CN111804333B - Magnetic material supported phosphine-functionalized polyether ionic liquid catalyst and application thereof in olefin hydroformylation reaction - Google Patents
Magnetic material supported phosphine-functionalized polyether ionic liquid catalyst and application thereof in olefin hydroformylation reaction Download PDFInfo
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Abstract
The invention relates to a phosphine-functionalized polyether ionic liquid catalyst supported by a magnetic material with a silica gel coated ferroferric oxide shell-core structure and application thereof in olefin hydroformylation reaction, wherein phosphine-functionalized polyether ionic liquid is immobilized on the surface of the magnetic material with the silica gel coated ferroferric oxide shell-core structure through a chemical bonding method, and the phosphine-functionalized polyether ionic liquid has higher molecular weight, and ether bonds have high flexibility and conformational freedom degree, so that the phosphine-functionalized polyether ionic liquid can extend on the surface of the material, an ionic liquid film layer is effectively formed, the solvent ionic liquid is not required to be immersed for the second time, and the dosage of the ionic liquid is reduced; meanwhile, the phosphine-functionalized polyether ionic liquid chemically bonded on the surface of the material realizes the integration of phosphine ligands and ionic liquid, so that the loss of rhodium catalyst is effectively reduced, and the defects in the prior art are overcome; the catalytic system has higher catalytic activity, can quickly and conveniently separate, recycle and recycle rhodium catalyst under the action of an externally applied magnetic field, and the rhodium catalyst can be recycled for a plurality of times without obvious reduction of catalytic activity and selectivity.
Description
Technical Field
The invention relates to the technical field of chemistry and chemical engineering, in particular to a phosphine-loaded functionalized polyether ionic liquid catalyst with a magnetic material of a silica gel coated ferroferric oxide shell-core structure and application thereof 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 particularly, the immobilized ionic liquid catalyst taking silicon dioxide base materials as carriers is widely reported and widely applied to hydroformylation reaction. At present, the method for loading the ionic liquid catalyst on the surface of the silicon dioxide base material 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.
In addition, as the particle size of the silica-based material supported ionic liquid phase catalyst is generally smaller, the sedimentation speed of the catalyst in the separation process is slower, and the efficiency of the catalytic reaction is affected.
Disclosure of Invention
Aiming at the limitations of the silica-based material supported ionic liquid catalyst in the olefin hydroformylation reaction, the invention aims to provide a silica gel coated ferroferric oxide shell-core structure magnetic material (Fe 3 O 4 @SiO 2 ) An application method of a phosphine-loaded functionalized polyether ionic liquid catalyst in olefin hydroformylation reaction.
The invention discloses a phosphine-functionalized polyether ionic liquid catalyst supported by a magnetic material with a silica gel coated ferroferric oxide shell-core structure, which is characterized in that the catalyst comprises phosphine-functionalized polyether ionic liquid chemically bonded on the surface of the magnetic material with the silica gel coated ferroferric oxide shell-core structure and a rhodium catalyst formed by the phosphine-functionalized polyether ionic liquid and a rhodium catalyst precursor, wherein the phosphine-functionalized polyether ionic liquid is shown in formula 1, formula 2, formula 3 or formula 4:
wherein n=4-140, r 1 Is C 1 –C 16 Alkyl or phenyl; x is the anion of phosphine-functionalized polyether ionic liquid, and the structure is as follows:
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 2 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 phosphine-functionalized polyether ionic liquid catalyst with the silica gel coated with the ferroferric oxide shell-core structure magnetic material is characterized by comprising phosphine-functionalized polyether ionic liquid with the surface chemically bonded with the magnetic material with the ferroferric oxide shell-core structure 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 n=4-45, r 1 Is C 1 –C 16 Alkyl or phenyl; x is the anion of phosphine-functionalized polyether ionic liquid, and the structure is as follows:
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 2 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 silica gel coated ferroferric oxide shell-core structure magnetic material supported phosphine functionalized polyether ionic liquid catalyst in olefin hydroformylation reaction, wherein a catalytic system comprises 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 phosphine-functionalized polyether ionic liquid with a silica gel coated ferroferric oxide shell-core structure magnetic material surface chemical bonding 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:
wherein n=4-140, r 1 Is C 1 –C 16 Alkyl or phenyl; x is the anion of phosphine-functionalized polyether ionic liquid, and the structure is as follows:
wherein 1,2,3,4,5,6,7,8. 9, 10 and 11 are each the parent moiety of a different water-soluble phosphine ligand of the sulfonic acid type, m is the total number of sulfonates on the phosphine ligand, m>1；R 2 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 silica gel coated ferroferric oxide shell-core structure magnetic material supported phosphine functionalized polyether ionic liquid catalyst in olefin hydroformylation reaction, wherein a catalytic system comprises 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 phosphine-functionalized polyether ionic liquid with a silica gel coated ferroferric oxide shell-core structure magnetic material surface chemical bonding 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:
wherein n=4-45, r 1 Is C 1 –C 16 Alkyl or phenyl; x is the anion of phosphine-functionalized polyether ionic liquid, and the structure is as follows:
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 2 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 magnetic material supported phosphine functionalized polyether ionic liquid catalyst with the silica gel coated ferroferric oxide shell-core structure in the hydroformylation reaction of olefin is characterized in that the catalyst is recovered and recycled through liquid/solid separation of an organic phase and a catalyst phase under the action of an externally applied magnetic field after the hydroformylation reaction is finished.
The application of a silica gel coated ferroferric oxide shell-core structure magnetic material supported phosphine functionalized polyether ionic liquid catalyst in an olefin hydroformylation reaction is characterized in that under inert atmosphere, a silica gel coated ferroferric oxide shell-core structure magnetic material with a phosphine functionalized polyether ionic liquid chemically bonded on the surface, a rhodium catalyst precursor and methanol are mixed according to a certain proportion, wherein the molar ratio of the phosphine functionalized polyether ionic liquid with the phosphine functionalized polyether ionic liquid chemically bonded on the surface of the silica gel coated ferroferric oxide shell-core structure magnetic material 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 the methanol is removed through distillation after the reaction is finished, so that the silica gel coated ferroferric oxide shell-core structure magnetic material with a rhodium catalyst chemically bonded on the surface is obtained; 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 two-phase separation of an organic phase and a catalyst phase under the action of an external magnetic field.
The application of a silica gel coated ferroferric oxide shell-core structure magnetic material supported phosphine functionalized polyether ionic liquid catalyst in an olefin hydroformylation reaction is characterized in that under inert atmosphere, a silica gel coated ferroferric oxide shell-core structure magnetic material with a phosphine functionalized polyether ionic liquid chemically bonded on the surface, a rhodium catalyst precursor and methanol are mixed according to a certain proportion, wherein the molar ratio of the phosphine functionalized polyether ionic liquid with the phosphine functionalized polyether ionic liquid chemically bonded on the surface of the silica gel coated ferroferric oxide shell-core structure magnetic material 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 ℃, the reaction time is 1-2h, and the methanol is removed through distillation after the reaction is finished, so that the silica gel coated ferroferric oxide shell-core structure magnetic material with a rhodium catalyst chemically bonded on the surface is obtained; then adding reaction substrate olefin, wherein the molar ratio of the olefin to rhodium in the rhodium catalyst is 1000:1-10000:1, 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 two-phase separation of an organic phase and a catalyst phase under the action of an external magnetic field.
A phosphine-loaded functionalized polyether ionic liquid catalyst with a magnetic material of a silica gel coated ferroferric oxide shell-core structure is characterized in that a rhodium catalyst precursor is acetylacetone 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.
Application of silica gel coated ferroferric oxide shell-core structure magnetic material supported phosphine functionalized polyether ionic liquid catalyst in olefin hydroformylation reaction is 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; the reaction product is one or a mixture of several of aldehyde, alcohol, isomerized alkene or alkane.
The invention has the significance that the phosphine-functionalized polyether ion liquid is immobilized on the surface of the silica gel coated ferroferric oxide shell-core structure magnetic material by a chemical bonding method, and the phosphine-functionalized polyether ion liquid has higher molecular weight and ether bond has high flexibility and conformational freedom degree, so that the phosphine-functionalized polyether ion liquid can extend on the surface of the material to effectively form an ion liquid film layer, the ion liquid does not need to be subjected to secondary physical impregnation of solvent ion liquid, and the dosage of the ion liquid is reduced; meanwhile, the phosphine-functionalized polyether ionic liquid chemically bonded on the surface of the material realizes the integration of phosphine ligands and ionic liquid, so that the loss of rhodium catalyst is effectively reduced, and the defects in the prior art are overcome; in addition, the magnetic material catalyst can be efficiently separated and recovered through an external magnetic field, so that the problems of slower sedimentation speed and low separation efficiency of the traditional immobilized ionic liquid catalyst are solved.
Compared with the two-phase olefin hydroformylation method based on phosphine-functionalized polyether onium salt ionic liquid and the traditional supported ionic liquid phase catalyst in the existing patents ZL201510250873.2 and ZL201510250176.7, the application method of the silica gel coated ferroferric oxide shell-core structure magnetic material supported phosphine-functionalized polyether ionic liquid catalyst in olefin hydroformylation reaction has the following advantages and remarkable technical progress:
1. high activity:
the application method of the silica gel coated ferroferric oxide shell-core structure magnetic material supported phosphine functionalized polyether ionic liquid catalyst in the olefin hydroformylation reaction has higher catalytic activity, and takes 1-octene as an example, and the TOF value is up to 4000h at most -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 magnetic material supported phosphine functionalized polyether ionic liquid catalyst with the silica gel coated ferroferric oxide shell-core structure can be recycled for 18 times in the olefin hydroformylation reaction, and the total conversion number (TTON) reaches more than 60000; 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
Because the magnetic material catalyst can be efficiently separated and recovered through an externally applied magnetic field, the problems of slower sedimentation speed and low separation efficiency of the traditional immobilized ionic liquid catalyst are solved.
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＝(SO 3 - ) 3 Hydroformylation of 1/1-octene systems
The material of formula 1 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 3 -1)、Rh(acac)(CO) 2 And methanol, phosphine-functionalized polyether ionic liquid and Rh (acac) (CO) chemically bonded to surface of material in formula 1 2 In a molar ratio of 10:1, followed by 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 100 ℃ for 1h, then the reaction is rapidly cooled to room temperature, the synthesis gas is discharged and then the reaction kettle is opened, under the action of an external magnetic field, the organic phase containing the product aldehyde is obtained through simple liquid/solid two-phase separation, and the analysis result of the gas chromatography is as follows: the conversion of 1-octene was 43.7%, the selectivity of aldehyde was 85.4%, the molar ratio of normal aldehyde to isopal was 2.6:1, and the TOF value was 3732h -1 。
Example 2
Material of formula 2 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 3 Hydroformylation of 1/1-octene systems
Material of formula 1 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 3 -1) the material of formula 2 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 3 -1) the remaining reaction conditions and steps are the same as in example 1, the result of the gas chromatographic analysis being: the conversion of 1-octene was 50.6%, the selectivity of aldehyde was 83.8%, the molar ratio of normal aldehyde to isopal was 2.6:1, and the TOF value was 4240h -1 。
Example 5
Material 3 (n=16, R 1 ＝Ph，X＝(SO 3 - ) 3 Hydroformylation reaction under-1)/1-octene systemShould be
Material of formula 1 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 3 -1) the material of formula 3 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 3 -1) the remaining reaction conditions and steps are the same as in example 1, the result of the gas chromatographic analysis being: the conversion of 1-octene was 51.6%, the selectivity of aldehyde was 82.6%, the molar ratio of normal aldehyde to isopal was 2.7:1, and the TOF value was 4262h -1 。
Example 6
Material of formula 4 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 3 Hydroformylation of 1/1-octene systems
Material of formula 1 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 3 -1) conversion to a material of formula 4 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 3 -1) the remaining reaction conditions and steps are the same as in example 1, the result of the gas chromatographic analysis being: the conversion of 1-octene was 52.6%, the selectivity of aldehyde was 81.2%, the molar ratio of normal aldehyde to iso aldehyde was 2.5:1, and the TOF value was 4271h -1 。
Example 7
Material of formula 1 (n=4, r 1 ＝CH 3 ，X＝(SO 3 - ) 3 Hydroformylation of 1/1-octene systems
Material of formula 1 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 3 -1) the material of formula 1 (n=4, r) 1 ＝CH 3 ，X＝(SO 3 - ) 3 -1) the remaining reaction conditions and steps are the same as in example 1, the result of the gas chromatographic analysis being: the conversion of 1-octene was 31.4%, the selectivity of aldehyde was 75.6%, the molar ratio of normal aldehyde to iso aldehyde was 2.4:1, and the TOF value was 2374h -1 。
Example 8
Material of formula 1 (n=16, r 1 ＝n-C 12 H 25 ，X＝(SO 3 - ) 3 Hydroformylation of 1/1-octene systems
Material of formula 1 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 3 -1) the material of formula 1 (n=16, r 1 ＝n-C 12 H 25 ，X＝(SO 3 - ) 3 -1) the remaining reaction conditions and steps are the same as in example 1, the result of the gas chromatographic analysis being: the conversion of 1-octene was 35.0%, the selectivity of aldehyde was 86.5%, the molar ratio of normal aldehyde to isomeric aldehyde was 2.6:1, and the TOF value was 3028h -1 。
Example 9
Material of formula 1 (n=45, r 1 ＝Ph，X＝(SO 3 - ) 3 Hydroformylation of 1/1-octene systems
Material of formula 1 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 3 -1) the material of formula 1 (n=45, r) 1 ＝Ph，X＝(SO 3 - ) 3 -1) the remaining reaction conditions and steps are the same as in example 1, the result of the gas chromatographic analysis being: the conversion of 1-octene was 51.3%, the selectivity of aldehyde was 84.6%, the molar ratio of normal aldehyde to iso aldehyde was 2.6:1, and the TOF value was 4340h -1 。
Example 10
Material of formula 1 (n=16, r 1 ＝n-C 12 H 25 ，X＝(SO 3 - ) 3 Hydroformylation of 1/1-decene System
Material of formula 1 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 3 -1) the material of formula 1 (n=16, r 1 ＝n-C 12 H 25 ，X＝(SO 3 - ) 3 -1) the 1-octene is replaced by 1-decene and the remaining reaction conditions and steps are the same as in example 1, the result of the gas chromatographic analysis being: the conversion of 1-decene was 22.2%, the selectivity of aldehyde was 72.7%, the molar ratio of normal aldehyde to isomeric aldehyde was 2.5:1, and the TOF value was 1614h -1 。
Example 11
Material of formula 1 (n=16, r 1 ＝n-C 12 H 25 ，X＝(SO 3 - ) 3 Hydroformylation of 1/1-dodecene systems
Material of formula 1 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 3 -1) the material of formula 1 (n=16, r 1 ＝n-C 12 H 25 ，X＝(SO 3 - ) 3 -1) the 1-octene is replaced by 1-dodecene, the remaining reaction conditions and steps are the same as in example 1, the result of the gas chromatographic analysis is: the conversion of 1-dodecene was 18.3%, the selectivity of aldehyde was 61.5%, the molar ratio of normal aldehyde to isomeric aldehyde was 2.3:1, and the TOF value was 1125h -1 。
Example 12
Material of formula 1 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 3 Hydroformylation of the 1/styrene System
The 1-octene was replaced by styrene and the remaining reaction conditions and steps were the same as in example 1, the results of gas chromatography analysis were: the conversion of styrene was 60.6%, the selectivity of aldehyde was 90.5%, the molar ratio of normal aldehyde to isomeric aldehyde was 1:4, and the TOF value was 5484h -1 。
Example 13
Material of formula 1 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 3 -1)/Fischer-Tropsch synthesis C 5 -C 7 Hydroformylation of mixed olefin systems
Conversion of 1-octene to Fischer-Tropsch synthesis C 5 -C 7 The olefin was mixed and the remaining reaction conditions and steps were the same as in example 1, and the results of the gas chromatography analysis were: fischer-Tropsch synthesis C 5 -C 7 The conversion of the mixed olefin was 59.8%, the selectivity of the aldehyde was 86.5%, the molar ratio of normal aldehyde to isopal was 8.0:1, and the TOF value was 5173h -1 。
Example 14
Material of formula 1 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 4 -2 (o=p=0, m=4))/1-octene system hydroformylation reaction
Material of formula 1 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 3 -1) the material of formula 1 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 4 -2(o＝p＝0,m＝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 1, gas phaseThe chromatographic analysis results were: the conversion of 1-octene was 38.3%, the selectivity of aldehyde was 78.2%, the molar ratio of normal aldehyde to isopal was 3.8:1, and the TOF value was 2995h -1 。
Example 15
Material of formula 1 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 2 Hydroformylation of-4 (m=2))/1-octene systems
Material of formula 1 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 3 -1) the material of formula 1 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 2 -4(m＝2))，(SO 3 - ) 2 -4/Rh(acac)(CO) 2 =5:1 (molar ratio), the remaining reaction conditions and steps are the same as in example 1, and the result of gas chromatography analysis is: the conversion of 1-octene was 36.0%, the selectivity of aldehyde was 84.2%, the molar ratio of normal aldehyde to isopal was 4:1, and the TOF value was 3031h -1 。
Example 16
Material of formula 1 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 2 -6 (o=2, q=r=1, s=t=0, m=2))/1-octene system hydroformylation reaction
Material of formula 1 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 3 -1) the material of formula 1 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 2 -6(o＝2,q＝r＝1,s＝t＝0,m＝2))，(SO 3 - ) 2 -6/Rh(acac)(CO) 2 =5:1 (molar ratio), the remaining reaction conditions and steps are the same as in example 1, and the result of gas chromatography analysis is: the conversion of 1-octene was 36.5%, the selectivity of aldehyde was 75.4%, the molar ratio of normal aldehyde to isomeric aldehyde was 6:1, and the TOF value was 2752h -1 。
Example 17
Material of formula 1 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 4 -8 (o=p=0, m=4))/1-octene system hydroformylation reaction
Material of formula 1 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 3 -1) the material of formula 1 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 4 -8(o＝p＝0,m＝4))，(SO 3 - ) 4 -8/Rh(acac)(CO) 2 =5:1 (molar ratio), the remaining reaction conditions and steps are the same as in example 1, and the result of gas chromatography analysis is: the conversion of 1-octene was 34.5%, the selectivity of aldehyde was 83.5%, the molar ratio of normal aldehyde to isomeric aldehyde was 12:1, and the TOF value was 2881h -1 。
Example 18
Material of formula 1 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 2 -10 (o=p=2, m=2))/1-octene system hydroformylation reaction
Material of formula 1 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 3 -1) the material of formula 1 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 2 -10(o＝p＝2,m＝2))，(SO 3 - ) 2 -10/Rh(acac)(CO) 2 =5:1 (molar ratio), the remaining reaction conditions and steps are the same as in example 1, and the result of gas chromatography analysis is: the conversion of 1-octene was 35.1%, the selectivity of aldehyde was 83.7%, the molar ratio of normal aldehyde to isomeric aldehyde was 34:1, and the TOF value was 2938h -1 。
Examples 19 to 36
Material of formula 1 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 3 Hydroformylation reaction cycle experiment under-1)/1-octene system
The material of formula 1 (n=16, r 1 ＝Ph，X＝(SO 3 - ) 3 -1)、Rh(acac)(CO) 2 And methanol, (SO) 3 - ) 3 -1/Rh(acac)(CO) 2 =20:1 (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 Co=1:1) pressure 5.0Mpa, reaction temperature 100 ℃ for 5h, then rapid cooling to the chamberAnd (3) after the synthesis gas is exhausted, opening the kettle, under the action of an external magnetic field, obtaining an organic phase containing product aldehyde and a catalyst phase through simple liquid/solid two-phase separation, and after new 1-octene is added into the catalyst phase, performing the next catalytic cycle under the same reaction condition. The gas chromatographic analysis results show that: after 18 catalytic cycles, the conversion rate of olefin is basically kept unchanged, and the accumulated TON value reaches 60079; the results of the cycling experiments are shown in Table 1 in examples 19-36.
TABLE 1 circulation experiments on rhodium catalysts
Claims (4)
1. The application of the silica gel coated ferroferric oxide shell-core structure magnetic material supported phosphine functionalized polyether ionic liquid catalyst in the hydroformylation reaction of olefin is characterized in that a catalytic system is composed of an organic phase and a catalyst phase: the organic phase is a reaction substrate olefin; the catalyst phase comprises phosphine-functionalized polyether ionic liquid with a silica gel coated ferroferric oxide shell-core structure magnetic material surface chemical bonding shown in 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; mixing a silica gel coated ferroferric oxide shell core structure magnetic material with a phosphine functionalized polyether ionic liquid chemically bonded on the surface, a rhodium catalyst precursor and methanol in a certain proportion in an inert atmosphere, wherein the molar ratio of the phosphine functionalized polyether ionic liquid chemically bonded on the surface of the silica gel coated ferroferric oxide shell core structure magnetic material to rhodium in the rhodium catalyst precursor is 1:1-100:1, the pressure of synthesis gas is 1-5MPa, the reaction temperature is 70-100 ℃, the reaction time is 0.5-2h, and the methanol is removed through distillation after the reaction is finished to obtain the silica gel coated ferroferric oxide shell core structure magnetic material with the rhodium catalyst chemically bonded on the surface; 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, under the action of an external magnetic field, the catalyst is recovered and recycled through liquid/solid two-phase separation of an organic phase and a catalyst phase;
wherein n=16-45, r 1 Is C 1 –C 16 Alkyl or phenyl; x is the anion of phosphine-functionalized polyether ionic liquid, and the structure is as follows:
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 2 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 application of the phosphine-functionalized polyether ionic liquid catalyst loaded on the magnetic material with the silica gel coated ferroferric oxide shell-core structure in the hydroformylation reaction of olefin, which is disclosed in claim 1, is characterized in that the silica gel coated ferroferric oxide shell-core structure magnetic material with the phosphine-functionalized polyether ionic liquid chemically bonded on the surface, rhodium catalyst precursor and methanol are mixed in a certain proportion under inert atmosphere, wherein the molar ratio of the phosphine-functionalized polyether ionic liquid chemically bonded on the surface of the silica gel coated ferroferric oxide shell-core structure magnetic material 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 ℃, the reaction time is 1-2h, and the methanol is removed through distillation after the reaction is finished, so that the silica gel coated ferroferric oxide shell-core structure magnetic material with the rhodium catalyst chemically bonded on the surface is obtained; then adding reaction substrate olefin, wherein the molar ratio of the olefin to rhodium in the rhodium catalyst is 1000:1-10000:1, 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 two-phase separation of an organic phase and a catalyst phase under the action of an external magnetic field.
3. The application of the silica gel coated ferroferric oxide shell-core structure magnetic material supported phosphine functionalized polyether ionic liquid catalyst in the hydroformylation reaction of olefins according to claim 1 or 2, wherein the rhodium catalyst precursor is rhodium acetylacetonate Rh (acac) (CO) 2 、RhCl 3 ·3H 2 O、[Rh(COD) 2 ]BF 4 Or [ Rh (COD) Cl ]] 2 COD is 1, 5-cyclooctadiene.
4. The application of the silica gel coated ferroferric oxide shell-core structure magnetic material supported phosphine functionalized polyether ionic liquid catalyst in the hydroformylation reaction of olefin, as claimed in claim 1 or 2, 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.
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