CN105669403B - A method of the alkene two-phase hydroformylation based on phosphine functionalization polyethers pyrrolidinium ionic liquid is highly selective to prepare n-alkanal - Google Patents

A method of the alkene two-phase hydroformylation based on phosphine functionalization polyethers pyrrolidinium ionic liquid is highly selective to prepare n-alkanal Download PDF

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CN105669403B
CN105669403B CN201610164282.8A CN201610164282A CN105669403B CN 105669403 B CN105669403 B CN 105669403B CN 201610164282 A CN201610164282 A CN 201610164282A CN 105669403 B CN105669403 B CN 105669403B
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CN105669403A (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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    • B01J31/0285—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
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
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    • 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
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    • 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
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    • B01J33/00—Protection of catalysts, e.g. by coating
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    • 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
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/82—Metals of the platinum group
    • B01J2531/822—Rhodium
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Abstract

The present invention relates to a kind of highly selective methods for preparing n-alkanal of alkene two-phase hydroformylation based on phosphine functionalization polyethers pyrrolidinium ionic liquid, the process employs a kind of biphase catalytic systems, catalyst system and catalyzing by phosphine functionalization polyethers pyrrolidinium ionic liquid, polyethers pyrrolidinium ionic liquid, rhodium catalyst and reaction substrate alkene and reaction product aldehyde composition, liquid liquid two-phase hydroformylation reaction is carried out under certain reaction temperature and synthesis atmospheric pressure, separation and the cycle of rhodium catalyst are realized by simple two-phase laminated flow after reaction, rhodium catalyst can be recycled repeatedly, catalytic activity and selectivity do not significantly decrease, the TOF values of the system reach 500 2700h‑1, catalytic cycle add up TON values reach 32215.

Description

A kind of alkene two-phase hydrogen formyl based on phosphine functionalization polyethers pyrrolidinium ionic liquid Change the highly selective method for preparing n-alkanal
Technical field
The present invention relates to technical field of chemistry and chemical engineering, and phosphine functionalization polyethers pyrrolidinium ion is based on more particularly to one kind The highly selective method for preparing n-alkanal of alkene two-phase hydroformylation of liquid.
Background technology
The hydroformylation of olefin of rhodium catalysis is typical atomic economy reaction, and the more carbonyl of document report at present Glycosylation reaction, it has also become prepare the ideal method of high-carbon aldehyde/alcohol.Homogeneous hydroformylation have that catalytic activity is high, selectivity is good and The mild advantage of reaction condition, but for a long time, the separation of rhodium catalyst and Recycling are always homogeneous catalysis field Focus of attention.
In recent years, ionic liquid is very rapid as the liquid liquid biphase catalytic system development of catalyst carrier, it has also become mesh One of the biphase catalytic system of preceding most application prospect.Non-aqueous ionic liquid hydroformylation is based on the extremely low steaming of ionic liquid Air pressure, good thermal stability and controllable solvability, rhodium catalyst is dissolved, and " the liquid of catalyst is served as with ionic liquid Body carrier ", and substrate olefin and product aldehyde and ionic liquid be not miscible, is realized after reaction by liquid liquid two-phase laminated flow The cycle of catalyst.
Although non-aqueous ionic liquid hydroformylation solves the separation circulatory problems of rhodium catalyst to a certain extent, from Sub- liquid still has significant limitation in practical applications.First, there is still a need for a large amount of for non-aqueous ionic liquid catalyst system and catalyzing Ionic liquid loaded and dissolving rhodium catalyst, either from the point of view of economic or toxicology, this does not meet Green Chemistry Requirement；Second is that the application of a large amount of ionic liquids makes the resistance to mass tranfer of substrate molecule increase, the negative effect of ionic liquid is (viscous by height The Various Complexes factor such as degree, residual impurity causes) become significantly, to lead to catalytic activity and selective degradation.
Recently, we have invented a kind of polyoxyalkylene alkyl guanidinium ionic liquids with the liquid-solid phase-change characteristic of room temperature (ZL201210064537.5), and it is applied in the higher olefins two-phase hydroformylation reaction of rhodium catalysis, it is this kind of novel Functionalized ion liquid can effective immobilized Rh-TPPTS catalyst, and with the significant ability for stablizing rhodium catalyst, hydrogen first Acylation reaction adds up TON values up to 31188.But there are still problems with for this two-phase system：First, needing larger amount of ionic liquid The mass ratio of carrier of the body as Rh-TPPTS catalyst, ionic liquid and rhodium catalyst precursor reaches 1000:1；Second is that due to It is limited by biphase catalytic system resistance to mass tranfer, catalytic activity is not high, and TOF values only have 10-200h-1；Third, the area of n-alkanal Field selectivity is poor, just different than being only 2.0:1-2.4:1 (n-alkanal regioselectivity 67-71%).
In another patent (CN201310370138.6), we have invented the polyoxyalkylene alkyls of a kind of novel phosphine functionalization Guanidinium ionic liquid, and the high carbene that a homogeneous catalysis system is applied to rhodium catalysis is constructed based on this novel ion liquid The advantages of hydroformylation reaction of hydrocarbon, this catalyst system and catalyzing is that catalytic activity is higher, but needs to introduce in catalyst system and catalyzing organic Solvent, this virtually increases catalyst recycling cycle and the difficulty and energy consumption of last handling process, while organic solvent also can Cause environmental and safety problems, does not also meet the requirement of Green Chemistry.
In patent CN201510250460.4, we construct the polyethers pyrrolidinium ionic liquid based on phosphine functionalization Alkene two-phase hydroformylation system.Under the system, the characteristic of the existing Phosphine ligands of ionic liquid of phosphine functionalization can be formed with rhodium Complex catalyst, and have both the solvent nature of ionic liquid, the carrier of rhodium catalyst is may act as, there is no need to additional a large amount of again Other ionic liquids fundamentally solve the problems, such as that ionic liquid dosage is excessively high, while also reacting ionic liquid in catalysis In negative effect minimize；But the n-alkanal regioselectivity of the system it is excessively poor (<80%).
Invention content
For the deficiencies in the prior art, polyethers pyrrolidinium ionic liquid of this patent based on phosphine functionalization, hair It is illustrated that a kind of alkene two-phase hydroformylation based on phosphine functionalization polyethers pyrrolidinium ionic liquid is highly selective prepares n-alkanal Method.The biphase catalytic system of invention only needs additional a small amount of polyethers pyrrolidinium ionic liquid PPYRILs as rhodium catalysis The carrier of agent not only has higher catalytic activity (TOF=500-2700h-1), (total TON values reach for the service life of overlength 32215) and extremely low rhodium number of dropouts (<0.2%), and the regioselectivity of n-alkanal is up to 95.0-98.0% (just different ratios 19:1-45:1)。
Technical solution：
Biphasic catalysis reaction system is made of ionic liquid phase and organic phase：Ionic liquid includes mutually the poly- of phosphine functionalization Ether pyrrolidinium ionic liquid PPPYRILs, polyethers pyrrolidinium ionic liquid PPYRILs and rhodium catalyst；Organic phase is reaction The mixture or reaction product or above-mentioned alkene and reaction product of substrate straight chain 1- alkene or linear internal or above-mentioned alkene Mixture；Organic phase can introduce solvent, also can not solubilizer；Hydroformylation reaction is in certain reaction temperature and synthesis air pressure Carried out under power, after reaction can directly by the two-phase laminated flow of ionic liquid phase and organic phase realize rhodium catalyst recycling and It recycles；Also extractant can be added, then realize the recycling and recycling of rhodium catalyst by two-phase laminated flow again；Phosphine work( The structure of the polyethers pyrrolidinium ionic liquid PPPYRILs of energyization 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；R3Indicate the anion of Water-soluble Sulphonated phosphines, n is the sum of sulfonic group anion on Phosphine ligands, structure It 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 are C1-C12 Alkyl.
Contrast experiment one (referring to embodiment 1-3)：This patent is constructed based on polyethers pyrrolidinium ionic liquid PPYRILs Alkene two-phase hydroformylation system is tested as a comparison.Biphase catalytic system is made of ionic liquid phase and organic phase：Ion Liquid includes mutually polyethers pyrrolidinium ionic liquid PPYRILs, 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 phase is reaction substrate straight chain 1- alkene；Hydroformylation reaction carries out under certain reaction temperature and synthesis atmospheric pressure, instead The recycling and recycling of rhodium catalyst can be directly realized after answering by the two-phase laminated flow of ionic liquid phase and organic phase.It is real Test the result shows that：The biphase catalytic system has higher catalytic activity (TOF=260-2000h-1), the service life of overlength (total TON values reach 34387) and extremely low rhodium number of dropouts (0.05-0.15%), and the regioselectivity of n-alkanal is up to 96- 98% is (just different to compare 24:1-45:1)；But there is still a need for a large amount of external ions liquid PPYRILs to dissolve rhodium catalyst for the system, The molar ratio of PPYRILs and rhodium catalyst reaches 300:1-500:1.
Contrast experiment two (referring to embodiment 4-6)：Polyethers pyrrolidinium ionic liquid of this patent based on phosphine functionalization PPPYRILs constructs alkene two-phase hydroformylation system and tests as a comparison.Biphase catalytic system is that by ionic liquid phase and have Machine is mutually constituted：Ionic liquid mutually includes the polyethers pyrrolidinium ionic liquid PPPYRILs and rhodium catalyst of phosphine functionalization；It is organic It is mutually reaction substrate straight chain 1- alkene；Hydroformylation reaction carries out under certain reaction temperature and synthesis atmospheric pressure, reaction knot Shu Houke directly realizes the recycling and recycling of rhodium catalyst by the two-phase laminated flow of ionic liquid phase and organic phase.Experiment knot Fruit shows：The catalytic activity of the biphase catalytic system is higher, and the molar ratio of PPPYRILs and rhodium catalyst is only 5:1-30:1, nothing External ions liquid is needed, needs a large amount of ionic liquids to be carried as catalyst to solve conventional ion liquid biphase catalytic system The problem of body；But the n-alkanal regioselectivity of the system is poor, and only 61.5-68.8% is (just different to compare 1.6:1-2.2:1), main It wants the reason is that may there is non-double coordination rhodium catalyst to be formed.
In the present invention, the advantages of 2 two catalyst system and catalyzings of contrast experiment one and contrast experiment, is merged：With phosphine work( The polyethers pyrrolidinium ionic liquid PPPYRILs of energyization replaces the sulfonic acid sodium form biphosphine ligand in contrast experiment one, due to The characteristic of the existing Phosphine ligands of PPPYRILs can form complex catalyst with rhodium, and have both the solvent nature of ionic liquid, with ion Liquid PPYRILs have good intermiscibility, therefore can substantially reduce external ions liquid PPYRILs dosage (PPYRILs with The molar ratio of rhodium catalyst is 30:1-50:1, it is the ten of contrast experiment one and ZL201210064537.5 intermediate ion volumes / mono-)；Meanwhile compared with contrast experiment two, due to introducing a small amount of PPYRILs in a two-phase system, PPPYRILs is diluted, It is more likely formed the rhodium catalyst of double coordination, the n-alkanal regioselectivity of the system is improved to 95.0-98.0% (just different ratios 19.0:1-45.0:1)。
The highly selective preparation of alkene two-phase hydroformylation typically based on phosphine functionalization polyethers pyrrolidinium ionic liquid The method of n-alkanal is as follows：Under an inert atmosphere, by polyethers pyrrolidinium ionic liquid PPPYRILs, the polyethers pyrrole of phosphine functionalization It coughs up alkane ionic liquid PPYRILs, rhodium catalyst, substrate olefin to mix in certain proportion, wherein substrate olefin is straight chain 1- The molar ratio of the mixture of alkene or linear internal or above-mentioned alkene, PPPYRILs and rhodium in rhodium catalyst is 3:1-100:1, Preferably 5:1-30:1；The molar ratio of PPYRILs and rhodium catalyst is 10:1-300:1, preferably 30:1-50:1；Substrate olefin Molar ratio with rhodium in rhodium catalyst is 100:1-20000:1, preferably 1000:1-10000:1；It is 1- to synthesize atmospheric pressure 10MPa, preferably 3-7MPa；Reaction temperature is 70-130 DEG C, preferably 80-110 DEG C；Reaction time is 0.25-15 hours；Body Solvent can be introduced in system, also can not solubilizer, if solvent is added, the volume ratio of solvent and alkene is 1:10-10:1；Reaction knot Shu Hou is realized the recycling of rhodium catalyst by the two-phase laminated flow of ionic liquid phase and organic phase, extractant can also be added, then Realize that the split-phase of rhodium catalyst and organic phase, ionic liquid can mutually carry out next time by adding new alkene by two-phase laminated flow Catalytic cycle.
In the present invention, rhodium catalyst is rhodium dicarbonyl acetylacetonate Rh (acac) (CO)2、RhCl3·3H2O、[Rh (COD)2]BF4Or [Rh (COD) Cl]2, COD 1,5- cyclo-octadiene.
In the present invention, reaction product is the mixture of one or more of aldehyde, isomerizing olefins, olefin hydrogenation product.
In the present invention, organic solvent or extractant that organic phase introduces are：Petroleum ether, hexamethylene, C6-C12Alkane, second Several mixture in one kind or above-mentioned solvent in ether, methyl tertiary butyl ether(MTBE).
Specific implementation mode
Embodiment 1
Rh(acac)(CO)2/BISBI-(SO3Na)2(o=p=1, q=r=2)/[(N- (EO)16Ph)(N-CH3)Pyrr] [CH3SO3 -Two-phase hydroformylation reaction under]/1- octene systems
Under an inert atmosphere, Rh (acac) (CO) is added into stainless steel autoclave2、BISBI-(SO3Na)2、[(N- (EO)16Ph)(N-CH3)Pyrr][CH3SO3 -] and 1- octenes, its ratio be：BISBI-(SO3Na)2/Rh(acac)(CO)2=5: 1 (molar ratio), 1- octenes/Rh (acac) (CO)2=1000:1 (molar ratio), [(N- (EO)16Ph)(N-CH3)Pyrr] [CH3SO3 -]/Rh(acac)(CO)2=300:1 (molar ratio) then uses synthesis gas (H2/ CO=1:1) it is forced into 5.0MPa, instead It answers 100 DEG C of temperature, 0.5 hour reaction time to be then quickly cooled to room temperature, opens kettle after being vented synthesis gas, pass through ionic liquid The recycling that rhodium catalyst is mutually realized with the two-phase laminated flow of organic phase can also be added normal heptane extraction, be obtained through simple two-phase laminated flow To the organic phase containing product aldehyde, gas chromatographic analysis result is：The conversion ratio of 1- octenes is 29.5%, the chemo-selective of aldehyde 88.0%, the molar ratio of n-alkanal and iso-aldehyde is 26.0:1.0 (regioselectivities 96.3% of n-alkanal), TOF values are 519h-1。
Embodiment 2
Rh(acac)(CO)2/BINA-(SO3Na)2(o=p=1, q=r=2)/[(N- (EO)16Ph)(N-CH3)Pyrr] [CH3SO3 -Two-phase hydroformylation reaction under]/1- octene systems
Under an inert atmosphere, Rh (acac) (CO) is added into stainless steel autoclave2、BINA-(SO3Na)2、[(N- (EO)16Ph)(N-CH3)Pyrr][CH3SO3 -] and 1- octenes, its ratio be：BINA-(SO3Na)2/Rh(acac)(CO)2=5:1 (molar ratio), 1- octenes/Rh (acac) (CO)2=5000:1 (molar ratio), [(N- (EO)16Ph)(N-CH3)Pyrr] [CH3SO3 -]/Rh(acac)(CO)2=300:1 (molar ratio) then uses synthesis gas (H2/ CO=1:1) it is forced into 5.0MPa, instead It answers 100 DEG C of temperature, 0.5 hour reaction time to be then quickly cooled to room temperature, opens kettle after being vented synthesis gas, pass through ionic liquid The recycling that rhodium catalyst is mutually realized with the two-phase laminated flow of organic phase can also be added normal heptane extraction, be obtained through simple two-phase laminated flow To the organic phase containing product aldehyde, gas chromatographic analysis result is：The conversion ratio of 1- octenes is 21.0%, the chemo-selective of aldehyde 94.5%, the molar ratio of n-alkanal and iso-aldehyde is 33.0:1.0 (regioselectivities 97.1% of n-alkanal), TOF values are 1985h-1。
Embodiment 3
Rh(acac)(CO)2/Xantphos-(SO3Na)2(o=p=1, q=r=2)/[(N- (EO)16Ph)(N-CH3) Pyrr][CH3SO3 -Two-phase hydroformylation reaction under]/1- octene systems
Under an inert atmosphere, Rh (acac) (CO) is added into stainless steel autoclave2、Xantphos-(SO3Na)2、 [(N-(EO)16Ph)(N-CH3)Pyrr][CH3SO3 -] and 1- octenes, its ratio be：Xantphos-(SO3Na)2/Rh(acac) (CO)2=5:1 (molar ratio), 1- octenes/Rh (acac) (CO)2=1000:1 (molar ratio), [(N- (EO)16Ph)(N-CH3) Pyrr][CH3SO3 -]/Rh(acac)(CO)2=300:1 (molar ratio) then uses synthesis gas (H2/ CO=1:1) it is forced into Then 5.0MPa, 100 DEG C of reaction temperature, 0.5 hour reaction time are quickly cooled to room temperature, open kettle after being vented synthesis gas, pass through The two-phase laminated flow of ionic liquid phase and organic phase realizes the recycling of rhodium catalyst, normal heptane extraction can also be added, through simple two Phase separation obtains the organic phase containing product aldehyde, and gas chromatographic analysis result is：The conversion ratio of 1- octenes is 31.6%, the change of aldehyde The molar ratio of selectivity 93.6%, n-alkanal and iso-aldehyde is 28.0:1.0 (regioselectivities 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] (o=p=1, q=r= 2) two-phase hydroformylation reaction under/1- octene systems
Under an inert atmosphere, Rh (acac) (CO) is added into stainless steel autoclave2、[(N-(EO)16Ph)(N- CH3)Pyrr]2[BISBI-(SO3 -)2] and 1- octenes, its ratio be：[(N-(EO)16Ph)(N-CH3)Pyrr]2[BISBI- (SO3 -)2]/Rh(acac)(CO)2=5:1 (molar ratio), 1- octenes/Rh (acac) (CO)2=1000:1 (molar ratio), is then used Synthesis gas (H2/ CO=1:1) it is forced into 5.0MPa, 100 DEG C of reaction temperature in 0.5 hour reaction time, is then quickly cooled to room Temperature opens kettle after being vented synthesis gas, and system is divided into two-phase naturally, and lower layer is the ionic liquid phase containing rhodium catalyst, and upper layer is to have Machine phase can also be added normal heptane extraction, the organic phase containing product aldehyde, gas chromatographic analysis knot are obtained through simple two-phase laminated flow Fruit is：The conversion ratio of 1- octenes is 94.5%, the selectivity 93.6% of aldehyde, and the molar ratio of n-alkanal and iso-aldehyde is 1.6:1 (just The regioselectivity 61.5% of structure aldehyde), TOF values are 1769h-1。
Embodiment 5
Rh(acac)(CO)2/[(N-(EO)16Ph)(N-CH3)Pyrr]2[BINA-(SO3 -)2] (o=p=1, q=r=2)/ Two-phase hydroformylation reaction under 1- octene systems
Under an inert atmosphere, Rh (acac) (CO) is added into stainless steel autoclave2、[(N-(EO)16Ph)(N- CH3)Pyrr]2[BINA-(SO3 -)2] and 1- octenes, its ratio be：[(N-(EO)16Ph)(N-CH3)Pyrr]2[BINA- (SO3 -)2]/Rh(acac)(CO)2=5:1 (molar ratio), 1- octenes/Rh (acac) (CO)2=5000:1 (molar ratio), is then used Synthesis gas (H2/ CO=1:1) it is forced into 5.0MPa, 100 DEG C of reaction temperature in 0.5 hour reaction time, is then quickly cooled to room Temperature opens kettle after being vented synthesis gas, and system is divided into two-phase naturally, and lower layer is the ionic liquid phase containing rhodium catalyst, and upper layer is to have Machine phase can also be added normal heptane extraction, the organic phase containing product aldehyde, gas chromatographic analysis knot are obtained through simple two-phase laminated flow Fruit is：The conversion ratio of 1- octenes is 32.2%, the selectivity 89.5% of aldehyde, and the molar ratio of n-alkanal and iso-aldehyde is 2.1:1 (just The regioselectivity 67.7% of structure aldehyde), TOF values are 2882h-1。
Embodiment 6
Rh(acac)(CO)2/[(N-(EO)16Ph)(N-CH3)Pyrr]2[Xantphos-(SO3 -)2] (o=p=1, q=r =2) two-phase hydroformylation reaction under/1- octene systems
Under an inert atmosphere, Rh (acac) (CO) is added into stainless steel autoclave2、[(N-(EO)16Ph)(N- CH3)Pyrr]2[Xantphos-(SO3 -)2] and 1- octenes, its ratio be：[(N-(EO)16Ph)(N-CH3)Pyrr]2 [Xantphos-(SO3 -)2]/Rh(acac)(CO)2=5:1 (molar ratio), 1- octenes/Rh (acac) (CO)2=1000:1 (mole Than), then use synthesis gas (H2/ CO=1:1) it is forced into 5.0MPa, 100 DEG C of reaction temperature, 0.5 hour reaction time, then soon Speed is cooled to room temperature, and opens kettle after being vented synthesis gas, system is divided into two-phase naturally, and lower layer is the ionic liquid containing rhodium catalyst Phase, upper layer are organic phase, and normal heptane extraction can also be added, the organic phase containing product aldehyde, gas are obtained through simple two-phase laminated flow Analysis of hplc result is：The conversion ratio of 1- octenes is 95.3%, the selectivity 95.5% of aldehyde, mole of n-alkanal and iso-aldehyde Than being 2.2:1 (regioselectivity 68.8% of n-alkanal), TOF values are 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 -Two-phase hydroformylation reaction under]/1- octene systems
Under an inert atmosphere, Rh (acac) (CO) is added into stainless steel autoclave2、[(N-(EO)16Ph)(N- CH3)Pyrr]2[BISBI-(SO3 -)2]、[(N-(EO)16Ph)(N-CH3)Pyrr][CH3SO3 -] and 1- octenes, its ratio be： [(N-(EO)16Ph)(N-CH3)Pyrr]2[BISBI-(SO3 -)2]/Rh(acac)(CO)2=5:1 (molar ratio), 1- octenes/Rh (acac)(CO)2=1000:1 (molar ratio), [(N- (EO)16Ph)(N-CH3)Pyrr][CH3SO3 -]/Rh(acac)(CO)2= 30:1 (molar ratio) then uses synthesis gas (H2/ CO=1:1) it is forced into 5.0MPa, 100 DEG C of reaction temperature, the reaction time 0.5 is small When, it is then quickly cooled to room temperature, kettle is opened after being vented synthesis gas, rhodium is realized by the two-phase laminated flow of ionic liquid phase and organic phase The recycling of catalyst can also be added normal heptane extraction, the organic phase containing product aldehyde, gas phase color are obtained through simple two-phase laminated flow Spectrum analysis result is：The conversion ratio of 1- octenes is 85.8%, the chemo-selective 84.3% of aldehyde, mole of n-alkanal and iso-aldehyde Than being 20.0:1.0 (regioselectivities 95.2% of n-alkanal), TOF values are 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 -Two-phase hydroformylation reaction under]/1- octene systems
Under an inert atmosphere, Rh (acac) (CO) is added into stainless steel autoclave2、[(N-(EO)16Ph)(N- CH3)Pyrr]2[BINA-(SO3 -)2]、[(N-(EO)16Ph)(N-CH3)Pyrr][CH3SO3 -] and 1- octenes, its ratio be：[(N- (EO)16Ph)(N-CH3)Pyrr]2[BINA-(SO3 -)2]/Rh(acac)(CO)2=5:1 (molar ratio), 1- octenes/Rh (acac) (CO)2=5000:1 (molar ratio), [(N- (EO)16Ph)(N-CH3)Pyrr][CH3SO3 -]/Rh(acac)(CO)2=30:1 (rubs That ratio), then use synthesis gas (H2/ CO=1:1) it is forced into 5.0MPa, 100 DEG C of reaction temperature, 0.5 hour reaction time, then It is quickly cooled to room temperature, kettle is opened after being vented synthesis gas, rhodium catalyst is realized by the two-phase laminated flow of ionic liquid phase and organic phase Recycling, can also be added normal heptane extraction, obtain the organic phase containing product aldehyde, gas chromatographic analysis through simple two-phase laminated flow As a result it is：The conversion ratio of 1- octenes is 30.6%, the chemo-selective 87.4% of aldehyde, and the molar ratio of n-alkanal and iso-aldehyde is 26.5:1.0 (regioselectivities 96.4% of n-alkanal), TOF values are 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 -Two-phase hydroformylation reaction under]/1- octene systems
Under an inert atmosphere, Rh (acac) (CO) is added into stainless steel autoclave2、[(N-(EO)16Ph)(N- CH3)Pyrr]2[Xantphos-(SO3 -)2]、[(N-(EO)16Ph)(N-CH3)Pyrr][CH3SO3 -] and 1- octenes, its ratio be： [(N-(EO)16Ph)(N-CH3)Pyrr]2[Xantphos-(SO3 -)2]/Rh(acac)(CO)2=5:1 (molar ratio), 1- octenes/ Rh(acac)(CO)2=1000:1 (molar ratio), [(N- (EO)16Ph)(N-CH3)Pyrr][CH3SO3 -]/Rh(acac)(CO)2= 30:1 (molar ratio) then uses synthesis gas (H2/ CO=1:1) it is forced into 5.0MPa, 100 DEG C of reaction temperature, the reaction time 0.5 is small When, it is then quickly cooled to room temperature, kettle is opened after being vented synthesis gas, rhodium is realized by the two-phase laminated flow of ionic liquid phase and organic phase The recycling of catalyst can also be added normal heptane extraction, the organic phase containing product aldehyde, gas phase color are obtained through simple two-phase laminated flow Spectrum analysis result is：The conversion ratio of 1- octenes is 90.4%, the chemo-selective 91.6% of aldehyde, mole of n-alkanal and iso-aldehyde Than being 22.0:1.0 (regioselectivities 95.7% of n-alkanal), TOF values are 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 -Two-phase hydroformylation reaction under]/1- octene systems
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 (molar ratio), with step with embodiment 9, gas chromatographic analysis result is remaining reaction condition：The conversion ratio of 1- octenes is 83.8%, the molar ratio of the chemo-selective 72.4% of aldehyde, n-alkanal and iso-aldehyde is 23.0:1.0 (the regional choices of n-alkanal Property 95.8%), TOF values be 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 -Two-phase hydroformylation reaction under]/1- octene systems
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 (rubs That ratio), with step with embodiment 9, gas chromatographic analysis result is remaining reaction condition：The conversion ratio of 1- octenes is 93.4%, The molar ratio of the chemo-selective 92.5% of aldehyde, n-alkanal and iso-aldehyde is 25.0:1.0 (the regioselectivities of n-alkanal 96.2%), TOF values are 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][BF4Two-phase hydroformylation reaction under]/1- octene systems
Ionic liquid is changed to [(N- (EO)16CH3)(N-CH3)Pyrr]2[Xantphos-(SO3 -)2] and [(N- (EO)16CH3) (N-CH3)Pyrr][BF4], with step with embodiment 9, gas chromatographic analysis result is remaining reaction condition：The conversion of 1- octenes Rate is 29.3%, the chemo-selective 86.3% of aldehyde, and the molar ratio of n-alkanal and iso-aldehyde is 19.0:1.0 (the regions of n-alkanal 95.0%), TOF values are 506h to selectivity-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 -Two-phase hydroformylation is anti-under]/1- octene systems It answers
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- octenes/Rh (acac) (CO)2=5000:1 (molar ratio), remaining With step with embodiment 9, gas chromatographic analysis result is reaction condition：The conversion ratio of 1- octenes is 20.6%, the chemistry choosing of aldehyde The molar ratio of selecting property 93.3%, n-alkanal and iso-aldehyde is 22.0:1.0 (regioselectivities 95.7% of n-alkanal), TOF values are 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 -Two-phase hydroformylation reaction under]/1- octene systems
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- octenes/Rh (acac) (CO)2=5000:1 (molar ratio), remaining reaction item With step with embodiment 9, gas chromatographic analysis result is part：The conversion ratio of 1- octenes is 26.3%, the chemo-selective of aldehyde 90.5%, the molar ratio of n-alkanal and iso-aldehyde is 25.0:1.0 (regioselectivities 96.2% of n-alkanal), TOF values are 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 -Two-phase hydroformylation reaction under]/1- octene systems
Rhodium catalyst is changed to RhCl3·3H2O, ionic liquid are 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 (molar ratio), remaining reaction condition is with step with embodiment 9, gas Analysis of hplc result is：The conversion ratio of 1- octenes is 97.6%, the chemo-selective 93.5% of aldehyde, n-alkanal and iso-aldehyde Molar ratio is 21.0:1.0 (regioselectivities 95.5% of n-alkanal), TOF values are 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 -Two-phase hydroformylation reaction under]/1- octenes/n-heptane system
It is added normal heptane in system, the volume ratio of normal heptane and 1- octenes is 2:1, remaining reaction condition is with step with implementation Example 9, gas chromatographic analysis result are：The conversion ratio of 1- octenes be 53.7%, the chemo-selective 84.6% of aldehyde, n-alkanal with it is different The molar ratio of structure aldehyde is 20.0:1.0 (regioselectivities 95.2% of n-alkanal), TOF values are 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 -Two-phase hydroformylation reaction under]/1- hexene systems
Alkene is changed to 1- hexenes, and with step with embodiment 9, gas chromatographic analysis result is remaining reaction condition：1- hexenes Conversion ratio be 92.4%, the molar ratio of the chemo-selective 95.3% of aldehyde, n-alkanal and iso-aldehyde is 25.0:1.0 (n-alkanals Regioselectivity 96.2%), TOF values be 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 -Two-phase hydroformylation reaction under]/1-tetradecylene system
Alkene is changed to 1-tetradecylene, and with step with embodiment 9, gas chromatographic analysis result is remaining reaction condition：1- ten The conversion ratio of tetraene is 61.0%, the chemo-selective 87.5% of aldehyde, and the molar ratio of n-alkanal and iso-aldehyde is 21.0:1.0 (just The regioselectivity 95.5% of structure aldehyde), TOF values are 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 -Two-phase hydroformylation reaction under]/2- octene systems
Alkene is changed to 2- octenes, and reaction time 1h, remaining reaction condition is with step with embodiment 9, gas chromatographic analysis As a result it is：The conversion ratio of 2- octenes is 70.8%, the chemo-selective 78.4% of aldehyde, and the molar ratio of n-alkanal and iso-aldehyde is 19.0:1.0 (regioselectivities 95.0% of n-alkanal), TOF values are 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 -Two-phase hydroformylation reaction circulation experiment under]/1- octene systems
Under an inert atmosphere, Rh (acac) (CO) is added into stainless steel autoclave2、[(N-(EO)16Ph)(N- CH3)Pyrr]2[Xantphos-(SO3 -)2]、[(N-(EO)16Ph)(N-CH3)Pyrr][CH3SO3 -] and 1- octenes, its ratio be： [(N-(EO)16Ph)(N-CH3)Pyrr]2[Xantphos-(SO3 -)2]/Rh(acac)(CO)2=20:1 (molar ratio), 1- octenes/ Rh(acac)(CO)2=1000:1 (molar ratio), [(N- (EO)16Ph)(N-CH3)Pyrr][CH3SO3 -]/Rh(acac)(CO)2= 60:1 (molar ratio) then uses synthesis gas (H2/ CO=1:1) it is forced into 5.0MPa, 100 DEG C of reaction temperature, the reaction time 6 is small When, it is then quickly cooled to room temperature, kettle is opened after being vented synthesis gas, system is divided into two-phase naturally, is decanted off the organic phase on upper layer, under Ionic liquid of the layer containing rhodium catalyst mutually can carry out catalytic cycle next time, gas chromatographic analysis by adding new 1- octenes The result shows that：After 37 catalytic cycles, the regioselectivity of the conversion ratio of alkene, aldehyde chemo-selective and n-alkanal is not bright Aobvious to decline, accumulative TON values reach 32215, the rhodium number of dropouts of single cycle<0.2%, embodiment during circulation experiment the results are shown in Table 1 20-56。
The circulation experiment of 1 rhodium catalyst of table

Claims (4)

1. a kind of alkene two-phase hydroformylation based on phosphine functionalization polyethers pyrrolidinium ionic liquid is highly selective to prepare positive structure The method of aldehyde, it is characterised in that：Biphasic catalysis reaction system is made of ionic liquid phase and organic phase, and ionic liquid includes mutually Phosphine functionalization polyethers pyrrolidinium ionic liquid, polyethers pyrrolidinium ionic liquid and rhodium catalyst, phosphine functionalization polyethers pyrroles Alkane ionic liquid and the molar ratio of rhodium in rhodium catalyst are 5:1-30:1, in polyethers pyrrolidinium ionic liquid and rhodium catalyst The molar ratio of rhodium is 30:1-50:1；Organic phase is the mixing of reaction substrate straight chain 1- alkene or linear internal or above-mentioned alkene The mixture of object or reaction product or above-mentioned alkene and reaction product；Organic phase does not introduce solvent；Hydroformylation reaction is one It is carried out under fixed reaction temperature and synthesis atmospheric pressure, directly passes through the two-phase laminated flow of ionic liquid phase and organic phase after reaction Realize the recycling and recycling of rhodium catalyst；The structure of the polyethers pyrrolidinium ionic liquid of phosphine functionalization is as follows：
R3Indicate the anion of Water-soluble Sulphonated phosphines, n is the sum of sulfonic group anion on Phosphine ligands, R3Structural formula It is as follows：
The structure of polyethers pyrrolidinium ionic liquid is as follows：
R4For C6H4-3-SO3 -；L=4 in formula, m=0, R1For phenyl, R2For methyl, o=p=1, q=r=2, n=2, R5For 4- CH3PhSO3 -；Or l=16, m=0, R1For phenyl, R2For methyl, o=p=1, q=r=2, n=2, R5For CH3SO3 -；Or l= 100, m=0, R1For phenyl, R2For methyl, o=p=1, q=r=2, n=2, R5For CH3SO3 -；Or l=16, m=0, R1For n- C12H25, R2For methyl, o=p=1, q=r=2, n=2, R5For CH3SO3 -；Or l=16, m=0, R1For phenyl, R2For n- C16H33, o=p=1, q=r=2, n=2, R5For CH3SO3 -；Or l=16, m=16, R1For phenyl, R2For phenyl, o=p=1, Q=r=2, n=2, R5For CH3SO3 -。
2. a kind of alkene two-phase hydroformylation based on phosphine functionalization polyethers pyrrolidinium ionic liquid according to claim 1 is high The method that selectivity prepares n-alkanal, it is characterized in that：Under an inert atmosphere, by the polyethers pyrrolidinium ionic liquid of phosphine functionalization Body, polyethers pyrrolidinium ionic liquid, rhodium catalyst, substrate olefin mix in certain proportion, wherein substrate olefin is straight chain The molar ratio of the mixture of 1- alkene or linear internal or above-mentioned alkene, substrate olefin and rhodium in rhodium catalyst is 1000:1- 10000:1；It is 3-7MPa to synthesize atmospheric pressure；Reaction temperature is 80-110 DEG C；Reaction time is 0.25-15 hours；In system not Solubilizer；After reaction, the recycling of rhodium catalyst, ionic liquid are realized by the two-phase laminated flow of ionic liquid phase and organic phase Mutually catalytic cycle next time is carried out by adding new alkene.
3. a kind of alkene two-phase hydroformylation based on phosphine functionalization polyethers pyrrolidinium ionic liquid according to claim 1 is high The method that selectivity prepares n-alkanal, it is characterised in that rhodium catalyst is rhodium dicarbonyl acetylacetonate Rh (acac) (CO)2Or RhCl3·3H2O。
4. a kind of alkene two-phase hydroformylation based on phosphine functionalization polyethers pyrrolidinium ionic liquid according to claim 1 is high The method that selectivity prepares n-alkanal, it is characterised in that reaction product is one kind in aldehyde, isomerizing olefins, olefin hydrogenation product Or several mixture.
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