CN105017316B - A kind of phosphine functionalization polyethers pyridiniujm ionic liquid and its application in hydroformylation of olefin - Google Patents
A kind of phosphine functionalization polyethers pyridiniujm ionic liquid and its application in hydroformylation of olefin Download PDFInfo
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- CN105017316B CN105017316B CN201510250843.1A CN201510250843A CN105017316B CN 105017316 B CN105017316 B CN 105017316B CN 201510250843 A CN201510250843 A CN 201510250843A CN 105017316 B CN105017316 B CN 105017316B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/584—Recycling of catalysts
Abstract
The present invention relates to the polyethers pyridine ionic liquid of a kind of phosphine functionalization,A kind of and method of the alkene two-phase hydroformylation based on phosphine functionalization polyethers pyridiniujm ionic liquid,The process employs a kind of biphase catalytic system,The catalyst system and catalyzing by phosphine functionalization polyethers pyridine ionic liquid,Rhodium catalyst and reaction substrate alkene and reaction product aldehyde composition,Liquid liquid two-phase hydroformylation reaction is carried out under certain reaction temperature and synthesis atmospheric pressure,The polyethers pyridine ionic liquid of phosphine functionalization is both Phosphine ligands,Serve as the carrier of rhodium catalyst again simultaneously,Without still further introducing other ionic liquids in system,The separation and circulation of rhodium catalyst are realized in reaction by simple liquid liquid two-phase laminated flow after terminating,The catalyst system and catalyzing has higher catalytic activity,Rhodium catalyst can be recycled repeatedly,Catalytic activity and selectivity do not significantly decrease.
Description
Technical field
The present invention relates to technical field of chemistry and chemical engineering, more particularly to a kind of phosphine functionalization polyethers pyridiniujm ionic liquid,
A kind of and method of the alkene two-phase hydroformylation based on phosphine functionalization polyethers pyridiniujm ionic liquid.
Background technology
The hydroformylation of olefin of rhodium catalysis is typical atomic economy reaction, and the more carbonyl of document report at present
Glycosylation reaction, it has also become prepare the Perfected process of high-carbon aldehyde/alcohol.Homogeneous hydroformylation have that catalytic activity is high, selectivity is good and
The advantages of reaction condition is gentle, but for a long time, the separation of rhodium catalyst and Recycling are always homogeneous catalysis field
Focus of attention.
In recent years, ionic liquid is very rapid as the liquid liquid biphase catalytic system development of catalyst carrier, it has also become mesh
One of biphase catalytic system of preceding most application prospect.Non-aqueous ionic liquid hydroformylation is based on the extremely low steaming of ionic liquid
Air pressure, good heat endurance and controllable solvability, rhodium catalyst is dissolved, and " the liquid of catalyst is served as with ionic liquid
Body carrier ", and substrate olefin and product aldehyde and ionic liquid be not miscible, reaction is realized after terminating by liquid liquid two-phase laminated flow
The circulation of catalyst.
Although non-aqueous ionic liquid hydroformylation solves the separation circulatory problems of rhodium catalyst to a certain extent, from
Sub- liquid still has significant limitation in actual applications.First, non-aqueous ionic liquid catalyst system and catalyzing stills need largely
Ionic liquid loaded and dissolving rhodium catalyst, either from the point of view of economic or toxicology, this does not meet Green Chemistry
Requirement；Second, the application of a large amount of ionic liquids increases the resistance to mass tranfer of substrate molecule, the negative effect of ionic liquid is (viscous by height
The Various Complex factor such as degree, residual impurity causes) become significantly, to cause catalytic activity and selective degradation.
Recently, we have invented a kind of polyoxyalkylene alkyl guanidinium ionic liquid with the liquid-solid phase-change characteristic of room temperature
(Chem.Commun., 2012,48,9017-9019 and patent ZL201210064537.5), and it is applied to the height of rhodium catalysis
In carbon olefin two-phase hydroformylation reaction, this kind of new functionalized ion liquid can effectively immobilized Rh-TPPTS catalyst,
And with the ability of significant stable rhodium catalyst, hydroformylation reaction adds up TON values up to 31188, but this two-phase system is still
Carrier of the larger amount of ionic liquid as Rh-TPPTS catalyst is needed, the mass ratio of ionic liquid and rhodium catalyst precursor reaches
To 1000:1, and due to being limited by biphase catalytic system resistance to mass tranfer, catalytic activity is not high, and TOF values only have 10-
200h-1。
In another patent (CN201310370138.6), we have invented the polyoxyalkylene alkyl of a kind of new phosphine functionalization
Guanidinium ionic liquid, and high carbene of the homogeneous catalysis system applied to rhodium catalysis is constructed based on this novel ion liquid
The hydroformylation reaction of hydrocarbon, it is that catalytic activity is higher the advantages of this catalyst system and catalyzing, but needs to introduce in catalyst system and catalyzing organic
Solvent, this virtually adds the difficulty and energy consumption of catalyst recovery circulation and last handling process, while organic solvent also can
Cause environmental and safety problems, also do not meet the requirement of Green Chemistry.
The content of the invention
For the deficiencies in the prior art, a kind of phosphine functionalization polyethers pyridiniujm ionic liquid of invention,
And this kind of phosphine functionalization polyethers pyridiniujm ionic liquid is based on, invent a kind of phosphine functionalized ion liquid two-phase hydroformylation
Method.Biphase catalytic system is made up of ionic liquid body phase and organic phase：Ionic liquid body phase includes the polyethers pyridine of phosphine functionalization
Ionic liquid and rhodium catalyst；Organic phase includes reaction substrate alkene and reaction product, or the mixture of the two；Organic phase can
Solvent is introduced, can not also introduce solvent；Hydroformylation reaction is carried out under certain reaction temperature and synthesis atmospheric pressure, reaction knot
Shu Houke directly realizes the recovery and recycling of rhodium catalyst by the liquid liquid two-phase laminated flow of ionic liquid body phase and organic phase；
Also extractant can be added, then realizes the recovery and recycling of rhodium catalyst by liquid liquid two-phase laminated flow again.
In the present invention, the characteristic of the existing Phosphine ligands of polyethers pyridine ionic liquid of phosphine functionalization, network can be formed with rhodium
Close catalyst, have both the solvent nature of ionic liquid again, may act as the carrier of rhodium catalyst, thus without again it is additional it is substantial amounts of its
Its ionic liquid, fundamentally solve the too high problem of ionic liquid dosage, while also by ionic liquid in catalytic reaction
Negative effect minimize.
In the present invention, the mass ratio of the polyethers pyridine ionic liquid of phosphine functionalization and rhodium catalyst is 10:1-300:
1, the only 1%-30% of patent of invention ZL201210064537.5 intermediate ions volume, so as to solve conventional ion liquid
Biphase catalytic system needs the problem of a large amount of ionic liquids are as catalyst carrier.
The catalytic activity of phosphine functionalization polyethers pyridiniujm non-aqueous ionic liquid hydroformylation system provided by the invention is higher,
TOF values reach 330-3300h-1, it is TOF values (10-200h in patent of invention ZL201210064537.5-1) 1.6-330 times,
Catalytic cycle adds up TON values up to 40223, is 1.3 times of the TON values (31188) reported in patent ZL201210064537.5.
Different from the homogeneous catalysis system of patent of invention CN201310370138.6 reports, catalyst system and catalyzing of the invention is two
Phase system, a kind of method for thus providing the separation and circulation of simpler rhodium catalyst.Due in reaction and separation process
In, organic phase can introduce solvent, can not also introduce solvent, react and realize rhodium catalyst by liquid liquid two-phase laminated flow after terminating
Circulation, therefore the step of reclaiming organic solvent can be saved, environment caused by organic solvent and safety problem are avoided, is reduced simultaneously
Catalyst recovery circulation and the difficulty and energy consumption of last handling process, are the methods for more meeting Green Chemistry requirement.
In the present invention, the structural formula of the phosphine functionalization polyethers pyridiniujm ionic liquid of application is as follows：
In formula：M=1-100；R1For H, C1-C16Alkyl or phenyl；R2、R3、R4、R5、R6For H, C1-C4Alkyl or benzyl；R7
The anion of Water-soluble Sulphonated phosphines is represented, n is the sum of sulfonic group anion on Phosphine ligands, R7Structural formula it is as follows：
In formula：R8For C6H4-3-SO3 -；1,2,3,4,5,6,7,8,9,10,11 and 12 is respectively that different sulfonic acid types is water-soluble
The parent fraction of property Phosphine ligands, n is the sum of sulfonic group anion on Phosphine ligands；O=0,1,2；P=0,1,2；Q=r=0,1；
S=t=0,1.
In the present invention, the key intermediate for synthesizing phosphine functionalization polyethers pyridiniujm ionic liquid is polyethers pyridine salt ion
Liquid, its structural formula are as follows：
In formula：M=1-100；R1For H, C1-C16Alkyl or phenyl；R2、R3、R4、R5、R6For H, C1-C4Alkyl or benzyl；R9
For Cl-, Br-, BF4 -, PF6 -, Tf2N-, MsO-, TsO-。
A kind of method of the alkene two-phase hydroformylation based on phosphine functionalization polyethers pyridiniujm ionic liquid is：Biphasic catalysis
System is made up of ionic liquid body phase and organic phase：Ionic liquid body phase includes the polyethers pyridine ionic liquid and rhodium of phosphine functionalization
Catalyst；Organic phase includes reaction substrate alkene and reaction product, or the mixture of the two；Organic phase can introduce solvent, also may be used
Do not introduce solvent；Hydroformylation reaction is carried out under certain reaction temperature and synthesis atmospheric pressure, and reaction can directly lead to after terminating
The liquid liquid two-phase laminated flow for crossing ionic liquid body phase and organic phase realizes the recovery and recycling of rhodium catalyst；Also extraction can be added
Solvent, the recovery and recycling of rhodium catalyst are then realized by liquid liquid two-phase laminated flow again.
A kind of side of alkene two-phase hydroformylation based on phosphine functionalization polyethers pyridiniujm ionic liquid provided by the invention
Method is as follows：Under an inert atmosphere, by the polyethers pyridine ionic liquid, rhodium catalyst, substrate olefin of phosphine functionalization with certain
Ratio mixes, wherein, the mol ratio of phosphine functionalization polyethers pyridiniujm ionic liquid and rhodium in rhodium catalyst is 3:1-100:1, most
It is well 5:1-30:1, the mol ratio for making substrate olefin and rhodium in rhodium catalyst is 100:1-20000:1, preferably 1000:1-
10000:1, synthesis atmospheric pressure is 1-10MPa, and reaction temperature is 70-130 DEG C, and the reaction time is 0.25-15 hours；Can in system
Introduce solvent, also can not solubilizer, if adding solvent, the volume ratio of solvent and alkene is 1:10-10:1；After reaction terminates,
The recovery of rhodium catalyst is realized by the liquid liquid two-phase laminated flow of ionic liquid body phase and organic phase, can also add extractant, then
The split-phase of rhodium catalyst and organic phase is realized by liquid liquid two-phase laminated flow, ionic liquid can mutually be carried out by adding new alkene
Catalytic cycle next time.
In the present invention, rhodium catalyst is rhodium dicarbonyl acetylacetonate Rh (acac) (CO)2、RhCl3·3H2O、[Rh
(COD)2]BF4Or [Rh (COD) Cl]2, COD 1,5- cyclo-octadiene.
The substrate olefin that the present invention uses is C3-C16Straight chain 1- alkene, cyclohexene, styrene, p-methylstyrene, adjacent first
Base styrene, p-tert-butylstyrene, p-isobutylstyrene, to methoxy styrene, p-chlorostyrene, ortho-chlorostyrene,
2- vinyl naphthalenes, 6- methoxyl group -2- vinyl naphthalenes；Reaction product be aldehyde, isomerizing olefins, one kind in olefin hydrogenation product or
Several mixtures.
In the present invention, organic solvent or extractant that organic phase introduces are：Petroleum ether, hexamethylene, C6-C12Alkane, second
Several mixture in one kind or above-mentioned solvent in ether, methyl tertiary butyl ether(MTBE).
Embodiment
Embodiment 1
Rh(acac)(CO)2/[(N-(EO)16CH3)Py]3[(SO3 -)3- 1] two-phase hydroformylation reaction under/1- octene systems
Under an inert atmosphere, Rh (acac) (CO) is added into stainless steel autoclave2、[(N-(EO)16CH3)Py]3
[(SO3 -)3- 1] and 1- octenes, its ratio are：[(N-(EO)16CH3)Py]3[(SO3 -)3-1]/Rh(acac)(CO)2=10:1 (rubs
That ratio), 1- octenes/Rh (acac) (CO)2=10000:1 (mol ratio), then with synthesis gas (H2/ CO=1:1) it is forced into
5.0MPa, 95 DEG C of reaction temperature, in 0.5 hour reaction time, room temperature is then quickly cooled to, kettle, system are opened after being vented synthesis gas
Naturally it is divided into two-phase, lower floor is the ionic liquid body phase containing rhodium catalyst, and upper strata is organic phase, can also add normal heptane extraction,
The organic phase containing product aldehyde is obtained through simple two-phase laminated flow, gas chromatographic analysis result is：The conversion ratio of 1- octenes is
7.5%, the selectivity 87.5% of aldehyde, the mol ratio of n-alkanal and iso-aldehyde is 2.6:1, TOF value is 1313h-1。
Embodiment 2
Rh(acac)(CO)2/[(N-(EO)16CH3)Py]3[(SO3 -)3- 1] two-phase hydrogen first under/1- octenes/n-heptane system
Acylation reaction
Under an inert atmosphere, Rh (acac) (CO) is added in stainless steel autoclave2、[(N-(EO)16CH3)Py]3
[(SO3 -)3- 1], 1- octenes and normal heptane, its ratio are：[(N-(EO)16CH3)Py]3[(SO3 -)3-1]/Rh(acac)(CO)2=
10:1 (mol ratio), 1- octenes/Rh (acac) (CO)2=10000:The volume ratio of 1 (mol ratio), normal heptane and 1- octenes is 2:
1, then with synthesis gas (H2/ CO=1:1) it is forced into 5.0MPa, 95 DEG C of reaction temperature, 0.5 hour reaction time, then quickly
Room temperature is cooled to, kettle is driven after being vented synthesis gas, system is divided into two-phase naturally, and lower floor is the ionic liquid body phase containing rhodium catalyst,
Upper strata is organic phase, obtains the organic phase containing product aldehyde through simple two-phase laminated flow, gas chromatographic analysis result is：1- octenes
Conversion ratio be 5.8%, the selectivity 78.6% of aldehyde, the mol ratio of n-alkanal and iso-aldehyde is 2.7:1, TOF value is 912h-1。
Embodiment 3
Rh(acac)(CO)2/[(N-(EO)16Ph)Py]3[(SO3 -)3- 1] two-phase hydroformylation reaction under/1- octene systems
Ionic liquid is changed to [(N- (EO)16Ph)Py]3[(SO3 -)3- 1], remaining reaction condition and step are the same as embodiment 1, gas
Analysis of hplc result is：The conversion ratio of 1- octenes is 13.1%, the selectivity 90.7% of aldehyde, mole of n-alkanal and iso-aldehyde
Than for 2.8:1, TOF value is 2376h-1。
Embodiment 4
Rh(acac)(CO)2/[(N-(EO)16C12H25)Py]3[(SO3 -)3- 1] two-phase hydroformylation is anti-under/1- octene systems
Should
Ionic liquid is changed to [(N- (EO)16C12H25)Py]3[(SO3 -)3- 1], remaining reaction condition and the same embodiment of step
1, gas chromatographic analysis result is：The conversion ratio of 1- octenes is 15.4%, the selectivity 91.7% of aldehyde, n-alkanal and iso-aldehyde
Mol ratio is 2.6:1, TOF value is 2824h-1。
Embodiment 5
Rh(acac)(CO)2/[(N-(EO)4Ph)Py]3[(SO3 -)3- 1] two-phase hydroformylation reaction under/1- octene systems
Ionic liquid is changed to [(N- (EO)4Ph)Py]3[(SO3 -)3- 1], remaining reaction condition and step are the same as embodiment 1, gas
Analysis of hplc result is：The conversion ratio of 1- octenes is 7.2%, the selectivity 71.1% of aldehyde, mole of n-alkanal and iso-aldehyde
Than for 2.8:1, TOF value is 1023h-1。
Embodiment 6
Rh(acac)(CO)2/[(N-(EO)35Ph)Py]3[(SO3 -)3- 1] two-phase hydroformylation reaction under/1- octene systems
Ionic liquid is changed to [(N- (EO)35Ph)Py]3[(SO3 -)3- 1], remaining reaction condition and step are the same as embodiment 1, gas
Analysis of hplc result is：The conversion ratio of 1- octenes is 12.3%, the selectivity 88.4% of aldehyde, mole of n-alkanal and iso-aldehyde
Than for 2.4:1, TOF value is 2175h-1。
Embodiment 7
Rh(acac)(CO)2/[(N-(EO)50Ph)Py]3[(SO3 -)3- 1] two-phase hydroformylation reaction under/1- octene systems
Ionic liquid is changed to [(N- (EO)50Ph)Py]3[(SO3 -)3- 1], remaining reaction condition and step are the same as embodiment 1, gas
Analysis of hplc result is：The conversion ratio of 1- octenes is 10.3%, the selectivity 89.6% of aldehyde, mole of n-alkanal and iso-aldehyde
Than for 2.8:1, TOF value is 1846h-1。
Embodiment 8
Rh(acac)(CO)2/[(N-(EO)4Ph)(3-CH3)Py]3[(SO3 -)3- 1] two-phase hydrogen formyl under/1- octene systems
Change reaction
Ionic liquid is changed to [(N- (EO)4Ph)(3-CH3)Py]3[(SO3 -)3- 1], remaining reaction condition and the same implementation of step
Example 1, gas chromatographic analysis result are：The conversion ratio of 1- octenes is 8.6%, the selectivity 72.6% of aldehyde, n-alkanal and iso-aldehyde
Mol ratio be 2.6:1, TOF value is 1249h-1.Embodiment 9
Rh(acac)(CO)2/[(N-(EO)4Ph)(4-CH3)Py]3[(SO3 -)3- 1] two-phase hydrogen formyl under/1- octene systems
Change reaction
Ionic liquid is changed to [(N- (EO)4Ph)(4-CH3)Py]3[(SO3 -)3- 1], remaining reaction condition and the same implementation of step
Example 1, gas chromatographic analysis result are：The conversion ratio of 1- octenes is 8.9%, the selectivity 73.2% of aldehyde, n-alkanal and iso-aldehyde
Mol ratio be 2.6:1, TOF value is 1303h-1.Embodiment 10
Rh(acac)(CO)2/[(N-(EO)4Ph)(4-n-C4H9)Py]3[(SO3 -)3- 1] two-phase hydrogen first under/1- octene systems
Acylation reaction
Ionic liquid is changed to [(N- (EO)4Ph)(4-n-C4H9)Py]3[(SO3 -)3- 1], remaining reaction condition and step are same
Embodiment 1, gas chromatographic analysis result are：The conversion ratio of 1- octenes be 10.1%, the selectivity 76.7% of aldehyde, n-alkanal with it is different
The mol ratio of structure aldehyde is 2.7:1, TOF value is 1549h-1。
Embodiment 11
Rh(acac)(CO)2/[(N-(EO)16Ph)Py]3[(SO3 -)3- 1] two-phase hydroformylation reaction under/1- decene systems
Alkene is changed to 1- decene, and remaining reaction condition is with embodiment 3, gas chromatographic analysis result with step：1- decene
Conversion ratio be 9.3%, the selectivity 67.4% of aldehyde, the mol ratio of n-alkanal and iso-aldehyde is 2.6:1, TOF value is 1254h-1。
Embodiment 12
Rh(acac)(CO)2/[(N-(EO)16Ph)Py]3[(SO3 -)3- 1] two-phase hydroformylation is anti-under/1- laurylene systems
Should
Alkene is changed to 1- laurylenes, and reaction time 2h, remaining reaction condition is with step with embodiment 3, gas chromatographic analysis
As a result it is：The conversion ratio of laurylene is 10.5%, the selectivity 72.1% of aldehyde, and the mol ratio of n-alkanal and iso-aldehyde is 2.5:1,
TOF values are 379h-1。
Embodiment 13
Rh(acac)(CO)2/[(N-(EO)16Ph)Py]3[(SO3 -)3- 1] two-phase hydroformylation reaction under/polystyrene systems
Alkene is changed to styrene, and remaining reaction condition is with embodiment 3, gas chromatographic analysis result with step：Styrene
Conversion ratio be 17.4%, the selectivity 92.9% of aldehyde, the mol ratio of n-alkanal and iso-aldehyde is 1:3.9, TOF values are 3233h-1。
Embodiment 14
Rh(acac)(CO)2/[(N-(EO)4Ph)Py]2[(SO3 -)2- 12] two under (o=p=2, n=2)/1- octene systems
Phase hydroformylation reaction
Under an inert atmosphere, Rh (acac) (CO) is added into stainless steel autoclave2、[(N-(EO)4Ph)Py]2
[(SO3 -)2- 12] and 1- octenes, its ratio are：[(N-(EO)4Ph)Py]2[(SO3 -)2-12]/Rh(acac)(CO)2=5:1 (rubs
That ratio), 1- octenes/Rh (acac) (CO)2=1000:1 (mol ratio), then with synthesis gas (H2/ CO=1:1) it is forced into
5.0MPa, 100 DEG C of reaction temperature, in 0.5 hour reaction time, room temperature is then quickly cooled to, kettle, system are opened after being vented synthesis gas
Naturally it is divided into two-phase, lower floor is the ionic liquid body phase containing rhodium catalyst, and upper strata is organic phase, can also add normal heptane extraction,
The organic phase containing product aldehyde is obtained through simple two-phase laminated flow, gas chromatographic analysis result is：The conversion ratio of 1- octenes is
98.4%, the selectivity 72.8% of aldehyde, the mol ratio of n-alkanal and iso-aldehyde is 1.8:1, TOF value is 1433h-1。
Embodiment 15
Rh(acac)(CO)2/[(N-(EO)16CH3)Py]2[(SO3 -)2- 12] under (o=p=2, n=2)/1- octene systems
Two-phase hydroformylation reaction
Ionic liquid is changed to [(N- (EO)16CH3)Py]2[(SO3 -)2- 12] (o=p=2, n=2), remaining reaction condition with
Step is with embodiment 14, gas chromatographic analysis result：The conversion ratio of 1- octenes is 55.1%, the selectivity 43.3% of aldehyde, just
The mol ratio of structure aldehyde and iso-aldehyde is 3.0:1, TOF value is 477h-1。
Embodiment 16
Rh(acac)(CO)2/[(N-(EO)4CH3)Py]2[(SO3 -)2- 12] under (o=p=2, n=2)/1- octene systems
Two-phase hydroformylation reaction
Ionic liquid is changed to [(N- (EO)4CH3)Py]2[(SO3 -)2- 12] (o=p=2, n=2), remaining reaction condition with
Step is with embodiment 14, gas chromatographic analysis result：The conversion ratio of 1- octenes is 39.5%, the selectivity 41.7% of aldehyde, just
The mol ratio of structure aldehyde and iso-aldehyde is 2.9:1, TOF value is 329h-1。
Embodiment 17
Rh(acac)(CO)2/[(N-(EO)4Ph)Py]2[(SO3 -)2- 12] under (o=p=2, n=2)/1- laurylene systems
Two-phase hydroformylation reaction
Alkene is changed to 1- laurylenes, and remaining reaction condition is with embodiment 14, gas chromatographic analysis result with step：1- ten
The conversion ratio of diene is 53.2%, the selectivity 78.7% of aldehyde, and the mol ratio of n-alkanal and iso-aldehyde is 1.9:1, TOF value is
837h-1。
Embodiment 18
Rh(acac)(CO)2/[(N-(EO)4Ph)Py]2[(SO3 -)2- 12] under (o=p=2, n=2)/1-tetradecylene system
Two-phase hydroformylation reaction
Alkene is changed to 1-tetradecylene, and remaining reaction condition is with embodiment 14, gas chromatographic analysis result with step：1- ten
The conversion ratio of tetraene is 48.7%, the selectivity 75.3% of aldehyde, and the mol ratio of n-alkanal and iso-aldehyde is 1.5:1, TOF value is
733h-1。
Embodiment 19
Rh(acac)(CO)2/[(N-(EO)4Ph)Py]2[(SO3 -)2- 2] two-phase hydroformylation reaction under/1- octene systems
Ionic liquid is changed to [(N- (EO)4Ph)Py]2[(SO3 -)2- 2], remaining reaction condition and step are the same as embodiment 1, gas
Analysis of hplc result is：The conversion ratio of 1- octenes is 8.3%, the selectivity 72.8% of aldehyde, mole of n-alkanal and iso-aldehyde
Than for 2.6:1, TOF value is 1208h-1。
Embodiment 20
Rh(acac)(CO)2/[(N-(EO)4Ph)Py][(SO3 -) -3] two-phase hydroformylation reaction under/1- octene systems
Ionic liquid is changed to [(N- (EO)4Ph)Py][(SO3 -) -3], remaining reaction condition is with step with embodiment 1, gas phase
Chromatography result is：The conversion ratio of 1- octenes is 8.5%, the selectivity 69.8% of aldehyde, the mol ratio of n-alkanal and iso-aldehyde
For 2.5:1, TOF value is 1187h-1。
Embodiment 21
Rh(acac)(CO)2/[(N-(EO)4Ph)Py]4[(SO3 -)4- 4] two under (o=p=0, n=4)/1- octene systems
Phase hydroformylation reaction
Ionic liquid is changed to [(N- (EO)4Ph)Py]4[(SO3 -)4- 4] (o=p=0, n=4), remaining reaction condition and step
Suddenly it is with embodiment 14, gas chromatographic analysis result：The conversion ratio of 1- octenes is 95.1%, the selectivity 58.6% of aldehyde, positive structure
The mol ratio of aldehyde and iso-aldehyde is 2.2:1, TOF value is 1115h-1。
Embodiment 22
Rh(acac)(CO)2/[(N-(EO)4Ph)Py]4[(SO3 -)4- 5] two under (o=p=0, n=4)/1- octene systems
Phase hydroformylation reaction
Ionic liquid is changed to [(N- (EO)4Ph)Py]4[(SO3 -)4- 5] (o=p=0, n=4), remaining reaction condition and step
Suddenly it is with embodiment 14, gas chromatographic analysis result：The conversion ratio of 1- octenes is 96.4%, the selectivity 65.3% of aldehyde, positive structure
The mol ratio of aldehyde and iso-aldehyde is 2.3:1, TOF value is 1259h-1。
Embodiment 23
Rh(acac)(CO)2/[(N-(EO)4Ph)Py]2[(SO3 -)2- 6] two under (o=p=2, n=2)/1- octene systems
Phase hydroformylation reaction
Ionic liquid is changed to [(N- (EO)4Ph)Py]2[(SO3 -)2- 6] (o=p=2, n=2), remaining reaction condition and step
Suddenly it is with embodiment 14, gas chromatographic analysis result：The conversion ratio of 1- octenes is 94.5%, the selectivity 67.7% of aldehyde, positive structure
The mol ratio of aldehyde and iso-aldehyde is 2.2:1, TOF value is 1280h-1。
Embodiment 24
Rh(acac)(CO)2/[(N-(EO)4Ph)Py]2[(SO3 -)2- 7] (o=2, q=r=1, s=t=0, n=2)/benzene
Two-phase hydroformylation reaction under ethene system
Ionic liquid is changed to [(N- (EO)4Ph)Py]2[(SO3 -)2- 7] (o=2, q=r=1, s=t=0, n=2), alkene
Styrene is changed to, remaining reaction condition is with embodiment 14, gas chromatographic analysis result with step：The conversion ratio of styrene is
98.1%, the selectivity 81.0% of aldehyde, the mol ratio of n-alkanal and iso-aldehyde is 1:4.3, ee values are that 34.9%, TOF values are
1589h-1。
Embodiment 25
Rh(acac)(CO)2/[(N-(EO)4Ph)Py]4[(SO3 -)4- 9] two under (o=p=0, n=4)/1- octene systems
Phase hydroformylation reaction
Ionic liquid is changed to [(N- (EO)4Ph)Py]4[(SO3 -)4- 9] (o=p=0, n=4), remaining reaction condition and step
Suddenly it is with embodiment 14, gas chromatographic analysis result：The conversion ratio of 1- octenes is 96.2%, the selectivity 58.4% of aldehyde, positive structure
The mol ratio of aldehyde and iso-aldehyde is 1.7:1, TOF value is 1124h-1。
Embodiment 26
Rh(acac)(CO)2/[(N-(EO)4Ph)Py]2[(SO3 -)2- 10] two under (o=p=2, n=2)/1- octene systems
Phase hydroformylation reaction
Ionic liquid is changed to [(N- (EO)4Ph)Py]2[(SO3 -)2- 10] (o=p=2, n=2), remaining reaction condition and step
Suddenly it is with embodiment 14, gas chromatographic analysis result：The conversion ratio of 1- octenes is 98.2%, the selectivity 74.6% of aldehyde, positive structure
The mol ratio of aldehyde and iso-aldehyde is 2.0:1, TOF value is 1465h-1。
Embodiment 27
Rh(acac)(CO)2/[(N-(EO)4Ph)Py]2[(SO3 -)2- 11] two under (o=p=2, n=2)/1- octene systems
Phase hydroformylation reaction
Ionic liquid is changed to [(N- (EO)4Ph)Py]2[(SO3 -)2- 11] (o=p=2, n=2), remaining reaction condition and step
Suddenly it is with embodiment 14, gas chromatographic analysis result：The conversion ratio of 1- octenes is 99.4%, the selectivity 83.6% of aldehyde, positive structure
The mol ratio of aldehyde and iso-aldehyde is 1.8:1, TOF value is 1662h-1。
Embodiment 28-36
Rh(acac)(CO)2/[(N-(EO)16Ph)Py]3[(SO3 -)3- 1] two-phase hydroformylation reaction under/1- octene systems
Circulation experiment
Under an inert atmosphere, Rh (acac) (CO) is added into stainless steel autoclave2、[(N-(EO)16Ph)Py]3
[(SO3 -)3- 1] and 1- octenes, its ratio are：[(N-(EO)16Ph)Py]3[(SO3 -)3-1]/Rh(acac)(CO)2=20:1 (rubs
That ratio), 1- octenes/Rh (acac) (CO)2=5000:1 (mol ratio), then with synthesis gas (H2/ CO=1:1) it is forced into
5.0MPa, 95 DEG C of reaction temperature, in 5 hours reaction time, room temperature is then quickly cooled to, drives kettle after being vented synthesis gas, system is certainly
So it is divided into two-phase, is decanted off the organic phase on upper strata, the ionic liquid that rhodium catalyst is contained in lower floor is mutually by adding new 1- octenes
Catalytic cycle next time can be carried out, gas chromatographic analysis result shows：After 9 catalytic cycles, the conversion ratio of alkene is protected substantially
Hold constant, the selectivity of aldehyde is declined slightly after circulation 10 times, and accumulative TON values reach 40223, reality during circulation experiment the results are shown in Table 1
Apply a 28-36.
The circulation experiment of the rhodium catalyst of table 1
Claims (4)
- A kind of 1. method of the alkene two-phase hydroformylation based on phosphine functionalization polyethers pyridiniujm ionic liquid, it is characterised in that： Biphase catalytic system is made up of ionic liquid body phase and organic phase, and ionic liquid body phase includes phosphine functionalization polyethers pyridiniujm ionic liquid And rhodium catalyst, the mol ratio of phosphine functionalization polyethers pyridiniujm ionic liquid and rhodium in rhodium catalyst is 5:1-30:1；Organic phase Including reaction substrate alkene and reaction product, or the mixture of the two；Organic phase does not introduce solvent；Hydroformylation reaction is certain Reaction temperature and synthesis atmospheric pressure under carry out, reaction terminate afterwards directly by ionic liquid body phase and the liquid liquid two-phase of organic phase The recovery and recycling of rhodium catalyst are realized in separation；The structural formula of phosphine functionalization polyethers pyridiniujm ionic liquid is：In formula, m=16, R1For phenyl, R2、R3、R4、R5、R6For H, R7 For (SO3 -)n- 1, n=3；Or m=4, R1For phenyl, R2、R3、R4、R5、R6For H, R7For (SO3 -)n- 1, n=3；Or m=35, R1For Phenyl, R2、R3、R4、R5、R6For H, R7For (SO3 -)n- 1, n=3；Or m=50, R1For phenyl, R2、R3、R4、R5、R6For H, R7For (SO3 -)n- 1, n=3；Or m=4, R1For phenyl, R3For CH3, R2、R4、R5、R6For H, R7For (SO3 -)n- 1, n=3；Or m=4, R1 For phenyl, R4For CH3, R2、R3、R5、R6For H, R7For (SO3 -)n- 1, n=3；Or m=4, R1For phenyl, R4For n-C4H9, R2、R3、 R5、R6For H, R7For (SO3 -)n- 1, n=3；Or m=4, R1For phenyl, R2、R3、R4、R5、R6For H, R7For (SO3 -)n- 2, n=2； Or m=4, R1For phenyl, R2、R3、R4、R5、R6For H, R7For (SO3 -)n- 3, n=1；Or m=4, R1For phenyl, R2、R3、R4、R5、 R6For H, R7For (SO3 -)n- 4, o=p=0, n=4；Or m=4, R1For phenyl, R2、R3、R4、R5、R6For H, R7For (SO3 -)n- 5, o =p=0, n=4；Or m=4, R1For phenyl, R2、R3、R4、R5、R6For H, R7For (SO3 -)n- 6, o=p=2, n=2；Or m=4, R1For phenyl, R2、R3、R4、R5、R6For H, R7For (SO3 -)n- 7, o=2, q=r=1, s=t=0, n=2；Or m=4, R1For benzene Base, R2、R3、R4、R5、R6For H, R7For (SO3 -)n- 9, o=p=0, n=4；Or m=4, R1For phenyl, R2、R3、R4、R5、R6For H, R7For (SO3 -)n- 10, o=p=2, n=2；Or m=4, R1For phenyl, R2、R3、R4、R5、R6For H, R7For (SO3 -)n- 11, o=p =2, n=2；Or m=4, R1For phenyl, R2、R3、R4、R5、R6For H, R7For (SO3 -)n- 12, o=p=2, n=2；In above formula (the SO occurred3 -)n- 1, (SO3 -)n- 2, (SO3 -)n- 3, (SO3 -)n- 4, (SO3 -)n- 5, (SO3 -)n- 6, (SO3 -)n- 7, (SO3 -)n- 9, (SO3 -)n- 10, (SO3 -)n- 11, (SO3 -)n- 12 are respectively： , n is the sum of sulfonic group anion on Phosphine ligands, R8For C6H4-3-SO3 -。
- A kind of 2. side of alkene two-phase hydroformylation based on phosphine functionalization polyethers pyridiniujm ionic liquid according to claim 1 Method, it is characterized in that：Under an inert atmosphere, by the polyethers pyridine ionic liquid, rhodium catalyst, substrate olefin of phosphine functionalization with one Fixed ratio mixing, wherein, the mol ratio of substrate olefin and rhodium in rhodium catalyst is 100:1-20000:1, synthesizing atmospheric pressure is 1-10MPa, reaction temperature are 70-130 DEG C, and the reaction time is 0.25-15 hours；Not solubilizer in system；After reaction terminates, lead to The liquid liquid two-phase laminated flow for crossing ionic liquid body phase and organic phase realizes the recovery of rhodium catalyst, and ionic liquid is mutually new by adding Alkene carries out catalytic cycle next time.
- A kind of 3. side of alkene two-phase hydroformylation based on phosphine functionalization polyethers pyridiniujm ionic liquid according to claim 1 Method, it is characterised in that rhodium catalyst is rhodium dicarbonyl acetylacetonate Rh (acac) (CO)2、RhCl3·3H2O、[Rh(COD)2]BF4 Or [Rh (COD) Cl]2, COD 1,5- cyclo-octadiene.
- A kind of 4. side of alkene two-phase hydroformylation based on phosphine functionalization polyethers pyridiniujm ionic liquid according to claim 1 Method, it is characterised in that the substrate olefin used is C3-C16Straight chain 1- alkene, cyclohexene, styrene, p-methylstyrene, adjacent first Base styrene, p-tert-butylstyrene, p-isobutylstyrene, to methoxy styrene, p-chlorostyrene, ortho-chlorostyrene, 2- vinyl naphthalenes, 6- methoxyl group -2- vinyl naphthalenes；Reaction product be aldehyde, isomerizing olefins, one kind in olefin hydrogenation product or Several mixtures.
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| CN103483381A (en) * | 2013-08-22 | 2014-01-01 | 青岛科技大学 | Preparation method of first-class phosphorus functionalized ionic liquid and application of ionic liquid in hydroformylation |
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| CN102617308A (en) * | 2012-03-13 | 2012-08-01 | 青岛科技大学 | Olefin two-phase hydroformylation method |
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