Nitrogen oxide ligand coordinated catalysts and methods for their preparation, catalyst systems and uses thereof, and processes for the continuous production of isononylaldehyde

Abstract

This invention provides a nitrogen-oxygen ligand-coordinated catalyst, its preparation method, catalyst system, application, and method for preparing isonononal. The catalyst is characterized by having the structure shown in formula (I). The nitrogen-oxygen ligand-coordinated catalyst of this invention can catalyze the reaction of diisobutylene, carbon monoxide, and hydrogen to generate isonononal, exhibiting high diisobutylene conversion and isonononal selectivity, and good stability, maintaining high diisobutylene conversion and isonononal selectivity even after multiple cycles.

Description

Technical Field

[0001] This invention relates to the field of catalytic preparation of isonononal, and particularly to a catalyst with nitrogen-oxygen ligand coordination, its preparation method, catalyst system and its application, and a method for continuous preparation of 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-supported Co, and 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% (CN110605145).

[0005] Internationally, Mitsubishi Chemical in Japan developed a rhodium-catalyzed hydroformylation reaction of isooctene. Using triphenylphosphine oxide and an initially active rhodium complex (Co-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 a Co 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). A. The reaction system using rhodium nonanoate as a catalyst precursor and a mixture of phosphites as ligands was tested under the conditions of 2 MPa pressure, 140 °C reaction temperature, 8 h reaction time and 200 ppm Co 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, Rh-based metals are commonly used in olefin hydroformylation catalysis systems, but Rh metals are expensive. Common ligands are mainly phosphine, hypophosphite, and phosphite, but traditional phosphorus compounds exhibit poor activity and selectivity in hydroformylation reactions due to electronic and steric effects. US20120253080 also found that using a mixture of monophosphite and diphosphite ligands resulted in 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). Most are also batch reactions, making it difficult to assess catalyst stability.

[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 at least one technical problem existing in the prior art, the present invention provides a nitrogen-oxygen ligand coordinated catalyst, its preparation method, catalyst system and its application, and a method for continuous preparation of isonononal. The nitrogen-oxygen ligand coordinated catalyst of the present invention can catalyze the reaction of diisobutylene, carbon monoxide and hydrogen to generate isonononal, and has high diisobutylene conversion rate and isonononal selectivity. Moreover, it has good stability and still has high diisobutylene conversion rate and isonononal selectivity after multiple cycles of use.

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

[0010] In a first aspect, the present invention provides a catalyst with nitrogen-oxygen ligand coordination, the catalyst having the structure shown in formula (I).

[0011] Secondly, the present invention provides a method for preparing the catalyst described in the first aspect, the method comprising: contacting a nitrogen-oxygen ligand with an Rh source compound in a solvent under an inert atmosphere to carry out an in-situ reaction. The nitrogen-oxygen ligand is 3-hydroxypyridine.

[0012] Preferably, the molar ratio of the nitrogen-oxygen ligand to the Rh source compound is 2-6:1, more preferably 4-6:1; wherein the amount of substance of the Rh source compound is calculated in terms of Rh atoms.

[0013] Preferably, the ratio of solvent to nitrogen-oxygen ligand is (1-10) mL: 1 mmol; more preferably, it is (3-8) mL: 1 mmol.

[0014] Preferably, the conditions for the in-situ reaction include: a reaction temperature of 20-25°C; a reaction time of 10-12 hours; and a stirring speed of 100-800 rpm, preferably 300-500 rpm.

[0015] Preferably, the Rh source compound is selected from at least one of dodecyltetrarhodium, 1,5-cyclooctadiene (acetylacetone) rhodium, and dicarbonylacetylacetone rhodium.

[0016] Preferably, the solvent is selected from at least one of toluene, hexane, benzene, toluene, and diethyl ether.

[0017] Preferably, the inert atmosphere is selected from at least one of nitrogen atmosphere, helium atmosphere, neon atmosphere, argon atmosphere, krypton atmosphere and xenon atmosphere.

[0018] Preferably, after the in-situ reaction is completed, the obtained reaction solution is subjected to reduced pressure to remove the solvent, and the pressure of the reduced pressure is 2-20 kPa.

[0019] Thirdly, the present invention provides a catalyst system comprising the catalyst described in the first aspect or the catalyst prepared by the preparation method described in the second aspect, an antioxidant stabilizer, and a metal additive.

[0020] Preferably, the molar ratio of the catalyst, antioxidant stabilizer and metal additive is 1:5-15:0.1-1, more preferably 1:8-12:0.3-0.7, and the amount of the catalyst is calculated as Rh.

[0021] Preferably, the antioxidant stabilizer is selected from at least one of triphenyl phosphite, antioxidant 168, antioxidant 618 and antioxidant 1010.

[0022] Preferably, the metal additive is a rhodium compound. More preferably, the metal additive is selected from at least one of tetrarhodium dodecylcarbonyl, rhodium 1,5-cyclooctadiene (acetylacetone), and rhodium dicarbonylacetylacetone.

[0023] Fourthly, the present invention provides the application of the catalyst described in the first aspect, the catalyst prepared by the preparation method described in the second aspect, or the catalyst system described in the third aspect in the preparation of isorandal.

[0024] Fifthly, the present invention provides a method for the continuous preparation of isononanal, the method comprising:

[0025] Step (1): Under an inert atmosphere and in an organic solvent, a mixture of diisobutylene and syngas is brought into contact with the catalyst described in the first aspect, the catalyst prepared by the preparation method described in the second aspect, or the catalyst system described in the third aspect to carry out a hydroformylation reaction.

[0026] Step (2): Isonononal is separated from the reaction solution obtained from the hydroformylation reaction, and then diisobutylene and syngas are added to the reaction solution from which isonononal is separated to carry out the hydroformylation reaction.

[0027] Preferably, the ratio of the catalyst, diisobutylene and the organic solvent is 1 mmol:(500-1500) mmol:(10-50) mL; more preferably, it is 1 mmol:(800-1200) mmol:(20-40) mL.

[0028] Preferably, the flow rate of the synthesis gas is 300-800 mL / min relative to 1 mmol of the catalyst.

[0029] Preferably, the synthesis gas comprises CO and H2, wherein the volume ratio of CO to H2 is 1-1.2:1.

[0030] Preferably, the organic solvent is selected from at least one of alcohols, phenols, ethers, and aromatic compounds.

[0031] Preferably, the inert atmosphere is selected from at least one of nitrogen atmosphere, helium atmosphere, neon atmosphere, argon atmosphere, krypton atmosphere and xenon atmosphere.

[0032] Preferably, the alcohol is selected from C10. 1- C 12 Alcohol, more preferably selected from at least one of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, cyclopentanol, cyclohexanol and benzyl alcohol.

[0033] Preferably, the phenol is selected from at least one of phenol, hydroquinone, methylphenol and 2-ethylphenol.

[0034] Preferably, the ether is selected from at least one of diethyl ether, tetrahydrofuran, and butyl ether.

[0035] Preferably, the aromatic compound is selected from at least one of benzene, toluene, xylene, and ethylbenzene.

[0036] Preferably, the hydroformylation reaction conditions include: a reaction temperature of 0-250℃, preferably 50-150℃; a reaction pressure of 0.1-20MPa, preferably 0.1-8MPa; and a reaction time of 0.01-100h, preferably 5-10h.

[0037] Preferably, the hydroformylation reaction is carried out under stirring at a stirring rate of 500-800 rpm.

[0038] This invention relates to a catalyst with nitrogen-oxygen ligand coordination, a catalyst system, its application, and a method for the continuous preparation of isonononal, which has the following advantages compared with the prior art:

[0039] The nitrogen-oxygen ligand coordinated catalyst of the present invention is used to catalyze the reaction of diisobutylene, carbon monoxide and hydrogen to generate isonononal, and has high diisobutylene conversion rate and isonononal selectivity. Moreover, it has good stability and still has high diisobutylene conversion rate and isonononal selectivity after multiple cycles. Attached Figure Description

[0040] Figure 1 The single-crystal X-ray diffraction structure of the catalyst prepared in Example 1 of this invention;

[0041] Figure 2 A cross-sectional view of the single-crystal X-ray diffraction structure of the catalyst prepared in Example 1 of this invention;

[0042] Figure 3 The side view of the single-crystal X-ray diffraction structure of the catalyst prepared in Example 1 of this invention. Detailed Implementation

[0043] The inventors of this invention have discovered that a rhodium metal catalyst coordinated with oxynitride ligands can effectively improve the conversion rate of diisobutylene and the selectivity of isononanal by catalyzing the hydroformylation of diisobutylene. Analysis suggests that the Rh metal center of the rhodium metal catalyst coordinated with oxynitride ligands of this invention has a promoting effect on the selective carbonylation of long-chain olefins (such as diisobutylene), accelerating the hydroformylation reaction rate of long-chain olefins and improving the product selectivity. Furthermore, due to its own steric skeletal structure, the catalyst structure is more stable.

[0044] Based on the above research, in a first aspect, the present invention provides a catalyst with nitrogen-oxygen ligand coordination, such as... Figure 1-3 As shown, the catalyst has the structure shown in formula (I). In equation (I), "*" indicates that O can be connected to H or Rh.

[0045] In this invention, in the structure of formula (I), one Rh metal center is coordinated with the N of four 3-hydroxypyridines and connected with the O of two 3-hydroxypyridines; in the structure of formula (I) In formula (I), O is connected to H or another Rh metal center, preferably to an Rh metal center. N in the structure is coordinated with another Rh metal center; in the structure of formula (I) The O-connected Rh metal center and The N-coordinated Rh metal centers can be the same Rh or different Rh, preferably connected to different Rh metal centers; as the number of Rh atoms increases, the catalyst is arranged into a three-dimensional structure in a regular manner as shown in formula (I); the three-dimensional structure of the catalyst can be analyzed and characterized by methods commonly used in the art, such as using a single-crystal X-ray diffractometer.

[0046] In a second aspect, the present invention provides a method for preparing the catalyst described in the first aspect, the method comprising: in an inert atmosphere, in a solvent, contacting a nitrogen-oxygen ligand with an Rh source compound to carry out an in-situ reaction; wherein the nitrogen-oxygen ligand is 3-hydroxypyridine.

[0047] In a preferred embodiment of the present invention, the molar ratio of the nitrogen-oxygen ligand to the Rh source compound is 2-6:1, preferably 4-6:1; wherein the amount of substance of the Rh source compound is calculated in terms of Rh atoms.

[0048] In a preferred embodiment of the present invention, the ratio of solvent to nitrogen-oxygen ligand is (1-10) mL: 1 mmol; preferably (3-8) mL: 1 mmol.

[0049] In a preferred embodiment of the present invention, the conditions for the in-situ reaction include: a reaction temperature of 20-25°C; a reaction time of 10-12 h; and a stirring speed of 100-800 rpm, preferably 300-500 rpm.

[0050] In a preferred embodiment of the present invention, the Rh source compound is selected from tetrarhodium dodecylcarbonyl (Rh4(CO)). 12At least one of 1,5-cyclooctadiene (acetylacetone) rhodium (Rh(acac)(COD)) and dicarbonyl acetylacetone rhodium (Rh(acac)(CO)2), preferably Rh4(CO) 12 .

[0051] In a preferred embodiment of the present invention, the solvent is selected from at least one of toluene, hexane, benzene, and diethyl ether; preferably toluene and / or hexane;

[0052] In a preferred embodiment of the present invention, the inert atmosphere is selected from at least one of nitrogen atmosphere, helium atmosphere, neon atmosphere, argon atmosphere, krypton atmosphere and xenon atmosphere; preferably, it is a nitrogen atmosphere.

[0053] In a preferred embodiment of the present invention, after the in-situ reaction is completed, the obtained reaction solution is subjected to reduced pressure to remove the solvent, and the pressure after reduced pressure is 2-20 kPa.

[0054] Thirdly, the present invention provides a catalyst system comprising the catalyst described in the first aspect or the catalyst prepared by the preparation method described in the second aspect, an antioxidant stabilizer, and a metal additive.

[0055] In a preferred embodiment of the present invention, the molar ratio of the catalyst, antioxidant stabilizer and metal additive is 1:5-15:0.1-1, preferably 1:8-12:0.3-0.7, and the amount of the catalyst is calculated in terms of Rh atoms.

[0056] 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 triphenyl phosphite and / or antioxidant 168.

[0057] In a preferred embodiment of the present invention, the metal auxiliary is selected from rhodium compounds; preferably, the metal auxiliary 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); preferably Rh(acac)(CO)2.

[0058] Fourthly, the present invention provides the application of the catalyst described in the first aspect, the catalyst prepared by the preparation method described in the second aspect, or the catalyst system described in the third aspect in the preparation of isorandal.

[0059] Fifthly, the present invention provides a method for the continuous preparation of isononanal, the method comprising:

[0060] Step (1): Under an inert atmosphere and in an organic solvent, a mixture of diisobutylene and syngas is brought into contact with the catalyst described in the first aspect, the catalyst prepared by the preparation method described in the second aspect, or the catalyst system described in the third aspect to carry out a hydroformylation reaction.

[0061] Step (2): Isonononal is separated from the reaction solution obtained from the hydroformylation reaction, and then diisobutylene and syngas are added to the reaction solution from which isonononal is separated to carry out the hydroformylation reaction.

[0062] In a preferred embodiment of the present invention, the ratio of the catalyst, diisobutylene and the organic solvent is 1 mmol:(500-1500) mmol:(10-50) mL; preferably 1 mmol:(800-1200) mmol:(20-40) mL.

[0063] In a preferred embodiment of the present invention, the flow rate of the synthesis gas is 300-800 mL / min relative to 1 mmol of the catalyst.

[0064] In a preferred embodiment of the present invention, the synthesis gas comprises CO and H2, wherein the volume ratio of CO to H2 is 1-1.2:1.

[0065] In a preferred embodiment of the present invention, the organic solvent is selected from at least one of alcohols, phenols, ethers and aromatic compounds.

[0066] In a preferred embodiment of the present invention, the inert atmosphere is selected from at least one of nitrogen atmosphere, helium atmosphere, neon atmosphere, argon atmosphere, krypton atmosphere and xenon atmosphere; preferably, it is a nitrogen atmosphere.

[0067] In a preferred embodiment of the present invention, the alcohol is selected from C 1- C 12 The alcohol is preferably selected from at least one of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, cyclopentanol, cyclohexanol, and benzyl alcohol.

[0068] In a preferred embodiment of the present invention, the phenol is selected from at least one of phenol, hydroquinone, methylphenol and 2-ethylphenol; preferably phenol.

[0069] In a preferred embodiment of the present invention, the ether is selected from at least one of diethyl ether, tetrahydrofuran, and butyl ether; preferably selected from diethyl ether and / or tetrahydrofuran.

[0070] In a preferred embodiment of the present invention, the aromatic compound is selected from at least one of benzene, toluene, xylene, and ethylbenzene; preferably benzene and / or toluene.

[0071] The hydroformylation reaction conditions selected from benzene and / or toluene include: a reaction temperature of 0-250°C, preferably 50-150°C; a reaction pressure of 0.1-20 MPa, preferably 0.1-8 MPa; and a reaction time of 0.01-100 h, preferably 5-10 h.

[0072] The hydroformylation reaction, selected from benzene and / or toluene, is carried out under stirring at a stirring rate of 500-800 rpm.

[0073] 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.

[0074] GC-MS (Gas Chromatography-Mass Spectrometry): Purchased from PerkinElmer, model Clarus 680;

[0075] 3-Hydroxypyridine, pyridine and pyrrole: purchased from Beijing Bailingwei Technology Co., Ltd.;

[0076] Rh4(CO) 12 Rh(acac)(COD) and Rh(acac)(CO)2: purchased from Beijing Bailingwei Technology Co., Ltd.

[0077] Preparation Example 1

[0078] Weigh out 16 mol of the nitrogen-oxygen ligand 3-hydroxypyridine and 1 mol of the carbonyl rhodium compound Rh4(CO). 12 The mixture was placed in a Schlenk flask, and toluene solvent (toluene to nitrile ligand ratio of 5 mL: 1 mmol) was added. The mixture was stirred at 400 rpm for 12 hours at room temperature. After the reaction was complete, the solvent was removed by reducing the pressure to 2 MPa to obtain the product containing... Catalyst M1 with a specific structure; its single-crystal structure was analyzed using a single-crystal X-ray diffractometer (Supernova model) as follows: Figure 1-3 As shown.

[0079] Preparation Example 2

[0080] The catalyst was prepared according to the method of Preparation Example 1, except that 3-hydroxypyridine was replaced with an equal amount of pyrrole.

[0081] The catalyst (C5H5N)6Rh was obtained.

[0082] Preparation Example 3

[0083] The catalyst was prepared according to the method of Preparation Example 1, except that 3-hydroxypyridine was replaced with an equal amount of pyridine.

[0084] The catalyst (C4H4N)6Rh was obtained.

[0085] Example 1

[0086] (1) In a 1L high-pressure reaction distillation vessel, under a N2 atmosphere, 3 mmol of catalyst M1 prepared in Preparation Example 1, 3 mol of diisobutylene, 1.5 mmol of metal auxiliary agent Rh(acac)(CO)2, 30 mmol of antioxidant triphenyl phosphite, and 100 mL of toluene were added in sequence. The injection valve was closed, and syngas (flow rate of 500 mL / min, syngas being CO and H2 in a volume ratio of 1:1) was introduced into the syngas cylinder to obtain the reaction system.

[0087] The reaction system was subjected to a temperature of 90℃, a pressure of 1MPa, and a stirring speed of 800rpm for 8 hours to obtain the first reaction solution containing isononanal, thus completing the first cycle.

[0088] Step (2): Close the syngas cylinder valve, rapidly cool the reaction distillation vessel to 0°C, slowly depressurize to atmospheric pressure, and separate isononanal from the obtained reaction solution; then, in a N2 atmosphere, add 3 mol of diisobutylene to the reaction solution from which isononanal has been separated and turn on the syngas cylinder to input syngas (flow rate of 500 mL / min) to continue the hydroformylation reaction.

[0089] Step (3): Repeat step (2) to obtain the second reaction solution and the third reaction solution in sequence, and complete the second cycle and the third cycle respectively;

[0090] Samples were taken from the first reaction solution, the second reaction solution, and the third reaction solution for GC-MS analysis. The results are shown in Table 1.

[0091] Example 2

[0092] Isocarnitine was prepared according to the method of Example 1, except that in step (1), the antioxidant triphenyl phosphite was replaced with an equal amount of antioxidant 168.

[0093] Samples were taken from the first, second, third, fourth, and fifth reaction solutions for GC-MS analysis. The results are shown in Table 1.

[0094] Example 3

[0095] Isocarnitine was prepared according to the method of Example 1, except that in step (1), the antioxidant triphenyl phosphite was replaced with an equal amount of antioxidant 618.

[0096] Samples were taken from the first reaction solution and the second reaction solution for GC-MS analysis. The results are shown in Table 1.

[0097] Example 4

[0098] Isocarnitine was prepared according to the method of Example 1, except that in step (1), the antioxidant triphenyl phosphite was replaced with an equal amount of antioxidant 1010.

[0099] Samples were taken from the first reaction solution and the second reaction solution for GC-MS analysis. The results are shown in Table 1.

[0100] Example 5

[0101] Isocarnet was prepared according to the method of Example 1, except that in step (1), the metal auxiliary agent Rh(acac)(CO)2 was replaced with an equal amount of metal auxiliary agent Rh(acac)(COD).

[0102] Samples were taken from the first reaction solution, the second reaction solution, and the third reaction solution for GC-MS analysis. The results are shown in Table 1.

[0103] Example 6

[0104] Isocarnet was prepared according to the method of Example 2, except that in step (1), the metal auxiliary agent Rh(acac)(CO)2 was replaced with an equal amount of metal auxiliary agent Rh(acac)(COD).

[0105] Samples were taken from the first reaction solution, the second reaction solution, and the third reaction solution for GC-MS analysis. The results are shown in Table 1.

[0106] Example 7

[0107] Isocarnet was prepared according to the method of Example 1, except that in step (1), the metal auxiliary agent Rh(acac)(CO)2 was replaced with an equal amount of the metal auxiliary agent Rh4(CO). 12 .

[0108] Samples were taken from the first reaction solution, the second reaction solution, and the third reaction solution for GC-MS analysis. The results are shown in Table 1.

[0109] Example 8

[0110] Isocarnet was prepared according to the method in Example 2, except that in step (1), the metal auxiliary agent Rh(acac)(CO)2 was replaced with an equal amount of the metal auxiliary agent Rh4(CO). 12 .

[0111] Samples were taken from the first reaction solution, the second reaction solution, and the third reaction solution for GC-MS analysis. The results are shown in Table 1.

[0112] Comparative Example 1

[0113] Isocarnet was prepared according to the method of Example 2, except that no metal additives were added in step (1).

[0114] Samples were taken from the first, second, third, fourth, and fifth reaction solutions for GC-MS analysis. The results are shown in Table 1.

[0115] Comparative Example 2

[0116] Isorenaldehyde was prepared according to the method of Example 2, except that no antioxidant stabilizer was added in step (1).

[0117] Samples were taken from the first, second, third, fourth, and fifth reaction solutions for GC-MS analysis. The results are shown in Table 1.

[0118] Comparative Example 3

[0119] Iso-anal was prepared according to the method of Example 2, except that in step (1), the catalyst M1 prepared in Preparation Example 1 was replaced with the catalyst of Preparation Example 2.

[0120] Samples were taken from the first, second, third, fourth, and fifth reaction solutions for GC-MS analysis. The results are shown in Table 1.

[0121] Comparative Example 4

[0122] Iso-anal was prepared according to the method of Example 2, except that in step (1), the catalyst M1 prepared in Preparation Example 1 was replaced with the catalyst of Preparation Example 3.

[0123] Samples were taken from the first, second, third, fourth, and fifth reaction solutions for GC-MS analysis. The results are shown in Table 1.

[0124] Table 1

[0125]

[0126]

[0127]

[0128] As shown in Table 1, the catalyst prepared by the method of the present invention has a high conversion rate of diisobutene hydroformylation and a high selectivity for isononal. Furthermore, the catalyst system obtained by combining the catalyst prepared by the present invention with antioxidant stabilizers and metal additives has good stability. Even after multiple cycles of use, it still has a high conversion rate of diisobutene hydroformylation (up to 98.8%) and a selectivity for isononal (up to 98.8%).

[0129] As can be seen from Examples 2 and 3, compared with Example 3 which uses a combination of antioxidant 618 and Rh(acac)(CO)2, the catalyst prepared by Example 2 using a combination of antioxidant 168 and metal additive Rh(acac)(CO)2 has a higher diisobutylene hydroformylation conversion rate and isononal selectivity, and has good catalytic stability, still exhibiting high conversion rate and selectivity after multiple cycles.

[0130] As can be seen from Examples 2 and 4, compared with Example 4, which uses a catalyst compounded with antioxidant 1010 and Rh(acac)(CO)2, the catalyst system prepared by Example 2 using a catalyst compounded with antioxidant 168 and metal promoter Rh(acac)(CO)2 has a higher diisobutylene hydroformylation conversion rate and isononal selectivity, and has good catalytic stability, still having a high conversion rate and selectivity after multiple cycles.

[0131] As can be seen from Example 2 and Comparative Example 1, compared with the catalyst system of Comparative Example 1 which only uses the catalyst and antioxidant 168, the catalyst system of Example 2 which uses the catalyst, antioxidant 168 and metal promoter Rh(acac)(CO)2 has a higher diisobutylene hydroformylation conversion rate and isononal selectivity, and has good catalytic stability, still having a high conversion rate and selectivity after multiple cycles.

[0132] As can be seen from Example 2 and Comparative Example 2, compared with the catalyst system of Comparative Example 2 which only uses a catalyst and metal promoter Rh(acac)(CO)2, the catalyst system of Example 2 which uses a catalyst, antioxidant 168 and metal promoter Rh(acac)(CO)2 has a higher diisobutylene hydroformylation conversion rate and isononal selectivity, and has good catalytic stability, still having a high conversion rate and selectivity after multiple cycles.

[0133] Compared to Comparative Example 3, which uses the catalyst from Preparation Example 2 combined with antioxidant 168 and metal promoter Rh(acac)(CO)2, and Comparative Example 4, which uses the catalyst from Preparation Example 3 combined with antioxidant 168 and metal promoter Rh(acac)(CO)2, the catalyst system prepared in Example 2 using the catalyst from Preparation Example 1 combined with antioxidant 168 and metal promoter Rh(acac)(CO)2 exhibits higher diisobutylene hydroformylation conversion and isononal selectivity, and also demonstrates good catalytic stability, maintaining high conversion and selectivity even after multiple cycles.

[0134] 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 nitrogen-oxygen ligand coordination, characterized in that, The catalyst has the structure shown in formula (I).

2. The method for preparing the catalyst according to claim 1, characterized in that, The preparation method includes: in an inert atmosphere and in a solvent, contacting a nitrogen-oxygen ligand with an Rh source compound to carry out an in-situ reaction; wherein the nitrogen-oxygen ligand is 3-hydroxypyridine; Preferably, the molar ratio of the nitrogen-oxygen ligand to the Rh source compound is 2-6:1, more preferably 4-6:1; wherein the amount of the Rh source compound is calculated in terms of Rh atoms; And / or, the ratio of the solvent to the nitrogen-oxygen ligand is (1-10) mL: 1 mmol; preferably (3-8) mL: 1 mmol; And / or, the conditions for the in-situ reaction include: a reaction temperature of 20-25°C; a reaction time of 10-12 h; and a stirring speed of 100-800 rpm, preferably 300-500 rpm.

3. The preparation method according to claim 2, characterized in that, The Rh source compound is selected from at least one of dodecyltetrarhodium, 1,5-cyclooctadiene (acetylacetone) rhodium, and dicarbonylacetylacetone rhodium; And / or, the solvent is selected from at least one of toluene, hexane, benzene, toluene, and diethyl ether; And / or, the inert atmosphere is selected from at least one of nitrogen atmosphere, helium atmosphere, neon atmosphere, argon atmosphere, krypton atmosphere and xenon atmosphere; And / or, after the in-situ reaction is completed, the obtained reaction solution is subjected to reduced pressure to remove the solvent, wherein the pressure of the reduced pressure is 2-20 kPa.

4. A catalyst system, characterized in that, The catalyst system includes the catalyst of claim 1 or the catalyst prepared by the preparation method of claim 2 or 3, an antioxidant stabilizer, and a metal additive.

5. The catalyst system according to claim 4, characterized in that, The molar ratio of the catalyst, antioxidant stabilizer, and metal additive is 1:5-15:0.1-1, preferably 1:8-12:0.3-0.7, and the amount of the catalyst is calculated as Rh. Preferably, the antioxidant stabilizer is selected from at least one of triphenyl phosphite, antioxidant 168, antioxidant 618, and antioxidant 1010; And / or, the metal additive is a rhodium compound; preferably, the metal additive is selected from at least one of tetrarhodium dodecylcarbonyl, rhodium 1,5-cyclooctadiene (acetylacetone) and rhodium dicarbonylacetylacetone.

6. The application of the catalyst of claim 1, the catalyst prepared by the method of claim 2 or 3, or the catalyst system of claim 4 or 5 in the preparation of isorandal.

7. A method for the continuous preparation of isononanal, characterized in that, The method includes: Step (1): Under an inert atmosphere and in an organic solvent, a mixture of diisobutylene and syngas is brought into contact with the catalyst described in claim 1, the catalyst prepared by the method described in claim 2 or 3, or the catalyst system described in claim 4 or 5 to carry out a hydroformylation reaction. Step (2): Isonononal is separated from the reaction solution obtained from the hydroformylation reaction, and then diisobutylene and syngas are added to the reaction solution from which isonononal is separated to carry out the hydroformylation reaction.

8. The method according to claim 7, characterized in that, The ratio of the catalyst, diisobutylene, and the organic solvent is 1 mmol:(500-1500) mmol:(10-50) mL; preferably 1 mmol:(800-1200) mmol:(20-40) mL. And / or, relative to 1 mmol of the catalyst, the flow rate of the synthesis gas is 300-800 mL / min.

9. The method according to claim 7 or 8, characterized in that, The synthesis gas comprises CO and H2, wherein the volume ratio of CO to H2 is 1-1.2:1; Preferably, the organic solvent is selected from at least one of alcohols, phenols, ethers, and aromatic compounds; And / or, the inert atmosphere is selected from at least one of nitrogen atmosphere, helium atmosphere, neon atmosphere, argon atmosphere, krypton atmosphere and xenon atmosphere; Preferably, the alcohol is selected from C10. 1- C 12 The alcohol is more preferably selected from at least one of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, cyclopentanol, cyclohexanol and benzyl alcohol; And / or, the phenol is selected from at least one of phenol, hydroquinone, methylphenol and 2-ethylphenol; And / or, the ether is selected from at least one of diethyl ether, tetrahydrofuran, and butyl ether; And / or, the aromatic compound is selected from at least one of benzene, toluene, xylene and ethylbenzene.

10. The method according to any one of claims 7-9, characterized in that, The hydroformylation reaction conditions include: a reaction temperature of 0-250℃, preferably 50-150℃; a reaction pressure of 0.1-20MPa, preferably 0.1-8MPa; and a reaction time of 0.01-100h, preferably 5-10h. And / or, the hydroformylation reaction is carried out under stirring at a stirring rate of 500-800 rpm.

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