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Binuclear nickel-series olefine oligomerization catalyst, and its preparation method and use

A technology for catalysts and olefins, which is applied in the field of binuclear nickel-based olefin oligomerization catalysts, production methods and applications, which can solve the problems of low ligand yield, low oligomerization activity, and difficulty in complete completion, and achieve high activity and good yield Effect

Inactive Publication Date: 2005-02-16
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The complex is used as the main catalyst for olefin oligomerization, and MAO is required as a cocatalyst, and the oligomerization activity is low, and the oligomerization activity under 1MPa pressure is only 10 4 g / (molNi) hr
In addition, the ligand used is a Schiff base compound produced by condensation of carbonyl compounds and amine compounds. The reaction is carried out in a protic solvent, which is an equilibrium reaction and difficult to complete, so the yield of the ligand is low.

Method used

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  • Binuclear nickel-series olefine oligomerization catalyst, and its preparation method and use
  • Binuclear nickel-series olefine oligomerization catalyst, and its preparation method and use
  • Binuclear nickel-series olefine oligomerization catalyst, and its preparation method and use

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Experimental program
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preparation example Construction

[0016] The preparation method of catalyst of the present invention comprises:

[0017] (1) In a non-polar organic solvent, using an organic acid as a catalyst, the carbonylpyridine compound represented by the formula (II) and the bridged phenylenediamine compound represented by the formula (III) are heated at 20 to 150° C. Carry out the condensation reaction at a molar ratio of 2:1, remove the solvent, and dry the resulting solid to obtain the ligand compound,

[0018]

[0019] In said formula (II), R 4 is a substituent on the pyridine ring, the number of which is 1 to 4, R 4 selected from hydrogen or C 1 ~C 6 the alkyl group, R 3 selected from hydrogen or C 1 ~C 4 The alkyl group; in formula (III), R 1 and R 2 are the substituents on the benzene ring, the number of substituents on each benzene ring is 1 to 4, R 1 and R 2 respectively selected from hydrogen or C 1 ~C 8 The alkyl group, Y is selected from -O-, -S-, -CH 2 -;

[0020] (2) In an ether solvent, mak...

example 1

[0031] Prepare the catalyst {bis[pyridinecarbaldehyde] acetal 4,4'-methylenebis(2,6-diethylaniline)} nickel dibromide.

[0032] (1) Preparation of Ligand Compounds

[0033] In a three-neck flask with a reflux condenser, add 10 milliliters of toluene and 0.005 moles of 4,4'-methylene-bis(2,6-diethylaniline) and 0.01 moles of 2-pyridinecarbaldehyde, drop into 2 Drop formic acid, stir and react at 60°C for 4 hours, let the reactant stand at -10°C for 48 hours, add 10 ml of hexane, filter, wash the solid with 10 ml of hexane twice, and dry under reduced pressure at 60°C for 1 hour. 2.35 g of white solid was obtained, which was ligand compound a: bis[pyridinecarbaldehyde] acetal 4,4'-methylene-bis(2,6-diethylaniline), yield 96% by mass,

[0034] Elemental analysis measured (calculated), mass %: C80.98 (81.11); H7.51 (7.43); N11.35 (11.46).

[0035] Infrared spectrum characteristic peak, cm -1 : 1630.70; 1578.94; 1562.60.

[0036] h 1 NMR: δ7.05; δ4.05; δ8.78; δ7.26-8.38.

[00...

example 2

[0043] Preparation of {bis[pyridinecarbaldehyde] acetal 4,4'-methylene-bis(2,6-diisopropylaniline)}nickel dibromide.

[0044] (1) Preparation of ligand compounds: prepare ligands according to the method of example 1 (1), differently use 4,4'-methylene-bis(2,6-diisopropylaniline) containing 0.005 moles and 0.01 Moles of 2-pyridinecarbaldehyde are subjected to condensation reaction, and the non-polar organic solvent used in the reaction is 10 milliliters of benzene to obtain ligand compound b: bis[pyridinecarbaldehyde] acetal 4,4'-methylene-bis(2,6-diiso Propylaniline), yield 98% by mass.

[0045] Elemental analysis measured (calculated), mass %: C81.18 (81.57); H8.13 (8.14); N10.26 (10.29).

[0046] Infrared spectrum characteristic peak, cm -1 : 1635.70; 1584.94; 1567.60.

[0047] h 1 NMR: δ7.02; δ4.02; δ8.74; δ7.26-8.38.

[0048] (2) Preparation of catalyst

[0049] Prepare catalyst by example 1 (2) step method, difference is with ligand b and NiBr 2 DME reaction to ob...

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Abstract

The invention relates to an olefine oligomerization catalyst. Its general formula is described in right figure. Thereinto, R1 and R2 are substituents on benzene ring. Numbers of substituent on each benzene ring is 1-4. R1 and R2 are respectively selected from hydrogen or alkyl of C1-C8. R3 is selected from hydrogen or alkyl of C1-C4. R4 is substituent on pyridine ring. Its number is 1-4. R4 is selected from hydrogen or alkyl of C1-C6. Y is selected from -O-, -S- and -CH2-. M is Ni or Pd. X is halogen. It has a high activation matching with aluminium alkyl oxygen alkyl or aluminium alkyl promoters in alpha- alkene or olefine oligomerization reaction.

Description

technical field [0001] The invention relates to a nickel-based olefin oligomerization catalyst with dinuclear coordination, a preparation method and application. Specifically, it is a binuclear nickel-based catalyst with pyridine ring-containing Schiffer's base as a ligand, a preparation method, and a method for olefin oligomerization using the catalyst. Background technique [0002] The linear α-olefin products synthesized by the oligomerization of low-carbon olefins have high commercial value and are mainly used in olefin comonomers, plasticizers, detergents, surfactants and lubricants. The homogeneous catalysts currently used in industry use complexes containing P^O chelating ligands as catalysts, and the yield of linear α-olefins in oligomerization products can reach more than 99%. [0003] The other two main catalysts for olefin oligomerization are α-diimine nickel, palladium catalysts and bisimine pyridinium iron, cobalt-based catalysts. Different products such as po...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/22C08F4/80C08F10/00
Inventor 纪洪波许学翔孙敏赵伟景振华时晓岚
Owner CHINA PETROLEUM & CHEM CORP