Phosphine-functionalized polyether imidazolium-based ionic liquid and application thereof in the hydroformylation of olefins

A technology of polyether imidazolium salt and ionic liquid, applied in the field of chemical industry, can solve the problems of small negative effect and high dosage of ionic liquid, and achieve the effect of high catalytic activity, simple separation and circulation

Active Publication Date: 2015-11-04

QINGDAO UNIV OF SCI & TECH

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Problems solved by technology

[0008] In the present invention, the polyether imidazolium salt ionic liquid of phosphine functionalization has the characteristic of phosphine ligand, can form complex catalyst with rhodium, has the solvent performance of ionic liquid again, can serve as the carri...

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Abstract

The present invention relates to a phosphine-functionalized polyether imidazolium-based ionic liquid and a method for biphasic hydroformaylation of olefins based on the phosphine-functionalized polyether imidazolium-based ionic liquid. The method uses a biphasic catalytic system, wherein the catalytic system consists of a phosphine functionalized polyether imidazolium-based ionic liquid, a rhodium catalyst, the reaction substrate, olefins and the reaction product, aldehydes; liquid/liquid biphasic hydroformylation of olefins is performed at a certain reaction temperature and syngas pressure; the phosphine-functionalized polyether imidazolium-based ionic liquid acts both as a phosphine ligand and as a rhodium catalyst carrier; there is no need to add any other ionic liquid to the system; and separation and recycle of the rhodium catalyst are realized by liquid/liquid biphasic separation after the reaction. The catalytic system provided by the present invention is high in catalytic activity. The rhodium catalyst is capable of being recycled for many times with no obvious decrease in catalytic activity and selectivity.

Application Domain

Group 5/15 element organic compoundsOrganic-compounds/hydrides/coordination-complexes catalysts +2

Technology Topic

SyngasAldehyde +8

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Examples

Experimental program(27)

Example Embodiment

[0025] Example 1

[0026] Rh(acac)(CO) 2 /[CH 3 (EO) 16 MICH 3 ] 3 [(SO 3 - ) 3 -1] Two-phase hydroformylation reaction in the/1-octene system

[0027] Under inert atmosphere, add Rh(acac)(CO) to the stainless steel autoclave 2 , [CH 3 (EO) 16 MICH 3 ] 3 [(SO 3 - ) 3 -1] and 1-octene, the ratio is: [CH 3 (EO) 16 MICH 3 ] 3 [(SO 3 - ) 3 -1]/Rh(acac)(CO) 2 =10:1 (molar ratio), 1-octene/Rh(acac)(CO) 2 =10000:1 (molar ratio), and then use synthesis gas (H 2 /CO=1:1) Pressurize to 5.0MPa, reaction temperature 95℃, reaction time 0.5 hours, then quickly cool to room temperature, vent the synthesis gas and open the kettle, the system is naturally divided into two phases, the lower layer is the ionic liquid containing rhodium catalyst The upper layer is the organic phase, which can also be extracted with n-heptane. After simple two-phase separation, the organic phase containing the product aldehyde is obtained. The result of gas chromatography analysis is: the conversion rate of 1-octene is 10.2%, and the selectivity of aldehyde 87.5%, the molar ratio of normal aldehyde to isomeric aldehyde is 2.7:1, and the TOF value is 1785h -1.

Example Embodiment

[0028] Example 2

[0029] Rh(acac)(CO) 2 /[CH 3 (EO) 16 MICH 3 ] 3 [(SO 3 - ) 3 -1] Two-phase hydroformylation reaction under the system of/1-octene/n-heptane

[0030] In an inert atmosphere, add Rh(acac)(CO) into the stainless steel autoclave 2 , [CH 3 (EO) 16 MICH 3 ] 3 [(SO 3 - ) 3 -1], 1-octene and n-heptane, the ratio is: [CH 3 (EO) 16 MICH 3 ] 3 [(SO 3 - ) 3 -1]/Rh(acac)(CO) 2 =10:1 (molar ratio), 1-octene/Rh(acac)(CO) 2 =10000:1 (molar ratio), the volume ratio of n-heptane to 1-octene is 2:1, and then syngas (H 2 /CO=1:1) Pressurize to 5.0MPa, reaction temperature 95℃, reaction time 0.5 hours, then quickly cool to room temperature, vent the synthesis gas and open the kettle, the system is naturally divided into two phases, the lower layer is the ionic liquid containing rhodium catalyst The upper layer is the organic phase. After simple two-phase separation, the organic phase containing the product aldehyde is obtained. The gas chromatography analysis result is: the conversion rate of 1-octene is 6.1%, the selectivity of aldehyde is 79.5%, normal aldehyde and isoform The molar ratio of aldehyde is 2.6:1, and the TOF value is 970h -1.

Example Embodiment

[0031] Example 3

[0032] Rh(acac)(CO) 2 /[Ph(EO) 16 MICH 3 ] 3 [(SO 3 - ) 3 -1] Two-phase hydroformylation reaction in the/1-octene system

[0033] Ionic liquid is replaced by [Ph(EO) 16 MICH 3 ] 3 [(SO 3 - ) 3 -1], the rest of the reaction conditions and steps are the same as in Example 1. The gas chromatography analysis results are: the conversion rate of 1-octene is 13.9%, the selectivity of aldehyde is 92.5%, and the molar ratio of normal aldehyde to isoformaldehyde is 2.7 :1, TOF value is 2572h -1.

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Classification and recommendation of technical efficacy words

High catalytic activity

Phosphine-functionalized polyether imidazolium-based ionic liquid and application thereof in the hydroformylation of olefins

A technology of polyether imidazolium salt and ionic liquid, applied in the field of chemical industry, can solve the problems of small negative effect and high dosage of ionic liquid, and achieve the effect of high catalytic activity, simple separation and circulation

AI-Extracted Technical Summary

Problems solved by technology

Abstract

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Examples

Example Embodiment

Example Embodiment

Example Embodiment

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Description & Claims & Application Information

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