CN105017314A - Phosphine-functionalized polyether piperidine salt ionic liquid and application thereof in the hydroformylation of olefins - Google Patents
Phosphine-functionalized polyether piperidine salt ionic liquid and application thereof in the hydroformylation of olefins Download PDFInfo
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- CN105017314A CN105017314A CN201510249832.1A CN201510249832A CN105017314A CN 105017314 A CN105017314 A CN 105017314A CN 201510249832 A CN201510249832 A CN 201510249832A CN 105017314 A CN105017314 A CN 105017314A
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- phosphine
- salt ionic
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 95
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 52
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 40
- 229920000570 polyether Polymers 0.000 title claims abstract description 38
- 150000003053 piperidines Chemical class 0.000 title claims abstract 6
- 239000004721 Polyphenylene oxide Substances 0.000 title abstract 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000010948 rhodium Substances 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 48
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 48
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 35
- 230000003197 catalytic effect Effects 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 6
- 239000003446 ligand Substances 0.000 claims abstract description 6
- 239000012071 phase Substances 0.000 claims description 72
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 63
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical group [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 claims description 42
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical class C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 claims description 32
- 238000007306 functionalization reaction Methods 0.000 claims description 31
- 239000012074 organic phase Substances 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 26
- 150000002500 ions Chemical class 0.000 claims description 16
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 11
- 238000011084 recovery Methods 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 238000000605 extraction Methods 0.000 claims description 9
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- 150000003003 phosphines Chemical class 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 125000005466 alkylenyl group Chemical group 0.000 claims description 4
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 4
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims description 2
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 claims description 2
- VTMSSJKVUVVWNJ-UHFFFAOYSA-N 1-ethenyl-4-(2-methylpropyl)benzene Chemical compound CC(C)CC1=CC=C(C=C)C=C1 VTMSSJKVUVVWNJ-UHFFFAOYSA-N 0.000 claims description 2
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 claims description 2
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical compound COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 0.000 claims description 2
- KXYAVSFOJVUIHT-UHFFFAOYSA-N 2-vinylnaphthalene Chemical compound C1=CC=CC2=CC(C=C)=CC=C21 KXYAVSFOJVUIHT-UHFFFAOYSA-N 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 2
- 230000002051 biphasic effect Effects 0.000 abstract 4
- 150000001299 aldehydes Chemical class 0.000 abstract 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 110
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 55
- 238000004587 chromatography analysis Methods 0.000 description 29
- 230000009466 transformation Effects 0.000 description 28
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 7
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical group CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 3
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000007172 homogeneous catalysis Methods 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 2
- -1 alkyl guanidinium Chemical compound 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000033772 system development Effects 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The present invention relates to a phosphine-functionalized polyether piperidine salt ionic liquid and a method for biphasic hydroformaylation of olefins based on the phosphine-functionalized polyether piperidine salt ionic liquid. The method uses a biphasic catalytic system, wherein the catalytic system consists of a phosphine-functionalized polyether piperidine salt 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 piperidine salt 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 recycling 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.
Description
Technical field
The present invention relates to technical field of chemistry and chemical engineering, relate to a class phosphine functionalization polyethers piperidinium salt ionic liquid particularly, and a kind of method of the alkene two-phase hydroformylation based on phosphine functionalization polyethers piperidinium salt ionic liquid.
Background technology
The hydroformylation of olefin of rhodium catalysis is typical atomic economy reaction, is also the more carbonylation reaction of current bibliographical information, has become the Perfected process preparing high-carbon aldehyde/alcohol.Homogeneous phase hydroformylation has the advantage that catalytic activity is high, selectivity good and reaction conditions is gentle, but for a long time, the separation of rhodium catalyst and Recycling are the focuses that homogeneous catalysis field is paid close attention to always.
In recent years, ionic liquid is very rapid as the liquid/liquid biphase catalytic system development of support of the catalyst, has become at present most one of biphase catalytic system with application prospect.Non-aqueous ionic liquid hydroformylation is based on extremely low vapour pressure, good thermostability and the controlled dissolving power of ionic liquid; rhodium catalyst is dissolved; serve as with ionic liquid " liquid vehicle " of catalyzer; and substrate olefin and product aldehyde and ionic liquid not miscible, realized the circulation of catalyzer after reaction terminates by liquid/liquid two-phase laminated flow.
Although non-aqueous ionic liquid hydroformylation to some extent solves the partitioning cycle problem of rhodium catalyst, still there is significant limitation in ionic liquid in actual applications.First, non-aqueous ionic liquid catalyst system still needs a large amount of ionic liquid loaded and dissolving rhodium catalysts, no matter is that this does not all meet the requirement of Green Chemistry from economical or toxicologic angle; Two is that the application of a large amount of ionic liquid makes the resistance to mass transfer of substrate molecule increase, and the negative effect (being caused by the Various Complex such as high viscosity, residual impurity factor) of ionic liquid becomes more remarkable, causes catalytic activity and selectivity degradation.
Recently, we have invented the polyoxyalkylene alkyl guanidinium ionic liquid (Chem.Commun. that a class has the liquid-solid phase-change characteristic of room temperature, 2012, 48, 9017-9019 and patent ZL201210064537.5), and be applied in the higher olefins two-phase hydroformylation reaction of rhodium catalysis, this kind of novel functionalized ion liquid can effective immobilized Rh-TPPTS catalyzer, and there is the ability stablizing rhodium catalyst significantly, hydroformylation reaction adds up TON value and reaches 31188, but this two-phase system still needs relatively large ionic liquid as the carrier of Rh-TPPTS catalyzer, the mass ratio of ionic liquid and rhodium catalyst precursor reaches 1000:1, and owing to being subject to the restriction of biphase catalytic system resistance to mass transfer, catalytic activity is not high, TOF value only has 10-200h
-1.
In another patent (CN201310370138.6), we have invented the polyoxyalkylene alkyl guanidinium ionic liquid of the novel phosphine functionalization of a class, and construct based on this novel ion liquid the hydroformylation reaction that a homogeneous catalysis system is applied to the higher olefins of rhodium catalysis, the advantage of this catalyst system is that catalytic activity is higher, but need to introduce organic solvent in catalyst system, this adds difficulty and the energy consumption of catalyst recovery circulation and last handling process virtually, organic solvent also can cause environment and safety problem simultaneously, the requirement of Green Chemistry is not met yet.
Summary of the invention
For the deficiencies in the prior art, invention one class phosphine functionalization polyethers piperidinium salt ionic liquid, and based on this kind of phosphine functionalization polyethers piperidinium salt ionic liquid, invented a kind of method of phosphine functionalized ion liquid two-phase hydroformylation.Biphase catalytic system is made up of with organic phase ionic liquid phase: ionic liquid comprises polyethers piperidinium salt ionic liquid and the rhodium catalyst of phosphine functionalization mutually; Organic phase comprises reaction substrate alkene and reaction product, or the mixture of the two; Organic phase can introduce solvent, also can not introduce solvent; Hydroformylation reaction carries out under certain temperature of reaction and synthetic gas pressure, can directly be realized the recovery of rhodium catalyst by the liquid/liquid two-phase laminated flow of ionic liquid phase and organic phase and be recycled after reaction terminates; Also can add extraction solvent, and then realize the recovery of rhodium catalyst by liquid/liquid two-phase laminated flow and recycle.
In the present invention, the characteristic of the existing Phosphine ligands of polyethers piperidinium salt ionic liquid of phosphine functionalization, complex catalyst can be formed with rhodium, have both again the solvent nature of ionic liquid, the carrier of rhodium catalyst can be served as, therefore without the need to additional other ionic liquid in a large number again, fundamentally solve the difficult problem that ionic liquid consumption is too high, also the negative effect of ionic liquid in catalyzed reaction is down to minimum simultaneously.
In the present invention, the polyethers piperidinium salt ionic liquid of phosphine functionalization and the mass ratio of rhodium catalyst are 10:1-300:1, be only the 1%-30% of patent of invention ZL201210064537.5 intermediate ion volume, thus solve conventional ion liquid biphase catalytic system and need a large amount of ionic liquid as the problem of support of the catalyst.
The catalytic activity of phosphine functionalization polyethers piperidinium salt non-aqueous ionic liquid hydroformylation system provided by the invention is higher, and TOF value reaches 380-3000h
-1, be TOF value (10-200h in patent of invention ZL201210064537.5
-1) 1.9-300 doubly, catalytic cycle adds up TON value and reaches 36918, is 1.2 times of the TON value (31188) reported in patent ZL201210064537.5.
Different from the homogeneous catalysis system that patent of invention CN201310370138.6 reports, catalyst system of the present invention is two-phase system, because herein is provided a kind of separation of simpler rhodium catalyst and the method for circulation.Due in reaction and separation processes process, organic phase can introduce solvent, also solvent can not be introduced, realized the circulation of rhodium catalyst by liquid/liquid two-phase laminated flow after reaction terminates, therefore the step reclaiming organic solvent can be saved, avoiding environment and safety problem that organic solvent causes, reduce difficulty and the energy consumption of catalyst recovery circulation and last handling process simultaneously, is more meet the method that Green Chemistry requires.
In the present invention, the structural formula of the phosphine functionalization polyethers piperidinium salt ionic liquid of application is as follows:
[(N-(EO)
mR
1)(N-(EO)
lR
2)Pi]
n[R
3]
In formula: m=1-100; R
1for H, C
1-C
16alkyl or phenyl; L=0-100, R
2for H, C
1-C
16alkyl, phenyl or benzyl; R
3represent the negatively charged ion of Water-soluble Sulphonated phosphines, n is the sum of sulfonic group negatively charged ion on Phosphine ligands, R
3structural formula as follows:
In formula: R
4for C
6h
4-3-SO
3 -; 1,2,3,4,5,6,7,8,9,10,11 and 12 parent fraction being respectively different Water-soluble Sulphonated phosphines, n is the sum of sulfonic group negatively charged ion 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 piperidinium salt ionic liquid is polyethers piperidinium salt ionic liquid, and its structural formula is as follows:
[(N-(EO)
mR
1)(N-(EO)
lR
2)Pi][R
5]
In formula: m=1-100; R
1for H, C
1-C
16alkyl or phenyl; L=0-100, R
2for H, C
1-C
16alkyl, phenyl or benzyl; R
5for Cl
-, Br
-, BF
4 -, PF
6 -, Tf
2n
-, MsO
-, TsO
-.
A kind of method of the alkene two-phase hydroformylation based on phosphine functionalization polyethers piperidinium salt ionic liquid is: biphase catalytic system is made up of with organic phase ionic liquid phase: ionic liquid comprises polyethers piperidinium salt ionic liquid and the rhodium catalyst of phosphine functionalization mutually; Organic phase comprises reaction substrate alkene and reaction product, or the mixture of the two; Organic phase can introduce solvent, also can not introduce solvent; Hydroformylation reaction carries out under certain temperature of reaction and synthetic gas pressure, can directly be realized the recovery of rhodium catalyst by the liquid/liquid two-phase laminated flow of ionic liquid phase and organic phase and be recycled after reaction terminates; Also can add extraction solvent, and then realize the recovery of rhodium catalyst by liquid/liquid two-phase laminated flow and recycle.
The method of a kind of alkene two-phase hydroformylation based on phosphine functionalization polyethers piperidinium salt ionic liquid provided by the invention is as follows: under an inert atmosphere, by the polyethers piperidinium salt ionic liquid of phosphine functionalization, rhodium catalyst, substrate olefin mixes in certain proportion, wherein, in phosphine functionalization polyethers piperidinium salt ionic liquid and rhodium catalyst, the mol ratio of rhodium is 3:1-100:1, preferably 5:1-30:1, the mol ratio of rhodium in substrate olefin and rhodium catalyst is made to be 100:1-20000:1, preferably 1000:1-10000:1, synthetic gas pressure is 1-10MPa, temperature of reaction is 70-130 DEG C, reaction times is 0.25-15 hour, can solvent be introduced in system, also can not solubilizing agent, if add 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 phase and organic phase, also extraction solvent can be added, then realized the phase-splitting of rhodium catalyst and organic phase by liquid/liquid two-phase laminated flow, ionic liquid can carry out catalytic cycle next time by adding new alkene.
In the present invention, rhodium catalyst is rhodium dicarbonyl acetylacetonate Rh (acac) (CO)
2, RhCl
33H
2o, [Rh (COD)
2] BF
4or [Rh (COD) Cl]
2, COD is 1,5-cyclooctadiene.
The substrate olefin that the present invention uses is C
3-C
16straight chain 1-alkene, tetrahydrobenzene, vinylbenzene, p-methylstyrene, o-methyl styrene, p-tert-butylstyrene, p-isobutylstyrene, to methoxy styrene, to chloro-styrene, chloro styrene, 2-vinyl naphthalene, 6-methoxyl group-2-vinyl naphthalene; Reaction product is the mixture of one or more in aldehyde, isomerizing olefins, olefin hydrogenation product.
In the present invention, the organic solvent that organic phase is introduced or extraction solvent are: sherwood oil, hexanaphthene, C
6-C
12mixtures several in a kind of or above-mentioned solvent in alkane, ether, methyl tertiary butyl ether.
Embodiment
Embodiment 1
Rh (acac) (CO)
2/ [(N-(EO)
16cH
3) (N-C
2h
5) Pi]
3[(SO
3 -)
3-1] two-phase hydroformylation reaction under/1-octene system
Under an inert atmosphere, add Rh (acac) (CO) in stainless steel autoclave
2, [(N-(EO)
16cH
3) (N-C
2h
5) Pi]
3[(SO
3 -)
3-1] and 1-octene, its ratio is: [(N-(EO)
16cH
3) (N-C
2h
5) Pi]
3[(SO
3 -)
3-1]/Rh (acac) (CO)
2=10:1 (mol ratio), 1-octene/Rh (acac) (CO)
2=10000:1 (mol ratio), then uses synthetic gas (H
2/ CO=1:1) be forced into 5.0MPa, temperature of reaction 95 DEG C, 0.5 hour reaction times, then room temperature is quickly cooled to, still is driven after emptying synthetic gas, system is divided into two-phase naturally, lower floor is the ionic liquid phase containing rhodium catalyst, upper strata is organic phase, also can add normal heptane extraction, obtain the organic phase containing product aldehyde through simple two-phase laminated flow, gas chromatographic analysis result is: the transformation efficiency of 1-octene is 8.1%, the selectivity 85.5% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 2.7:1, TOF value is 1385h
-1.
Embodiment 2
Rh (acac) (CO)
2/ [(N-(EO)
16cH
3) (N-C
2h
5) Pi]
3[(SO
3 -)
3-1] two-phase hydroformylation reaction under/1-octene/n-heptane system
Under an inert atmosphere, add in stainless steel autoclave Rh (acac) (CO)
2, [(N-(EO)
16cH
3) (N-C
2h
5) Pi]
3[(SO
3 -)
3-1], 1-octene and normal heptane, its ratio is: [(N-(EO)
16cH
3) (N-C
2h
5) Pi]
3[(SO
3 -)
3-1]/Rh (acac) (CO)
2=10:1 (mol ratio), 1-octene/Rh (acac) (CO)
2=10000:1 (mol ratio), the volume ratio of normal heptane and 1-octene is 2:1, then uses synthetic gas (H
2/ CO=1:1) be forced into 5.0MPa, temperature of reaction 95 DEG C, 0.5 hour reaction times, then room temperature is quickly cooled to, drive still after emptying synthetic gas, system is divided into two-phase naturally, and lower floor is the ionic liquid phase containing rhodium catalyst, upper strata is organic phase, obtain the organic phase containing product aldehyde through simple two-phase laminated flow, gas chromatographic analysis result is: the transformation efficiency of 1-octene is 6.2%, the selectivity 79.5% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 2.6:1, TOF value is 986h
-1.
Embodiment 3
Rh (acac) (CO)
2/ [(N-(EO)
16ph) (N-C
2h
5) Pi]
3[(SO
3 -)
3-1] two-phase hydroformylation reaction under/1-octene system
Ionic liquid is changed to [(N-(EO)
16ph) (N-C
2h
5) Pi]
3[(SO
3 -)
3-1], remaining reaction condition and step are with embodiment 1, and gas chromatographic analysis result is: the transformation efficiency of 1-octene is 11.9%, the selectivity 91.4% of aldehyde, and the mol ratio of n-alkanal and isomery aldehyde is 2.9:1, TOF value is 2175h
-1.
Embodiment 4
Rh (acac) (CO)
2/ [(N-(EO)
16c
12h
25) (N-C
2h
5) Pi]
3[(SO
3 -)
3-1] two-phase hydroformylation reaction under/1-octene system
Ionic liquid is changed to [(N-(EO)
16c
12h
25) (N-C
2h
5) Pi]
3[(SO
3 -)
3-1], remaining reaction condition and step are with embodiment 1, and gas chromatographic analysis result is: the transformation efficiency of 1-octene is 15.7%, the selectivity 90.1% of aldehyde, and the mol ratio of n-alkanal and isomery aldehyde is 2.6:1, TOF value is 2829h
-1.
Embodiment 5
Rh (acac) (CO)
2/ [(N-(EO)
4ph) (N-C
2h
5) Pi]
3[(SO
3 -)
3-1] two-phase hydroformylation reaction under/1-octene system
Ionic liquid is changed to [(N-(EO)
4ph) (N-C
2h
5) Pi]
3[(SO
3 -)
3-1], remaining reaction condition and step are with embodiment 1, and gas chromatographic analysis result is: the transformation efficiency of 1-octene is 6.6%, the selectivity 74.3% of aldehyde, and the mol ratio of n-alkanal and isomery aldehyde is 2.7:1, TOF value is 981h
-1.
Embodiment 6
Rh (acac) (CO)
2/ [(N-(EO)
35ph) (N-C
2h
5) Pi]
3[(SO
3 -)
3-1] two-phase hydroformylation reaction under/1-octene system
Ionic liquid is changed to [(N-(EO)
35ph) (N-C
2h
5) Pi]
3[(SO
3 -)
3-1], remaining reaction condition and step are with embodiment 1, and gas chromatographic analysis result is: the transformation efficiency of 1-octene is 10.2%, the selectivity 86.7% of aldehyde, and the mol ratio of n-alkanal and isomery aldehyde is 2.5:1, TOF value is 1769h
-1.
Embodiment 7
Rh (acac) (CO)
2/ [(N-(EO)
50ph) (N-C
2h
5) Pi]
3[(SO
3 -)
3-1] two-phase hydroformylation reaction under/1-octene system
Ionic liquid is changed to [(N-(EO)
50ph) (N-C
2h
5) Pi]
3[(SO
3 -)
3-1], remaining reaction condition and step are with embodiment 1, and gas chromatographic analysis result is: the transformation efficiency of 1-octene is 11.6%, the selectivity 90.2% of aldehyde, and the mol ratio of n-alkanal and isomery aldehyde is 2.6:1, TOF value is 2093h
-1.
Embodiment 8
Rh (acac) (CO)
2/ [(N-(EO)
16ph) (N-n-C
4h
9) Pi]
3[(SO
3 -)
3-1] two-phase hydroformylation reaction under/1-octene system
Ionic liquid is changed to [(N-(EO)
16ph) (N-n-C
4h
9) Pi]
3[(SO
3 -)
3-1], remaining reaction condition and step are with embodiment 1, and gas chromatographic analysis result is: the transformation efficiency of 1-octene is 12.3%, the selectivity 89.6% of aldehyde, and the mol ratio of n-alkanal and isomery aldehyde is 2.6:1, TOF value is 2204h
-1.
Embodiment 9
Rh (acac) (CO)
2/ [(N-(EO)
16ph) (N-n-C
8h
17) Pi]
3[(SO
3 -)
3-1] two-phase hydroformylation reaction under/1-octene system
Ionic liquid is changed to [(N-(EO)
16ph) (N-n-C
8h
17) Pi]
3[(SO
3 -)
3-1], remaining reaction condition and step are with embodiment 1, and gas chromatographic analysis result is: the transformation efficiency of 1-octene is 13.9%, the selectivity 90.6% of aldehyde, and the mol ratio of n-alkanal and isomery aldehyde is 2.9:1, TOF value is 2519h
-1.
Embodiment 10
Rh (acac) (CO)
2/ [(N-(EO)
16ph) (N-n-C
12h
25) Pi]
3[(SO
3 -)
3-1] two-phase hydroformylation reaction under/1-octene system
Ionic liquid is changed to [(N-(EO)
16ph) (N-n-C
12h
25) Pi]
3[(SO
3 -)
3-1], remaining reaction condition and step are with embodiment 1, and gas chromatographic analysis result is: the transformation efficiency of 1-octene is 14.5%, the selectivity 91.9% of aldehyde, and the mol ratio of n-alkanal and isomery aldehyde is 2.8:1, TOF value is 2665h
-1.
Embodiment 11
Rh (acac) (CO)
2/ [(N-(EO)
16ph) (N-(EO)
16ph) Pi]
3[(SO
3 -)
3-1] two-phase hydroformylation reaction under/1-octene system
Ionic liquid is changed to [(N-(EO)
16ph) (N-(EO)
16ph) Pi]
3[(SO
3 -)
3-1], remaining reaction condition and step are with embodiment 1, and gas chromatographic analysis result is: the transformation efficiency of 1-octene is 11.4%, the selectivity 87.5% of aldehyde, and the mol ratio of n-alkanal and isomery aldehyde is 2.6:1, TOF value is 1995h
-1.
Embodiment 12
Rh (acac) (CO)
2/ [(N-(EO)
16ph) (N-C
2h
5) Pi]
3[(SO
3 -)
3-1] two-phase hydroformylation reaction under/1-decene system
Alkene is changed to 1-decene, and remaining reaction condition and step are with embodiment 3, and gas chromatographic analysis result is: the transformation efficiency of 1-decene is 10.3%, the selectivity 69.1% of aldehyde, and the mol ratio of n-alkanal and isomery aldehyde is 2.6:1, TOF value is 1423h
-1.
Embodiment 13
Rh (acac) (CO)
2/ [(N-(EO)
16ph) (N-C
2h
5) Pi]
3[(SO
3 -)
3-1] two-phase hydroformylation reaction under/1-laurylene system
Alkene is changed to 1-laurylene, reaction times 2h, and remaining reaction condition and step are with embodiment 3, and gas chromatographic analysis result is: the transformation efficiency of laurylene is 11.7%, the selectivity 74.4% of aldehyde, and the mol ratio of n-alkanal and isomery aldehyde is 2.5:1, TOF value is 435h
-1.
Embodiment 14
Rh (acac) (CO)
2/ [(N-(EO)
16ph) (N-C
2h
5) Pi]
3[(SO
3 -)
3-1] two-phase hydroformylation reaction under/polystyrene systems
Alkene is changed to vinylbenzene, and remaining reaction condition and step are with embodiment 3, and gas chromatographic analysis result is: cinnamic transformation efficiency is 16.5%, the selectivity 88.7% of aldehyde, and the mol ratio of n-alkanal and isomery aldehyde is 1:4.1, TOF value is 2927h
-1.
Embodiment 15
Rh (acac) (CO)
2/ [(N-(EO)
4ph) (N-C
2h
5) Pi]
2[(SO
3 -)
2-12] two-phase hydroformylation reaction under (o=p=2, n=2)/1-octene system
Under an inert atmosphere, add Rh (acac) (CO) in stainless steel autoclave
2, [(N-(EO)
4ph) (N-C
2h
5) Pi]
2[(SO
3 -)
2-12] and 1-octene, its ratio is: [(N-(EO)
4ph) (N-C
2h
5) Pi]
2[(SO
3 -)
2-12]/Rh (acac) (CO)
2=5:1 (mol ratio), 1-octene/Rh (acac) (CO)
2=1000:1 (mol ratio), then uses synthetic gas (H
2/ CO=1:1) be forced into 5.0MPa, temperature of reaction 100 DEG C, 0.5 hour reaction times, then room temperature is quickly cooled to, still is driven after emptying synthetic gas, system is divided into two-phase naturally, lower floor is the ionic liquid phase containing rhodium catalyst, upper strata is organic phase, also can add normal heptane extraction, obtain the organic phase containing product aldehyde through simple two-phase laminated flow, gas chromatographic analysis result is: the transformation efficiency of 1-octene is 99.2%, the selectivity 74.1% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 1.9:1, TOF value is 1470h
-1.
Embodiment 16
Rh (acac) (CO)
2/ [(N-(EO)
16cH
3) (N-C
2h
5) Pi]
2[(SO
3 -)
2-12] two-phase hydroformylation reaction under (o=p=2, n=2)/1-octene system
Ionic liquid is changed to [(N-(EO)
16cH
3) (N-C
2h
5) Pi]
2[(SO
3 -)
2-12] (o=p=2, n=2), remaining reaction condition and step are with embodiment 15, gas chromatographic analysis result is: the transformation efficiency of 1-octene is 57.3%, the selectivity 46.5% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 2.8:1, TOF value is 533h
-1.
Embodiment 17
Rh (acac) (CO)
2/ [(N-(EO)
4cH
3) (N-C
2h
5) Pi]
2[(SO
3 -)
2-12] two-phase hydroformylation reaction under (o=p=2, n=2)/1-octene system
Ionic liquid is changed to [(N-(EO)
4cH
3) (N-C
2h
5) Pi]
2[(SO
3 -)
2-12] (o=p=2, n=2), remaining reaction condition and step are with embodiment 15, gas chromatographic analysis result is: the transformation efficiency of 1-octene is 42.9%, the selectivity 44.3% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 2.9:1, TOF value is 380h
-1.
Embodiment 18
Rh (acac) (CO)
2/ [(N-(EO)
4ph) (N-C
2h
5) Pi]
2[(SO
3 -)
2-12] two-phase hydroformylation reaction under (o=p=2, n=2)/1-laurylene system
Alkene is changed to 1-laurylene, and remaining reaction condition and step are with embodiment 15, and gas chromatographic analysis result is: the transformation efficiency of 1-laurylene is 43.2%, the selectivity 71.9% of aldehyde, and the mol ratio of n-alkanal and isomery aldehyde is 2.0:1, TOF value is 621h
-1.
Embodiment 19
Rh (acac) (CO)
2/ [(N-(EO)
4ph) (N-C
2h
5) Pi]
2[(SO
3 -)
2-12] two-phase hydroformylation reaction under (o=p=2, n=2)/1-tetradecylene system
Alkene is changed to 1-tetradecylene, and remaining reaction condition and step are with embodiment 15, and gas chromatographic analysis result is: the transformation efficiency of 1-tetradecylene is 40.7%, the selectivity 67.3% of aldehyde, and the mol ratio of n-alkanal and isomery aldehyde is 1.7:1, TOF value is 548h
-1.
Embodiment 20
Rh (acac) (CO)
2/ [(N-(EO)
4ph) (N-C
2h
5) Pi]
2[(SO
3 -)
2-2] two-phase hydroformylation reaction under/1-octene system
Ionic liquid is changed to [(N-(EO)
4ph) (N-C
2h
5) Pi]
2[(SO
3 -)
2-2], remaining reaction condition and step are with embodiment 1, and gas chromatographic analysis result is: the transformation efficiency of 1-octene is 8.8%, the selectivity 74.6% of aldehyde, and the mol ratio of n-alkanal and isomery aldehyde is 2.6:1, TOF value is 1313h
-1.
Embodiment 21
Rh (acac) (CO)
2/ [(N-(EO)
4ph) (N-C
2h
5) Pi] [(SO
3 -)-3] two-phase hydroformylation reaction under/1-octene system
Ionic liquid is changed to [(N-(EO)
4ph) (N-C
2h
5) Pi] [(SO
3 -)-3], remaining reaction condition and step are with embodiment 1, and gas chromatographic analysis result is: the transformation efficiency of 1-octene is 9.2%, the selectivity 70.5% of aldehyde, and the mol ratio of n-alkanal and isomery aldehyde is 2.5:1, TOF value is 1297h
-1.
Embodiment 22
Rh (acac) (CO)
2/ [(N-(EO)
4ph) (N-C
2h
5) Pi]
4[(SO
3 -)
4-4] two-phase hydroformylation reaction under (o=p=0, n=4)/1-octene system
Ionic liquid is changed to [(N-(EO)
4ph) (N-C
2h
5) Pi]
4[(SO
3 -)
4-4] (o=p=0, n=4), remaining reaction condition and step are with embodiment 15, gas chromatographic analysis result is: the transformation efficiency of 1-octene is 96.4%, the selectivity 60.4% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 2.4:1, TOF value is 1165h
-1.
Embodiment 23
Rh (acac) (CO)
2/ [(N-(EO)
4ph) (N-C
2h
5) Pi]
4[(SO
3 -)
4-5] two-phase hydroformylation reaction under (o=p=0, n=4)/1-octene system
Ionic liquid is changed to [(N-(EO)
4ph) (N-C
2h
5) Pi]
4[(SO
3 -)
4-5] (o=p=0, n=4), remaining reaction condition and step are with embodiment 15, gas chromatographic analysis result is: the transformation efficiency of 1-octene is 94.8%, the selectivity 64.6% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 2.4:1, TOF value is 1225h
-1.
Embodiment 24
Rh (acac) (CO)
2/ [(N-(EO)
4ph) (N-C
2h
5) Pi]
2[(SO
3 -)
2-6] two-phase hydroformylation reaction under (o=p=2, n=2)/1-octene system
Ionic liquid is changed to [(N-(EO)
4ph) (N-C
2h
5) Pi]
2[(SO
3 -)
2-6] (o=p=2, n=2), remaining reaction condition and step are with embodiment 15, gas chromatographic analysis result is: the transformation efficiency of 1-octene is 92.4%, the selectivity 65.1% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 2.0:1, TOF value is 1203h
-1.
Embodiment 25
Rh (acac) (CO)
2/ [(N-(EO)
4ph) (N-C
2h
5) Pi]
2[(SO
3 -)
2-7] two-phase hydroformylation reaction under (o=2, q=r=1, s=t=0, n=2)/polystyrene systems
Ionic liquid is changed to [(N-(EO)
4ph) (N-C
2h
5) Pi]
2[(SO
3 -)
2-7] (o=2, q=r=1, s=t=0, n=2), alkene is changed to vinylbenzene, remaining reaction condition and step are with embodiment 15, gas chromatographic analysis result is: cinnamic transformation efficiency is 97.1%, the selectivity 76.7% of aldehyde, and the mol ratio of n-alkanal and isomery aldehyde is 1:4.5, ee value is 39.1%, TOF value is 1490h
-1.
Embodiment 26
Rh (acac) (CO)
2/ [(N-(EO)
4ph) (N-C
2h
5) Pi]
4[(SO
3 -)
4-9] two-phase hydroformylation reaction under (o=p=0, n=4)/1-octene system
Ionic liquid is changed to [(N-(EO)
4ph) (N-C
2h
5) Pi]
4[(SO
3 -)
4-9] (o=p=0, n=4), remaining reaction condition and step are with embodiment 15, gas chromatographic analysis result is: the transformation efficiency of 1-octene is 97.5%, the selectivity 61.0% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 1.9:1, TOF value is 1190h
-1.
Embodiment 27
Rh (acac) (CO)
2/ [(N-(EO)
4ph) (N-C
2h
5) Pi]
2[(SO
3 -)
2-10] two-phase hydroformylation reaction under (o=p=2, n=2)/1-octene system
Ionic liquid is changed to [(N-(EO)
4ph) (N-C
2h
5) Pi]
2[(SO
3 -)
2-10] (o=p=2, n=2), remaining reaction condition and step are with embodiment 15, gas chromatographic analysis result is: the transformation efficiency of 1-octene is 99.1%, the selectivity 71.6% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 2.1:1, TOF value is 1419h
-1.
Embodiment 28
Rh (acac) (CO)
2/ [(N-(EO)
4ph) (N-C
2h
5) Pi]
2[(SO
3 -)
2-11] two-phase hydroformylation reaction under (o=p=2, n=2)/1-octene system
Ionic liquid is changed to [(N-(EO)
4ph) (N-C
2h
5) Pi]
2[(SO
3 -)
2-11] (o=p=2, n=2), remaining reaction condition and step are with embodiment 15, gas chromatographic analysis result is: the transformation efficiency of 1-octene is 98.4%, the selectivity 81.6% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 1.7:1, TOF value is 1606h
-1.
Embodiment 29-36
Rh (acac) (CO)
2/ [(N-(EO)
16ph) (N-C
2h
5) Pi]
3[(SO
3 -)
3-1] two-phase hydroformylation reaction circulation experiment under/1-octene system
Under an inert atmosphere, add Rh (acac) (CO) in stainless steel autoclave
2, [(N-(EO)
16ph) (N-C
2h
5) Pi]
3[(SO
3 -)
3-1] and 1-octene, its ratio is: [(N-(EO)
16ph) (N-C
2h
5) Pi]
3[(SO
3 -)
3-1]/Rh (acac) (CO)
2=20:1 (mol ratio), 1-octene/Rh (acac) (CO)
2=5000:1 (mol ratio), then uses synthetic gas (H
2/ CO=1:1) be forced into 5.0MPa, temperature of reaction 95 DEG C, 5 hours reaction times, then room temperature is quickly cooled to, still is driven after emptying synthetic gas, system is divided into two-phase naturally, decant goes out the organic phase on upper strata, the ionic liquid that rhodium catalyst is contained in lower floor can carry out catalytic cycle next time by adding new 1-octene, gas chromatographic analysis result shows: after 8 catalytic cycle, the selectivity of conversion of olefines rate and aldehyde remains unchanged substantially, and accumulative TON value reaches 36918, and circulation experiment the results are shown in Table embodiment 29-36 in 1.
The circulation experiment of table 1 rhodium catalyst
Claims (8)
1. the polyethers piperidinium salt ionic liquid of a class phosphine functionalization, is characterized in that: the positively charged ion of this kind of phosphine functionalization polyethers piperidinium salt ionic liquid is polyethers piperidines positively charged ion, and negatively charged ion is Water-soluble Sulphonated phosphines negatively charged ion, and its structural formula is:
In formula: m=1-100; R
1for H, C
1-C
16alkyl or phenyl; L=0-100, R
2for H, C
1-C
16alkyl, phenyl or benzyl; R
3represent the negatively charged ion of Water-soluble Sulphonated phosphines, n is the sum of sulfonic group negatively charged ion on Phosphine ligands.
2., according to a class phosphine functionalization polyethers piperidinium salt ionic liquid of claim 1, it is characterized in that Water-soluble Sulphonated phosphines negatively charged ion R in phosphine functionalization polyethers piperidinium salt ionic liquid
3structural formula as follows:
In formula: R
4for C
6h
4-3-SO
3 -; 1,2,3,4,5,6,7,8,9,10,11 and 12 parent fraction being respectively different Water-soluble Sulphonated phosphines, n is the sum of sulfonic group negatively charged ion on Phosphine ligands; O=0,1,2; P=0,1,2; Q=r=0,1; S=t=0,1.
3. according to a class phosphine functionalization polyethers piperidinium salt ionic liquid of claim 1, it is characterized in that: the key intermediate of synthesis phosphine functionalization polyethers piperidinium salt ionic liquid is polyethers piperidinium salt ionic liquid, and its structural formula is as follows:
In formula: m=1-100; R
1for H, C
1-C
16alkyl or phenyl; L=0-100, R
2for H, C
1-C
16alkyl, phenyl or benzyl; R
5for Cl
-, Br
-, BF
4 -, PF
6 -, Tf
2n
-, MsO
-, TsO
-.
4., based on the method for a kind of alkene two-phase hydroformylation of phosphine functionalization polyethers piperidinium salt ionic liquid in claim 1, it is characterized in that: biphase catalytic system is made up of with organic phase ionic liquid phase: ionic liquid comprises polyethers piperidinium salt ionic liquid and the rhodium catalyst of phosphine functionalization mutually; Organic phase comprises reaction substrate alkene and reaction product, or the mixture of the two; Organic phase can introduce solvent, also can not introduce solvent; Hydroformylation reaction carries out under certain temperature of reaction and synthetic gas pressure, can directly be realized the recovery of rhodium catalyst by the liquid/liquid two-phase laminated flow of ionic liquid phase and organic phase and be recycled after reaction terminates; Also can add extraction solvent, and then realize the recovery of rhodium catalyst by liquid/liquid two-phase laminated flow and recycle.
5. according to the method for a kind of alkene two-phase hydroformylation based on phosphine functionalization polyethers piperidinium salt ionic liquid of claim 3, it is characterized in that: under an inert atmosphere, by the polyethers piperidinium salt ionic liquid of phosphine functionalization, rhodium catalyst, substrate olefin mixes in certain proportion, wherein, in phosphine functionalization polyethers piperidinium salt ionic liquid and rhodium catalyst, the mol ratio of rhodium is 3:1-100:1, preferably 5:1-30:1, the mol ratio of rhodium in substrate olefin and rhodium catalyst is made to be 100:1-20000:1, preferably 1000:1-10000:1, synthetic gas pressure is 1-10MPa, temperature of reaction is 70-130 DEG C, reaction times is 0.25-15 hour, can solvent be introduced in system, also can not solubilizing agent, if add 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 phase and organic phase, also extraction solvent can be added, then realized the phase-splitting of rhodium catalyst and organic phase by liquid/liquid two-phase laminated flow, ionic liquid can carry out catalytic cycle next time by adding new alkene.
6., according to the method for a kind of alkene two-phase hydroformylation based on phosphine functionalization polyethers piperidinium salt ionic liquid of claim 3 and 4, it is characterized in that rhodium catalyst is rhodium dicarbonyl acetylacetonate Rh (acac) (CO)
2, RhCl
33H
2o, [Rh (COD)
2] BF
4or [Rh (COD) Cl]
2, COD is 1,5-cyclooctadiene.
7., according to the method for a kind of alkene two-phase hydroformylation based on phosphine functionalization polyethers piperidinium salt ionic liquid of claim 3 and 4, it is characterized in that the substrate olefin used is C
3-C
16straight chain 1-alkene, tetrahydrobenzene, vinylbenzene, p-methylstyrene, o-methyl styrene, p-tert-butylstyrene, p-isobutylstyrene, to methoxy styrene, to chloro-styrene, chloro styrene, 2-vinyl naphthalene, 6-methoxyl group-2-vinyl naphthalene; Reaction product is the mixture of one or more in aldehyde, isomerizing olefins, olefin hydrogenation product.
8. according to the method for a kind of alkene two-phase hydroformylation based on phosphine functionalization polyethers piperidinium salt ionic liquid of claim 3 and 4, it is characterized in that: the organic solvent that organic phase is introduced or extraction solvent are: sherwood oil, hexanaphthene, C
6-C
12mixtures several in a kind of or above-mentioned solvent in alkane, ether, methyl tertiary butyl ether.
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| CN105669404A (en) * | 2016-03-19 | 2016-06-15 | 青岛科技大学 | Method of preparing normal aldehyde in highly selective manner through olefin two-phase hydroformylation on basis of polyether piperidine salt ion liquid |
| CN105693485A (en) * | 2016-03-19 | 2016-06-22 | 青岛科技大学 | Method for preparing normal aldehyde on basis of high selectivity of olefin two-phase hydroformylation of phosphine functionalized polyether piperidine salt ionic liquid |
| CN105753671A (en) * | 2016-03-19 | 2016-07-13 | 青岛科技大学 | Method for high-selectivity preparation of normal aldehyde through olefin two-phase hydroformylation on basis of polyether alkyl guanidinium ionic liquid |
| CN105837419A (en) * | 2016-03-19 | 2016-08-10 | 青岛科技大学 | Method for highly selective preparation of linear aldehyde by olefin two-phase hydroformylation based on phosphine functionalized polyether alkyl guanidine salt ionic liquid |
| CN107790178A (en) * | 2017-11-10 | 2018-03-13 | 福州大学 | Based on three（2,4,6 trimethoxyphenyls）Phosphine ionic-liquid catalyst and preparation method thereof |
| CN107790178B (en) * | 2017-11-10 | 2019-03-12 | 福州大学 | Based on three (2,4,6- trimethoxyphenyl) phosphine ionic-liquid catalysts and preparation method thereof |
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| CN105017314B (en) | 2017-11-03 |
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