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2-imino-9-phenyl-1,10-phenanthroline transient metal complex, and preparation and use thereof

A transition metal and imine-based technology, applied in the field of 2-imino-9-phenyl-1,10-phenanthroline transition metal complexes and their preparation and application, can solve the problem of harsh operating conditions and blockage It can achieve high 1-butene selectivity, excellent catalytic activity, and wide industrial application prospects.

Inactive Publication Date: 2009-01-21
INST OF CHEM CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Nickel-based catalysts require high-pressure catalytic technology and technology, and there is a potential danger of double bond displacement to generate internal olefins, and the operating conditions are harsh; other types of catalysts are modified and modified on the basis of polyolefin catalysts, and are often damaged by careless operation. Cause high polyolefin formation and block the discharge port

Method used

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  • 2-imino-9-phenyl-1,10-phenanthroline transient metal complex, and preparation and use thereof
  • 2-imino-9-phenyl-1,10-phenanthroline transient metal complex, and preparation and use thereof
  • 2-imino-9-phenyl-1,10-phenanthroline transient metal complex, and preparation and use thereof

Examples

Experimental program
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Effect test

preparation example Construction

[0061] Concrete preparation process is as follows:

[0062] 1. General method of ligand synthesis

[0063] 1.2-Acetyl-9-phenyl-1,10-phenanthroline and alkyl-substituted aniline were refluxed in toluene with p-toluenesulfonic acid as a catalyst for 1 day, after the reaction solution was concentrated, it was perbasic alumina column, and petroleum After washing with ether / ethyl acetate (20:1), the second fraction was divided into the product, and the solvent was removed to obtain a yellow solid, which was the corresponding ligand.

[0064] 2.2-Benzoyl-9-phenyl-1,10-phenanthroline and alkyl-substituted aniline use p-toluenesulfonic acid as a catalyst, use ethyl orthosilicate as solvent and dehydrating agent, at 140-150°C Heat the reaction for 1.5 days, remove tetraethyl orthosilicate under reduced pressure, then rinse the perbasic alumina column with petroleum ether / ethyl acetate (6:1), the second stream is divided into products, and the solvent is removed to obtain a yellow soli...

Embodiment 1

[0072] 1. Preparation of 2-acetyl-9-phenyl-1,10-phenanthroline:

[0073] 1) 2-acetyl-1,10-phenanthroline (2.823g, 10.0mmol), ethylene glycol (3.254g, 52.4mmol) and p-toluenesulfonic acid (206mg) were refluxed in toluene (100mL) for 18 hours until No water was generated in the oil-water separator, and after removing the solvent toluene, the residue was purified by an alkaline alumina column, rinsed with petroleum ether / ethyl acetate (1:2), and the second stream was divided into products, and a light yellow solid was obtained after concentration 1.691 g, 50% yield. The melting point is 119-121°C.

[0074] FT-IR (KBr disc): 3054, 2993, 2980, 2938, 2900, 1619, 1589, 1552, 1505, 1490, 1476, 1445, 1391, 1376, 1256, 1232, 1204, 1147, 1129, 1106, 1029, 1009, 953, 855, 789, 752, 675cm-1.

[0075] 1H NMR (400MHz, CDCl3): δ=9.24(d, J=4.4Hz, 1H), 8.25(d, J=8.4Hz, 1H), 8.22(d, J=8.4Hz, 1H), 7.93(d, J=8.4Hz, 1H), 7.77(s, 2H), 7.61(dd, J=4.4Hz, 1H), 4.18(t, J=6.4Hz, 2H), 4.01(t, J=6.4Hz...

Embodiment 2

[0093] 1. The preparation of complex 1 is the same as in Example 1.

[0094] 2. Ethylene oligomerization at normal pressure: Dry a 250ml three-necked round bottom flask equipped with a magnetic stirrer at 130°C for 6hrs continuously, vacuumize while hot and use N 2 Air replacement 3 times. 2.6 mg (5 μmol) of complex 1 were added and then evacuated and replaced with ethylene 3 times. Inject 30 ml of toluene with a syringe, and then add 1.3 ml of modified methylaluminoxane (MMAO) (1.93 mol / l heptane solution) to make Al / Fe=500. At 20°C, the ethylene pressure was maintained at 1 atm, and the reaction was vigorously stirred for 30 min. After the reaction, a small amount of the mixture was taken out with a syringe and neutralized with 5% dilute hydrochloric acid for GC analysis: the oligomerization activity was 4.78×10 5 g·mol -1 (Fe)·h -1 , the resulting oligomer is only 1-butene. The remaining mixture was neutralized with 5% hydrochloric acid in ethanol, and no polymer was ...

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Abstract

The invention discloses a 2-imdo group-9-phenyl group-1, 10-phenanthrolines transition metal complex and a preparation method thereof and an application thereof. The structural formula of the 2-imdo group-9-phenyl group-1, 10-phenanthrolines transition metal complex of the invention is shown as the formula(I), wherein M is transition metal, and R and R<1> are independently selected from hydrogen, alkyl and phenyl respectively. In the invention, the ligand and the transition metal complex of 2-imdo group-9-phenyl group-1, 10-phenanthrolines containing N^N^N ligand are designed and synthesized; when the transition metal complex is used to catalyze the ethylene oligomerization reaction, the transition metal complex performs good catalytic activity and high selectivity of 1-butylene, so that the transition metal complex has broad industrial application prospect.

Description

technical field [0001] The invention relates to a 2-imino-9-phenyl-1,10-phenanthroline transition metal complex and a preparation method thereof, as well as a catalyst composition composed of the transition metal complex and the catalyst composition in Applications in catalytic ethylene oligomerization. Background technique [0002] Linear α-olefin is a very important organic chemical intermediate, which has different properties and uses according to the length of its carbon chain. C 4 ~C 8 It is a comonomer for the production of linear low density polyethylene (LLDPE); C 8 ~C 12 It can be used as the basic raw material for the production of high-grade lubricating oil; C 10 ~C 18 It is an important raw material for the production of surfactants, detergents and cleaning agents; high-carbon α-olefins are widely used in oilfield chemistry and paper setting agents. At present, the industrial production of linear α-olefins is mainly realized by the method of ethylene oligo...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F15/00C08F4/70C08F10/02C07D487/04
Inventor 孙文华介素云张树
Owner INST OF CHEM CHINESE ACAD OF SCI
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