Method for high-selectivity preparation of normal aldehyde through olefin two-phase hydroformylation on basis of phosphine-functionalized polyether imidazolium salt ionic liquid

A polyether imidazolium salt and ionic liquid technology, applied in the direction of carbon monoxide reaction preparation, chemical instruments and methods, organic compound/hydride/coordination complex catalyst, etc., can solve the problem of low catalytic activity and poor regioselectivity of normal aldehydes , High dosage of ionic liquid, etc.

Active Publication Date: 2016-07-13
永春县产品质量检验所福建省香产品质量检验中心国家燃香类产品质量监督检验中心福建
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Problems solved by technology

Homogeneous hydroformylation has the advantages of high catalytic activity, good selectivity and mild reaction conditions, but for a long time, the separation and recycling of rhodium catalysts has been the focus of attention in the field of homogeneous catalysis
But this two-phase system still has the following problems: one is that a large amount of ionic liquid is required as the carrier of the Rh-TPPTS catalyst, and the mass ratio of the ionic liquid to the rhodium catalyst precursor reaches 1000:1; Due to the limitation of mass transfer resistance, the catalytic activity is not high, and the TOF value is only 10-200h -1 The third is that the regioselectivity of nor

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  • Method for high-selectivity preparation of normal aldehyde through olefin two-phase hydroformylation on basis of phosphine-functionalized polyether imidazolium salt ionic liquid
  • Method for high-selectivity preparation of normal aldehyde through olefin two-phase hydroformylation on basis of phosphine-functionalized polyether imidazolium salt ionic liquid
  • Method for high-selectivity preparation of normal aldehyde through olefin two-phase hydroformylation on basis of phosphine-functionalized polyether imidazolium salt ionic liquid

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Rh(acac)(CO) 2 / BISBI-(SO 3 Na) 2 (o=p=1, q=r=2) / [Ph(EO) 16 MI(CH 3 )][CH 3 SO 3 - ] / 1-octene two-phase hydroformylation reaction

[0027] Under an inert atmosphere, add Rh(acac)(CO) to a stainless steel autoclave 2 , BISBI-(SO 3 Na) 2 , [Ph(EO) 16 MI(CH 3 )][CH 3 SO 3 - ] and 1-octene, the ratio is: BISBI-(SO 3 Na) 2 / Rh(acac)(CO) 2 =5:1 (molar ratio), 1-octene / Rh(acac)(CO) 2 =1000:1 (molar ratio), [Ph(EO) 16 MI(CH 3 )][CH 3 SO 3 - ] / Rh(acac)(CO) 2 =300:1 (molar ratio), then use synthesis gas (H 2 / CO=1:1) pressurized to 5.0MPa, reaction temperature 100°C, reaction time 0.5 hours, then rapidly cooled to room temperature, vented the synthesis gas and opened the kettle, realized rhodium catalyst by two-phase separation of ionic liquid phase and organic phase The recovery of n-heptane can also be added for extraction, and the organic phase containing product aldehyde is obtained through simple two-phase separation. The gas chromatography analysis ...

Embodiment 2

[0029] Rh(acac)(CO) 2 / BINA-(SO 3 Na) 2 (o=p=1, q=r=2) / [Ph(EO) 16 MI(CH 3 )][CH 3 SO 3 - ] / 1-octene two-phase hydroformylation reaction

[0030] Under an inert atmosphere, add Rh(acac)(CO) to a stainless steel autoclave 2 , BINA-(SO 3 Na) 2 , [Ph(EO) 16 MI(CH 3 )][CH 3 SO 3 - ] and 1-octene in a ratio of: BINA-(SO 3 Na) 2 / Rh(acac)(CO) 2 =5:1 (molar ratio), 1-octene / Rh(acac)(CO) 2 =5000:1 (molar ratio), [Ph(EO) 16 MI(CH 3 )][CH 3 SO 3 - ] / Rh(acac)(CO) 2 =300:1 (molar ratio), then use synthesis gas (H 2 / CO=1:1) pressurized to 5.0MPa, reaction temperature 100°C, reaction time 0.5 hours, then rapidly cooled to room temperature, vented the synthesis gas and opened the kettle, realized rhodium catalyst by two-phase separation of ionic liquid phase and organic phase The recovery of n-heptane can also be added for extraction, and the organic phase containing product aldehyde can be obtained through simple two-phase separation. The gas chromatography analysis...

Embodiment 3

[0032] Rh(acac)(CO) 2 / Xantphos-(SO 3 Na) 2 (o=p=1, q=r=2) / [Ph(EO) 16 MI(CH 3 )][CH 3 SO 3 - ] / 1-octene two-phase hydroformylation reaction

[0033] Under an inert atmosphere, add Rh(acac)(CO) to a stainless steel autoclave 2 , Xantphos-(SO 3 Na) 2 , [Ph(EO) 16 MI(CH 3 )][CH 3 SO 3 - ] and 1-octene in a ratio of: Xantphos-(SO 3 Na) 2 / Rh(acac)(CO) 2 =5:1 (molar ratio), 1-octene / Rh(acac)(CO) 2 =1000:1 (molar ratio), [Ph(EO) 16 MI(CH 3 )][CH 3 SO 3 - ] / Rh(acac)(CO) 2 =300:1 (molar ratio), then use synthesis gas (H 2 / CO=1:1) pressurized to 5.0MPa, reaction temperature 100°C, reaction time 0.5 hours, then rapidly cooled to room temperature, vented the synthesis gas and opened the kettle, realized rhodium catalyst by two-phase separation of ionic liquid phase and organic phase The recovery of n-heptane can also be added for extraction, and the organic phase containing product aldehyde is obtained through simple two-phase separation. The gas chromatography ...

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Abstract

The invention relates to a method for high-selectivity preparation of normal aldehyde through olefin two-phase hydroformylation on the basis of a phosphine-functionalized polyether imidazolium salt ionic liquid. According to the method, a two-phase catalytic system is adopted, the catalytic system comprises a phosphine-functionalized polyether imidazolium salt ionic liquid, a polyether imidazolium salt ionic liquid, a rhodium catalyst, a reaction substrate olefin and a reaction product aldehyde, a liquid/liquid two-phase hydroformylation reaction is performed at certain reaction temperature and under certain synthesis gas pressure, the rhodium catalyst is separated and cycled through simple two-phase separation after the reaction ends, the rhodium catalyst can be recycled multiple times, and the catalytic activity and the selectivity are not remarkably reduced. The TOF value of the system reaches 400-3,300 h<-1> and the catalytic cycle accumulated TON value reaches 33,975.

Description

technical field [0001] The invention relates to the technical field of chemistry and chemical engineering, in particular to a method for preparing normal aldehyde with high selectivity by two-phase hydroformylation of olefins based on phosphine functionalized polyether imidazolium salt ionic liquid. Background technique [0002] The rhodium-catalyzed hydroformylation of olefins is a typical atom-economical reaction, and it is also a carbonylation reaction with more reports in the literature. It has become an ideal method for the preparation of high-carbon aldehydes / alcohols. Homogeneous hydroformylation has the advantages of high catalytic activity, good selectivity and mild reaction conditions, but the separation and recycling of rhodium catalysts has been the focus of attention in the field of homogeneous catalysis for a long time. [0003] In recent years, the liquid / liquid two-phase catalytic system with ionic liquid as the catalyst carrier has developed very rapidly, an...

Claims

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Application Information

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IPC IPC(8): C07C45/50C07C47/02B01J31/30B01J31/24B01J31/06
CPCB01J31/0285B01J31/06B01J31/2414B01J31/2457B01J31/30B01J2231/321C07C45/50C07C47/02Y02P20/50Y02P20/584
Inventor 金欣郑魁星李淑梅
Owner 永春县产品质量检验所福建省香产品质量检验中心国家燃香类产品质量监督检验中心福建
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