Diphosphine coordinated bimetallic catalyst as well as preparation method and application thereof

Abstract

The invention provides a bimetallic catalyst of a diphosphine ligand as well as a preparation method and application of the bimetallic catalyst, and belongs to the technical field of catalysts. The Ru metal center in the bimetallic catalyst can promote isomerization of internal olefin in isooctene into terminal olefin, the A metal center can promote selective carbonylation of high-branch olefin, and the two metal active centers cooperate with each other, so that the hydroformylation reaction speed of isooctene is increased, the utilization rate of active metal atoms is greatly increased, and the yield of isooctene is increased. In addition, active components are not prone to loss, the bimetallic catalyst is long in service life, the phosphine ligand in the framework has a remarkable stereo effect, and the prepared bimetallic catalyst can remarkably improve the conversion rate of isooctene and the selectivity of isononanal.

Description

Technical Field

[0001] The present application relates to the field of catalyst technology, and in particular to a diphosphine-coordinated bimetallic catalyst and a preparation method and application thereof. Background Art

[0002] Highly branched isononanal (3,5,5-trimethylhexanal) is an important organic chemical raw material. It can be used to synthesize many high value-added fine chemical products, and is widely used in plasticizers, surfactants, fragrances, detergents and organic synthesis industries. Isononanal can be hydrogenated to prepare isononanol and oxidized to prepare isononanoic acid, which can be used as a topcoat solvent for nitro spray paint, and is also used in printing inks, lubricant additives, plasticizers, etc.

[0003] Olefin hydroformylation is an important method for industrial production of aldehydes. Since the German chemist Otto Roelen discovered the hydroformylation catalyst in the late 1930s, it has developed to the fourth generation. According to the evolution process, it can be roughly divided into: the first generation is cobalt carbonyl catalyst; the second generation is cobalt carbonyl catalyst modified by phosphine ligand; the third generation is rhodium / triphenylphosphine catalyst and water-soluble rhodium phosphine catalyst; the fourth generation is diphosphite modified rhodium catalyst.

[0004] The hydroformylation reaction activity of high-carbon olefins (above C7) is low, and the high boiling point of high-carbon olefins makes it difficult to separate the product catalyst, and the rhodium catalyst has the disadvantage of decomposition and loss at high temperatures. Currently, cobalt catalysts are widely used for the production of high-carbon aldehydes at home and abroad, but this process has the disadvantages of low activity, harsh reaction conditions, high equipment requirements, and high energy consumption.

[0005] US4528403 discloses a method for producing isononanal using rhodium as a catalyst by Mitsubishi Chemical of Japan. The process is carried out under a rhodium / triphenylphosphine oxide catalyst, with a reaction pressure of 20 MPa, a reaction temperature of 130°C, and an isononanal yield of 95%. During the separation of the catalyst and the product, triphenylphosphine needs to be added to stabilize the rhodium catalyst, and an oxidant needs to be used to control the oxidation to rhodium / triphenylphosphine oxide and circulate back to the reactor. The process has problems such as harsh reaction conditions, high equipment requirements, and complex process flow.

[0006] US20120253080 discloses that when a mixture of monophosphite and bisphosphite ligands is used as a ligand, the catalytic activity in the hydroformylation of long-chain olefins is very poor; and the preparation process thereof is usually relatively complicated.

[0007] The cost is high.

[0008] According to the current process, isooctene hydroformylation suffers from low olefin conversion and low isononanal selectivity. Summary of the invention

[0009] The purpose of the present disclosure is to overcome the deficiencies of the prior art and to provide a diphosphine-coordinated bimetallic catalyst and a preparation method and application thereof. The bimetallic catalyst of the present application can achieve excellent catalytic effect in the isooctene hydroformylation reaction.

[0010] To achieve the above-mentioned purpose, the technical solution adopted by the present disclosure is: a bimetallic catalyst coordinated by a bisphosphine, the structural formula of the bimetallic catalyst coordinated by a bisphosphine is shown in formula (1):

[0011]

[0012] In formula (1), A is Co or Rh; E is one of N, O, alkyl, substituted or unsubstituted C1-C20 amine, substituted or unsubstituted silane, and substituted or unsubstituted borane;

[0013] The R 1 , R 2 , R 3 , R 4 Each is independently one of alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, substituted or unsubstituted C6-C26 aryl, and heteroaryl;

[0014] X is any one of H, carbonyl, halogen, pseudohalogen, alkyl, alkoxy, alkanethio, substituted or unsubstituted C6-C26 aryl, substituted or unsubstituted C1-C20 amine, hydroxyl, and acyloxy;

[0015] The substituent is at least one of a C1-C10 alkyl group, a C1-C10 alkoxy group, and a C6-C26 aryl group.

[0016] Optionally, the R 1 , R 2 , R 3 , R 4 Each is independently any one of a C1-C20 alkyl group, a C1-C20 heteroalkyl group, a C3-C20 cycloalkyl group, a C3-C20 heterocycloalkyl group, a substituted or unsubstituted C6-C26 aryl group, or a substituted or unsubstituted C6-C26 heteroaryl group.

[0017] In a second aspect, a method for preparing the bimetallic catalyst is provided, comprising the following steps:

[0018] Under an inert atmosphere, a diphosphine ligand, a Ru-containing compound, and a first compound are reacted in situ to obtain a bimetallic catalyst;

[0019] The first compound is a Co-containing compound or an Rh-containing compound, and the general structural formula of the diphosphine ligand is R 1 R 2 PEPR 3 R4 , wherein E is one of N, O, alkyl, substituted or unsubstituted C1-C20 amine, substituted or unsubstituted silyl, and substituted or unsubstituted borane;

[0020] The R 1 , R 2 , R 3 , R 4 Each is independently one of an alkyl group, a heteroalkyl group, a cycloalkyl group, a heterocycloalkyl group, a substituted or unsubstituted C6-C26 aryl group, and a heteroaryl group.

[0021] Optionally, the Ru-containing compound is at least one of triruthenium dodecacarbonyl and ruthenium hexacarbonyl chloride;

[0022] And / or, the Co-containing compound is at least one of dicobalt octacarbonyl and cobalt tetracarbonyl hydrogen;

[0023] And / or, the Rh-containing compound is at least one of tetracarbonyl dirhodium dichloride and dodecacarbonyl tetrarhodium;

[0024] and / or, the molar ratio of the bisphosphine ligand, the first compound, and the Ru-containing compound is (1-2):1:1, wherein the amount of the first compound is calculated as Co atoms or Rh atoms, and the amount of the Ru-containing compound is calculated as Ru atoms;

[0025] And / or, the in-situ reaction conditions are as follows: stirring the reaction at a temperature of 20°C to 25°C for 10 to 12 hours; preferably, the stirring rate is 100 r / min to 800 r / min;

[0026] And / or, the inert atmosphere is nitrogen or argon.

[0027] Optionally, the in-situ reaction is carried out in a solvent; preferably, the addition ratio of the solvent to the bisphosphine ligand is (1-10) mL: 1 mmol;

[0028] And / or, the preparation method further comprises: after the in-situ reaction is completed, removing the solvent under reduced pressure; preferably, the pressure of the reduced pressure is 2 kPa to 20 kPa.

[0029] In a third aspect, provided is the use of the bimetallic catalyst in the preparation of isononanal.

[0030] Optionally, the method comprises the following steps: reacting isooctene, synthesis gas, an organic solvent and the bimetallic catalyst according to any one of claims 1 to 3 under an inert atmosphere, 0-250° C. and 0.1-20 MPa for 0.01-100 h to obtain isononanal, wherein the addition ratio of the bimetallic catalyst, isooctene and the organic solvent is 1 mmol: (50-200) mmol: (40-100) mL.

[0031] Optionally, the reaction temperature is 50-150°C, the pressure is 0.1-5MPa, and the time is 5-10h;

[0032] and / or, the flow rate of the synthesis gas is 300 mL / min to 800 mL / min;

[0033] And / or, the synthesis gas is carbon monoxide and hydrogen, and the volume ratio of the carbon monoxide to the hydrogen is (1-1.2):1;

[0034] And / or, the inert atmosphere is nitrogen or argon;

[0035] And / or, the reaction also includes a stirring operation, and the stirring rate is 500 rpm to 800 rpm.

[0036] Optionally, the organic solvent is at least one of organic alcohol, phenol, ether, and aromatic solvents; preferably, the organic solvent is at least one of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, cyclopentanol, cyclohexanol, benzyl alcohol, phenol, benzene, toluene, ether, and tetrahydrofuran.

[0037] Compared with the prior art, the beneficial effects of the present disclosure are as follows: the Ru metal center in the bimetallic catalyst of the present application can promote the isomerization of internal olefins in isooctene to terminal olefins, the A metal center can promote the selective carbonylation of highly branched olefins, the two metal active centers cooperate with each other, the hydroformylation reaction rate of isooctene is increased, the utilization rate of active metal atoms is greatly increased, and the active components are not easily lost. The bimetallic catalyst has a long life, the phosphine ligand in the framework has a significant stereo effect, and the prepared bimetallic catalyst can significantly increase the conversion rate of isooctene and the selectivity of isononanal. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] Figure 1 is the H NMR spectrum of the bimetallic catalyst obtained in Example 16;

[0039] Figure 2 This is a graph showing the chromatographic analysis results of the reaction product obtained by the hydroformylation of isooctene catalyzed by a bimetallic catalyst in Example 16. DETAILED DESCRIPTION

[0040] In order to make the purpose, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application are described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present application.

[0041] In the present application, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions containing the listed features.

[0042] In this application, when it comes to numerical ranges, unless otherwise specified, the above numerical ranges are deemed to be continuous and include the minimum and maximum values ​​of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be merged. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges included therein.

[0043] In the present application, there is no particular limitation on the specific dispersion and stirring treatment methods.

[0044] The reagents or instruments used in this application without indicating the manufacturer are all conventional products that can be obtained through commercial purchase.

[0045] In addition, the terms "first" and "second" are used for descriptive purposes only and should not be understood as indicating or implying relative importance or implicitly indicating the number of the indicated technical features. Therefore, the features defined as "first" and "second" may explicitly or implicitly include at least one of the features. In the description of the present invention, the meaning of "plurality" is at least two, such as two, three, etc., unless otherwise clearly and specifically defined.

[0046] In order to solve the problems of low olefin conversion rate and low isononanal selectivity in the prior art of isooctene hydroformylation.

[0047] The present application provides a bimetallic catalyst coordinated by a bisphosphine, and the structural formula of the bimetallic catalyst coordinated by a bisphosphine is shown in formula (1):

[0048]

[0049] In formula (1), A is Co or Rh; E is one of N, O, alkyl, substituted or unsubstituted C1-C20 amine, substituted or unsubstituted silane, and substituted or unsubstituted borane;

[0050] The R 1 , R 2 , R 3 , R 4 Each is independently one of alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, substituted or unsubstituted C6-C26 aryl, and heteroaryl;

[0051] X is any one of H, carbonyl, halogen, pseudohalogen, alkyl, alkoxy, alkanethio, substituted or unsubstituted C6-C26 aryl, substituted or unsubstituted C1-C20 amine, hydroxyl, and acyloxy;

[0052] The substituent is at least one of a C1-C10 alkyl group, a C1-C10 alkoxy group, and a C6-C26 aryl group.

[0053] In the bimetallic catalyst of the structure shown in formula (1) of the present application, the two P atoms on the biphosphine ligand form chemical bonds with the two active metal atoms, R 1 , R 2 , R 3 and R 4 They are substituents on two P atoms, E is a bridging group connecting two phosphine groups, X represents a group bonded to Co and Ru except the diphosphine ligand, n and m refer to the number of X groups, n is 1 or 2 or 3, and m is 1 or 2 or 3; the setting of n and m values ​​is based on two aspects, one is to maintain the oxidation state balance of the entire molecule, and the other is to maintain the stable coordination geometry of the central metal; the Ru metal center can promote the isomerization of internal olefins in isooctene to terminal olefins, and the A metal center can promote the selective carbonylation of highly branched olefins. The two metal active centers cooperate with each other to improve the hydroformylation reaction rate of isooctene, greatly improve the utilization rate of active metal atoms, and the active components are not easy to lose. The bimetallic catalyst has a long life, and the phosphine ligand in the skeleton has a significant stereo effect. The prepared bimetallic catalyst can significantly improve the conversion rate of isooctene and the selectivity of isononanal.

[0054] Optionally, the R 1 , R 2 , R 3 , R 4 Each is independently any one of a C1-C20 alkyl group, a C1-C20 heteroalkyl group, a C3-C20 cycloalkyl group, a C3-C20 heterocycloalkyl group, a substituted or unsubstituted C6-C26 aryl group, or a substituted or unsubstituted C6-C26 heteroaryl group.

[0055] Optionally, X is any one of H, carbonyl, halogen, pseudohalogen, C1-C20 alkyl, C1-C20 alkoxy, C3-C20 alkanethio, substituted or unsubstituted C6-C26 aryl, substituted or unsubstituted C1-C20 amine, hydroxyl, and acyloxy.

[0056] In the above formula (1), the substituents are as follows:

[0057] The alkyl group in C1-C10 alkyl (alkyl group with 1 to 10 carbon atoms) refers to a free radical of a saturated or unsaturated aliphatic group, including straight-chain alkyl, straight-chain alkenyl, straight-chain alkynyl, branched-chain alkyl, branched-chain alkenyl, branched-chain alkynyl, cycloalkyl, cycloalkenyl, and cycloalkynyl.

[0058] Exemplarily, C1-C10 alkyl includes C1-C10 saturated alkyl, C2-C10 alkenyl and C2-C10 alkynyl. More preferably, a straight chain alkyl with 1 to 6 carbon atoms, a branched chain alkyl with 1 to 6 carbon atoms, a cyclic alkyl with 3 to 6 carbon atoms, a straight chain alkenyl with 2 to 6 carbon atoms, a branched chain alkenyl with 1 to 6 carbon atoms, and a cyclic alkenyl with 3 to 6 carbon atoms are selected. Examples of alkyl include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, cyclopentyl, and cyclohexyl; examples of alkenyl include: vinyl, allyl, isopropenyl, pentenyl, cyclohexenyl, cycloheptenyl, and cyclooctenyl; examples of alkynyl include: ethynyl, propargyl, isopropynyl, pentynyl, and cyclohexynyl.

[0059] The term "substituted or unsubstituted C1-C10 alkyl" includes substituted C1-C10 alkyl and unsubstituted C1-C10 alkyl; wherein substituted C1-C10 alkyl refers to one or more substituents replacing the hydrogen on one or more carbons on the alkyl chain, and such substituents are selected from at least one of C1-C5 alkyl, C1-C5 alkoxy, and C6-C26 aryl.

[0060] When the aforementioned alkyl group with 1 to 10 carbon atoms contains an oxygen atom, it may be an alkoxy group, for example, an alkoxy group with 1 to 10 carbon atoms. More preferably, an alkoxy group with 1 to 6 carbon atoms is selected. Examples of alkoxy groups include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentyloxy, cyclopentyloxy, and cyclohexyloxy.

[0061] The term "substituted or unsubstituted C1-C10 alkoxy" includes substituted C1-C10 alkoxy and unsubstituted C1-C10 alkoxy; wherein the substituted C1-C10 alkoxy means that one or more substituents replace the hydrogen on one or more carbons in the alkoxy chain, and such substituents are selected from at least one of C1-C5 alkyl, C1-C5 alkoxy, and C6-C26 aryl.

[0062] The term "substituted or unsubstituted C6-C26 aryl" includes substituted C6-C26 aryl and unsubstituted C6-C26 aryl; wherein the substituted C6-C26 aryl means that one or more substituents replace the hydrogen on one or more carbons of the aryl, and such substituents are selected from at least one of C1-C5 alkyl, C1-C5 alkoxy, and C6-C26 aryl. Specific examples of substituted or unsubstituted C6-C26 aryl groups include phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-ethylphenyl, 4-isopropylphenyl, 4-tert-butylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl, 2,6-diisopropylphenyl, 2,6-di-tert-butylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triisopropylphenyl, 2,4,6-tri-tert-butylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl and cyclohexylphenyl.

[0063] The alkyl group in C1-C5 alkyl (alkyl group with 1 to 5 carbon atoms) refers to a free radical of a saturated or unsaturated aliphatic group, including straight-chain alkyl, straight-chain alkenyl, straight-chain alkynyl, branched-chain alkyl, branched-chain alkenyl, branched-chain alkynyl, cycloalkyl, cycloalkenyl, and cycloalkynyl.

[0064] Exemplarily, C1-C5 alkyl includes C1-C5 saturated alkyl, C2-C5 alkenyl and C2-C5 alkynyl. Examples of alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl and cyclopentyl; examples of alkenyl include vinyl, allyl, isopropenyl and pentenyl.

[0065] For example, when the aforementioned alkyl group with 1 to 5 carbon atoms contains an oxygen atom, it may be an alkoxy group, for example, an alkoxy group with 1 to 5 carbon atoms, specifically including: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentoxy, isopentyloxy, and cyclopentyloxy.

[0066] In one embodiment, the C6-C26 aryl group is selected from one of phenyl, benzyl, biphenyl, p-tolyl, o-tolyl, m-tolyl, and phenol.

[0067] The term "substituted or unsubstituted C1-C20 amine" includes substituted C1-C20 amine and unsubstituted C1-C20 amine; wherein the substituted C1-C20 amine refers to one or more substituents replacing the hydrogen on one or more carbons of the amine, and such substituents are selected from at least one of C1-C5 alkyl, C1-C5 alkoxy, and C6-C26 aryl. As examples of substituted or unsubstituted C1-C20 amine, specifically, there can be mentioned: amine, isopropylamine, methylamine, anilino, n-butylamine, methylethyl etheramine, 2,4,6-trimethylphenylamine, 2,6-diisopropylphenylamine, dimethylamine, diethylamine, diisopropylamine, di-tert-butylamine, and di(trimethylsilyl)amine.

[0068] Examples of the substituted or unsubstituted silyl group include a silyl group and dimethylsilane.

[0069] The term "substituted or unsubstituted boryl" includes substituted C1-C12 boryl and unsubstituted C1-C12 boryl; wherein substituted C1-C12 boryl means one or more substituents replace the hydrogen on one or more carbons of the boryl, and such substituents are selected from at least one of C1-C5 alkyl, C1-C5 alkoxy, and C6-C26 aryl. As examples of substituted or unsubstituted C1-C12 boryl, specifically, phenyl boryl and boryl can be cited.

[0070] The term "heteroaryl" refers to a monocyclic or polycyclic or condensed aromatic hydrocarbon in which one or more carbon atoms have been replaced by heteroatoms such as nitrogen, oxygen or sulfur. If the heteroaryl contains more than one heteroatom, these heteroatoms may be the same or different. Heteroaryl groups include, but are not limited to, benzofuranyl, benzothiophenyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, benzopyranyl, furanyl, imidazolyl, indazolyl, indolizinyl, indolyl, isobenzofuranyl, isoindolyl, isoquinolyl, isothiazolyl, isoxazolyl, naphthyridinyl, oxadiazolyl, oxazinyl, oxazolyl, phthalazinyl, pteridinyl, purinyl, pyranyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridin[3,4-b]indolyl, pyridyl, pyrimidinyl, pyrrolyl, quinolizinyl, quinolyl, quinoxalinyl, thiadiazolyl, thiatriazolyl, thiazolyl, thienyl, triazinyl, triazolyl, xanthenyl and other similar groups.

[0071] Specifically, when E is a substituted or unsubstituted C1-C20 amine group, the N atom in the amine group is respectively connected to the P atoms in the two phosphinyl groups; when E is a substituted or unsubstituted silyl group, the Si atom in the silyl group is respectively connected to the P atoms in the two phosphinyl groups; when E is a substituted or unsubstituted boryl group, the B atom is respectively connected to the P atoms in the two phosphinyl groups.

[0072] Compounds of formula (1) can be synthesized by a variety of routes; the choice of reaction route depends on the availability of the corresponding starting materials and the desired substitution pattern. Next, exemplary selections will be introduced by way of implementation to illustrate the different ligand systems obtained by the methods described herein, without excluding the optional synthesis routes of formula (1) and other alternative patents and ligand structures.

[0073] The preparation method of formula (1) is described below.

[0074] Optionally, the method for preparing the bimetallic catalyst comprises the following steps:

[0075] Under an inert atmosphere, a diphosphine ligand, a Ru-containing compound, and a first compound are reacted in situ to obtain a bimetallic catalyst;

[0076] The first compound is a Co-containing compound or an Rh-containing compound, and the general structural formula of the diphosphine ligand is R 1 R 2 PEPR 3 R 4 , wherein E is one of N, O, alkyl, substituted or unsubstituted C1-C20 amine, substituted or unsubstituted silyl, and substituted or unsubstituted borane;

[0077] The R 1 , R 2 , R 3 , R 4 Each is independently one of an alkyl group, a heteroalkyl group, a cycloalkyl group, a heterocycloalkyl group, a substituted or unsubstituted C6-C26 aryl group, and a heteroaryl group.

[0078] Optionally, the Ru-containing compound is at least one of triruthenium dodecacarbonyl and ruthenium hexacarbonyl chloride;

[0079] Optionally, the Co-containing compound is at least one of dicobalt octacarbonyl and cobalt tetracarbonyl hydrogen;

[0080] Optionally, the Rh-containing compound is at least one of tetracarbonyl dirhodium dichloride and dodecacarbonyl tetrarhodium;

[0081] Optionally, the molar ratio of the bisphosphine ligand, the first compound, and the Ru-containing compound is (1-2): 1:1, wherein the amount of the substance of the first compound is calculated as Co atoms or Rh atoms, and the amount of the substance of the Ru-containing compound is calculated as Ru atoms; illustratively, the molar ratio of the bisphosphine ligand, the first compound, and the Ru-containing compound can be 1:1:1, 1.2:1:1, 1.4:1:1, 1.5:1:1, 1.7:1:1, 2:1:1, and the present application is not limited thereto.

[0082] Optionally, the conditions of the in situ reaction are as follows: stirring the reaction at a temperature of 20°C to 25°C for 10 to 12 hours; illustratively, the temperature can be: 20°C, 21°C, 22°C, 23°C, 24°C, 25°C, and the reaction time can be 10h, 10.5h, 11h, 11.5h, 12h, but the present application is not limited thereto.

[0083] Preferably, the stirring rate is 100 r / min to 800 r / min, for example, it can be 100 r / min, 200 r / min, 300 r / min, 400 r / min, 500 r / min, 600 r / min, 700 r / min, 800 r / min, but the present application is not limited thereto.

[0084] Optionally, the inert atmosphere is nitrogen or argon.

[0085] Optionally, the in situ reaction is carried out in a solvent; preferably, the addition ratio of the solvent to the bisphosphine ligand is (1-10) mL:1 mmol, for example 1 mL:1 mmol, 2 mL:1 mmol, 3 mL:1 mmol, 4 mL:1 mmol, 5 mL:1 mmol, 6 mL:1 mmol, 7 mL:1 mmol, 8 mL:1 mmol, 9 mL:1 mmol, 10 mL:1 mmol, and the present application is not limited thereto.

[0086] And / or, the preparation method further comprises: after completion of the in-situ reaction, removing the solvent under reduced pressure; preferably, the reduced pressure is 2 kPa to 20 kPa, for example, 2 kPa, 4 kPa, 6 kPa, 8 kPa, 10 kPa, 12 kPa, 14 kPa, 16 kPa, 18 kPa, 20 kPa, but the present application is not limited thereto.

[0087] In a third aspect, provided is the use of the bimetallic catalyst in the preparation of isononanal.

[0088] Optionally, the method comprises the following steps: reacting isooctene, synthesis gas, an organic solvent and the bimetallic catalyst according to any one of claims 1 to 3 under an inert atmosphere, 0-250° C. and 0.1-20 MPa for 0.01-100 h to obtain isononanal, wherein the addition ratio of the bimetallic catalyst, isooctene and the organic solvent is 1 mmol: (50-200) mmol: (40-100) mL.

[0089] Optionally, the reaction temperature can be 0°C, 30°C, 50°C, 70°C, 100°C, 120°C, 150°C, 180°C, 200°C, 220°C, 250°C, but the present application is not limited thereto; preferably, it is 50-150°C.

[0090] Optionally, the reaction pressure may be 0.1 MPa, 1 MPa, 2 MPa, 4 MPa, 7 MPa, 10 MPa, 12 MPa, 15 MPa, 17 MPa, or 20 MPa, but the present application is not limited thereto; preferably, it is 0.1-5 MPa.

[0091] Optionally, the reaction time can be 0.01h, 0.5h, 1h, 5h, 7h, 10h, 15h, 20h, 25h, 30h, 35h, 40h, 50h, 60h, 70h, 80h, 90h, 100h, and the present application is not limited thereto; preferably, it is 5-10h.

[0092] Optionally, the flow rate of the synthesis gas is 300 mL / min to 800 mL / min; for example, it can be: 300 mL / min, 400 mL / min, 500 mL / min, 600 mL / min, 700 mL / min, 800 mL / min, but the present application is not limited thereto.

[0093] Optionally, the synthesis gas is carbon monoxide and hydrogen, and the volume ratio of the carbon monoxide to hydrogen is (1-1.2):1; for example, it can be: 1:1, 1:1.1, 1.2:1, and the present application is not limited thereto.

[0094] Optionally, the inert atmosphere is nitrogen or argon;

[0095] Optionally, the reaction also includes a stirring operation, and the stirring rate is 500rpm to 800rpm, for example, it can be: 500rpm, 550rpm, 600rpm, 650rpm, 700rpm, 750rpm, 800rpm, but the present application is not limited thereto.

[0096] Optionally, the organic solvent is at least one of organic alcohol, phenol, ether, and aromatic solvents; preferably, the organic solvent is at least one of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, cyclopentanol, cyclohexanol, benzyl alcohol, phenol, benzene, toluene, ether, and tetrahydrofuran.

[0097] The present application is further described below with specific embodiments:

[0098] In the following examples, nBu represents n-butyl, tBu represents tert-butyl, Pr represents propyl, iPr represents isopropyl, Ph represents phenyl, Me represents methyl, OMe represents methoxy, and Cyclo represents cyclohexyl;

[0099] The instrument used for gas chromatography testing was Clarus 680 from PerkinElmer;

[0100] The bidentate phosphorus ligand, ruthenium-containing compound, cobalt-containing compound, and rhodium-containing compound were purchased from Beijing Bailingwei Technology Co., Ltd.;

[0101] Isooctene includes 2,4,4-trimethyl-1-pentene and 2,4,4-trimethyl-2-pentene, and the mass ratio of 2,4,4-trimethyl-1-pentene to 2,4,4-trimethyl-2-pentene is 76:24.

[0102] Example 1

[0103] This embodiment provides a bimetallic catalyst coordinated by diphosphine, and the preparation method thereof is as follows:

[0104] Under argon atmosphere, weigh 2mmol of bisphosphine ligand Ph2PN(iPr)PPh2, 0.5mmol of octacarbonyl dicobalt Co2(CO)8, and 0.33mmol of dodecacarbonyl tetraruthenium Ru3(CO)8. 12 , placed in a Schlenk flask, added with 10 mL of toluene, and stirred at 100 r / min at a temperature of 25°C for 12 hours. After the reaction is completed, the product is decompressed to remove toluene at a pressure of 20 kPa to obtain a bisphosphine-coordinated bimetallic catalyst. The structural formula of the bisphosphine-coordinated bimetallic catalyst is [Ph2PN(iPr)PPh2]Co(CO)3[Ph2PN(iPr)PPh2]Ru(CO)2.

[0105] Example 2

[0106] This embodiment provides a diphosphine-coordinated bimetallic catalyst, and its preparation method differs from that of Example 1 only in that the diphosphine ligand is different. The diphosphine ligand of this embodiment is Ph2PN(Me)PPh2, and the structural formula of the obtained diphosphine-coordinated bimetallic catalyst is [Ph2PN(Me)PPh2]Co(CO)3[Ph2PN(Me)PPh2]Ru(CO)2.

[0107] Example 3

[0108] This embodiment provides a diphosphine-coordinated bimetallic catalyst, and its preparation method differs from that of Example 1 only in that the diphosphine ligand is different. The diphosphine ligand of this embodiment is Ph2PN(nBu)PPh2, and the structural formula of the obtained diphosphine-coordinated bimetallic catalyst is [Ph2PN(nBu)PPh2]Co(CO)3[Ph2PN(nBu)PPh2]Ru(CO)2.

[0109] Example 4

[0110] This embodiment provides a bimetallic catalyst coordinated by a bisphosphine, and the preparation method thereof differs from the preparation method of the bimetallic catalyst with a bisphosphine ligand in Example 1 only in that the bisphosphine ligand is different. The bisphosphine ligand in this embodiment is Ph2PN(Ph)PPh2, and the structural formula of the obtained bimetallic catalyst coordinated by a bisphosphine is [Ph2PN(Ph)PPh2]Co(CO)3[Ph2PN(Ph)PPh2]Ru(CO)2.

[0111] Example 5

[0112] This embodiment provides a bimetallic catalyst coordinated by a bisphosphine, and the preparation method thereof is different from the preparation method of the bimetallic catalyst with a bisphosphine ligand in Example 1 only in that the bisphosphine ligand is different. The bisphosphine ligand in this embodiment is Ph2PN(OCH2CH2CH3)PPh2, and the structural formula of the obtained bimetallic catalyst coordinated by a bisphosphine is [Ph2PN(OCH2CH2CH3)PPh2]Co(CO)3[Ph2PN(OCH2CH2CH3)PPh2]Ru(CO)2. .

[0113] Example 6

[0114] This embodiment provides a bimetallic catalyst coordinated by a bisphosphine, and the preparation method thereof differs from the preparation method of the bimetallic catalyst with a bisphosphine ligand in Example 1 only in that the bisphosphine ligand is different. The bisphosphine ligand in this embodiment is Ph2PN(2,4,6-Me3C6H2)PPh2, and the structural formula of the obtained bimetallic catalyst coordinated by a bisphosphine is [Ph2PN(2,4,6-Me3C6H2)PPh2]Co(CO)3[Ph2PN(2,4,6-Me3C6H2)PPh2]Ru(CO)2.

[0115] Example 7

[0116] This embodiment provides a bimetallic catalyst coordinated by a bisphosphine, and the preparation method thereof differs from the preparation method of the bimetallic catalyst with a bisphosphine ligand in Example 1 only in that the bisphosphine ligand is different. The bisphosphine ligand in this embodiment is Ph2PN(2,6-iPr2C6H3)PPh2, and the structural formula of the obtained bimetallic catalyst coordinated by a bisphosphine is [Ph2PN(2,6-iPr2C6H3)PPh2]Co(CO)3[Ph2PN(2,6-iPr2C6H3)PPh2]Ru(CO)2.

[0117] Example 8

[0118] This embodiment provides a bimetallic catalyst coordinated by a bisphosphine, and the preparation method thereof differs from the preparation method of the bimetallic catalyst with a bisphosphine ligand in Embodiment 1 only in that the bisphosphine ligand is different. The bisphosphine ligand in this embodiment is Ph2PN(Ph)P(2,4,6-Me3C6H2)2, and the structural formula of the obtained bimetallic catalyst coordinated by a bisphosphine is [Ph2PN(Ph)P(2,4,6-Me3C6H2)2]Co(CO)3[Ph2PN(Ph)P(2,4,6-Me3C6H2)2]Ru(CO)2.

[0119] Example 9

[0120] This embodiment provides a bimetallic catalyst coordinated by a bisphosphine, and the preparation method thereof differs from the preparation method of the bimetallic catalyst with a bisphosphine ligand in Embodiment 1 only in that the bisphosphine ligand is different. The bisphosphine ligand in this embodiment is (2,4,6-Me3C6H2)2PN(Ph)P(2,4,6-Me3C6H2)2, and the structural formula of the obtained bimetallic catalyst coordinated by a bisphosphine is [(2,4,6-Me3C6H2)2PN(Ph)P(2,4,6-Me3C6H2)2]Co(CO)3[(2,4,6-Me3C6H2)2PN(Ph)P(2,4,6-Me3C6H2)2]Ru(CO)2.

[0121] Example 10

[0122] This embodiment provides a bimetallic catalyst coordinated by a bisphosphine, and the preparation method thereof differs from the preparation method of the bimetallic catalyst with a bisphosphine ligand in Embodiment 1 only in that the bisphosphine ligand is different. The bisphosphine ligand in this embodiment is (2-OMeC6H4)2PN(Ph)P(2-OMeC6H4)2, and the structural formula of the obtained bimetallic catalyst coordinated by a bisphosphine is [(2-OMeC6H4)2PN(Ph)P(2-OMeC6H4)2]Co(CO)3[(2-OMeC6H4)2PN(Ph)P(2-OMeC6H4)2]Ru(CO)3.

[0123] Embodiment 11

[0124] This embodiment provides a diphosphine-coordinated bimetallic catalyst, and the preparation method thereof differs from the preparation method of the diphosphine-liganded bimetallic catalyst in Example 1 only in that the diphosphine ligand is different. The diphosphine ligand in this embodiment is Ph2POPPh2, and the structural formula of the obtained diphosphine-coordinated bimetallic catalyst is [Ph2POPPh2]Co(CO)3[Ph2POPPh2]Ru(CO)2.

[0125] Example 12

[0126] This embodiment provides a bimetallic catalyst coordinated by a bisphosphine, and the preparation method thereof differs from the preparation method of the bimetallic catalyst with a bisphosphine ligand in Example 1 only in that the bisphosphine ligand is different. The bisphosphine ligand in this embodiment is Ph2PCH2PPh2, and the structural formula of the obtained bimetallic catalyst coordinated by a bisphosphine is [Ph2PCH2PPh2]Co(CO)3[Ph2PCH2PPh2]Ru(CO)2.

[0127] Example 13

[0128] This embodiment provides a bimetallic catalyst coordinated by a bisphosphine, and the preparation method thereof differs from the preparation method of the bimetallic catalyst with a bisphosphine ligand in Example 1 only in that the bisphosphine ligand is different. The bisphosphine ligand in this embodiment is Ph2PCH2CH2PPh2, and the structural formula of the obtained bimetallic catalyst coordinated by a bisphosphine is [Ph2PCH2CH2PPh2]Co(CO)3[Ph2PCH2CH2PPh2]Ru(CO)2.

[0129] Embodiment 14

[0130] This embodiment provides a bimetallic catalyst coordinated by a bisphosphine, and the preparation method thereof differs from the preparation method of the bimetallic catalyst with a bisphosphine ligand in Example 1 only in that the bisphosphine ligand is different. The bisphosphine ligand in this embodiment is Ph2PSi(Me2)PPh2, and the structural formula of the obtained bimetallic catalyst coordinated by a bisphosphine is [Ph2PSi(Me2)PPh2]Co(CO)3[Ph2PSi(Me2)PPh2]Ru(CO)2.

[0131] Embodiment 15

[0132] This embodiment provides a bimetallic catalyst coordinated by a bisphosphine, and the preparation method thereof differs from the preparation method of the bimetallic catalyst with a bisphosphine ligand in Example 1 only in that the bisphosphine ligand is different. The bisphosphine ligand in this embodiment is Ph2PB(Ph)PPh2, and the structural formula of the obtained bimetallic catalyst coordinated by a bisphosphine is [Ph2PB(Ph)PPh2]Co(CO)3[Ph2PB(Ph)PPh2]Ru(CO)2.

[0133] Example 16

[0134] This embodiment provides a bimetallic catalyst coordinated by diphosphine, and the preparation method thereof is as follows:

[0135] Under argon atmosphere, weigh 2 mmol of bisphosphine ligand Ph2PN(iPr)PPh2 and 0.33 mmol of tetraruthenium dodecacarbonyl Ru3(CO) 12, 1mmol dicarbonyl acetylacetonate rhodium Rh(CO)2(C5H7O2), placed in a Schlenk bottle, added with 10mL toluene, stirred at 25°C at a rate of 100r / min for 12 hours, after the reaction is completed, the obtained product is decompressed to remove toluene at a pressure of 20kPa to obtain a bisphosphine-coordinated bimetallic catalyst, the chemical formula of the bisphosphine-coordinated bimetallic catalyst is [Ph2PN(iPr)PPh2]Ru(CO)2[Ph2PN(iPr)PPh2]Rh(CO)2, the structural formula is shown in formula (2); its H NMR spectrum is shown in Figure 1 As shown;

[0136]

[0137] Embodiment 17

[0138] This embodiment provides a bimetallic catalyst coordinated by a bisphosphine, and the preparation method thereof differs from the preparation method of the bimetallic catalyst with a bisphosphine ligand in Example 16 only in that the bisphosphine ligand is different. The bisphosphine ligand in this embodiment is Ph2PN(Me)PPh2, and the structural formula of the obtained bimetallic catalyst coordinated by a bisphosphine is [Ph2PN(Me)PPh2]Ru(CO)2[Ph2PN(Me)PPh2]Rh(CO)2.

[0139] Embodiment 18

[0140] This embodiment provides a bimetallic catalyst coordinated by a bisphosphine, and the preparation method thereof differs from the preparation method of the bimetallic catalyst with a bisphosphine ligand in Example 16 only in that the bisphosphine ligand is different. The bisphosphine ligand in this embodiment is Ph2PN(nBu)PPh2, and the structural formula of the obtained bimetallic catalyst coordinated by a bisphosphine is [Ph2PB(Ph)PPh2]Co(CO)3[Ph2PB(Ph)PPh2]Ru(CO)2.

[0141] Embodiment 19

[0142] This embodiment provides a bimetallic catalyst coordinated by a bisphosphine, and the preparation method thereof differs from the preparation method of the bimetallic catalyst with a bisphosphine ligand in Example 16 only in that the bisphosphine ligand is different. The bisphosphine ligand in this embodiment is Ph2PN(Ph)PPh2, and the structural formula of the obtained bimetallic catalyst coordinated by a bisphosphine is [Ph2PN(Ph)PPh2]Ru(CO)2[Ph2PN(Ph)PPh2]Rh(CO)2.

[0143] Embodiment 20

[0144] This embodiment provides a bimetallic catalyst coordinated by a bisphosphine, and the preparation method thereof differs from the preparation method of the bimetallic catalyst with a bisphosphine ligand in Example 16 only in that the bisphosphine ligand is different. The bisphosphine ligand in this embodiment is Ph2PN(OCH2CH2CH3)PPh2, and the structural formula of the obtained bimetallic catalyst coordinated by a bisphosphine is [Ph2PN(OCH2CH2CH3)PPh2]Ru(CO)2[Ph2PN(OCH2CH2CH3)PPh2]Rh(CO)2.

[0145] Embodiment 21

[0146] This embodiment provides a bimetallic catalyst coordinated by a bisphosphine, and the preparation method thereof differs from the preparation method of the bimetallic catalyst with a bisphosphine ligand in Example 16 only in that the bisphosphine ligand is different. The bisphosphine ligand in this embodiment is Ph2PN(2,4,6-Me3C6H2)PPh2, and the structural formula of the obtained bimetallic catalyst coordinated by a bisphosphine is [Ph2PN(2,4,6-Me3C6H2)PPh2]Ru(CO)2[Ph2PN(2,4,6-Me3C6H2)PPh2]Rh(CO)2.

[0147] Embodiment 22

[0148] This embodiment provides a bimetallic catalyst coordinated by a bisphosphine, and the preparation method thereof differs from the preparation method of the bimetallic catalyst with a bisphosphine ligand in Example 16 only in that the bisphosphine ligand is different. The bisphosphine ligand in this embodiment is Ph2PN(2,6-iPr2C6H3)PPh2, and the structural formula of the obtained bimetallic catalyst coordinated by a bisphosphine is [Ph2PN(2,6-iPr2C6H3)PPh2]Ru(CO)2[Ph2PN(2,6-iPr2C6H3)PPh2]Rh(CO)2.

[0149] Embodiment 23

[0150] This embodiment provides a bimetallic catalyst coordinated by a bisphosphine, and the preparation method thereof differs from the preparation method of the bimetallic catalyst with a bisphosphine ligand in Example 16 only in that the bisphosphine ligand is different. The bisphosphine ligand in this embodiment is Ph2PN(Ph)P(2,4,6-Me3C6H2)2, and the structural formula of the obtained bimetallic catalyst coordinated by a bisphosphine is [Ph2PN(Ph)P(2,4,6-Me3C6H2)2]Ru(CO)2[Ph2PN(Ph)P(2,4,6-Me3C6H2)2]Rh(CO)2.

[0151] Embodiment 24

[0152] This embodiment provides a bimetallic catalyst coordinated by a bisphosphine, and the preparation method thereof differs from the preparation method of the bimetallic catalyst with a bisphosphine ligand in Example 16 only in that the bisphosphine ligand is different. The bisphosphine ligand in this embodiment is (2,4,6-Me3C6H2)2PN(Ph)P(2,4,6-Me3C6H2)2, and the structural formula of the obtained bimetallic catalyst coordinated by a bisphosphine is [(2,4,6-Me3C6H2)2PN(Ph)P(2,4,6-Me3C6H2)2]Ru(CO)2[(2,4,6-Me3C6H2)2PN(Ph)P(2,4,6-Me3C6H2)2]Rh(CO)2.

[0153] Embodiment 25

[0154] This embodiment provides a bimetallic catalyst coordinated by a bisphosphine, and the preparation method thereof differs from the preparation method of the bimetallic catalyst with a bisphosphine ligand in Example 16 only in that the bisphosphine ligand is different. The bisphosphine ligand in this embodiment is (2-OMeC6H4)2PN(Ph)P(2-OMeC6H4)2, and the structural formula of the obtained bimetallic catalyst coordinated by a bisphosphine is [(2-OMeC6H4)2PN(Ph)P(2-OMeC6H4)2]Ru(CO)2[(2-OMeC6H4)2PN(Ph)P(2-OMeC6H4)2]Rh(CO)3.

[0155] Embodiment 26

[0156] This embodiment provides a diphosphine-coordinated bimetallic catalyst, and its preparation method differs from the preparation method of the diphosphine-liganded bimetallic catalyst in Example 16 only in that the diphosphine ligand is different. The diphosphine ligand in this embodiment is Ph2POPPh2, and the structural formula of the obtained diphosphine-coordinated bimetallic catalyst is [Ph2POPPh2]Ru(CO)2[Ph2POPPh2]Rh(CO)2.

[0157] Embodiment 27

[0158] This embodiment provides a bimetallic catalyst coordinated by a bisphosphine, and the preparation method thereof differs from the preparation method of the bimetallic catalyst with a bisphosphine ligand in Example 16 only in that the bisphosphine ligand is different. The bisphosphine ligand in this embodiment is Ph2PCH2PPh2, and the structural formula of the obtained bimetallic catalyst coordinated by a bisphosphine is [Ph2PCH2PPh2]Ru(CO)2[Ph2PCH2PPh2]Rh(CO)2.

[0159] Embodiment 28

[0160] This embodiment provides a bimetallic catalyst coordinated by a bisphosphine, and the preparation method thereof differs from the preparation method of the bimetallic catalyst with a bisphosphine ligand in Example 16 only in that the bisphosphine ligand is different. The bisphosphine ligand in this embodiment is Ph2PCH2CH2PPh2, and the structural formula of the obtained bimetallic catalyst coordinated by a bisphosphine is [Ph2PCH2CH2PPh2]Ru(CO)2[Ph2PCH2CH2PPh2]Rh(CO)2.

[0161] Embodiment 29

[0162] This embodiment provides a bimetallic catalyst coordinated by a bisphosphine, and the preparation method thereof differs from the preparation method of the bimetallic catalyst with a bisphosphine ligand in Example 16 only in that the bisphosphine ligand is different. The bisphosphine ligand in this embodiment is Ph2PSi(Me2)PPh2, and the structural formula of the obtained bimetallic catalyst coordinated by a bisphosphine is [Ph2PSi(Me2)PPh2]Ru(CO)2[Ph2PSi(Me2)PPh2]Rh(CO)2.

[0163] Embodiment 30

[0164] This embodiment provides a bimetallic catalyst coordinated by a bisphosphine, and the preparation method thereof differs from the preparation method of the bimetallic catalyst with a bisphosphine ligand in Example 16 only in that the bisphosphine ligand is different. The bisphosphine ligand in this embodiment is Ph2PB(Ph)PPh2, and the structural formula of the obtained bimetallic catalyst coordinated by a bisphosphine is [Ph2PB(Ph)PPh2]Ru(CO)2[Ph2PB(Ph)PPh2]Rh(CO)2.

[0165] Embodiment 31

[0166] The diphosphine-coordinated bimetallic catalyst obtained in Example 1-30 is used to prepare isononanal. The preparation method of the isononanal is as follows:

[0167] A 300mL high-pressure reactor was selected, and after N2 flushing, 1mmol of bimetallic catalyst, 100mmol of isooctene, and 40mL of toluene were added in sequence. The injection valve was closed, and the synthesis gas cylinder was connected. The reaction was heated to 80°C, and the reaction was carried out for 5 hours under the conditions of a pressure of 5.0MPa and a stirring rate of 800rpm. After the reaction was completed, the reactor was cooled to 0°C, and the pressure of the reactor was released to normal pressure within 5min. The reaction product was extracted for gas chromatography analysis, wherein the synthesis gas was carbon monoxide and H2, and the volume ratio of carbon monoxide to H2 was 1:1; the flow rate of the synthesis gas was 500mL / min;

[0168] According to gas chromatography analysis, the content of each component in the reaction product was determined, and the isooctene conversion rate and isononanal selectivity were calculated. The calculation formula is as follows:

[0169] Conversion rate of isooctene = (amount of isooctene added - amount of isooctene unreacted) / amount of isooctene added × 100%;

[0170] Yield of isononanal = mass of isononanal actually prepared / mass of isononanal theoretically obtained × 100%;

[0171] Selectivity of isononanal = yield of isononanal / conversion rate of isooctene × 100%;

[0172] The calculation results are shown in Table 1.

[0173] Table 1

[0174]

[0175]

[0176] It can be seen from the experimental data in Table 1 that the bimetallic catalyst of the bisphosphine ligand of the present application has excellent isooctene conversion rate and isononanal selectivity.

[0177] Finally, it should be noted that the above embodiments are used to illustrate the technical solution of the present disclosure rather than to limit the protection scope of the present disclosure. Although the present disclosure has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present disclosure can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present disclosure.

Claims

1. A bimetallic catalyst coordinated by diphosphine, characterized in that: The structural formula of the bimetallic catalyst coordinated by the diphosphine is shown in formula (1): In formula (1), A is Co or Rh; E is one of N, O, alkyl, substituted or unsubstituted C1-C20 amine, substituted or unsubstituted silane, and substituted or unsubstituted borane; The R 1 , R 2 , R 3 , R 4 Each is independently one of alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, substituted or unsubstituted C6-C26 aryl, and heteroaryl; X is any one of H, carbonyl, halogen, pseudohalogen, alkyl, alkoxy, alkanethio, substituted or unsubstituted C6-C26 aryl, substituted or unsubstituted C1-C20 amine, hydroxyl, and acyloxy; The substituent is at least one of a C1-C10 alkyl group, a C1-C10 alkoxy group, and a C6-C26 aryl group.

2. The bimetallic catalyst according to claim 1, characterized in that The R 1 , R 2 , R 3 , R 4 Each is independently any one of a C1-C20 alkyl group, a C1-C20 heteroalkyl group, a C3-C20 cycloalkyl group, a C3-C20 heterocycloalkyl group, a substituted or unsubstituted C6-C26 aryl group, or a substituted or unsubstituted C6-C26 heteroaryl group.

3. The method for preparing a bimetallic catalyst according to any one of claims 1 to 2, characterized in that: The following steps are involved: Under an inert atmosphere, a diphosphine ligand, a Ru-containing compound, and a first compound are reacted in situ to obtain a bimetallic catalyst; The first compound is a Co-containing compound or an Rh-containing compound, and the general structural formula of the diphosphine ligand is R 1 R 2 PEPR 3 R 4 , wherein E is one of N, O, alkyl, substituted or unsubstituted C1-C20 amine, substituted or unsubstituted silyl, and substituted or unsubstituted borane; The R 1 , R 2 , R 3 , R 4 Each is independently one of alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, substituted or unsubstituted C6-C26 aryl, and heteroaryl; The substituent is at least one of a C1-C10 alkyl group, a C1-C10 alkoxy group, and a C6-C26 aryl group.

4. The preparation method according to claim 3, characterized in that: The Ru-containing compound is at least one of triruthenium dodecacarbonyl and ruthenium hexacarbonyl chloride; And / or, the Co-containing compound is at least one of dicobalt octacarbonyl and cobalt tetracarbonyl hydrogen; And / or, the Rh-containing compound is at least one of tetracarbonyl dirhodium dichloride, dicarbonyl acetylacetonate rhodium, and dodecacarbonyl tetrarhodium; and / or, the molar ratio of the bisphosphine ligand, the first compound, and the Ru-containing compound is (1-2):1:1, wherein the amount of the first compound is calculated as Co atoms or Rh atoms, and the amount of the Ru-containing compound is calculated as Ru atoms; And / or, the conditions of the in-situ reaction are as follows: stirring the reaction at a temperature of 20°C to 25°C for 10 to 12 hours; preferably, the stirring rate is 100 r / min to 800 r / min; And / or, the inert atmosphere is nitrogen or argon.

5. The preparation method according to claim 4, characterized in that: The in-situ reaction is carried out in a solvent; preferably, the addition ratio of the solvent to the bisphosphine ligand is (1-10) mL: 1 mmol; And / or, the preparation method further comprises: after the in-situ reaction is completed, removing the solvent under reduced pressure; preferably, the pressure of the reduced pressure is 2 kPa to 20 kPa.

6. Use of the bimetallic catalyst according to any one of claims 1 to 2 in the preparation of isononanal.

7. The use according to claim 6, characterized in that The following steps are involved: Isooctene, synthesis gas, an organic solvent and the bimetallic catalyst according to any one of claims 1 to 2 are reacted for 0.01 to 100 hours under the conditions of an inert atmosphere, 0 to 250° C. and 0.1 to 20 MPa to obtain isononanal, wherein the addition ratio of the bimetallic catalyst, isooctene and the organic solvent is 1 mmol: (50 to 200) mmol: (40 to 100) mL.

8. The use according to claim 7, characterized in that The reaction temperature is 50-150°C, the pressure is 0.1-5MPa, and the reaction time is 5-10h; and / or, the flow rate of the synthesis gas is 300 mL / min to 800 mL / min; And / or, the synthesis gas is carbon monoxide and hydrogen, and the volume ratio of the carbon monoxide to the hydrogen is (1-1.2):1; And / or, the inert atmosphere is nitrogen or argon; And / or, the reaction also includes a stirring operation, and the stirring rate is 500 rpm to 800 rpm.

9. The use according to claim 7, characterized in that The organic solvent is at least one of organic alcohol, phenol, ether, and aromatic solvents; preferably, the organic solvent is at least one of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, cyclopentanol, cyclohexanol, benzyl alcohol, phenol, benzene, toluene, ether, and tetrahydrofuran.

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