CN103483381B - The preparation of one class phosphine functionalized ion liquid and the application in hydroformylation reaction thereof - Google Patents
The preparation of one class phosphine functionalized ion liquid and the application in hydroformylation reaction thereof Download PDFInfo
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Abstract
The present invention relates to the synthesis of the polyoxyalkylene alkyl guanidinium ionic liquid of a class phosphine functionalization and the application in homogeneous catalytic reaction thereof, this kind of functional ion liquid easily can be prepared by the ion-exchange reactions between polyoxyalkylene alkyl guanidinium ionic liquid and Water-soluble Sulphonated phosphines, phosphine functionalized ion liquid designed by the present invention can be applicable to transition metal-catalyzed organic reaction, including hydroformylation, hydroesterification, hydrocarboxylation and catalytic hydrogenation, the consumption of catalytic reaction intermediate ion liquid can be reduced, improve the activity of catalytic reaction, realize easy catalyst to separate and circulation.
Description
Technical field
The present invention relates to technical field of chemistry and chemical engineering, more particularly to the preparation of a class phosphine functionalized ion liquid and the application in hydroformylation reaction thereof.
Background technology
Homogeneous noble metal catalyst has the advantage that catalysis activity is high, selectivity is good, reaction condition is gentle, receives more and more attention in recent decades.How from homogeneous catalytic reaction product, high efficiency separation and circulation noble metal catalyst are always a challenging research topic.Water/organic two-phase system is successfully applied in the separation of homogeneous catalyst and the production of hydroformylation of propene producing butyladehyde, but a lot of organic reaction substrate dissolubility in water is relatively low, causes reaction mass transfer problem so that it is range of application is restricted.In recent years, concept based on " homogeneous catalysis heterogenize ", various new methods are constantly developed to solve this problem, as: Organic fluoride is biphase, ionic liquid at room temperature, supercritical fluid two-phase system etc., wherein the development of non-aqueous ionic liquid system is the rapidest, it has also become most one of biphase catalytic system of application prospect.
Realize biphasic catalysis reaction proved by a large amount of successfully researchs and report although noble metal catalyst is carried in ionic liquid, but the problem of some keys still has to be solved.One of problem is: supported precious metal catalyst needs substantial amounts of ionic liquid, and the preparation cost of ionic liquid is higher, and economy is the best；Two are: under most non-aqueous ionic liquid systems, be must pull against mass transfer and diffusional resistance gets to active sites owing to reactant molecule limits by dissolubility in ionic liquid, cause being catalyzed activity and reduce.
Recently; we are at Chem.Commun.2012; 48,9017-9019 and patent CN201210064537.5 in report a class there is the polyoxyalkylene alkyl guanidine pyrovinic acid ionic liquid of the liquid-solid phase-change characteristic of room temperature and the application in the biphase hydroformylation reaction of higher olefins thereof.This kind of novel functional ion liquid can effective immobilized Rh-TPPTS catalyst, and there is the ability significantly stablizing rhodium catalytic activity species.But owing to being limited by biphase catalytic system resistance to mass tranfer, to C10Above straight chain its activity of 1-alkene has and reduces by a relatively large margin.
Summary of the invention
For the deficiencies in the prior art, the advantage of polyoxyalkylene alkyl guanidinium ionic liquid and Water-soluble Sulphonated phosphines is combined by the present invention, and design has synthesized the polyoxyalkylene alkyl guanidinium ionic liquid (PPGIL) of a class phosphine functionalization.
The advantage that the polyoxyalkylene alkyl guanidinium ionic liquid of this kind of Novel phosphine functionalization has following uniqueness: (1) synthesis is very simple, can be prepared with the ion-exchange reactions between sulfonic acid sodium form water-soluble phosphine ligand by polyoxyalkylene alkyl guanidine pyrovinic acid ionic liquid；(2) dystectic sulfonic acid sodium form water-soluble phosphine ligand can be transformed into ionic liquid by the introducing of polyoxyalkylene alkyl guanidine salt cation, can regulate and control easily by changing EO value, N-alkyl and O-alkyl on polyoxyalkylene alkyl guanidine salt cation according to the needs of application, the physics of PPGIL and chemical property (polarity, dissolubility, viscosity, freezing point, electrical conductivity, hydrophile-lipophile balance and heat stability etc.).As, sulfonic acid sodium form water-soluble phosphine ligand typically organic solvent insoluble in low pole (as, benzene, toluene, dichloromethane etc.) and some polar solvents (as, methanol, acetonitrile, oxolane etc.), and PPGIL is soluble in above-mentioned solvent, this extends the range of application of Water-soluble Sulphonated phosphines to a great extent；(3) the Water-soluble Sulphonated phosphines synthetic method as PPGIL anion is ripe, abundance, and range of choice width can regulate and control the activity of catalyst, chemo-selective, regioselectivity and stereo selectivity easily by the structure changing anion；(4) in catalystic converter system, PPGIL plays the role of catalyst carrier and part as ionic liquid simultaneously, need not other ionic liquid the most additional as carrier, therefore greatly reduce the consumption of ionic liquid；(5) intensive polar solvent such as the weak polar solvents such as benzene, toluene, dichloromethane and methanol, acetonitrile, oxolane it is soluble in due to PPGIL, it is insoluble in alkane solvent, therefore catalytic reaction can be carried out in benzene, toluene, dichloromethane, methanol, acetonitrile, oxolane equal solvent, realize homogeneous reaction, after reaction terminates, decompression removes lower boiling solvent, for being less than the alkene of 8 containing carbon number, directly decompression distillation obtains product aldehyde, and residual ion liquid phase can continue next catalytic cycle；For being more than or equal to the alkene of 8 containing carbon number, use C6-C8Alkane or petroleum ether extraction product aldehyde, the ionic liquid of residual continues catalytic cycle next time after being separated, owing to reaction is to carry out under homogeneous phase condition, there is not mass transfer problem, while improving catalysis activity and selectivity, also achieve high efficiency separation and the circulation of catalyst.
The present invention designs the ionic liquid having synthesized a class phosphine functionalization, it is characterised in that: the cation of this kind of phosphine functionalized ion liquid is polyoxyalkylene alkyl guanidine salt cation, and anion is Water-soluble Sulphonated phosphines anion, and its structural formula is:
In formula: m=1-100；R1For C1-C16Normal chain alkyl；R2For H, C1-C16Normal chain alkyl or benzyl；R3For C1-C16Normal chain alkyl or phenyl；R4For the anion of Water-soluble Sulphonated phosphines shown below, n is the number of sulfonic group anion, n=1-8 on Phosphine ligands；
In formula: R5For C6H5Or C6H4-3-SO3 -；R6, R7, R8, R9, R10, R11, R12And R13It is respectively the parent fraction of different Water-soluble Sulphonated phosphines.
The synthetic method of the ionic liquid 1 of phosphine functionalization is as follows:
In formula: R14For CH3Or p-CH3-C6H4。
The ionic liquid 1 of phosphine functionalization is by polyoxyalkylene alkyl guanidinium ionic liquid 2 and sulfonic acid sodium form water-soluble phosphine ligand [Na+]n[R4]n-At CH3Carrying out prepared by ion-exchange reactions in CN, reaction temperature is 0-80 DEG C, response time 8-72h.
The ionic liquid 1 of phosphine functionalization can be applicable to hydroformylation; hydroesterification; hydrocarboxylation and catalytic hydrogenation, have for forming the metal of transition metal complex catalysts with phosphine functionalized ion liquid described in claim 1: rhodium (Rh), ruthenium (Ru), iridium (Ir), palladium (Pd), platinum (Pt), osmium (Os), gold (Au) or cobalt (Co).
The ionic liquid 1 of phosphine functionalization can be applicable to the hydroformylation reaction of alkene, and the alkene of use is C3-C16Linear alpha-olefin, cyclohexene, styrene, p-methylstyrene, o-methyl styrene, p-tert-butylstyrene, p-isobutylstyrene, to methoxy styrene, to chlorostyrene, chloro styrene or 2-vinyl naphthalene, the transition metal complex catalysts precursor of employing is RhCl3·3H2O、Rh(acac)(CO)2(rhodium dicarbonyl acetylacetonate), [Rh (COD)2]BF4(COD:1,5-cyclo-octadiene) or [Rh (COD) Cl]2, transition metal complex catalysts be by phosphine functionalized ion liquid 1 and transition metal complex catalysts precursor under the conditions of hydroformylation reaction generated in-situ.
The ionic liquid 1 of phosphine functionalization is for the hydroformylation reaction of alkene; it is characterized in that: phosphine functionalized ion liquid 1, transition metal complex catalysts precursor, alkene and organic solvent are added in rustless steel autoclave; making 1 is 1:1-50:1 with the mol ratio of rhodium in transition metal complex catalysts precursor; alkene is 100:1-10000:1 with the mol ratio of rhodium in transition metal complex catalysts precursor; organic solvent is 1:1-10:1 with the volume ratio of alkene; by nitrogen or argon displaced air 4-6 time, then with synthesis gas (H2/ CO=1:1) it is forced into 1.0-7.0MPa, start stirring, reaction temperature 70-130 DEG C, 0.5-24 hour response time, being then cooled to room temperature, be vented synthesis gas, decompression removes organic solvent, obtaining product aldehyde for the alkene distillation of directly reducing pressure less than 8 containing carbon number, residual catalyst phase (including ionic liquid 1 and catalyst) continues next one catalytic cycle after adding new organic solvent and alkene；For being more than or equal to the alkene of 8 containing carbon number, use C6-C8N-alkane or petroleum ether extraction product aldehyde, through the simple upper strata product phase being separated and obtaining containing product aldehyde, lower catalyst agent phase (including ionic liquid 1 and catalyst) continues next catalytic cycle after adding new organic solvent and alkene；The single transformation rate of alkene is 90-99%, and the selectivity of aldehyde is 90-99%, and n-alkanal is 0.05:1-50:1 with the mol ratio of isomery aldehyde.
The ionic liquid 1 of phosphine functionalization, for the hydroformylation reaction of alkene, is characterized in that: the organic solvent applied is benzene, toluene, methanol, ethanol, acetonitrile, dichloromethane or oxolane.
Detailed description of the invention
Embodiment 1
The ionic liquid 1:[R of phosphine functionalization3(EO)mN+R2=C(NR1 2)2]n[R4] synthesis (R1=CH3；R2=H；R3=CH3；R4=(SO3 -)n-R6；M=16, n=3)
Under argon shield, 50mLSchlenk bottle adds the (SO of 1.56mmol3Na)3-R6, [the CH of 4.73mmol3(EO)16N+H=C(N(CH3)2)2][CH3SO3 -] and 10mL acetonitrile, reactant mixture is stirred at room temperature 72 hours, filters, and filtrate decompression removes acetonitrile and obtains orange-yellow thick liquid, yield 95%.
Embodiment 2
The ionic liquid 1:[R of phosphine functionalization3(EO)mN+R2=C(NR1 2)2]n[R4] synthesis (R1=CH3；R2=H；R3=C6H5；R4=(SO3 -)n-R6；M=16, n=3)
Under argon shield, 50mLSchlenk bottle adds the (SO of 1.56mmol3Na)3 -R6, [the C of 4.73mmol6H5(EO)16N+H=C(N(CH3)2)2][CH3SO3 -] and 10mL acetonitrile, reactant mixture is stirred at room temperature 72 hours, filters, and filtrate decompression removes acetonitrile and obtains orange-yellow thick liquid, yield 90%.
Embodiment 3
The ionic liquid 1:[R of phosphine functionalization3(EO)mN+R2=C(NR1 2)2]n[R4] synthesis (R1=CH3；R2=H；R3=n-C16H33；R4=(SO3 -)n-R6；M=16, n=3)
Under argon shield, 50mLSchlenk bottle adds the (SO of 1.56mmol3Na)3-R6, [the n-C of 4.73mmol16H33(EO)16N+H=C(N(CH3)2)2][CH3SO3 -] and 20mL acetonitrile, reactant mixture is stirred at room temperature 72 hours, filters, and filtrate decompression removes acetonitrile and obtains orange-yellow thick liquid, yield 94%.
Embodiment 4
The ionic liquid 1:[R of phosphine functionalization3(EO)mN+R2=C(NR1 2)2]n[R4] synthesis (R1=CH3；R2=n-C6H13；R3=CH3；R4=(SO3 -)n-R6；M=16, n=3)
Under argon shield, 50mLSchlenk bottle adds the (SO of 1.56mmol3Na)3-R6, [the CH of 4.73mmol3(EO)16N+(n-C6H13)=C(N(CH3)2)2][CH3SO3 -] and 10mL acetonitrile, reactant mixture is stirred at room temperature 72 hours, filters, and filtrate decompression removes acetonitrile and obtains orange-yellow thick liquid, yield 95%.
Embodiment 5
The ionic liquid 1:[R of phosphine functionalization3(EO)mN+R2=C(NR1 2)2]n[R4] synthesis (R1=CH3；R2=C6H5CH2；R3=CH3；R4=(SO3 -)n-R6；M=16, n=3)
Under argon shield, 50mLSchlenk bottle adds the (SO of 1.56mmol3Na)3-R6, [the CH of 4.73mmol3(EO)16N+(C6H5CH2)=C(N(CH3)2)2][CH3SO3 -] and 10mL acetonitrile, reactant mixture is stirred at room temperature 72 hours, filters, and filtrate decompression removes acetonitrile and obtains orange-yellow thick liquid, yield 92%.
Embodiment 6
The ionic liquid 1:[R of phosphine functionalization3(EO)mN+R2=C(NR1 2)2]n[R4] synthesis (R1=n-C16H33；R2=H；R3=CH3；R4=(SO3 -)n-R6；M=16, n=3)
Under argon shield, 50mLSchlenk bottle adds the (SO of 1.56mmol3Na)3-R6, [the CH of 4.73mmol3(EO)16N+H=C(N(n-C16H33)2)2][CH3SO3 -] and 20mL acetonitrile, reactant mixture is stirred at room temperature 72 hours, filters, and filtrate decompression removes acetonitrile and obtains orange-yellow thick liquid, yield 96%.
Embodiment 7
The ionic liquid 1:[R of phosphine functionalization3(EO)mN+R2=C(NR1 2)2]n[R4] synthesis (R1=CH3；R2=H；R3=CH3；R4=(SO3 -)n-R6；M=4, n=3)
Under argon shield, 50mLSchlenk bottle adds the (SO of 1.56mmol3Na)3-R6, [the CH of 4.73mmol3(EO)4N+H=C(N(CH3)2)2][CH3SO3 -] and 10mL acetonitrile, reactant mixture is stirred at room temperature 72 hours, filters, and filtrate decompression removes acetonitrile and obtains orange-yellow thick liquid, yield 91%.
Embodiment 8
The ionic liquid 1:[R of phosphine functionalization3(EO)mN+R2=C(NR1 2)2]n[R4] synthesis (R1=CH3；R2=H；R3=CH3；R4=(SO3 -)n-R6；M=42, n=3)
Under argon shield, 50mLSchlenk bottle adds the (SO of 1.56mmol3Na)3-R6, [the CH of 4.73mmol3(EO)42N+H=C(N(CH3)2)2][CH3SO3 -] and 25mL acetonitrile, reactant mixture is stirred at room temperature 72 hours, filters, and filtrate decompression removes acetonitrile and obtains orange-yellow thick liquid, yield 96%.
Embodiment 9
The ionic liquid 1:[R of phosphine functionalization3(EO)mN+R2=C(NR1 2)2]n[R4] synthesis (R1=CH3；R2=H；R3=CH3；R4=(SO3 -)n-R7；M=16, n=4)
Under argon shield, 50mLSchlenk bottle adds the (SO of 1.56mmol3Na)4-R7, [the CH of 6.30mmol3(EO)16N+H=C(N(CH3)2)2][CH3SO3 -] and 15mL acetonitrile, reactant mixture is stirred at room temperature 72 hours, filters, and filtrate decompression removes acetonitrile and obtains orange-yellow thick liquid, yield 94%.
Embodiment 10
The ionic liquid 1:[R of phosphine functionalization3(EO)mN+R2=C(NR1 2)2]n[R4] synthesis (R1=CH3；R2=H；R3=CH3；R4=(SO3 -)n-R8；M=16, n=4)
Under argon shield, 50mLSchlenk bottle adds the (SO of 1.56mmol3Na)4-R8, [the CH of 6.30mmol3(EO)16N+H=C(N(CH3)2)2][CH3SO3 -] and 15mL acetonitrile, reactant mixture is stirred at room temperature 72 hours, filters, and filtrate decompression removes acetonitrile and obtains orange-yellow thick liquid, yield 92%.
Embodiment 11
The ionic liquid 1:[R of phosphine functionalization3(EO)mN+R2=C(NR1 2)2]n[R4] synthesis (R1=CH3；R2=H；R3=CH3；R4=(SO3 -)n-R9；M=16, n=4)
Under argon shield, 50mLSchlenk bottle adds the (SO of 1.56mmol3Na)4-R9, [the CH of 6.30mmol3(EO)16N+H=C(N(CH3)2)2][CH3SO3 -] and 15mL acetonitrile, reactant mixture is stirred at room temperature 72 hours, filters, and filtrate decompression removes acetonitrile and obtains orange-yellow thick liquid, yield 93%.
Embodiment 12
The ionic liquid 1:[R of phosphine functionalization3(EO)mN+R2=C(NR1 2)2]n[R4] synthesis (R1=CH3；R2=H；R3=CH3；R4=(SO3 -)n-R10；M=16, n=4)
Under argon shield, 50mLSchlenk bottle adds the (SO of 1.56mmol3Na)4-R10, [the CH of 6.30mmol3(EO)16N+H=C(N(CH3)2)2][CH3SO3 -] and 15mL acetonitrile, reactant mixture is stirred at room temperature 72 hours, filters, and filtrate decompression removes acetonitrile and obtains orange-yellow thick liquid, yield 90%.
Embodiment 13
The ionic liquid 1:[R of phosphine functionalization3(EO)mN+R2=C(NR1 2)2]n[R4] synthesis (R1=CH3；R2=H；R3=CH3；R4=(SO3 -)n-R11；M=16, n=2)
Under argon shield, 50mLSchlenk bottle adds the (SO of 1.56mmol3Na)2-R11, [the CH of 3.20mmol3(EO)16N+H=C(N(CH3)2)2][CH3SO3 -] and 15mL acetonitrile, reactant mixture is stirred at room temperature 72 hours, filters, and filtrate decompression removes acetonitrile and obtains orange-yellow thick liquid, yield 89%.
Embodiment 14
The ionic liquid 1:[R of phosphine functionalization3(EO)mN+R2=C(NR1 2)2]n[R4] synthesis (R1=CH3；R2=H；R3=CH3；R4=(SO3 -)n-R12；M=16, n=4)
Under argon shield, 50mLSchlenk bottle adds the (SO of 1.56mmol3Na)4-R12, [the CH of 6.30mmol3(EO)16N+H=
C(N(CH3)2)2][CH3SO3 -] and 20mL acetonitrile, reactant mixture is stirred at room temperature 72 hours, filters, and filtrate decompression removes acetonitrile and obtains orange-yellow thick liquid, yield 93%.
Embodiment 15
The ionic liquid 1:[R of phosphine functionalization3(EO)mN+R2=C(NR1 2)2]n[R4] synthesis (R1=CH3；R2=H；R3=CH3；R4=(SO3 -)n-R13；M=16, n=2)
Under argon shield, 50mLSchlenk bottle adds the (SO of 1.56mmol3Na)2-R13, [the CH of 3.20mmol3(EO)16N+H=C(N(CH3)2)2][CH3SO3 -] and 20mL acetonitrile, reactant mixture is stirred at room temperature 72 hours, filters, and filtrate decompression removes acetonitrile and obtains orange-yellow thick liquid, yield 90%.
Embodiment 16
RhCl3·3H2O/[CH3(EO)16N+H=C(N(CH3)2)2]3[(SO3 -)3-R61-hexene hydroformylation reaction under]/toluene system
RhCl is added in rustless steel autoclave3·3H2O、[CH3(EO)16N+H=C(N(CH3)2)2]3[(SO3 -)3-R6], toluene and 1-hexene, its ratio is: [CH3(EO)16N+H=C(N(CH3)2)2]3[(SO3 -)3-R6]/RhCl3·3H2O=10:1 (mol ratio), 1-hexene/RhCl3·3H2O=1000:1 (mol ratio), toluene/1-hexene=3:1-5:1 (volume ratio), by nitrogen or argon displaced air 4-6 time, then with synthesis gas (H2/ CO=1:1) it is forced into 5.0MPa, reaction temperature 85 DEG C, in 2 hours response time, it is then cooled to room temperature, after emptying, decompression removes toluene, then decompression product of distillation aldehyde.Gas chromatographic analysis, the conversion ratio of 1-hexene is 96%, the selectivity 96% of aldehyde, and n-alkanal is 2.8:1 with the mol ratio of isomery aldehyde, and the ionic liquid of residual continues next catalytic cycle after adding new toluene and 1-hexene.
Embodiment 17
RhCl3·3H2O/[CH3(EO)16N+H=C(N(CH3)2)2]3[(SO3 -)3-R61-octene hydroformylation reaction under]/toluene system
RhCl is added in rustless steel autoclave3·3H2O、[CH3(EO)16N+H=C(N(CH3)2)2]3[(SO3 -)3-R6], toluene and 1-octene, its ratio is: [CH3(EO)16N+H=C(N(CH3)2)2]3[(SO3 -)3-R6]/RhCl3·3H2O=10:1 (mol ratio), 1-octene/RhCl3·3H2O=1000:1 (mol ratio), toluene/1-octene=3:1-5:1 (volume ratio), by nitrogen or argon displaced air 4-6 time, then with synthesis gas (H2/ CO=1:1) it is forced into 5.0MPa, reaction temperature 85 DEG C, in 2 hours response time, is then cooled to room temperature, after emptying, decompression removes toluene, add normal heptane extraction, separate upper strata product aldehyde phase, through gas chromatographic analysis, the conversion ratio of 1-octene is 90%, the selectivity 95% of aldehyde, n-alkanal is 2.7:1 with the mol ratio of isomery aldehyde, and lower catalyst agent continues next catalytic cycle after adding new toluene and 1-octene.
Embodiment 18
RhCl3·3H2O/[CH3(EO)16N+H=C(N(CH3)2)2]3[(SO3 -)3-R61-decene hydroformylation reaction under]/toluene system
RhCl is added in rustless steel autoclave3·3H2O、[CH3(EO)16N+H=C(N(CH3)2)2]3[(SO3 -)3-R6], toluene and 1-decene, its ratio is: [CH3(EO)16N+H=C(N(CH3)2)2]3[(SO3 -)3-R6]/RhCl3·3H2O=10:1 (mol ratio), 1-decene/RhCl3·3H2O=1000:1 (mol ratio), toluene/1-decene=3:1-5:1 (volume ratio), by nitrogen or argon displaced air 4-6 time, then with synthesis gas (H2/ CO=1:1) it is forced into 5.0MPa, reaction temperature 85 DEG C, in 2 hours response time, is then cooled to room temperature, after emptying, decompression removes toluene, add normal heptane extraction, separate upper strata product aldehyde phase, through gas chromatographic analysis, the conversion ratio of 1-decene is 95%, the selectivity 96% of aldehyde, n-alkanal is 2.6:1 with the mol ratio of isomery aldehyde, and lower catalyst agent continues next catalytic cycle after adding new toluene and 1-decene.
Embodiment 19
RhCl3·3H2O/[CH3(EO)16N+H=C(N(CH3)2)2]3[(SO3 -)3-R61-laurylene hydroformylation reaction under]/toluene system
RhCl is added in rustless steel autoclave3·3H2O、[CH3(EO)16N+H=C(N(CH3)2)2]3[(SO3 -)3-R6], toluene and 1-laurylene, its ratio is: [CH3(EO)16N+H=C(N(CH3)2)2]3[(SO3 -)3-R6]/RhCl3·3H2O=10:1 (mol ratio), 1-laurylene/RhCl3·3H2O=1000:1 (mol ratio), toluene/1-laurylene=3:1-5:1 (volume ratio), by nitrogen or argon displaced air 4-6 time, then with synthesis gas (H2/ CO=1:1) it is forced into 5.0MPa, reaction temperature 85 DEG C, in 2 hours response time, is then cooled to room temperature, after emptying, decompression removes toluene, add normal heptane extraction, separate upper strata product aldehyde phase, through gas chromatographic analysis, the conversion ratio of 1-laurylene is 93%, the selectivity 94% of aldehyde, n-alkanal is 2.6:1 with the mol ratio of isomery aldehyde, and lower catalyst agent continues next catalytic cycle after adding new toluene and 1-laurylene.
Embodiment 20
RhCl3·3H2O/[CH3(EO)16N+H=C(N(CH3)2)2]3[(SO3 -)3-R61-tetradecylene hydroformylation reaction under]/toluene system
RhCl is added in rustless steel autoclave3·3H2O、[CH3(EO)16N+H=C(N(CH3)2)2]3[(SO3 -)3-R6], toluene and 1-tetradecylene, its ratio is: [CH3(EO)16N+H=C(N(CH3)2)2]3[(SO3 -)3-R6]/RhCl3·3H2O=10:1 (mol ratio), 1-tetradecylene/RhCl3·3H2O=1000:1 (mol ratio), toluene/1-tetradecylene=3:1-5:1 (volume ratio), by nitrogen or argon displaced air 4-6 time, then with synthesis gas (H2/ CO=1:1) it is forced into 5.0MPa, reaction temperature 85 DEG C, in 2 hours response time, is then cooled to room temperature, after emptying, decompression removes toluene, add normal heptane extraction, separate upper strata product aldehyde phase, through gas chromatographic analysis, the conversion ratio of 1-tetradecylene is 92%, the selectivity 93% of aldehyde, n-alkanal is 2.5:1 with the mol ratio of isomery aldehyde, and lower catalyst agent continues next catalytic cycle after adding new toluene and 1-tetradecylene.
Embodiment 21
RhCl3·3H2O/[CH3(EO)16N+H=C(N(CH3)2)2]3[(SO3 -)3-R6Styrene hydroformylation reaction under]/toluene system
RhCl is added in rustless steel autoclave3·3H2O、[CH3(EO)16N+H=C(N(CH3)2)2]3[(SO3 -)3-R6], toluene and styrene, its ratio is: [CH3(EO)16N+H=C(N(CH3)2)2]3[(SO3 -)3-R6]/RhCl3·3H2O=10:1 (mol ratio), styrene/RhCl3·3H2O=1000:1 (mol ratio), toluene/styrene=3:1-5:1 (volume ratio), by nitrogen or argon displaced air 4-6 time, then with synthesis gas (H2/ CO=1:1) it is forced into 5.0MPa, reaction temperature 85 DEG C, in 2 hours response time, is then cooled to room temperature, after emptying, decompression removes toluene, add normal heptane extraction, separate upper strata product aldehyde phase, through gas chromatographic analysis, cinnamic conversion ratio is 98%, the selectivity 97% of aldehyde, n-alkanal is 1:11 with the mol ratio of isomery aldehyde, and lower catalyst agent continues next catalytic cycle after adding new toluene and styrene.
Embodiment 22
Rh(acac)(CO)2/[CH3(EO)16N+H=C(N(CH3)2)2]3[(SO3 -)3-R61-octene hydroformylation reaction under]/methanol system
Rh (acac) (CO) is added in rustless steel autoclave2、[CH3(EO)16N+H=C(N(CH3)2)2]3[(SO3 -)3-R6], methanol and 1-octene, its ratio is: [CH3(EO)16N+H=C(N(CH3)2)2]3[(SO3 -)3-R6]/Rh(acac)(CO)2=10:1 (mol ratio), 1-octene/Rh (acac) (CO)2=1000:1 (mol ratio), methanol/1-octene=3:1-5:1 (volume ratio), by nitrogen or argon displaced air 4-6 time, then with synthesis gas (H2/ CO=1:1) it is forced into 5.0MPa, reaction temperature 85 DEG C, in 2 hours response time, is then cooled to room temperature, after emptying, decompression removes methanol, add normal heptane extraction, separate upper strata product aldehyde phase, through gas chromatographic analysis, the conversion ratio of 1-octene is 97%, the selectivity 97% of aldehyde, n-alkanal is 2.8:1 with the mol ratio of isomery aldehyde, and lower catalyst agent continues next catalytic cycle after adding new methanol and 1-octene.
Embodiment 23
RhCl3·3H2O/[CH3(EO)16N+H=C(N(CH3)2)2]2[(SO3 -)2-R111-octene hydroformylation reaction under]/toluene system
RhCl is added in rustless steel autoclave3·3H2O、[CH3(EO)16N+H=C(N(CH3)2)2]2[(SO3 -)2-R11], toluene and 1-octene, its ratio is: [CH3(EO)16N+H=C(N(CH3)2)2]2[(SO3 -)2-R11]/RhCl3·3H2O=10:1 (mol ratio), 1-octene/RhCl3·3H2O=1000:1 (mol ratio), toluene/1-octene=3:1-5:1 (volume ratio), by nitrogen or argon displaced air 4-6 time, then with synthesis gas (H2/ CO=1:1) it is forced into 5.0MPa, reaction temperature 110 DEG C, in 2 hours response time, is then cooled to room temperature, after emptying, decompression removes toluene, add normal heptane extraction, separate upper strata product aldehyde phase, through gas chromatographic analysis, the conversion ratio of 1-octene is 96%, the selectivity 95% of aldehyde, n-alkanal is 19:1 with the mol ratio of isomery aldehyde, and lower catalyst agent continues next catalytic cycle after adding new toluene and 1-octene.
Embodiment 24
RhCl3·3H2O/[CH3(EO)16N+H=C(N(CH3)2)2]4[(SO3 -)4-R121-octene hydroformylation reaction under]/toluene system
RhCl is added in rustless steel autoclave3·3H2O、[CH3(EO)16N+H=C(N(CH3)2)2]4[(SO3 -)4-R12], toluene and 1-octene, its ratio is: [CH3(EO)16N+H=C(N(CH3)2)2]4[(SO3 -)4-R12]/RhCl3·3H2O=10:1 (mol ratio), 1-octene/RhCl3·3H2O=1000:1 (mol ratio), toluene/1-octene=3:1-5:1 (volume ratio), by nitrogen or argon displaced air 4-6 time, then with synthesis gas (H2/ CO=1:1) it is forced into 5.0MPa, reaction temperature 110 DEG C, in 2 hours response time, is then cooled to room temperature, after emptying, decompression removes toluene, add normal heptane extraction, separate upper strata product aldehyde phase, through gas chromatographic analysis, the conversion ratio of 1-octene is 97%, the selectivity 96% of aldehyde, n-alkanal is 21:1 with the mol ratio of isomery aldehyde, and lower catalyst agent continues next catalytic cycle after adding new toluene and 1-octene.
Embodiment 25
RhCl3·3H2O/[CH3(EO)16N+H=C(N(CH3)2)2]2[(SO3 -)2-R131-octene hydroformylation reaction under]/toluene system
RhCl is added in rustless steel autoclave3·3H2O、[CH3(EO)16N+H=C(N(CH3)2)2]2[(SO3 -)2-R13], toluene and 1-octene, its ratio is: [CH3(EO)16N+H=C(N(CH3)2)2]2[(SO3 -)2-R13]/RhCl3·3H2O=10:1 (mol ratio), 1-octene/RhCl3·3H2O=1000:1 (mol ratio), toluene/1-octene=3:1-5:1 (volume ratio), by nitrogen or argon displaced air 4-6 time, then with synthesis gas (H2/ CO=1:1) it is forced into 5.0MPa, reaction temperature 110 DEG C, in 2 hours response time, is then cooled to room temperature, after emptying, decompression removes toluene, add normal heptane extraction, separate upper strata product aldehyde phase, through gas chromatographic analysis, the conversion ratio of 1-octene is 97%, the selectivity 95% of aldehyde, n-alkanal is 25:1 with the mol ratio of isomery aldehyde, and lower catalyst agent continues next catalytic cycle after adding new toluene and 1-octene.
Claims (5)
1. the ionic liquid of a class phosphine functionalization, it is characterised in that: the cation of this kind of phosphine functionalized ion liquid is polyoxyalkylene alkyl guanidine salt cation, cloudy
Ion is Water-soluble Sulphonated phosphines anion, and its structural formula is:
In formula: m=1-100；R1For C1-C16Normal chain alkyl；R2For H, C1-C16Normal chain alkyl or benzyl；R3For C1-C16Normal chain alkyl or benzene
Base；R4It is expressed as follows the anion of Water-soluble Sulphonated phosphines:
In formula: R6, R7, R8, R9, R10, R11, R12And R13Being respectively the parent fraction of different Water-soluble Sulphonated phosphines, n is that phosphine is joined
The number of sulfonic group anion on body.
2. the preparation method of the ionic liquid of the phosphine functionalization described in claim 1, it is characterised in that the synthesis of the ionic liquid 1 of described phosphine functionalization
Method is as follows:
In formula: R14For CH3Or p-CH3-C6H4。
3. according to the preparation method of ionic liquid of the phosphine functionalization described in claim 2, it is characterised in that: the ionic liquid 1 of phosphine functionalization is to pass through
Polyoxyalkylene alkyl guanidinium ionic liquid 2 and sulfonic acid sodium form water-soluble phosphine ligand [Na+]n[R4]n-At CH3CN carries out prepared by ion-exchange reactions,
Reaction temperature is 0-80 DEG C, response time 8-72h.
4. the ionic liquid of the phosphine functionalization described in claim 1 is for the hydroformylation reaction of alkene, it is characterized in that: by phosphine functionalized ion liquid 1,
Transition metal complex catalysts precursor, alkene and organic solvent add in rustless steel autoclave, make 1 with transition metal complex catalysts before
In body, the mol ratio of rhodium is 1:1-50:1, and alkene is 100:1-10000:1 with the mol ratio of rhodium in transition metal complex catalysts precursor, You Jirong
The volume ratio of agent and alkene is 1:1-10:1, by nitrogen or argon displaced air 4-6 time, then uses synthesis gas, H2/ CO=1:1, is forced into
1.0-7.0MPa, starts stirring, reaction temperature 70-130 DEG C, in 0.5-24 hour response time, is then cooled to room temperature, and is vented synthesis gas,
Decompression removes organic solvent, obtains product aldehyde for the alkene distillation of directly reducing pressure less than 8 containing carbon number, including ionic liquid 1 and catalyst
Residual catalyst continues next catalytic cycle after adding new organic solvent and alkene；For being more than or equal to the alkene of 8 containing carbon number, use
C6-C8N-alkane or petroleum ether extraction product aldehyde, through the simple upper strata product phase being separated and obtaining containing product aldehyde, lower floor includes ionic liquid
The catalyst of body 1 and catalyst continues next catalytic cycle after adding new organic solvent and alkene；The single transformation rate of alkene is
90-99%, the selectivity of aldehyde is 90-99%, and n-alkanal is 0.05:1-50:1 with the mol ratio of isomery aldehyde；The alkene used is C3-C16Straight chain alpha
-alkene, cyclohexene, styrene, p-methylstyrene, o-methyl styrene, p-tert-butylstyrene, p-isobutylstyrene, to methoxy
Base styrene, to chlorostyrene, chloro styrene or 2-vinyl naphthalene；The transition metal complex catalysts precursor used is RhCl3·3H2O or
Rhodium dicarbonyl acetylacetonate Rh (acac) (CO)2；Transition metal complex catalysts is to be catalyzed by phosphine functionalized ion liquid 1 and transition metal complex
Agent precursor is generated in-situ under the conditions of hydroformylation reaction.
5. the ionic liquid according to the phosphine functionalization described in claim 4 is used for the hydroformylation reaction of alkene, it is characterized in that: the organic solvent applied
It is benzene, toluene, methanol, ethanol, acetonitrile, dichloromethane or oxolane.
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