Immobilized rhodium-based catalyst as well as preparation method and application thereof

A catalyst, rhodium-based technology, applied in catalytic olefin hydroformylation reaction, immobilized rhodium-based catalyst and its preparation field, can solve the problem of low catalytic activity and selectivity, swelling effect, low specific surface area, etc. problems, to achieve the effect of simple preparation method, easy recovery and high product selectivity

Active Publication Date: 2021-03-05
CHINA PETROLEUM & CHEM CORP +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, traditional organic polymers often have low specific surface area, high diffusion resistance, and swelling effect, which makes the hydroformylation

Method used

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  • Immobilized rhodium-based catalyst as well as preparation method and application thereof
  • Immobilized rhodium-based catalyst as well as preparation method and application thereof
  • Immobilized rhodium-based catalyst as well as preparation method and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0052] This example is used to illustrate the preparation process of microgel-supported rhodium-based catalyst Rh@G1.

[0053] In a 50mL three-necked flask, add 10mL of toluene, then add 87mg of diphenyl p-styrylphosphine and 15mg of rhodium dicarbonyl acetylacetonate to the toluene, blow the resulting solution with nitrogen for 30 minutes, then add 1.28mL of methyl methacrylate , 30mg of benzoyl peroxide and 237mg of ethylene glycol dimethacrylate, the temperature was raised to 80°C and the reaction was continued for 12 hours. After cooling, the reaction solution was poured into methanol, and a black precipitate was precipitated, which was filtered to obtain the microgel-immobilized rhodium-based catalyst Rh@G1.

Embodiment 2

[0055] This example is used to illustrate the preparation process of microgel-immobilized rhodium-based catalyst Rh@G2.

[0056] In a 50mL three-neck flask, add 10mL toluene, then add 87mg diphenyl p-styryl phosphine and 15mg rhodium dicarbonyl acetylacetonate to the toluene, blow the resulting solution with nitrogen for 30 minutes, then add 1.23mL N,N'- Dimethacrylamide, 30mg of benzoyl peroxide and 184mg of N,N'-methylenebisacrylamide were heated to 80°C and continued to react for 12 hours. After cooling, the reaction solution was poured into methanol, and a black precipitate was precipitated, which was filtered to obtain a microgel-immobilized rhodium-based catalyst Rh@G2.

Embodiment 3

[0058] This example is used to illustrate the preparation process of microgel-immobilized rhodium-based catalyst Rh@G3.

[0059] In a 50mL three-neck flask, add 10mL toluene, then add 87mg diphenyl p-styryl phosphine and 15mg rhodium dicarbonyl acetylacetonate to the toluene, blow the resulting solution with nitrogen for 30 minutes, then add 1.23mL N,N'- Dimethacrylamide, 30mg of benzoyl peroxide and 92mg of N,N'-methylenebisacrylamide were heated to 80°C and continued to react for 12 hours. After cooling, the reaction solution was poured into methanol, and a black precipitate was precipitated, which was filtered to obtain the microgel-immobilized rhodium-based catalyst Rh@G3.

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Abstract

The invention provides an immobilized rhodium-based catalyst. The immobilized rhodium-based catalyst comprises a rhodium complex and an organic ligand polymer; and the organic ligand polymer is a polymer of an organic phosphine ligand and a comonomer. The invention also provides a preparation method of the immobilized rhodium-based catalyst. The method comprises the following steps: complexing theorganic phosphine ligand with the rhodium complex, and polymerizing with the comonomer to obtain the immobilized rhodium-based catalyst. The rhodium-based catalyst disclosed by the invention is of acompact structure that metal rhodium is wrapped by netty macromolecules, and the metal rhodium can be immobilized on microgel very effectively, so that the catalyst is prevented from being lost. The catalyst has the advantages of high activity, high regioselectivity, easiness in separation, recyclability and the like, and can be used for hydroformylation reaction of olefin.

Description

technical field [0001] The invention belongs to the field of catalyst preparation, and in particular relates to a solid-supported rhodium-based catalyst, a preparation method thereof, and an application in catalytic olefin hydroformylation. Background technique [0002] Hydroformylation refers to the carbonylation process in which olefins react with synthesis gas (a mixture of carbon monoxide and hydrogen) to form aldehydes. It was first discovered in 1938 by German scientist Otto Roelen. At present, the global output of hydroformylation has exceeded 10 million tons per year, and it has developed into one of the largest homogeneous catalytic industrial processes in the world. The mainstream catalytic system of industrial hydroformylation reaction is homogeneous rhodium catalyst. As early as the 1970s, German Ruhr Chemical Company, American Union Carbide Corporation, and Japan Mitsubishi Chemical Corporation successively established homogeneous rhodium-catalyzed hydroformylat...

Claims

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Application Information

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IPC IPC(8): B01J31/24C07C45/50C07C47/02C08F220/14C08F220/54C08F230/04
CPCB01J31/2404C07C45/505C08F220/14C08F220/54B01J2531/822B01J2231/321C07C47/02C08F230/04
Inventor 武陈李爽朱丽琴包天舒董岩
Owner CHINA PETROLEUM & CHEM CORP
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