, but at least one of R1 and R2 is aryl or aryl derivatives; R4 and R5 do not form a ring with N, P and N, or R4 and R5 form a polycyclic ring with N, P and N; and R3 to R10 can be the same or different and are independently selected from hydrogen, alkyl or aryl respectively. The catalyst system provided by the invention is mainly used for ethylene selective oligomerization, and has the characteristics of high catalytic activity, high selectivity of product linear alpha-olefin, low 1-butene content, high selectivity of C6-C8 linear alpha-olefin, and few polymer by-products.

Description

technical field [0001] The invention belongs to the technical field of homogeneous catalysis, and in particular relates to a catalyst system for selective oligomerization of ethylene, a reaction method and an application thereof. Background technique [0002] With the continuous development of the global economy and the high performance requirements for polyolefin materials and lubricating base oils, advanced linear α-olefins such as 1-hexene, 1-octene, 1-decene and 1-dodecene are in the market. Applications in high-performance polyolefins, high-end synthetic lubricants and other fields continue to increase, and their demand continues to grow. The ethylene oligomerization method is one of the main methods to produce high-purity 1-hexene, 1-octene, 1-decene and 1-dodecene and other advanced linear α-olefins, generally including non-selective ethylene oligomerization and selective Polyethylene oligomerization. [0003] For the nonselective ethylene oligomerization technology...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/24C07F9/50C07F9/6584C07C2/36
CPCB01J31/2409B01J31/2423C07F9/5022C07F9/5072C07F9/65848C07C2/36C07C2531/24B01J2531/62B01J2531/0213B01J2231/20Y02P20/52
Inventor 姜涛马静
Owner TIANJIN UNIVERSITY OF SCIENCE AND TECHNOLOGY
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