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Catalyst for preparing linear-chain aldehyde in high-selectivity manner as well as preparation and application thereof

A high-selectivity, catalyst technology, applied in the direction of carbon monoxide reaction preparation, physical/chemical process catalyst, organic compound/hydride/coordination complex catalyst, etc., can solve the problem of supported catalyst activity and selectivity reduction, catalyst activity and The stability needs to be improved, and the activity of the supported ionic liquid phase catalyst is reduced, so as to achieve high stability, high activity and stability, and improve the utilization efficiency.

Active Publication Date: 2019-05-28
DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the biggest disadvantage of this process is that the preparation process of the catalyst is more complicated, and compared with the homogeneous catalyst, the activity of the prepared supported ion liquid phase catalyst is significantly lower.
[0009] In 2005, E.Monflier (Organometallics, 2005, 24, 2070) also sulfonated the diphosphine ligand Xantphos, and based on this, developed a two-phase hydroformylation catalytic process, which is suitable for high-carbon Olefin hydroformylation, but the catalyst preparation process is complicated, and the catalyst activity and stability need to be improved
The catalyst realizes the heterogeneity of the hydroformylation homogeneous catalyst, but compared with the homogeneous catalyst, the activity and selectivity of the ligand-modified supported catalyst are greatly reduced, and the Rh metal is formed as a nanoparticle Dispersed form, low metal utilization

Method used

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  • Catalyst for preparing linear-chain aldehyde in high-selectivity manner as well as preparation and application thereof
  • Catalyst for preparing linear-chain aldehyde in high-selectivity manner as well as preparation and application thereof
  • Catalyst for preparing linear-chain aldehyde in high-selectivity manner as well as preparation and application thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0052] Preparation of the diphosphine ligand 2v-Xantphos: The synthetic route of the 2v-Xantphos ligand is attached figure 1 shown. Since 9,9-dimethylxanthene (with figure 1 Compound No. 1) has heteroatom O at the β-positions of the 4 and 5 positions, so it is easier to undergo deprotonated lithiation to generate dilithium reagent 2. Compound 5 was obtained by reacting p-bromostyrene 3 with phenylphosphine chloride after activation by Grignard reagent. The 2v-Xantphos ligand can be obtained by reacting compound 5 with dilithium reagent 2 at a molar ratio of 2:1. According to the calculation of raw material 1, the reaction yield is about 60%, and no purification and separation steps are required in the intermediate preparation process. The finally obtained 2v-Xantphos ligand is recrystallized from acetonitrile to obtain a white powdery solid. attached Figure 4 And attached Figure 5 NMR for the prepared 2v-Xantphos ligand 1 H and 31 P Spectrum.

[0053] Preparation of ...

Embodiment 2

[0056] In Example 2, except taking 10.0 grams of comonomer tris (4-vinylphenyl) phosphine (L1), replacing 2.5 grams of comonomer tris (4-vinylphenyl) phosphine, the rest of the catalyst synthesis process Same as Example 1.

Embodiment 3

[0058] In Example 3, except that 0.01 gram of free radical initiator azobisisobutyronitrile was weighed instead of 1.0 gram of free radical initiator azobisisobutyronitrile, the rest of the catalyst preparation process was the same as that of Example 1.

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Abstract

The invention discloses a high-selectivity method for preparing linear-chain aldehyde. According to the method disclosed by the invention, a phosphine-containing organic polymer self-loaded type high-dispersity metal catalyst is used, and olefin hydroformylation reaction is used for preparing the linear-chain aldehyde in a high-selectivity manner. The organic polymer self-loaded type catalyst takes one, two and three of metal Rh, Co, Pd, Ir and Rt as active components and a phosphine-containing organic polymer is used as a carrier, wherein the phosphine-containing organic polymer carrier is formed by co-polymerizing or self-polymerizing a multi-dentate organic phosphine ligand and a single-dentate organic phosphine ligand. The phosphine-containing organic polymer self-loaded type high-dispersity metal catalyst provided by the invention is applied to reactors including fixed beds, slurry beds, bubbling beds, trickle beds and the like. The method disclosed by the invention has very goodpresentation in the olefin hydroformylation reaction and can be used for producing a target product linear-chain aldehyde in the high-selectivity manner.

Description

technical field [0001] The invention belongs to the field of heterogeneous catalysis and fine chemical industry, and specifically relates to a method for preparing linear aldehydes with high selectivity through olefin hydroformylation. Background technique [0002] Aldehydes are very useful chemical intermediates with relatively active chemical properties. Aldehydes can be hydrogenated and reduced to produce alcohols. Alcohols themselves can be used as organic solvents, plasticizers and surfactants in the field of fine chemicals; aldehydes can be oxidized to form carboxyl Acids and corresponding esters, and fatty amines are very useful chemical intermediates. There are many ways to synthesize aldehydes in industry, among which the green synthesis of aldehydes through olefin hydroformylation has attracted more and more attention. The hydroformylation reaction of olefins is a typical atom-economic reaction, which can combine olefins with synthesis gas (CO / H 2 ) 100% selectiv...

Claims

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Application Information

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IPC IPC(8): B01J31/24C07C45/50C07C47/02
Inventor 李存耀丁云杰严丽
Owner DALIAN INST OF CHEM PHYSICS CHINESE ACAD OF SCI
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