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Ternary catalyst system and applications of ternary catalyst system in selective oligomerization of ethylene

A three-way catalyst, catalyst technology, applied in physical/chemical process catalysts, organic compound/hydride/coordination complex catalysts, organic chemistry and other directions, can solve problems such as unsatisfactory 1-octene selectivity

Active Publication Date: 2017-06-16
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

The highly selective oligomerization catalysts reported so far can obtain nearly 90% 1-hexene / 1-octene co-selectivity, especially the selectivity of 1-octene is not ideal and cannot meet the requirements of industrialization. Therefore, Ligands with novel framework structures still need to be further developed

Method used

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  • Ternary catalyst system and applications of ternary catalyst system in selective oligomerization of ethylene
  • Ternary catalyst system and applications of ternary catalyst system in selective oligomerization of ethylene
  • Ternary catalyst system and applications of ternary catalyst system in selective oligomerization of ethylene

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0069] 1 Preparation of Ligand 5

[0070] At minus 20 degrees, add n-butyllithium (1.2 equiv) dropwise to the ether solution of α-phenylethylamine, and then stir for 15 minutes, then add trimethylchlorosilane (1.1 equiv) dropwise, and stir after the drop 1h, add n-butyllithium (3equiv) dropwise to it, after dropping, stir for 3h, rise to room temperature and stir for 2h, cool down to minus 20 degrees, add diphenylphosphorous chloride (1.1equiv) dropwise, finish adding After stirring for 2 h, it was raised to room temperature and stirred for 4 h, then the reaction was quenched with 10% HCl (aq), the layers were separated, the organic layer was spin-dried, and recrystallized with n-hexane to obtain a white solid (abbreviated as DPPNH 2 ), yield 38%.

[0071] Under ice bath, drop DPPNH into the solution of diphenylphosphorous chloride 2 (1equiv) and triethylamine (1.5equiv) mixed solution, rose to room temperature and stirred for 5h after completion. Then the reaction was quen...

Embodiment 2

[0077] 1 Preparation of Ligands 8

[0078] At 50 degrees, DPPNH 2 React with ethyl formate (20equiv) for 5h, distill off unreacted ethyl formate, then add tetrahydrofuran, then drop into tetrahydrofuran solution of lithium aluminum hydride, heat to reflux for 3h after completion, cool to 0 degrees, slowly drop into it Add 10% KOH (aq) to quench the reaction, filter with suction, spin the filtrate to dryness, and recrystallize with n-hexane to obtain compound DPPNHMe with a yield of 50%.

[0079] Under ice-cooling, add a mixed solution of DPPNHMe (1 equiv) and triethylamine (1.5 equiv) dropwise into the solution of diphenylphosphorus chloride, and then rise to room temperature and stir for 5 h. Then the reaction was quenched with water, the layers were separated, the organic layer was spin-dried, and recrystallized with n-hexane to obtain ligand 8 with a yield of 88%.

[0080] NMR spectrum of Ligand 8:

[0081] 1 H NMR (400MHz, CDCl 3 ):δ6.92-7.59(m,24H),5.24(m,1H),2.30(s,...

Embodiment 3

[0085] 1 Preparation of Ligands 25

[0086] Under ice-cooling, add a mixed solution of DPPNHMe (1 equiv) and triethylamine (1.5 equiv) dropwise into the solution of bis(4-methylphenyl)phosphorous chloride, and then rise to room temperature and stir for 5 h. Then the reaction was quenched with water, the layers were separated, the organic layer was spin-dried, and the ligand 25 was obtained by recrystallization from n-hexane with a yield of 85%.

[0087] NMR spectrum of Ligand 25:

[0088] 1 H NMR (400MHz, CDCl 3 ):δ6.91-7.60(m,22H),5.20(m,1H),2.30(s,6H),2.15(s,3H),1.49(d,J=8.0Hz,3H); 31 P NMR (CDCl 3 ):δ-17.25,48.58; 13 C NMR (100MHz, CDCl 3 ): δ22.3, 22.7, 59.9, 126.8, 126.9, 128.4, 128.5, 128.6, 128.8, 129.1, 133.8, 132.0, 132.7, 132.9, 133.8, 134.0, 137.6, 150.2, 150.5.

[0089] 2 ethylene oligomerization reaction

[0090] Ethylene oligomerization was carried out in a 200mL autoclave. Before the oligomerization started, the reactor was replaced with nitrogen three ...

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Abstract

The invention relates to synthesis of a series of novel asymmetric hybridized phosphine-aminophosphine ligands for alpha-olefin catalytic system preparation through selective oligomerization of ethylene, belongs to the field of organic synthesis, relates to synthesis of a phosphine-aminophosphine structure skeleton-containing ligand in an alpha-olefin catalytic system prepared through selective oligomerization of ethylene, and provides a ternary catalyst system using chromium as a central metal precursor and using a phosphine-aminophosphine compound as a ligand, activator or co-catalyst, and applications of the ternary catalyst system in catalytic synthesis of 1-hexene through high selectivity ethylene trimerization and in catalytic synthesis of 1-octene through high selectivity ethylene tetramerization. Compared to the traditional PNP chromium-based catalyst system, the ternary catalyst system of the present invention has the following advantages that the co-selectivity and the activity of 1-hexene and 1-octene are improved, the waxy product is reduced, the reaction conditions are mild, and the high activity is maintained.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and specifically relates to the synthesis of a phosphine-aminophosphine structural skeleton ligand in a catalytic system for preparing α-olefins by selective oligomerization of ethylene, and provides a phosphine-aminophosphine compound with chromium as the central metal precursor It is a three-way catalyst system for ligand, activator or co-catalyst and it catalyzes highly selective ethylene trimerization into 1-hexene and tetramerization into 1-octene. Background technique [0002] Olefins, especially linear α-olefins are an important class of chemical intermediates, which are widely used in polyethylene comonomers, surfactant synthesis intermediates, synthetic lubricating oils, petroleum additives, oilfield chemicals and other fields. At present, the main method of industrial production of α-olefin in the world is ethylene oligomerization, especially for the highly selective synthesis of 1-hexe...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J31/24C07C2/36C07C11/107C07C11/02
CPCY02P20/52
Inventor 胡向平胡信虎
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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