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Catalyst system for ethylene selective oligomerization, preparation method and ethylene oligomerization reaction method

A catalyst and selectivity technology, applied in the field of catalysis, can solve the problems of large amount of activator, low total selectivity of 1-hexene and 1-octene, etc., and achieve the effects of long catalyst life, low cost and simple synthesis

Active Publication Date: 2018-10-02
TIANJIN UNIVERSITY OF SCIENCE AND TECHNOLOGY
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0006] In view of this, the present invention aims to propose a catalyst system for ethylene selective oligomerization, to solve the technology that the total selectivity of 1-hexene and 1-octene is not high and the amount of activator is large in the ethylene oligomerization reaction question

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  • Catalyst system for ethylene selective oligomerization, preparation method and ethylene oligomerization reaction method
  • Catalyst system for ethylene selective oligomerization, preparation method and ethylene oligomerization reaction method
  • Catalyst system for ethylene selective oligomerization, preparation method and ethylene oligomerization reaction method

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preparation example Construction

[0108] In one embodiment of the present invention, the preparation method of catalyst system comprises the following steps:

[0109] Components a, b, and c are pre-mixed or directly added to the reaction system for in-situ synthesis. That is to say, the catalyst is prepared by pre-mixing ligand a, transition metal compound b, and activator c connected by a linking group containing heteroatoms; it is also possible to mix the ligands connected by chain groups containing heteroatoms a, the transition metal compound b, and the activator c are directly added to the reaction system for in-situ synthesis;

[0110] The reaction mode of ligand a, transition metal compound b and activator c connected by a linking group containing heteroatoms in general formula I can be reacted by liquid phase, such as reacting under the action of a solvent, and the optional solvent Such as toluene, benzene and its derivatives, etc.; also through solid-state reaction; or through in-situ reaction in the ...

Embodiment 1

[0119] 1. Preparation of ligands:

[0120] When A is -CH 2 (CH 3 ) 2 SiCH 2 -, E is a sulfur atom, R 1 Is isopropyl, R 2 is phenyl, R 3 is cyclopentyl, and the ligand is N-((cyclopentylmercaptomethyl)dimethylsilyl)-1,1-diisopropyl-N-phenylphosphineamine (C 21 h 38 NPSSi)

[0121] (1) Preparation of Lithium Anilide

[0122] in the N 2 Add dehydrated THF (200ml) and aniline (9.31g, 0.1mol) into a fully replaced stirred 500ml reactor, stir well and cool to -78°C with liquid nitrogen. Use a 100ml syringe to extract n-butyllithium hexane solution (41.6ml, 2.4mol / L), slowly add it dropwise to the above solution while stirring, keep stirring at -78°C for 1h, then rise to room temperature and continue stirring for 1 hour, then vacuum pump The solvent was removed, n-hexane (100ml) was added, stirred and dispersed, and then filtered. The obtained filtrate was vacuum-extracted at room temperature to obtain 9.97g (0.098mol, 97.8%) of the product.

[0123] (2) prepare 1,1-diiso...

Embodiment 2

[0139] With embodiment 1. The difference is that R 2 For 2,6-diisopropylphenyl. 135.7 g of oligomerization product was obtained, and the catalyst activity was 8.22×10 6 g oligomer / mol Cr·h. The distribution of the oligomerization products is shown in Table 1.

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Abstract

Belonging to the technical field of catalysis, the invention provides a catalyst system for ethylene selective oligomerization. The catalyst system consists of three components: a ligand a; a transition metal compound b, which is a metal compound of IVB-VIII group; specifically, the ligand a at least contains one group shown as general formula I in the specification, the linking group A in the formula I has a main chain containing alkyl, alkenyl or aryl and a heteroatom, wherein the heteroatom is one of silicon, tin, boron, phosphorus and nitrogen; the group E is a sixth main group element oxygen or sulfur; and R1, R2 and R3 are substituent groups of phosphorus atom, nitrogen atom and group E respectively, and can be the same or different. The catalyst system provided by the invention hashigh activity, the target products 1-hexene and 1-octene have high selectivity, the mass percentage content of C6-C8 linear alpha-olefin in the products is greater than 90%, and the catalyst has the advantages of simple synthesis, low cost and long service life.

Description

technical field [0001] The invention belongs to the technical field of catalysis, and relates to a catalyst system for selective ethylene oligomerization and an ethylene oligomerization reaction method. Background technique [0002] With the continuous development of the global economy, the demand for high-performance polyethylene is also increasing. 1-hexene and 1-octene are used as comonomers to prepare polyethylene, and their demand continues to grow at an average annual rate of more than 5.4%. . The main methods for industrial production of 1-hexene and 1-octene include paraffin cracking, ethylene oligomerization and extraction separation, among which ethylene oligomerization is the main method for producing 1-hexene and 1-octene. [0003] US6184428 discloses a nickel catalyst, using a boron compound as an activator, which can catalyze the oligomerization of ethylene to obtain a mixture of linear α-olefins, wherein the content of 1-hexene accounts for 22%, and the conte...

Claims

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Application Information

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IPC IPC(8): B01J31/24C07C2/32C07C11/107C07C11/02
CPCC07C2/32B01J31/143B01J31/188C07C2531/24B01J2531/62B01J2231/20B01J35/19C07C11/107C07C11/02Y02P20/52
Inventor 姜涛张乐阿兰法赫陈延辉邵怀启李健闫冰
Owner TIANJIN UNIVERSITY OF SCIENCE AND TECHNOLOGY
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