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High-activity and high-selectivity ethylene trimerization catalyst as well as preparation method and application thereof

A high-selectivity, ethylene trimerization technology, applied in chemical instruments and methods, physical/chemical process catalysts, organic compound/hydride/coordination complex catalysts, etc., can solve the problem of low activity and achieve good catalytic effect , the effect of reducing the cost of industrialization

Inactive Publication Date: 2014-01-15
EAST CHINA UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Further modification of this type of complex found that when a large substituent trimethylsilyl is attached to the 4-position of the thiophene ring, the highest catalytic activity is 485 kg / (mol-Ti h), and the selectivity of 1-hexene is 90%. (CN 101062961A, 2007), although this type of compound has better selectivity, it is less active than the complex compound containing benzene ring in the side chain

Method used

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  • High-activity and high-selectivity ethylene trimerization catalyst as well as preparation method and application thereof
  • High-activity and high-selectivity ethylene trimerization catalyst as well as preparation method and application thereof
  • High-activity and high-selectivity ethylene trimerization catalyst as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] Preparation of Substituted Indene Titanium Complex C1

[0035] (1) Preparation of Ligand Compound L1

[0036] At -78°C, n-BuLi (2.4mol / L, 30mL) was added dropwise to a petroleum ether solution of bromobenzene (0.072mol), and reacted for 2-7 days. Filter, dissolve the solid with 60 mL of ether, add 6,6-dimethylbenzofulvene (6.065 g), react for 2 days, hydrolyze and purify to obtain 1.8 g of yellow viscous liquid with a yield of 20%. The structural formula is as follows:

[0037]

[0038] 1 H NMR (400MHz, CDCl3 ): δ7.35(d, J=7.4Hz, 1H), 7.27-7.22(m, 2H), 7.20-7.13(m, 2H), 7.12-7.05(m, 1H), 6.99(td, J=7.4 Hz, J=0.7Hz, 1H), 6.91(t, J=7.4Hz, 1H), 6.63(d, J=7.7Hz, 1H), 6.40(t, J=2.1Hz, 1H), 3.33(d, J=2.1Hz, 2H), 1.59(s, 6H).

[0039] (2) Preparation of indene-titanium complex C1

[0040] Add n-BuLi (6mmol) dropwise to ligand L1 (1.40g, 0.006mol) in 50mL petroleum ether solution at 0°C, react overnight, then add TiCl at -78°C 4 (0.006mol), react for 12-24h. The solv...

Embodiment 2

[0046] Preparation of Substituted Indene Titanium Complex C2

[0047] (1) Preparation of Ligand Compound L2

[0048] At -78°C, add n-BuLi (2.4mol / L, 30mL) dropwise to a solution of bromobenzene (0.072mol) in petroleum ether, react for 2-7 days, filter, dissolve in ether, add 6,6- 8.326 g of pentylbenzofulvene was reacted for 2 days, hydrolyzed and purified to obtain 5.4 g of a light yellow solid with a yield of 46%. The structural formula is as follows:

[0049]

[0050] 1 H NMR (400MHz, CDCl 3 ): δ7.45-7.38(m, 3H), 7.29-7.23(m, 2H), 7.13(t, J=7.3Hz, 1H), 7.09-6.97(m, 3H), 6.52(t, J=2.1 Hz, 1H), 3.41(d, J=2.1Hz, 2H), 2.40-2.32(m, 2H), 2.26-2.13(m, 2H), 1.71-1.56(m, 5H), 1.53-1.39(m, 1H).

[0051] (2) Preparation of complex C2

[0052] Add n-BuLi (6 mmol) dropwise to ligand L2 (1.65 g, 0.006 mol) in 50 mL of n-hexane solution at 0°C, react overnight, then add TiCl at -78°C 4 (0.006mol), react for 12-24h. The solvent was removed, washed with n-hexane, filtered, and t...

Embodiment 3

[0058] Preparation of Substituted Indene Titanium Complex C3

[0059] (1) Preparation of Ligand Compound L3

[0060] At -78°C, add n-BuLi (2.4mol / L, 30mL) dropwise to a petroleum ether solution of p-methylbromobenzene (0.072mol), react for 2-7 days, filter, dissolve with ether, add 6, 6.177 g of 6-dimethylbenzofulvene was reacted for 2 days, hydrolyzed and purified to obtain 2.3 g of a light yellow viscous liquid with a yield of 23%. The structural formula is as follows:

[0061]

[0062] 1 H NMR (400MHz, CDCl 3 ): δ7.49(d, J=7.3Hz, 1H), 7.31-7.23(m, 2H), 7.18-7.10(m, 3H), 7.06(t, J=7.4Hz, 1H), 6.81(d, J=7.6Hz, 1H), 6.52(s, 1H), 3.46(s, 2H), 2.36(s, 3H,), 1.73(s, 6H).

[0063] (2) Preparation of complex C3

[0064] Add n-BuLi (6mmol) dropwise to ligand L3 (1.49g, 0.006mol) in 50mL petroleum ether solution at 0°C, react overnight, then add TiCl at -78°C 4 (0.006mol), react for 12-24h. The solvent was removed, petroleum ether was added to wash, and the filtrate was re...

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Abstract

The invention provides a high-activity and high-selectivity ethylene trimerization catalyst as well as a preparation method and an application thereof. The invention discloses a substituted indene titanium metal complex with a pendulous-aryl-containing side chain as well as a synthesis method and an application thereof in olefine oligomerization. The substituted indene titanium metal catalyst with a pendulous-aryl-containing side chain is characterized in that: R1 and R2 are the same or different C1-C12 alkyls or annular alkyls formed by the two alkyls; and the R3-R7 are the same or different C1-C12 alkyls, halogen or hydrogen. The indene titanium complex catalyst with pendulous aryl-containing side chain has a very good catalytic effect to the olefine oligomerization and can catalyze the ethylene trimerization with high activity under the existence of cocatalyst, the highest activity is 106g / (mol-Ti.h), the 1-hexane selectivity is as high as 97.0%, and the other C6 isomers are not existed in a trimerization product, so that many follow-up separate operation links can be avoided, the industrial cost can be reduced, and the requirement of the industrial part can be met. The structure has the following formula.

Description

technical field [0001] The invention relates to an olefin trimerization catalyst, in particular to a synthesis method of an indene titanium metal catalyst substituted with a pendant aryl group in the side chain and its application in alpha-olefin oligomerization. Background technique [0002] Ethylene oligomerization products linear α-olefins (LAOs) are useful intermediates for the preparation of detergents, lubricants, and plasticizers, and have important applications in industry. In particular, 1-hexene and 1-octene, as a comonomer, are widely used in the chemical and chemical fields, mainly for the preparation of linear low-density polyethylene (LLDPE) with great industrial value. Most ethylene oligomerization reactions catalyzed by transition metal complex catalysts mainly yield a multi-component olefin, which does not meet the market demand, especially for single-component α-olefins. On the other hand, the existing single-component olefin oligomerization catalysts have...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07F7/28B01J31/22C07C2/32C07C11/107
Inventor 黄吉玲张延路何乐马海燕
Owner EAST CHINA UNIV OF SCI & TECH
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