A catalyst, catalyst system, and method of making isoneraldehyde

Abstract

This invention provides an asymmetric bidentate phosphine ligand-coordinated catalyst, a catalyst system, its application, and a method for preparing isorandal. The catalyst comprises a compound as shown in formula (I), where R1-R4 are independently selected from C1-C2. 12 Straight-chain alkyl, C3-C 12 Branched alkyl, C4-C 12 Heteroalkyl, C3-C 12 cycloalkyl, C4-C 20 Heterocyclic alkyl groups and C6-C 20 Aryl group; R5 is selected from hydrogen, C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl groups, C3-C 12 cycloalkyl and C6-C 20 aryl; X is selected from hydrogen, carbonyl, halogen, pseudohalogen, C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl, C1-C 12 Alkoxy, C1-C 12 Alkyl mercapto, C6-C 20 Aryl, C7-C 20 Alkyl aryl, C1-C 12 Alkylamine, hydroxyl, and phenolic groups; 1 ≤ n ≤ 4, where n is an integer; the substituents are selected from alkyl, alkoxy, alkylsilyl, and alkylamine groups; the catalyst of the present invention can improve the hydroformylation conversion of diisobutylene and the selectivity of the product isononanal, and has good stability; moreover, the catalyst preparation method is simple.

Description

Technical Field

[0001] This invention relates to the field of catalyst technology, and in particular to a catalyst, a catalyst system, its application, and a method for preparing isonononal. Background Technology

[0002] Isonononal (3,5,5-trimethyl-1-hexanal) is an important organic chemical raw material widely used in plasticizers, surfactants, fragrances, detergents, and organic synthesis industries. Many high-value-added fine chemical products can be synthesized from isonononal, especially isononanoic acid (3,5,5-trimethyl-1-hexanoic acid) through oxidation. Due to the excellent wettability, penetrability, and emulsifying properties of highly branched isononanoic acid, it has important applications in lubricants and industrial detergents.

[0003] Currently, the industrial production technology of 3,5,5-trimethyl-1-hexanal is not yet perfect, and the reaction conditions are harsh. Among them, Tsinghua University, China University of Petroleum and Wanhua Chemical have reported related hydroformylation processes. At present, research mainly focuses on homogeneous catalytic systems, water / oil two-phase catalytic systems and heterogeneous solid-supported catalytic systems.

[0004] Ma Zhanhua et al. prepared a supported rhodium-based catalyst using activated carbon to support metal Rh. They studied the hydroformylation reaction of mixed octene (70% 2,4,4-trimethyl-1-pentene and 20% 2,4,4-trimethyl-2-pentene and other octene isomers). Under the reaction conditions of 0.90 wt% rhodium loading, 5.0 h reaction time, 107 °C temperature, and 5.0 MPa initial pressure, the conversion rate of mixed octene reached 63.6%, and the aldehyde yield was 48.5% (Fuel Processing Technology, 2009, 90, 1241-1246). Liu Zhenfeng et al. used nitrogen-containing heterocyclic phosphine ligands with cobalt and rhodium as catalysts to carry out the hydromethylation reaction of diisobutylene, methanol, and CO to prepare methyl isononanoate, which was then further hydrolyzed to obtain isononanoic acid. Under the conditions of 0.01 wt% rhodium content (relative to diisobutylene), 6.0 h reaction time, 100 °C temperature, and 12.0 MPa reaction pressure, the diisobutylene conversion rate can reach 95.6% and the ester yield is 90.9% (CN 110605145).

[0005] Internationally, Mitsubishi Chemical in Japan developed a rhodium-catalyzed hydroformylation reaction of isooctene. Using triphenylphosphine oxide and an initially active rhodium complex (Rh-TPPO) as catalysts, the reaction was carried out at 20 MPa and 130 °C, achieving a 95% yield of isononanal (Ungvary F. Coord. Chem. Rev., 1997, 167: 233-260.). M. Glass et al. used an unmodified rhodium nonanoate catalyst with 2,4,4-trimethyl-1-pentene as the substrate, reacting at a syngas pressure of 27 MPa, a temperature of 135 °C, and an Rh concentration of 20 ppm (based on isooctene). The isooctene conversion 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). The reaction system using rhodium nonanoate as a catalyst precursor and a mixture of phosphonates as ligands was carried out under the conditions of 2 MPa pressure, 140 °C reaction temperature, 8 h reaction time and 200 ppm Rh concentration. The isooctene conversion rate was 93%, the isononal yield was 66.1%, and the positive-to-iso ratio was 0.71 (EP1099678).

[0006] Currently, the commonly used ligands in olefin hydroformylation catalysis systems are mainly phosphonanes (phosphine), phosphonides, and phosphonites. However, traditional phosphine compounds exhibit poor activity and selectivity in hydroformylation reactions due to electronic and steric effects. US20120253080 also found that using a mixture of monophosphonates and diphosphonates as ligands resulted in very poor catalytic activity in the hydroformylation of long-chain olefins. Furthermore, their preparation processes are typically complex and costly (Journal of Catalysis, 2013, 298, 198-205).

[0007] In summary, existing technologies suffer from low conversion rates and product selectivity in the hydroformylation of diisobutylene, as well as high catalyst production costs. Summary of the Invention

[0008] To address the problems of low conversion rate and product selectivity in the hydroformylation of diisobutylene and high catalyst production cost in existing technologies, this invention provides an asymmetric bidentate phosphine ligand-coated catalyst, a catalyst system, its application, and a method for preparing isonononal. The catalyst provided by this invention can effectively improve the conversion rate of diisobutylene hydroformylation and the selectivity of the product isonononal when used to prepare isonononal from diisobutylene, and it also has good stability. Moreover, the preparation method of the catalyst is simple and can reduce the preparation cost.

[0009] The objective of this invention is mainly achieved through the following technical solutions.

[0010] The present invention provides a catalyst with asymmetric bidentate phosphine ligand coordination, the catalyst comprising a compound as shown in formula (I).

[0011]

[0012] Among them, R1-R4 are each independently selected from C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl groups, C4-C 12 heteroalkyl, C3-C 12 cycloalkyl, C4-C 20 Heterocyclic alkyl groups and C6-C 20 The aryl group; for R1-R4, the C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl groups, C4-C 12 heteroalkyl, C3-C 12 cycloalkyl, C4-C 20 Heterocyclic alkyl groups and C6-C 20 The hydrogen atom on the aryl group can be optionally substituted with a substituent.

[0013] R5 is selected from hydrogen, C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl groups, C3-C 12 cycloalkyl and C6-C 20 The aryl group; for R5, the C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl groups, C3-C 12 cycloalkyl and C6-C 20 The hydrogen atom on the aryl group can be optionally substituted with a substituent.

[0014] X is selected from hydrogen, carbonyl, halogen, pseudohalogen, C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl groups, C1-C 12 alkoxy groups, C1-C 12 alkyl thiol group, C6-C 20 aryl, C7-C 20 alkylaryl, C1-C 12 Alkylamine, hydroxyl, and phenolic groups; for X, the C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl groups, C1-C 12 alkoxy groups, C1-C 12 alkyl thiol group, C6-C 20 aryl, C7-C 20 alkylaryl, C1-C12 The hydrogen atoms on the alkylamine, hydroxyl, and phenolic groups may optionally be substituted with substituents.

[0015] 1 ≤ n ≤ 4, where n is an integer.

[0016] The substituents are selected from alkyl, alkoxy, alkylsilyl and alkylamine groups.

[0017] Preferably, the substituent is selected from C1-C6 straight-chain alkyl, C3-C6 branched alkyl, C1-C6 alkyloxy, C3-C6 alkylsilyl, and C1-C6 alkylamine.

[0018] Preferably, R1-R4 are each independently selected from C1-C 10 Straight-chain alkyl, C3-C 10 Branched alkyl groups, C3-C 10 heteroalkyl, C3-C 10 cycloalkyl, C3-C 10 Heterocyclic alkyl groups and C6-C 18 The aryl group; preferably, R1-R4 are each independently selected from 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-ditert-butylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triisopropylphenyl, 2,4,6-tritert-butylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, and 4-methoxyphenyl.

[0019] Preferably, R5 is selected from hydrogen, C1-C 10 Straight-chain alkyl, C3-C 10 Branched alkyl groups, C3-C 10 cycloalkyl and C6-C 18 The aryl group; preferably, R5 is selected from hydrogen, 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-ditert-butylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triisopropylphenyl and 2,4,6-tritert-butylphenyl.

[0020] Preferably, X is selected from hydrogen, CO, chlorine, bromine, methyl, ethyl, butyl, trimethylsilylmethyl, phenyl, benzyl, methoxy, ethoxy, phenol, formic acid, acetate, dimethylamino, diethylamino, diisopropylamino, di-tert-butylamino, di(trimethylsilyl)amino, acetylacetone, and hydroxyl.

[0021] Preferably, the compound with the structure shown in formula (I) is selected from at least one of [PPh2C6H4N(H)PPh2]Rh(CO)2, [PPh2C6H4N(iPr)PPh2]Rh(CO)2, [PPh2C6H4N(tBu)PPh2]Rh(CO)2, [PPh2C6H4N(Ph)PPh2]Rh(CO)2 and [PPh2C6H4N(H)PPh2]Rh(C2H5)2.

[0022] In a second aspect, the present invention provides an asymmetric bidentate phosphine ligand-coordinated catalyst system, the catalyst system comprising the catalyst described in the first aspect and an antioxidant stabilizer.

[0023] Preferably, the antioxidant stabilizer is selected from at least one of triphenyl phosphite, antioxidant 168, antioxidant 618 and antioxidant 1010.

[0024] Preferably, the amount of catalyst used is calculated in Rh, and the molar ratio of the catalyst to the antioxidant stabilizer is 0.001-100:5-200, more preferably 0.5-20:5-200.

[0025] Thirdly, the present invention provides the application of the catalyst described in the first aspect or the catalyst system described in the second aspect in the preparation of isonononal.

[0026] Fourthly, the present invention provides a method for preparing isononanal, the method comprising: reacting diisobutylene, CO and H2 with the catalyst described in the first aspect or the catalyst system described in the second aspect in an organic solvent.

[0027] Preferably, the molar ratio of the catalyst to diisobutylene is 1:500-1500, more preferably 1:800-1200, and the amount of the catalyst is expressed as Rh.

[0028] Preferably, the total flow rate of CO and H2 is 300-800 mL / min relative to 1 mmol of the catalyst, and the amount of the catalyst is expressed as Rh.

[0029] Preferably, the volume ratio of CO to H2 is 1-1.2:1.

[0030] Preferably, the amount of catalyst, expressed as Rh, is 0.001-100 mmol, more preferably 0.5-20 mmol, relative to 1 L of the organic solvent.

[0031] And / or, relative to 1L of the organic solvent, the content of the antioxidant stabilizer is 5-200 mmol.

[0032] Preferably, the organic solvent is selected from alcohols, phenols, ethers and aromatic compounds, and more preferably from at least one of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, cyclopentanol, cyclohexanol, benzyl alcohol, phenol, benzene, toluene, diethyl ether and tetrahydrofuran.

[0033] Preferably, the reaction conditions include: a reaction temperature of 0-250℃, preferably 50-150℃; a reaction time of 0.01-100h, preferably 5-10h; and a reaction pressure of 0.1-20MPa, preferably 0.1-5MPa.

[0034] The present invention relates to an asymmetric bidentate phosphine ligand-coordinated catalyst, a catalyst system thereof, its application, and a method for preparing isonononal, which has the following advantages:

[0035] 1) The catalyst provided by this invention can effectively improve the conversion rate of diisobutylene hydroformylation to isononanal, and the conversion rate can reach 99%.

[0036] 2) The product isononanal has high selectivity, reaching 98.9%;

[0037] 3) The preparation method of the catalyst of the present invention is simple and can reduce the preparation cost;

[0038] 4) The catalyst system prepared by this invention and the antioxidant stabilizer have good stability. Even after multiple cycles, it still has a high diisobutylene hydroformylation conversion rate and isononal selectivity. Attached Figure Description

[0039] Figure 1 The nuclear magnetic resonance spectrum of the catalyst prepared in Example 1;

[0040] Figure 2 The nuclear magnetic resonance spectrum of the catalyst prepared in Example 2;

[0041] Figure 3 The nuclear magnetic resonance spectrum of the catalyst prepared in Example 3;

[0042] Figure 4 The nuclear magnetic resonance spectrum of the catalyst prepared in Example 4. Detailed Implementation

[0043] In a first aspect, the present invention provides a catalyst with asymmetric bidentate phosphine ligand coordination, the catalyst comprising a compound as shown in formula (I).

[0044]

[0045] Among them, R1-R4 are each independently selected from C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl groups, C4-C 12 heteroalkyl, C3-C 12 cycloalkyl, C4-C 20 Heterocyclic alkyl groups and C6-C 20 The aryl group; for R1-R4, the C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl groups, C4-C 12 heteroalkyl, C3-C 12 cycloalkyl, C4-C 20 Heterocyclic alkyl groups and C6-C 20 The hydrogen atom on the aryl group can be optionally substituted with a substituent;

[0046] R5 is selected from hydrogen, C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl groups, C3-C 12 cycloalkyl and C6-C 20 The aryl group; for R5, the C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl groups, C3-C 12 cycloalkyl and C6-C 20 The hydrogen atom on the aryl group can be optionally substituted with a substituent;

[0047] X is selected from hydrogen, carbonyl, halogen, pseudohalogen, C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl groups, C1-C 12 alkoxy groups, C1-C 12 alkyl thiol group, C6-C 20 aryl, C7-C 20 alkylaryl, C1-C 12 Alkylamine, hydroxyl, and phenolic groups; for X, the C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl groups, C1-C 12 alkoxy groups, C1-C 12 alkyl thiol group, C6-C 20 aryl, C7-C 20 alkylaryl, C1-C12 The hydrogen atoms on the alkylamine, hydroxyl, and phenolic groups may optionally be substituted with substituents;

[0048] 1 ≤ n ≤ 4, where n is an integer;

[0049] The substituents are selected from alkyl, alkoxy, alkylsilyl and alkylamine groups.

[0050] In this invention, n represents the number of X groups.

[0051] In this invention, the general structural formula of the compound with the structure shown in formula (I) is [R1R2PC6H4NR5PR3R4]RhX n .

[0052] In a preferred embodiment of the present invention, the substituent is selected from C1-C6 straight-chain alkyl, C3-C6 branched-chain alkyl, C1-C6 alkoxy, C3-C6 alkylsilyl, and C1-C6 alkylamine.

[0053] In a preferred embodiment of the present invention, R1-R4 are each independently selected from C1-C 10 Straight-chain alkyl, C3-C 10 Branched alkyl groups, C3-C 10 heteroalkyl, C3-C 10 cycloalkyl, C3-C 10 Heterocyclic alkyl groups and C6-C 18 The aryl group; preferably, R1-R4 are each independently selected from 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-ditert-butylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triisopropylphenyl, 2,4,6-tritert-butylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, and 4-methoxyphenyl.

[0054] In a preferred embodiment of the present invention, R5 is selected from hydrogen, C1-C 10 Straight-chain alkyl, C3-C 10 Branched alkyl groups, C3-C 10 cycloalkyl and C6-C 18The aryl group; preferably, R5 is selected from hydrogen, 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-ditert-butylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triisopropylphenyl and 2,4,6-tritert-butylphenyl.

[0055] In a preferred embodiment of the present invention, X is selected from hydrogen, CO, chlorine, bromine, methyl, ethyl, butyl, trimethylsilylmethyl, phenyl, benzyl, methoxy, ethoxy, phenol, formic acid, acetate, dimethylamino, diethylamino, diisopropylamino, di-tert-butylamino, di(trimethylsilyl)amino, acetylacetone, and hydroxyl.

[0056] In a preferred embodiment of the present invention, the compound with the structure shown in formula (I) is selected from at least one of [PPh2C6H4N(H)PPh2]Rh(CO)2, [PPh2C6H4N(iPr)PPh2]Rh(CO)2, [PPh2C6H4N(tBu)PPh2]Rh(CO)2, [PPh2C6H4N(Ph)PPh2]Rh(CO)2 and [PPh2C6H4N(H)PPh2]Rh(C2H5)2; preferably selected from at least one of [PPh2C6H4N(H)PPh2]Rh(CO)2, [PPh2C6H4N(iPr)PPh2]Rh(CO)2, [PPh2C6H4N(tBu)PPh2]Rh(CO)2 and [PPh2C6H4N(Ph)PPh2]Rh(CO)2.

[0057] In this invention, tBu represents tert-butyl, iPr represents isopropyl, and Ph represents phenyl.

[0058] In this invention, the compound with the structure shown in formula (I) is prepared by an in-situ reaction: the asymmetric bisphosphorus ligand compound shown in formula (II) is contacted with a rhodium source compound in an in-situ reaction solvent to carry out an in-situ reaction, and the in-situ reaction solvent is removed under reduced pressure to obtain the compound with the structure shown in formula (I). R1-R6 in formula (II) are the same as R1-R6 in formula (I).

[0059]

[0060] In this invention, the molar ratio of the asymmetric bisphosphonium ligand compound represented by formula (II) to the rhodium source compound is 1:0.5-2.

[0061] In this invention, the amount of the in-situ reaction solvent used is 50-150 ml relative to 1 mmol of the asymmetric bisphosphonium ligand compound with the structure shown in formula (II).

[0062] In this invention, the conditions for the in-situ reaction include: a reaction time of 8-14 hours and a reaction temperature of 20-30°C.

[0063] In this invention, the in-situ reaction is carried out in a Schlenk flask under stirring conditions.

[0064] In this invention, the rhodium source compound is selected from tetrarhodium dodecylcarbonyl (Rh4(CO)). 12 At least one of 1,5-cyclooctadiene (acetylacetone) rhodium (Rh(acac)(COD)) and dicarbonyl acetylacetone rhodium (Rh(acac)(CO)2).

[0065] In this invention, the in-situ reaction solvent is selected from at least one of toluene, hexane, phenol, and benzene; preferably toluene and / or hexane.

[0066] In this invention, the compound with the structure shown in formula (1) prepared can be characterized by conventional methods in the art, and the proportion can be characterized by nuclear magnetic resonance spectroscopy.

[0067] In a second aspect, the present invention provides an asymmetric bidentate phosphine ligand-coordinated catalyst system, the catalyst system comprising the catalyst described in the first aspect and an antioxidant stabilizer.

[0068] In a preferred embodiment of the present invention, the antioxidant stabilizer is selected from at least one of triphenyl phosphite, antioxidant 168, antioxidant 618 and antioxidant 1010; preferably selected from antioxidant 168 and / or antioxidant 1010.

[0069] In a preferred embodiment of the present invention, the amount of catalyst used is calculated as Rh, and the molar ratio of the catalyst to the antioxidant stabilizer is 0.001-100:5-200, preferably 0.5-20:5-200.

[0070] Thirdly, the present invention provides the application of the catalyst described in the first aspect or the catalyst system described in the second aspect in the preparation of isonononal.

[0071] Fourthly, the present invention provides a method for preparing isononanal, the method comprising: reacting diisobutylene, CO and H2 with the catalyst described in the first aspect or the catalyst system described in the second aspect in an organic solvent.

[0072] In a preferred embodiment of the present invention, the molar ratio of the catalyst to diisobutylene is 1:500-1500, preferably 1:800-1200, and the amount of the catalyst is expressed as Rh.

[0073] In a preferred embodiment of the present invention, the total flow rate of CO and H2 is 300-800 mL / min relative to 1 mmol of the catalyst, and the amount of the catalyst is expressed as Rh.

[0074] In a preferred embodiment of the present invention, the volume ratio of CO to H2 is 1-1.2:1;

[0075] In a preferred embodiment of the present invention, the amount of the catalyst, expressed as Rh, is 0.001-100 mmol / L relative to 1 L of the organic solvent, preferably 0.5-20 mmol / L.

[0076] In a preferred embodiment of the present invention, the content of the antioxidant stabilizer is 5-200 mmol relative to 1L of the organic solvent.

[0077] In a preferred embodiment of the present invention, the organic solvent is selected from at least one of alcohols, phenols, ethers and aromatic compounds, and preferably from at least one of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, cyclopentanol, cyclohexanol, benzyl alcohol, phenol, benzene, toluene, diethyl ether and tetrahydrofuran.

[0078] In a preferred embodiment of the present invention, the reaction conditions include: a reaction temperature of 0-250℃, preferably 50-150℃; a reaction time of 0.01-100h, preferably 5-10h; and a reaction pressure of 0.1-20MPa, preferably 0.1-5MPa.

[0079] In this invention, the reaction is carried out in an inert atmosphere, which is selected from at least one of nitrogen, helium, argon, neon, krypton, and xenon atmospheres, preferably a nitrogen atmosphere.

[0080] The following detailed description of preferred embodiments of the present invention illustrates the principles of the invention and is not intended to limit the scope of the invention.

[0081] Preparation Example 1

[0082] Catalyst preparation:

[0083] 1 mmol of the asymmetric bisphosphine ligand PPh2C6H4N(H)PPh2 (structure shown in formula (II)) and 1 mmol of the rhodium dicarbonyl acetylacetone compound Rh(CO)2C5H7O2 (structure shown in formula (III)) were weighed into Schlenk flasks, 100 mL of toluene solvent was added, and the mixture was stirred at room temperature for 12 hours. After the reaction was complete, the solvent was removed under reduced pressure, and the catalyst [PPh2C6H4N(H)PPh2]Rh(CO)2, with the structure shown in formula (I), was obtained by nuclear magnetic resonance spectroscopy. The NMR spectrum is shown in […]. Figure 1 .

[0084] Preparation Example 2

[0085] The preparation was carried out according to the method of Preparation Example 1, except that PPh2C6H4N(H)PPh2 was replaced with an equal amount of (PPh2C6H4N(iPr)PPh2.

[0086] The catalyst [PPh2C6H4N(iPr)PPh2]Rh(CO)2, with the structure shown in formula (I), was obtained by nuclear magnetic resonance spectroscopy. The NMR spectrum is shown below. Figure 2 .

[0087] Preparation Example 3

[0088] The preparation was carried out according to the method of Preparation Example 1, except that PPh2C6H4N(H)PPh2 was replaced with an equal amount of PPh2C6H4N(tBu)PPh2.

[0089] The catalyst [PPh2C6H4N(tBu)PPh2]Rh(CO)2, with the structure shown in formula (I), was obtained by nuclear magnetic resonance spectroscopy. The NMR spectrum is shown below. Figure 3 .

[0090] Preparation Example 4

[0091] The preparation was carried out according to the method of Preparation Example 1, except that PPh2C6H4N(H)PPh2 was replaced with an equal amount of PPh2C6H4N(Ph)PPh2.

[0092] The catalyst [PPh2C6H4N(Ph)PPh2]Rh(CO)2, with the structure shown in formula (I), was obtained by nuclear magnetic resonance spectroscopy. The NMR spectrum is shown below. Figure 4 .

[0093] Preparation Example 5

[0094] The preparation was carried out according to the method of Preparation Example 1, except that the dicarbonyl acetylacetone rhodium compound Rh(CO)2C5H7O2 was replaced with an equal amount of diethylacetylacetone rhodium compound Rh(C2H5)2C5H7O2.

[0095] The catalyst [PPh2C6H4N(H)PPh2]Rh(C2H5)2, with the structure shown in formula (I), was obtained by nuclear magnetic resonance spectroscopy.

[0096] Example 1

[0097] (1) In a 1L high-pressure reaction distillation vessel, under a N2 atmosphere, 3 mmol of the catalyst prepared in Preparation Example 1 (calculated as Rh, the same below), 3 mol of diisobutylene, and 100 mL of toluene were added in sequence. The injection valve was closed, and the synthesis gas was turned on. The flow rate of the synthesis gas was 900 mL / min (the volume ratio of CO to H2 was 1:1), and the reaction system was obtained.

[0098] (2) The reaction system was then reacted for 8 hours at a temperature of 90℃, a pressure of 1MPa and a stirring speed of 800rpm. The reaction distillation vessel was then rapidly cooled to 0℃ and slowly depressurized to atmospheric pressure to obtain a reaction solution containing isononal.

[0099] Samples were taken from the reaction solution for gas chromatography analysis, and the results are shown in Table 1.

[0100] Example 2

[0101] Isononanal was prepared according to the method of Example 1, except that in step (1), 3 mmol of the catalyst prepared in Example 1, 3 mol of diisobutylene, 50 mmol of the antioxidant triphenyl phosphite and 100 mL of toluene were added sequentially in a 1 L high-pressure reaction distillation vessel under a N2 atmosphere.

[0102] A reaction solution containing isononal was obtained.

[0103] Samples were taken from the reaction solution for gas chromatography analysis, and the results are shown in Table 1.

[0104] Example 3

[0105] Isonononal was prepared according to the method of Example 2, except that in step (1), the antioxidant triphenyl phosphite was replaced with an equal amount of antioxidant 168.

[0106] A reaction solution containing isononal was obtained.

[0107] Samples were taken from the reaction solution for gas chromatography analysis, and the results are shown in Table 1.

[0108] Example 4

[0109] Isonononal was prepared according to the method of Example 2, except that in step (1), the antioxidant triphenyl phosphite was replaced with an equal amount of antioxidant 618.

[0110] A reaction solution containing isononal was obtained.

[0111] Samples were taken from the reaction solution for gas chromatography analysis, and the results are shown in Table 1.

[0112] Example 5

[0113] Isonononal was prepared according to the method of Example 2, except that in step (1), the antioxidant triphenyl phosphite was replaced with an equal amount of antioxidant 1010.

[0114] A reaction solution containing isononal was obtained.

[0115] Samples were taken from the reaction solution for gas chromatography analysis, and the results are shown in Table 1.

[0116] Example 6

[0117] Isonononaldehyde was prepared according to the method of Example 1, except that in step (1), the catalyst prepared in Preparation Example 1 was replaced with an equal amount of the catalyst prepared in Preparation Example 2.

[0118] A reaction solution containing isononal was obtained.

[0119] Samples were taken from the reaction solution for gas chromatography analysis, and the results are shown in Table 1.

[0120] Example 7

[0121] Isonononal was prepared according to the method of Example 2, except that in step (1), the catalyst prepared in Preparation Example 1 was replaced with an equal amount of the catalyst prepared in Preparation Example 2.

[0122] A reaction solution containing isononal was obtained.

[0123] Samples were taken from the reaction solution for gas chromatography analysis, and the results are shown in Table 1.

[0124] Example 8

[0125] (1) In a 1L high-pressure reaction distillation vessel, under N2 atmosphere, 3 mmol of the catalyst prepared in Preparation Example 2, 3 mol of diisobutylene, antioxidant 168 and 100 mL of toluene were added in sequence. The injection valve was closed and the synthesis gas was turned on. The flow rate of the synthesis gas was 900 mL / min (the volume ratio of CO to H2 was 1:1) to obtain the reaction system.

[0126] (2) The reaction system was then reacted for 8 hours at a temperature of 90℃, a pressure of 1MPa and a stirring speed of 800rpm. The reaction distillation vessel was then rapidly cooled to 0℃ and slowly depressurized to atmospheric pressure to obtain the first reaction solution containing isononanal. A sample was taken from the first reaction solution for gas chromatography analysis. The analysis results are shown in Table 1.

[0127] (3) Then, isononanaldehyde was separated by vacuum distillation in the reaction vessel, and the reaction system solution was retained at the bottom of the reaction vessel. 3 mol of diisobutylene was added and syngas was turned on. The flow rate of syngas was 900 mL / min (the volume ratio of CO to H2 was 1:1). The reaction was carried out for 8 h at a temperature of 90℃, a pressure of 1 MPa and a stirring speed of 800 rpm. Then, the reaction vessel was rapidly cooled to 0℃ and slowly depressurized to atmospheric pressure to obtain a second reaction solution containing isononanaldehyde. The second cycle was completed. A sample was taken from the second reaction solution for gas chromatography analysis. The analysis results are shown in Table 1.

[0128] (4) Repeat step (3) 3 times to obtain the third reaction solution, the fourth reaction solution and the fifth reaction solution in sequence. Complete the third cycle, the fourth cycle and the fifth cycle in sequence. Take samples from the third reaction solution, the fourth reaction solution and the fifth reaction solution for gas chromatography analysis. The analysis results are shown in Table 1.

[0129] Example 9

[0130] Isonononal was prepared according to the method of Example 4, except that in step (1), the catalyst prepared in Preparation Example 1 was replaced with an equal amount of the catalyst prepared in Preparation Example 2.

[0131] A reaction solution containing isononal was obtained.

[0132] Samples were taken from the reaction solution for gas chromatography analysis, and the results are shown in Table 1.

[0133] Example 10

[0134] Isonononal was prepared according to the method of Example 5, except that in step (1), the catalyst prepared in Preparation Example 1 was replaced with an equal amount of the catalyst prepared in Preparation Example 2.

[0135] A reaction solution containing isononal was obtained.

[0136] Samples were taken from the reaction solution for gas chromatography analysis, and the results are shown in Table 1.

[0137] Example 11

[0138] Isonononal was prepared according to the method of Example 1, except that in step (1), the catalyst prepared in Preparation Example 1 was replaced with an equal amount of the catalyst prepared in Preparation Example 3.

[0139] A reaction solution containing isononal was obtained.

[0140] Samples were taken from the reaction solution for gas chromatography analysis, and the results are shown in Table 1.

[0141] Example 12

[0142] Isonononal was prepared according to the method of Example 1, except that in step (1), the catalyst prepared in Preparation Example 1 was replaced with an equal amount of the catalyst prepared in Preparation Example 4.

[0143] A reaction solution containing isononal was obtained.

[0144] Samples were taken from the reaction solution for gas chromatography analysis, and the results are shown in Table 1.

[0145] Example 13

[0146] Isonononal was prepared according to the method of Example 1, except that in step (1), the catalyst prepared in Preparation Example 1 was replaced with an equal amount of the catalyst prepared in Preparation Example 5.

[0147] A reaction solution containing isononal was obtained.

[0148] Samples were taken from the reaction solution for gas chromatography analysis, and the results are shown in Table 1.

[0149] Example 14

[0150] Isonononal was prepared according to the method of Example 8, except that in step (1), antioxidant 168 was replaced with an equal amount of antioxidant 1076.

[0151] A reaction solution containing isononal was obtained.

[0152] Samples were taken from the reaction solution for gas chromatography analysis, and the results are shown in Table 1.

[0153] Comparative Example 1

[0154] Isonononaldehyde was prepared according to the method of Example 6, except that in step (1), the catalyst prepared in Preparation Example 2 was replaced with an equal amount of [P(tBu)2C6H4N(iPr)P(tBu)2]Rh(CO)2 catalyst.

[0155] A reaction solution containing isononal was obtained.

[0156] Samples were taken from the reaction solution for gas chromatography analysis, and the results are shown in Table 1.

[0157] Comparative Example 2

[0158] Isonononaldehyde was prepared according to the method of Example 6, except that in step (1), the catalyst prepared in Preparation Example 2 was replaced with an equal amount of [PPh2C6H4PPh2]Rh(CO)2 catalyst.

[0159] A reaction solution containing isononal was obtained.

[0160] Samples were taken from the reaction solution for gas chromatography analysis, and the results are shown in Table 1.

[0161] Table 1

[0162]

[0163]

[0164]

[0165] As shown in Table 1, the catalyst prepared by the method of the present invention has a high conversion rate of diisobutylene hydroformylation and a high selectivity for the product isononal. Furthermore, the catalyst system obtained by combining the catalyst prepared by the present invention with an antioxidant stabilizer has good stability and still has a high conversion rate of diisobutylene hydroformylation and a high selectivity for isononal after multiple cycles of use.

[0166] As can be seen from Examples 8 and 14, compared with Comparative Example 2, which uses the catalyst of Preparation Example 2 and antioxidant 1076 to prepare the catalyst system, the catalyst system of Example 8 uses the catalyst of Preparation Example 2 and antioxidant 618 to prepare isorandal, and the conversion rate of diisobutylene hydroformylation can still reach more than 98.7%, and the selectivity of isorandal can still reach more than 98.3%.

[0167] As can be seen from Example 6 and Comparative Example 1, compared with Comparative Example 1 which uses the [P(tBu)2C6H4N(iPr)P(tBu)2]Rh(CO)2 catalyst, Example 6 uses the catalyst of Preparation Example 2 to prepare isononal with higher conversion rate of butene hydroformylation and selectivity of product isononal.

[0168] As can be seen from Example 6 and Comparative Example 2, compared with Comparative Example 2 which uses the [PPh2C6H4PPh2]Rh(CO)2 catalyst, Example 6 uses the catalyst of Preparation Example 2 to prepare isononal with higher conversion rate of butene hydroformylation and higher selectivity of product isononal.

[0169] It should be noted that the embodiments described above are only for explaining the present invention and do not constitute any limitation on the present invention. The present invention has been described with reference to typical embodiments, but it should be understood that the words used therein are descriptive and explanatory terms, not limiting terms. Modifications can be made to the present invention within the scope of the claims, and revisions can be made to the present invention without departing from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and embodiments, it does not mean that the present invention is limited to the specific examples disclosed herein; on the contrary, the present invention can be extended to all other methods and applications with the same function.

Claims

1. A catalyst with asymmetric bidentate phosphine ligand coordination, characterized in that, The catalyst comprises compounds as shown in formula (I), Among them, R1-R4 are each independently selected from C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl groups, C4-C 12 heteroalkyl, C3-C 12 cycloalkyl, C4-C 20 Heterocyclic alkyl groups and C6-C 20 The aryl group; for R1-R4, the C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl groups, C4-C 12 heteroalkyl, C3-C 12 cycloalkyl, C4-C 20 Heterocyclic alkyl groups and C6-C 20 The hydrogen atom on the aryl group can be optionally substituted with a substituent; R5 is selected from hydrogen, C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl groups, C3-C 12 cycloalkyl and C6-C 20 The aryl group; for R5, the C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl groups, C3-C 12 cycloalkyl and C6-C 20 The hydrogen atom on the aryl group can be optionally substituted with a substituent; X is selected from hydrogen, carbonyl, halogen, pseudohalogen, C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl groups, C1-C 12 alkoxy groups, C1-C 12 alkyl thiol group, C6-C 20 aryl, C7-C 20 alkylaryl, C1-C 12 Alkylamine, hydroxyl, and phenolic groups; for X, the C1-C 12 Straight-chain alkyl, C3-C 12 Branched alkyl groups, C1-C 12 alkoxy groups, C1-C 12 alkyl thiol group, C6-C 20 aryl, C7-C 20 alkylaryl, C1-C 12 The hydrogen atoms on the alkylamine, hydroxyl, and phenolic groups may optionally be substituted with substituents; 1 ≤ n ≤ 4, where n is an integer; The substituents are selected from alkyl, alkoxy, alkylsilyl and alkylamine groups.

2. The catalyst according to claim 1, characterized in that, The substituents are selected from C1-C6 straight-chain alkyl, C3-C6 branched alkyl, C1-C6 alkyloxy, C3-C6 alkylsilyl, and C1-C6 alkylamino. And / or, R1-R4 are each independently selected from C1-C 10 Straight-chain alkyl, C3-C 10 Branched alkyl groups, C3-C 10 heteroalkyl, C3-C 10 cycloalkyl, C3-C 10 Heterocyclic alkyl groups and C6-C 18 The aryl group; preferably, R1-R4 are each independently selected from 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-ditert-butylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triisopropylphenyl, 2,4,6-tritert-butylphenyl, 2-methoxyphenyl, 3-methoxyphenyl and 4-methoxyphenyl; And / or, R5 is selected from hydrogen, C1-C 10 Straight-chain alkyl, C3-C 10 Branched alkyl groups, C3-C 10 cycloalkyl and C6-C 18 The aryl group; preferably, R5 is selected from hydrogen, 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-ditert-butylphenyl, 2,4,6-trimethylphenyl, 2,4,6-triisopropylphenyl and 2,4,6-tritert-butylphenyl; And / or, X is selected from hydrogen, CO, chlorine, bromine, methyl, ethyl, butyl, trimethylsilylmethyl, phenyl, benzyl, methoxy, ethoxy, phenol, formic acid, acetate, dimethylamino, diethylamino, diisopropylamino, di-tert-butylamino, di(trimethylsilyl)amino, acetylacetone, and hydroxyl.

3. The catalyst according to claim 1 or 2, characterized in that, The compound with the structure shown in formula (I) is selected from at least one of [PPh2C6H4N(H)PPh2]Rh(CO)2, [PPh2C6H4N(iPr)PPh2]Rh(CO)2, [PPh2C6H4N(tBu)PPh2]Rh(CO)2, [PPh2C6H4N(Ph)PPh2]Rh(CO)2 and [PPh2C6H4N(H)PPh2]Rh(C2H5)2.

4. A catalyst system with asymmetric bidentate phosphine ligand coordination, characterized in that, The catalyst system comprises the catalyst and antioxidant stabilizer as described in any one of claims 1-3.

5. The catalyst system according to claim 4, characterized in that, The antioxidant stabilizer is selected from at least one of triphenyl phosphite, antioxidant 168, antioxidant 618, and antioxidant 1010; And / or, the amount of the catalyst, calculated in Rh, is such that the molar ratio of the catalyst to the antioxidant stabilizer is 0.001-100:5-200, preferably 0.5-20:5-200.

6. The use of the catalyst according to any one of claims 1-3 or the catalyst system according to claim 4 or 5 in the preparation of isononanal.

7. A method for preparing isononanal, characterized in that, The method comprises reacting diisobutylene, CO, and H2 in an organic solvent with any one of the catalysts of claims 1-3 or the catalyst system of claim 4 or 5.

8. The method according to claim 7, characterized in that, The molar ratio of the catalyst to diisobutylene is 1:500-1500, preferably 1:800-1200, and the amount of the catalyst is calculated as Rh. And / or, relative to 1 mmol of the catalyst, the total flow rate of CO and H2 is 300-800 mL / min, and the amount of the catalyst is expressed as Rh; And / or, the volume ratio of CO to H2 is 1-1.2:1; And / or, the amount of the catalyst, expressed as Rh, is 0.001-100 mmol, preferably 0.5-20 mmol, relative to 1 L of the organic solvent; And / or, relative to 1L of the organic solvent, the content of the antioxidant stabilizer is 5-200 mmol.

9. The method according to claim 7 or 8, characterized in that, The organic solvent is selected from alcohols, phenols, ethers and aromatic compounds, preferably from at least one of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, cyclopentanol, cyclohexanol, benzyl alcohol, phenol, benzene, toluene, diethyl ether and tetrahydrofuran.

10. The method according to any one of claims 7-9, characterized in that, The reaction conditions include: a reaction temperature of 0-250℃, preferably 50-150℃; a reaction time of 0.01-100h, preferably 5-10h; and a reaction pressure of 0.1-20MPa, preferably 0.1-5MPa.

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