CN105753669A - Method for high-selectivity preparation of normal aldehyde through olefin two-phase hydroformylation on basis of phosphine-functionalized polyether imidazolium salt ionic liquid - Google Patents
Method for high-selectivity preparation of normal aldehyde through olefin two-phase hydroformylation on basis of phosphine-functionalized polyether imidazolium salt ionic liquid Download PDFInfo
- Publication number
- CN105753669A CN105753669A CN201610165808.4A CN201610165808A CN105753669A CN 105753669 A CN105753669 A CN 105753669A CN 201610165808 A CN201610165808 A CN 201610165808A CN 105753669 A CN105753669 A CN 105753669A
- Authority
- CN
- China
- Prior art keywords
- ionic liquid
- alkene
- rhodium catalyst
- polyethers
- phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 86
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims abstract description 58
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 49
- 238000007037 hydroformylation reaction Methods 0.000 title claims abstract description 43
- 229920000570 polyether Polymers 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 15
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 239000004721 Polyphenylene oxide Substances 0.000 title abstract 4
- 150000004693 imidazolium salts Chemical class 0.000 title abstract 4
- 238000002360 preparation method Methods 0.000 title abstract 2
- 239000010948 rhodium Substances 0.000 claims abstract description 79
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 65
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 65
- 239000003054 catalyst Substances 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 26
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 26
- 239000000758 substrate Substances 0.000 claims abstract description 12
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 56
- 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 54
- 239000012071 phase Substances 0.000 claims description 48
- 208000035126 Facies Diseases 0.000 claims description 37
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 29
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 28
- 238000007306 functionalization reaction Methods 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 15
- 238000006555 catalytic reaction Methods 0.000 claims description 14
- 238000011084 recovery Methods 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 12
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 238000000605 extraction Methods 0.000 claims description 9
- 239000004912 1,5-cyclooctadiene Substances 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 6
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000005466 alkylenyl group Chemical group 0.000 claims description 4
- 150000001450 anions Chemical class 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
- 239000003960 organic solvent Substances 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 4
- -1 C6-C12Alkane Chemical compound 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- VYXHVRARDIDEHS-UHFFFAOYSA-N 1,5-cyclooctadiene Chemical compound C1CC=CCCC=C1 VYXHVRARDIDEHS-UHFFFAOYSA-N 0.000 claims description 2
- 230000002051 biphasic effect Effects 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 238000005984 hydrogenation reaction Methods 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 150000003003 phosphines Chemical class 0.000 claims description 2
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 239000007788 liquid Substances 0.000 abstract description 14
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 238000005191 phase separation Methods 0.000 abstract 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 103
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 50
- 239000007789 gas Substances 0.000 description 41
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 15
- 238000002512 chemotherapy Methods 0.000 description 15
- 238000004587 chromatography analysis Methods 0.000 description 15
- 239000011734 sodium Substances 0.000 description 12
- 229910000831 Steel Inorganic materials 0.000 description 10
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 7
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- HFDVRLIODXPAHB-UHFFFAOYSA-N 1-tetradecene Chemical group CCCCCCCCCCCCC=C HFDVRLIODXPAHB-UHFFFAOYSA-N 0.000 description 2
- ILPBINAXDRFYPL-UHFFFAOYSA-N 2-octene Chemical compound CCCCCC=CC ILPBINAXDRFYPL-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 description 2
- 238000007172 homogeneous catalysis Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 230000006315 carbonylation Effects 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
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000005672 tetraenes Chemical class 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
- C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
- B01J31/2414—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
- B01J31/2447—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring
- B01J31/2452—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom
- B01J31/2457—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems and phosphine-P atoms as substituents on a ring of the condensed system or on a further attached ring with more than one complexing phosphine-P atom comprising aliphatic or saturated rings, e.g. Xantphos
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
- B01J31/30—Halides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
- B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
-
- 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
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a method for high-selectivity preparation of normal aldehyde through olefin two-phase hydroformylation on the basis of a phosphine-functionalized polyether imidazolium salt ionic liquid. According to the method, a two-phase catalytic system is adopted, the catalytic system comprises a phosphine-functionalized polyether imidazolium salt ionic liquid, a polyether imidazolium salt ionic liquid, a rhodium catalyst, a reaction substrate olefin and a reaction product aldehyde, a liquid/liquid two-phase hydroformylation reaction is performed at certain reaction temperature and under certain synthesis gas pressure, the rhodium catalyst is separated and cycled through simple two-phase separation after the reaction ends, the rhodium catalyst can be recycled multiple times, and the catalytic activity and the selectivity are not remarkably reduced. The TOF value of the system reaches 400-3,300 h<-1> and the catalytic cycle accumulated TON value reaches 33,975.
Description
Technical field
The present invention relates to technical field of chemistry and chemical engineering, more particularly to a kind of alkene biphase hydrogen formyl based on phosphine functionalization polyethers imidazolium ionic liquid
Change the method that high selectivity prepares n-alkanal.
Background technology
The hydroformylation of olefin of rhodium catalysis is typical atomic economy reaction, is also that more carbonylation reported by current document, it has also become system
The Perfected process of standby high-carbon aldehyde/alcohol.The advantage that homogeneous hydroformylation has catalysis activity height, selectivity is good and 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 develops the rapidest as the liquid liquid biphase catalytic system of catalyst carrier, it has also become at present most have application prospect
One of biphase catalytic system.Non-aqueous ionic liquid hydroformylation is vapour pressure, good heat stability and the controlled dissolving extremely low based on ionic liquid
Ability, dissolves rhodium catalyst, serves as " liquid-carrier " of catalyst with ionic liquid, and substrate olefin and product aldehyde are the most miscible with ionic liquid,
React the circulation being realized catalyst after terminating by liquid liquid two-phase laminated flow.
Although non-aqueous ionic liquid hydroformylation to some extent solves the separation circulatory problems of rhodium catalyst, but ionic liquid is in actual applications
Yet suffer from significant limitation.First, non-aqueous ionic liquid catalyst system and catalyzing remains a need for substantial amounts of ionic liquid loaded and dissolves rhodium catalyst no matter
It is that this does not all meet the requirement of Green Chemistry from the point of view of economy or toxicology；Two is the mass transfer that the application of a large amount of ionic liquid makes substrate molecule
Resistance increases, and the negative effect (being caused by the Various Complex factor such as high viscosity, residual impurity) of ionic liquid becomes more notable, causes catalysis activity and choosing
Selecting property degradation.
Recently, we have invented a class and there is the polyoxyalkylene alkyl guanidinium ionic liquid (ZL201210064537.5) of the liquid-solid phase-change characteristic of room temperature, and will
It is applied in the biphase hydroformylation reaction of higher olefins of rhodium catalysis, and this kind of novel functionalized ion liquid can effective immobilized Rh-TPPTS catalysis
Agent, and there is the ability significantly stablizing rhodium catalyst, hydroformylation reaction adds up TON value and reaches 31188.But this two-phase system still suffers from following
Problem: one is to need larger amount of ionic liquid as the carrier of Rh-TPPTS catalyst, and ionic liquid reaches with the mass ratio of rhodium catalyst precursor
1000:1；Two is owing to being limited by biphase catalytic system resistance to mass tranfer, and catalysis activity is the highest, and TOF value only has 10-200h-1；Three is n-alkanal
Regioselectivity poor, the most different than only 2.0:1-2.4:1 (n-alkanal regioselectivity 67-71%).
In another patent (CN201310370138.6), we have invented the polyoxyalkylene alkyl guanidinium ionic liquid of the novel phosphine functionalization of a class, and
The hydroformylation reaction that a homogeneous catalysis system is applied to the higher olefins of rhodium catalysis, this catalyst system and catalyzing is constructed based on this novel ion liquid
Advantage be catalysis activity higher, but need in catalyst system and catalyzing introduce organic solvent, this virtually add catalyst reclaim circulation and post processing
The difficulty of process and energy consumption, organic solvent also can cause environmental and safety problems simultaneously, does not also meet the requirement of Green Chemistry.
In patent CN201510250176.7, we construct alkene biphase hydroformylation body at polyethers imidazolium ionic liquid based on phosphine functionalization
System.Under this system, the characteristic of the existing Phosphine ligands of ionic liquid of phosphine functionalization, complex catalyst can be formed with rhodium, have both again the molten of ionic liquid
Agent performance, may act as the carrier of rhodium catalyst, therefore without the most additional other ionic liquid substantial amounts of, fundamentally solves ionic liquid consumption mistake
A high difficult problem, is simultaneously the most also down to minimum by ionic liquid negative effect in catalytic reaction；But the n-alkanal regioselectivity of this system excessively poor (<
80%).
Summary of the invention
For the deficiencies in the prior art, this patent polyethers based on phosphine functionalization imidazolium ionic liquid, invent a kind of based on phosphine functionalization
The method that the alkene biphase hydroformylation height selectivity of polyethers imidazolium ionic liquid prepares n-alkanal.Invention biphase catalytic system only need additional on a small quantity
Polyethers imidazolium ionic liquid PMILs as the carrier of rhodium catalyst, not only there is higher catalysis activity (TOF=400-3300h-1), super
Long service life (total TON value reaches 33975) and extremely low rhodium number of dropouts (0.03-0.1%), and the regioselectivity of n-alkanal is up to
94.0-98.0% (the most different than 18:1-45:1).
Technical scheme:
Biphasic catalysis reaction system is to be made up of with organic facies ionic liquid phase: ionic liquid includes the polyethers imidazolium ionic liquid of phosphine functionalization mutually
PPMILs, polyethers imidazolium ionic liquid PMILs and rhodium catalyst；Organic facies is reaction substrate straight chain 1-alkene or linear internal or above-mentioned alkene
Mixture, or product, or above-mentioned alkene and the mixture of product；Organic facies can introduce solvent, it is possible to not solubilizer；Hydroformylation
Reaction is carried out under certain reaction temperature and synthesis gas pressure, and reaction can directly be realized by the two-phase laminated flow of ionic liquid phase and organic facies after terminating
The recovery of rhodium catalyst and recycling；Also extractant be can add, recovery and the recycling of rhodium catalyst realized the most again by two-phase laminated flow；
The structure of polyethers imidazolium ionic liquid PPMILs of phosphine functionalization is as follows:
In formula: l=1-100；R1For H, C1-C16Alkyl or phenyl；M=0-100, R2For H, C1-C16Alkyl, phenyl or benzyl；R3Table
Showing the anion of Water-soluble Sulphonated phosphines, n is the sum of sulfonic group anion on Phosphine ligands, and its structure is as follows:
In formula: R4For C6H4-3-SO3 -；Q=0,1 or 2；R=0,1 or 2；O=0,1 or 2；P=0,1 or 2；N=4+o+p-q-r.
In the present invention, the structural formula of polyethers imidazolium ionic liquid PMILs of application is as follows:
In formula: l=1-100；R1For H, C1-C16Alkyl or phenyl；M=0-100, R2For H, C1-C16Alkyl, phenyl or benzyl；R5For BF4 -,
PF6 -, Tf2N-, R6SO3 -, wherein R6For alkyl, phenyl, alkyl-substituted phenyl, wherein alkyl is C1-C12Alkyl.
Contrast experiment one (seeing embodiment 1-3): this patent constructs alkene biphase hydroformylation system based on polyethers imidazolium ionic liquid PMILs
Test as a comparison.Biphase catalytic system is to be made up of with organic facies ionic liquid phase: ionic liquid include mutually polyethers imidazolium ionic liquid PMILs,
Rhodium catalyst and biphosphine ligand BISBI-(SO3Na)2(o=p=1, q=r=2), BINA-(SO3Na)2(o=p=1, q=r=2) or
Xantphos-(SO3Na)2(o=p=1, q=r=2)；Organic facies is reaction substrate straight chain 1-alkene；Hydroformylation reaction is in certain reaction temperature
Carrying out under degree and synthesis gas pressure, reaction directly can realize the recovery of rhodium catalyst by the two-phase laminated flow of ionic liquid phase and organic facies and follow after terminating
Ring uses.Test result indicate that: this biphase catalytic system has higher catalysis activity (TOF=150-2100h-1), service life of overlength (total
TON value reaches 38634) and extremely low rhodium number of dropouts (0.03-0.1%), and the regioselectivity of n-alkanal is up to 96-98% (the most different ratio
24:1-45:1)；But this system remains a need for substantial amounts of external ions liquid PMILs dissolves rhodium catalyst, and PMILs reaches with the mol ratio of rhodium catalyst
300:1-500:1。
Contrast experiment two (seeing embodiment 4-6): it is biphase that this patent polyethers based on phosphine functionalization imidazolium ionic liquid PPMILs constructs alkene
Hydroformylation system is tested as a comparison.Biphase catalytic system is to be made up of with organic facies ionic liquid phase: ionic liquid includes the poly-of phosphine functionalization mutually
Ether imidazolium ionic liquid PPMILs and rhodium catalyst；Organic facies is reaction substrate straight chain 1-alkene；Hydroformylation reaction in certain reaction temperature and
Carrying out under synthesis gas pressure, reaction directly can realize the recovery of rhodium catalyst by the two-phase laminated flow of ionic liquid phase and organic facies after terminating and circulation makes
With.Test result indicate that: the catalysis activity of this biphase catalytic system is higher, PPMILs is only 5:1-30:1 with the mol ratio of rhodium catalyst, it is not necessary to outer
Add ionic liquid, thus solve conventional ion liquid biphase catalytic system and need a large amount of ionic liquids as the problem of catalyst carrier；But this system
N-alkanal regioselectivity poor, only 64.3-69.7% (the most different than 1.8:1-2.3:1), main cause is possible to have non-double coordination rhodium catalyst
Formed.
In the present invention, the advantage of contrast experiment one and 2 two catalyst system and catalyzings of contrast experiment is merged: with the polyethers imidazole salts of phosphine functionalization from
Sub-liquid PPMILs replaces the sulfonic acid sodium form biphosphine ligand in contrast experiment one, due to the characteristic of the existing Phosphine ligands of PPMILs, can form complexation with rhodium
Catalyst, has both again the solvent nature of ionic liquid, has good intermiscibility with ionic liquid PMILs, therefore can be substantially reduced external ions liquid
(PMILs is 30:1-50:1 with the mol ratio of rhodium catalyst to the consumption of body PMILs, is contrast experiment one and ZL201210064537.5 intermediate ion liquid
/ 10th of consumption)；Meanwhile, compared with contrast experiment two, owing to introducing a small amount of PMILs in a two-phase system, PPMILs is diluted, and is more easy to
Forming the rhodium catalyst of double coordination, the n-alkanal regioselectivity of this system improves to 94.0-98.0% (the most different than 18.0:1-45.0:1).
The method that typical alkene biphase hydroformylation height selectivity based on phosphine functionalization polyethers imidazolium ionic liquid prepares n-alkanal is as follows: lazy
Under property atmosphere, by polyethers imidazolium ionic liquid PPMILs of phosphine functionalization, polyethers imidazolium ionic liquid PMILs, rhodium catalyst, substrate olefin
Mixing in certain proportion, wherein, substrate olefin is straight chain 1-alkene or linear internal or the mixture of above-mentioned alkene, PPMILs and rhodium catalyst
The mol ratio of middle rhodium is 3:1-100:1, preferably 5:1-30:1；PMILs is 10:1-300:1 with the mol ratio of rhodium catalyst, preferably 30:1-50:1；The end
Thing alkene is 100:1-20000:1 with the mol ratio of rhodium in rhodium catalyst, preferably 1000:1-10000:1；Synthesis gas pressure is 1-10MPa, preferably
3-7MPa；Reaction temperature is 70-130 DEG C, preferably 80-110 DEG C；Response time is 0.25-15 hour；System can introduce solvent, it is possible to be not added with
Solvent, if adding solvent, solvent is 1:10-10:1 with the volume ratio of alkene；After reaction terminates, by ionic liquid phase and biphase point of organic facies
From the recovery realizing rhodium catalyst, it is possible to add extractant, then realized the split-phase of rhodium catalyst and organic facies, ionic liquid by two-phase laminated flow
Catalytic cycle next time can be carried out by adding new alkene.
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.
In the present invention, product is the mixture of one or more in aldehyde, isomerizing olefins, olefin hydrogenation product.
In the present invention, organic facies introduce organic solvent or extractant be: petroleum ether, hexamethylene, C6-C12Alkane, ether, methyl tertbutyl
Mixture several in a kind of or above-mentioned solvent in ether.
Detailed description of the invention
Embodiment 1
Rh(acac)(CO)2/BISBI-(SO3Na)2(o=p=1, q=r=2)/[Ph (EO)16MI(CH3)][CH3SO3 -Biphase hydrogen formyl under]/1-octene system
Change reaction
Under an inert atmosphere, in rustless steel autoclave, Rh (acac) (CO) is added2、BISBI-(SO3Na)2、
[Ph(EO)16MI(CH3)][CH3SO3 -] and 1-octene, its ratio is: BISBI-(SO3Na)2/Rh(acac)(CO)2=5:1 (mol ratio), 1-octene
/Rh(acac)(CO)2=1000:1 (mol ratio), [Ph (EO)16MI(CH3)][CH3SO3 -]/Rh(acac)(CO)2=300:1 (mol ratio), then with closing
Become gas (H2/ CO=1:1) it is forced into 5.0MPa, reaction temperature 100 DEG C, 0.5 hour response time, then it is quickly cooled to room temperature, emptying synthesis
Drive still after gas, realized the recovery of rhodium catalyst by the two-phase laminated flow of ionic liquid phase and organic facies, it is possible to add normal heptane extraction, through simple two
Being separated and obtain the organic facies containing product aldehyde, gas chromatographic analysis result is: the conversion ratio of 1-octene is 23.3%, the chemo-selective 86.5% of aldehyde,
N-alkanal is 24.5:1.0 (regioselectivity 96.1% of n-alkanal) with the mol ratio of isomery aldehyde, and TOF value is 403h-1。
Embodiment 2
Rh(acac)(CO)2/BINA-(SO3Na)2(o=p=1, q=r=2)/[Ph (EO)16MI(CH3)][CH3SO3 -Biphase hydrogen formyl under]/1-octene system
Change reaction
Under an inert atmosphere, in rustless steel autoclave, Rh (acac) (CO) is added2、BINA-(SO3Na)2、[Ph(EO)16MI(CH3)]
[CH3SO3 -] and 1-octene, its ratio is: BINA-(SO3Na)2/Rh(acac)(CO)2=5:1 (mol ratio), 1-octene/Rh (acac) (CO)2=
5000:1 (mol ratio), [Ph (EO)16MI(CH3)][CH3SO3 -]/Rh(acac)(CO)2=300:1 (mol ratio), then with synthesis gas (H2/ CO=1:1)
Be forced into 5.0MPa, reaction temperature 100 DEG C, 0.5 hour response time, be then quickly cooled to room temperature, after emptying synthesis gas, drive still, by from
The two-phase laminated flow of sub-liquid phase and organic facies realizes the recovery of rhodium catalyst, it is possible to add normal heptane extraction, obtains containing producing through simple two-phase laminated flow
The organic facies of thing aldehyde, gas chromatographic analysis result is: the conversion ratio of 1-octene is 21.4%, the chemo-selective 96.5% of aldehyde, n-alkanal and isomery
The mol ratio of aldehyde is 34.0:1.0 (regioselectivity 97.1% of n-alkanal), and TOF value is 2065h-1。
Embodiment 3
Rh(acac)(CO)2/Xantphos-(SO3Na)2(o=p=1, q=r=2)/[Ph (EO)16MI(CH3)][CH3SO3 -Biphase hydrogen first under]/1-octene system
Acylation reaction
Under an inert atmosphere, in rustless steel autoclave, Rh (acac) (CO) is added2、Xantphos-(SO3Na)2、[Ph(EO)16MI(CH3)]
[CH3SO3 -] and 1-octene, its ratio is: Xantphos-(SO3Na)2/Rh(acac)(CO)2=5:1 (mol ratio), 1-octene/Rh (acac) (CO)2=
1000:1 (mol ratio), [Ph (EO)16MI(CH3)][CH3SO3 -]/Rh(acac)(CO)2=300:1 (mol ratio), then with synthesis gas (H2/ CO=1:1)
Be forced into 5.0MPa, reaction temperature 100 DEG C, 0.5 hour response time, be then quickly cooled to room temperature, after emptying synthesis gas, drive still, by from
The two-phase laminated flow of sub-liquid phase and organic facies realizes the recovery of rhodium catalyst, it is possible to add normal heptane extraction, obtains containing producing through simple two-phase laminated flow
The organic facies of thing aldehyde, gas chromatographic analysis result is: the conversion ratio of 1-octene is 27.6%, the chemo-selective 95.0% of aldehyde, n-alkanal and isomery
The mol ratio of aldehyde is 27.0:1.0 (regioselectivity 96.4% of n-alkanal), and TOF value is 524h-1。
Embodiment 4
Rh(acac)(CO)2/[Ph(EO)16MI(CH3)]2[BISBI-(SO3 -)2] biphase hydroformylation reaction under (o=p=1, q=r=2)/1-octene system
Under an inert atmosphere, in rustless steel autoclave, Rh (acac) (CO) is added2、[Ph(EO)16MI(CH3)]2[BISBI-(SO3 -)2] and 1-
Octene, its ratio is: [Ph (EO)16MI(CH3)]2[BISBI-(SO3 -)2]/Rh(acac)(CO)2=5:1 (mol ratio), 1-octene/Rh (acac) (CO)2=
1000:1 (mol ratio), then with synthesis gas (H2/ CO=1:1) it is forced into 5.0MPa, reaction temperature 100 DEG C, 0.5 hour response time, then
Being quickly cooled to room temperature, drive still after emptying synthesis gas, system is divided into biphase naturally, and lower floor is the ionic liquid phase containing rhodium catalyst, and upper strata is for having
Machine phase, it is possible to adding normal heptane extraction, obtain the organic facies containing product aldehyde through simple two-phase laminated flow, gas chromatographic analysis result is: 1-octene
Conversion ratio be 91.6%, the selectivity 94.7% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 1.8:1 (regioselectivity 64.3% of n-alkanal),
TOF value is 1735h-1。
Embodiment 5
Rh(acac)(CO)2/[Ph(EO)16MI(CH3)]2[BINA-(SO3 -)2] biphase hydroformylation reaction under (o=p=1, q=r=2)/1-octene system
Under an inert atmosphere, in rustless steel autoclave, Rh (acac) (CO) is added2、[Ph(EO)16MI(CH3)]2[BINA-(SO3 -)2] and 1-
Octene, its ratio is: [Ph (EO)16MI(CH3)]2[BINA-(SO3 -)2]/Rh(acac)(CO)2=5:1 (mol ratio), 1-octene/Rh (acac) (CO)2=
5000:1 (mol ratio), then with synthesis gas (H2/ CO=1:1) it is forced into 5.0MPa, reaction temperature 100 DEG C, 0.5 hour response time, then
Being quickly cooled to room temperature, drive still after emptying synthesis gas, system is divided into biphase naturally, and lower floor is the ionic liquid phase containing rhodium catalyst, and upper strata is for having
Machine phase, it is possible to adding normal heptane extraction, obtain the organic facies containing product aldehyde through simple two-phase laminated flow, gas chromatographic analysis result is: 1-octene
Conversion ratio be 35.2%, the selectivity 91.5% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 2.3:1 (regioselectivity 69.7% of n-alkanal),
TOF value is 3221h-1。
Embodiment 6
Rh(acac)(CO)2/[Ph(EO)16MI(CH3)]2[Xantphos-(SO3 -)2] biphase hydroformylation is anti-under (o=p=1, q=r=2)/1-octene system
Should
Under an inert atmosphere, in rustless steel autoclave, Rh (acac) (CO) is added2、[Ph(EO)16MI(CH3)]2[Xantphos-(SO3 -)2]
With 1-octene, its ratio is: [Ph (EO)16MI(CH3)]2[Xantphos-(SO3 -)2]/Rh(acac)(CO)2=5:1 (mol ratio), 1-octene
/Rh(acac)(CO)2=1000:1 (mol ratio), then with synthesis gas (H2/ CO=1:1) it is forced into 5.0MPa, reaction temperature 100 DEG C, response time
0.5 hour, being then quickly cooled to room temperature, drive still after emptying synthesis gas, system is divided into biphase naturally, and lower floor is the ionic liquid containing rhodium catalyst
Body phase, upper strata is organic facies, it is possible to adds normal heptane extraction, obtains the organic facies containing product aldehyde, gas chromatographic analysis through simple two-phase laminated flow
Result is: the conversion ratio of 1-octene is 95.6%, the selectivity 93.5% of aldehyde, and n-alkanal is the 1.9:1 (region of n-alkanal with the mol ratio of isomery aldehyde
Selectivity 65.5%), TOF value is 1788h-1。
Embodiment 7
Rh(acac)(CO)2/[Ph(EO)16MI(CH3)]2[BISBI-(SO3 -)2] (o=p=1, q=r=2)/[Ph (EO)16MI(CH3)][CH3SO3 -]/1-octene
Biphase hydroformylation reaction under system
Under an inert atmosphere, in rustless steel autoclave, Rh (acac) (CO) is added2、[Ph(EO)16MI(CH3)]2[BISBI-(SO3 -)2]、
[Ph(EO)16MI(CH3)][CH3SO3 -] and 1-octene, its ratio is: [Ph (EO)16MI(CH3)]2[BISBI-(SO3 -)2]/Rh(acac)(CO)2=5:1 (rubs
That ratio), 1-octene/Rh (acac) (CO)2=1000:1 (mol ratio), [Ph (EO)16MI(CH3)][CH3SO3 -]/Rh(acac)(CO)2=30:1 (mole
Than), then with synthesis gas (H2/ CO=1:1) it is forced into 5.0MPa, reaction temperature 100 DEG C, in 0.5 hour response time, then it is quickly cooled to room
Temperature, is driven still after emptying synthesis gas, is realized the recovery of rhodium catalyst by the two-phase laminated flow of ionic liquid phase and organic facies, it is possible to add normal heptane extraction,
Obtaining the organic facies containing product aldehyde through simple two-phase laminated flow, gas chromatographic analysis result is: the conversion ratio of 1-octene is 88.0%, the chemistry of aldehyde
Selectivity 86.5%, n-alkanal is 18.0:1.0 (regioselectivity 94.7% of n-alkanal) with the mol ratio of isomery aldehyde, and TOF value is 1522h-1。
Embodiment 8
Rh(acac)(CO)2/[Ph(EO)16MI(CH3)]2[BINA-(SO3 -)2] (o=p=1, q=r=2)/[Ph (EO)16MI(CH3)][CH3SO3 -]/1-octene body
Biphase hydroformylation reaction under system
Under an inert atmosphere, in rustless steel autoclave, Rh (acac) (CO) is added2、[Ph(EO)16MI(CH3)]2[BINA-(SO3 -)2]、
[Ph(EO)16MI(CH3)][CH3SO3 -] and 1-octene, its ratio is: [Ph (EO)16MI(CH3)]2[BINA-(SO3 -)2]/Rh(acac)(CO)2=5:1 (rubs
That ratio), 1-octene/Rh (acac) (CO)2=5000:1 (mol ratio), [Ph (EO)16MI(CH3)][CH3SO3 -]/Rh(acac)(CO)2=30:1 (mole
Than), then with synthesis gas (H2/ CO=1:1) it is forced into 5.0MPa, reaction temperature 100 DEG C, in 0.5 hour response time, then it is quickly cooled to room
Temperature, is driven still after emptying synthesis gas, is realized the recovery of rhodium catalyst by the two-phase laminated flow of ionic liquid phase and organic facies, it is possible to add normal heptane extraction,
Obtaining the organic facies containing product aldehyde through simple two-phase laminated flow, gas chromatographic analysis result is: the conversion ratio of 1-octene is 32.6%, the chemistry of aldehyde
Selectivity 90.7%, n-alkanal is 27.0:1.0 (regioselectivity 96.4% of n-alkanal) with the mol ratio of isomery aldehyde, and TOF value is 2957h-1。
Embodiment 9
Rh(acac)(CO)2/[Ph(EO)16MI(CH3)]2[Xantphos-(SO3 -)2] (o=p=1, q=r=2)/[Ph (EO)16MI(CH3)][CH3SO3 -]/1-is pungent
Biphase hydroformylation reaction under alkene system
Under an inert atmosphere, in rustless steel autoclave, Rh (acac) (CO) is added2、[Ph(EO)16MI(CH3)]2[Xantphos-(SO3 -)2]、
[Ph(EO)16MI(CH3)][CH3SO3 -] and 1-octene, its ratio is: [Ph (EO)16MI(CH3)]2[Xantphos-(SO3 -)2]/Rh(acac)(CO)2=
5:1 (mol ratio), 1-octene/Rh (acac) (CO)2=1000:1 (mol ratio), [Ph (EO)16MI(CH3)][CH3SO3 -]/Rh(acac)(CO)2=
30:1 (mol ratio), then with synthesis gas (H2/ CO=1:1) it is forced into 5.0MPa, reaction temperature 100 DEG C, 0.5 hour response time, the most quickly
It is cooled to room temperature, drives still after emptying synthesis gas, realized the recovery of rhodium catalyst by the two-phase laminated flow of ionic liquid phase and organic facies, it is possible to just adding
Heptane extraxtion, obtains the organic facies containing product aldehyde through simple two-phase laminated flow, and gas chromatographic analysis result is: the conversion ratio of 1-octene is 87.5%,
The chemo-selective 88.8% of aldehyde, n-alkanal is 20.0:1.0 (regioselectivity 95.2% of n-alkanal) with the mol ratio of isomery aldehyde, and TOF value is 1554
h-1。
Embodiment 10
Rh(acac)(CO)2/[Ph(EO)4MI(CH3)]2[Xantphos-(SO3 -)2] (o=p=1, q=r=2)/[Ph (EO)4MI(CH3)][4-CH3PhSO3 -]/1-
Biphase hydroformylation reaction under octene system
Ionic liquid is changed to [Ph (EO)4MI(CH3)]2[Xantphos-(SO3 -)2] and [Ph (EO)4MI(CH3)][4-CH3PhSO3 -],
[Ph(EO)4MI(CH3)][4-CH3PhSO3 -]/Rh(acac)(CO)2=50:1 (mol ratio), remaining reaction condition and step are with embodiment 9, gas phase color
Analysis of spectrum result is: the conversion ratio of 1-octene is 89.5%, the chemo-selective 72.7% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde be 21.0:1.0 (just
The regioselectivity 95.5% of structure aldehyde), TOF value is 1301h-1。
Embodiment 11
Rh(acac)(CO)2/[Ph(EO)100MI(CH3)]2[Xantphos-(SO3 -)2] (o=p=1, q=r=2)/[Ph (EO)100MI(CH3)][CH3SO3 -]/1-
Biphase hydroformylation reaction under octene system
Ionic liquid is changed to [Ph (EO)100MI(CH3)]2[Xantphos-(SO3 -)2] and [Ph (EO)100MI(CH3)][CH3SO3 -],
[Ph(EO)100MI(CH3)][CH3SO3 -]/Rh(acac)(CO)2=10:1 (mol ratio), remaining reaction condition and step are with embodiment 9, and gas chromatogram is divided
Analysis result is: the conversion ratio of 1-octene is 91.4%, the chemo-selective 83.2% of aldehyde, and n-alkanal is 23.0:1.0 (n-alkanal with the mol ratio of isomery aldehyde
Regioselectivity 95.8%), TOF value is 1521h-1。
Embodiment 12
Rh(acac)(CO)2/[CH3(EO)16MI(CH3)]2[Xantphos-(SO3 -)2] (o=p=1, q=r=2)/[CH3(EO)16MI(CH3)][BF4]/1-octene
Biphase hydroformylation reaction under system
Ionic liquid is changed to [CH3(EO)16MI(CH3)]2[Xantphos-(SO3 -)2] and [CH3(EO)16MI(CH3)][BF4], remaining reaction condition and step
Rapid with embodiment 9, gas chromatographic analysis result is: the conversion ratio of 1-octene is 25.7%, the chemo-selective 88.7% of aldehyde, n-alkanal and isomery aldehyde
Mol ratio be 18.0:1.0 (regioselectivity 94.7% of n-alkanal), TOF value is 456h-1。
Embodiment 13
Rh(acac)(CO)2/[n-C12H25(EO)16MI(CH3)]2[Xantphos-(SO3 -)2] (o=p=1, q=r=2)/[n-C12H25(EO)16
MI(CH3)][CH3SO3 -Biphase hydroformylation reaction under]/1-octene system
Ionic liquid is changed to [n-C12H25(EO)16MI(CH3)]2[Xantphos-(SO3 -)2] and [n-C12H25(EO)16MI(CH3)][CH3SO3 -], 1-octene
/Rh(acac)(CO)2=5000:1 (mol ratio), remaining reaction condition and step with embodiment 9, gas chromatographic analysis result be: the conversion of 1-octene
Rate is 22.6%, the chemo-selective 91.5% of aldehyde, and n-alkanal is 21.0:1.0 (regioselectivity 95.5% of n-alkanal) with the mol ratio of isomery aldehyde,
TOF value is 2068h-1。
Embodiment 14
Rh(acac)(CO)2/[Ph(EO)16MI(n-C8H17)]2[Xantphos-(SO3 -)2] (o=p=1, q=r=2)/[Ph (EO)16MI(CH3)][CH3SO3 -]/1-
Biphase hydroformylation reaction under octene system
Phosphine functionalized ion liquid is changed to [Ph (EO)16MI(n-C8H17)]2[Xantphos-(SO3 -)2], remaining reaction condition and step are with embodiment 9, gas
Analysis of hplc result is: the conversion ratio of 1-octene is 92.3%, the chemo-selective 91.4% of aldehyde, and n-alkanal is 24.0:1.0 with the mol ratio of isomery aldehyde
(regioselectivity 96.0% of n-alkanal), TOF value is 1687h-1。
Embodiment 15
RhCl3·3H2O/[Ph(EO)16MI(EO)16Ph]2[Xantphos-(SO3 -)2] (o=p=1, q=r=2)/[Ph (EO)16MI(EO)16Ph]
[CH3SO3 -Biphase hydroformylation reaction under]/1-octene system
Rhodium catalyst is changed to RhCl3·3H2O, ionic liquid is changed to [Ph (EO)16MI(EO)16Ph]2[Xantphos-(SO3 -)2] and
[Ph(EO)16MI(EO)16Ph][CH3SO3 -], [Ph (EO)16MI(EO)16Ph][CH3SO3 -]/Rh(acac)(CO)2=20:1 (mol ratio), remaining is anti-
Condition and the step is answered with embodiment 9, gas chromatographic analysis result to be: the conversion ratio of 1-octene is 95.3%, the chemo-selective 94.5% of aldehyde, positive structure
Aldehyde is 23.0:1.0 (regioselectivity 95.8% of n-alkanal) with the mol ratio of isomery aldehyde, and TOF value is 1801h-1。
Embodiment 16
Rh(acac)(CO)2/[Ph(EO)16MI(CH3)]2[Xantphos-(SO3 -)2] (o=p=1, q=r=2)/[Ph (EO)16MI(CH3)][CH3SO3 -]/1-is pungent
Biphase hydroformylation reaction under alkene/n-heptane system
Adding normal heptane in system, normal heptane is 2:1 with the volume ratio of 1-octene, and remaining reaction condition and step are with embodiment 9, gas chromatographic analysis
Result is: the conversion ratio of 1-octene is 48.5%, the chemo-selective 80.6% of aldehyde, and n-alkanal is 18.0:1.0 (n-alkanal with the mol ratio of isomery aldehyde
Regioselectivity 94.7%), TOF value is 782h-1。
Embodiment 17
Rh(acac)(CO)2/[Ph(EO)16MI(CH3)]2[Xantphos-(SO3 -)2] (o=p=1, q=r=2)/[Ph (EO)16MI(CH3)][CH3SO3 -]/1-is own
Biphase hydroformylation reaction under alkene system
Alkene is changed to 1-hexene, remaining reaction condition and step: the conversion ratio of 1-hexene is 93.5%,
The chemo-selective 92.0% of aldehyde, n-alkanal is 24.0:1.0 (regioselectivity 96.0% of n-alkanal) with the mol ratio of isomery aldehyde, and TOF value is
1720h-1。
Embodiment 18
Rh(acac)(CO)2/[Ph(EO)16MI(CH3)]2[Xantphos-(SO3 -)2] (o=p=1, q=r=2)/[Ph (EO)16MI(CH3)][CH3SO3 -]/1-ten
Biphase hydroformylation reaction under tetraene system
Alkene is changed to 1-tetradecylene, remaining reaction condition and step: the conversion ratio of 1-tetradecylene is
59.4%, the chemo-selective 83.7% of aldehyde, n-alkanal is 20.0:1.0 (regioselectivity 95.2% of n-alkanal) with the mol ratio of isomery aldehyde, TOF
Value is 994h-1。
Embodiment 19
Rh(acac)(CO)2/[Ph(EO)16MI(CH3)]2[Xantphos-(SO3 -)2] (o=p=1, q=r=2)/[Ph (EO)16MI(CH3)][CH3SO3 -]/2-is pungent
Biphase hydroformylation reaction under alkene system
Alkene is changed to 2-octene, and the response time is 1h, and remaining reaction condition and step with embodiment 9, gas chromatographic analysis result be: 2-octene
Conversion ratio is 65.5%, the chemo-selective 83.6% of aldehyde, and n-alkanal is 18.0:1.0 (regioselectivity 94.7% of n-alkanal) with the mol ratio of isomery aldehyde,
TOF value is 548h-1。
Embodiment 20-59
Rh(acac)(CO)2/[Ph(EO)16MI(CH3)]2[Xantphos-(SO3 -)2] (o=p=1, q=r=2)/[Ph (EO)16MI(CH3)][CH3SO3 -]/1-is pungent
Biphase hydroformylation reaction circulation experiment under alkene system
Under an inert atmosphere, in rustless steel autoclave, Rh (acac) (CO) is added2、[Ph(EO)16MI(CH3)]2[Xantphos-(SO3 -)2]、
[Ph(EO)16MI(CH3)][CH3SO3 -] and 1-octene, its ratio is: [Ph (EO)16MI(CH3)]2[Xantphos-(SO3 -)2]/Rh(acac)(CO)2=
20:1 (mol ratio), 1-octene/Rh (acac) (CO)2=1000:1 (mol ratio), [Ph (EO)16MI(CH3)][CH3SO3 -]/Rh(acac)(CO)2=
60:1 (mol ratio), then with synthesis gas (H2/ CO=1:1) it is forced into 5.0MPa, reaction temperature 100 DEG C, 6 hours response time, the most quickly
Being cooled to room temperature, drive still after emptying synthesis gas, system is divided into biphase naturally, is decanted off the organic facies on upper strata, and the ionic liquid of rhodium catalyst is contained in lower floor
Body can carry out catalytic cycle next time by adding new 1-octene, and gas chromatographic analysis result shows: after 40 catalytic cycle, alkene
The regioselectivity of conversion ratio, aldehyde chemo-selective and n-alkanal is not decreased obviously, and accumulative TON value reaches 33975, and the rhodium of single cycle runs off
Amount is 0.03-0.1%, and circulation experiment the results are shown in Table embodiment 20-59 in 1.
The circulation experiment of table 1 rhodium catalyst
Claims (6)
1. the method that an alkene biphase hydroformylation height selectivity based on phosphine functionalization polyethers imidazolium ionic liquid prepares n-alkanal, it is characterised in that:
Biphasic catalysis reaction system is to be made up of with organic facies ionic liquid phase: ionic liquid includes the polyethers imidazolium ionic liquid of phosphine functionalization mutually
PPMILs, polyethers imidazolium ionic liquid PMILs and rhodium catalyst；Organic facies be reaction substrate straight chain 1-alkene or linear internal or on
State the mixture of alkene, or product, or above-mentioned alkene and the mixture of product；Organic facies can introduce solvent, it is possible to not solubilizer；
Hydroformylation reaction is carried out under certain reaction temperature and synthesis gas pressure, and reaction can be directly by ionic liquid phase and organic facies after terminating
Two-phase laminated flow realizes recovery and the recycling of rhodium catalyst；Also can add extractant, realize rhodium catalyst by two-phase laminated flow the most again
Reclaim and recycle；The structure of polyethers imidazolium ionic liquid PPMILs of phosphine functionalization is as follows:
In formula: l=1-100；R1For H, C1-C16Alkyl or phenyl；M=0-100, R2For H, C1-C16Alkyl, phenyl or benzyl；R3Table
Showing the anion of Water-soluble Sulphonated phosphines, n is the sum of sulfonic group anion on Phosphine ligands, and its structure is as follows:
In formula: R4For C6H4-3-SO3 -；Q=0,1 or 2；R=0,1 or 2；O=0,1 or 2；P=0,1 or 2；N=4+o+p-q-r.
2. prepare n-alkanal according to a kind of based on phosphine functionalization polyethers imidazolium ionic liquid the alkene biphase hydroformylation height selectivity of claim 1
Method, it is characterised in that the structural formula of polyethers imidazolium ionic liquid PMILs is as follows:
In formula: l=1-100；R1For H, C1-C16Alkyl or phenyl；M=0-100, R2For H, C1-C16Alkyl, phenyl or benzyl；R5For
BF4 -, PF6 -, Tf2N-, R6SO3 -, wherein R6For alkyl, phenyl, alkyl-substituted phenyl, wherein alkyl is C1-C12Alkyl.
3. prepare n-alkanal according to a kind of based on phosphine functionalization polyethers imidazolium ionic liquid the alkene biphase hydroformylation height selectivity of claim 1
Method, is characterized in that: under an inert atmosphere, by polyethers imidazolium ionic liquid PPMILs of phosphine functionalization, polyethers imidazolium ionic liquid
PMILs, rhodium catalyst, substrate olefin mix in certain proportion, and wherein, substrate olefin is straight chain 1-alkene or linear internal or above-mentioned
The mixture of alkene, PPMILs is 3:1-100:1 with the mol ratio of rhodium in rhodium catalyst, preferably 5:1-30:1；PMILs and rhodium catalyst
Mol ratio is 10:1-300:1, preferably 30:1-50:1；Substrate olefin is 100:1-20000:1 with the mol ratio of rhodium in rhodium catalyst, preferably
1000:1-10000:1；Synthesis gas pressure is 1-10MPa, preferably 3-7MPa；Reaction temperature is 70-130 DEG C, preferably 80-110 DEG C；
Response time is 0.25-15 hour；Can introduce solvent in system, it is possible to not solubilizer, if adding solvent, solvent with the volume ratio of alkene is
1:10-10:1；After reaction terminates, realized the recovery of rhodium catalyst by the two-phase laminated flow of ionic liquid phase and organic facies, it is possible to add extraction molten
Agent, then realizes the split-phase of rhodium catalyst and organic facies by two-phase laminated flow, and ionic liquid can be urged by adding new alkene next time
Change circulation.
4. prepare positive structure according to a kind of based on phosphine functionalization polyethers imidazolium ionic liquid the alkene biphase hydroformylation height selectivity of claim 1 and 3
The method of aldehyde, it is characterised in that 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.
5. prepare n-alkanal according to a kind of based on phosphine functionalization polyethers imidazolium ionic liquid the alkene biphase hydroformylation height selectivity of claim 1
Method, it is characterised in that product is the mixture of one or more in aldehyde, isomerizing olefins, olefin hydrogenation product.
6. prepare positive structure according to a kind of based on phosphine functionalization polyethers imidazolium ionic liquid the alkene biphase hydroformylation height selectivity of claim 1 and 3
The method of aldehyde, is characterized in that: organic facies introduce organic solvent or extractant be: petroleum ether, hexamethylene, C6-C12Alkane, ether,
Mixture several in a kind of or above-mentioned solvent in methyl tertiary butyl ether(MTBE).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610165808.4A CN105753669B (en) | 2016-03-19 | 2016-03-19 | A method of the alkene two-phase hydroformylation based on phosphine functionalization polyethers imidazolium ionic liquid is highly selective to prepare n-alkanal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610165808.4A CN105753669B (en) | 2016-03-19 | 2016-03-19 | A method of the alkene two-phase hydroformylation based on phosphine functionalization polyethers imidazolium ionic liquid is highly selective to prepare n-alkanal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105753669A true CN105753669A (en) | 2016-07-13 |
| CN105753669B CN105753669B (en) | 2018-10-12 |
Family
ID=56346124
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610165808.4A Active CN105753669B (en) | 2016-03-19 | 2016-03-19 | A method of the alkene two-phase hydroformylation based on phosphine functionalization polyethers imidazolium ionic liquid is highly selective to prepare n-alkanal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105753669B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111760591A (en) * | 2020-06-12 | 2020-10-13 | 青岛科技大学 | Application of silica-based material loaded polyether functionalized ionic liquid catalyst in olefin hydroformylation reaction |
| CN111804332A (en) * | 2020-06-12 | 2020-10-23 | 青岛科技大学 | Application of polyether functionalized ionic liquid catalyst loaded by resin material in olefin hydroformylation reaction |
| CN116063162A (en) * | 2021-11-01 | 2023-05-05 | 中国石油化工股份有限公司 | Method for hydroformylation of high-carbon olefin and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260147A (en) * | 2011-06-01 | 2011-11-30 | 中国科学院过程工程研究所 | Method for hydroformylation of olefins in ionic liquid solvent |
| CN103478381A (en) * | 2013-09-14 | 2014-01-01 | 陶峰 | Method for making bitter melon preserves |
| CN103570514A (en) * | 2013-10-07 | 2014-02-12 | 青岛科技大学 | Olefin hydroformylation method by homogeneous catalysis-biphase separation |
| CN105017315A (en) * | 2015-04-02 | 2015-11-04 | 青岛科技大学 | Phosphine-functionalized polyether imidazolium-based ionic liquid and application thereof in the hydroformylation of olefins |
-
2016
- 2016-03-19 CN CN201610165808.4A patent/CN105753669B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102260147A (en) * | 2011-06-01 | 2011-11-30 | 中国科学院过程工程研究所 | Method for hydroformylation of olefins in ionic liquid solvent |
| CN103478381A (en) * | 2013-09-14 | 2014-01-01 | 陶峰 | Method for making bitter melon preserves |
| CN103570514A (en) * | 2013-10-07 | 2014-02-12 | 青岛科技大学 | Olefin hydroformylation method by homogeneous catalysis-biphase separation |
| CN105017315A (en) * | 2015-04-02 | 2015-11-04 | 青岛科技大学 | Phosphine-functionalized polyether imidazolium-based ionic liquid and application thereof in the hydroformylation of olefins |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111760591A (en) * | 2020-06-12 | 2020-10-13 | 青岛科技大学 | Application of silica-based material loaded polyether functionalized ionic liquid catalyst in olefin hydroformylation reaction |
| CN111804332A (en) * | 2020-06-12 | 2020-10-23 | 青岛科技大学 | Application of polyether functionalized ionic liquid catalyst loaded by resin material in olefin hydroformylation reaction |
| CN111804332B (en) * | 2020-06-12 | 2023-06-27 | 青岛科技大学 | Application of polyether functionalized ionic liquid catalyst loaded by resin material in olefin hydroformylation reaction |
| CN111760591B (en) * | 2020-06-12 | 2023-06-27 | 青岛科技大学 | Application of silica-based material supported polyether functionalized ionic liquid catalyst in olefin hydroformylation reaction |
| CN116063162A (en) * | 2021-11-01 | 2023-05-05 | 中国石油化工股份有限公司 | Method for hydroformylation of high-carbon olefin and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105753669B (en) | 2018-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105017315B (en) | A kind of phosphine functionalization polyethers imidazolium ionic liquid and its application in hydroformylation of olefin | |
| CN103570514B (en) | The method of a kind of homogeneous catalysis-two-phase laminated flow olefin hydroformylation | |
| CN103483381B (en) | The preparation of one class phosphine functionalized ion liquid and the application in hydroformylation reaction thereof | |
| CN105017319B (en) | One class phosphine functionalization polyethers quaternary phosphonium salt ionic liquid and its application in hydroformylation of olefin | |
| CN105017314B (en) | One class phosphine functionalization polyethers piperidinium salt ionic liquid and its application in hydroformylation of olefin | |
| CN105753669A (en) | Method for high-selectivity preparation of normal aldehyde through olefin two-phase hydroformylation on basis of phosphine-functionalized polyether imidazolium salt ionic liquid | |
| CN105017317B (en) | A method of the alkene two-phase hydroformylation based on phosphine functionalization polyethers ionic liquid of alkyl guanidine salt | |
| CN105001260B (en) | A kind of phosphine functionalization polyethers alkylbenzyldimethylasaltsum saltsum ionic liquid and its application in hydroformylation of olefin | |
| CN105837419A (en) | Method for highly selective preparation of linear aldehyde by olefin two-phase hydroformylation based on phosphine functionalized polyether alkyl guanidine salt ionic liquid | |
| CN105669403B (en) | A method of the alkene two-phase hydroformylation based on phosphine functionalization polyethers pyrrolidinium ionic liquid is highly selective to prepare n-alkanal | |
| CN105732345A (en) | Method for preparing normal aldehyde on basis of high two-phase hydroformylation selectivity of alkene of phosphine-functionalized polyether quaternary ammonium salt ionic liquid | |
| CN105001407B (en) | A kind of phosphine functionalization polyethers pyrrolidinium ions liquid and its application in hydroformylation of olefin | |
| CN105669402B (en) | A method of the alkene two-phase hydroformylation based on phosphine functionalization polyethers quaternary alkylphosphonium salt ionic liquid is highly selective to prepare n-alkanal | |
| CN105693485B (en) | A method of the alkene two-phase hydroformylation based on phosphine functionalization polyethers piperidinium salt ionic liquid is highly selective to prepare n-alkanal | |
| CN105777509B (en) | A method of the alkene two-phase hydroformylation based on phosphine functionalization polyethers pyridiniujm ionic liquid is highly selective to prepare n-alkanal | |
| CN105037421B (en) | A kind of phosphine functionalization polyethers quaternary ammonium salt ionic liquid and its application in hydroformylation of olefin | |
| CN105017316B (en) | A kind of phosphine functionalization polyethers pyridiniujm ionic liquid and its application in hydroformylation of olefin | |
| CN105753670B (en) | A method of the alkene two-phase hydroformylation based on polyethers pyridine ionic liquid is highly selective to prepare n-alkanal | |
| CN105837418A (en) | Method for highly selective preparation of linear aldehyde by olefin two-phase hydroformylation based on phosphine functionalized polyether morpholine salt ionic liquid | |
| CN105777513B (en) | A method of the alkene two-phase hydroformylation based on polyethers pyrrolidinium ionic liquid is highly selective to prepare n-alkanal | |
| CN105669404B (en) | A method of the alkene two-phase hydroformylation based on polyethers piperidines ionic liquid is highly selective to prepare n-alkanal | |
| CN105669401B (en) | A method of the alkene two-phase hydroformylation based on polyethers imidazolium ionic liquid is highly selective to prepare n-alkanal | |
| CN105669405B (en) | A method of the alkene two-phase hydroformylation based on polyethers morpholine ionic liquid is highly selective to prepare n-alkanal | |
| CN105753671B (en) | A method of the alkene two-phase hydroformylation based on polyoxyalkylene alkyl guanidinium ionic liquid is highly selective to prepare n-alkanal | |
| CN105777512B (en) | A method of the alkene two-phase hydroformylation based on polyethers quaternary phosphonium ionic liquid is highly selective to prepare n-alkanal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210910 Address after: No.7 xiazhou Road, Taocheng Town, Yongchun County, Quanzhou City, Fujian Province Patentee after: Ye Hui Address before: 266000 Qingdao University of Science & Technology, 99 Songling Road, Laoshan District, Qingdao, Shandong Patentee before: QINGDAO University OF SCIENCE AND TECHNOLOGY |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211012 Address after: Liu'an Development Zone, Yongchun County, Quanzhou City, Fujian Province (east side of Taoxi bridge) Patentee after: Yongchun County Product Quality Inspection Institute Fujian fragrance product quality inspection center, national incense burning product quality supervision and Inspection Center (Fujian) Address before: No.7 xiazhou Road, Taocheng Town, Yongchun County, Quanzhou City, Fujian Province Patentee before: Ye Hui |
|
| TR01 | Transfer of patent right |