CN111804332B - Application of polyether functionalized ionic liquid catalyst loaded by resin material in olefin hydroformylation reaction - Google Patents

Application of polyether functionalized ionic liquid catalyst loaded by resin material in olefin hydroformylation reaction Download PDF

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CN111804332B
CN111804332B CN202010534921.1A CN202010534921A CN111804332B CN 111804332 B CN111804332 B CN 111804332B CN 202010534921 A CN202010534921 A CN 202010534921A CN 111804332 B CN111804332 B CN 111804332B
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金欣
徐冰莹
姚甲俊
李淑梅
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Qingdao University of Science and Technology
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
    • B01J31/0292—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 immobilised on a substrate
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    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
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Abstract

The invention relates to a polyether-loaded functionalized ionic liquid catalyst of a Merrifield resin material and application thereof in olefin hydroformylation reaction, in particular to a method for immobilizing polyether-functionalized ionic liquid on the surface of the Merrifield resin material by a chemical bonding method, wherein the polyether-functionalized ionic liquid has higher molecular weight, and ether bonds have high flexibility and conformational freedom degree, so that polyether chains can extend on the surface of the material to effectively form an ionic liquid film layer, and solvent ionic liquid is not required to be immersed for the second time, thereby reducing the dosage of the ionic liquid; meanwhile, the phosphine-functionalized polyether ionic liquid and the rhodium catalyst formed by the rhodium catalyst precursor and the chemically bonded polyether ionic liquid on the surface of the Merrifield resin material generate stronger intermolecular affinity, so that the loss of the rhodium catalyst is effectively reduced, and the defects in the prior art are overcome; the catalytic system has higher catalytic activity, the rhodium catalyst can be recycled for a plurality of times, and the catalytic activity and the selectivity are not obviously reduced.

Description

Application of polyether functionalized ionic liquid catalyst loaded by resin material in olefin hydroformylation reaction
Technical Field
The invention relates to the technical field of chemistry and chemical engineering, in particular to application of a polyether functionalized ionic liquid catalyst loaded by Merrifield resin materials in olefin hydroformylation reaction.
Background
Rhodium catalyzed hydroformylation of olefins is a typical atom economic reaction and is also a relatively large number of carbonylation reactions reported in the literature and has become an ideal process for preparing higher aldehydes/alcohols. The homogeneous hydroformylation has the advantages of high catalytic activity, good selectivity and mild reaction conditions, but the problems of separation and recycling of rhodium catalysts have been the focus of attention in the field of homogeneous catalysis for a long time.
In recent years, with increasing importance of green chemistry and the need for environmentally friendly solvents, green solvent ionic liquids have attracted great attention. Unlike conventional organic solvents, ionic liquids have the advantages of extremely low saturated vapor pressure, high thermal and chemical stability, good solubility for transition metal catalysts, designability of structures, and the like, so that the application of ionic liquids as catalyst carriers becomes an effective means for separating, recovering and recycling transition metal catalysts.
Although ionic liquid two-phase hydroformylation solves the problem of separation and circulation of rhodium catalysts to a certain extent, ionic liquids still have great limitations in practical application. First, ionic liquid two-phase catalytic systems still require large amounts of ionic liquid to support and dissolve rhodium catalyst, which is not in accordance with the green chemistry requirements, both from an economic and toxicological perspective; secondly, mass transfer resistance of substrate molecules is increased by the application of a large amount of ionic liquid, negative effects of the ionic liquid (caused by various complex factors such as high viscosity, residual impurities and the like) become more remarkable, and catalytic efficiency is reduced. Thus, how to environmentally friendly and economically apply ionic liquids to build efficient ionic liquid catalytic systems is a current urgent need to be addressed.
The patent ZL201310370138.6, ZL201510250873.2 and ZL201510250176.7 invent phosphine-functionalized polyether imidazolium salt and guanidine salt ionic liquid, and the integration of phosphine ligands and ionic liquid is realized. In the hydroformylation reaction, the phosphine-functionalized ionic liquid has the characteristics of phosphine ligands, can form a complex catalyst with rhodium, has the solvent property of the ionic liquid, and can serve as a carrier of the rhodium catalyst, so that a large amount of other ionic liquids are not needed, the problem of excessively high dosage of the ionic liquid is fundamentally solved, and meanwhile, the negative effect of the ionic liquid in the hydroformylation reaction is minimized.
The immobilized ionic liquid is a novel material which appears in recent years, the concept of immobilized ionic liquid (phase) catalysis developed based on the immobilized ionic liquid integrates the advantages of excellent solubility of the ionic liquid and high specific surface area of a carrier material, not only reduces the dosage of the ionic liquid, but also improves the activity and selectivity of catalytic reaction, is one of research hot spots in the field of the ionic liquid in recent years, and is widely applied to hydroformylation reaction. At present, the preparation method of the supported ionic liquid catalyst mainly comprises the following steps: physical impregnation, chemical bonding and chemical bonding-physical impregnation combinations.
The impregnation method based on the physical adsorption principle is a common method for preparing the immobilized ionic liquid, and has the advantages of simplicity and convenience, but the ionic liquid and the rhodium catalyst dissolved in the ionic liquid layer are easy to run off from the surface of the carrier; the method has the advantages that the defects of a physical impregnation method are overcome by the immobilized ionic liquid through a chemical bonding method, the ionic liquid is not easy to run off from the surface of the carrier due to the fact that cations or anions of the ionic liquid are coupled with active functional groups on the surface of the carrier through covalent bonds, but the ionic liquid is difficult to effectively form an ionic liquid film on the surface of the carrier due to the fact that the quantity of active groups on the surface of the carrier is limited and small-molecule ionic liquid is usually loaded, and the rhodium catalyst cannot be effectively immobilized in an ionic liquid layer due to the simple chemical bonding method; the combined method of chemical bonding and physical impregnation overcomes the defects of the physical impregnation and chemical bonding method to a certain extent, and on the basis of the chemical bonding ionic liquid, a certain amount of solvent ionic liquid is further physically adsorbed on the surface of the material through secondary impregnation to form an ionic liquid film, and then the rhodium catalyst is immobilized in the solvent ionic liquid layer.
Disclosure of Invention
Aiming at the limitations of the supported ionic liquid catalyst in the olefin hydroformylation reaction, the invention aims to provide a polyether functionalized ionic liquid catalyst supported by Merrifield resin materials.
The invention further aims to provide an application method of the polyether functionalized ionic liquid catalyst loaded by the Merrifield resin material in the olefin hydroformylation reaction.
The catalyst comprises a Merrifield resin material with a surface chemically bonded with a polyether functionalized ionic liquid shown in formula 1, formula 2, formula 3 or formula 4, and a phosphine functionalized polyether ionic liquid physically adsorbed on the surface of the Merrifield resin material shown in formula 1, formula 2, formula 3 or formula 4, and a rhodium catalyst formed by the phosphine functionalized polyether ionic liquid and a rhodium catalyst precursor, wherein the surface of the Merrifield resin material is shown in formula 1, formula 2, formula 3 or formula 4:
Figure BDA0002536676680000021
wherein n=4-140, r 1 Is C 1 –C 16 Alkyl or phenyl; x is - OMs， - OTs; the phosphine-functionalized polyether ionic liquid is Y m Z and Y are cations of phosphine-functionalized polyether ionic liquid, and the structure is as follows:
Figure BDA0002536676680000022
wherein l=4-45, r 2 Is C 1 –C 12 Alkyl or phenyl; z is the anion of phosphine-functionalized polyether ionic liquid, and has the structure:
Figure BDA0002536676680000031
wherein 1,2,3,4,5,6,7, 8, 9, 10 and 11 are each the parent moiety of a different sulfonic acid type water-soluble phosphine ligand, m is the total number of sulfonate groups on the phosphine ligand, m>1；R 3 Is C 6 H 4 -3-SO 3 - ；o＝0，1，2；p＝0，1，2；q＝r＝0，1；s＝t＝0，1。
The catalyst comprises a Merrifield resin material with a surface chemically bonded with a polyether functionalized ionic liquid shown in formula 1, formula 2, formula 3 or formula 4, and a phosphine functionalized polyether ionic liquid physically adsorbed on the surface of the Merrifield resin material shown in formula 1, formula 2, formula 3 or formula 4, and a rhodium catalyst formed by the phosphine functionalized polyether ionic liquid and a rhodium catalyst precursor, wherein the surface of the Merrifield resin material is shown in formula 1, formula 2, formula 3 or formula 4:
Figure BDA0002536676680000032
wherein n=4-45, r 1 Is C 1 –C 16 Alkyl or phenyl; x is - OMs， - OTs; the phosphine-functionalized polyether ionic liquid is Y m Z and Y are cations of phosphine-functionalized polyether ionic liquid, and the structure is as follows:
Figure BDA0002536676680000033
wherein l=4-34, r 2 Is C 1 –C 12 Alkyl or phenyl; z is the anion of phosphine-functionalized polyether ionic liquid, and has the structure:
Figure BDA0002536676680000041
wherein 1,2,3,4,5,6,7, 8, 9, 10 and 11 are each the parent moiety of a different sulfonic acid type water-soluble phosphine ligand, m is the total number of sulfonate groups on the phosphine ligand, m>1；R 3 Is C 6 H 4 -3-SO 3 - ；o＝0，1，2；p＝0，1，2；q＝r＝0，1；s＝t＝0，1。
Application of a class of Merrifield resin material supported polyether functionalized ionic liquid catalysts in olefin hydroformylation reaction, wherein a catalytic system is composed of an organic phase and a catalyst phase: the organic phase is a reaction substrate olefin or a reaction product or a mixture of the two; the catalyst phase comprises a Merrifield resin material with a surface chemically bonded with a polyether functionalized ionic liquid shown in formula 1, formula 2, formula 3 or formula 4, and a phosphine functionalized polyether ionic liquid physically adsorbed on the surface of the Merrifield resin material shown in formula 1, formula 2, formula 3 or formula 4 and a rhodium catalyst formed by the phosphine functionalized polyether ionic liquid and a rhodium catalyst precursor; the hydroformylation reaction is carried out at a certain reaction temperature and synthesis gas pressure:
Figure BDA0002536676680000042
wherein n=4-140, r 1 Is C 1 –C 16 Alkyl or phenyl; x is - OMs， - OTs; the phosphine-functionalized polyether ionic liquid is Y m Z and Y are cations of phosphine-functionalized polyether ionic liquid, and the structure is as follows:
Figure BDA0002536676680000043
wherein l=4-45, r 2 Is C 1 –C 12 Alkyl or phenyl; z is the anion of phosphine-functionalized polyether ionic liquid, and has the structure:
Figure BDA0002536676680000051
wherein 1,2,3,4,5,6,7, 8, 9, 10 and 11 are each the parent moiety of a different sulfonic acid type water-soluble phosphine ligand, m is the total number of sulfonate groups on the phosphine ligand, m>1；R 3 Is C 6 H 4 -3-SO 3 - ；o＝0，1，2；p＝0，1，2；q＝r＝0，1；s＝t＝0，1。
Application of a class of Merrifield resin material supported polyether functionalized ionic liquid catalysts in olefin hydroformylation reaction, wherein a catalytic system is composed of an organic phase and a catalyst phase: the organic phase is a reaction substrate olefin or a reaction product or a mixture of the two; the catalyst phase comprises a Merrifield resin material with a surface chemically bonded with a polyether functionalized ionic liquid shown in formula 1, formula 2, formula 3 or formula 4, and a phosphine functionalized polyether ionic liquid physically adsorbed on the surface of the Merrifield resin material shown in formula 1, formula 2, formula 3 or formula 4 and a rhodium catalyst formed by the phosphine functionalized polyether ionic liquid and a rhodium catalyst precursor; the hydroformylation reaction is carried out at a certain reaction temperature and synthesis gas pressure:
Figure BDA0002536676680000052
wherein n=4-45, r 1 Is C 1 –C 16 Alkyl or phenyl; x is - OMs， - OTs; the phosphine-functionalized polyether ionic liquid is Y m Z and Y are cations of phosphine-functionalized polyether ionic liquid, and the structure is as follows:
Figure BDA0002536676680000053
wherein l=4-34, r 2 Is C 1 –C 12 Alkyl or phenyl; z is the anion of phosphine-functionalized polyether ionic liquid, and has the structure:
Figure BDA0002536676680000061
wherein 1,2,3,4,5,6,7, 8, 9, 10 and 11 are each the parent moiety of a different sulfonic acid type water-soluble phosphine ligand, m is the total number of sulfonate groups on the phosphine ligand, m>1；R 3 Is C 6 H 4 -3-SO 3 - ；o＝0，1，2；p＝0，1，2；q＝r＝0，1；s＝t＝0，1。
The application of the polyether functionalized ionic liquid catalyst loaded by the Merrifield resin material in the hydroformylation reaction of olefin, and the recovery and recycling of the catalyst are realized through the liquid/solid two-phase separation of an organic phase and a catalyst phase after the hydroformylation reaction is finished.
The method comprises the steps of mixing a Merrifield resin material with a polyether functionalized ionic liquid chemically bonded to the surface, a phosphine functionalized polyether ionic liquid, a rhodium catalyst precursor and methanol in a certain proportion under an inert atmosphere, wherein the mass ratio of the Merrifield resin material with the polyether functionalized ionic liquid chemically bonded to the surface to the rhodium catalyst precursor is 500:1-2000:1, the molar ratio of the phosphine functionalized polyether ionic liquid to rhodium in the rhodium catalyst precursor is 1:1-100:1, the synthesis gas pressure is 1-5MPa, the reaction temperature is 70-100 ℃, the reaction time is 0.5-2h, and removing the methanol through distillation after the reaction is finished to obtain the Merrifield resin material with the phosphine functionalized polyether ionic liquid physically adsorbed on the surface and the rhodium catalyst formed by the phosphine functionalized polyether ionic liquid and the rhodium catalyst precursor; then adding reaction substrate olefin, wherein the molar ratio of the olefin to rhodium in the rhodium catalyst is 100:1-20000:1, the pressure of synthesis gas is 1-10MPa, the reaction temperature is 70-130 ℃, and the reaction time is 0.5-10h; after the hydroformylation reaction is finished, the catalyst is recovered and recycled through liquid/solid phase separation of an organic phase and a catalyst phase.
The method comprises the steps of mixing a Merrifield resin material with a polyether functionalized ionic liquid chemically bonded to the surface, a phosphine functionalized polyether ionic liquid, a rhodium catalyst precursor and methanol in a certain proportion under an inert atmosphere, wherein the mass ratio of the Merrifield resin material with the polyether functionalized ionic liquid chemically bonded to the surface to the rhodium catalyst precursor is 800:1-1200:1, the molar ratio of the phosphine functionalized polyether ionic liquid to rhodium in the rhodium catalyst precursor is 3:1-30:1, the synthesis gas pressure is 1-3MPa, the reaction temperature is 80-90 ℃ and the reaction time is 1-2h, and removing the methanol through distillation after the reaction is finished to obtain the Merrifield resin material with the phosphine functionalized polyether ionic liquid and the rhodium catalyst formed by the phosphine functionalized polyether ionic liquid and the rhodium catalyst precursor; then adding a reaction substrate olefin, wherein the molar ratio of the olefin to rhodium in the rhodium catalyst is 1000:1-5000:1, the pressure of synthesis gas is 3-6MPa, the reaction temperature is 90-110 ℃, and the reaction time is 1-5h; after the hydroformylation reaction is finished, the catalyst is recovered and recycled through liquid/solid phase separation of an organic phase and a catalyst phase.
Polyether functionalized ionic liquid catalyst loaded by Merrifield resin material, and rhodium catalyst precursor is acetyl acetone dicarbonyl rhodium Rh (acac) (CO) 2 、RhCl 3 ·3H 2 O、[Rh(COD) 2 ]BF 4 Or [ Rh (COD) Cl ]] 2 COD is 1, 5-cyclooctadiene.
Polyether function loaded by Merrifield resin materialApplication of ionic liquid catalyst in olefin hydroformylation reaction, wherein the reaction substrate olefin is C 3 、C 4 、C 5 、C 6 、C 7 、C 8 、C 9 、C 10 、C 11 、C 12 、C 13 、C 14 、C 15 、C 16 、C 17 、C 18 、C 19 、C 20 Linear 1-olefins, fischer-Tropsch olefins, cyclohexene, styrene, p-methylstyrene, o-methylstyrene, p-tert-butylstyrene, p-isobutylstyrene, p-methoxystyrene, p-chlorostyrene, o-chlorostyrene, 2-vinylnaphthalene, 6-methoxy-2-vinylnaphthalene or mixtures of the above olefins; the reaction product is one or a mixture of several of aldehyde, alcohol, isomerized alkene or alkane.
The invention has the significance that the polyether functionalized ionic liquid is immobilized on the surface of the Merrifield resin material by a chemical bonding method, and the polyether chain can extend on the surface of the material due to the fact that the polyether functionalized ionic liquid has higher molecular weight and ether bonds have high flexibility and conformational freedom degree, so that an ionic liquid film layer can be effectively formed, the ionic liquid does not need to be subjected to secondary physical impregnation, and the dosage of the ionic liquid is reduced; meanwhile, the phosphine-functionalized polyether ionic liquid and the rhodium catalyst formed by the rhodium catalyst precursor and the chemically bonded polyether ionic liquid on the surface of the Merrifield resin material generate stronger intermolecular affinity, so that the loss of the rhodium catalyst is effectively reduced, and the defects in the prior art are overcome.
Compared with the two-phase olefin hydroformylation methods based on phosphine-functionalized polyether onium salt ionic liquid in the prior patents ZL201510250873.2 and ZL201510250176.7, the application method of the Merrifield resin material supported polyether functionalized ionic liquid catalyst in olefin hydroformylation reaction has the following advantages and remarkable technical progress:
1. high activity:
the application method of the Merrifield resin material supported polyether functionalized ionic liquid catalyst in the olefin hydroformylation reaction has higher catalysisThe activity of the catalyst, for example 1-octene, is up to 4000 hours -1 The above; whereas the TOF value of the two-phase hydroformylation method of olefins based on phosphine-functionalized polyether onium salt ionic liquid in ZL201510250873.2 and ZL201510250176.7 is up to 3000h -1 Left and right.
2. Long service life
The Merrifield resin material loaded polyether functionalized ionic liquid catalyst can be recycled for more than 20 times in the olefin hydroformylation reaction, and the total conversion number (TTON) reaches more than 70000; whereas the TTON values of the two-phase hydroformylation process of olefins based on phosphine-functionalized polyetheronium salt ionic liquids in ZL201510250873.2 and ZL201510250176.7 are from 45000 to 47000.
3. High catalyst separation efficiency
Compared with the olefin two-phase hydroformylation method, the Merrifield resin material loaded polyether functionalized ionic liquid catalyst has simpler, more convenient and more efficient separation and circulation operation.
Detailed Description
The following examples are intended to illustrate the invention and are not intended to be limiting.
Example 1
Material of formula 1 (n=16, r 1 ＝Ph，X＝ - OMs)/[Ph(OCH 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]Hydroformylation of 1-octene systems
The material of formula 1 (n=16, r 1 ＝Ph，X＝ - OMs)、[Ph(OCH 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]、Rh(acac)(CO) 2 And methanol, materials 1 and Rh (acac) (CO) 2 The mass ratio of (C) is 1000:1, [ Ph (OCH) 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]/Rh(acac)(CO) 2 =10:1 (molar ratio), then with synthesis gas (H 2 Co=1:1) to 5.0MPa, a reaction temperature of 80 ℃, a reaction time of 1h, forming a rhodium catalyst in situ; then rapidly cooled to room temperatureAfter the synthesis gas is vented, the methanol is distilled off under reduced pressure, and then 1-octene, 1-octene/Rh (acac) (CO) is added 2 =10000:1 (molar ratio), in synthesis gas (H 2 Co=1:1) pressure 5.0Mpa, reaction temperature 110 ℃ for 1h, then cooling to room temperature, discharging synthesis gas, opening the kettle, and obtaining an organic phase containing product aldehyde through simple liquid/solid two-phase separation, wherein the analysis result of gas chromatography is: the conversion of 1-octene was 88.0%, the selectivity of aldehyde was 42.5%, the molar ratio of normal aldehyde to iso aldehyde was 2.6:1, and the TOF value was 3740h -1 。
Example 2
Material of formula 2 (n=16, r 1 ＝Ph，X＝ - OMs)/[Ph(OCH 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]Hydroformylation of 1-octene systems
The material of formula 2 (n=16, r 1 ＝Ph，X＝ - OMs)、[Ph(OCH 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]、Rh(acac)(CO) 2 And methanol, material 2 and Rh (acac) (CO) 2 The mass ratio of (C) is 1000:1, [ Ph (OCH) 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]/Rh(acac)(CO) 2 =10:1 (molar ratio), then with synthesis gas (H 2 Co=1:1) to 5.0MPa, a reaction temperature of 80 ℃, a reaction time of 1h, forming a rhodium catalyst in situ; then rapidly cooling to room temperature, venting the synthesis gas, removing methanol by decompression, and then adding 1-octene, 1-octene/Rh (acac) (CO) 2 =10000:1 (molar ratio), in synthesis gas (H 2 Co=1:1) pressure 5.0Mpa, reaction temperature 110 ℃ for 1h, then cooling to room temperature, discharging synthesis gas, opening the kettle, and obtaining an organic phase containing product aldehyde through simple liquid/solid two-phase separation, wherein the analysis result of gas chromatography is: the conversion of 1-octene was 87.7%, the selectivity of aldehyde was 44.0%, the molar ratio of normal aldehyde to isopal was 2.6:1, and the TOF value was 3859h -1 。
Example 3
Material 3 (n=16，R 1 ＝Ph，X＝ - OMs)/[Ph(OCH 2 CH 2 ) 16 TMG] 3 [(SO 3 - ) 3 -1]Hydroformylation of 1-octene systems
The material of formula 3 (n=16, r 1 ＝Ph，X＝ - OMs)、[Ph(OCH 2 CH 2 ) 16 TMG] 3 [(SO 3 - ) 3 -1]、Rh(acac)(CO) 2 And methanol, material 3 and Rh (acac) (CO) 2 The mass ratio of (C) is 1000:1, [ Ph (OCH) 2 CH 2 ) 16 TMG] 3 [(SO 3 - ) 3 -1]/Rh(acac)(CO) 2 =10:1 (molar ratio), then with synthesis gas (H 2 Co=1:1) to 5.0MPa, a reaction temperature of 80 ℃, a reaction time of 1h, forming a rhodium catalyst in situ; then rapidly cooling to room temperature, venting the synthesis gas, removing methanol by decompression, and then adding 1-octene, 1-octene/Rh (acac) (CO) 2 =10000:1 (molar ratio), in synthesis gas (H 2 Co=1:1) pressure 5.0Mpa, reaction temperature 110 ℃ for 1h, then cooling to room temperature, discharging synthesis gas, opening the kettle, and obtaining an organic phase containing product aldehyde through simple liquid/solid two-phase separation, wherein the analysis result of gas chromatography is: the conversion of 1-octene was 81.4%, the selectivity of aldehyde was 51.3%, the molar ratio of normal aldehyde to iso aldehyde was 2.5:1, and the TOF value was 4176h -1 。
Example 4
Material of formula 4 (n=16, r 1 ＝Ph，X＝ - OMs)/[Ph(OCH 2 CH 2 ) 16 TBD] 3 [(SO 3 - ) 3 -1]Hydroformylation of 1-octene systems
The material of formula 4 (n=16, r 1 ＝Ph，X＝ - OMs)、[Ph(OCH 2 CH 2 ) 16 TBD] 3 [(SO 3 - ) 3 -1]、Rh(acac)(CO) 2 And methanol, material 4 and Rh (acac) (CO) 2 The mass ratio of (C) is 1000:1, [ Ph (OCH) 2 CH 2 ) 16 TBD] 3 [(SO 3 - ) 3 -1]/Rh(acac)(CO) 2 =10:1 (molar ratio), then with synthesis gas (H 2 Co=1:1) to 5.0MPa, a reaction temperature of 80 ℃, a reaction time of 1h, forming a rhodium catalyst in situ; then rapidly cooling to room temperature, venting the synthesis gas, removing methanol by decompression, and then adding 1-octene, 1-octene/Rh (acac) (CO) 2 =10000:1 (molar ratio), in synthesis gas (H 2 Co=1:1) pressure 5.0Mpa, reaction temperature 110 ℃ for 1h, then cooling to room temperature, discharging synthesis gas, opening the kettle, and obtaining an organic phase containing product aldehyde through simple liquid/solid two-phase separation, wherein the analysis result of gas chromatography is: the conversion of 1-octene was 77.6%, the selectivity of aldehyde was 52.5%, the molar ratio of normal aldehyde to iso aldehyde was 2.6:1, and the TOF value was 4074h -1 。
Example 5
Material of formula 2 (n=4, r 1 ＝CH 3 ，X＝ - OMs)/[Ph(OCH 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]Hydroformylation of 1-octene systems
The material of formula 2 (n=4, r 1 ＝CH 3 ，X＝ - OMs)、[Ph(OCH 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]、Rh(acac)(CO) 2 And methanol, material 2 and Rh (acac) (CO) 2 The mass ratio of (C) is 1000:1, [ Ph (OCH) 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]/Rh(acac)(CO) 2 =10:1 (molar ratio), then with synthesis gas (H 2 Co=1:1) to 5.0MPa, a reaction temperature of 80 ℃, a reaction time of 1h, forming a rhodium catalyst in situ; then rapidly cooling to room temperature, venting the synthesis gas, removing methanol by decompression, and then adding 1-octene, 1-octene/Rh (acac) (CO) 2 =10000:1 (molar ratio), in synthesis gas (H 2 The pressure of/CO=1:1) is 5.0Mpa, the reaction temperature is 110 ℃ for 1h, then the reaction is carried out quickly to room temperature, the synthesis gas is discharged and then the kettle is opened, and the product is obtained through simple liquid/solid two-phase separationThe organic phase of the aldehyde, the gas chromatography analysis result is: the conversion of 1-octene was 79.8%, the selectivity of aldehyde was 36.9%, the molar ratio of normal aldehyde to isopal was 2.7:1, and the TOF value was 2945h -1 。
Example 6
Material of formula 2 (n=4, r 1 ＝n-C 12 H 25 ，X＝ - OMs)/[Ph(OCH 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]Hydroformylation of 1-octene systems
The material of formula 2 (n=4, r 1 ＝n-C 12 H 25 ，X＝ - OMs)、[Ph(OCH 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]、Rh(acac)(CO) 2 And methanol, material 2 and Rh (acac) (CO) 2 The mass ratio of (C) is 1000:1, [ Ph (OCH) 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]/Rh(acac)(CO) 2 =10:1 (molar ratio), then with synthesis gas (H 2 Co=1:1) to 5.0MPa, a reaction temperature of 80 ℃, a reaction time of 1h, forming a rhodium catalyst in situ; then rapidly cooling to room temperature, venting the synthesis gas, removing methanol by decompression, and then adding 1-octene, 1-octene/Rh (acac) (CO) 2 =10000:1 (molar ratio), in synthesis gas (H 2 Co=1:1) pressure 5.0Mpa, reaction temperature 110 ℃ for 2h, then cooling to room temperature, discharging synthesis gas, opening the kettle, and obtaining an organic phase containing product aldehyde through simple liquid/solid two-phase separation, wherein the analysis result of gas chromatography is: the conversion of 1-octene was 97.2%, the selectivity of aldehyde was 77.7%, the molar ratio of normal aldehyde to isopal was 2.3:1, and the TOF value was 3776h -1 。
Example 7
Material of formula 2 (n=4, r 1 ＝n-C 12 H 25 ，X＝ - OMs)/[Ph(OCH 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]Hydroformylation of 1-decene systems
In the inert stateThe material of formula 2 (n=4, r 1 ＝n-C 12 H 25 ，X＝ - OMs)、[Ph(OCH 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]、Rh(acac)(CO) 2 And methanol, material 2 and Rh (acac) (CO) 2 The mass ratio of (C) is 1000:1, [ Ph (OCH) 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]/Rh(acac)(CO) 2 =10:1 (molar ratio), then with synthesis gas (H 2 Co=1:1) to 5.0MPa, a reaction temperature of 80 ℃, a reaction time of 1h, forming a rhodium catalyst in situ; then rapidly cooled to room temperature, after venting the synthesis gas, the methanol is distilled off under reduced pressure, and then 1-decene, 1-decene/Rh (acac) (CO) is added 2 =10000:1 (molar ratio), in synthesis gas (H 2 Co=1:1) pressure 5.0Mpa, reaction temperature 110 ℃ for 1h, then cooling to room temperature, discharging synthesis gas, opening the kettle, and obtaining an organic phase containing product aldehyde through simple liquid/solid two-phase separation, wherein the analysis result of gas chromatography is: the conversion of 1-octene was 34.3%, the selectivity of aldehyde was 53.8%, the molar ratio of normal aldehyde to isomeric aldehyde was 2.4:1, and the TOF value was 1846h -1 。
Example 8
Material of formula 2 (n=4, r 1 ＝n-C 12 H 25 ，X＝ - OMs)/[Ph(OCH 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]Hydroformylation of 1-dodecene systems
The material of formula 2 (n=4, r 1 ＝n-C 12 H 25 ，X＝ - OMs)、[Ph(OCH 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]、Rh(acac)(CO) 2 And methanol, material 2 and Rh (acac) (CO) 2 The mass ratio of (C) is 1000:1, [ Ph (OCH) 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]/Rh(acac)(CO) 2 =10:1 (molar ratio), then with synthesis gas (H 2 /CO＝1:1) Pressurizing to 5.0MPa, reacting at 80 ℃ for 1h to form rhodium catalyst in situ; then rapidly cooling to room temperature, venting the synthesis gas, evaporating the methanol under reduced pressure, and then adding 1-dodecene, 1-dodecene/Rh (acac) (CO) 2 =10000:1 (molar ratio), in synthesis gas (H 2 Co=1:1) pressure 5.0MPa, reaction temperature 110 ℃ for 1h, then cooling to room temperature quickly, opening the kettle after discharging the synthesis gas, obtaining the organic phase containing the product aldehyde through simple liquid/solid two-phase separation, and the gas chromatography analysis result is: the conversion of 1-octene was 31.1%, the selectivity of aldehyde was 40.0%, the molar ratio of normal aldehyde to isomeric aldehyde was 2.6:1, and the TOF value was 1244h -1 。
Example 9
Material of formula 2 (n=4, r 1 ＝n-C 12 H 25 ，X＝ - OMs)/[Ph(OCH 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]Hydroformylation of 1-tetradecene systems
The material of formula 2 (n=4, r 1 ＝n-C 12 H 25 ，X＝ - OMs)、[Ph(OCH 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]、Rh(acac)(CO) 2 And methanol, material 2 and Rh (acac) (CO) 2 The mass ratio of (C) is 1000:1, [ Ph (OCH) 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]/Rh(acac)(CO) 2 =10:1 (molar ratio), then with synthesis gas (H 2 Co=1:1) to 5.0MPa, a reaction temperature of 80 ℃, a reaction time of 1h, forming a rhodium catalyst in situ; then rapidly cooling to room temperature, venting the synthesis gas, evaporating methanol under reduced pressure, and then adding 1-tetradecene, 1-tetradecene/Rh (acac) (CO) 2 =10000:1 (molar ratio), in synthesis gas (H 2 Co=1:1) pressure 5.0MPa, reaction temperature 110 ℃ for 1h, then cooling to room temperature quickly, opening the kettle after discharging the synthesis gas, obtaining the organic phase containing the product aldehyde through simple liquid/solid two-phase separation, and the gas chromatography analysis result is: the conversion of 1-octene was 23.8% and the selectivity to aldehyde was 43.6, the molar ratio of normal aldehyde to isomeric aldehyde is 2.2:1, and TOF value is 1038h -1 。
Example 10
Material of formula 2 (n=16, r 1 ＝Ph，X＝ - OMs)/[Ph(OCH 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]Hydroformylation of styrene systems
The material of formula 2 (n=16, r 1 ＝Ph，X＝ - OMs)、[Ph(OCH 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]、Rh(acac)(CO) 2 And methanol, material 2 and Rh (acac) (CO) 2 The mass ratio of (C) is 1000:1, [ Ph (OCH) 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]/Rh(acac)(CO) 2 =10:1 (molar ratio), then with synthesis gas (H 2 Co=1:1) to 5.0MPa, a reaction temperature of 80 ℃, a reaction time of 1h, forming a rhodium catalyst in situ; then rapidly cooling to room temperature, venting the synthesis gas, evaporating the methanol under reduced pressure, and then adding 1-styrene, 1-styrene/Rh (acac) (CO) 2 =10000:1 (molar ratio), in synthesis gas (H 2 Co=1:1) pressure 5.0Mpa, reaction temperature 110 ℃ for 1h, then cooling to room temperature, discharging synthesis gas, opening the kettle, and obtaining an organic phase containing product aldehyde through simple liquid/solid two-phase separation, wherein the analysis result of gas chromatography is: the conversion of 1-octene was 58.5%, the selectivity of aldehyde was 91.4%, the molar ratio of normal aldehyde to isopal was 1:4, and the TOF value was 5347h -1 。
Example 11
Material of formula 2 (n=16, r 1 ＝Ph，X＝ - OMs)/[Ph(OCH 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]Fischer-Tropsch synthesis C 5 -C 7 Hydroformylation of mixed olefin systems
The material of formula 2 (n=16, r 1 ＝Ph，X＝ - OMs)、[Ph(OCH 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]、Rh(acac)(CO) 2 And methanol, material 2 and Rh (acac) (CO) 2 The mass ratio of (C) is 1000:1, [ Ph (OCH) 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]/Rh(acac)(CO) 2 =10:1 (molar ratio), then with synthesis gas (H 2 Co=1:1) to 5.0MPa, a reaction temperature of 80 ℃, a reaction time of 1h, forming a rhodium catalyst in situ; then quickly cooling to room temperature, after the synthesis gas is discharged, decompressing and evaporating the methanol, then adding Fischer-Tropsch synthesis C 5 -C 7 Fischer-Tropsch synthesis of C from mixed olefins 5 -C 7 Mixed olefins/Rh (acac) (CO) 2 =10000:1 (molar ratio), in synthesis gas (H 2 Co=1:1) pressure 5.0Mpa, reaction temperature 110 ℃ for 1h, then cooling to room temperature, discharging synthesis gas, opening the kettle, and obtaining an organic phase containing product aldehyde through simple liquid/solid two-phase separation, wherein the analysis result of gas chromatography is: the conversion of 1-octene was 57.6%, the selectivity of aldehyde was 90.4%, the molar ratio of normal aldehyde to isomeric aldehyde was 6:1, and the TOF value was 5207h -1 。
Example 12
Material of formula 2 (n=45, r 1 ＝Ph，X＝ - OMs)/[Ph(OCH 2 CH 2 ) 4 MIM] 3 [(SO 3 - ) 3 -1]Hydroformylation of 1-octene systems
The material of formula 2 (n=45, r 1 ＝Ph，X＝ - OMs)、[Ph(OCH 2 CH 2 ) 4 MIM] 3 [(SO 3 - ) 3 -1]、Rh(acac)(CO) 2 And methanol, material 2 and Rh (acac) (CO) 2 The mass ratio of (C) is 1000:1, [ Ph (OCH) 2 CH 2 ) 4 MIM] 3 [(SO 3 - ) 3 -1]/Rh(acac)(CO) 2 =10:1 (molar ratio), then with synthesis gas (H 2 Co=1:1) to 5.0MPa, a reaction temperature of 80 ℃, a reaction time of 1h, forming a rhodium catalyst in situ; then rapidly cooling to room temperature, after the synthesis gas is discharged,removing methanol by vacuum distillation, adding 1-octene, 1-octene/Rh (acac) (CO) 2 =10000:1 (molar ratio), in synthesis gas (H 2 Co=1:1) pressure 5.0Mpa, reaction temperature 110 ℃ for 1h, then cooling to room temperature, discharging synthesis gas, opening the kettle, and obtaining an organic phase containing product aldehyde through simple liquid/solid two-phase separation, wherein the analysis result of gas chromatography is: the conversion of 1-octene was 80.3%, the selectivity of aldehyde was 48.5%, the molar ratio of normal aldehyde to isomeric aldehyde was 2.6:1, and the TOF value was 3895h -1 。
Example 13
Material of formula 2 (n=16, r 1 ＝Ph，X＝ - OMs)/[Ph(OCH 2 CH 2 ) 16 MIM] 4 [(SO 3 - ) 4 -2](o=p=0, m=4)/1-octene system hydroformylation reaction
Phosphine-functionalized ionic liquid is changed into [ Ph (OCH) 2 CH 2 ) 16 MIM] 4 [(SO 3 - ) 4 -2](o＝p＝0,m＝4)，[Ph(OCH 2 CH 2 ) 16 MIM] 4 [(SO 3 - ) 4 -2]/Rh(acac)(CO) 2 =5:1 (molar ratio), the rest of the reaction conditions and steps are the same as in example 2, the result of gas chromatography analysis is: the conversion of 1-octene was 37.0%, the selectivity of aldehyde was 83.8%, the molar ratio of normal aldehyde to isopal was 3.4:1, and the TOF value was 3101h -1 。
Example 14
Material of formula 2 (n=16, r 1 ＝Ph，X＝ - OMs)/[Ph(OCH 2 CH 2 ) 16 MIM] 2 [(SO 3 - ) 2 -4]Hydroformylation of (m=2)/1-octene systems
Phosphine-functionalized ionic liquid is changed into [ Ph (OCH) 2 CH 2 ) 16 MIM] 2 [(SO 3 - ) 2 -4](m＝2)，[Ph(OCH 2 CH 2 ) 16 MIM] 2 [(SO 3 - ) 2 -4]/Rh(acac)(CO) 2 =5:1 (molar ratio), the rest of the reaction conditions and steps are the same as in example 2, the result of gas chromatography analysis is: conversion of 1-octeneThe ratio was 37.7%, the selectivity of aldehyde was 84.3%, the molar ratio of normal aldehyde to isomeric aldehyde was 4:1, and the TOF value was 3178h -1 。
Example 15
Material of formula 2 (n=16, r 1 ＝Ph，X＝ - OMs)/[Ph(OCH 2 CH 2 ) 16 MIM] 2 [(SO 3 - ) 2 -6](o=2, q=r=1, s=t=0, m=2)/1-octene system hydroformylation reaction
Phosphine-functionalized ionic liquid is changed into [ Ph (OCH) 2 CH 2 ) 16 MIM] 2 [(SO 3 - ) 2 -6](o＝2,q＝r＝1,s＝t＝0,m＝2)，[Ph(OCH 2 CH 2 ) 16 MIM] 2 [(SO 3 - ) 2 -6]/Rh(acac)(CO) 2 =5:1 (molar ratio), the rest of the reaction conditions and steps are the same as in example 2, the result of gas chromatography analysis is: the conversion of 1-octene was 33.5%, the selectivity of aldehyde was 80.4%, the molar ratio of normal aldehyde to isomeric aldehyde was 4:1, and the TOF value was 2693h -1 。
Example 16
Material of formula 2 (n=16, r 1 ＝Ph，X＝ - OMs)/[Ph(OCH 2 CH 2 ) 16 MIM] 4 [(SO 3 - ) 4 -8](o=p=0, m=4)/1-octene system hydroformylation reaction
Phosphine-functionalized ionic liquid is changed into [ Ph (OCH) 2 CH 2 ) 16 MIM] 4 [(SO 3 - ) 4 -8](o＝p＝0,m＝4)，[Ph(OCH 2 CH 2 ) 16 MIM] 4 [(SO 3 - ) 4 -8]/Rh(acac)(CO) 2 =5:1 (molar ratio), the rest of the reaction conditions and steps are the same as in example 2, the result of gas chromatography analysis is: the conversion of 1-octene was 33.7%, the selectivity of aldehyde was 82.6%, the molar ratio of normal aldehyde to isomeric aldehyde was 10:1, and the TOF value was 2784h -1 。
Example 17
Material of formula 2 (n=16, r 1 ＝Ph，X＝ - OMs)/[Ph(OCH 2 CH 2 ) 16 MIM] 2 [(SO 3 - ) 2 -10]Hydroformylation of (o=p=2, m=2)/1-octene systems
Phosphine-functionalized ionic liquid is changed into [ Ph (OCH) 2 CH 2 ) 16 MIM] 2 [(SO 3 - ) 2 -10](o＝p＝2,m＝2)，[Ph(OCH 2 CH 2 ) 16 MIM] 4 [(SO 3 - ) 2 -10]/Rh(acac)(CO) 2 =5:1 (molar ratio), the rest of the reaction conditions and steps are the same as in example 2, the result of gas chromatography analysis is: the conversion of 1-octene was 38.8%, the selectivity of aldehyde was 85.3%, the molar ratio of normal aldehyde to iso aldehyde was 33:1, and the TOF value was 3310h -1 。
Example 18
Material of formula 2 (n=16, r 1 ＝Ph，X＝ - OMs)/[Ph(OCH 2 CH 2 ) 16 MIM] 2 [(SO 3 - ) 2 -11]Hydroformylation of (o=p=2, m=2)/1-octene systems
Phosphine-functionalized ionic liquid is changed into [ Ph (OCH) 2 CH 2 ) 16 MIM] 2 [(SO 3 - ) 2 -11](o＝p＝2,m＝2)，[Ph(OCH 2 CH 2 ) 16 MIM] 2 [(SO 3 - ) 2 -11]/Rh(acac)(CO) 2 =5:1 (molar ratio), the rest of the reaction conditions and steps are the same as in example 2, the result of gas chromatography analysis is: the conversion of 1-octene was 19.5%, the selectivity of aldehyde was 86.3%, the molar ratio of normal aldehyde to iso aldehyde was 36:1, and the TOF value was 1683h -1 。
Examples 19 to 32
Material of formula 2 (n=16, r 1 ＝Ph，X＝ - OMs)/[Ph(OCH 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]Hydroformylation reaction cycle experiment under 1-octene system
The material of formula 2 (n=16, r 1 ＝Ph，X＝ - OMs)、[Ph(OCH 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]、Rh(acac)(CO) 2 And methanol, material 2 and Rh (acac) (CO) 2 The mass ratio of (C) is 1000:1, [ Ph (OCH) 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]/Rh(acac)(CO) 2 =10:1 (molar ratio), then with synthesis gas (H 2 Co=1:1) to 5.0MPa, a reaction temperature of 80 ℃, a reaction time of 1h, forming a rhodium catalyst in situ; then rapidly cooling to room temperature, venting the synthesis gas, removing methanol by decompression, and then adding 1-octene, 1-octene/Rh (acac) (CO) 2 =5000:1 (molar ratio), in synthesis gas (H 2 The pressure of/CO=1:1) is 5.0Mpa, the reaction temperature is 110 ℃ for 5 hours, then the reaction is rapidly cooled to room temperature, the reactor is opened after the synthesis gas is discharged, the organic phase containing the product aldehyde and the catalyst phase are obtained through simple liquid/solid two-phase separation, and the next catalytic cycle is carried out under the same reaction condition after the new 1-octene is added into the catalyst phase. The gas chromatographic analysis results show that: after 14 catalytic cycles, the conversion of the olefin remained essentially unchanged, and the cumulative TON value reached 45090. The results of the cycling experiments are shown in Table 1 for examples 19-32.
TABLE 1 circulation experiments on rhodium catalysts
Figure BDA0002536676680000121
Examples 33 to 54
Material of formula 2 (n=4, r 1 ＝n-C 12 H 25 ，X＝ - OMs)/[Ph(OCH 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]Hydroformylation reaction cycle experiment under 1-octene system
The material of formula 2 (n=4, r 1 ＝n-C 12 H 25 ，X＝ - OMs)、[Ph(OCH 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]、Rh(acac)(CO) 2 And methanol, material 2 and Rh (acac) (CO) 2 The mass ratio of (C) is 1000:1, [ Ph (OCH) 2 CH 2 ) 16 MIM] 3 [(SO 3 - ) 3 -1]/Rh(acac)(CO) 2 =10:1 (molar ratio), then with synthesis gas (H 2 Co=1:1) to 5.0MPa, a reaction temperature of 80 ℃, a reaction time of 1h, forming a rhodium catalyst in situ; then rapidly cooling to room temperature, venting the synthesis gas, removing methanol by decompression, and then adding 1-octene, 1-octene/Rh (acac) (CO) 2 =5000:1 (molar ratio), in synthesis gas (H 2 The pressure of/CO=1:1) is 5.0Mpa, the reaction temperature is 110 ℃ for 5 hours, then the reaction is rapidly cooled to room temperature, the reactor is opened after the synthesis gas is discharged, the organic phase containing the product aldehyde and the catalyst phase are obtained through simple liquid/solid two-phase separation, and the next catalytic cycle is carried out under the same reaction condition after the new 1-octene is added into the catalyst phase. The gas chromatographic analysis results show that: after 22 catalytic cycles, the conversion of the olefin remained essentially unchanged, and the cumulative TON value reached 70375. The results of the cycling experiments are shown in Table 1, examples 33-54.
TABLE 1 circulation experiments on rhodium catalysts
Figure BDA0002536676680000131
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Claims (6)

1. The application of a catalytic system in the hydroformylation of olefins is characterized in that the catalytic system is composed of an organic phase and a catalyst phase: the organic phase is a reaction substrate olefin; the catalyst phase comprises a Merrifield resin material with a surface chemically bonded with a polyether functionalized ionic liquid shown in formula 1, formula 2, formula 3 or formula 4, and a phosphine functionalized polyether ionic liquid physically adsorbed on the surface of the Merrifield resin material shown in formula 1, formula 2, formula 3 or formula 4 and a rhodium catalyst formed by the phosphine functionalized polyether ionic liquid and a rhodium catalyst precursor; the hydroformylation reaction is carried out at a certain reaction temperature and synthesis gas pressure:
Figure FDA0004116170580000011
wherein n=4-45，R 1 Is C 1 –C 16 Alkyl or phenyl; x is - OMs， - OTs; the phosphine-functionalized polyether ionic liquid is Y m Z and Y are cations of phosphine-functionalized polyether ionic liquid, and the structure is as follows:
Figure FDA0004116170580000012
wherein l=4-45, r 2 Is C 1 –C 12 Alkyl or phenyl; z is the anion of phosphine-functionalized polyether ionic liquid, and has the structure:
Figure FDA0004116170580000013
wherein 1,2,3,4,5,6,7, 8, 9, 10 and 11 are each the parent moiety of a different sulfonic acid type water-soluble phosphine ligand, m is the total number of sulfonate groups on the phosphine ligand, m>1；R 3 Is C 6 H 4 -3-SO 3 - ；o＝0，1，2；p＝0，1，2；q＝r＝0，1；s＝t＝0，1。
2. The use of a catalytic system according to claim 1 in the hydroformylation of olefins, characterized in that the recovery and recycling of the catalyst is achieved by liquid/solid separation of the organic phase and the catalyst phase after the end of the hydroformylation.
3. The use of a catalytic system according to claim 1 in the hydroformylation of olefins, wherein the Merrifield resin material with surface chemically bound polyether functionalized ionic liquid, phosphine functionalized polyether ionic liquid, rhodium catalyst precursor and methanol are mixed in a certain ratio under an inert atmosphere, wherein the mass ratio of Merrifield resin material with surface chemically bound polyether functionalized ionic liquid to rhodium catalyst precursor is 500:1-2000:1, the molar ratio of phosphine functionalized polyether ionic liquid to rhodium in rhodium catalyst precursor is 1:1-100:1,
the pressure of the synthesis gas is 1-5MPa, the reaction temperature is 70-100 ℃, the reaction time is 0.5-2h, and methanol is removed by distillation after the reaction is finished to obtain a catalyst phase; then adding reaction substrate olefin, wherein the molar ratio of the olefin to rhodium in the rhodium catalyst is 100:1-20000:1, the pressure of synthesis gas is 1-10MPa, the reaction temperature is 70-130 ℃, and the reaction time is 0.5-10h; after the hydroformylation reaction is finished, the catalyst is recovered and recycled through liquid/solid phase separation of an organic phase and a catalyst phase.
4. The use of a catalytic system according to claim 1 in the hydroformylation of olefins, characterized in that in an inert atmosphere, merrifield resin material with surface chemically bound polyether functionalized ionic liquid, phosphine functionalized polyether ionic liquid, rhodium catalyst precursor and methanol are mixed in a certain ratio, wherein the mass ratio of Merrifield resin material with surface chemically bound polyether functionalized ionic liquid to rhodium catalyst precursor is 800:1-1200:1, the molar ratio of phosphine functionalized polyether ionic liquid to rhodium in rhodium catalyst precursor is 3:1-30:1, the synthesis gas pressure is 1-3MPa, the reaction temperature is 80-90 ℃, the reaction time is 1-2h, and after the reaction is finished, the methanol is removed by distillation to obtain catalyst phase; then adding a reaction substrate olefin, wherein the molar ratio of the olefin to rhodium in the rhodium catalyst is 1000:1-5000:1, the pressure of synthesis gas is 3-6MPa, the reaction temperature is 90-110 ℃, and the reaction time is 1-5h; after the hydroformylation reaction is finished, the catalyst is recovered and recycled through liquid/solid phase separation of an organic phase and a catalyst phase.
5. The use of a catalytic system according to claim 1, 3 or 4 for the hydroformylation of olefins, wherein the rhodium catalyst precursor is rhodium acetylacetonate dicarbonyl Rh (acac) (CO) 2 、RhCl 3 ·3H 2 O、[Rh(COD) 2 ]BF 4 Or [ Rh (COD) Cl ]] 2 COD is 1, 5-cyclooctadiene.
6. According to claim 1 or 3 or 4The use of a catalytic system for the hydroformylation of olefins, characterized in that the reaction substrate olefin is C 3 、C 4 、C 5 、C 6 、C 7 、C 8 、C 9 、C 10 、C 11 、C 12 、C 13 、C 14 、C 15 、C 16 、C 17 、C 18 、C 19 、C 20 Linear 1-olefins, fischer-Tropsch olefins, cyclohexene, styrene, p-methylstyrene, o-methylstyrene, p-tert-butylstyrene, p-isobutylstyrene, p-methoxystyrene, p-chlorostyrene, o-chlorostyrene, 2-vinylnaphthalene, 6-methoxy-2-vinylnaphthalene or mixtures of the above olefins.
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