Bidentate phosphine ligand coordination metal catalyst as well as preparation method and application thereof

Abstract

The invention discloses a bidentate phosphine ligand coordination metal catalyst as well as a preparation method and application thereof, and belongs to the technical field of catalysts. The metal atom M in the bidentate phosphine ligand coordination metal catalyst provided by the invention is specifically selected as Co or Rh, and the Co or Rh metal center has a promotion advantage on selective carbonylation of high-branch-chain olefin, so that the hydroformylation reaction speed of the high-branch-chain olefin is accelerated, the selectivity of the product is improved, and the yield of the product is increased. The conversion rate of isooctene can be up to 98%, and the generation selectivity of isononanal can be up to 99%; the preparation method of the bidentate phosphine ligand coordination metal catalyst and the preparation method of isononanal provided by the invention are simple and easy for actual production.

Description

Technical Field

[0001] The invention belongs to the technical field of catalysts, and in particular relates to a bidentate phosphine ligand coordinated metal catalyst and a preparation method and application thereof. Background Art

[0002] Isononanal is an important organic chemical raw material, widely used in plasticizers, surfactants, fragrances, detergents and organic synthesis industries. From isononanal, many fine chemical products with high added value can be synthesized, especially isononanoic acid can be obtained by oxidation. Due to the unique properties of high-branched isononanoic acid such as excellent wettability, permeability and emulsification, it has important uses in lubricants, industrial detergents and other industries.

[0003] At present, the industrial production technology of isononanal at home and abroad is still imperfect, and the reaction conditions are harsh. Among them, Tsinghua University, China University of Petroleum and Wanhua Chemical have reported related hydroformylation processes. At present, the research mainly focuses on homogeneous catalytic systems, water / oil two-phase catalytic systems, and multiphase solid-supported catalytic systems. Ma Zhanhua et al. prepared a solid-supported rhodium-based catalyst using activated carbon-supported metal Co to study the hydroformylation reaction of mixed octenes (70% 2,4,4-trimethyl-1-pentene and 20% 2,4,4-trimethyl-2-pentene and other octenes isomers). Under the reaction conditions of rhodium loading of 0.90wt%, reaction time of 5.0h, temperature of 107°C, and initial pressure of 5.0MPa, the conversion rate of mixed octenes can reach 63.6%, and the aldehyde yield is 48.5% (FuelProcessing Technology, 2009, 90, 1241-1246). Liu Zhenfeng et al. used nitrogen-containing heterocyclic phosphine ligands and metal cobalt and rhodium as catalysts to prepare methyl isononanoate by hydromethylation of isooctene, methanol and CO, and then further hydrolyzed to obtain isononanoic acid. Under the conditions of rhodium content of 0.01wt% (relative to isooctene), reaction time of 6.0h, temperature of 100°C and reaction pressure of 12.0MPa, the isooctene conversion rate can reach 95.6% and the ester yield is 90.9% (CN110605145). Abroad, Mitsubishi Chemical of Japan has developed an isooctene hydroformylation reaction using rhodium as catalyst, using triphenylphosphine oxide and a rhodium complex with initial activity (Co-TPPO) as catalysts to react at 20MPa and 130°C, and the isononanal yield is 95% (Ungvary F. Coord. Chem. Rev., 1997, 167: 233-260.). M. Glass et al. used unmodified rhodium nonanoate catalyst, 2,4,4-trimethyl-1-pentene as substrate, and carried out reaction at 27 MPa synthesis gas pressure, 135°C temperature, and 20 ppm Co concentration (based on isooctene). The isooctene conversion rate was 99.9%, and the reaction product contained 93.5 wt% 3,5,5-trimethylhexanal, 2.5 wt% 3,5,5-trimethylhexanol, 3.4 wt% residual C8 hydrocarbons, and 0.6 wt% heavy components (WO2006 / 136471). A. The reaction system using rhodium nonanoate as a catalyst precursor and a phosphite mixture as a ligand was reacted under the conditions of pressure 2MPa, reaction temperature 140°C, reaction time 8h, and Co concentration 200ppm. The isooctene conversion rate was 93%, the isononaldehyde yield was 66.1%, and the positive-iso ratio was 0.71 (EP1099678). At present, the universal metal in the olefin hydroformylation catalytic system is Rh-based metal, but Rh metal is expensive. The universal ligands are mainly phosphanes (phosphines), hypophosphites and phosphites, but the traditional phosphorus compounds have poor hydroformylation reaction activity and selectivity when used as ligands due to the influence of electronic and spatial effects. It is also found in US20120253080 that when a mixture of monophosphite and diphosphite ligands is used as a ligand, the catalytic activity in the hydroformylation of long-chain olefins is very poor. And its preparation process is usually complicated and costly (Journal of Catalysis, 2013, 298, 198-205).

[0004] In summary, the prior art has the problems of low conversion rate and product selectivity of isooctene hydroformylation and high catalyst production cost. Selecting suitable ligands and catalysts and controlling corresponding reaction conditions are crucial to the conversion rate of isooctene and the selectivity of isononanal. Summary of the invention

[0005] The purpose of the present invention is to overcome the shortcomings of the above-mentioned prior art and provide a bidentate phosphine ligand coordinated metal catalyst which can effectively catalyze the synthesis of isononanoic acid from isooctanoic acid, and a preparation method and application thereof.

[0006] To achieve the above object, in a first aspect of the present invention, the present invention provides a bidentate phosphine ligand coordinated metal catalyst, the structural formula of the bidentate phosphine ligand coordinated metal catalyst is shown in Formula I:

[0007]

[0008] Wherein, R1, R2, R3, and R4 are each independently selected from any one of substituted or unsubstituted alkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl;

[0009] X is selected from any one of hydrogen, carbonyl, halogen, pseudohalogen, alkyl, alkoxy, alkanethio, substituted or unsubstituted aryl, substituted or unsubstituted amine, hydroxyl, and carboxylic acid;

[0010] M is selected from Co or Rh;

[0011] E is selected from any one of N, O, substituted or unsubstituted alkyl, substituted or unsubstituted amine, substituted or unsubstituted silyl, and substituted or unsubstituted boryl;

[0012] n is 1, 2 or 3.

[0013] The bidentate phosphine ligand coordinated metal catalyst provided by the invention can be effectively used for isooctanoic acid hydroformylation reaction, and the conversion rate and selectivity of the obtained product are high.

[0014] Specifically, the structural formula of the bidentate phosphine ligand coordinated metal catalyst is [R1R2PEPR3R4]MX n ; Wherein, R1, R2, R3, and R4 represent substituents on two P atoms, E is a bridging group connecting two phosphine groups, X represents a group bonded to M except the diphosphine ligand, and n refers to the number of X groups. The selection of n can maintain the oxidation state balance of the entire molecule on the one hand, and the stable coordination geometry of the intermediate metal M on the other hand.

[0015] Among them, in the selection of E, when E is a substituted or unsubstituted amino group, the N atom in the amino group is respectively connected to the P atoms in the two phosphino 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 phosphino groups; when E is a substituted or unsubstituted boryl group, the B atom in the boryl group is respectively connected to the P atoms in the two phosphino groups.

[0016] As a preferred embodiment of the bidentate phosphine ligand coordinated metal catalyst of the present invention, R1, R2, R3, and R4 are independently selected from any one of C1-C10 straight-chain alkyl, C3-C10 branched-chain alkyl, cycloalkyl, phenyl, substituted phenyl, and heteroaryl;

[0017] and / or, X is selected from any one of hydrogen, chlorine, bromine, carbonyl, C1-C10 straight-chain alkyl, C3-C10 branched alkyl, C1-C6 alkoxy, alkylthiol, phenyl, substituted phenyl, C1-C6 alkyl substituted amine, hydroxyl, and C1-C3 carboxylic acid;

[0018] And / or, E is selected from any one of N, O, C1-C10 straight-chain alkyl, C3-C10 branched alkyl, substituted or unsubstituted amine, substituted or unsubstituted silicon, and substituted or unsubstituted boron.

[0019] As a preferred embodiment of the bidentate phosphine ligand coordinated metal catalyst of the present invention, the R1, R2, R3, and R4 are each independently selected from any one of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, 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, cyclohexylphenyl, and thienyl;

[0020] and / or, X is selected from any one of hydrogen, chlorine, bromine, carbonyl, methyl, ethyl, butyl, methoxy, ethoxy, propoxy, alkylthio, phenyl, benzyl, phenol, dimethylamino, diethylamino, diisopropylamino, di-tert-butylamino, di(trimethylsilyl)amino, hydroxyl, formate, and acetate;

[0021] And / or, E is selected from any one of N, O, methyl, ethyl, n-propyl, isopropyl, n-butyl, amine (-NH2), isopropylamine, methylamine, aniline, n-butylamine, methylethyletheramine, 2,4,6-trimethylphenylamine, 2,6-diisopropylphenylamine, silane (-SiH3), dimethylsilyl, phenylborane, and borane (-BH2).

[0022] As a preferred embodiment of the bidentate phosphine ligand coordinated metal catalyst of the present invention, R1, R2, R3, and R4 are each independently selected from any one of hexyl, phenyl, 2,4,6-trimethylphenyl, and 2-methoxyphenyl;

[0023] And / or, X is selected from carbonyl;

[0024] And / or, E is selected from any one of O, methyl, ethyl, isopropylamino, methylamino, aniline, n-butylamino, methylethyletheramino, 2,4,6-trimethylphenylamino, 2,6-diisopropylphenylamino, dimethylsilyl, and phenylboryl;

[0025] And / or, n is 2 or 3.

[0026] In the second aspect of the present invention, the present invention provides a method for preparing the bidentate phosphine ligand coordinated metal catalyst, the preparation method comprising the following steps: reacting a raw material as shown in structural formula II with a Rh source or a Co source in an organic solvent under an inert atmosphere, and removing the organic solvent after the reaction to obtain a bidentate phosphine ligand coordinated metal catalyst;

[0027]

[0028] Wherein, R1, R2, R3, and R4 are each independently selected from any one of substituted or unsubstituted alkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl;

[0029] E is selected from any one of N, O, substituted or unsubstituted alkyl, substituted or unsubstituted amine, substituted or unsubstituted silyl, and substituted or unsubstituted boryl.

[0030] Specifically, the structural formula of the raw material represented by formula II is R1R2PEPR3R4.

[0031] As a preferred embodiment of the preparation method of the present invention, R1, R2, R3, and R4 are independently selected from any one of C1-C10 straight-chain alkyl, C3-C10 branched-chain alkyl, cycloalkyl, phenyl, substituted phenyl, and heteroaryl;

[0032] And / or, E is selected from any one of N, O, C1-C10 straight chain alkyl, C3-C10 branched chain alkyl, substituted or unsubstituted amine, substituted or unsubstituted silane, and substituted or unsubstituted borane.

[0033] Preferably, R1, R2, R3, and R4 are each independently selected from any one of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, 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, cyclohexylphenyl, and thienyl;

[0034] And / or, E is selected from any one of N, O, methyl, ethyl, n-propyl, isopropyl, n-butyl, amino, isopropylamino, methylamino, aniline, n-butylamino, methylethyletheramino, 2,4,6-trimethylphenylamino, 2,6-diisopropylphenylamino, silyl, dimethylsilyl, phenylboryl and boryl.

[0035] More preferably, R1, R2, R3, and R4 are each independently selected from any one of hexyl, phenyl, 2,4,6-trimethylphenyl, and 2-methoxyphenyl;

[0036] And / or, E is selected from any one of O, methyl, ethyl, isopropylamino, methylamino, aniline, n-butylamino, methylethyletheramino, 2,4,6-trimethylphenylamino, 2,6-diisopropylphenylamino, dimethylsilyl, and phenylboryl.

[0037] As a preferred embodiment of the preparation method of the present invention, the Rh source is selected from at least one of tetracarbonyl dirhodium dichloride, dodecacarbonyl tetrarhodium, and acetylacetonato carbonyl rhodium;

[0038] And / or, the Co source is selected from at least one of dicobalt octacarbonyl and cobalt tetracarbonyl hydrogen.

[0039] As a preferred embodiment of the preparation method of the present invention, at least one of the following (a)-(d) is selected:

[0040] (a) The reaction temperature is 20-25°C, the reaction time is 10-12h, and the stirring speed is 100-800r / min;

[0041] (b) the organic solvent is selected from toluene or hexane;

[0042] (c) the molar ratio of the raw material represented by formula II to the Rh element or the Co element in the Rh source or the Co source is (1-2):1;

[0043] (d) The molar volume ratio of the raw material represented by formula II to the organic solvent is 1 mmol: (1-10) mL.

[0044] The inventors have found that when the above substances and parameter conditions are selected, the yield of the bidentate phosphine ligand coordinated metal catalyst is better.

[0045] Illustratively, the reaction temperature may be 20°C, 21°C, 22°C, 23°C, 24°C, 25°C, etc., the reaction time may be 10h, 11h, 12h, etc., and the stirring speed may be 100r / min, 200r / min, 300r / min, 400r / min, 500r / min, 600r / min, 700r / min, 800r / min, etc.

[0046] Illustratively, the molar ratio of the raw material represented by Formula II to the Rh element or the Co element in the Rh source or the Co source may be 1:1, 1.5:1, 2:1, etc.

[0047] Illustratively, the molar volume ratio of the raw material represented by formula II to the organic solvent may be 1 mmol: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, etc.

[0048] Preferably, the inert atmosphere is nitrogen or argon.

[0049] Preferably, the organic solvent is removed by reducing pressure, and the pressure of the reduced pressure is 2-20 kPa.

[0050] Exemplarily, the reduced pressure may be 2 kPa, 4 kPa, 6 kPa, 8 kPa, 10 kPa, 12 kPa, 14 kPa, 16 kPa, 18 kPa, 20 kPa, etc.

[0051] In the third aspect of the present invention, the present invention provides the use of the bidentate phosphine ligand coordinated metal catalyst in the preparation of isononanal.

[0052] In the fourth aspect of the present invention, the present invention provides a method for preparing isononanal, which comprises the following steps: under an inert atmosphere, reacting isooctene with a mixed synthesis gas of carbon monoxide and hydrogen in the presence of the bidentate phosphine ligand coordinated metal catalyst of the present invention to obtain isononanal.

[0053] As a preferred embodiment of the preparation method of the present invention, the molar volumes of the isooctene, the bidentate phosphine ligand coordinated metal catalyst of the present invention, and the organic solvent are (50-200) mmol: 1 mmol: (40-100) mL;

[0054] And / or, the reaction temperature is 0-250, the reaction pressure is 0.1-20MPa, and the reaction time is 0.01-100h;

[0055] and / or, the flow rate of the mixed synthesis gas is 300-800 mL / min;

[0056] And / or, the volume ratio of carbon monoxide to hydrogen is (1-1.2):1;

[0057] And / or, the organic solvent is selected from any one of organic alcohol, phenol, ether and aromatic solvent.

[0058] Preferably, the reaction temperature is 50-150° C., the reaction pressure is 0.1-8 MPa, and the reaction time is 5-10 h.

[0059] Illustratively, the reaction temperature may be 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, etc., the reaction pressure may be 0.1MPa, 0.5MPa, 1MPa, 1.5MPa, 2MPa, 2.5MPa, 3MPa, 3.5MPa, 4MPa, 4.5MPa, 5MPa, 5.5MPa, 6MPa, 6.5MPa, 7MPa, 7.5MPa, 8MPa, etc., and the reaction time may be 5h, 6h, 7h, 8h, 9h, 10h, etc.

[0060] Illustratively, the flow rate of the mixed synthesis gas may be 300 mL / min, 400 mL / min, 500 mL / min, 600 mL / min, 700 mL / min, 800 mL / min, etc.

[0061] Exemplarily, the volume ratio of carbon monoxide to hydrogen is 1:1, 1.1:1, 1.2:1, etc.

[0062] Preferably, the organic alcohol is selected from C1-C10 alcohols; illustratively, the organic alcohol may be at least one of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, cyclopentanol, cyclohexanol, and benzyl alcohol.

[0063] Preferably, the phenol is phenol; the ether is selected from at least one of diethyl ether and tetrahydrofuran; and the aromatic solvent is selected from at least one of benzene and toluene.

[0064] Preferably, the inert atmosphere is nitrogen or argon.

[0065] Compared with the prior art, the present invention has the following beneficial effects:

[0066] The metal atom M in the bidentate phosphine ligand coordinated metal catalyst provided by the present invention is specifically selected as Co or Rh, wherein the Co or Rh metal center has a promoting advantage for the selective carbonylation of highly branched olefins, accelerates the hydroformylation reaction rate of highly branched olefins, and improves the selectivity of the product, and can achieve a conversion rate of isooctene of up to 98% and a generation selectivity of isononanal of up to 99%; and the preparation method of the bidentate phosphine ligand coordinated metal catalyst and the preparation method of isononanal provided by the present invention are simple and easy to actually produce. BRIEF DESCRIPTION OF THE DRAWINGS

[0067] Figure 1 This is the hydrogen spectrum of the bidentate phosphine ligand coordinated metal catalyst prepared in Example 1;

[0068] Figure 2This is a chromatographic analysis result diagram of the synthesis of isononanal using the bidentate phosphine ligand coordinated metal catalyst in Example 1 (chromatographic analysis result diagram of isooctene hydroformylation) in Effect Example 1. DETAILED DESCRIPTION

[0069] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0070] Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0071] In the embodiments of the present invention, 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;

[0072] The instrument used for gas chromatography testing in the present invention is Clarus 680 from PerkinElmer;

[0073] The bidentate phosphine ligand in the present invention was purchased from Beijing Bailingwei Technology Co., Ltd.;

[0074] The carbonyl rhodium and carbonyl cobalt compounds in the present invention are purchased from Beijing Bailingwei Technology Co., Ltd.

[0075] Example 1

[0076] The embodiment of the present invention provides a bidentate phosphine ligand coordinated metal catalyst, the structural formula of the bidentate phosphine ligand coordinated metal catalyst is [Ph2PN(nBu)PPh2]Rh(CO)2, and the raw materials used are Ph2PN(nBu)PPh2 and Rh(CO)2(C5H7O2);

[0077] The preparation method of the bidentate phosphine ligand coordinated metal catalyst is as follows: under an argon atmosphere, 1 mmol of a phosphorus-nitrogen-phosphine skeleton biphosphine ligand Ph2PN(nBu)PPh2 and 1 mmol of a carbonyl rhodium compound Rh(CO)2(C5H7O2) are weighed, placed in a Schlenk bottle, 10 mL of toluene is added, and the mixture is stirred at a temperature of 25° C. and a rate of 100 r / min for 12 hours. After the reaction is completed, toluene is removed under reduced pressure at a pressure of 20 kPa to obtain a bidentate phosphine ligand coordinated metal catalyst;

[0078] The NMR spectrum of the bidentate phosphine ligand coordinated metal catalyst is as follows: Figure 1 As shown, its structure is shown in formula III;

[0079]

[0080] Example 2

[0081] An embodiment of the present invention provides a bidentate phosphine ligand coordinated metal catalyst. The only difference between the bidentate phosphine ligand coordinated metal catalyst and Example 1 is that the structural formula of this embodiment is [Ph2PN(Me)PPh2]Rh(CO)2, and the raw materials used are Ph2PN(Me)PPh2 and Rh(CO)2(C5H7O2).

[0082] Example 3

[0083] An embodiment of the present invention provides a bidentate phosphine ligand coordinated metal catalyst. The only difference between the bidentate phosphine ligand coordinated metal catalyst and Example 1 is that the structural formula of this embodiment is [Ph2PN(iPr)PPh2]Rh(CO)2, and the raw materials used are Ph2PN(iPr)PPh2 and Rh(CO)2(C5H7O2).

[0084] Example 4

[0085] An embodiment of the present invention provides a bidentate phosphine ligand coordinated metal catalyst. The only difference between the bidentate phosphine ligand coordinated metal catalyst and Example 1 is that the structural formula of this embodiment is [Ph2PN(Ph)PPh2]Rh(CO)2, and the raw materials used are Ph2PN(Ph)PPh2 and Rh(CO)2(C5H7O2).

[0086] Example 5

[0087] An embodiment of the present invention provides a bidentate phosphine ligand coordinated metal catalyst. The only difference between the bidentate phosphine ligand coordinated metal catalyst and Example 1 is that the structural formula of this embodiment is [Ph2PN(OCH2CH2CH3)PPh2]Rh(CO)2, and the raw materials used are Ph2PN(OCH2CH2CH3)PPh2 and Rh(CO)2(C5H7O2).

[0088] Example 6

[0089] An embodiment of the present invention provides a bidentate phosphine ligand coordinated metal catalyst. The only difference between the bidentate phosphine ligand coordinated metal catalyst and Example 1 is that the structural formula of this embodiment is [Ph2PN(2,4,6-Me3C6H2)PPh2]Rh(CO)2, and the raw materials used are Ph2PN(2,4,6-Me3C6H2)PPh2 and Rh(CO)2(C5H7O2).

[0090] Example 7

[0091] An embodiment of the present invention provides a bidentate phosphine ligand coordinated metal catalyst. The only difference between the bidentate phosphine ligand coordinated metal catalyst and Example 1 is that the structural formula of this embodiment is [Ph2PN(2,6-iPr2C6H3)PPh2]Rh(CO)2, and the raw materials used are Ph2PN(2,6-iPr2C6H3)PPh2 and Rh(CO)2(C5H7O2).

[0092] Example 8

[0093] An embodiment of the present invention provides a bidentate phosphine ligand coordinated metal catalyst. The only difference between the bidentate phosphine ligand coordinated metal catalyst and Example 1 is that the structural formula of this embodiment is [Ph2PN(Ph)P(2,4,6-Me3C6H2)2]Rh(CO)2, and the raw materials used are Ph2PN(Ph)P(2,4,6-Me3C6H2)2 and Rh(CO)2(C5H7O2).

[0094] Example 9

[0095] The embodiment of the present invention provides a bidentate phosphine ligand coordinated metal catalyst, the bidentate phosphine ligand coordinated metal catalyst is only different from the embodiment 1 in that the structural formula of the embodiment is [(2,4,6-Me3C6H2)2PN(Ph)P(2,4,6-Me3C6H2)2]Rh(CO)2, and the raw materials used are (2,4,6-Me3C6H2)2PN(Ph)P(2,4,6-Me3C6H2)2 and Rh(CO)2(C5H7O2). .

[0096] Example 10

[0097] An embodiment of the present invention provides a bidentate phosphine ligand coordinated metal catalyst. The only difference between the bidentate phosphine ligand coordinated metal catalyst and Example 1 is that the structural formula of this embodiment is [(2-OMeC6H4)2PN(Ph)P(2-OMeC6H4)2]Rh(CO)2, and the raw materials used are (2-OMeC6H4)2PN(Ph)P(2-OMeC6H4)2 and Rh(CO)2(C5H7O2).

[0098] Embodiment 11

[0099] An embodiment of the present invention provides a bidentate phosphine ligand coordinated metal catalyst. The only difference between the bidentate phosphine ligand coordinated metal catalyst and Example 1 is that the structural formula of this embodiment is [Ph2POPPh2]Rh(CO)2, and the raw materials used are Ph2POPPh2 and Rh(CO)2(C5H7O2).

[0100] Example 12

[0101] An embodiment of the present invention provides a bidentate phosphine ligand coordinated metal catalyst. The only difference between the bidentate phosphine ligand coordinated metal catalyst and Example 1 is that the structural formula of this embodiment is [Ph2PCH2PPh2]Rh(CO)2, and the raw materials used are Ph2PCH2PPh2 and Rh(CO)2(C5H7O2).

[0102] Example 13

[0103] An embodiment of the present invention provides a bidentate phosphine ligand coordinated metal catalyst. The only difference between the bidentate phosphine ligand coordinated metal catalyst and Example 1 is that the structural formula of this embodiment is [Ph2PCH2CH2PPh2]Rh(CO)2, and the raw materials used are Ph2PCH2CH2PPh2 and Rh(CO)2(C5H7O2).

[0104] Embodiment 14

[0105] An embodiment of the present invention provides a bidentate phosphine ligand coordinated metal catalyst. The only difference between the bidentate phosphine ligand coordinated metal catalyst and Example 1 is that the structural formula of this embodiment is [Ph2PSi(Me2)PPh2]Rh(CO)2, and the raw materials used are Ph2PSi(Me2)PPh2 and Rh(CO)2(C5H7O2).

[0106] Embodiment 15

[0107] An embodiment of the present invention provides a bidentate phosphine ligand coordinated metal catalyst. The only difference between the bidentate phosphine ligand coordinated metal catalyst and Example 1 is that the structural formula of this embodiment is [Ph2PB(Ph)PPh2]Rh(CO)2, and the raw materials used are Ph2PB(Ph)PPh2 and Rh(CO)2(C5H7O2).

[0108] Example 16

[0109] An embodiment of the present invention provides a bidentate phosphine ligand coordinated metal catalyst. The only difference between the bidentate phosphine ligand coordinated metal catalyst and Example 1 is that the structural formula of this embodiment is [(CH3CH2CH2CH2CH2CH2CH2)2PN(Me)P(CH3CH2CH2CH2CH2CH2CH2)2]Rh(CO)2, and the raw materials used are (CH3CH2CH2CH2CH2CH2CH2)2PN(Me)P(CH3CH2CH2CH2CH2CH2CH2)2 and Rh(CO)2(C5H7O2).

[0110] Embodiment 17

[0111] The embodiment of the present invention provides a bidentate phosphine ligand coordinated metal catalyst, the structural formula of the bidentate phosphine ligand coordinated metal catalyst is [Ph2PN(iPr)PPh2]Co(CO)3, and the raw materials used are Ph2PN(iPr)PPh2 and Co2(CO)8;

[0112] The preparation method of the bidentate phosphine ligand coordinated metal catalyst is as follows: under an argon atmosphere, 1 mmol of a phosphorus-nitrogen-phosphine skeleton diphosphine ligand Ph2PN(iPr)PPh2 and 1 mmol of a carbonyl cobalt compound Co2(CO)8 are weighed, placed in a Schlenk bottle, 10 mL of toluene is added, and the reaction is stirred at a rate of 100 r / min at a temperature of 25°C for 12 hours. After the reaction is completed, the toluene is removed under reduced pressure at a pressure of 20 kPa to obtain a bidentate phosphine ligand coordinated metal catalyst.

[0113] Embodiment 18

[0114] An embodiment of the present invention provides a bidentate phosphine ligand coordinated metal catalyst. The only difference between the bidentate phosphine ligand coordinated metal catalyst and Example 17 is that the structural formula of this embodiment is [Ph2PN(nBu)PPh2]Co(CO)3, and the raw materials used are Ph2PN(nBu)PPh2 and Co2(CO)8.

[0115] Embodiment 19

[0116] An embodiment of the present invention provides a bidentate phosphine ligand coordinated metal catalyst. The only difference between the bidentate phosphine ligand coordinated metal catalyst and Example 17 is that the structural formula of this embodiment is [Ph2PN(OCH2CH2CH3)PPh2]Co(CO)3, and the raw materials used are Ph2PN(OCH2CH2CH3)PPh2 and Co2(CO)8.

[0117] Embodiment 20

[0118] An embodiment of the present invention provides a bidentate phosphine ligand coordinated metal catalyst. The only difference between the bidentate phosphine ligand coordinated metal catalyst and Example 17 is that the structural formula of this embodiment is [Ph2PN(2,4,6-Me3C6H2)PPh2]Co(CO)3, and the raw materials used are Ph2PN(2,4,6-Me3C6H2)PPh2 and Co2(CO)8.

[0119] Embodiment 21

[0120] An embodiment of the present invention provides a bidentate phosphine ligand coordinated metal catalyst. The only difference between the bidentate phosphine ligand coordinated metal catalyst and Example 17 is that the structural formula of this embodiment is [Ph2PN(Ph)P(2,4,6-Me3C6H2)2]Co(CO)3, and the raw materials used are Ph2PN(Ph)P(2,4,6-Me3C6H2)2 and Co2(CO)8.

[0121] Embodiment 22

[0122] An embodiment of the present invention provides a bidentate phosphine ligand coordinated metal catalyst. The only difference between the bidentate phosphine ligand coordinated metal catalyst and Example 17 is that the structural formula of this embodiment is [(2-OMeC6H4)2PN(Ph)P(2-OMeC6H4)2]Co(CO)3, and the raw materials used are (2-OMeC6H4)2PN(Ph)P(2-OMeC6H4)2 and Co2(CO)8.

[0123] Embodiment 23

[0124] An embodiment of the present invention provides a bidentate phosphine ligand coordinated metal catalyst. The only difference between the bidentate phosphine ligand coordinated metal catalyst and Example 17 is that the structural formula of this embodiment is [Ph2POPPh2]Co(CO)3, and the raw materials used are Ph2POPPh2 and Co2(CO)8.

[0125] Embodiment 24

[0126] An embodiment of the present invention provides a bidentate phosphine ligand coordinated metal catalyst. The only difference between the bidentate phosphine ligand coordinated metal catalyst and Example 17 is that the structural formula of this embodiment is [Ph2PCH2CH2PPh2]Co(CO)3, and the raw materials used are Ph2PCH2CH2PPh2 and Co2(CO)8.

[0127] Embodiment 25

[0128] An embodiment of the present invention provides a bidentate phosphine ligand coordinated metal catalyst. The only difference between the bidentate phosphine ligand coordinated metal catalyst and Example 17 is that the structural formula of this embodiment is [Ph2PSi(Me2)PPh2]Co(CO)3, and the raw materials used are Ph2PSi(Me2)PPh2 and Co2(CO)8.

[0129] Embodiment 26

[0130] An embodiment of the present invention provides a bidentate phosphine ligand coordinated metal catalyst. The only difference between the bidentate phosphine ligand coordinated metal catalyst and Example 17 is that the structural formula of this embodiment is [Ph2PB(Ph)PPh2]Co(CO)3, and the raw materials used are Ph2PB(Ph)PPh2 and Co2(CO)8.

[0131] Effect example

[0132] The effect examples of the present invention verify the effect of the catalyst prepared by Examples 1-26, wherein the specific operation is as follows:

[0133] The bidentate phosphine ligand coordinated metal catalysts prepared in Examples 1-26 were respectively used to synthesize isononanal. The synthesis method is: a 300mL high-pressure reactor is selected, and after N2 flushing, 1mmol of bidentate phosphine ligand coordinated metal catalyst, 100mmol of isooctene, and 40mL of toluene are added in sequence, and then the injection valve is closed, and the synthesis gas cylinder is connected (the synthesis gas is CO and H2, and the volume ratio of CO and H2 is 1:1; the flow rate of the synthesis gas is 500mL / min), and the oil bath is heated to 80°C, and the system reaction pressure is adjusted to 8.0MPa, the stirring rate is 800rpm, and the reaction is maintained for 10 hours. After the reaction is completed, the reactor is cooled to 0°C using liquid nitrogen, and the reactor is depressurized to normal pressure within 5min, and the reaction liquid is extracted for gas chromatography analysis; the chromatographic analysis results of the synthesis of isononanal using the bidentate phosphine ligand coordinated metal catalyst prepared in Example 1 are shown in the figure Figure 2 As shown;

[0134] Among them, in the present invention, after the reaction is completed, sampling is performed for GC-MS analysis to determine the content of each component, and the isooctene conversion rate and isononanal selectivity are calculated. The calculation formula is as follows:

[0135] Conversion rate of isooctene = (amount of isooctene added - amount of isooctene unreacted) / amount of isooctene added × 100%;

[0136] Yield of isononanal = mass of isononanal actually prepared / mass of isononanal theoretically obtained × 100%;

[0137] Selectivity of isononanal = yield of isononanal / conversion rate of isooctene × 100%;

[0138] The results obtained by analysis and calculation are shown in Table 1;

[0139] Table 1

[0140]

[0141] It can be seen from Table 1 that the bidentate phosphine ligand coordinated metal catalyst prepared by the present invention can effectively improve the conversion rate of isooctene and the selectivity of isononanal, wherein the conversion rate of isooctene is above 86.2% and can reach 98.0%; the selectivity of isononanal is above 89.9% and can reach 99.0%.

[0142] Finally, it should be noted that the above embodiments are intended to illustrate the technical solution of the present invention rather than to limit the scope of protection of the present invention. Although the present invention 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 invention may be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A bidentate phosphine ligand coordinated metal catalyst, characterized in that: The structural formula of the bidentate phosphine ligand coordinated metal catalyst is shown in Formula I: Wherein, R1, R2, R3, and R4 are each independently selected from any one of substituted or unsubstituted alkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl; X is selected from any one of hydrogen, carbonyl, halogen, pseudohalogen, alkyl, alkoxy, alkanethio, substituted or unsubstituted aryl, substituted or unsubstituted amine, hydroxyl, and carboxylic acid; M is selected from Co or Rh; E is selected from any one of N, O, substituted or unsubstituted alkyl, substituted or unsubstituted amine, substituted or unsubstituted silyl, and substituted or unsubstituted boryl; n is 1, 2 or 3.

2. The bidentate phosphine ligand coordinated metal catalyst according to claim 1, characterized in that: The R1, R2, R3, and R4 are each independently selected from any one of a C1-C10 straight-chain alkyl group, a C3-C10 branched-chain alkyl group, a cycloalkyl group, a phenyl group, a substituted phenyl group, and a heteroaryl group; and / or, X is selected from any one of hydrogen, chlorine, bromine, carbonyl, C1-C10 straight-chain alkyl, C3-C10 branched alkyl, C1-C6 alkoxy, alkylthiol, phenyl, substituted phenyl, C1-C6 alkyl substituted amine, hydroxyl, and C1-C3 carboxylic acid; And / or, E is selected from any one of N, O, C1-C10 straight chain alkyl, C3-C10 branched chain alkyl, substituted or unsubstituted amine, substituted or unsubstituted silane, and substituted or unsubstituted borane.

3. The bidentate phosphine ligand coordinated metal catalyst according to claim 2, characterized in that: The R1, R2, R3, and R4 are each independently selected from any one of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, cyclopentyl, cyclohexyl, 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, cyclohexylphenyl, and thienyl; and / or, X is selected from any one of hydrogen, chlorine, bromine, carbonyl, methyl, ethyl, butyl, methoxy, ethoxy, propoxy, alkylthio, phenyl, benzyl, phenol, dimethylamino, diethylamino, diisopropylamino, di-tert-butylamino, di(trimethylsilyl)amino, hydroxyl, formate, and acetate; And / or, E is selected from any one of N, O, methyl, ethyl, n-propyl, isopropyl, n-butyl, amino, isopropylamino, methylamino, aniline, n-butylamino, methylethyletheramino, 2,4,6-trimethylphenylamino, 2,6-diisopropylphenylamino, silyl, dimethylsilyl, phenylboryl and boryl.

4. The bidentate phosphine ligand coordinated metal catalyst according to claim 3, characterized in that: R1, R2, R3, and R4 are each independently selected from any one of hexyl, phenyl, 2,4,6-trimethylphenyl, and 2-methoxyphenyl; And / or, X is selected from carbonyl; And / or, E is selected from any one of O, methyl, ethyl, isopropylamino, methylamino, aniline, n-butylamino, methylethyletheramino, 2,4,6-trimethylphenylamino, 2,6-diisopropylphenylamino, dimethylsilyl, and phenylboryl; And / or, n is 2 or 3.

5. The method for preparing a bidentate phosphine ligand coordinated metal catalyst according to any one of claims 1 to 4, characterized in that: The preparation method comprises the following steps: Under an inert atmosphere, reacting a raw material as shown in structural formula II with a Rh source or a Co source in an organic solvent, removing the organic solvent after the reaction is completed, and obtaining a bidentate phosphine ligand coordinated metal catalyst; Wherein, R1, R2, R3, and R4 are each independently selected from any one of substituted or unsubstituted alkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl; E is selected from any one of N, O, substituted or unsubstituted alkyl, substituted or unsubstituted amine, substituted or unsubstituted silyl, and substituted or unsubstituted boryl.

6. The preparation method according to claim 5, characterized in that: The Rh source is selected from at least one of tetracarbonyl dirhodium dichloride, dodecacarbonyl tetrarhodium, and acetylacetonato carbonyl rhodium; And / or, the Co source is selected from at least one of dicobalt octacarbonyl and cobalt tetracarbonyl hydrogen.

7. The preparation method according to claim 5, characterized in that: At least one of the following (a)-(d), (a) The reaction temperature is 20-25°C, the reaction time is 10-12h, and the stirring speed is 100-800r / min; (b) the organic solvent is selected from toluene or hexane; (c) the molar ratio of the raw material represented by formula II to the Rh element or the Co element in the Rh source or the Co source is (1-2):1; (d) The molar volume ratio of the raw material represented by formula II to the organic solvent is 1 mmol: (1-10) mL.

8. Use of the bidentate phosphine ligand coordinated metal catalyst according to any one of claims 1 to 4 in the preparation of isononanal.

9. A method for preparing isononanal, characterized in that: The preparation method comprises the following steps: under an inert atmosphere, reacting isooctene with a mixed synthesis gas of carbon monoxide and hydrogen in the presence of a bidentate phosphine ligand coordinated metal catalyst as described in any one of claims 1 to 4 to obtain isononanal.

10. The preparation method according to claim 9, characterized in that: The molar volumes of the isooctene, the bidentate phosphine ligand coordinated metal catalyst according to any one of claims 1 to 4, and the organic solvent are (50-200) mmol: 1 mmol: (40-100) mL; And / or, the reaction temperature is 0-250°C, the reaction pressure is 0.1-20MPa, and the reaction time is 0.01-100h; and / or, the flow rate of the mixed synthesis gas is 300-800 mL / min; And / or, the volume ratio of carbon monoxide to hydrogen is (1-1.2):1; And / or, the organic solvent is selected from any one of organic alcohol, phenol, ether and aromatic solvent.

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