CN105017319B - One class phosphine functionalization polyethers quaternary phosphonium salt ionic liquid and its application in hydroformylation of olefin - Google Patents
One class phosphine functionalization polyethers quaternary phosphonium salt ionic liquid and its application in hydroformylation of olefin Download PDFInfo
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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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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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- Y02P20/584—Recycling of catalysts
Abstract
The present invention relates to the polyethers quaternary phosphonium salt ionic liquid of a class phosphine functionalization, and a kind of method of the alkene two-phase hydroformylation based on phosphine functionalization polyethers quaternary phosphonium salt ionic liquid, the process employs a kind of biphase catalytic system, the catalyst system and catalyzing by phosphine functionalization polyethers quaternary phosphonium salt 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 quaternary phosphonium salt 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 class phosphine functionalization polyethers quaternary phosphonium salt ionic liquid,
And a kind of method of the alkene two-phase hydroformylation based on phosphine functionalization polyethers quaternary phosphonium salt ionic liquid.
Background technology
The hydroformylation of olefin of rhodium catalysis is typical atomic economy reaction, is also the more carbonyl of current document report
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 gentle advantage of reaction condition, 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 substantial amounts of
Ionic liquid loaded and dissolving rhodium catalyst, either from the point of view of economic or toxicology, this does not meet Green Chemistry
Requirement；Two be that the applications of a large amount of ionic liquids increases the resistance to mass tranfer of substrate molecule, and 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 the polyoxyalkylene alkyl guanidinium ionic liquid that a class has 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
Need larger amount of ionic liquid as the carrier of Rh-TPPTS catalyst, 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 the new phosphine functionalization of a class
Guanidinium ionic liquid, and the high carbene that a homogeneous catalysis system is applied to rhodium catalysis is constructed based on this novel ion liquid
The hydroformylation reaction of hydrocarbon, the advantage of this catalyst system and catalyzing is that catalytic activity is higher, but needs to introduce organic in catalyst system and catalyzing
Solvent, this virtually adds the difficulty and energy consumption that catalyst reclaims 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, one class phosphine functionalization polyethers quaternary phosphonium salt ionic liquid of invention,
And based on this kind of phosphine functionalization polyethers quaternary phosphonium salt ionic liquid, invented 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 quaternary phosphine 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, solvent can not be also introduced；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, the recovery and recycling of rhodium catalyst is then realized by liquid liquid two-phase laminated flow again.
In the present invention, the characteristic of the existing Phosphine ligands of polyethers quaternary phosphonium salt ionic liquid of phosphine functionalization, can be with rhodium formation network
Close catalyst, the solvent nature of ionic liquid had both 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 solves the too high problem of ionic liquid consumption, while also by ionic liquid in catalytic reaction
Negative effect minimize.
In the present invention, the mass ratio of the polyethers quaternary phosphonium salt 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 for the phosphine functionalization polyethers quaternary phosphonium salt ionic liquid two-phase hydroformylation system that the present invention is provided is higher,
TOF values reach 360-2700h-1, it is TOF values (10-200h in patent of invention ZL201210064537.5-1) 1.8-270 times,
Catalytic cycle adds up TON values up to 44237, is 1.4 times of the TON values (31188) reported in patent ZL201210064537.5.
Different from the homogeneous catalysis system that patent of invention CN201310370138.6 is reported, 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, and reaction realizes rhodium catalyst after terminating by liquid liquid two-phase laminated flow
Circulation, thus the step of recovery organic solvent can be saved, it is to avoid environment and safety problem caused by organic solvent, reduce simultaneously
Catalyst reclaims the difficulty and energy consumption of circulation and last handling process, is the method for more meeting Green Chemistry requirement.
In the present invention, the structural formula of the phosphine functionalization polyethers quaternary phosphonium salt ionic liquid of application is：[(R1(OCH2CH2)m)lPR2 4-l]+ n[R3]n-, wherein：M=1-100；L=1,2,3 or 4；R1For H, C1-C16Alkyl or phenyl；R2For C1-C16Alkyl or
Benzyl；R3The anion of Water-soluble Sulphonated phosphines is represented, n is the sum of sulfonic group anion on Phosphine ligands.
Water-soluble Sulphonated phosphines anion R in phosphine functionalization polyethers quaternary phosphonium salt ionic liquid3Structural formula it is as follows：
In formula：R4For 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 of synthesis phosphine functionalization polyethers quaternary phosphonium salt ionic liquid is polyethers quaternary phosphine salt ion
Liquid, its structural formula is：[(R1(OCH2CH2)m)lPR2 4-l][R5], wherein：M=1-100；L=1,2,3 or 4；R1For H, C1-C16
Alkyl or phenyl；R2For C1-C16Alkyl or benzyl；R5For Cl-, Br-, BF4 -, PF6 -, Tf2N-, MsO-, TsO-。
A kind of method of the alkene two-phase hydroformylation based on phosphine functionalization polyethers quaternary phosphonium salt ionic liquid is：Biphasic catalysis
System is made up of ionic liquid body phase and organic phase：Ionic liquid body phase includes the polyethers quaternary phosphonium salt 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, then realizes the recovery and recycling of rhodium catalyst by liquid liquid two-phase laminated flow again.
A kind of side for alkene two-phase hydroformylation based on phosphine functionalization polyethers quaternary phosphonium salt ionic liquid that the present invention is provided
Method is as follows：Under an inert atmosphere, by the polyethers quaternary phosphonium salt ionic liquid of phosphine functionalization, rhodium catalyst, substrate olefin with certain
Ratio is mixed, wherein, phosphine functionalization polyethers quaternary phosphonium salt ionic liquid and the mol ratio of rhodium in rhodium catalyst are 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, extractant can be also added, then
The split-phase of rhodium catalyst and organic phase is realized by liquid liquid two-phase laminated flow, the ionic liquid alkene new by adding can be carried out
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 is 1,5- cyclo-octadiene.
The substrate olefin that the present invention is 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.
In the present invention, the organic solvent or extractant that organic phase is introduced 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/[CH3(OCH2CH2)16P(C2H5)3]3[(SO3 -)3- 1] two-phase hydrogen formyl under/1- octene systems
Change reaction
Under an inert atmosphere, Rh (acac) (CO) is added into stainless steel autoclave2、[CH3(OCH2CH2)16P
(C2H5)3]3[(SO3 -)3- 1] and 1- octenes, its ratio is：[CH3(OCH2CH2)16P(C2H5)3]3[(SO3 -)3-1]/Rh(acac)
(CO)2=10:1 (mol ratio), 1- octenes/Rh (acac) (CO)2=10000:1 (mol ratio), then with synthesis gas (H2/ CO=
1:1) 5.0MPa is forced into, 95 DEG C of reaction temperature in 0.5 hour reaction time, is then quickly cooled to after room temperature, emptying synthesis gas
Kettle is driven, system is divided into two-phase naturally, and lower floor is the ionic liquid body phase containing rhodium catalyst, and upper strata is organic phase, can also be added just
Heptane extraxtion, the organic phase containing product aldehyde is obtained through simple two-phase laminated flow, and gas chromatographic analysis result is：Turn of 1- octenes
Rate is 7.1%, the selectivity 83.4% of aldehyde, and the mol ratio of n-alkanal and iso-aldehyde is 2.6:1, TOF value is 1184h-1。
Embodiment 2
Rh(acac)(CO)2/[CH3(OCH2CH2)16P(C2H5)3]3[(SO3 -)3- 1] two under/1- octenes/n-heptane system
Phase hydroformylation reaction
Under an inert atmosphere, Rh (acac) (CO) is added in stainless steel autoclave2、[CH3(OCH2CH2)16P
(C2H5)3]3[(SO3 -)3- 1], 1- octenes and normal heptane, its ratio is：[CH3(OCH2CH2)16P(C2H5)3]3[(SO3 -)3-1]/
Rh(acac)(CO)2=10:1 (mol ratio), 1- octenes/Rh (acac) (CO)2=10000:1 (mol ratio), normal heptane is pungent with 1-
The volume ratio of alkene is 2:1, then with synthesis gas (H2/ CO=1:1) 5.0MPa, 95 DEG C of reaction temperature, reaction time 0.5 are forced into
Hour, then it is quickly cooled to after room temperature, emptying synthesis gas and drives kettle, system is divided into two-phase naturally, lower floor is to contain rhodium catalyst
Ionic liquid body phase, upper strata is organic phase, and the organic phase containing product aldehyde, gas chromatographic analysis are obtained through simple two-phase laminated flow
As a result it is：The conversion ratio of 1- octenes is 4.9%, the selectivity 81.5% of aldehyde, and the mol ratio of n-alkanal and iso-aldehyde is 2.6:1,
TOF values are 799h-1。
Embodiment 3
Rh(acac)(CO)2/[Ph(OCH2CH2)16P(C2H5)3]3[(SO3 -)3- 1] two-phase hydrogen formyl under/1- octene systems
Change reaction
Ionic liquid is changed to [Ph (OCH2CH2)16P(C2H5)3]3[(SO3 -)3- 1], remaining reaction condition and the same implementation of step
Example 1, gas chromatographic analysis result is：The conversion ratio of 1- octenes is 12.6%, the selectivity 88.5% of aldehyde, n-alkanal and iso-aldehyde
Mol ratio be 2.8:1, TOF value is 2230h-1。
Embodiment 4
Rh(acac)(CO)2/[C12H25(OCH2CH2)16P(C2H5)3]3[(SO3 -)3- 1] two-phase hydrogen first under/1- octene systems
Acylation reaction
Ionic liquid is changed to [C12H25(OCH2CH2)16P(C2H5)3]3[(SO3 -)3- 1], remaining reaction condition and step are same real
Example 1 is applied, gas chromatographic analysis result is：The conversion ratio of 1- octenes is 14.4%, the selectivity 89.7% of aldehyde, n-alkanal and isomery
The mol ratio of aldehyde is 2.6:1, TOF value is 2583h-1。
Embodiment 5
Rh(acac)(CO)2/[Ph(OCH2CH2)4P(C2H5)3]3[(SO3 -)3- 1] two-phase hydroformylation under/1- octene systems
Reaction
Ionic liquid is changed to [Ph (OCH2CH2)4P(C2H5)3]3[(SO3 -)3- 1], remaining reaction condition and the same implementation of step
Example 1, gas chromatographic analysis result is：The conversion ratio of 1- octenes is 6.9%, the selectivity 69.5% of aldehyde, n-alkanal and iso-aldehyde
Mol ratio be 2.8:1, TOF value is 959h-1。
Embodiment 6
Rh(acac)(CO)2/[Ph(OCH2CH2)35P(C2H5)3]3[(SO3 -)3- 1] two-phase hydrogen formyl under/1- octene systems
Change reaction
Ionic liquid is changed to [Ph (OCH2CH2)35P(C2H5)3]3[(SO3 -)3- 1], remaining reaction condition and the same implementation of step
Example 1, gas chromatographic analysis result is：The conversion ratio of 1- octenes is 10.7%, the selectivity 85.1% of aldehyde, n-alkanal and iso-aldehyde
Mol ratio be 2.5:1, TOF value is 1821h-1。
Embodiment 7
Rh(acac)(CO)2/[Ph(OCH2CH2)50P(C2H5)3]3[(SO3 -)3- 1] two-phase hydrogen formyl under/1- octene systems
Change reaction
Ionic liquid is changed to [Ph (OCH2CH2)50P(C2H5)3]3[(SO3 -)3- 1], remaining reaction condition and the same implementation of step
Example 1, gas chromatographic analysis result is：The conversion ratio of 1- octenes is 9.7%, the selectivity 81.7% of aldehyde, n-alkanal and iso-aldehyde
Mol ratio be 2.7:1, TOF value is 1585h-1。
Embodiment 8
Rh(acac)(CO)2/[(Ph(OCH2CH2)8)2P(C2H5)2]3[(SO3 -)3- 1] two-phase hydrogen first under/1- octene systems
Acylation reaction
Ionic liquid is changed to [(Ph (OCH2CH2)8)2P(C2H5)2]3[(SO3 -)3- 1], remaining reaction condition and step are same real
Example 1 is applied, gas chromatographic analysis result is：The conversion ratio of 1- octenes is 10.9%, the selectivity 76.7% of aldehyde, n-alkanal and isomery
The mol ratio of aldehyde is 2.6:1, TOF value is 1672h-1。
Embodiment 9
Rh(acac)(CO)2/[Ph(OCH2CH2)16P(n-C4H9)3]3[(SO3 -)3- 1] two-phase hydrogen first under/1- octene systems
Acylation reaction
Ionic liquid is changed to [Ph (OCH2CH2)16P(n-C4H9)3]3[(SO3 -)3- 1], remaining reaction condition and step are same real
Example 1 is applied, gas chromatographic analysis result is：The conversion ratio of 1- octenes is 11.5%, the selectivity 92.8% of aldehyde, n-alkanal and isomery
The mol ratio of aldehyde is 2.6:1, TOF value is 2134h-1。
Embodiment 10
Rh(acac)(CO)2/[Ph(OCH2CH2)16P(C2H5)3]3[(SO3 -)3- 1] two-phase hydrogen formyl under/1- decene systems
Change reaction
Alkene is changed to 1- decene, remaining reaction condition and step be the same as Example 3, and gas chromatographic analysis result is：1- decene
Conversion ratio be 8.7%, the selectivity 64.8% of aldehyde, the mol ratio of n-alkanal and iso-aldehyde is 2.4:1, TOF value is 1128h-1。
Embodiment 11
Rh(acac)(CO)2/[Ph(OCH2CH2)16P(C2H5)3]3[(SO3 -)3- 1] two-phase hydrogen first under/1- laurylene systems
Acylation reaction
Alkene is changed to 1- laurylenes, reaction time 2h, remaining reaction condition and step be the same as Example 3, gas chromatographic analysis
As a result it is：The conversion ratio of laurylene is 9.8%, the selectivity 74.0% of aldehyde, and the mol ratio of n-alkanal and iso-aldehyde is 2.3:1,
TOF values are 362h-1。
Embodiment 12
Rh(acac)(CO)2/[Ph(OCH2CH2)16P(C2H5)3]3[(SO3 -)3- 1] two-phase hydrogen formyl under/polystyrene systems
Change reaction
Alkene is changed to styrene, remaining reaction condition and step be the same as Example 3, and gas chromatographic analysis result is：Styrene
Conversion ratio be 14.5%, the selectivity 91.6% of aldehyde, the mol ratio of n-alkanal and iso-aldehyde is 1:3.5, TOF values are 2656h-1。
Embodiment 13
Rh(acac)(CO)2/[Ph(OCH2CH2)16P(C2H5)3]2[(SO3 -)2- 12] (o=p=2, n=2)/1- octene bodies
The lower two-phase hydroformylation reaction of system
Under an inert atmosphere, Rh (acac) (CO) is added into stainless steel autoclave2、[Ph(OCH2CH2)16P
(C2H5)3]2[(SO3 -)2- 12] and 1- octenes, its ratio is：[Ph(OCH2CH2)16P(C2H5)3]2[(SO3 -)2-12]/Rh
(acac)(CO)2=5:1 (mol ratio), 1- octenes/Rh (acac) (CO)2=1000:1 (mol ratio), then with synthesis gas (H2/
CO=1:1) 5.0MPa is forced into, 100 DEG C of reaction temperature in 0.5 hour reaction time, is then quickly cooled to room temperature, emptying is closed
Kettle is driven after into gas, system is divided into two-phase naturally, and lower floor is the ionic liquid body phase containing rhodium catalyst, and upper strata is organic phase, also may be used
Normal heptane extraction is added, the organic phase containing product aldehyde is obtained through simple two-phase laminated flow, gas chromatographic analysis result is：1- is pungent
The conversion ratio of alkene is 91.4%, the selectivity 71.9% of aldehyde, and the mol ratio of n-alkanal and iso-aldehyde is 1.8:1, TOF value is
1314h-1。
Embodiment 14
Rh(acac)(CO)2/[CH3(OCH2CH2)16P(C2H5)3]2[(SO3 -)2- 12] (o=p=2, n=2)/1- octenes
Two-phase hydroformylation reaction under system
Ionic liquid is changed to [CH3(OCH2CH2)16P(C2H5)3]2[(SO3 -)2- 12] (o=p=2, n=2), remaining reaction
Condition and step be the same as Example 13, gas chromatographic analysis result is：The conversion ratio of 1- octenes is 45.4%, the selectivity of aldehyde
43.6%, the mol ratio of n-alkanal and iso-aldehyde is 2.6:1, TOF value is 396h-1。
Embodiment 15
Rh(acac)(CO)2/[CH3(OCH2CH2)4P(C2H5)3]2[(SO3 -)2- 12] (o=p=2, n=2)/1- octene bodies
The lower two-phase hydroformylation reaction of system
Ionic liquid is changed to [CH3(OCH2CH2)4P(C2H5)3]2[(SO3 -)2- 12] (o=p=2, n=2), remaining reaction bar
Part and step be the same as Example 13, gas chromatographic analysis result is：The conversion ratio of 1- octenes is 40.9%, the selectivity of aldehyde
44.5%, the mol ratio of n-alkanal and iso-aldehyde is 2.9:1, TOF value is 364h-1。
Embodiment 16
Rh(acac)(CO)2/[Ph(OCH2CH2)4P(C2H5)3]2[(SO3 -)2- 12] (o=p=2, n=2)/1- laurylenes
Two-phase hydroformylation reaction under system
Alkene is changed to 1- laurylenes, remaining reaction condition and step be the same as Example 13, and gas chromatographic analysis result is：1- ten
The conversion ratio of diene is 51.4%, the selectivity 77.5% of aldehyde, and the mol ratio of n-alkanal and iso-aldehyde is 2.0:1, TOF value is
797h-1。
Embodiment 17
Rh(acac)(CO)2/[Ph(OCH2CH2)4P(C2H5)3]2[(SO3 -)2- 12] (o=p=2, n=2)/1-tetradecylene
Two-phase hydroformylation reaction under system
Alkene is changed to 1-tetradecylene, remaining reaction condition and step be the same as Example 13, and gas chromatographic analysis result is：1- ten
The conversion ratio of tetraene is 47.6%, the selectivity 68.8% of aldehyde, and the mol ratio of n-alkanal and iso-aldehyde is 1.8:1, TOF value is
655h-1。
Embodiment 18
Rh(acac)(CO)2/[Ph(OCH2CH2)4P(C2H5)3]2[(SO3 -)2- 2] two-phase hydroformylation under/1- octene systems
Reaction
Ionic liquid is changed to [Ph (OCH2CH2)4P(C2H5)3]2[(SO3 -)2- 2], remaining reaction condition and the same implementation of step
Example 1, gas chromatographic analysis result is：The conversion ratio of 1- octenes is 7.8%, the selectivity 71.6% of aldehyde, n-alkanal and iso-aldehyde
Mol ratio be 2.5:1, TOF value is 1117h-1。
Embodiment 19
Rh(acac)(CO)2/[Ph(OCH2CH2)4P(C2H5)3][(SO3 -) -3] two-phase hydroformylation under/1- octene systems
Reaction
Ionic liquid is changed to [Ph (OCH2CH2)4P(C2H5)3][(SO3 -) -3], remaining reaction condition and step be the same as Example
1, gas chromatographic analysis result is：The conversion ratio of 1- octenes is 9.2%, the selectivity 73.4% of aldehyde, n-alkanal and iso-aldehyde
Mol ratio is 2.7:1, TOF value is 1351h-1。
Embodiment 20
Rh(acac)(CO)2/[Ph(OCH2CH2)4P(C2H5)3]4[(SO3 -)4- 4] (o=p=0, n=4)/1- octene systems
Lower two-phase hydroformylation reaction
Ionic liquid is changed to [Ph (OCH2CH2)4P(C2H5)3]4[(SO3 -)4- 4] (o=p=0, n=4), remaining reaction bar
Part and step be the same as Example 13, gas chromatographic analysis result is：The conversion ratio of 1- octenes is 90.6%, the selectivity of aldehyde
64.6%, the mol ratio of n-alkanal and iso-aldehyde is 2.4:1, TOF value is 1171h-1。
Embodiment 21
Rh(acac)(CO)2/[Ph(OCH2CH2)4P(C2H5)3]4[(SO3 -)4- 5] (o=p=0, n=4)/1- octene systems
Lower two-phase hydroformylation reaction
Ionic liquid is changed to [Ph (OCH2CH2)4P(C2H5)3]4[(SO3 -)4- 5] (o=p=0, n=4), remaining reaction bar
Part and step be the same as Example 13, gas chromatographic analysis result is：The conversion ratio of 1- octenes is 86.5%, the selectivity of aldehyde
61.6%, the mol ratio of n-alkanal and iso-aldehyde is 2.6:1, TOF value is 1066h-1。
Embodiment 22
Rh(acac)(CO)2/[Ph(OCH2CH2)4P(C2H5)3]2[(SO3 -)2- 6] (o=p=2, n=2)/1- octene systems
Lower two-phase hydroformylation reaction
Ionic liquid is changed to [Ph (OCH2CH2)4P(C2H5)3]2[(SO3 -)2- 6] (o=p=2, n=2), remaining reaction bar
Part and step be the same as Example 13, gas chromatographic analysis result is：The conversion ratio of 1- octenes is 83.6%, the selectivity of aldehyde
72.5%, the mol ratio of n-alkanal and iso-aldehyde is 2.3:1, TOF value is 1212h-1。
Embodiment 23
Rh(acac)(CO)2/[Ph(OCH2CH2)4P(C2H5)3]2[(SO3 -)2- 7] (o=2, q=r=1, s=t=0, n=
2) two-phase hydroformylation reaction under/polystyrene systems
Ionic liquid is changed to [Ph (OCH2CH2)4P(C2H5)3]2[(SO3 -)2- 7] (o=2, q=r=1, s=t=0, n=
2), alkene is changed to styrene, remaining reaction condition and step be the same as Example 13, and gas chromatographic analysis result is：Turn of styrene
Rate is 95.6%, the selectivity 78.9% of aldehyde, and the mol ratio of n-alkanal and iso-aldehyde is 1:4.5, ee values are 36.1%, TOF
It is worth for 1509h-1。
Embodiment 24
Rh(acac)(CO)2/[Ph(OCH2CH2)4P(C2H5)3]4[(SO3 -)4- 9] (o=p=0, n=4)/1- octene systems
Lower two-phase hydroformylation reaction
Ionic liquid is changed to [Ph (OCH2CH2)4P(C2H5)3]4[(SO3 -)4- 9] (o=p=0, n=4), remaining reaction bar
Part and step be the same as Example 13, gas chromatographic analysis result is：The conversion ratio of 1- octenes is 90.4%, the selectivity of aldehyde
59.6%, the mol ratio of n-alkanal and iso-aldehyde is 2.0:1, TOF value is 1078h-1。
Embodiment 25
Rh(acac)(CO)2/[Ph(OCH2CH2)4P(C2H5)3]2[(SO3 -)2- 10] (o=p=2, n=2)/1- octene bodies
The lower two-phase hydroformylation reaction of system
Ionic liquid is changed to [Ph (OCH2CH2)4P(C2H5)3]2[(SO3 -)2- 10] (o=p=2, n=2), remaining reaction bar
Part and step be the same as Example 13, gas chromatographic analysis result is：The conversion ratio of 1- octenes is 93.3%, the selectivity of aldehyde
74.0%, the mol ratio of n-alkanal and iso-aldehyde is 1.7:1, TOF value is 1381h-1。
Embodiment 26
Rh(acac)(CO)2/[Ph(OCH2CH2)4P(C2H5)3]2[(SO3 -)2- 11] (o=p=2, n=2)/1- octene bodies
The lower two-phase hydroformylation reaction of system
Ionic liquid is changed to [Ph (OCH2CH2)4P(C2H5)3]2[(SO3 -)2- 11] (o=p=2, n=2), remaining reaction bar
Part and step be the same as Example 13, gas chromatographic analysis result is：The conversion ratio of 1- octenes is 97.4%, the selectivity of aldehyde
83.3%, the mol ratio of n-alkanal and iso-aldehyde is 1.8:1, TOF value is 1623h-1。
Embodiment 27-36
Rh(acac)(CO)2/[Ph(OCH2CH2)16P(C2H5)3]3[(SO3 -)3- 1] two-phase hydrogen formyl under/1- octene systems
Change reaction cycle experiment
Under an inert atmosphere, Rh (acac) (CO) is added into stainless steel autoclave2、[Ph(OCH2CH2)16P
(C2H5)3]3[(SO3 -)3- 1] and 1- octenes, its ratio is：[Ph(OCH2CH2)16P(C2H5)3]3[(SO3 -)3-1]/Rh(acac)
(CO)2=20:1 (mol ratio), 1- octenes/Rh (acac) (CO)2=5000:1 (mol ratio), then with synthesis gas (H2/ CO=
1:1) 5.0MPa is forced into, 95 DEG C of reaction temperature in 5 hours reaction time, is opened after being then quickly cooled to room temperature, emptying synthesis gas
Kettle, system is divided into two-phase naturally, is decanted off the organic phase on upper strata, and the ionic liquid that rhodium catalyst is contained in lower floor is new by adding
1- octenes can carry out catalytic cycle next time, gas chromatographic analysis result shows：After 10 catalytic cycles, the conversion of alkene
Rate is held essentially constant, and the selectivity of aldehyde is declined slightly after circulating 10 times, and accumulative TON values reach 44237, and circulation experiment result is shown in
Embodiment 27-36 in table 1.
The circulation experiment of the rhodium catalyst of table 1
Claims (5)
1. a kind of method of the alkene two-phase hydroformylation based on phosphine functionalization polyethers quaternary phosphonium salt ionic liquid, it is characterised in that：
Biphase catalytic system is made up of ionic liquid body phase and organic phase：Ionic liquid body phase includes the polyethers quaternary phosphine salt ion of phosphine functionalization
Liquid and rhodium catalyst；Organic phase is reaction substrate alkene；Organic phase does not introduce solvent；Hydroformylation reaction is in certain reaction
Carried out under temperature and synthesis atmospheric pressure, reaction terminates rear directly real by the liquid liquid two-phase laminated flow of ionic liquid body phase and organic phase
The recovery and recycling of existing rhodium catalyst；Or reaction terminate after add extractant, then pass through liquid liquid two-phase laminated flow again
Realize the recovery and recycling of rhodium catalyst；The cation of phosphine functionalization polyethers quaternary phosphonium salt ionic liquid is polyethers quaternary alkylphosphonium salt sun
Ion, anion is Water-soluble Sulphonated phosphines anion, and its structural formula is：[(R1(OCH2CH2)m)lPR2 4-l]+ n[R3]n-,
Wherein：M=1-100；L=1,2,3 or 4；R1For H, C1-C16Alkyl or phenyl；R2For C1-C16Alkyl or benzyl；R3Represent sulfonic acid
The anion of type water-soluble phosphine ligand, n is the sum of sulfonic group anion on Phosphine ligands, R3Structural formula it is as follows：
In formula：R4For C6H4-3-SO3 -；1,2,3,4,5,6,7,8,9,10,11 and 12 is respectively different sulfonic acid type water-soluble phosphines
The parent fraction of part, 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.
2. a kind of side of alkene two-phase hydroformylation based on phosphine functionalization polyethers quaternary phosphonium salt ionic liquid according to claim 1
Method, it is characterized in that：Under an inert atmosphere, by the polyethers quaternary phosphonium salt ionic liquid of phosphine functionalization, rhodium catalyst, substrate olefin with one
Fixed ratio mixing, wherein, phosphine functionalization polyethers quaternary phosphonium salt ionic liquid and the mol ratio of rhodium in rhodium catalyst are 3:1-100:
1, the mol ratio for making substrate olefin and rhodium in rhodium catalyst is 100:1-20000:1, synthesis atmospheric pressure is 1-10MPa, reaction temperature
Degree is 70-130 DEG C, and the reaction time is 0.25-15 hours；Solvent is added without in reaction system；After reaction terminates, pass through ionic liquid
The liquid liquid two-phase laminated flow of body phase and organic phase realizes the recovery of rhodium catalyst；Or reaction terminate after add extractant, then
The split-phase of rhodium catalyst and organic phase is realized by liquid liquid two-phase laminated flow again, the ionic liquid alkene new by adding is carried out
Catalytic cycle next time.
3. a kind of side of alkene two-phase hydroformylation based on phosphine functionalization polyethers quaternary phosphonium salt 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 is 1,5- cyclo-octadiene.
4. a kind of side of alkene two-phase hydroformylation based on phosphine functionalization polyethers quaternary phosphonium salt 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.
5. a kind of side of alkene two-phase hydroformylation based on phosphine functionalization polyethers quaternary phosphonium salt ionic liquid according to claim 1
Method, it is characterized in that：Extractant is：Petroleum ether, hexamethylene, C6-C12One kind in alkane, ether, methyl tertiary butyl ether(MTBE) or on
State mixtures several in solvent.
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| CN107537564B (en) * | 2016-06-24 | 2020-04-07 | 中国科学院大连化学物理研究所 | Heterogeneous catalyst containing quaternary phosphonium salt-phosphorus ligand organic porous copolymer and preparation and application thereof |
| CN111450880B (en) * | 2020-05-09 | 2022-11-29 | 青岛科技大学 | Sulfonated BINAP and polyether functionalized ionic liquid integrated chiral catalyst |
| CN111389468B (en) * | 2020-05-09 | 2022-11-29 | 青岛科技大学 | Application of sulfonated BINAP and polyether functionalized ionic liquid integrated chiral catalyst in asymmetric hydrogenation reaction |
| CN111517952B (en) * | 2020-05-09 | 2023-05-19 | 青岛科技大学 | Solvent-free asymmetric hydrogenation method based on sulfonated BINAP and polyether functionalized ionic liquid integrated chiral catalyst |
| CN111825542B (en) * | 2020-06-24 | 2023-01-13 | 万华化学集团股份有限公司 | Method for hydroformylating high-carbon olefin with carbon number not less than 8 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5773666A (en) * | 1995-09-26 | 1998-06-30 | Kuraray Co., Ltd. | Hydroformylation process |
| 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 |
| CN103570514A (en) * | 2013-10-07 | 2014-02-12 | 青岛科技大学 | Olefin hydroformylation method by homogeneous catalysis-biphase separation |
-
2015
- 2015-05-16 CN CN201510249835.5A patent/CN105017319B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5773666A (en) * | 1995-09-26 | 1998-06-30 | Kuraray Co., Ltd. | Hydroformylation process |
| 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 |
| CN103570514A (en) * | 2013-10-07 | 2014-02-12 | 青岛科技大学 | Olefin hydroformylation method by homogeneous catalysis-biphase separation |
Non-Patent Citations (2)
| Title |
|---|
| Clean catalysis with ionic solvents—phosphonium tosylates for hydroformylation;Nazira Karodia et al;《Chem. Commun.》;19981231;第2341-2342页 * |
| 以季鏻盐离子液体为反应介质的绿色有机反应;黄强等;《化学进展》;20091231;第21卷(第9期);第1782-1791页 * |
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