A nitrogen-containing ligand supramolecular polymer catalyst, a preparation method and application thereof

Abstract

The application discloses a nitrogen-containing ligand supramolecular polymer catalyst and a preparation method and application thereof, and relates to the technical field of organic synthesis. The preparation method comprises the following steps: mixing a nitrogen-containing ligand, an inorganic salt and a rhodium precursor under an inert gas atmosphere, adding an organic solvent to obtain a reaction solution; stirring, first standing, ultrasonic dispersion, second standing, then suction filtration, and washing to obtain the nitrogen-containing ligand supramolecular polymer catalyst. The application utilizes the π-π stacking and Rh I …Rh I interaction between the trispyridine rhodium complex molecules to form a rhodium-based supramolecular coordination polymer catalyst, the supramolecular polymer catalyst can catalyze an olefin hydroformylation reaction to prepare aldehyde compounds, realizes efficient conversion of the olefin, and effectively solves the technical problems of poor separation of the catalyst from the product, low recycling efficiency and poor stability in the existing olefin hydroformylation reaction.

Description

Technical Field

[0001] This invention relates to the field of organic synthesis technology, specifically to a nitrogen-containing ligand supramolecular polymer catalyst, its preparation method, and its application. Background Technology

[0002] The hydroformylation of olefins uses transition metals as the active component of a catalyst. With the participation of ligands, olefins react with hydrogen and carbon monoxide to produce aldehydes, while simultaneously increasing the carbon chain length. It is one of the most important catalytic reactions in industry. The aldehydes produced by the hydroformylation of olefins are intermediates for many important chemical products. Through further hydrogenation, oxidation, reductive amination, and other reactions, downstream products such as alcohols, acids, amines, and esters are generated, which have high economic value. Aldehydes can also undergo condensation processes to generate various high-value-added fine chemicals such as detergents, surfactants, pharmaceuticals, and fragrances.

[0003] Phosphine ligand-modified rhodium complexes are currently recognized as the most efficient hydroformylation catalysts. However, the separation and recovery of these expensive catalysts has long been a scientific challenge, limiting their commercial application in industry. To overcome rhodium loss, many solid materials have been developed for supporting rhodium in heterogeneous hydroformylation, such as porous organic polymers (POPs), carbon materials, SiO2, and zeolites. However, reports of phosphine ligand loss due to oxidation and hydrolysis are rare. To find more suitable alternatives, phosphorus-free and nitrogen-containing ligand catalytic systems have emerged as a new trend in the last decade. Besides the activity of their Rh complexes in hydroformylation, nitrogen ligands are more stable in oxidation and less environmentally toxic than widely used phosphorus ligands. Summary of the Invention

[0004] To address the aforementioned technical problems, the present invention aims to provide a nitrogen-containing ligand supramolecular polymer catalyst, its preparation method, and its application, thereby solving the problems of difficulty in separating the catalyst from the product, low recycling efficiency, and poor stability in the olefin hydroformylation reaction of the prior art.

[0005] The technical solution of this invention to solve the above-mentioned technical problems is as follows: A method for preparing a nitrogen-containing ligand supramolecular polymer catalyst is provided, comprising the following steps:

[0006] (1) Under an inert gas atmosphere, nitrogen-containing ligands, inorganic salts and rhodium precursors are mixed and an organic solvent is added to obtain a reaction solution;

[0007] (2) Stir the reaction solution obtained in step (1), let it stand for the first time, disperse it by ultrasonication, let it stand for the second time, then filter it, wash it, and obtain the nitrogen-containing ligand supramolecular polymer catalyst.

[0008] Based on the above technical solution, the present invention can be further improved as follows:

[0009] Furthermore, in step (1), the molar ratio of nitrogen-containing ligand, inorganic salt and rhodium precursor is 1:1-3:1-4.

[0010] Furthermore, in step (1), the molar ratio of nitrogen-containing ligand, inorganic salt and rhodium precursor is 1:1:1.

[0011] Furthermore, in step (1), the molar ratio of the nitrogen-containing ligand, the inorganic salt, and the rhodium precursor is 1:1.5:1.

[0012] Furthermore, in step (1), the molar volume ratio of the rhodium precursor to the organic solvent is 0.1-0.4 mmol: 10-20 mL.

[0013] Furthermore, in step (1), the molar volume ratio of the rhodium precursor to the organic solvent is 0.1 mmol: 10 mL.

[0014] Furthermore, in step (1), the nitrogen-containing ligand is an NNN-type tridentate ligand with the following molecular structure: Where R = H, alkyl, or substituted phenyl.

[0015] The beneficial effects of adopting the above-mentioned further technical solutions are as follows: The advantages of using this type of ligand are: 1. It eliminates the contamination of phosphine ligands and the nitrogen ligands have lower toxicity; 2. This type of NNN tridentate ligand is in the same plane after coordination, which is conducive to supramolecular assembly.

[0016] Further, in step (1), the inorganic salt is magnesium perchlorate, sodium perchlorate, potassium perchlorate, copper perchlorate, cadmium perchlorate, lithium perchlorate, lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, magnesium trifluoromethanesulfonate, potassium trifluoromethanesulfonate, zinc trifluoromethanesulfonate, copper trifluoromethanesulfonate, zinc tetrafluoroborate, magnesium tetrafluoroborate, copper tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, copper tetrafluoroborate, cadmium tetrafluoroborate, sodium tetraphenylborate, copper nitrate, sodium nitrate, potassium nitrate, zinc nitrate, zinc chloride, copper dichloride, sodium chloride, lithium chloride, or magnesium dichloride.

[0017] The beneficial effects of adopting the above-mentioned further technical solution are that inorganic salts can remove the acac group in Rh(acac)(CO)2 and also provide the required counter anions.

[0018] Furthermore, in step (1), the rhodium precursor is Rh(acac)(CO)2; where acac is acetylacetone.

[0019] Furthermore, in step (1), the organic solvent is at least one of methanol, ethanol, dichloromethane, chloroform, 1,2-dichloroethane, acetone, dimethyl sulfoxide, tetrahydrofuran, toluene, xylene, and acetonitrile.

[0020] Furthermore, in step (1), the inert gas is argon or nitrogen.

[0021] Furthermore, in step (2), the mixture is stirred at room temperature for 2-3 hours.

[0022] Furthermore, in step (2), the first time it is left to stand for 15-30 minutes.

[0023] Furthermore, in step (2), ultrasonic dispersion is performed for 10-20 minutes.

[0024] Furthermore, in step (2), the second standing time is 30-55 minutes.

[0025] Furthermore, in step (2), the product is washed 2-3 times with n-hexane.

[0026] The present invention also provides nitrogen-containing ligand supramolecular polymer catalysts prepared by the above method.

[0027] The present invention also provides the application of the above-described catalyst in the hydroformylation reaction of olefins.

[0028] Furthermore, the molar ratio of olefin and nitrogen-containing ligand supramolecular polymer catalyst is 1000:1-3.

[0029] Furthermore, the solvent used in the hydroformylation reaction is at least one of anisole, toluene, diethyl ether, tetrahydrofuran, xylene, trimethylbenzene, 1,4-dioxane, dichloromethane, tridecane, and chloroform.

[0030] Furthermore, the reaction atmosphere in the hydroformylation reaction is syngas prepared by CO and H2 in a volume ratio of 1-2:1-2, the reaction pressure is 2-4 MPa, the reaction temperature is 60-110℃, and the reaction time is 5-10 h.

[0031] Furthermore, the reaction atmosphere in the hydroformylation reaction is a synthesis gas prepared by CO and H2 in a volume ratio of 2:1, the reaction pressure is 2-4 MPa, the reaction temperature is 100℃, and the reaction time is 8h.

[0032] The present invention has the following beneficial effects:

[0033] 1. This invention utilizes the π-π stacking between molecules of the terpyridine rhodium complex and Rh I ···Rh I The interaction forms a rhodium-based supramolecular coordination polymer catalyst, which can catalyze the hydroformylation of olefins to prepare aldehydes, achieving efficient conversion of olefins. This effectively solves the technical problems of difficult separation of catalyst and product, low recycling efficiency, and poor stability in existing olefin hydroformylation reactions.

[0034] 2. The catalyst prepared by this invention has the characteristics of good catalytic activity and wide applicability. After being recycled 10 times, the catalyst structure does not change significantly and the performance does not decrease significantly, resulting in a high recycling rate.

[0035] 3. Due to the high stability of supramolecular polymer catalysts and their insolubility with solvents and products, the catalyst can be directly filtered and separated from olefin feedstocks and hydroformylation products after the reaction, which greatly reduces the difficulty and cost of catalyst separation.

[0036] 4. The catalyst can achieve efficient conversion of olefins under mild conditions, and can prepare aldehyde products with high selectivity and high yield, thereby reducing production costs. Attached Figure Description

[0037] Figure 1 This is a schematic diagram of the catalyst synthesis route;

[0038] Figure 2 A schematic diagram of the synthesis route for the catalyst, omitting solvent molecules and counteracting anions. Detailed Implementation

[0039] The principles and features of the present invention are described below with reference to the accompanying drawings. The examples given are for illustrative purposes only and are not intended to limit the scope of the invention. Unless otherwise specified in the examples, conventional conditions or conditions recommended by the manufacturer should be followed. Reagents or instruments whose manufacturers are not specified are all commercially available products.

[0040] Example 1:

[0041] A nitrogen-ligand supramolecular polymer catalyst, the preparation method of which includes the following steps: (synthetic route see...) Figure 1-2 )

[0042] (1) Add nitrogen-containing ligand (0.1 mmol terpyridine), inorganic salt (0.1 mmol sodium tetrafluoroborate) and rhodium precursor (0.1 mmol Rh(acac)(CO)2, acac is acetylacetone) to the reactor, purge the reaction vessel three times under nitrogen protection, add organic solvent (10 mL ethanol) to obtain the reaction solution;

[0043] (2) The reaction solution obtained in step (1) was stirred at room temperature for 2 hours, allowed to stand for 30 minutes for the first time, ultrasonically dispersed for 10 minutes, allowed to stand for 30 minutes for the second time, and then filtered. The filter cake was washed three times with n-hexane to obtain the nitrogen-containing ligand supramolecular polymer catalyst. (Catalyst 1)

[0044] Among them, the terpyridine ligand L1 reacts with sodium tetrafluoroborate and Rh(acac)(CO)2 to form compound Rh. I (CO)L1, Rh I(CO)L1 utilizes Rh I ···Rh I Interactions yield Rh I (CO)L1 dimer (Rh) I (CO)L1)2, and then through the π-π interaction between dimers, supramolecular polymer catalyst 1 was obtained.

[0045] The structure of catalyst 1 was characterized, and the results are as follows: 1 H NMR (600MHz, DMSO-d6) δ8.21(d,J=5.5Hz,2H),8.18(dd,J=7.9,5.6Hz,4H),8.15–8.12(m,1H),8.09(t,J=7.8Hz,2H),7.59(t,J=6.6Hz,2H).

[0046] Example 2:

[0047] A nitrogen-ligand supramolecular polymer catalyst, the preparation method of which includes the following steps:

[0048] (1) Add nitrogen-containing ligand (0.1 mmol terpyridine), inorganic salt (0.1 mmol magnesium perchlorate) and rhodium precursor (0.1 mmol Rh(acac)(CO)2, acac is acetylacetone) to the reactor, purge the reaction vessel three times under nitrogen protection, add organic solvent (20 mL ethanol) to obtain the reaction solution;

[0049] (2) The reaction solution obtained in step (1) was stirred at room temperature for 3 hours, allowed to stand for 15 minutes for the first time, ultrasonically dispersed for 20 minutes, allowed to stand for 55 minutes for the second time, and then filtered. The filter cake was washed three times with n-hexane to obtain the nitrogen-containing ligand supramolecular polymer catalyst. (Catalyst 2)

[0050] The structure of catalyst 2 was characterized, and the results are as follows: 1 H NMR (600MHz, DMSO-d6) δ8.21(d,J=5.5Hz,2H),8.18(dd,J=7.9,5.6Hz,4H),8.15–8.12(m,1H),8.09(t,J=7.8Hz,2H),7.59(t,J=6.6Hz,2H).

[0051] Example 3:

[0052] A nitrogen-ligand supramolecular polymer catalyst, the preparation method of which includes the following steps:

[0053] (1) Add nitrogen-containing ligand (0.1 mmol of 2,6-bis(1-pyrazolyl)pyridine), inorganic salt (0.15 mmol of copper trifluoromethanesulfonate) and rhodium precursor (0.1 mmol of Rh(acac)(CO)2, where acac is acetylacetone) to the reactor, purge the reaction vessel four times under nitrogen protection, add organic solvent (10 mL of methanol) to obtain the reaction solution;

[0054] (2) The reaction solution obtained in step (1) was stirred at room temperature for 2.5 h, allowed to stand for 20 min for the first time, ultrasonically dispersed for 15 min, allowed to stand for 50 min for the second time, and then filtered. The filter cake was washed three times with n-hexane to obtain the nitrogen-containing ligand supramolecular polymer catalyst. (Catalyst 3)

[0055] The structure of catalyst 3 was characterized, and the results are as follows: 1 H NMR (600MHz, DMSO-d6) δ8.95(d,J=2.6Hz,2H),8.16(d,J=8.0Hz,1H),7.87(d,J=1.6Hz,2H),7.82(d,J=8.0Hz,2H),6.64(dd,J=2.7,1.7Hz,2H).

[0056] Example 4:

[0057] A nitrogen-ligand supramolecular polymer catalyst, the preparation method of which includes the following steps:

[0058] A nitrogen-containing ligand (0.1 mmol terpyridine), an inorganic salt (0.3 mmol sodium tetrafluoroborate), and a rhodium precursor (0.4 mmol Rh(acac)(CO)2, where acac is acetylacetone) were added to the reactor; the rest was the same as in Example 1.

[0059] Test case

[0060] I. The catalytic effect of catalyst 1 prepared in Example 1 was tested, and the method is as follows:

[0061] The application of catalyst 1 in the hydroformylation reaction is shown in the following reaction equation:

[0062]

[0063] Includes the following steps:

[0064] S1: Mix 2 mL of cyclohexene, 0.01 g of catalyst 1 and 4 mL of toluene. Place the mixture in a high-pressure reactor with magnetic stirring. Replace the air in the reactor with nitrogen and introduce 4 MPa of syngas (CO and H2 volume ratio of 2:1). React at 100 °C for 8 h. After the reaction is completed, cool to room temperature, centrifuge and filter. The filtrate is toluene and hydroformylation product, and the filter cake is catalyst 1. The conversion rate of olefins and the yield of aldehydes are detected by gas chromatography.

[0065] S2: Use the filter cake obtained in step S1 as the catalyst 1 for the new round, and repeat step S1 until it is repeated 9 times.

[0066] The performance test results of catalyst 1 are shown in Table 1 (molar ratio).

[0067] Table 1 Performance test results of catalyst 1

[0068] frequency Conversion rate (%) Cyclohexene (%) Cyclohexylformaldehyde (%) 1 99.31 0.69 99.31 2 99.7 0.30 99.70 3 99.57 0.43 99.57 4 99.47 0.53 99.47 5 99.32 0.68 99.32 6 99.42 0.58 99.42 7 99.8 0.20 99.80 8 99.82 0.18 99.82 9 99.43 0.57 99.43 10 99.82 0.18 99.82

[0069] As shown in Table 1, GC analysis revealed that catalyst 1 exhibited excellent catalytic activity towards cyclohexane, and no cyclohexane, the hydrogenation product of olefins, was found in the product. Furthermore, after 10 cycles, the activity of catalyst 1 did not show a significant decrease.

[0070] II. The catalytic effect of catalyst 2 prepared in Example 2 was tested, and the method is as follows:

[0071] The application of catalyst 2 in hydroformylation is shown in the following reaction equation:

[0072]

[0073] (1) Mix 2 mL of 1-hexene, 0.01 g of catalyst 2 and 4 mL of toluene. Place the mixture in a high-pressure reactor with magnetic stirring. Replace the air in the reactor with nitrogen and introduce 4 MPa of syngas (CO and H2 volume ratio of 1:1). React at 80 °C for 10 h. After the reaction is completed, cool to room temperature, centrifuge and filter. The filtrate is toluene and hydroformylation product, and the filter cake is catalyst 2. The conversion rate of olefins and the yield of aldehydes are detected by gas chromatography.

[0074] (2) Use the filter cake obtained in step (1) as the catalyst 2 for the new round and repeat step (1); until the process is repeated 9 times.

[0075] The performance test results of catalyst 2 are shown in Table 2 (molar ratio).

[0076] Table 2 Performance test results of catalyst 2

[0077] frequency Conversion rate (%) Isohexene (%) Heptanal (%) 1 99.99 2.96 97.04 2 99.99 3.80 96.20 3 99.99 2.78 97.22 4 99.99 3.00 97.00 5 99.99 6.16 96.84 6 99.99 2.67 97.33 7 99.99 3.09 96.91 8 99.99 2.91 97.09 9 99.99 5.44 94.56 10 99.99 3.50 96.50

[0078] GC analysis showed that catalyst 2 exhibited excellent catalytic activity towards 1-hexene, and no hexane, the hydrogenation product of the olefin, was found in the product. Furthermore, after 10 cycles, the activity of catalyst 2 did not significantly decrease.

[0079] III. The catalytic effect of catalyst 3 prepared in Example 3 was tested, and the method is as follows:

[0080] The application of catalyst 3 in hydroformylation is shown in the following reaction equation:

[0081]

[0082] Includes the following steps:

[0083] (1) Mix 2 mL of 1-octene, 0.02 g of catalyst 2 and 4 mL of toluene. Place the mixture in a high-pressure reactor with magnetic stirring. Replace the air in the reactor with nitrogen and introduce 3 MPa of syngas (CO and H2 volume ratio of 1:1). React at 60 °C for 10 h. After the reaction is completed, cool to room temperature, centrifuge and filter. The filtrate is toluene and hydroformylation product, and the filter cake is catalyst 3. The conversion rate of olefins and the yield of aldehydes are detected by gas chromatography.

[0084] (2) Use the filter cake obtained in step (1) as the catalyst 3 for the new round and repeat step (1); until the process is repeated 9 times.

[0085] The performance test results of catalyst 3 are shown in Table 3 (molar ratio).

[0086] Table 3 Performance test results of catalyst 3

[0087] frequency Conversion rate (%) Isooctene (%) Nononal (%) 1 99.99 2.89 97.11 2 99.99 3.03 96.97 3 99.99 3.15 96.85 4 99.99 3.01 96.99 5 99.99 2.8 97.2 6 99.99 2.13 97.87 7 99.99 2.14 97.86 8 99.99 2.91 97.09 9 99.99 2.89 97.11 10 99.99 3.1 96.9

[0088] GC analysis showed that catalyst 3 exhibited excellent catalytic activity towards 1-octene, and no octane, the hydrogenation product of the olefin, was found in the product. Furthermore, after 10 cycles, the activity of catalyst 3 did not significantly decrease.

[0089] IV. The catalytic effect of catalyst 1 prepared in Example 1 was tested, and the method is as follows:

[0090] The application of catalyst 1 in hydroformylation is shown in the following reaction equation:

[0091]

[0092] Includes the following steps:

[0093] (1) Mix 2 mL of styrene, 0.02 g of catalyst 1 and 4 mL of tridecane. Place the mixture in a high-pressure reactor with magnetic stirring. Replace the air in the reactor with nitrogen and introduce 2 MPa of syngas (CO and H2 volume ratio of 2:1). React at 90 °C for 9 h. After the reaction is completed, cool to room temperature, centrifuge and filter. The filtrate is toluene and hydroformylation product, and the filter cake is catalyst 1. The conversion rate of olefins and the yield of aldehydes are detected by gas chromatography.

[0094] (2) Use the filter cake obtained in step (1) as the catalyst 1 for the new round and repeat step (1); until the process is repeated 9 times.

[0095] The performance test results of catalyst 1 are shown in Table 4 (molar ratio).

[0096] Table 4 Performance test results of catalyst 1

[0097]

[0098]

[0099] GC analysis showed that catalyst 1 exhibited excellent catalytic activity towards styrene, and no phenylethane, the hydrogenation product of the olefin, was found in the product. Furthermore, after 10 cycles, the activity of catalyst 1 did not significantly decrease.

[0100] V. The catalytic effect of catalyst 1 prepared in Example 1 was tested, and the method is as follows:

[0101] The application of catalyst 1 in hydroformylation is shown in the following reaction equation:

[0102]

[0103] Includes the following steps:

[0104] (1) Mix 2 mL of α-methylstyrene, 0.02 g of catalyst 1 and 4 mL of toluene. Place the mixture in a high-pressure reactor with magnetic stirring. Replace the air in the reactor with nitrogen and introduce 2 MPa of syngas (CO and H2 volume ratio of 2:1). React at 90 °C for 9 h. After the reaction is completed, cool to room temperature, centrifuge and filter. The filtrate is toluene and hydroformylation product, and the filter cake is catalyst 1. The conversion rate of olefins and the yield of aldehydes are detected by gas chromatography.

[0105] (2) Use the filter cake obtained in step (1) as the catalyst 1 for the new round and repeat step (1); until the process is repeated 9 times.

[0106] The performance test results of catalyst 1 are shown in Table 5 (molar ratio).

[0107] Table 5 Performance test results of catalyst 1

[0108]

[0109]

[0110] GC analysis showed that catalyst 1 exhibited excellent catalytic activity for α-methylstyrene, and no phenylethane, the hydrogenation product of the olefin, was found in the product. Furthermore, after 10 cycles, the activity of catalyst 1 did not significantly decrease.

[0111] VI. The catalytic effect of catalyst 1 prepared in Example 1 was tested, and the method is as follows:

[0112] The application of catalyst 1 in hydroformylation is shown in the following reaction equation:

[0113]

[0114] Includes the following steps:

[0115] (1) Mix 3 mL of 1-decene, 0.02 g of catalyst 1 and 3 mL of xylene. Place the mixture in a high-pressure reactor with magnetic stirring. Replace the air in the reactor with nitrogen and introduce 4 MPa of syngas (CO and H2 volume ratio of 1:1). React at 110 °C for 10 h. After the reaction is completed, cool to room temperature, centrifuge and filter. The filtrate is toluene and hydroformylation product, and the filter cake is catalyst 1. The conversion rate of olefins and the yield of aldehydes are detected by gas chromatography.

[0116] (2) Use the filter cake obtained in step (1) as the catalyst 1 for the new round and repeat step (1); until the process is repeated 9 times.

[0117] The performance test results of catalyst 1 are shown in Table 6.

[0118] Table 6 Performance test results of catalyst 1

[0119] frequency Conversion rate (%) Isomerized decene (%) Undecaldehyde (%) 1 99.99 7.34 92.66 2 99.99 10.17 89.83 3 99.99 8.88 91.12 4 99.99 12.01 87.99 5 99.99 10.60 89.40 6 99.99 13.02 86.98 7 99.99 14.21 85.79 8 99.99 12.10 87.90 9 99.99 12.22 87.78 10 99.99 10.44 89.56

[0120] GC analysis showed that catalyst 1 exhibited excellent catalytic activity towards 1-decene, and no decane, the hydrogenation product of the olefin, was found in the product. Furthermore, after 10 cycles, the activity of catalyst 1 did not significantly decrease.

[0121] VII. The catalytic effect of catalyst 1 prepared in Example 1 was tested, and the method is as follows:

[0122] The application of catalyst 1 in hydroformylation is shown in the following reaction equation:

[0123]

[0124] Includes the following steps:

[0125] (1) Mix 1 mL of mixed octene, 0.15 g of catalyst 1 and 4 mL of anisole. Place the mixture in a high-pressure reactor with magnetic stirring. Replace the air in the reactor with nitrogen and introduce 2 MPa of syngas (CO and H2 volume ratio of 1:1). React at 85 °C for 6 h. After the reaction is completed, cool to room temperature, centrifuge and filter. The filtrate is toluene and hydroformylation product, and the filter cake is catalyst 1. The conversion rate of olefins and the yield of aldehydes are detected by gas chromatography.

[0126] (2) Use the filter cake obtained in step (1) as the catalyst 1 for the new round and repeat step (1); until the process is repeated 9 times.

[0127] The performance test results of catalyst 1 are shown in Table 7.

[0128] Table 7 Performance test results of catalyst 1

[0129] frequency Conversion rate (%) Isooctene (%) Isonononal (%) 1 62.25 47.75 52.25 2 62.48 46.89 52.49 3 63.11 46.89 53.11 4 65.11 47.49 52.51 5 62.79 47.26 52.74 6 62.59 47.49 52.51 7 62.66 47.65 52.35 8 62.98 47.21 52.79 9 62.82 47.13 52.87 10 62.61 47.19 52.81

[0130] GC analysis showed that catalyst 1 exhibited excellent catalytic activity towards mixed octenes, and no octane, the hydrogenation product of the olefins, was found in the product. Furthermore, after 10 cycles, the activity of catalyst 1 did not significantly decrease.

[0131] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. Use of a nitrogen-containing ligand supramolecular polymer catalyst in an olefin hydroformylation reaction, characterized in that, The preparation method of the nitrogen-containing ligand supramolecular polymer catalyst comprises the following steps: (1) mixing the nitrogen-containing ligand, the inorganic salt and the rhodium precursor under an inert gas atmosphere, adding an organic solvent to obtain a reaction solution; (2) stirring the reaction solution obtained in step (1), first standing, ultrasonic dispersion, second standing, then suction filtration, washing to obtain the nitrogen-containing ligand supramolecular polymer catalyst; In step (1), the nitrogen-containing ligand is a NNN type tridentate ligand, and the molecular structural formula is: or ; wherein R = H or substituted phenyl; In step (1), the inorganic salt is magnesium perchlorate, sodium perchlorate, potassium perchlorate, copper perchlorate, cadmium perchlorate, lithium perchlorate, lithium triflate, sodium triflate, magnesium triflate, potassium triflate, zinc triflate, copper triflate, zinc tetrafluoroborate, magnesium tetrafluoroborate, copper tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, cadmium tetrafluoroborate, sodium tetraphenylborate, copper nitrate, sodium nitrate, potassium nitrate, zinc nitrate, zinc chloride, copper dichloride, sodium chloride, lithium chloride or magnesium dichloride; In step (1), the rhodium precursor is Rh(acac)(CO)2; wherein, acac is acetylacetone; In step (1), the molar ratio of the nitrogen-containing ligand, the inorganic salt and the rhodium precursor is 1:1-3:1-4; In step (1), the molar volume ratio of the rhodium precursor and the organic solvent is 0.1-0.4 mmol: 10-20 mL; In step (1), the organic solvent is at least one of methanol, ethanol, dichloromethane, trichloromethane, 1,2-dichloroethane, acetone, dimethyl sulfoxide, toluene, xylene and acetonitrile.

2. Use of the nitrogenous ligand supramolecular polymer catalyst according to claim 1 in an olefin hydroformylation reaction, characterized in that, The molar ratio of the olefin and the nitrogen-containing ligand supramolecular polymer catalyst is 1000:1-3.

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