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Catalyst system and catalyzing method of propylene hydrogenation and formylation

A propylene hydroformylation catalysis and system technology, applied in chemical instruments and methods, organic compound/hydride/coordination complex catalysts, physical/chemical process catalysts, etc., can solve the problem of low butyraldehyde normal/iso ratio , Expensive epoxy compounds, accelerated butyraldehyde polymerization, etc., to achieve high activity and selectivity, prolong service life, and reduce dosage

Active Publication Date: 2007-06-27
SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Rh(I) / triphenylphosphine is a widely used catalyst system for the synthesis of butyraldehyde from propylene hydroformylation at present, but the problem is that the amount of noble metal Rh(I) (200mg / L) and triphenylphosphine is large (triphenyl The molar ratio of base phosphine to rhodium is generally 200:1), and the normal / iso ratio of the product butyraldehyde is not high (<20)
The disadvantage of this method is that it will inevitably cause a certain degree of catalyst loss when the ion exchange resin bed processes the reaction mixture, and it is necessary to supplement the catalyst in the reaction system to make it reach a suitable concentration; moreover, this method also needs to add A large additional equipment, which significantly increases the cost of investment and operation
However, epoxy compounds are relatively expensive, and controlling the reaction solution in a weakly alkaline environment will accelerate the polymerization of butyraldehyde, and the impact of the decomposition of epoxy compounds on product quality is not very clear

Method used

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  • Catalyst system and catalyzing method of propylene hydrogenation and formylation
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  • Catalyst system and catalyzing method of propylene hydrogenation and formylation

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Experimental program
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Effect test

Embodiment 1

[0040]

[0041] Synthesis of bidentate phosphite L1: addition of 2,2'-biphenol to excess PCl 3 In, after heating to reflux (reflux) for 5 hours, the excess PCl was distilled off under reduced pressure 3 , to obtain white solid compound A (yield 71%). A solution of 2,2'-biphenol (0.37 g, 2 mmol) and triethylamine (2.8 mL, 20 mmol) in tetrahydrofuran (THF) was added dropwise to a solution of A (1.25 g, 5 mmol) in THF at ice bath temperature After the dropwise addition, it was gradually raised to room temperature (r.t,) and stirred for 24 hours before processing, and recrystallized after silica gel column purification to obtain the product L1, white crystals, the yield was 90% (1.1g), 1 H NMR and 31 The structure was identified by P NMR, and the melting point was 124°C.

Embodiment 2

[0043]

[0044] Synthesis of bidentate phosphite L2:

[0045] At -40°C, a solution of binaphthyldiol (1.43g, 5mmol) and triethylamine (5.6mL, 40mmol) in tetrahydrofuran was added dropwise to PCl 3 (0.43mL, 5mmol) in tetrahydrofuran solution, gradually warmed up to room temperature after the dropwise addition, cooled to -40°C after stirring for 2 hours, then added dropwise Compound B (0.82g, 2mmol) and triethylamine (2.8mL, 20mmol ) tetrahydrofuran solution, after the dropwise addition, the temperature was gradually raised to room temperature, and after stirring for 2 hours, it was processed and purified through a silica gel column to obtain the product L2, a white solid, with a yield of 67% (1.39g), 1 H NMR and 31 The structure was identified by P NMR with a melting point of 249-251°C.

Embodiment 3

[0047]

[0048] Synthesis of bidentate phosphite L3: At room temperature, a toluene solution of compound B (1.0 g, 2.5 mmol) and triethylamine (2.8 mL, 20 mmol) was added dropwise to PCl 3 (0.22mL, 2.5mmol) in toluene solution, heat up and reflux for 2 hours, then cool to room temperature, then add dropwise the toluene solution of 2,2'-biphenol (0.18g, 1mmol) and triethylamine (1.4mL, 10mmol) , after the dropwise addition, the temperature was raised to reflux for 2 hours, cooled and processed, and purified through a silica gel column to obtain the product L3, a white solid, with a yield of 30% (0.31g), 1 H NMR and 31 The structure was identified by P NMR with a melting point of 145-147°C.

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Abstract

The present invention relates to catalyst system for propylene hydrogenation and formylation and process of catalytically synthesizing butyl aldehyde. The catalyst system is triaryl phosphine-Rh(I) catalyst system with proper additive, such as bisphosphite ester, in proper amount. Compared with similar available catalyst, the catalyst system has obviously higher catalytic acitivity, higher selectivity, higher stability and raised n-butyl aldehyde / isobutyl aldehyde ratio in the catalytically synthesized product.

Description

technical field [0001] The invention uses rhodium salt, triaryl phosphine and bisphosphite additives to prepare a novel catalyst system for propylene hydroformylation, and is used in the method for catalyzing propylene hydroformylation to synthesize butyraldehyde. In the propylene hydroformylation reaction system catalyzed by triarylphosphine-Rh(I), the present invention finds that the efficiency of the Rh(I) / triarylphosphine catalyst can be significantly improved by using bisphosphite additives, such as bisphosphite. The activity and the butyraldehyde in the product are positively different (the molar ratio of n-butyraldehyde / isobutyraldehyde>20), and significantly prolong the service life of the bisphosphite ligand, and significantly reduce the amount of triarylphosphine. This type of catalyst system is characterized by higher activity and selectivity than the third-generation Rh(I) / triphenylphosphine catalyst, and better stability than the fourth-generation Rh(I) / bisphos...

Claims

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Application Information

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IPC IPC(8): B01J31/24B01J31/28C07C47/02C07C45/49
CPCY02P20/582
Inventor 丁奎岭侯雪龙李欣朱霞珍吴良泉蒋文赖春波陈建伟
Owner SHANGHAI INST OF ORGANIC CHEM CHINESE ACAD OF SCI
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