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Phosphine-nitrogen ligand, preparation method thereof, ethylene oligomerization three-way catalyst system and application

A nitrogen ligand and reaction technology, applied in the field of three-way catalyst system, can solve the problems of unfavorable long-term operation of the device, huge influence on activity and selectivity, and poor production stability

Active Publication Date: 2021-09-10
WANHUA CHEM GRP CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005]The performance of currently disclosed ethylene oligomerization catalysts is mainly affected by the ligand structure, and the steric hindrance effect and electron donating effect of the ligand have a great influence on the activity and selectivity , under the premise of ensuring the catalytic activity, the product selectivity is basically below 85wt%, the polymer selectivity is generally above 0.2wt%, and the catalyst tolerance temperature is generally less than 60°C, and abnormal temperature, high temperature fluctuations, etc. The production stability is poor, which is very unfavorable to the long-term operation of the device

Method used

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  • Phosphine-nitrogen ligand, preparation method thereof, ethylene oligomerization three-way catalyst system and application
  • Phosphine-nitrogen ligand, preparation method thereof, ethylene oligomerization three-way catalyst system and application
  • Phosphine-nitrogen ligand, preparation method thereof, ethylene oligomerization three-way catalyst system and application

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0085] Preparation of phosphine-nitrogen ligands:

[0086] 1) Under nitrogen atmosphere, dissolve 1mol (139.2g) 1,5,7-triazidebicyclo(4.4.0)dec-5-ene in 800ml of methanol, add 1mol (37.8g) sodium borohydride, 25℃ The reaction was carried out for 3 hours, and the compound was spin-dried at 30-50° C. to obtain 0.95 mol (138.7 g) of the compound shown in formula II under the condition of vacuum pump negative pressure:

[0087]

[0088] The nuclear magnetic data of compound shown in formula II is as follows:

[0089] 1H NMR (400MHz, CDCl 3 ): 2.29-2.63(m,8H), 1.91(s,2H), 1.48-1.55(m,4H).

[0090] 2) Under anhydrous and oxygen-free conditions, dissolve 100mmol (13.9g) of the compound shown in formula II in 200ml of dichloromethane; add 220mmol (22.3g) of triethylamine dropwise to the reaction solution at -5°C with stirring, First slowly add 110mmol (24.3g) of diphenylphosphine chloride to it, the temperature of the system is controlled at 0°C during the feeding process of dip...

Embodiment 2

[0096] Preparation of phosphine-nitrogen ligands:

[0097] Prepare the phosphine-nitrogen ligand L2 according to the method in Example 1, the difference is that the compound shown in the formula III added is different, and the molar ratio of raw materials shown in Table 1 and the reaction conditions are different: the compound shown in the formula III is selected from chlorine (2-fluorobenzene base) (phenyl) phosphine to obtain the phosphine-nitrogen ligand shown in the following formula L2:

[0098]

[0099] The NMR data of ligand L2 are as follows: 1H NMR (400MHz, CDCl 3 ): 7.22-7.75(m,18H), 4.92(s,1H), 2.33~2.65(m,8H), 1.49~1.58(m,4H).

[0100] Vinyl oligomerization:

[0101] Before the reaction, the 500ml reactor was heated to 120°C, vacuumed for 4 hours, and replaced with nitrogen three times. After the temperature is cooled to 35°C, ethylene is replaced twice. First add 200ml of dehydration and deoxygenation solvent methylcyclohexane and 0.96ml (1.75mmol) MMAO-3a, ...

Embodiment 3

[0103] Preparation of phosphine-nitrogen ligands:

[0104] Prepare the phosphine-nitrogen ligand L3 according to the method in Example 1, the difference is that the compound shown in the formula III added is different, and the molar ratio of raw materials shown in Table 1 and the reaction conditions are different: the compound shown in the formula III is selected from chlorine (3-fluorobenzene base) (phenyl) phosphine to obtain the phosphine-nitrogen ligand shown in the following formula L3:

[0105]

[0106] The NMR data of ligand L3 are as follows: 1H NMR (400MHz, CDCl 3 ): 7.15-7.45(m,18H), 4.88(s,1H), 2.33~2.65(m,8H), 1.49~1.58(m,4H).

[0107] Vinyl oligomerization:

[0108] Before the reaction, the 500ml reactor was heated to 120°C, vacuumed for 2 hours, and replaced with nitrogen three times. After the temperature was cooled to 35°C, ethylene was replaced twice. First, 200 ml of dehydration and deoxygenation solvent toluene and 1.14 ml (1.75 mmol) MAO were added, t...

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Abstract

The invention provides a phosphine-nitrogen ligand, a preparation method of the phosphine-nitrogen ligand, an ethylene oligomerization three-way catalyst system and application of the ethylene oligomerization three-way catalyst system. The structure of the phosphine-nitrogen ligand is shown as a formula I. The phosphine-nitrogen ligand has high stability, high catalyst activity and high product selectivity, and the temperature tolerance of the catalyst is improved. The three-way catalyst system comprises a phosphine-nitrogen ligand as shown in a formula I, a chromium metal compound and an alkylaluminoxane cocatalyst. When the three-way catalyst system is used for ethylene oligomerization, the beneficial effects that the reaction is performed at a relatively high temperature, the generation of polymers is reduced, the activity can reach 1500kg / (gCr.h) or above, and the total selectivity of 1-hexene and 1-octene is greater than 90% can be realized, the production cost can be reduced, and the economic added value is high.

Description

technical field [0001] The invention relates to a three-way catalyst system, in particular to a phosphine-nitrogen ligand, a preparation method thereof, and an ethylene oligomerization catalyst system and application. Background technique [0002] Linear alpha-olefins refer to C with double bonds at the ends of the molecule 4 The above linear olefin is an important raw material in petrochemical industry, and can be used in many fields such as comonomer, surfactant synthesis intermediate, plasticizer alcohol, synthetic lubricating oil and oil additive. Polyethylene comonomer accounts for the largest proportion of α-olefin consumption. Among them, polyethylene produced with 1-hexene and 1-octene as comonomers has better tear resistance and impact resistance, and has attracted more and more attention from the market. [0003] At present, most of the linear α-olefin products come from the ethylene oligomerization process. The products in the ethylene oligomerization process h...

Claims

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Application Information

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IPC IPC(8): C07F9/6561C07C2/32B01J31/22C07C11/107C07C11/02
CPCC07F9/6561B01J31/2247B01J31/143C07C2/32B01J2531/62B01J2231/20C07C2531/22B01J35/19C07C11/107C07C11/02Y02P20/52
Inventor 刘帮明郭华陈海波黄玲燕刘声谊
Owner WANHUA CHEM GRP CO LTD