Reaction method and catalyst system for selective oligomerization of ethylene, and application of catalyst system

A catalyst and selective technology, applied in the field of catalysis, can solve the problems of low total selectivity of 1-hexene and 1-octene and high activator dosage, and achieve low cost, low activator dosage, and total selectivity. high effect

Active Publication Date: 2019-10-25
TIANJIN UNIVERSITY OF SCIENCE AND TECHNOLOGY
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0008] The present invention aims to propose a catalyst system for selective oligomerization of ethylene to solve the technical problems of low total selectivity of 1-hexene and 1-octene and high dosage of activator in ethylene oligomerization

Method used

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  • Reaction method and catalyst system for selective oligomerization of ethylene, and application of catalyst system
  • Reaction method and catalyst system for selective oligomerization of ethylene, and application of catalyst system
  • Reaction method and catalyst system for selective oligomerization of ethylene, and application of catalyst system

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preparation example Construction

[0090] In an embodiment of the present invention, the preparation method of ligand a may include the following steps:

[0091] (1) Prepare R 5 R 6 PLi, R 3 R 4 PLi

[0092] Take a certain amount of R 5 R 6 PH, add a small amount of n-hexane and cool 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 10-15 minutes, then take out the above two medicines, slowly add n-BuLi dropwise into diphenylphosphine, let it rise to room temperature naturally, stir and react for about 12-24h, filter with a sand core funnel, wash twice with n-hexane, and get yellow R after vacuum drying 5 R 6 PLi solid.

[0093] R 3 R 4 The preparation method of PLi is the same as above.

[0094] (2) Preparation of R 5 R 6 P(R 1 SiR 2 ) n PR 3 R 4

[0095] A certain amount of Cl(R 1 SiR 2 ) n Cl was dissolved in n-hexane, and cooled in the refrigerator for 10-20 minutes for later ...

Embodiment 1

[0107] 1. Preparation of 1,2-bis(diphenylphosphineamine)-1,1,2,2-tetramethyldisilane ligand:

[0108] (1) Prepare R 5 R 6 PLi, R 3 R 4 PLi

[0109] Take 5.0 g of diphenylphosphine hydrogen, add a small amount of n-hexane and cool it in the refrigerator for 15-20 minutes for later use. Take 11.75mL of n-BuLi, add a small amount of n-hexane and cool it in the refrigerator for 10-15 minutes. Then the above two medicines were taken out, n-BuLi was slowly added dropwise into diphenylphosphine, naturally raised to room temperature, stirred and reacted for more than 12 hours, filtered with a sand core funnel, washed twice with n-hexane, and vacuum-dried to obtain 5.4g yellow LiPPh 2 solid.

[0110] (2) Preparation of R 5 R 6 P(R 1 SiR 2 ) n PR 3 R 4

[0111] Take 0.5g of tetramethyldichlorodisilane, add a small amount of n-hexane, and cool in the refrigerator for 10-15 minutes for later use. Take 1.0263g LiPPh 2 Add a small amount of n-hexane and put it in the refrig...

Embodiment 2

[0118] With embodiment 1. The difference is that R 2 For 2,4-dimethylphenyl. 113.9 g of the oligomerization product was obtained, and the catalyst activity was 6.90×10 6 g oligomer / mol Cr·h. The distribution of the oligomerization products is shown in Table 1.

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Abstract

The invention provides a catalyst system for selective oligomerization of ethylene, and belongs to the technical field of catalysis. The catalyst system includes a ligand a and a transition metal compound b which is a metal compound of an IVB-VIII group; the general structural formula of the ligand a is shown in a formula I (please see the specification for the formula I), wherein R1, R2, R3, R4,R5 and R6 in the formula I are correspondingly and independently selected from hydrogen, alkyl or aryl; and n in the formula I is an integer and greater than or equal to 2 and less than or equal to 10. The catalyst system is used for selective oligomerization of the ethylene, the catalyst system has high catalytic activity, the total selectivity of target products, namely 1-hexene and 1-octylene is high, and the mass percentage content of C6-C8 linear alpha-olefin in the products reaches 90% or above; and at the same time, the dosage of activators is small, and the cost of the catalyst systemis low.

Description

technical field [0001] The invention belongs to the technical field of catalysis, and in particular relates to a reaction method for selective oligomerization of ethylene, a catalyst system and an application thereof. Background technique [0002] With the continuous development of the global economy and the continuous expansion of the application fields of polyolefin materials, the demand for high-performance polyolefins is also increasing. The demand for 1-hexene and 1-octene as comonomers for the preparation of polyolefins continues to grow. Ethylene oligomerization is the main method for producing 1-hexene and 1-octene. Ethylene oligomerization generally includes non-selective ethylene oligomerization and selective ethylene oligomerization. [0003] For the nonselective ethylene oligomerization technology, some novel ligand-coordinated metal-chromium-based homogeneous catalysts have been reported for the synthesis of linear α-olefins with a broad carbon number distribu...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/24C07C2/36C07C11/02C07C11/107
CPCB01J31/2409C07C2/36B01J2531/0213B01J2531/62C07C11/02C07C11/107
Inventor 姜涛常琪琪翟阳陈延辉曹晨刚
Owner TIANJIN UNIVERSITY OF SCIENCE AND TECHNOLOGY
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