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Cycloheptatriene-base rare-earth metal catalyst, and preparation method and application thereof

A technology of cycloheptatrienyl rare earth and metal catalysts, which is applied in chemical instruments and methods, organic chemistry, and compounds containing elements of Group 3/13 of the periodic table, etc. Reporting, long response time, etc.

Active Publication Date: 2015-05-06
BEIJING INSTITUTE OF TECHNOLOGYGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the preparation route of the cycloheptatrienyl metal complex is relatively complicated, usually starting from the cycloheptatrienyl ligand, reacting with KH at -78°C to remove the hydrogen atom on the cycloheptatriene ligand, and then Add metal halide reaction
This process takes a long time to react, so that the method does not have the possibility of large-scale industrialization process. Therefore, those skilled in the art are eager to find a method for preparing cycloheptatrienyl metal compounds that is more economical, environmentally friendly and suitable for industrialization.
At present, cycloheptatrienyl rare earth metal catalysts, preparation methods and their application in polymerization have not yet been reported

Method used

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  • Cycloheptatriene-base rare-earth metal catalyst, and preparation method and application thereof
  • Cycloheptatriene-base rare-earth metal catalyst, and preparation method and application thereof
  • Cycloheptatriene-base rare-earth metal catalyst, and preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0073] (1) Preparation of cycloheptatrienyl ligand

[0074]

[0075] First, weigh 5.3 g (43 mmol) of tropolone and 8.2 g (43 mmol) of p-toluenesulfonyl chloride into the reactor, add 60 mL of dichloromethane at room temperature, start stirring the mixture, and then add 6 mL of (43mmol) triethylamine, this moment will produce yellow muddy substance. Another 60 mL of dichloromethane was added. Compound a was obtained after stirring for about 32 h at room temperature under an atmosphere of nitrogen protection.

[0076]Next, isopropylamine (60 mL) was slowly added dropwise into a (10.92 g, 40.0 mmol) at low temperature. After the mixture was stirred overnight at room temperature, it was rotary evaporated under reduced pressure, and the obtained substance was washed with 2mol / L NaOH (60mL) and CH 2 Cl 2 (120 mL) was dissolved, the layers were separated and the organic phase was separated. CH 2 Cl 2 (120 mL) was extracted twice. The organic phases were combined, washed wi...

Embodiment 2

[0083] (1) Preparation of cycloheptatrienyl ligand

[0084]

[0085] First, weigh 5.3 g (43 mmol) of tropolone and 8.2 g (43 mmol) of p-toluenesulfonyl chloride into the reactor, add 60 mL of dichloromethane at room temperature, and then add 4.4 g (6 mL, 43mmol) triethylamine, and another 60mL of dichloromethane was added. Under the protection of nitrogen at room temperature, after stirring for about 32 h, compound a was obtained. The operation of compound b is the same as in Example 1. Second, the CH of b product (1.37g, 9.20mmol) 2 Cl 2 The solution was slowly added to the Et 3 OBF 4 (1.75g, 9.21mmol) solution, after stirring at room temperature for 3h, spot the plate until the point of the new product no longer changes, then cool the reaction to 0°C, and then slowly add isopropylamine (20mL) dropwise to the above In the reaction flask, after the reaction returned to room temperature, it was stirred overnight to obtain a mixture e containing the target product. The...

Embodiment 3

[0092] (1) Preparation of cycloheptatrienyl ligand

[0093]

[0094] The operation of compounds a and b is the same as in Example 1. Afterwards, the CH of b product (1.37g, 9.20mmol) 2 Cl 2 The solution was slowly added to the Et 3 OBF 4 (1.75g, 9.21mmol) solution, after stirring at room temperature for 3h, point the plate, confirm that there is a new product, until the point of the new product does not change, the reaction is cooled to 0 ° C, and then isopropylamine (20mL ) was slowly added dropwise at a rate of 1 s / drop into the reaction flask, and after the reaction returned to room temperature, it was stirred overnight to obtain a mixture e containing the target product. The product was purified by column chromatography to obtain 1.39 g of the cycloheptatrienyl ligand f with a yield of 47.9%.

[0095] (2) Preparation of Cycloheptatrienyl Lutetium Catalyst

[0096]

[0097] First, the reactor was placed in a glove box, and the cycloheptatrienyl ligand f (326.9 m...

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Abstract

The invention discloses a cycloheptatriene-base rare-earth metal catalyst, and a preparation method and application thereof, belonging to the field of catalysts. The method comprises the following steps: adding tropolone, paratoluensulfonyl chloride and triethylamine into a reactor, reacting in a nitrogen atmosphere for some time, adding amino substitute, reacting over night, recrystallizing to obtain a pure product, reacting with an Et3OBF4 solution for several hours, dropwisely adding the amino substitute, stirring over night, purifying by column chromatography to obtain a cycloheptatriene-base ligand; and dropwisely adding the ligand into an LnR3-dissolved toluene solution, stirring to react at room temperature for some time, filtering, concentrating, and recrystallizing to obtain the cycloheptatriene-base rare-earth metal catalyst. The catalyst has the advantage of accessible raw materials, and is applicable to polymerization reaction of multiple monomers, including homopolymerization and copolymerization of olefins, alkynes and polar monomers or copolymerization with CO2. The preparation method is simple, economical and environment-friendly, has wide application range, and is suitable for industrial production.

Description

technical field [0001] The invention relates to a cycloheptatrienyl rare earth metal catalyst, a preparation method and an application, and belongs to the technical field of catalysts. Background technique [0002] The conjugation effect refers to an electronic effect that changes the distribution of π electrons (or p electrons) in the system due to the interaction between atoms in the conjugated system. It is an important electronic effect in organic chemistry. It can change the distribution of electron cloud density in the molecule (coplanarization), reduce the internal energy, average the bond length, increase the refractive index, and make the whole molecule more stable. The research on the structure and properties of these molecules is of great significance both in theory and in practice, so this kind of compounds has aroused people's wide interest. [0003] Cycloheptatrienyl ligands have been widely used as non-cene ligands in the field of coordination chemistry. Thi...

Claims

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Application Information

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IPC IPC(8): C08F4/52C08G63/08C08G63/84C08F138/02C08G64/34C08F132/08C08F112/08C08F110/02C08F136/08C08F212/08C08G65/16C07F5/00
Inventor 李晓芳周玥宁张绍文杜改霞贺剑云
Owner BEIJING INSTITUTE OF TECHNOLOGYGY
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