CN105669403A - Method of preparing normal aldehyde in highly selective manner through olefin two-phase hydroformylation on basis of phosphine functionalized polyether pyrrolidine salt ion liquid - Google Patents

Method of preparing normal aldehyde in highly selective manner through olefin two-phase hydroformylation on basis of phosphine functionalized polyether pyrrolidine salt ion liquid Download PDF

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CN105669403A
CN105669403A CN201610164282.8A CN201610164282A CN105669403A CN 105669403 A CN105669403 A CN 105669403A CN 201610164282 A CN201610164282 A CN 201610164282A CN 105669403 A CN105669403 A CN 105669403A
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ionic liquid
alkene
rhodium catalyst
polyethers
alkanal
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CN105669403B (en
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金欣
李淑梅
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Yongchun County Product Quality Inspection Institute Fujian Fragrance Product Quality Inspection Center National Incense Burning Product Quality Supervision And Inspection Center Fujian
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Qingdao University of Science and Technology
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    • 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
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    • 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
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Abstract

The invention relates to a method of preparing normal aldehyde in a highly selective manner through olefin two-phase hydroformylation on the basis of phosphine functionalized polyether pyrrolidine salt ion liquid. The method includes: adopting a two-phase catalysis system which is composed of phosphine functionalized polyether pyrrolidine salt ion liquid, polyether pyrrolidine salt ion liquid, rhodium catalyst, reaction substrate olefin and reaction product aldehyde; performing liquid/liquid two-phase hydroformylation at certain reaction temperature and synthetic gas pressure; after reaction is finished, separation and circulating the rhodium catalyst through simple two-phase separation, wherein the rhodium catalyst can be circulated for use for dozens of times without obviously lowering catalytic activity and selectivity. TOF value of the system reaches 500-2700 h<-1>, catalytic circulating accumulated TON value reaches 32215.

Description

A kind of method preparing n-alkanal based on the biphase hydroformylation height selectivity of alkene of phosphine functionalization polyethers pyrrolidinium ionic liquid
Technical field
The present invention relates to technical field of chemistry and chemical engineering, more particularly to a kind of method preparing n-alkanal based on the biphase hydroformylation height selectivity of alkene of phosphine functionalization polyethers pyrrolidinium ionic liquid.
Background technology
The hydroformylation of olefin of rhodium catalysis is typical atomic economy reaction, is also the more carbonylation of current bibliographical information, it has also become prepare the Perfected process of high-carbon aldehyde/alcohol. Homogeneous hydroformylation has the advantage that catalysis activity is high, selectivity is good and reaction condition is gentle, but for a long time, the separation of rhodium catalyst and Recycling are always up the focus that homogeneous catalysis field is paid close attention to.
In recent years, ionic liquid develops very rapid as the liquid liquid biphase catalytic system of catalyst carrier, it has also become at present most one of biphase catalytic system with application prospect. Non-aqueous ionic liquid hydroformylation is based on the extremely low vapour pressure of ionic liquid, good heat stability and controlled solvability; rhodium catalyst is dissolved; " liquid-carrier " of catalyst is served as with ionic liquid; and substrate olefin and product aldehyde and ionic liquid are not miscible, 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 yet suffers from significant limitation in actual applications. 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 is that this does not all meet the requirement of Green Chemistry from economic or toxicologic angle; Two is that the application of a large amount of ionic liquid makes the resistance to mass tranfer of substrate molecule increase, 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 selectivity 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 in the biphase hydroformylation reaction of higher olefins being applied to rhodium catalysis; this kind of novel functionalized ion liquid can effective immobilized Rh-TPPTS catalyst; and there is the ability stablizing rhodium catalyst significantly, the accumulative TON value of hydroformylation reaction reaches 31188. But this two-phase system still suffers from problems with: one is need larger amount of ionic liquid to reach 1000:1 as the mass ratio of the carrier of Rh-TPPTS catalyst, ionic liquid and rhodium catalyst precursor; Two is the restriction owing to being subject to biphase catalytic system resistance to mass tranfer, and catalysis activity is not high, and TOF value only has 10-200h-1; Three is that the regioselectivity of n-alkanal is poor, and just different ratio is 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 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 and catalyzing is that catalysis activity is higher, but need to introduce organic solvent in catalyst system and catalyzing, this virtually adds catalyst and reclaims difficulty and the energy consumption of circulation and last handling process, organic solvent also can cause environment and safety problem simultaneously, the requirement of Green Chemistry is not met yet.
In patent CN201510250460.4, we construct the biphase hydroformylation system of alkene based on the polyethers pyrrolidinium ionic liquid of phosphine functionalization. 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 solvent nature of ionic liquid, may act as the carrier of rhodium catalyst, therefore without additional other ionic liquid substantial amounts of again, fundamentally solve the difficult problem that ionic liquid consumption is too high, also ionic liquid negative effect in catalytic reaction is minimized simultaneously; But the n-alkanal regioselectivity of this system excessively poor (< 80%).
Summary of the invention
For the deficiencies in the prior art, this patent, based on the polyethers pyrrolidinium ionic liquid of phosphine functionalization, has invented a kind of method preparing n-alkanal based on the biphase hydroformylation height selectivity of alkene of phosphine functionalization polyethers pyrrolidinium ionic liquid. The biphase catalytic system of invention only needs additional a small amount of polyethers pyrrolidinium ionic liquid PPYRILs as the carrier of rhodium catalyst, not only has higher catalysis activity (TOF=500-2700h-1), service life (total TON value reaches 32215) of overlength and extremely low rhodium number of dropouts (< 0.2%), and the regioselectivity of n-alkanal is up to 95.0-98.0% (just different from 19:1-45:1).
Technical scheme:
Biphasic catalysis reaction system is to be made up of with organic facies ionic liquid phase: ionic liquid includes the polyethers pyrrolidinium ionic liquid PPPYRILs of phosphine functionalization, polyethers pyrrolidinium ionic liquid PPYRILs and rhodium catalyst mutually; Organic facies is the mixture of reaction substrate straight chain 1-alkene or linear internal or above-mentioned alkene, or product, or the mixture of above-mentioned alkene and product; Organic facies can introduce solvent, it is possible to not solubilizer; Hydroformylation reaction carries out under certain reaction temperature and synthesis gas pressure, and reaction can realize recovery and the recycling of rhodium catalyst either directly through the two-phase laminated flow of ionic liquid phase and organic facies after terminating; Also extractant be can add, recovery and the recycling of rhodium catalyst then realized again through two-phase laminated flow; The structure of the polyethers pyrrolidinium ionic liquid PPPYRILs of phosphine functionalization is as follows:
In formula: l=1-100; R1For H, C1-C16Alkyl, phenyl or benzyl; M=0-100, R2For H, C1-C16Alkyl, phenyl or benzyl; R3Representing 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 the polyethers pyrrolidinium ionic liquid PPYRILs of application is as follows:
In formula: l=1-100; R1For H, C1-C16Alkyl, phenyl or benzyl; 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 (referring to embodiment 1-3): this patent constructs the biphase hydroformylation system of alkene based on polyethers pyrrolidinium ionic liquid PPYRILs and tests as a comparison. Biphase catalytic system is to be made up of with organic facies ionic liquid phase: ionic liquid includes polyethers pyrrolidinium ionic liquid PPYRILs, rhodium catalyst and biphosphine ligand BISBI-(SO mutually3Na)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 carries out under certain reaction temperature and synthesis gas pressure, and reaction can realize recovery and the recycling of rhodium catalyst either directly through the two-phase laminated flow of ionic liquid phase and organic facies after terminating. Test result indicate that: this biphase catalytic system has higher catalysis activity (TOF=260-2000h-1), service life (total TON value reaches 34387) of overlength and extremely low rhodium number of dropouts (0.05-0.15%), and the regioselectivity of n-alkanal is up to 96-98% (just different from 24:1-45:1); But this system remains a need for substantial amounts of external ions liquid PPYRILs dissolving rhodium catalyst, and the mol ratio of PPYRILs and rhodium catalyst reaches 300:1-500:1.
Contrast experiment two (referring to embodiment 4-6): this patent constructs the biphase hydroformylation system of alkene based on the polyethers pyrrolidinium ionic liquid PPPYRILs of phosphine functionalization and tests as a comparison. Biphase catalytic system is to be made up of with organic facies ionic liquid phase: ionic liquid includes polyethers pyrrolidinium ionic liquid PPPYRILs and the rhodium catalyst of phosphine functionalization mutually; Organic facies is reaction substrate straight chain 1-alkene; Hydroformylation reaction carries out under certain reaction temperature and synthesis gas pressure, and reaction can realize recovery and the recycling of rhodium catalyst either directly through the two-phase laminated flow of ionic liquid phase and organic facies after terminating. Test result indicate that: the catalysis activity of this biphase catalytic system is higher, the mol ratio of PPPYRILs and rhodium catalyst is only 5:1-30:1, without external ions liquid, need a large amount of ionic liquids as the problem of catalyst carrier thus solving conventional ion liquid biphase catalytic system; But the n-alkanal regioselectivity of this system is poor, being only 61.5-68.8% (just different from 1.6:1-2.2:1), main cause is possible have non-double coordination rhodium catalyst to be formed.
In the present invention, the advantage of contrast experiment one and 2 two catalyst system and catalyzings of contrast experiment is merged: replace the sulfonic acid sodium form biphosphine ligand in contrast experiment one with the polyethers pyrrolidinium ionic liquid PPPYRILs of phosphine functionalization, characteristic due to the existing Phosphine ligands of PPPYRILs, complex catalyst can be formed with rhodium, have both again the solvent nature of ionic liquid, with ionic liquid PPYRILs, there is good intermiscibility, therefore (mol ratio of PPYRILs and rhodium catalyst is 30:1-50:1 can be substantially reduced the consumption of external ions liquid PPYRILs, it is 1/10th of contrast experiment one and ZL201210064537.5 intermediate ion volume), simultaneously, compared with contrast experiment two, it is diluted owing to introducing a small amount of PPYRILs, PPPYRILs in a two-phase system, being more likely formed the rhodium catalyst of double coordination, the n-alkanal regioselectivity of this system is increased to 95.0-98.0% (just different from 19.0:1-45.0:1).
The method that the typical alkene biphase hydroformylation height selectivity based on phosphine functionalization polyethers pyrrolidinium ionic liquid prepares n-alkanal is as follows: under an inert atmosphere, the polyethers pyrrolidinium ionic liquid PPPYRILs of phosphine functionalization, polyethers pyrrolidinium ionic liquid PPYRILs, rhodium catalyst, substrate olefin are mixed in certain proportion, wherein, substrate olefin is the mixture of straight chain 1-alkene or linear internal or above-mentioned alkene, PPPYRILs is 3:1-100:1 with the mol ratio of rhodium in rhodium catalyst, it is preferred to 5:1-30:1; The mol ratio of PPYRILs and rhodium catalyst is 10:1-300:1, it is preferred to 30:1-50:1; Substrate olefin is 100:1-20000:1 with the mol ratio of rhodium in rhodium catalyst, it is preferred to 1000:1-10000:1; Synthesis gas pressure is 1-10MPa, it is preferred to 3-7MPa; Reaction temperature is 70-130 DEG C, it is preferred to 80-110 DEG C; Response time is 0.25-15 hour; System can introduce solvent, it is possible to not solubilizer, if the volume ratio adding solvent, solvent and alkene is 1:10-10:1; After reaction terminates, the recovery of rhodium catalyst is realized by the two-phase laminated flow of ionic liquid phase and organic facies, also can adding extractant, then pass through two-phase laminated flow and realize point phase of rhodium catalyst and organic facies, ionic liquid passes through to add new alkene mutually can carry out catalytic cycle next time.
In the present invention, rhodium catalyst is rhodium dicarbonyl acetylacetonate Rh (acac) (CO)2、RhCl3·3H2O、[Rh(COD)2]BF4Or [Rh (COD) Cl]2, COD is 1,5-cyclo-octadiene.
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-C12Mixture several in a kind of or above-mentioned solvent in alkane, ether, methyl tertiary butyl ether(MTBE).
Detailed description of the invention
Embodiment 1
Rh(acac)(CO)2/BISBI-(SO3Na)2(o=p=1, q=r=2)/[(N-(EO)16Ph)(N-CH3)Pyrr][CH3SO3 -Biphase hydroformylation reaction under]/1-octene system
Under an inert atmosphere, in rustless steel autoclave, Rh (acac) (CO) is added2、BISBI-(SO3Na)2、[(N-(EO)16Ph)(N-CH3)Pyrr][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), [(N-(EO)16Ph)(N-CH3)Pyrr][CH3SO3 -]/Rh(acac)(CO)2=300:1 (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 room temperature it is quickly cooled to, still is driven after emptying synthesis gas, the recovery of rhodium catalyst is realized by the two-phase laminated flow of ionic liquid phase and organic facies, also can add normal heptane to extract, the organic facies containing product aldehyde is obtained through simple two-phase laminated flow, gas chromatographic analysis result is: the conversion ratio of 1-octene is 29.5%, the mol ratio of the chemo-selective 88.0% of aldehyde, n-alkanal and isomery aldehyde is 26.0:1.0 (regioselectivity 96.3% of n-alkanal), and TOF value is 519h-1。
Embodiment 2
Rh(acac)(CO)2/BINA-(SO3Na)2(o=p=1, q=r=2)/[(N-(EO)16Ph)(N-CH3)Pyrr][CH3SO3 -Biphase hydroformylation reaction under]/1-octene system
Under an inert atmosphere, in rustless steel autoclave, Rh (acac) (CO) is added2、BINA-(SO3Na)2、[(N-(EO)16Ph)(N-CH3)Pyrr][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), [(N-(EO)16Ph)(N-CH3)Pyrr][CH3SO3 -]/Rh(acac)(CO)2=300:1 (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 room temperature it is quickly cooled to, still is driven after emptying synthesis gas, the recovery of rhodium catalyst is realized by the two-phase laminated flow of ionic liquid phase and organic facies, also can add normal heptane to extract, the organic facies containing product aldehyde is obtained through simple two-phase laminated flow, gas chromatographic analysis result is: the conversion ratio of 1-octene is 21.0%, the mol ratio of the chemo-selective 94.5% of aldehyde, n-alkanal and isomery aldehyde is 33.0:1.0 (regioselectivity 97.1% of n-alkanal), and TOF value is 1985h-1。
Embodiment 3
Rh(acac)(CO)2/Xantphos-(SO3Na)2(o=p=1, q=r=2)/[(N-(EO)16Ph)(N-CH3)Pyrr][CH3SO3 -Biphase hydroformylation reaction under]/1-octene system
Under an inert atmosphere, in rustless steel autoclave, Rh (acac) (CO) is added2、Xantphos-(SO3Na)2、[(N-(EO)16Ph)(N-CH3)Pyrr][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), [(N-(EO)16Ph)(N-CH3)Pyrr][CH3SO3 -]/Rh(acac)(CO)2=300:1 (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 room temperature it is quickly cooled to, still is driven after emptying synthesis gas, the recovery of rhodium catalyst is realized by the two-phase laminated flow of ionic liquid phase and organic facies, also can add normal heptane to extract, the organic facies containing product aldehyde is obtained through simple two-phase laminated flow, gas chromatographic analysis result is: the conversion ratio of 1-octene is 31.6%, the chemo-selective 93.6% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 28.0:1.0 (regioselectivity 96.6% of n-alkanal), TOF value is 592h-1。
Embodiment 4
Rh(acac)(CO)2/[(N-(EO)16Ph)(N-CH3)Pyrr]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、[(N-(EO)16Ph)(N-CH3)Pyrr]2[BISBI-(SO3 -)2] and 1-octene, its ratio is: [(N-(EO)16Ph)(N-CH3)Pyrr]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 room temperature it is quickly cooled to, still is driven after emptying synthesis gas, system is divided into biphase naturally, lower floor is the ionic liquid phase containing rhodium catalyst, upper strata is organic facies, also can add normal heptane to extract, the organic facies containing product aldehyde is obtained through simple two-phase laminated flow, gas chromatographic analysis result is: the conversion ratio of 1-octene is 94.5%, the selectivity 93.6% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 1.6:1 (regioselectivity 61.5% of n-alkanal), TOF value is 1769h-1。
Embodiment 5
Rh(acac)(CO)2/[(N-(EO)16Ph)(N-CH3)Pyrr]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、[(N-(EO)16Ph)(N-CH3)Pyrr]2[BINA-(SO3 -)2] and 1-octene, its ratio is: [(N-(EO)16Ph)(N-CH3)Pyrr]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 room temperature it is quickly cooled to, still is driven after emptying synthesis gas, system is divided into biphase naturally, lower floor is the ionic liquid phase containing rhodium catalyst, upper strata is organic facies, also can add normal heptane to extract, the organic facies containing product aldehyde is obtained through simple two-phase laminated flow, gas chromatographic analysis result is: the conversion ratio of 1-octene is 32.2%, the selectivity 89.5% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 2.1:1 (regioselectivity 67.7% of n-alkanal), TOF value is 2882h-1。
Embodiment 6
Rh(acac)(CO)2/[(N-(EO)16Ph)(N-CH3)Pyrr]2[Xantphos-(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、[(N-(EO)16Ph)(N-CH3)Pyrr]2[Xantphos-(SO3 -)2] and 1-octene, its ratio is: [(N-(EO)16Ph)(N-CH3)Pyrr]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, 0.5 hour response time, then room temperature it is quickly cooled to, still is driven after emptying synthesis gas, system is divided into biphase naturally, lower floor is the ionic liquid phase containing rhodium catalyst, upper strata is organic facies, also can add normal heptane to extract, the organic facies containing product aldehyde is obtained through simple two-phase laminated flow, gas chromatographic analysis result is: the conversion ratio of 1-octene is 95.3%, the selectivity 95.5% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 2.2:1 (regioselectivity 68.8% of n-alkanal), TOF value is 1820h-1。
Embodiment 7
Rh(acac)(CO)2/[(N-(EO)16Ph)(N-CH3)Pyrr]2[BISBI-(SO3 -)2] (o=p=1, q=r=2)/[(N-(EO)16Ph)(N-CH3)Pyrr][CH3SO3 -Biphase hydroformylation reaction under]/1-octene system
Under an inert atmosphere, in rustless steel autoclave, Rh (acac) (CO) is added2、[(N-(EO)16Ph)(N-CH3)Pyrr]2 [BISBI-(SO3 -)2]、[(N-(EO)16Ph)(N-CH3)Pyrr][CH3SO3 -] and 1-octene, its ratio is: [(N-(EO)16Ph)(N-CH3)Pyrr]2[BISBI-(SO3 -)2]/Rh(acac)(CO)2=5:1 (mol ratio), 1-octene/Rh (acac) (CO)2=1000:1 (mol ratio), [(N-(EO)16Ph)(N-CH3)Pyrr][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, then room temperature it is quickly cooled to, still is driven after emptying synthesis gas, the recovery of rhodium catalyst is realized by the two-phase laminated flow of ionic liquid phase and organic facies, also can add normal heptane to extract, the organic facies containing product aldehyde is obtained through simple two-phase laminated flow, gas chromatographic analysis result is: the conversion ratio of 1-octene is 85.8%, the mol ratio of the chemo-selective 84.3% of aldehyde, n-alkanal and isomery aldehyde is 20.0:1.0 (regioselectivity 95.2% of n-alkanal), and TOF value is 1447h-1。
Embodiment 8
Rh(acac)(CO)2/[(N-(EO)16Ph)(N-CH3)Pyrr]2[BINA-(SO3 -)2] (o=p=1, q=r=2)/[(N-(EO)16Ph)(N-CH3)Pyrr][CH3SO3 -Biphase hydroformylation reaction under]/1-octene system
Under an inert atmosphere, in rustless steel autoclave, Rh (acac) (CO) is added2、[(N-(EO)16Ph)(N-CH3)Pyrr]2[BINA-(SO3 -)2]、[(N-(EO)16Ph)(N-CH3)Pyrr][CH3SO3 -] and 1-octene, its ratio is: [(N-(EO)16Ph)(N-CH3)Pyrr]2[BINA-(SO3 -)2]/Rh(acac)(CO)2=5:1 (mol ratio), 1-octene/Rh (acac) (CO)2=5000:1 (mol ratio), [(N-(EO)16Ph)(N-CH3)Pyrr][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, then room temperature it is quickly cooled to, still is driven after emptying synthesis gas, the recovery of rhodium catalyst is realized by the two-phase laminated flow of ionic liquid phase and organic facies, also can add normal heptane to extract, the organic facies containing product aldehyde is obtained through simple two-phase laminated flow, gas chromatographic analysis result is: the conversion ratio of 1-octene is 30.6%, the mol ratio of the chemo-selective 87.4% of aldehyde, n-alkanal and isomery aldehyde is 26.5:1.0 (regioselectivity 96.4% of n-alkanal), and TOF value is 2674h-1。
Embodiment 9
Rh(acac)(CO)2/[(N-(EO)16Ph)(N-CH3)Pyrr]2[Xantphos-(SO3 -)2] (o=p=1, q=r=2)/[(N-(EO)16Ph)(N-CH3)Pyrr][CH3SO3 -Biphase hydroformylation reaction under]/1-octene system
Under an inert atmosphere, in rustless steel autoclave, Rh (acac) (CO) is added2、[(N-(EO)16Ph)(N-CH3)Pyrr]2[Xantphos-(SO3 -)2]、[(N-(EO)16Ph)(N-CH3)Pyrr][CH3SO3 -] and 1-octene, its ratio is: [(N-(EO)16Ph)(N-CH3)Pyrr]2[Xantphos-(SO3 -)2]/Rh(acac)(CO)2=5:1 (mol ratio), 1-octene/Rh (acac) (CO)2=1000:1 (mol ratio), [(N-(EO)16Ph)(N-CH3)Pyrr][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, then room temperature it is quickly cooled to, still is driven after emptying synthesis gas, the recovery of rhodium catalyst is realized by the two-phase laminated flow of ionic liquid phase and organic facies, also can add normal heptane to extract, the organic facies containing product aldehyde is obtained through simple two-phase laminated flow, gas chromatographic analysis result is: the conversion ratio of 1-octene is 90.4%, the mol ratio of the chemo-selective 91.6% of aldehyde, n-alkanal and isomery aldehyde is 22.0:1.0 (regioselectivity 95.7% of n-alkanal), and TOF value is 1656h-1。
Embodiment 10
Rh(acac)(CO)2/[(N-(EO)4Ph)(N-CH3)Pyrr]2[Xantphos-(SO3 -)2] (o=p=1, q=r=2)/[(N-(EO)4Ph)(N-CH3)Pyrr][4-CH3PhSO3 -Biphase hydroformylation reaction under]/1-octene system
Ionic liquid is changed to [(N-(EO)4Ph)(N-CH3)Pyrr]2[Xantphos-(SO3 -)2] and [(N-(EO)4Ph)(N-CH3)Pyrr][4-CH3PhSO3 -], [(N-(EO)4Ph)(N-CH3)Pyrr][4-CH3PhSO3 -]/Rh(acac)(CO)2=50:1 (mol ratio), remaining reaction condition and step are with embodiment 9, gas chromatographic analysis result is: the conversion ratio of 1-octene is 83.8%, the chemo-selective 72.4% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 23.0:1.0 (regioselectivity 95.8% of n-alkanal), and TOF value is 1213h-1。
Embodiment 11
Rh(acac)(CO)2/[(N-(EO)100Ph)(N-CH3)Pyrr]2[Xantphos-(SO3 -)2] (o=p=1, q=r=2)/[(N-(EO)100Ph)(N-CH3)Pyrr][CH3SO3 -Biphase hydroformylation reaction under]/1-octene system
Ionic liquid is changed to [(N-(EO)100Ph)(N-CH3)Pyrr]2[Xantphos-(SO3 -)2] and [(N-(EO)100Ph)(N-CH3)Pyrr][CH3SO3 -], [(N-(EO)100Ph)(N-CH3)Pyrr][CH3SO3 -]/Rh(acac)(CO)2=10:1 (mol ratio), remaining reaction condition and step are with embodiment 9, gas chromatographic analysis result is: the conversion ratio of 1-octene is 93.4%, the chemo-selective 92.5% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 25.0:1.0 (regioselectivity 96.2% of n-alkanal), and TOF value is 1728h-1。
Embodiment 12
Rh(acac)(CO)2/[(N-(EO)16CH3)(N-CH3)Pyrr]2[Xantphos-(SO3 -)2] (o=p=1, q=r=2)/[(N-(EO)16CH3)(N-CH3)Pyrr][BF4Biphase hydroformylation reaction under]/1-octene system
Ionic liquid is changed to [(N-(EO)16CH3)(N-CH3)Pyrr]2[Xantphos-(SO3 -)2] and [(N-(EO)16CH3)(N-CH3)Pyrr][BF4], remaining reaction condition and step are with embodiment 9, and gas chromatographic analysis result is: the conversion ratio of 1-octene is 29.3%, the chemo-selective 86.3% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 19.0:1.0 (regioselectivity 95.0% of n-alkanal), and TOF value is 506h-1。
Embodiment 13
Rh(acac)(CO)2/[(N-(EO)16(n-C12H25))(N-CH3)Pyrr]2[Xantphos-(SO3 -)2] (o=p=1, q=r=2)/[(N-(EO)16(n-C12H25))(N-CH3)Pyrr][CH3SO3 -Biphase hydroformylation reaction under]/1-octene system
Ionic liquid is changed to [(N-(EO)16(n-C12H25))(N-CH3)Pyrr]2[Xantphos-(SO3 -)2] and [(N-(EO)16(n-C12H25))(N-CH3)Pyrr][CH3SO3 -], 1-octene/Rh (acac) (CO)2=5000:1 (mol ratio), remaining reaction condition and step are with embodiment 9, gas chromatographic analysis result is: the conversion ratio of 1-octene is 20.6%, the chemo-selective 93.3% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 22.0:1.0 (regioselectivity 95.7% of n-alkanal), and TOF value is 1922h-1。
Embodiment 14
Rh(acac)(CO)2/[(N-(EO)16Ph)(N-n-C16H33)Pyrr]2[Xantphos-(SO3 -)2] (o=p=1, q=r=2)/[(N-(EO)16Ph)(N-n-C16H33)Pyrr][CH3SO3 -Biphase hydroformylation reaction under]/1-octene system
Ionic liquid is changed to [(N-(EO)16Ph)(N-n-C16H33)Pyrr]2[Xantphos-(SO3 -)2] and [(N-(EO)16Ph)(N-n-C16H33)Pyrr][CH3SO3 -], 1-octene/Rh (acac) (CO)2=5000:1 (mol ratio), remaining reaction condition and step are with embodiment 9, gas chromatographic analysis result is: the conversion ratio of 1-octene is 26.3%, the chemo-selective 90.5% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 25.0:1.0 (regioselectivity 96.2% of n-alkanal), and TOF value is 2380h-1。
Embodiment 15
RhCl3·3H2O/[(N-(EO)16Ph)(N-(EO)16Ph)Pyrr]2[Xantphos-(SO3 -)2] (o=p=1, q=r=2)/[(N-(EO)16Ph)(N-(EO)16Ph)Pyrr][CH3SO3 -Biphase hydroformylation reaction under]/1-octene system
Rhodium catalyst is changed to RhCl3·3H2O, ionic liquid is changed to [(N-(EO)16Ph)(N-(EO)16Ph)Pyrr]2[Xantphos-(SO3 -)2] and [(N-(EO)16Ph)(N-(EO)16Ph)Pyrr][CH3SO3 -], [(N-(EO)16Ph)(N-(EO)16Ph)Pyrr][CH3SO3 -]/Rh(acac)(CO)2=20:1 (mol ratio), remaining reaction condition and step are with embodiment 9, gas chromatographic analysis result is: the conversion ratio of 1-octene is 97.6%, the chemo-selective 93.5% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 21.0:1.0 (regioselectivity 95.5% of n-alkanal), and TOF value is 1825h-1。
Embodiment 16
Rh(acac)(CO)2/[(N-(EO)16Ph)(N-CH3)Pyrr]2[Xantphos-(SO3 -)2] (o=p=1, q=r=2)/[(N-(EO)16Ph)(N-CH3)Pyrr][CH3SO3 -Biphase hydroformylation reaction under]/1-octene/n-heptane system
System adds normal heptane, the volume ratio of normal heptane and 1-octene is 2:1, remaining reaction condition and step are with embodiment 9, gas chromatographic analysis result is: the conversion ratio of 1-octene is 53.7%, the chemo-selective 84.6% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 20.0:1.0 (regioselectivity 95.2% of n-alkanal), and TOF value is 909h-1。
Embodiment 17
Rh(acac)(CO)2/[(N-(EO)16Ph)(N-CH3)Pyrr]2[Xantphos-(SO3 -)2] (o=p=1, q=r=2)/[(N-(EO)16Ph)(N-CH3)Pyrr][CH3SO3 -Biphase hydroformylation reaction under]/1-hexene system
Alkene is changed to 1-hexene, remaining reaction condition and step are with embodiment 9, gas chromatographic analysis result is: the conversion ratio of 1-hexene is 92.4%, the chemo-selective 95.3% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 25.0:1.0 (regioselectivity 96.2% of n-alkanal), and TOF value is 1761h-1。
Embodiment 18
Rh(acac)(CO)2/[(N-(EO)16Ph)(N-CH3)Pyrr]2[Xantphos-(SO3 -)2] (o=p=1, q=r=2)/[(N-(EO)16Ph)(N-CH3)Pyrr][CH3SO3 -Biphase hydroformylation reaction under]/1-tetradecylene system
Alkene is changed to 1-tetradecylene, remaining reaction condition and step are with embodiment 9, gas chromatographic analysis result is: the conversion ratio of 1-tetradecylene is 61.0%, the chemo-selective 87.5% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 21.0:1.0 (regioselectivity 95.5% of n-alkanal), and TOF value is 1068h-1。
Embodiment 19
Rh(acac)(CO)2/[(N-(EO)16Ph)(N-CH3)Pyrr]2[Xantphos-(SO3 -)2] (o=p=1, q=r=2)/[(N-(EO)16Ph)(N-CH3)Pyrr][CH3SO3 -Biphase hydroformylation reaction under]/2-octene system
Alkene is changed to 2-octene, response time is 1h, remaining reaction condition and step are with embodiment 9, gas chromatographic analysis result is: the conversion ratio of 2-octene is 70.8%, the chemo-selective 78.4% of aldehyde, the mol ratio of n-alkanal and isomery aldehyde is 19.0:1.0 (regioselectivity 95.0% of n-alkanal), and TOF value is 555h-1。
Embodiment 20-56
Rh(acac)(CO)2/[(N-(EO)16Ph)(N-CH3)Pyrr]2[Xantphos-(SO3 -)2] (o=p=1, q=r=2)/[(N-(EO)16Ph)(N-CH3)Pyrr][CH3SO3 -Biphase hydroformylation reaction circulation experiment under]/1-octene system
Under an inert atmosphere, in rustless steel autoclave, Rh (acac) (CO) is added2、[(N-(EO)16Ph)(N-CH3)Pyrr]2[Xantphos-(SO3 -)2]、[(N-(EO)16Ph)(N-CH3)Pyrr][CH3SO3 -] and 1-octene, its ratio is: [(N-(EO)16Ph)(N-CH3)Pyrr]2[Xantphos-(SO3 -)2]/Rh(acac)(CO)2=20:1 (mol ratio), 1-octene/Rh (acac) (CO)2=1000:1 (mol ratio), [(N-(EO)16Ph)(N-CH3)Pyrr][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, then room temperature it is quickly cooled to, still is driven after emptying synthesis gas, system is divided into biphase naturally, it is decanted off the organic facies on upper strata, the ionic liquid that rhodium catalyst is contained in lower floor passes through to add new 1-octene mutually can carry out catalytic cycle next time, gas chromatographic analysis result shows: after 37 catalytic cycle, conversion of olefines rate, the regioselectivity of aldehyde chemo-selective and n-alkanal is not decreased obviously, accumulative TON value reaches 32215, the rhodium number of dropouts < 0.2% of single cycle, circulation experiment result is in embodiment 20-56 in Table 1.
The circulation experiment of table 1 rhodium catalyst

Claims (6)

1. the method preparing n-alkanal based on the biphase hydroformylation height selectivity of alkene of phosphine functionalization polyethers pyrrolidinium ionic liquid, it is characterized in that: biphasic catalysis reaction system is to be made up of with organic facies ionic liquid phase: ionic liquid includes the polyethers pyrrolidinium ionic liquid PPPYRILs of phosphine functionalization, polyethers pyrrolidinium ionic liquid PPYRILs and rhodium catalyst mutually; Organic facies is the mixture of reaction substrate straight chain 1-alkene or linear internal or above-mentioned alkene, or product, or the mixture of above-mentioned alkene and product; Organic facies can introduce solvent, it is possible to not solubilizer; Hydroformylation reaction carries out under certain reaction temperature and synthesis gas pressure, and reaction can realize recovery and the recycling of rhodium catalyst either directly through the two-phase laminated flow of ionic liquid phase and organic facies after terminating; Also extractant be can add, recovery and the recycling of rhodium catalyst then realized again through two-phase laminated flow; The structure of the polyethers pyrrolidinium ionic liquid PPPYRILs of phosphine functionalization is as follows:
In formula: l=1-100; R1For H, C1-C16Alkyl, phenyl or benzyl; M=0-100, R2For H, C1-C16Alkyl, phenyl or benzyl;
R3Representing 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. according to a kind of method preparing n-alkanal based on the biphase hydroformylation height selectivity of alkene of phosphine functionalization polyethers pyrrolidinium ionic liquid of claim 1, it is characterised in that the structural formula of polyethers pyrrolidinium ionic liquid PPYRILs is as follows:
In formula: l=1-100; R1For H, C1-C16Alkyl, phenyl or benzyl; 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. according to a kind of method preparing n-alkanal based on the biphase hydroformylation height selectivity of alkene of phosphine functionalization polyethers pyrrolidinium ionic liquid of claim 1, it is characterized in that: under an inert atmosphere, the polyethers pyrrolidinium ionic liquid PPPYRILs of phosphine functionalization, polyethers pyrrolidinium ionic liquid PPYRILs, rhodium catalyst, substrate olefin are mixed in certain proportion, wherein, substrate olefin is the mixture of straight chain 1-alkene or linear internal or above-mentioned alkene, PPPYRILs is 3:1-100:1 with the mol ratio of rhodium in rhodium catalyst, it is preferred to 5:1-30:1; The mol ratio of PPYRILs and rhodium catalyst is 10:1-300:1, it is preferred to 30:1-50:1; Substrate olefin is 100:1-20000:1 with the mol ratio of rhodium in rhodium catalyst, it is preferred to 1000:1-10000:1; Synthesis gas pressure is 1-10MPa, it is preferred to 3-7MPa; Reaction temperature is 70-130 DEG C, it is preferred to 80-110 DEG C; Response time is 0.25-15 hour; System can introduce solvent, it is possible to not solubilizer, if the volume ratio adding solvent, solvent and alkene is 1:10-10:1; After reaction terminates, the recovery of rhodium catalyst is realized by the two-phase laminated flow of ionic liquid phase and organic facies, also can adding extractant, then pass through two-phase laminated flow and realize point phase of rhodium catalyst and organic facies, ionic liquid passes through to add new alkene mutually can carry out catalytic cycle next time.
4. according to a kind of method preparing n-alkanal based on the biphase hydroformylation height selectivity of alkene of phosphine functionalization polyethers pyrrolidinium ionic liquid of claim 1 and 3, 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. according to a kind of method preparing n-alkanal based on the biphase hydroformylation height selectivity of alkene of phosphine functionalization polyethers pyrrolidinium ionic liquid of claim 1, it is characterised in that product is the mixture of one or more in aldehyde, isomerizing olefins, olefin hydrogenation product.
6., according to a kind of method preparing n-alkanal based on the biphase hydroformylation height selectivity of alkene of phosphine functionalization polyethers pyrrolidinium ionic liquid of claim 1 and 3, it is characterized in that: organic facies introduce organic solvent or extractant be: petroleum ether, hexamethylene, C6-C12Mixture several in a kind of or above-mentioned solvent in alkane, ether, methyl tertiary butyl ether(MTBE).
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