CN105669401B - A method of the alkene two-phase hydroformylation based on polyethers imidazolium ionic liquid is highly selective to prepare n-alkanal - Google Patents

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

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CN105669401B
CN105669401B CN201610164128.0A CN201610164128A CN105669401B CN 105669401 B CN105669401 B CN 105669401B CN 201610164128 A CN201610164128 A CN 201610164128A CN 105669401 B CN105669401 B CN 105669401B
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alkene
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CN105669401A (en
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金欣
马青青
郑魁星
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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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    • B01J31/16—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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    • B01J31/16—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
    • 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
    • B01J2231/70—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
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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 highly selective method for preparing n-alkanal of alkene two-phase hydroformylation based on polyethers imidazolium ionic liquid that the present invention relates to a kind of, the process employs a kind of biphase catalytic systems, the catalyst system and catalyzing is by the polyethers imidazolium ionic liquid PMILs with the liquid-solid phase-change characteristic of room temperature, rhodium catalyst, biphosphine ligand 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, recycling and the cycle of rhodium catalyst are realized by simple two-phase laminated flow after reaction, rhodium catalyst can be recycled tens times, catalytic activity and selectivity do not significantly decrease, the TOF values of the system reach 150-2100h‑1, catalytic cycle add up TON values be up to 38634 or more, the regioselectivity of n-alkanal is up to 96-98%, and rhodium number of dropouts is only 0.03-0.1%.

Description

A kind of alkene two-phase hydroformylation based on polyethers imidazolium ionic liquid is highly selective The method for preparing n-alkanal
Technical field
The present invention relates to technical field of chemistry and chemical engineering, more particularly to a kind of alkene based on polyethers imidazolium ionic liquid The highly selective method for preparing n-alkanal of two-phase hydroformylation.
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.
But the outstanding problem that non-aqueous ionic liquid catalyst system and catalyzing faces is：How by rhodium-Phosphine ligands complex catalysis Agent is effectively dissolved and is supported in ionic liquid, keep high catalytic activity and it is highly selective while effectively extend rhodium catalyst Service life.Its research is concentrated on two aspects:(1) Phosphine ligands for designing synthesizing new, to improve ligand and catalysis Dissolubility of the agent in ionic liquid, enhances the activity of catalyst, reduces the loss of rhodium；(2) novel functionalization is designed and developed Ionic liquid enhances rhodium catalyst under two-phase system and improves catalytic activity and selectivity to the affinity of ionic liquid, extends rhodium The service life of catalyst.
The Phosphine ligands for designing and developing new construction are larger in the upper difficulty of synthesis, are very unfavorable from the point of view of commercial Application 's；And one of the characteristics of ionic liquid be exactly zwitterion in structure have adjustability, in contrast to the knot of ionic liquid Structure is improved and optimizes more economy and operability.Some novel functional ion liquids were applied to rhodium and urged in recent years The hydroformylation reaction of the higher olefins of change, e.g., in document Appl.Catal.A:In General 2007,328,83-87, one Kind is designed to synthesize by the imidazole type ion liquid of anion of p-methyl benzenesulfonic acid root, with sodium trisulfonate between triphenylphosphine (TPPTS) be ligand rhodium catalysis 1- hexene hydroformylation reactions in, catalyst circulation use 7 times after selectively slightly have under Drop, rhodium are not obviously lost in；A kind of aliphatic amine polyoxyethylene ether to first in document Catal.Lett.2004,96,63-65 Benzene sulfonate is used for the hydroformylation of 1-tetradecylene as ionic liquid, and 7 activity of catalyst circulation reduce, and rhodium is lost in 0.5% or so；And in document Appl.Organometal.Chem.2008,22,620-623 and patent CN200610046355 In, there is one kind the polyether quaternary ammonium salt ionic liquid of " high temperature is miscible, low temperature split-phase " feature to be used for the hydrogen formyl of 1- laurylenes Change, catalyst can recycle 8 times, and rhodium is lost in 0.5-1.0%.
Although the studies above solves the problems, such as that rhodium catalyst is immobilized in ionic liquid to a certain extent, and certain Cycle-index in (10-15 times most) higher catalytic activity and selectivity can be kept, but up to the present, in document institute In all ionic liquid catalyst systems of report, there are no a systems can be provided simultaneously with high catalytic activity, highly selective (packet Include chemo-selective and regioselectivity) and overlength service life, main cause：First, the application of a large amount of ionic liquids makes bottom The resistance to mass tranfer of object molecule increases, and the negative effect (being caused by the Various Complexes factor such as high viscosity, residual impurity) of ionic liquid becomes Must be more notable, lead to catalytic activity and selective degradation；Second is that rhodium catalyst may occur oxidation, divide in ionic liquid Solution, cluster close or the behaviors such as loss, so as to cause the reduction of its stability and reduced service life.
Recently, we are based on a kind of polyoxyalkylene alkyl guanidinium ionic liquid with the liquid-solid phase-change characteristic of room temperature (ZL201210064537.5), an alkene two-phase hydroformylation system is constructed, due to this kind of novel functionalization ionic liquid Body can effective immobilized Rh-TPPTS catalyst, and with the significant ability for stablizing rhodium catalyst, rhodium catalyst recycles Reach 35 times, catalytic activity and selectivity remain unchanged, and add up TON values up to 31188, still, this biphase catalytic system is urged Change activity is relatively low, and TOF values only have 10-200h-1, in particular, from 1- octenes to 1-tetradecylene, with the growth of carbochain, reaction speed Rate declines to a great extent, and mass transfer becomes the key factor for inhibiting catalytic activity to improve；In addition, most distinct issues are the systems to positive structure The regioselectivity of aldehyde is poor, just different than being only 2.0:1-2.4:1 (n-alkanal regioselectivity 67-71%), and n-alkanal exists There is important application in many fields.
Invention content
For the deficiencies in the prior art, this patent is based on polyethers imidazolium ionic liquid, has invented a kind of alkene The biphase catalytic system of the highly selective method for preparing n-alkanal of two-phase hydroformylation, invention not only has higher catalytic activity (TOF=150-2100h-1), the service life (total TON values reach 38634) of overlength and extremely low rhodium number of dropouts (0.03- 0.1%), and the regioselectivity of n-alkanal to be up to 96-98% (just different to compare 24:1-45:1).
Technical solution：
Dissolubility of the common Phosphine ligands in ionic liquid is preferable, but is easy to be lost in since affinity is insufficient；Sulfonic acid The affinity of sodium form water-soluble phosphine ligand and ionic liquid is stronger, but the solubility in ionic liquid is smaller, leads to rhodium catalysis The activity and selectivity (chemo-selective and regioselectivity) of agent is poor.Studies have shown that polyether chain is assembled into ionic liquid In molecule, it is not only able to effectively reduce the viscosity of ionic liquid, and can by the structure of modulation polyethers cation and anion The solubility of rhodium catalyst and substrate olefin in ionic liquid is improved, and then improves mass transfer, improves catalytic activity；It is optional simultaneously Selecting with polyethers functionalized ion liquid can couple and can generate the Phosphine ligands of stronger synergistic effect, to improve catalysis reaction Regioselectivity；Using the controllability of polyethers functionalized ion liquid fusing point, the characteristic of the liquid-solid phase transformation of room temperature is made it have, To reach effective protection rhodium catalyst, extend the purpose of rhodium catalyst service life.
The biphase catalytic system of the present invention is made of ionic liquid phase and organic phase：Ionic liquid includes mutually having room temperature Polyethers imidazolium ionic liquid PMILs, rhodium catalyst and the biphosphine ligand 1,2 or 3 of liquid-solid phase-change characteristic；Organic phase is reaction Substrate C3-C141- alkene or internal olefin or reaction product or above-mentioned alkene and reaction product mixture；Organic phase can draw Enter solvent, can not also introduce solvent；Hydroformylation reaction carries out under certain reaction temperature and synthesis atmospheric pressure, and reaction terminates The recycling and recycling of rhodium catalyst can be directly realized by the two-phase laminated flow of ionic liquid phase and organic phase afterwards；Also it can be added Then extractant realizes the recycling and recycling of rhodium catalyst by two-phase laminated flow again；Polyethers imidazolium ionic liquid The structure of PMILs and biphosphine ligand 1,2,3 is as follows：
In formula：N=1-100；R1For H, C1-C16Alkyl or phenyl；O=0-100, R2For H, C1-C16Alkyl, phenyl or benzyl Base；R3For alkyl, phenyl, alkyl-substituted phenyl, wherein alkyl are C1-C12Alkyl；R4For C6H4-3-SO3 -；M is H+、NH4 +, it is single Valence metal ion, a stoichiometric polyvalent metal ion；P=1 or 2, q=1 or 2, l=0,1 or 2, m=0,1 or 2.
The experimental results showed that：Polyethers imidazolium ionic liquid (PMILs) is preferable to the dissolubility of biphosphine ligand 1,2 and 3, and And PMILs is coupled with biphosphine ligand 1,2 and 3 has good synergistic effect, the alkene two-phase hydroformylation system of structure has Higher catalytic activity, TOF reach 150-2100h-1, e.g., the R on PMILs1Become dodecyl from methyl (embodiment 6) (embodiment 11), TOF is from 295h-1Increase to 1588h-1；Especially the catalyst system and catalyzing has high regional choice to n-alkanal Property, reach 96-98%, the n-alkanal selectivity of the 67-71% far above patent ZL201210064537.5；In addition, PMILs The liquid-solid phase-change characteristic of room temperature effective protection and can stablize rhodium catalyst, and the separation of catalyst is made to recycle easier, rhodium Catalyst shows the service life of overlength, recycles 43 times, and catalytic activity and selectivity are not decreased obviously, total TON values Reach 38634, rhodium number of dropouts is only 0.03-0.1%.
The typically highly selective side for preparing n-alkanal of alkene two-phase hydroformylation based on polyethers imidazolium ionic liquid Method is as follows：Under an inert atmosphere, by polyethers imidazolium ionic liquid PMILs, biphosphine ligand 1,2 or 3, rhodium catalyst, substrate C3- C141- alkene or internal olefin mix in certain proportion, wherein the molar ratio of rhodium in biphosphine ligand 1,2 or 3 and rhodium catalyst It is 3:1-100:1, preferably 10:1-50:1, PMILs with the molar ratio of rhodium in rhodium catalyst is 30:1-1000:1, preferably 300:1-500:1, it is 100 to make the molar ratio of substrate olefin and rhodium in rhodium catalyst:1-10000:1, preferably 1000:1- 5000:1, synthesis atmospheric pressure is 1-10MPa, and preferably 3-5MPa, reaction temperature is 70-130 DEG C, preferably 80-100 DEG C, instead It it is 0.25-15 hours between seasonable；Solvent can be introduced in system, also can not solubilizer, if be added solvent, the body of solvent and alkene Product ratio is 1:10-10:1；Reaction system is down to room temperature after reaction, lower layer's ionic liquid mutually solidifies, and passes through ionic liquid The recycling that rhodium catalyst is mutually realized with the liquid/solid two-phase laminated flow of organic phase, can also be added extractant, then pass through liquid/solid two Phase separation realizes that the split-phase of rhodium catalyst and organic phase, ionic liquid can be mutually catalyzed by adding new alkene and be followed next time Ring.
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(1)/[Ph(EO)16MI(CH3)][CH3SO3 -Under]/1- octene systems Two-phase hydroformylation reaction (l=m=2)
Under an inert atmosphere, Rh (acac) (CO) is added into stainless steel autoclave2、BISBI-(SO3Na)2(1)、 [Ph(EO)16MI(CH3)][CH3SO3 -] and 1- octenes, its ratio be：BISBI-(SO3Na)2(1)/Rh(acac)(CO)2=5:1 (molar ratio), 1- octenes/Rh (acac) (CO)2=1000:1 (molar ratio), [Ph (EO)16MI(CH3)][CH3SO3 -]/Rh (acac)(CO)2=300:1 (molar ratio) then uses synthesis gas (H2/ CO=1:1) it is forced into 5.0MPa, 100 DEG C of reaction temperature, In 0.5 hour reaction time, be then quickly cooled to room temperature, kettle opened after being vented synthesis gas, lower layer's ionic liquid mutually solidifies, by from The liquid/solid two-phase laminated flow of sub- liquid phase and organic phase realizes the recycling of rhodium catalyst, normal heptane extraction can also be added, through simple Liquid/solid two-phase laminated flow obtains the organic phase containing product aldehyde, and gas chromatographic analysis result is：The conversion ratio of 1- octenes is 23.3%, the molar ratio of the chemo-selective 86.5% of aldehyde, n-alkanal and iso-aldehyde is 24.5:1.0 (the regional choices of n-alkanal Property 96.1%), TOF values be 403h-1.Embodiment 2
Rh(acac)(CO)2/BINA-(SO3Na)2(2)/[Ph(EO)16MI(CH3)][CH3SO3 -Two under]/1- octene systems Phase hydroformylation reaction (o=p=1；L=m=2)
Under an inert atmosphere, Rh (acac) (CO) is added into stainless steel autoclave2、BINA-(SO3Na)2(2)、 [Ph(EO)16MI(CH3)][CH3SO3 -] and 1- octenes, its ratio be：BINA-(SO3Na)2(2)/Rh(acac)(CO)2=5:1 (molar ratio), 1- octenes/Rh (acac) (CO)2=5000:1 (molar ratio), [Ph (EO)16MI(CH3)][CH3SO3 -]/Rh (acac)(CO)2=300:1 (molar ratio) then uses synthesis gas (H2/ CO=1:1) it is forced into 5.0MPa, 100 DEG C of reaction temperature, In 0.5 hour reaction time, be then quickly cooled to room temperature, kettle opened after being vented synthesis gas, lower layer's ionic liquid mutually solidifies, by from The liquid/solid two-phase laminated flow of sub- liquid phase and organic phase realizes the recycling of rhodium catalyst, normal heptane extraction can also be added, through simple Liquid/solid two-phase laminated flow obtains the organic phase containing product aldehyde, and gas chromatographic analysis result is：The conversion ratio of 1- octenes is 21.4%, the molar ratio of the chemo-selective 96.5% of aldehyde, n-alkanal and iso-aldehyde is 34.0:1.0 (the regional choices of n-alkanal Property 97.1%), TOF values be 2065h-1.Embodiment 3
Rh(acac)(CO)2/Xantphos-(SO3Na)2(3)/[Ph(EO)16MI(CH3)][CH3SO3 -]/1- octene systems Lower two-phase hydroformylation reaction (l=m=2)
Under an inert atmosphere, Rh (acac) (CO) is added into stainless steel autoclave2、Xantphos-(SO3Na)2 (3)、[Ph(EO)16MI(CH3)][CH3SO3 -] and 1- octenes, its ratio be：Xantphos-(SO3Na)2(3)/Rh(acac) (CO)2=5:1 (molar ratio), 1- octenes/Rh (acac) (CO)2=1000:1 (molar ratio), [Ph (EO)16MI(CH3)] [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, kettle, lower layer's ionic liquid is opened after being vented synthesis gas It mutually solidifies, the recycling of rhodium catalyst is realized by the liquid/solid two-phase laminated flow of ionic liquid phase and organic phase, normal heptane can also be added Extraction, obtains the organic phase containing product aldehyde, gas chromatographic analysis result is through simple liquid/solid two-phase laminated flow：1- octenes Conversion ratio is 27.6%, the chemo-selective 95.0% of aldehyde, and the molar ratio of n-alkanal and iso-aldehyde is 27.0:1.0 (n-alkanal Regioselectivity 96.4%), TOF values are 524h-1。
Embodiment 4
RhCl3·3H2O/Xantphos-(SO3Na)2(3)/[Ph(EO)16MI(CH3)][CH3SO3 -Under]/1- octene systems Two-phase hydroformylation reaction (l=m=2)
Rhodium catalyst is changed to RhCl3·3H2O, remaining reaction condition is with step with embodiment 3, gas chromatographic analysis result For：The conversion ratio of 1- octenes is 26.8%, the chemo-selective 86.6% of aldehyde, and the molar ratio of n-alkanal and iso-aldehyde is 27.5: 1.0 (regioselectivities 96.5% of n-alkanal), TOF values are 464h-1。
Embodiment 5
Rh(acac)(CO)2/Xantphos-(SO3Na)2(3)/[Ph(EO)16MI(CH3)][CH3SO3 -]/1- octenes/just Two-phase hydroformylation reaction (l=m=2) under 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 3, gas chromatographic analysis result are：The conversion ratio of 1- octenes be 22.8%, the chemo-selective 84.4% of aldehyde, n-alkanal with it is different The molar ratio of structure aldehyde is 27.0:1.0 (regioselectivities 96.4% of n-alkanal), TOF values are 385h-1。
Embodiment 6
Rh(acac)(CO)2/Xantphos-(SO3Na)2(3)/[CH3(EO)16MI(CH3)][CH3SO3 -]/1- octene bodies The lower two-phase hydroformylation reaction (l=m=2) of system
Ionic liquid is changed to [CH3(EO)16MI(CH3)][CH3SO3 -], remaining reaction condition is with step with embodiment 3, gas Analysis of hplc result is：The conversion ratio of 1- octenes is 15.6%, the chemo-selective 94.6% of aldehyde, n-alkanal and iso-aldehyde Molar ratio is 29.0:1.0 (regioselectivities 96.7% of n-alkanal), TOF values are 295h-1。
Embodiment 7
Rh(acac)(CO)2/Xantphos-(SO3Na)2(3)/[Ph(EO)4MI(CH3)][CH3SO3 -]/1- octene systems Lower two-phase hydroformylation reaction (l=m=2)
Ionic liquid is changed to [Ph (EO)4MI(CH3)][CH3SO3 -], [Ph (EO)4MI(CH3)][CH3SO3 -]/Rh(acac) (CO)2=500:1 (molar ratio), with step with embodiment 3, gas chromatographic analysis result is remaining reaction condition：1- octenes Conversion ratio is 19.2%, the chemo-selective 94.5% of aldehyde, and the molar ratio of n-alkanal and iso-aldehyde is 27.0:1.0 (n-alkanal Regioselectivity 96.4%), TOF values are 363h-1。
Embodiment 8
Rh(acac)(CO)2/Xantphos-(SO3Na)2(3)/[CH3(EO)4MI(CH3)][CH3SO3 -]/1- octene systems Lower two-phase hydroformylation reaction (l=m=2)
Ionic liquid is changed to [CH3(EO)4MI(CH3)][CH3SO3 -], [CH3(EO)4MI(CH3)][CH3SO3 -]/Rh (acac)(CO)2=600:1 (molar ratio), with step with embodiment 3, gas chromatographic analysis result is remaining reaction condition：1- The conversion ratio of octene is 11.5%, the chemo-selective 92.8% of aldehyde, and the molar ratio of n-alkanal and iso-aldehyde is 29.5:1.0 (just The regioselectivity 96.7% of structure aldehyde), TOF values are 213h-1。
Embodiment 9
Rh(acac)(CO)2/Xantphos-(SO3Na)2(3)/[H(EO)4MI(CH3)][CH3SO3 -Under]/1- octene systems Two-phase hydroformylation reaction (l=m=2)
Ionic liquid is changed to [H (EO)4MI(CH3)][CH3SO3 -], [H (EO)4MI(CH3)][CH3SO3 -]/Rh(acac) (CO)2=600:1 (molar ratio), with step with embodiment 3, gas chromatographic analysis result is remaining reaction condition：1- octenes Conversion ratio is 8.9%, the chemo-selective 85.6% of aldehyde, and the molar ratio of n-alkanal and iso-aldehyde is 26.0:1.0 (n-alkanal Regioselectivity 96.3%), TOF values are 152h-1。
Embodiment 10
Rh(acac)(CO)2/Xantphos-(SO3Na)2(3)/[Ph(EO)16MI(H)][CH3SO3 -Under]/1- octene systems Two-phase hydroformylation reaction (l=m=2)
Ionic liquid is changed to [Ph (EO)16MI(H)][CH3SO3 -], remaining reaction condition is with step with embodiment 3, gas phase color Spectrum analysis result is：The conversion ratio of 1- octenes is 25.8%, the chemo-selective 95.5% of aldehyde, mole of n-alkanal and iso-aldehyde Than being 27.0:1.0 (regioselectivities 96.4% of n-alkanal), TOF values are 493h-1。
Embodiment 11
Rh(acac)(CO)2/Xantphos-(SO3Na)2(3)/[n-C12H25(EO)16MI(CH3)][CH3SO3 -]/1- is pungent Two-phase hydroformylation reaction (l=m=2) under alkene system
Ionic liquid is changed to [n-C12H25(EO)16MI(CH3)][CH3SO3 -], 1- octenes/Rh (acac) (CO)2=5000:1 (molar ratio), with step with embodiment 3, gas chromatographic analysis result is remaining reaction condition：The conversion ratio of 1- octenes is 16.3%, the molar ratio of the chemo-selective 97.4% of aldehyde, n-alkanal and iso-aldehyde is 31.0:1.0 (the regional choices of n-alkanal Property 96.9%), TOF values be 1588h-1。
Embodiment 12
Rh(acac)(CO)2/Xantphos-(SO3Na)2(3)/[Ph(EO)50MI(n-C16H33)][CH3SO3 -]/1- octenes Two-phase hydroformylation reaction (l=m=2) under system
Ionic liquid is changed to [Ph (EO)50MI(n-C16H33)][CH3SO3 -], 1- octenes/Rh (acac) (CO)2=5000:1 (molar ratio), with step with embodiment 3, gas chromatographic analysis result is remaining reaction condition：The conversion ratio of 1- octenes is 15.0%, the molar ratio of the chemo-selective 93.5% of aldehyde, n-alkanal and iso-aldehyde is 29.0:1.0 (the regional choices of n-alkanal Property 96.7%), TOF values be 1403h-1。
Embodiment 13
Rh(acac)(CO)2/Xantphos-(SO3Na)2(3)/[CH3(EO)16MI(EO)16CH3][4-CH3PhSO3 -]/1- Two-phase hydroformylation reaction (l=m=2) under octene system
Ionic liquid is changed to [CH3(EO)16MI(EO)16CH3][4-CH3PhSO3 -], remaining reaction condition is with step with implementation Example 3, gas chromatographic analysis result are：The conversion ratio of 1- octenes be 20.5%, the chemo-selective 94.6% of aldehyde, n-alkanal with it is different The molar ratio of structure aldehyde is 28.5:1.0 (regioselectivities 96.6% of n-alkanal), TOF values are 388h-1。
Embodiment 14
Rh(acac)(CO)2/Xantphos-(SO3K)2(3)/[Ph(EO)16MI(CH3)][n-C12H25SO3 -]/1- octenes Two-phase hydroformylation reaction (l=m=2) under system
Ionic liquid is changed to [Ph (EO)16MI(CH3)][n-C12H25SO3 -], biphosphine ligand is Xantphos- (SO3K)2 (3), 1- octenes/Rh (acac) (CO)2=5000:1 (molar ratio), remaining reaction condition is with step with embodiment 3, gas-chromatography Analysis result is：The conversion ratio of 1- octenes is 13.9%, the chemo-selective 95.0% of aldehyde, the molar ratio of n-alkanal and iso-aldehyde It is 27.0:1.0 (regioselectivities 96.4% of n-alkanal), TOF values are 1321h-1。
Embodiment 15
Rh(acac)(CO)2/Xantphos-(SO3NH4)2(3)/[Ph(EO)16MI(CH3)][4-n-C12H25PhSO3 -]/ Two-phase hydroformylation reaction (l=m=2) under 1- octene systems
Ionic liquid is changed to [Ph (EO)16MI(CH3)][4-n-C12H25PhSO3 -], biphosphine ligand Xantphos- (SO3NH4)2(3), 1- octenes/Rh (acac) (CO)2=5000:1 (molar ratio), remaining reaction condition and step with embodiment 3, Gas chromatographic analysis result is：The conversion ratio of 1- octenes is 12.9%, the chemo-selective 88.4% of aldehyde, n-alkanal and iso-aldehyde Molar ratio be 28.0:1.0 (regioselectivities 96.6% of n-alkanal), TOF values are 1140h-1。
Embodiment 16
Rh(acac)(CO)2/Xantphos-(SO3Na)6(3)/[Ph(EO)16MI(CH3)][CH3SO3 -]/1- octene systems Lower two-phase hydroformylation reaction (l=m=0)
Biphosphine ligand is changed to Xantphos- (SO3Na)6(3), remaining reaction condition and step are the same as embodiment 3, gas-chromatography Analysis result is：The conversion ratio of 1- octenes is 21.3%, the chemo-selective 94.1% of aldehyde, the molar ratio of n-alkanal and iso-aldehyde It is 28.0:1.0 (regioselectivities 96.6% of n-alkanal), TOF values are 401h-1。
Embodiment 17
Rh(acac)(CO)2/Xantphos-(SO3Na)2(3)/[Ph(EO)16MI(CH3)][CH3SO3 -]/2- octene systems Lower two-phase hydroformylation reaction (l=m=2)
Alkene is changed to 2- octenes, and reaction time 1h, remaining reaction condition is with step with embodiment 3, gas chromatographic analysis As a result it is：The conversion ratio of 2- octenes is 27.5%, the chemo-selective 78.2% of aldehyde, and the molar ratio of n-alkanal and iso-aldehyde is 26.0:1.0 (regioselectivities 96.3% of n-alkanal), TOF values are 215h-1。
Embodiment 18
Rh(acac)(CO)2/Xantphos-(SO3Na)2(3)/[Ph(EO)16MI(CH3)][CH3SO3 -]/1- hexene systems Lower two-phase hydroformylation reaction (l=m=2)
Alkene is changed to 1- hexenes, and with step with embodiment 3, gas chromatographic analysis result is remaining reaction condition：1- octenes Conversion ratio be 41.5%, the molar ratio of the chemo-selective 94.7% of aldehyde, n-alkanal and iso-aldehyde is 34.5:1.0 (n-alkanals Regioselectivity 97.2%), TOF values be 786h-1。
Embodiment 19
Rh(acac)(CO)2/Xantphos-(SO3Na)2(3)/[Ph(EO)16MI(CH3)][CH3SO3 -]/1- decene systems Lower two-phase hydroformylation reaction (l=m=2)
Alkene is changed to 1- decene, and with step with embodiment 3, gas chromatographic analysis result is remaining reaction condition：1- octenes Conversion ratio be 23.5%, the molar ratio of the chemo-selective 95.0% of aldehyde, n-alkanal and iso-aldehyde is 31.5:1.0 (n-alkanals Regioselectivity 96.9%), TOF values be 447h-1。
Embodiment 20
Rh(acac)(CO)2/Xantphos-(SO3Na)2(3)/[Ph(EO)16MI(CH3)][CH3SO3 -]/1- laurylene bodies The lower two-phase hydroformylation reaction (l=m=2) of system
Alkene is changed to 1- laurylenes, and with step with embodiment 3, gas chromatographic analysis result is remaining reaction condition：1- ten The conversion ratio of diene is 17.8%, the chemo-selective 92.5% of aldehyde, and the molar ratio of n-alkanal and iso-aldehyde is 30.0:1.0 (just The regioselectivity 96.8% of structure aldehyde), TOF values are 329h-1。
Embodiment 21
Rh(acac)(CO)2/Xantphos-(SO3Na)2(3)/[Ph(EO)16MI(CH3)][CH3SO3 -]/1-tetradecylene body The lower two-phase hydroformylation reaction (l=m=2) of system
Alkene is changed to 1-tetradecylene, and with step with embodiment 3, gas chromatographic analysis result is remaining reaction condition：1- ten The conversion ratio of tetraene is 16.5%, the chemo-selective 90.5% of aldehyde, and the molar ratio of n-alkanal and iso-aldehyde is 29.0:1.0 (just The regioselectivity 96.7% of structure aldehyde), TOF values are 299h-1。
Embodiment 22-64
Rh(acac)(CO)2/Xantphos-(SO3Na)2(3)/[Ph(EO)16MI(CH3)][CH3SO3 -]/1- octene systems Lower two-phase hydroformylation reaction circulation experiment (l=m=2)
Under an inert atmosphere, Rh (acac) (CO) is added into stainless steel autoclave2、Xantphos-(SO3Na)2 (3)、[Ph(EO)16MI(CH3)][CH3SO3 -] and 1- octenes, its ratio be：Xantphos-(SO3Na)2(3)/Rh(acac) (CO)2=20:1 (molar ratio), 1- octenes/Rh (acac) (CO)2=1000:1 (molar ratio), [Ph (EO)16MI(CH3)] [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, 5 hours reaction time to be then quickly cooled to room temperature, opens kettle after being vented synthesis gas, system is divided into two naturally Phase, lower layer's ionic liquid mutually solidify, and are decanted off the organic phase on upper layer, and the ionic liquid of rhodium catalyst is contained mutually by adding in lower layer New 1- octenes can carry out catalytic cycle next time, gas chromatographic analysis the result shows that：After 43 catalytic cycles, alkene turns The regioselectivity of rate, aldehyde chemo-selective and n-alkanal is not decreased obviously, and accumulative TON values reach 38634, single cycle Rhodium number of dropouts be 0.03-0.1%, embodiment 22-64 during circulation experiment the results are shown in Table 1.
The circulation experiment of 1 rhodium catalyst of table
Continuous upper table

Claims (4)

1. a kind of highly selective method for preparing n-alkanal of alkene two-phase hydroformylation based on polyethers imidazolium ionic liquid, It is characterized in that：Biphase catalytic system is made of ionic liquid phase and organic phase, and ionic liquid includes mutually polyethers imidazolium ion Liquid, rhodium catalyst and biphosphine ligand 1,2 or 3；Organic phase is reaction substrate C6-C10The mixing of straight chain 1- alkene 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 biphosphine ligand 1,2,3 is as follows：
In formula：R4For C6H4-3-SO3 -；M is H+、NH4 +, valent metal ion, a stoichiometric polyvalent metal ion；P=1 Or 2, q=1 or 2, l=0,1 or 2, m=0,1 or 2；The structure of polyethers imidazolium ionic liquid is as follows：
In formula：N=16, o=0, R1For phenyl, R2For methyl, R3For methyl；Or n=16, o=0, R1For n-C12H25, R2For first Base, R3For methyl；Or n=50, o=0, R1For phenyl, R2For n-C16H33, R3For methyl；Or n=16, o=0, R1For phenyl, R2 For methyl, R3For n-C12H25-；Or n=16, o=0, R1For phenyl, R2For methyl, R3For 4-n-C12H25Ph-。
2. according to a kind of highly selective preparation of alkene two-phase hydroformylation based on polyethers imidazolium ionic liquid of claim 1 The method of n-alkanal, it is characterized in that：Under an inert atmosphere, by polyethers imidazolium ionic liquid, biphosphine ligand 1,2 or 3, rhodium catalysis Agent, substrate olefin mix in certain proportion, wherein reaction substrate is C6-C10The mixture of straight chain 1- alkene or above-mentioned alkene, Biphosphine ligand 1,2 or 3 and the molar ratio of rhodium in rhodium catalyst are 3:1-100:1, polyethers imidazolium ionic liquid and rhodium catalyst The molar ratio of middle rhodium is 30:1-1000:1, it is 100 to make the molar ratio of substrate olefin and rhodium in rhodium catalyst:1-10000:1, it closes It is 1-10MPa at atmospheric pressure, reaction temperature is 70-130 DEG C, and the reaction time is 0.25-15 hours；Not solubilizer in system；Instead After answering, realize that the recycling of rhodium catalyst, ionic liquid mutually pass through benefit by the two-phase laminated flow of ionic liquid phase and organic phase New alkene is added to carry out catalytic cycle next time.
3. according to a kind of highly selective preparation of alkene two-phase hydroformylation based on polyethers imidazolium ionic liquid of claim 1 The method of n-alkanal, 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 1,5- cyclo-octadiene.
4. according to a kind of highly selective preparation of alkene two-phase hydroformylation based on polyethers imidazolium ionic liquid of claim 1 The method of n-alkanal, it is characterised in that reaction product is the mixed of one or more of aldehyde, isomerizing olefins, olefin hydrogenation product Close object.
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