Bi-metal center Mo-Rh catalyst as well as preparation method and application thereof

Abstract

The invention relates to the technical field of catalysis, and discloses a bimetallic center Mo-Rh catalyst and a preparation method and application thereof.The bimetallic center Mo-Rh catalyst has the structure shown in the formula (1), R1, R2 and R3 are independently selected from C1-C10 alkyl, C6-C15 aryl and-O-R ', and R' is selected from C1-C10 alkyl, C6-C15 aryl and C7-C15 alkaryl. The invention provides a Mo-Rh catalyst with double metal centers. The Mo-Rh catalyst with the double metal centers has relatively high conversion rate and relatively high aldehyde selectivity when being used for a hydroformylation reaction. # imgabs0 #

Description

Technical Field

[0001] The invention relates to the field of catalytic technology, and in particular to a bimetallic center Mo-Rh catalyst and a preparation method and application thereof. Background Art

[0002] The global production of aldehydes through hydroformylation has reached tens of millions of tons, but the cobalt-based catalysts used in hydroformylation reactions have relatively poor stability and rhodium-based catalysts suffer from severe loss.

[0003] Hydroformylation is the reaction of olefins and synthesis gas (CO+H2) to generate aldehydes under the action of transition metal catalysts. At present, rhodium (Rh) or cobalt (Co) complexes are mainly used as catalysts. Cobalt carbonyl is the earliest discovered catalyst with high activity, but due to its high requirements for reaction conditions, scientists have invented rhodium phosphine catalysts. Rhodium phosphine catalysts have high catalytic activity and high positive isomer ratio of products, and the reaction conditions are relatively mild. Therefore, rhodium phosphine catalyst systems are mostly used in industry. However, Rh is expensive, and the loss of rhodium and ligands in industrial production processes is relatively serious. In order to reduce costs, on the one hand, researchers actively develop easily separable catalytic systems to reduce the deactivation and loss of rhodium catalysts caused by distillation separation in traditional homogeneous systems, such as water / organic two-phase catalysts and supported catalysts. However, the former has high requirements for the water solubility of olefins, and the catalytic effect of long-chain olefins with poor water solubility is often not ideal, and the two-phase mass transfer problem has not been well solved. The biggest problem of the latter is that the stability of the active center on the carrier is insufficient, which often leads to the shedding of the metal active center, limiting its application. 。 Summary of the invention

[0004] The object of the present invention is to overcome the above-mentioned technical problems, and to provide a bimetallic center Mo-Rh catalyst. The catalyst of the present invention is a solid catalyst, which can overcome the loss of ligands and metal components present in homogeneous catalysts, and the problem that the catalyst and the product are not easily separated. At the same time, the catalyst of the present invention has comparable catalytic performance (feedstock conversion rate and product selectivity) as the homogeneous catalyst. Further, the catalyst separation method of the present invention is simple, can be used repeatedly, is more conducive to environmental protection, and reduces industrial costs. Furthermore, the present invention improves the synthesis efficiency of the catalyst, reduces the synthesis cost, and is more conducive to large-scale industrial use.

[0005] In order to achieve the above object, the first aspect of the present invention provides a bimetallic center Mo-Rh catalyst having a structure shown in formula (1):

[0006]

[0007] Wherein, R1, R2, and R3 are each independently selected from C1-C 10Alkyl, C6-C 15 aryl, -O-R', wherein R' is selected from C1-C 10 Alkyl, C6-C 15 Aryl, C7-C 15 of alkylaryl.

[0008] According to the present invention, preferably, R1, R2, and R3 are each independently selected from C1-C5 alkyl, C6-C 10 The aryl group is more preferably a methyl group, an ethyl group, a propyl group, a butyl group or a phenyl group.

[0009] The second aspect of the present invention provides a method for preparing a bimetallic center Mo-Rh catalyst, the method comprising: contacting RhH(CO)(PR1R2R3)3 with Mo(CO)6 to carry out a complex reaction, followed by extraction and crystallization;

[0010] Wherein, R1, R2, and R3 are each independently selected from C1-C 10 Alkyl, C6-C 15 aryl, -O-R', wherein R' is selected from C1-C 10 Alkyl, C6-C 15 Aryl, C7-C 15 of alkylaryl.

[0011] The third aspect of the present invention provides a catalyst prepared by the method described above.

[0012] The fourth aspect of the present invention provides the use of the above-mentioned catalyst in hydroformylation reaction, oxidation reaction and cycloaddition reaction.

[0013] A fifth aspect of the present invention provides a method for hydroformylating olefins, the method comprising: contacting the olefin with the above-mentioned catalyst under hydroformylation reaction conditions to react;

[0014] Alternatively, the catalyst is prepared according to the above method, and then the olefin is contacted with the prepared catalyst under hydroformylation reaction conditions to react.

[0015] A sixth aspect of the present invention provides a method for hydroformylation of alcohols, the method comprising: contacting alcohol with the above-mentioned catalyst under hydroformylation reaction conditions to react;

[0016] Alternatively, the catalyst is prepared according to the method described above, and then alcohol is contacted with the prepared catalyst under hydroformylation reaction conditions to react.

[0017] A seventh aspect of the present invention provides a method for oxidizing sulfide, characterized in that the method comprises: contacting sulfide with the above-mentioned catalyst under oxidation reaction conditions for reaction;

[0018] Alternatively, the catalyst is prepared according to the method described above, and then the sulfide is contacted with the prepared catalyst under oxidation reaction conditions to react.

[0019] The eighth aspect of the present invention provides a method for cycloaddition reaction of olefins, characterized in that the method comprises: contacting olefins with the above-mentioned catalyst under cycloaddition reaction conditions for reaction;

[0020] Alternatively, the catalyst is prepared according to the method described above, and then the olefin is contacted with the prepared catalyst under cycloaddition reaction conditions to react.

[0021] Through the above technical solution, the present invention achieves the following beneficial effects:

[0022] (1) The present invention provides a bimetallic center Mo-Rh catalyst, which has a high conversion rate and high aldehyde selectivity when used in a hydroformylation reaction.

[0023] (2) The bimetallic center Mo-Rh catalyst provided by the present invention can be reused, which is beneficial to environmental protection and reduces industrial costs.

[0024] (3) The preparation method of the bimetallic center Mo-Rh catalyst provided by the present invention can obtain a higher catalyst yield, reduce the synthesis cost of the catalyst, and is conducive to the industrial large-scale use of the catalyst. DETAILED DESCRIPTION

[0025] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0026] The first aspect of the present invention provides a bimetallic center Mo-Rh catalyst having a structure shown in formula (1):

[0027]

[0028] Wherein, R1, R2, and R3 are each independently selected from C1-C 10 Alkyl, C6-C 15 aryl, -O-R', wherein R' is selected from C1-C 10 Alkyl, C6-C 15 Aryl, C7-C 15 of alkylaryl.

[0029] In the present invention, C1-C 10 The alkyl group may be a straight-chain alkyl group or a branched alkyl group, for example, it may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyl, isooctyl, 2-ethylhexyl, etc.

[0030] In the present invention, C6-C 15 The aryl group may be phenyl, biphenyl, naphthyl or the like.

[0031] According to the present invention, preferably, R1, R2, and R3 are each independently selected from C1-C5 alkyl, C6-C 10 The aryl group is more preferably a methyl group, an ethyl group, a propyl group (eg, n-propyl group, isopropyl group), a butyl group (eg, n-butyl group, isobutyl group), or a phenyl group.

[0032] In the present invention, C7-C 15 The alkylaryl group may be methylphenyl, ethylphenyl, n-propylphenyl, isopropylphenyl, n-butylphenyl, sec-butylphenyl, isobutylphenyl, tert-butylphenyl, n-pentylphenyl, isopentylphenyl, tert-pentylphenyl, neopentylphenyl, hexylphenyl, isohexylphenyl, heptylphenyl, isoheptylphenyl, octylphenyl, isooctylphenyl, 2-ethylhexylphenyl, etc. The oxygen atom in -O-R' may be C7-C 15 The alkyl group in the alkylaryl group can also be connected to the C7-C 15 The aryl group of the alkylaryl is connected to the aryl group, preferably, the oxygen atom in -O-R' is connected to the C7-C 15 The alkyl groups in the alkylaryl groups are connected, that is, -O-R' is -O-alkylene-aryl, for example, -OCH2Ph.

[0033] According to the present invention, preferably, R' is selected from C1-C5 alkyl, C6-C 10 Aryl, C7-C 10 more preferably methyl, ethyl, propyl (eg, n-propyl, isopropyl), butyl (eg, n-butyl, isobutyl), phenyl, (methylene) phenyl.

[0034] In the present invention, phenyl group may be abbreviated as Ph.

[0035] The second aspect of the present invention provides a method for preparing a bimetallic center Mo-Rh catalyst, the method comprising: contacting RhH(CO)(PR1R2R3)3 with Mo(CO)6 to carry out a complex reaction, followed by extraction and crystallization;

[0036] Wherein, R1, R2, and R3 are each independently selected from C1-C 10 Alkyl, C6-C15 aryl, -O-R', wherein R' is selected from C1-C 10 Alkyl, C6-C 15 Aryl, C7-C 15 of alkylaryl.

[0037] According to the present invention, preferably, R1, R2, and R3 are each independently selected from C1-C5 alkyl, C6-C 10 The aryl group is more preferably a methyl group, an ethyl group, a propyl group, a butyl group or a phenyl group.

[0038] According to the present invention, preferably, R' is selected from C1-C5 alkyl, C6-C 10 Aryl, C7-C 10 alkylaryl; more preferably methyl, ethyl, propyl, butyl, phenyl, methylphenyl.

[0039] R1, R2, R3 and R' in the second aspect are defined as R1, R2, R3 and R' in the first aspect, and are not described in detail here.

[0040] According to the present invention, in order to further improve the yield of the catalyst, improve the conversion rate and selectivity, preferably, the weight ratio of RhH(CO)(PR1R2R3)3 to Mo(CO)6 is 0.1-5:1, more preferably 0.5-3.5:1; further preferably 3-3.5:1.

[0041] According to the present invention, the conditions of the complexation reaction are not particularly limited, and can be the complexation reaction conditions commonly used in the art. Preferably, the conditions of the complexation reaction include: a temperature of 15-40° C. and a time of 0.5-5 h.

[0042] According to the present invention, preferably, the complexation reaction is carried out in the presence of a solvent. The solvent is a solvent capable of dissolving RhH(CO)(PR1R2R3)3 and Mo(CO)6.

[0043] According to the present invention, preferably, the solvent used in the complexation reaction is a polar solvent, more preferably a C2-C 10 The polar organic solvent is further preferably a C2-C6 polar organic solvent containing a heteroatom, wherein the heteroatom is at least one of N, O, and S.

[0044] More preferably, the solvent used in the complexation reaction is at least one of tetrahydrofuran, dioxane, N,N-dimethylformamide, dimethyl sulfoxide, diethyl ether and ethyl acetate.

[0045] In the present invention, RhH(CO)(PR1R2R3)3 and Mo(CO)6 can be directly added to a solvent for complex reaction, or RhH(CO)(PR1R2R3)3 and Mo(CO)6 can be mixed with solvents to prepare solutions and then mixed. Preferably, the process of the complex reaction includes: mixing a solution containing RhH(CO)(PR1R2R3)3 with a solution containing Mo(CO)6 for complex reaction; more preferably, the process of the complex reaction includes: dropping a solution containing RhH(CO)(PR1R2R3)3 into a solution containing Mo(CO)6 for complex reaction.

[0046] According to the present invention, preferably, the dripping rate of the solution containing RhH(CO)(PR1R2R3)3 is 0.1-1 g / min, more preferably 0.5-0.8 mg / min, based on the weight of RhH(CO)(PR1R2R3)3 per gram of Mo(CO)6.

[0047] According to the present invention, in order to shorten the synthesis time of the catalyst and improve the yield of the catalyst, preferably, the concentration of the solution containing RhH(CO)(PR1R2R3)3 and the solution containing Mo(CO)6 are each independently 0.001-0.1 mol / L, more preferably 0.002-0.02 mol / L.

[0048] According to the present invention, preferably, the extraction agent used in the extraction is C6-C 15 Aromatics, C1-C 10 Halogenated alkanes and C1-C 10 At least one of the ethers of 10 At least one of aromatic hydrocarbons, C1-C3 halogenated alkanes and C1-C3 ethers; more preferably at least one of toluene, benzene, xylene, dichloromethane, chloroform, diethyl ether and diethyl ether. In the present invention, unless otherwise specified, the halogen atom or halogen can be selected from F, Cl, Br, and I.

[0049] According to the present invention, preferably, the extraction method is: removing the solvent in the complex reaction liquid to obtain a complex product (usually a yellow-green oily substance), then using an extractant to extract the complex product to obtain an extract, then filtering the extract to obtain a filtrate, and then concentrating the filtrate to obtain a concentrated solution.

[0050] According to the present invention, preferably, the total amount of the extractant used is 10-100 mL per gram of the oil.

[0051] In the present invention, the solvent in the complex reaction liquid can be removed by vacuum distillation. The conditions of the vacuum distillation can be determined according to the type of solvent, as long as the weight of the complex product can be guaranteed not to change. For example, when tetrahydrofuran is used as the solvent, the conditions of the vacuum distillation can be 0.03-0.05MPa; for another example, when dioxane is used as the solvent, the conditions of the vacuum distillation can be 0.01-0.04MPa.

[0052] In the present invention, it is understood that the extraction is to use an extractant to dissolve the active ingredient (catalyst) in the complex product, and then remove the solid (unreacted raw material or reaction by-product) by filtering. The extractant can be divided into several parts to extract the complex product in batches. Usually, the extractant is divided into 3-6 parts according to the total amount for extraction.

[0053] In the present invention, the filtrate can be concentrated by vacuum distillation, and the conditions of the vacuum distillation can be determined according to the type of solvent.

[0054] According to the present invention, preferably, the crystallization temperature is -70° C. to -40° C. The coking time is not particularly limited, and usually, it can be 5-15 hours.

[0055] According to the present invention, the crystallization method may be a crystallization method commonly used in the art, for example, the concentrated solution obtained by extraction is contacted with a crystallization solvent for crystallization.

[0056] According to the present invention, preferably, the crystallization solvent is selected from at least one of diethyl ether, petroleum ether, cyclohexane, n-hexane and ethyl acetate.

[0057] According to the present invention, preferably, the crystallization solvent comprises a crystallization solvent A and a crystallization solvent B, wherein the crystallization solvent A is selected from diethyl ether and / or ethyl acetate; and the crystallization solvent B is selected from at least one of cyclohexane, normal hexane and petroleum ether. The crystallization solvent may be at least one of a combination of diethyl ether / petroleum ether, a combination of diethyl ether / cyclohexane, a combination of diethyl ether / normal hexane, a combination of ethyl acetate / petroleum ether, a combination of ethyl acetate / cyclohexane, and a combination of ethyl acetate / normal hexane. More preferably, the volume ratio of the crystallization solvent A to the crystallization solvent B is 0.3-1:1.

[0058] According to the present invention, preferably, the crystallization solvent is diethyl ether and petroleum ether, and further preferably, the volume ratio of diethyl ether to petroleum ether is 0.3-1:1.

[0059] According to the present invention, preferably, the amount of the crystallization solvent used is 10-50 mL, preferably 30-40 mL, relative to 1 mL of the concentrated solution.

[0060] The third aspect of the present invention provides a catalyst prepared by the method described above.

[0061] The fourth aspect of the present invention provides the use of the above-mentioned catalyst in hydroformylation reaction, oxidation reaction and cycloaddition reaction.

[0062] A fifth aspect of the present invention provides a method for hydroformylating olefins, the method comprising: contacting the olefin with the above-mentioned catalyst under hydroformylation reaction conditions to react;

[0063] Alternatively, the catalyst is prepared according to the above method, and then the olefin is contacted with the prepared catalyst under hydroformylation reaction conditions to react.

[0064] According to the present invention, preferably, the mass ratio of the catalyst to the olefin is 0.0001-1:1 (for example, 0.0001:1, 0.001:1, 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, 0.2:1, 0.5:1, 1:1, and the range composed of any two of the above points), more preferably 0.01-0.1:1.

[0065] According to the present invention, preferably, the olefin includes C2-C10 olefin, more preferably C3-C7 olefin, further preferably at least one of butene, pentene, hexene and heptene; further preferably at least one of n-butene, n-pentene, n-hexene and n-heptene.

[0066] According to the present invention, preferably, the olefin is an α-olefin.

[0067] According to the present invention, preferably, the hydroformylation reaction conditions include: temperature of 70° C.-150° C., and time of 0.1-2 h.

[0068] According to the present invention, preferably, the raw material for the hydroformylation reaction also includes synthesis gas, which is a mixture of carbon monoxide and hydrogen; more preferably, the volume ratio of carbon monoxide to hydrogen in the mixture is 0.1-10:1, and further preferably 0.1-7:1.

[0069] According to the present invention, preferably, the pressure of the synthesis gas in the hydroformylation reaction is controlled to be 1-8 MPa, more preferably 4-7 MPa.

[0070] In the present invention, the hydroformylation reaction can be carried out in the presence of a solvent, and the solvent can be n-hexane, cyclohexane, toluene, xylene, dioxane, chlorobenzene, 1,2-dichloroethane and the like. The weight ratio of the solvent to the olefin can be 0.1-100:1, or 5-10:1. The amount of the solvent used can be 100-300 mL per gram of the catalyst.

[0071] A sixth aspect of the present invention provides a method for hydroformylation of alcohols, the method comprising: contacting alcohol with the above-mentioned catalyst under hydroformylation reaction conditions to react;

[0072] Alternatively, the catalyst is prepared according to the method described above, and then alcohol is contacted with the prepared catalyst under hydroformylation reaction conditions to react.

[0073] According to the present invention, preferably, the mass ratio of the catalyst to the alcohol is 0.0001-1:1 (for example, 0.0001:1, 0.001:1, 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, 0.2:1, 0.5:1, 1:1, and the range formed by any two of the above points), more preferably 0.01-0.1:1.

[0074] According to the present invention, preferably, the alcohol includes (monohydric) C1-C10 alcohol, more preferably (monohydric) C1-C4 alcohol, and further preferably at least one of methanol, ethanol and propanol.

[0075] According to the present invention, preferably, the hydroformylation reaction conditions include: temperature of 70° C.-150° C., and time of 0.1-2 h.

[0076] According to the present invention, preferably, the raw material for the hydroformylation reaction also includes synthesis gas, which is a mixture of carbon monoxide and hydrogen; more preferably, the volume ratio of carbon monoxide to hydrogen in the mixture is 0.1-10:1, and further preferably 0.1-7:1.

[0077] According to the present invention, preferably, the pressure of the synthesis gas in the hydroformylation reaction is controlled to be 1-8 MPa, more preferably 4-7 MPa.

[0078] In the present invention, the hydroformylation reaction can be carried out in the presence of a solvent, and the solvent can be n-hexane, cyclohexane, toluene, xylene, dioxane, chlorobenzene, 1,2-dichloroethane and the like. The weight ratio of the solvent to the alcohol can be 0.1-100:1, or 5-10:1. The amount of the solvent used can be 100-300 mL per gram of the catalyst.

[0079] A seventh aspect of the present invention provides a method for oxidizing sulfide, characterized in that the method comprises: contacting sulfide with the above-mentioned catalyst under oxidation reaction conditions for reaction;

[0080] Alternatively, the catalyst is prepared according to the method described above, and then the sulfide is contacted with the prepared catalyst under oxidation reaction conditions to react.

[0081] According to the present invention, preferably, the mass ratio of the catalyst to the sulfide is 0.0001-1:1 (for example, 0.0001:1, 0.001:1, 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, 0.2:1, 0.5:1, 1:1, and the range formed by any two of the above points), more preferably 0.01-0.1:1.

[0082] According to the present invention, preferably, the thioether includes C2-C15 thioether, more preferably C6-C10 thioether, further preferably C7-C10 thioether containing a benzene ring; further preferably at least one of anisyl thioether, phenethyl thioether and phenylpropyl thioether.

[0083] According to the present invention, preferably, the oxidation reaction conditions include: temperature of 70°C-150°C, and time of 0.1-2h.

[0084] According to the present invention, preferably, the oxidation reaction is carried out in air.

[0085] In the present invention, the oxidation reaction can be carried out in the presence of a solvent, and the solvent can be n-hexane, cyclohexane, toluene, xylene, dioxane, chlorobenzene, 1,2-dichloroethane and the like. The weight ratio of the solvent to the thioether can be 0.1-100:1, or 5-10:1. The amount of the solvent used can be 100-300 mL per gram of the catalyst.

[0086] The eighth aspect of the present invention provides a method for cycloaddition reaction of olefins, characterized in that the method comprises: contacting olefins with the above-mentioned catalyst under cycloaddition reaction conditions for reaction;

[0087] Alternatively, the catalyst is prepared according to the method described above, and then the olefin is contacted with the prepared catalyst under cycloaddition reaction conditions to react.

[0088] According to the present invention, preferably, the mass ratio of the catalyst to the olefin is 0.0001-1:1 (for example, 0.0001:1, 0.001:1, 0.01:1, 0.02:1, 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1, 0.08:1, 0.09:1, 0.1:1, 0.2:1, 0.5:1, 1:1, and the range composed of any two of the above points), more preferably 0.01-0.1:1.

[0089] According to the present invention, preferably, the olefin contains at least two double bonds, more preferably, the olefin contains 2-5 double bonds.

[0090] According to the present invention, preferably, the olefin is a C5-C20 olefin containing 2-3 double bonds, and more preferably a C10-C15 olefin containing 2-3 double bonds.

[0091] According to the present invention, preferably, the structural formula of the olefin is as shown in formula (2):

[0092]

[0093] According to the present invention, preferably, the conditions of the cycloaddition reaction include: temperature of 70°C-150°C, and time of 0.1-2h.

[0094] In the present invention, the cycloaddition reaction can be carried out in the presence of a solvent, and the solvent can be n-hexane, cyclohexane, toluene, xylene, dioxane, chlorobenzene, 1,2-dichloroethane and the like. The weight ratio of the solvent to the olefin can be 0.1-100:1, or 5-10:1. The amount of the solvent used can be 100-300 mL per gram of the catalyst.

[0095] The present invention will be described in detail below by way of examples. In the following examples,

[0096] The room temperature is about 25°C;

[0097] The RhH(CO)(PPh3)3 raw material is a commercial product of Inotech with brand number A05962.

[0098] The Mo(CO)6 raw material is a commercial product of Aladdin Company with the brand number M465782-25g.

[0099] In the test example, the synthesis gas is carbon monoxide and hydrogen, and the volume ratio of carbon monoxide to hydrogen is 1:1.

[0100] Catalyst yield mol% = amount of catalyst ÷ amount of RhH(CO)(PPh3)3 × 100%

[0101] Olefin conversion rate mol % = (the amount of olefin substance added to the reaction system - the amount of olefin substance remaining in the system) ÷ the amount of olefin substance added to the reaction system × 100%.

[0102] Aldehyde selectivity mol%=the amount of aldehyde substance generated / (the amount of olefin substance added to the reaction system-the amount of olefin substance remaining in the system)×100%.

[0103] Example 1

[0104] This example is used to illustrate the preparation method of the bimetallic center Mo-Rh catalyst

[0105] (1) Mix 1.0 g of RhH(CO)(PPh3)3 with 100 mL of tetrahydrofuran to obtain a tetrahydrofuran solution of RhH(CO)(PPh3)3; mix 0.287 g of Mo(CO)6 with 100 mL of tetrahydrofuran to obtain a tetrahydrofuran solution of Mo(CO)6. Slowly drop the tetrahydrofuran solution of RhH(CO)(PPh3)3 into the tetrahydrofuran solution of Mo(CO)6, and stir the reaction at room temperature for 2 h to obtain a complex reaction solution (yellow-green). The drop rate of the solution containing RhH(CO)(PPh3)3 is 0.5 g / min, based on the weight of RhH(CO)(PPh3)3 per gram of Mo(CO)6.

[0106] (2) The complex reaction solution is then subjected to vacuum distillation to remove tetrahydrofuran, and the vacuum distillation is stopped after the weight of the residue no longer changes, to obtain a yellow-green oily substance. The oily substance is washed with toluene for several times, and after the color of the toluene no longer changes, the washings are combined as an extract. The extract is filtered through diatomaceous earth to obtain a filtrate, and the filtrate is concentrated to obtain a concentrated solution (5 mL). The total amount of toluene used is 60 mL per gram of the oily substance.

[0107] (3) Ether and petroleum ether were added to the flask containing the concentrated solution, and then the flask was left to stand at -60°C overnight (about 10 hours) to precipitate yellow-green crystals, which were filtered and dried to obtain a bimetallic Mo-Rh catalyst. The amount of ether used was 16 mL and the amount of petroleum ether used was 20 mL relative to 1 mL of the concentrated solution. The catalyst yield was 58 mol%.

[0108] The catalyst of Example 1 31 P NMR (CDCl3): 12.47 (s).

[0109] Example 2

[0110] This example is used to illustrate the preparation method of the bimetallic center Mo-Rh catalyst

[0111] (1) 0.8 g of RhH(CO)(PPh3)3 was mixed with 80 mL of dioxane to obtain a dioxane solution of RhH(CO)(PPh3)3; 0.287 g of Mo(CO)6 was mixed with 80 mL of dioxane to obtain a dioxane solution of Mo(CO)6. The dioxane solution of RhH(CO)(PPh3)3 was slowly added dropwise to the dioxane solution of Mo(CO)6, and the reaction was stirred at room temperature for 3 h to obtain a complex reaction solution (yellow-green). The dripping rate of the solution containing RhH(CO)(PPh3)3 was 0.6 g / min based on the weight of RhH(CO)(PPh3)3 per gram of Mo(CO)6.

[0112] (2) The complex reaction solution is then subjected to vacuum distillation to remove dioxane, and the vacuum distillation is stopped after the weight of the residue no longer changes, to obtain a yellow-green oily substance. The oily substance is washed with toluene for several times, and after the color of the toluene no longer changes, the washing liquid is combined as an extract. The extract is filtered through diatomaceous earth to obtain a filtrate, and the filtrate is concentrated to obtain a concentrated solution (5 mL). The total amount of toluene used is 60 mL per gram of the oily substance.

[0113] (3) Ether and petroleum ether were added to the flask containing the concentrated solution, and then the flask was left to stand at -50°C overnight (about 10 h) to precipitate yellow-green crystals, which were filtered and dried to obtain a bimetallic Mo-Rh catalyst. The amount of ether used was 16 mL and the amount of petroleum ether used was 20 mL relative to 1 mL of the concentrated solution. The catalyst yield was 63 mol%.

[0114] Example 3

[0115] The method of Example 1 was followed, except that tetrahydrofuran in step (1) was replaced by an equal volume of pyridine. The catalyst yield was 13 mol%.

[0116] Example 4

[0117] The method of Example 1 was followed, except that the tetrahydrofuran in step (1) was replaced by an equal volume of diethyl ether. The catalyst yield was 21 mol%.

[0118] Test Examples 1-7 and Comparative Test 1

[0119] This test example is used to illustrate the catalytic performance of the catalyst in the olefin hydroformylation reaction.

[0120] Add raw materials, bimetallic center Mo-Rh catalyst, and 40 mL toluene to a 100 mL reactor, close the reactor, replace with nitrogen three times, replace with synthesis gas three times, control the pressure of synthesis gas in the reactor to 4 MPa, heat to 110 ° C for 0.5 h, terminate the reaction, and cool to room temperature. Among them, the type and amount of raw materials, the type and amount of catalyst are shown in Table 1. The reaction solution was detected by gas chromatography (GC), and the conversion rate of raw materials and the selectivity of aldehyde were calculated, and the results are shown in Table 1.

[0121] Test Example 8 and Comparative Example Test Example 2

[0122] This test example is used to illustrate the catalytic performance of the recovered catalyst in the olefin hydroformylation reaction.

[0123] The catalyst in the reaction solution of Test Example 1 and Comparative Example 1 was recovered, wherein the specific process of recovering the catalyst was as follows: filtering the reaction system and the catalyst, washing the catalyst with 100 ml of ether, and drying under reduced pressure for 3 hours, and then testing the catalytic performance of the recovered catalyst according to the method of Test Example 1. The results are shown in Table 1.

[0124] Comparative test example 3

[0125] The method of Test Example 1 was followed, except that the catalyst was replaced by a mixture of equal weights of Rh(H)(CO)(PPh3)3 and Mo(CO)6, wherein the molar ratio of Rh to Mo in the mixture was 1:1.

[0126] Table 1

[0127]

[0128] Test Example 9

[0129] This test example is used to illustrate the catalytic performance of the catalyst in the alcohol hydroformylation reaction.

[0130] In a 100 mL reactor, 5.0 g of methanol, 0.2 g of the bimetallic center Mo-Rh catalyst prepared in Example 1, and 40 mL of toluene were added, the reactor was closed, nitrogen was replaced three times, and synthesis gas was replaced three times, the pressure of the synthesis gas in the reactor was controlled to be 2 MPa, and the reaction was heated to 110 ° C for 0.2 h, the reaction was terminated, and the temperature was cooled to room temperature. The reaction solution was detected by GC, and the methanol conversion rate was calculated to be 90.2 mol%, and the acetic acid selectivity was 98.3 mol%.

[0131] Test Example 10

[0132] This test example is used to illustrate the catalytic performance of the catalyst in the partial oxidation reaction of anisole to produce anisole sulfoxide.

[0133] 6.0 g of thioanisole, 0.2 g of the bimetallic center Mo-Rh catalyst prepared in Example 1, and 40 mL of toluene were added to a 100 mL reactor, and then heated to 110 ° C. in an air atmosphere for 5 h, the reaction was terminated, and the temperature was lowered to room temperature. After the reaction was completed, the reaction solution was detected by GC, and the conversion rate of thioanisole was calculated to be 99.9 mol%, and the selectivity of phenyl sulfoxide was 96.4 mol%.

[0134] Test Example 11

[0135] This test case is used to illustrate the catalytic performance of the catalyst in the endocyclic [4+2] reaction

[0136] In a 100 mL three-necked flask, 3.0 g of a polyolefin feedstock, 0.2 g of the bimetallic center Mo-Rh catalyst prepared in Example 1, and 40 mL of toluene were added, and the mixture was heated to 130° C. for reaction for 2 h. After the reaction was completed, the mixture was cooled to room temperature, and the reaction solution was filtered to obtain a solution. The solution was subjected to GC detection, and the conversion rate of the polyolefin feedstock was calculated to be 78 mol%, and the selectivity of the cycloaddition product was 97.6 mol%.

[0137] The structural formula of the polyolefin raw material is shown in formula (2):

[0138]

[0139] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A bimetallic center Mo-Rh catalyst, characterized in that: The catalyst has a structure shown in formula (1): Wherein, R1, R2, and R3 are each independently selected from C1-C 10 Alkyl, C6-C 15 aryl, -O-R', wherein R' is selected from C1-C 10 Alkyl, C6-C 15 Aryl, C7-C 15 of alkylaryl.

2. The catalyst according to claim 1, wherein R1, R2, and R3 are each independently selected from C1-C5 alkyl, C6-C 10 The aryl group is more preferably methyl, ethyl, propyl, butyl, or phenyl; and / or, R' is selected from C1-C5 alkyl, C6-C 10 Aryl, C7-C 10 alkylaryl; more preferably methyl, ethyl, propyl, butyl, phenyl, methylphenyl.

3. A method for preparing a bimetallic center Mo-Rh catalyst, characterized in that: The method comprises: contacting RhH(CO)(PR1R2R3)3 with Mo(CO)6 to carry out complexation reaction, and then extracting and crystallizing; Wherein, R1, R2, and R3 are each independently selected from C1-C 10 Alkyl, C6-C 15 aryl, -O-R', wherein R' is selected from C1-C 10 Alkyl, C6-C 15 Aryl, C7-C 15 of alkylaryl.

4. The method according to claim 3, wherein: R1, R2, and R3 are each independently selected from C1-C5 alkyl, C6-C 10 The aryl group is more preferably methyl, ethyl, propyl, butyl, or phenyl; and / or, R' is selected from C1-C5 alkyl, C6-C 10 Aryl, C7-C 10 Alkaryl; more preferably methyl, ethyl, propyl, butyl, phenyl, methylphenyl; and / or, the weight ratio of RhH(CO)(PR1R2R3)3 to Mo(CO)6 is 0.1-5:1, preferably 0.5-3.5:1; And / or, the conditions of the complexation reaction include: temperature of 15-40° C. and time of 0.5-5 h.

5. The method according to claim 3, wherein: The complex reaction is carried out in the presence of a solvent, and the solvent used in the complex reaction is a polar solvent, preferably C2-C 10 The polar organic solvent is preferably a C2-C6 polar organic solvent containing a heteroatom, wherein the heteroatom is at least one of N, O, and S; and further preferably at least one of tetrahydrofuran, dioxane, N,N-dimethylformamide, dimethyl sulfoxide, diethyl ether, and ethyl acetate.

6. The method according to any one of claims 3 to 5, wherein: The process of the complex reaction comprises: mixing a solution containing RhH(CO)(PR1R2R3)3 with a solution containing Mo(CO)6 to carry out a complex reaction; Preferably, the process of the complex reaction comprises: dropping a solution containing RhH(CO)(PR1R2R3)3 into a solution containing Mo(CO)6 to carry out a complex reaction; More preferably, the dripping rate of the solution containing RhH(CO)(PR1R2R3)3 is 0.1-1 g / min, based on the weight of RhH(CO)(PR1R2R3)3 per gram of Mo(CO)6; More preferably, the concentrations of the solution containing RhH(CO)(PR1R2R3)3 and the solution containing Mo(CO)6 are each independently 0.001-0.1 mol / L, preferably 0.002-0.02 mol / L.

7. The method according to claim 5, wherein: The extraction agent used in the extraction is C6-C 15 Aromatics, C1-C 10 Halogenated alkanes and C1-C 10 At least one of ethers, preferably at least one of toluene, benzene, xylene, dichloromethane, chloroform, ethylene glycol diethyl ether and diethyl ether; Preferably, the extraction method is: removing the solvent in the complex reaction liquid to obtain a complex product, then using an extractant to extract the complex product to obtain an extract, then filtering the extract to obtain a filtrate, and then concentrating the filtrate to obtain a concentrated solution.

8. The method according to claim 7, wherein: The crystallization temperature is -70°C to -40°C; Preferably, the crystallization solvent is selected from at least one of diethyl ether, petroleum ether, cyclohexane, n-hexane and ethyl acetate, more preferably diethyl ether and petroleum ether, wherein the volume ratio of diethyl ether to petroleum ether is 0.3-1:1; More preferably, the amount of the crystallization solvent used is 10-50 mL, preferably 30-40 mL, relative to 1 mL of the concentrate.

9. The catalyst prepared by the method according to any one of claims 3 to 8.

10. Use of the catalyst according to any one of claims 1, 2 and 9 in hydroformylation reaction, oxidation reaction and cycloaddition reaction.

11. A method for hydroformylation of olefins, characterized in that: The method comprises: contacting an olefin with a catalyst as described in any one of claims 1, 2 and 9 under hydroformylation reaction conditions to react; Alternatively, the catalyst is prepared according to the method of any one of claims 3 to 8, and then an olefin is contacted with the prepared catalyst under hydroformylation reaction conditions for reaction.

12. A method for the hydroformylation of alcohols, characterized in that: The method comprises: contacting an alcohol with a catalyst as described in any one of claims 1, 2, and 9 under hydroformylation reaction conditions to react; Alternatively, the catalyst is prepared according to the method of any one of claims 3 to 8, and then alcohol is contacted with the prepared catalyst under hydroformylation reaction conditions to react.

13. A method for oxidizing thioether, characterized in that: The method comprises: contacting sulfide with the catalyst described in any one of claims 1, 2 and 9 under oxidation reaction conditions to react; Alternatively, the catalyst is prepared according to the method of any one of claims 3 to 8, and then the sulfide is contacted with the prepared catalyst under oxidation reaction conditions to react.

14. A method for olefin cycloaddition reaction, characterized in that: The method comprises: contacting an olefin with a catalyst as described in any one of claims 1, 2, and 9 under cycloaddition reaction conditions to react; Alternatively, the catalyst is prepared according to the method of any one of claims 3 to 8, and then an olefin is contacted with the prepared catalyst under cycloaddition reaction conditions for reaction.

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