Catalytic system for olefin hydroformylation reaction and method for olefin hydroformylation reaction

Abstract

The present application relates to a kind of catalytic system for olefin hydroformylation reaction and the method of olefin hydroformylation reaction;Catalytic system includes: fluorine-containing bisphosphinite ligand Ln and rhodium-manganese bimetallic synergistic system.The present application also relates to the preparation method of fluorine-containing bisphosphinite ligand Ln.The fluorine-containing bisphosphinite ligand of the present application is creatively introduced, and its fluorine-containing structure can significantly enhance the chemical inertness of ligand molecule itself, effectively resist decomposition, hydrolysis and degradation under high temperature.The introduction of manganese can not only adjust the catalytic performance of rhodium center through electronic effect, but also can form synergistic effect with rhodium in the reaction, and stabilize the key reaction intermediate, so as to enhance the firmness of the entire catalytic framework at the molecular level, further inhibit the precipitation and agglomeration of rhodium metal and inactivation.In propylene hydroformylation reaction, the conversion rate is generally as high as 99%;In the wide process parameter interval, the conversion rate is not less than 96%, the activity window is wide, and it has great industrial application prospect and economic benefit.

Description

Technical Field

[0001] This invention discloses a catalytic system and a method for the hydroformylation of olefins. Background Technology

[0002] Hydroformylation, also known as the OXO reaction, is a key chemical process in which olefins react with syngas (carbon monoxide and hydrogen) in the presence of a transition metal catalyst to form aldehydes with one more carbon atom. This reaction is one of the most successful applications of homogeneous catalysis in industrial production. Aldehydes, alcohols, and their derivatives produced through this process are produced on a massive scale and play a central role in the synthesis of high-value-added chemicals such as plasticizers, surfactants, and solvents.

[0003] In industrial applications, rhodium-based catalytic systems have become the mainstream in hydroformylation processes due to their significantly higher catalytic performance compared to traditional cobalt catalysts. The design and selection of ligands are crucial for optimizing rhodium catalytic performance. Among these, phosphite ligands, especially bisphosphonite ligands, have attracted considerable attention because they impart excellent catalytic properties to the catalysts.

[0004] However, existing rhodium-based catalytic systems, especially those using bisphosphonates as ligands, still face significant challenges. Taking the bisphosphonate ligand 6,6′-[(3,3′-di-tert-butyl-5,5′-dimethoxy-1,1′-diphenyl-2,2′-diyl)bis(oxy)]bis(dibenzo[d,f][1,3,2]dioxophosphatane), with the following structural formula (hereinafter referred to as ligand D1), as an example, our research team conducted preliminary studies on its catalytic performance in the hydroformylation of propylene. The optimal reaction temperature is 60–80 °C, and the time-to-flight (TOF) frequency can reach 863 h⁻¹. -1 ~1240 h -1 The reaction conversion rate is 95%–99%. However, when using rhodium-based catalysts for hydroformylation, the reaction typically needs to be carried out at 70°C–120°C to ensure the reaction rate. During product distillation, catalyst regeneration, or recovery, the temperature often rises to 130°C–190°C. When the reaction temperature exceeds 80°C, the reaction rate of the Rh-ligand D1 catalyst system decreases significantly, and the TOF drops to 400 h⁻¹. -1 ~800 h -1The reaction conversion rate drops to 20%–80%, and the catalyst deactivates rapidly. This profoundly reveals that high-temperature environments readily cause ligands to decompose, hydrolyze, or degrade, especially phosphite structures sensitive to water and oxygen. Ligand deactivation directly leads to the precipitation and agglomeration of the central rhodium metal, resulting in rapid deactivation of the entire catalytic system, shortened catalyst lifetime, and decreased selectivity for the target product. This problem severely restricts the single-cycle operation and recycling efficiency of catalysts in industrial plants, increasing production costs and the frequency of catalyst replenishment and replacement, and affecting the continuity and stability of the production process. Therefore, developing long-lasting catalytic systems with both high catalytic performance and excellent stability under high-temperature conditions has become a core problem urgently needing to be solved in the field of hydroformylation technology.

[0005] The above ligand D1 has the following structure and can be used directly after being purchased from the reagent platform:

[0006] . Summary of the Invention

[0007] The purpose of this invention is to overcome the shortcomings of existing olefin hydroformylation catalysts, such as easy deactivation at high temperatures and short catalyst cycle life, and to provide a novel catalytic system. This system extends the life of the rhodium catalyst by introducing fluorinated bisphosphonates ligands and the synergistic effect of rhodium-manganese bimetallic compounds, thereby obtaining a highly efficient, stable, and economical industrial solution.

[0008] This invention proposes a catalytic system and a method for the hydroformylation of olefins.

[0009] The technical solution of the present invention is as follows:

[0010] A catalytic system for the hydroformylation of olefins, comprising: a fluorinated bisphosphonite ligand Ln and a rhodium-manganese bimetallic synergistic system; the general structural formula of the fluorinated bisphosphonite ligand Ln is:

[0011]

[0012] Where X is C6~C 32 The substituted or unsubstituted organic divalent bridged arylene group; the molecular structure of X contains only two arylene units, which are directly linked by a carbon-carbon single bond; preferably, X is C 22 ~C 28 The substituted organic divalent bridging aryl group;

[0013] The C mentioned 22 ~C 28The preferred substituted organic divalent bridged aryl group is 3,3'-bis-tert-butyl-5,5'-bis-methoxy-1,1”-biphenyl-2,2'-diyl or 3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl.

[0014] In the aforementioned rhodium-manganese bimetallic synergistic system, the rhodium source is selected from: rhodium oxide ( ), Tweldodecyl tetrarhodium Hexadecyl carbonyl hexarhodium Trinitrorhodium rhodium diacetate Rhodium dicarbonylacetylacetone (I) ), acetylacetone (1,5-cyclooctadiene) rhodium ( ), dichlorotetracarbonyl dirhodium ( One of the following; the manganese source is selected from: decacarbonyldimanganese ( ), Methylcyclopentadienyl manganese tricarbonyl (MMT), manganese acetate ( ), manganese acetylacetonate ( One of them.

[0015] Preferably, the rhodium source is rhodium dicarbonyl acetylacetone (I) ( The manganese source is methylcyclopentadienyl manganese tricarbonyl (MMT).

[0016] The catalytic system for the hydroformylation of olefins has a catalyst ligand ratio of 1 to 10:1 for the fluorinated bisphosphonate ligand Ln and the molar ratio of 5:1 to 20:1 for the manganese and rhodium.

[0017] The method for synthesizing the fluorinated bisphosphonite ligand Ln in the catalytic system for olefin hydroformylation of the present invention includes the following steps:

[0018] (1) At room temperature, the tetrahydrofuran solution of organic divalent bridged aromatic phenols was added dropwise to the tetrahydrofuran solution of sodium hydride to carry out the reaction and obtain a mixed solution;

[0019] (2) The bis(o-fluorophenyl)phosphorus chloride intermediate was added dropwise to the mixed solution obtained in step (1), and the reaction was continued to be stirred at room temperature to obtain the reaction mixture;

[0020] (3) Under an inert atmosphere, the reaction mixture obtained in step (2) is filtered through diatomaceous earth to obtain a filtrate;

[0021] (4) Remove the solvent from the filtrate of step (3) by vacuum distillation to obtain a crude product containing the fluorinated bisphosphonates ligand Ln;

[0022] (5) The crude product of the fluorinated bisphosphonate ligand Ln obtained in step (4) is purified to obtain the purified fluorinated bisphosphonate ligand Ln.

[0023] The molar ratio of the raw material organic divalent bridged arylphenol: sodium hydride: intermediate bis(o-fluorophenyl)phosphorus chloride is 1: 2.2: 2.

[0024] The purification methods include recrystallization or column chromatography.

[0025] The catalytic system of the present invention is used in a method for the hydroformylation of olefins. A catalyst system containing a rhodium-manganese (Rh-Mn) bimetallic compound and a fluorinated bisphosphonate ligand Ln is used to catalyze the reaction of hydrogen, carbon monoxide, and olefins to produce aldehydes. The reaction temperature range is 60–150°C; the total gas pressure is 1–5 MPa; the molar ratio of hydrogen, carbon monoxide, and olefins is 1:1:1; and the reaction is carried out in a solvent capable of dissolving the catalyst and reactants.

[0026] The solvents used in the method of this invention are generally those used in the hydroformylation reaction. Any suitable solvent that will not cause too much adverse effect on the reaction can be used. Preferred solvents are toluene and the product aldehyde self-solvent (e.g., butyraldehyde produced by the hydroformylation of propylene; pentanal produced by the hydroformylation of butene).

[0027] The catalytic system for the hydroformylation of olefins has a rhodium concentration of 60-250 ppm in the solvent.

[0028] The steps of olefin hydroformylation of the present invention include: adding a composition of a rhodium source, a manganese source, and a fluorinated bisphosphonate ligand Ln catalyst into a reaction vessel and sealing it; sequentially replacing the atmosphere inside the vessel with an inert atmosphere and a mixed gas of olefin, carbon monoxide, and hydrogen; pressurizing the system with the mixed gas, heating the system to the reaction temperature, and controlling the temperature and pressure; and cooling and depressurizing the reaction vessel when no further gas is consumed, and analyzing the reaction solution by gas chromatography to obtain an aldehyde solution.

[0029] Compared with the prior art, the beneficial effects of the technical solution of the present invention are as follows:

[0030] (1) Significantly improved the high-temperature stability and lifespan of the catalytic system:

[0031] This invention creatively introduces fluorinated bisphosphonates ligands, whose fluorinated structure can significantly enhance the chemical inertness of the ligand molecules themselves, effectively resisting decomposition, hydrolysis and degradation at high temperatures.

[0032] The existing catalyst system, represented by ligand D1, and the novel catalyst system of this invention exhibit significant differences in performance during the hydroformylation of propylene, especially in terms of stability at high temperatures:

[0033] The D1 ligand system exhibits significant high-temperature deactivation defects. At a reaction temperature of 150℃, the catalytic conversion frequency is only 432.3 h⁻¹. -1 This indicates that the catalyst structure is unstable at high temperatures.

[0034] The propylene hydroformylation system of this invention maintains an excellent conversion frequency (TOF > 1232.9 h) at a high temperature of 150°C. -1 This clearly demonstrates that the catalyst system has excellent stability under high temperature conditions, successfully overcoming the problem of rapid deactivation of the ligand D1 system at high temperatures.

[0035] (2) Achieved synergistic enhancement of bimetallic effects and strengthened the catalytic system:

[0036] The introduction of manganese can not only modulate the catalytic performance of the rhodium center through electronic effects, but also form a synergistic effect with rhodium in the reaction to jointly stabilize key reaction intermediates, thereby improving the robustness of the entire catalytic framework at the molecular level and further inhibiting the precipitation and agglomeration deactivation of rhodium metal.

[0037] (3) It provides a universal, efficient and stable new catalytic strategy:

[0038] The "fluorine-containing ligand + bimetallic synergy" strategy adopted in this invention provides a novel and effective solution to the long-standing problem of catalyst deactivation at high temperatures in the field of hydroformylation. This strategy is not limited to specific olefin substrates and has broad application prospects in a variety of hydroformylation reactions. Detailed Implementation

[0039] The present invention further illustrates the catalytic system and method for olefin hydroformylation reaction through the following examples, but does not constitute a limitation on the scope of protection of the present invention.

[0040] The fluorinated bisphosphonate ligand Ln used in the following examples has the following structure:

[0041]

[0042] Example 1:

[0043]

[0044] Synthesis of fluorinated bisphosphonates ligand L1:

[0045] (1) At room temperature, a solution of 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methoxyphenyl)-4-methoxyphenol (0.5 g, 1.39 mmol) in tetrahydrofuran (15 mL) was added dropwise to a solution of sodium hydride (0.0734 g, 3.058 mmol) in tetrahydrofuran (12 mL) to obtain a mixed solution;

[0046] (2) Next, bis(o-fluorophenyl)phosphorus chloride (0.7134 g, 2.78 mmol) was added dropwise to the mixed solution obtained in step (1), and the mixture was stirred at room temperature for 5 hours to obtain the reaction mixture;

[0047] (3) The reaction mixture obtained in step (2) is filtered through diatomaceous earth under nitrogen protection to obtain the filtrate;

[0048] (4) Remove the solvent from the filtrate of step (3) by vacuum distillation to obtain the crude product containing fluorinated bisphosphonates ligand L1;

[0049] (5) The crude product of fluorinated bisphosphonates ligand L1 was recrystallized with acetonitrile at -20°C to obtain white crystalline product L1 (0.76 g, 69%).

[0050] Example 2:

[0051]

[0052] Synthesis of fluorinated bisphosphonates ligand L2:

[0053] (1) At room temperature, a solution of 3,3',5,5'-tetra-tert-butyl-2,2'-biphenyl (0.5 g, 1.22 mmol) in tetrahydrofuran (20 mL) was added dropwise to a solution of sodium hydride (0.0643 g, 2.68 mmol) in tetrahydrofuran (16 mL) to obtain a mixed solution;

[0054] (2) Next, bis(o-fluorophenyl)phosphorus chloride (0.631 g, 2.44 mmol) was added dropwise to the mixed solution obtained in step (1), and the reaction was continued to be stirred at room temperature for 3 hours to obtain the reaction mixture;

[0055] (3) The reaction mixture obtained in step (2) is filtered through diatomaceous earth under nitrogen protection to obtain the filtrate;

[0056] (4) Remove the solvent from the filtrate of step (3) by vacuum distillation to obtain the crude product containing fluorinated bisphosphonates ligand L2;

[0057] (5) The crude product of fluorinated bisphosphonates ligand L2 was purified by silica gel column chromatography to obtain a white solid product L2 (0.33 g, 32%).

[0058] Example 3:

[0059] The experiment was conducted using a 300 mL autoclave. First, rhodium dicarbonylacetylacetone (I) (0.0583 mmol, 15.04 mg), methylcyclopentadienylmanganese tricarbonyl (0.2915 mmol, 63.55 mg), fluorinated bisphosphonate ligand L1 (0.0583 mmol, 46.58 mg), and 100 mL of toluene were added sequentially to the autoclave, which was then sealed. The atmosphere inside the autoclave was then purged three times with nitrogen and a mixture of propylene, carbon monoxide, and hydrogen in a 1:1:1 molar ratio. The mixture was pressurized to 1.0 MPa (gauge pressure), heated to 60 °C, and the autoclave pressure was maintained at 1.0 MPa. Gas consumption was observed, and once no further gas consumption occurred, the autoclave was cooled and depressurized. The reaction solution was analyzed by gas chromatography, and the results are shown in Table 1.

[0060] Example 4:

[0061] The experiment was conducted using a 300 mL autoclave. First, rhodium dicarbonylacetylacetone (I) (0.0583 mmol, 15.04 mg), methylcyclopentadienylmanganese tricarbonyl (0.2915 mmol, 63.55 mg), fluorinated bisphosphonate ligand L1 (0.2332 mmol, 186.33 mg), and 100 mL of toluene were added sequentially to the autoclave, which was then sealed. The atmosphere inside the autoclave was then purged three times with nitrogen and a mixture of propylene, carbon monoxide, and hydrogen in a 1:1:1 molar ratio. The mixture was pressurized to 1.0 MPa (gauge pressure), heated to 80 °C, and the autoclave pressure was maintained at 1.0 MPa. Gas consumption was observed, and once no further gas consumption occurred, the autoclave was cooled and depressurized. The reaction solution was analyzed by gas chromatography, and the results are shown in Table 1.

[0062] Example 5:

[0063] The experiment was conducted using a 300 mL autoclave. First, rhodium dicarbonylacetylacetone (I) (0.0583 mmol, 15.04 mg), methylcyclopentadienylmanganese tricarbonyl (0.583 mmol, 127.09 mg), fluorinated bisphosphonate ligand L1 (0.2332 mmol, 186.33 mg), and 100 mL of toluene were added sequentially to the autoclave, which was then sealed. The atmosphere inside the autoclave was then purged three times with nitrogen and a mixture of propylene, carbon monoxide, and hydrogen in a 1:1:1 molar ratio. The mixture was pressurized to 2.5 MPa (gauge pressure), heated to 100 °C, and the autoclave pressure was maintained at 2.5 MPa. Gas consumption was observed, and once no further gas consumption occurred, the autoclave was cooled and depressurized. The reaction solution was analyzed by gas chromatography, and the results are shown in Table 1.

[0064] Example 6:

[0065] The experiment was conducted using a 300 mL autoclave. First, rhodium dicarbonylacetylacetone (I) (0.0583 mmol, 15.04 mg), methylcyclopentadienylmanganese tricarbonyl (1.166 mmol, 254.19 mg), fluorinated bisphosphonate ligand L1 (0.583 mmol, 465.82 mg), and 100 mL of toluene were added sequentially to the autoclave, which was then sealed. The atmosphere inside the autoclave was then purged three times with nitrogen and a mixture of propylene, carbon monoxide, and hydrogen in a 1:1:1 molar ratio. The mixture was pressurized to 5.0 MPa (gauge pressure), heated to 150 °C, and the autoclave pressure was maintained at 5.0 MPa. Gas consumption was observed, and once no further gas consumption occurred, the autoclave was cooled and depressurized. The reaction solution was analyzed by gas chromatography, and the results are shown in Table 1.

[0066] Example 7:

[0067] The experiment was conducted using a 300 mL autoclave. First, rhodium dicarbonylacetylacetone (I) (0.0583 mmol, 15.04 mg), methylcyclopentadienylmanganese tricarbonyl (0.583 mmol, 127.09 mg), fluorinated bisphosphonate ligand L1 (0.2332 mmol, 186.33 mg), and 100 mL of toluene were added sequentially to the autoclave, which was then sealed. The atmosphere inside the autoclave was then purged three times with nitrogen and a mixture of propylene, carbon monoxide, and hydrogen in a 1:1:1 molar ratio. The mixture was pressurized to 5.0 MPa (gauge pressure), heated to 150 °C, and the autoclave pressure was maintained at 5.0 MPa. Gas consumption was observed, and once no further gas consumption occurred, the autoclave was cooled and depressurized. The reaction solution was analyzed by gas chromatography, and the results are shown in Table 1.

[0068] Example 8:

[0069] The experiment was conducted using a 300 mL autoclave. First, rhodium dicarbonylacetylacetone (I) (0.0583 mmol, 15.04 mg), methylcyclopentadienylmanganese tricarbonyl (0.583 mmol, 127.09 mg), fluorinated bisphosphonate ligand L1 (0.2332 mmol, 186.33 mg), and 100 mL of toluene were added sequentially to the autoclave, which was then sealed. The atmosphere inside the autoclave was then purged three times with nitrogen and a mixture of propylene, carbon monoxide, and hydrogen in a 1:1:1 molar ratio. The mixture was pressurized to 2.5 MPa (gauge pressure), heated to 150 °C, and the autoclave pressure was maintained at 2.5 MPa. Gas consumption was observed, and once no further gas consumption occurred, the autoclave was cooled and depressurized. The reaction solution was analyzed by gas chromatography, and the results are shown in Table 1.

[0070] Example 9:

[0071] The experiment was conducted using a 300 mL autoclave. First, rhodium dicarbonylacetylacetone (I) (0.0583 mmol, 15.04 mg), methylcyclopentadienylmanganese tricarbonyl (0.583 mmol, 127.09 mg), fluorinated bisphosphonate ligand L2 (0.2332 mmol, 198.45 mg), and 100 mL of toluene were added sequentially to the autoclave, which was then sealed. The atmosphere inside the autoclave was then purged three times with nitrogen and a mixture of propylene, carbon monoxide, and hydrogen in a 1:1:1 molar ratio. The mixture was pressurized to 2.5 MPa (gauge pressure), heated to 150 °C, and the autoclave pressure was maintained at 2.5 MPa. Gas consumption was observed, and once no further gas consumption occurred, the autoclave was cooled and depressurized. The reaction solution was analyzed by gas chromatography, and the results are shown in Table 1.

[0072] Table 1

[0073]

[0074] As can be seen from Table 1, the catalytic system not only has good catalytic effect at a reaction temperature of 60℃, but also maintains a high conversion frequency and reaction conversion rate under high temperature conditions (temperatures exceeding 80℃), indicating that the catalyst system can still catalyze reactions efficiently under high temperature and high pressure, and the catalyst system has good high temperature stability.

[0075] Note: The bis(o-fluorophenyl)phosphorus chloride used in Examples 1-2 can be purchased directly or synthesized according to the article Ligand Synthesis (IP.com No.: IPCOM000177393D) published in the IP.com Prior Art Database. The structure of bis(o-fluorophenyl)phosphorus chloride is shown in the figure below.

[0076]

[0077] To verify the superiority of the technical solution of the embodiments of the present invention, comparative experiments were conducted, as shown in Comparative Examples 1-5.

[0078] First, to verify the necessity of introducing the second metal manganese (Mn), comparative examples 1-2 were set up, i.e., systems without the introduction of a second metal. By rigorously comparing these with examples 8-9 using the same ligand under the same reaction conditions, the aim was to establish a performance benchmark for single-metal catalytic systems and clarify whether the introduction of a second metal can significantly improve the time-to-flight (TOF) and reaction conversion rate.

[0079] Secondly, to verify the selection of a second metal, comparative examples 3-5 were set up, introducing other second metals such as cobalt (Co), nickel (Ni), and copper (Cu). By comparing the data with that of Example 8, the aim was to rule out the possibility that other transition metals would produce similar synergistic effects and to verify the advantages of manganese.

[0080] Comparative Example 1:

[0081] The experiment was conducted using a 300 mL autoclave. First, rhodium dicarbonyl acetylacetone (I) (0.0583 mmol, 15.04 mg), ligand L1 (0.2332 mmol, 186.33 mg), and 100 mL of toluene were added sequentially to the autoclave, which was then sealed. The atmosphere inside the autoclave was then purged three times with nitrogen and a mixture of propylene, carbon monoxide, and hydrogen in a 1:1:1 molar ratio. The mixture was pressurized to 2.5 MPa (gauge pressure), heated to 150 °C, and the autoclave pressure was maintained at 2.5 MPa. Gas consumption was observed, and once no further gas consumption occurred, the autoclave was cooled and depressurized. The reaction solution was analyzed by gas chromatography, and the results are shown in Table 2.

[0082] Comparative Example 2:

[0083] The experiment was conducted using a 300 mL autoclave. First, rhodium dicarbonyl acetylacetone (I) (0.0583 mmol, 15.04 mg), fluorinated bisphosphonates ligand L2 (0.2332 mmol, 198.45 mg), and 100 mL of toluene were added sequentially to the autoclave, which was then sealed. The atmosphere inside the autoclave was then purged three times with nitrogen and a mixture of propylene, carbon monoxide, and hydrogen in a 1:1:1 molar ratio. The mixture was pressurized to 2.5 MPa (gauge pressure), heated to 150 °C, and the autoclave pressure was maintained at 2.5 MPa. Gas consumption was observed, and once no further gas consumption occurred, the autoclave was cooled and depressurized. The reaction solution was analyzed by gas chromatography, and the results are shown in Table 2.

[0084] Comparative Example 3:

[0085] The experiment was conducted using a 300 mL autoclave. First, rhodium dicarbonylacetylacetone (I) (0.0583 mmol, 15.04 mg), cobalt octacarbonyl (0.2915 mmol, 99.69 mg), ligand L1 (0.2332 mmol, 186.33 mg), and 100 mL of toluene were added sequentially to the autoclave, which was then sealed. The atmosphere inside the autoclave was then purged three times with nitrogen and a mixture of propylene, carbon monoxide, and hydrogen in a 1:1:1 molar ratio. The mixture was pressurized to 2.5 MPa (gauge pressure), heated to 150 °C, and the autoclave pressure was maintained at 2.5 MPa. Gas consumption was observed, and once no further gas consumption occurred, the autoclave was cooled and depressurized. The reaction solution was analyzed by gas chromatography, and the results are shown in Table 2.

[0086] Comparative Example 4:

[0087] The experiment was conducted using a 300 mL autoclave. First, rhodium dicarbonyl acetylacetone (I) (0.0583 mmol, 15.04 mg), bis(1,5-cyclooctadiene) nickel (0.583 mmol, 160.33 mg), ligand L1 (0.2332 mmol, 186.33 mg), and 100 mL of toluene were added sequentially to the autoclave, and the vessel was sealed. Then, the atmosphere inside the autoclave was purged three times with nitrogen and a mixture of propylene, carbon monoxide, and hydrogen in a 1:1:1 molar ratio. The mixture was pressurized to 2.5 MPa (gauge pressure), and the temperature was raised to 150 °C. The pressure in the autoclave was maintained at 2.5 MPa, and gas consumption was observed. Once no further gas consumption occurred, the autoclave was cooled and depressurized. The reaction solution was analyzed by gas chromatography, and the results are shown in Table 2.

[0088] Comparative Example 5:

[0089] The experiment was conducted using a 300 mL autoclave. First, rhodium dicarbonyl acetylacetone (I) (0.0583 mmol, 15.04 mg), copper(II) dihydrate (0.583 mmol, 99.40 mg), ligand L1 (0.2332 mmol, 186.33 mg), and 100 mL of toluene were added sequentially to the autoclave, which was then sealed. The atmosphere inside the autoclave was then purged three times with nitrogen and a mixture of propylene, carbon monoxide, and hydrogen in a 1:1:1 molar ratio. The mixture was pressurized to 2.5 MPa (gauge pressure), heated to 150 °C, and the autoclave pressure was maintained at 2.5 MPa. Gas consumption was observed, and once no further gas consumption occurred, the autoclave was cooled and depressurized. The reaction solution was analyzed by gas chromatography, and the results are shown in Table 2.

[0090] Table 2

[0091]

[0092] Comparing the data from Comparative Examples 1-2 in Table 2 with the data from Examples 8-9 in Table 1, it can be seen that under the same reaction conditions and using the same ligand, the conversion frequency (TOF) and reaction conversion rate are significantly improved after the introduction of the second metal manganese. This demonstrates that the introduction of manganese (Mn) as the second metal enhances the catalytic performance.

[0093] Comparing the data from Comparative Examples 3-5 in Table 2 with the data from Example 8 in Table 1, under the same reaction conditions, the performance of the catalytic systems in Comparative Examples 3-5, which tested other second metals such as cobalt, nickel, and copper, was significantly inferior. Even the best-performing comparative example only achieved a TOF of 856.1 h⁻¹. -1 This clearly demonstrates that the introduction of manganese is crucial; compared to other secondary metals, manganese can produce a better synergistic catalytic effect with rhodium and ligands.

[0094] To verify the superiority of the ligand structure described in this invention, comparative examples 6-8 using ligands D1, D2, and D3 were provided. These comparative ligands have certain similarities or correlations with the ligands of this invention in structure, but key structural features differ. By applying them to the propylene hydroformylation reaction under the same reaction conditions and comparing them in parallel with the embodiments of this invention, it is intended to demonstrate that the ligands described in this invention are not equivalent replacements or simple extrapolations of structurally similar ligands, and that their structural design plays a decisive role in achieving high conversion frequency, high conversion rate, and high stability at high temperatures.

[0095] Comparative Example 6:

[0096] The experiment was conducted using a 300 mL autoclave. First, rhodium dicarbonylacetylacetonate (I) (0.0583 mmol, 15.04 mg), methylcyclopentadienylmanganese tricarbonyl (0.583 mmol, 127.09 mg), ligand D1 (0.2332 mmol, 183.47 mg), and 100 mL of toluene were added sequentially to the autoclave, which was then sealed. The atmosphere inside the autoclave was then purged three times with nitrogen and a mixture of propylene, carbon monoxide, and hydrogen in a 1:1:1 molar ratio. The mixture was pressurized to 2.5 MPa (gauge pressure), heated to 150 °C, and the autoclave pressure was maintained at 2.5 MPa. Gas consumption was observed, and once no further gas consumption occurred, the autoclave was cooled and depressurized. The reaction solution was analyzed by gas chromatography, and the results are shown in Table 3.

[0097] Comparative Example 7:

[0098] The experiment was conducted using a 300 mL autoclave. First, rhodium dicarbonylacetylacetonate (I) (0.0583 mmol, 15.04 mg), methylcyclopentadienylmanganese tricarbonyl (0.583 mmol, 127.09 mg), ligand D2 (0.2332 mmol, 195.65 mg), and 100 mL of toluene were added sequentially to the autoclave, and the vessel was sealed. Then, the atmosphere inside the autoclave was purged three times with nitrogen and a mixture of propylene, carbon monoxide, and hydrogen in a 1:1:1 molar ratio. The mixture was pressurized to 2.5 MPa (gauge pressure), and the temperature was raised to 150 °C. The pressure in the autoclave was maintained at 2.5 MPa, and gas consumption was observed. Once no further gas consumption occurred, the autoclave was cooled and depressurized. The reaction solution was analyzed by gas chromatography, and the results are shown in Table 3.

[0099] Comparative Example 8:

[0100] The experiment was conducted using a 300 mL autoclave. First, rhodium dicarbonylacetylacetonate (I) (0.0583 mmol, 15.04 mg), methylcyclopentadienylmanganese tricarbonyl (0.583 mmol, 127.09 mg), ligand D3 (0.2332 mmol, 272.09 mg), and 100 mL of toluene were added sequentially to the autoclave, which was then sealed. The atmosphere inside the autoclave was then purged three times with nitrogen and a mixture of propylene, carbon monoxide, and hydrogen in a 1:1:1 molar ratio. The mixture was pressurized to 2.5 MPa (gauge pressure), heated to 150 °C, and the autoclave pressure was maintained at 2.5 MPa. Gas consumption was observed, and once no further gas consumption occurred, the autoclave was cooled and depressurized. The reaction solution was analyzed by gas chromatography, and the results are shown in Table 3.

[0101] Table 3

[0102]

[0103] The comparison data between the examples in Table 1 and the comparative examples in Table 3 show that when using the ligands described in this invention for catalytic reactions, both the time-to-flight (TOF) and the reaction conversion rate are higher than those using ligands D1, D2, and D3 in the comparative examples. This comparison indicates that the ligands described in this invention can effectively stabilize the catalytic active center under high-temperature conditions, significantly suppress catalyst deactivation, maintain high regioselectivity, and exhibit high-temperature stability.

[0104]

[0105] For the preparation of ligands D1 and D2, please refer to the preparation method in patent CN1986055A. Ligand D3 is prepared according to the preparation method in patent CN1610688A.

[0106] Example 10:

[0107] The experiment was conducted using a 300 mL autoclave. First, rhodium dicarbonylacetylacetone (I) (0.068 mmol, 17.55 mg), methylcyclopentadienylmanganese tricarbonyl (0.34 mmol, 0.074 g), fluorinated bisphosphonate ligand L1 (0.34 mmol, 0.272 g), and 100 mL of toluene were added sequentially to the autoclave, which was then sealed. The atmosphere inside the autoclave was then purged three times with argon and a 1:1 molar ratio of carbon monoxide and hydrogen. Simultaneously, 1-butene and syngas were introduced in a 1:1 molar ratio, and the syngas pressure was increased to 1.5 MPa (gauge pressure). The temperature was raised to 120 °C, and the autoclave pressure was maintained at 1.5 MPa. Gas consumption was observed, and when no further gas consumption occurred, the autoclave was cooled and depressurized. The reaction solution was analyzed by gas chromatography, and the results are shown in Table 4.

[0108] Example 11:

[0109] The experiment was conducted using a 300 mL autoclave. First, rhodium dicarbonylacetylacetone (I) (0.126 mmol, 32.59 mg), methylcyclopentadienylmanganese tricarbonyl (0.63 mmol, 0.137 g), fluorinated bisphosphonate ligand L1 (0.63 mmol, 0.503 g), and 100 mL of toluene were added sequentially to the autoclave, which was then sealed. The atmosphere inside the autoclave was then purged three times with argon and a 1:1 molar ratio of carbon monoxide and hydrogen. Simultaneously, 1-butene and syngas were introduced in a 1:1 molar ratio, and the syngas pressure was increased to 1.5 MPa (gauge pressure). The temperature was raised to 120 °C, and the autoclave pressure was maintained at 1.5 MPa. Gas consumption was observed, and when no further gas consumption occurred, the autoclave was cooled and depressurized. The reaction solution was analyzed by gas chromatography, and the results are shown in Table 4.

[0110] Example 12:

[0111] The experiment was conducted using a 300 mL autoclave. First, rhodium dicarbonylacetylacetone (I) (0.185 mmol, 47.64 mg), methylcyclopentadienylmanganese tricarbonyl (0.925 mmol, 0.202 g), fluorinated bisphosphonate ligand L1 (0.925 mmol, 0.739 g), and 100 mL of toluene were added sequentially to the autoclave, which was then sealed. The atmosphere inside the autoclave was then purged three times with argon and a 1:1 molar ratio of carbon monoxide and hydrogen. Simultaneously, 1-butene and syngas were introduced in a 1:1 molar ratio, and the syngas pressure was increased to 1.5 MPa (gauge pressure). The temperature was raised to 120 °C, and the autoclave pressure was maintained at 1.5 MPa. Gas consumption was observed, and when no further gas consumption occurred, the autoclave was cooled and depressurized. The reaction solution was analyzed by gas chromatography, and the results are shown in Table 4.

[0112] Example 13:

[0113] The experiment was conducted using a 300 mL autoclave. First, rhodium dicarbonylacetylacetone (I) (0.243 mmol, 62.68 mg), methylcyclopentadienylmanganese tricarbonyl (1.215 mmol, 0.265 g), fluorinated bisphosphonates ligand L2 (1.215 mmol, 1.034 g), and 100 mL of n-pentanal were added sequentially to the autoclave, which was then sealed. The atmosphere inside the autoclave was then purged three times with argon and a 1:1 molar ratio of carbon monoxide and hydrogen. Simultaneously, 1-butene and syngas were introduced in a 1:1 molar ratio, and the syngas pressure was increased to 1.5 MPa (gauge pressure). The temperature was raised to 120 °C, and the autoclave pressure was maintained at 1.5 MPa. Gas consumption was observed, and when no further gas consumption occurred, the autoclave was cooled and depressurized. The reaction solution was analyzed by gas chromatography, and the results are shown in Table 4.

[0114] Table 4

[0115]

[0116] As can be seen from Table 4, under suitable reaction conditions, the catalyst system of the present invention is also applicable to the carbonyl synthesis of 1-butene and has good catalytic performance.

[0117] The catalytic system of this invention comprises: (a) a fluorinated bisphosphonite ligand Ln; and (b) a rhodium-manganese bimetallic synergistic system. This invention also relates to a method for preparing the fluorinated bisphosphonite ligand Ln and its complex with a metal. The catalytic system composed of the fluorinated bisphosphonite ligand Ln and the rhodium-manganese bimetallic compound of this invention can significantly enhance the stability of the olefin hydroformylation catalytic system under high-temperature reaction conditions, effectively extend the catalytic lifetime of the catalyst, and improve the catalyst recycling efficiency. This catalytic system possesses both excellent high-temperature stability and long service life, and has great application prospects and economic benefits in the industrial production of olefin hydroformylation.

[0118] The above embodiments are for illustrative purposes only and are not intended to limit the scope of protection of this invention. Any equivalent modifications, substitutions, or improvements made using the specification and related content of this invention, and any direct or indirect application of the design principles of the catalytic system described in this invention to other related technical fields, should be considered to be included within the patent protection scope of this invention. Specifically, although the embodiments of this invention use propylene and 1-butene as examples, their application is by no means limited to these. Those skilled in the art can reasonably infer that this catalytic system is universally applicable to the hydroformylation reactions of other aliphatic olefins, including but not limited to the examples described above, and all similar substitutions and modifications are obvious to those skilled in the art, and they are all considered to be included in the spirit, scope, and content of this invention.

Claims

1. A catalytic system for the hydroformylation of olefins, characterized in that, The catalytic system comprises: a fluorinated bisphosphonate ligand Ln and a rhodium-manganese bimetallic synergistic system; the general structural formula of the fluorinated bisphosphonate ligand Ln is: Where X is C6~C 32 Substituted or unsubstituted organic divalent bridged arylene units; the X molecule contains only two arylene units, which are directly connected by carbon-carbon single bonds; In the rhodium-manganese bimetallic synergistic system: the rhodium source is selected from one of rhodium oxide, tetrarhodium dodecylcarbonyl, hexadecylcarbonyl hexarhodium, trinitrorhodium, dipolyacetate rhodium, acetylacetone dicarbonyl rhodium, acetylacetone (1,5-cyclooctadiene) rhodium, or dichlorotetracarbonyl dirhodium; the manganese source is selected from one of decacarbonyl dimanganese, methylcyclopentadienyl tricarbonyl manganese, manganese acetate, or acetylacetone manganese.

2. The catalytic system for olefin hydroformylation as described in claim 1, characterized in that, X is C 22 ~C 28 The substituted organic divalent bridging aryl group.

3. The catalytic system for olefin hydroformylation as described in claim 2, characterized in that, The C mentioned 22 ~C 28 The substituted organic divalent bridged aryl group is 3,3'-bis-tert-butyl-5,5'-bis-methoxy-1,1”-biphenyl-2,2'-diyl and 3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl.

4. The catalytic system for olefin hydroformylation as described in claim 1, characterized in that, The molar ratio of fluorinated bisphosphonates ligand Ln to rhodium is 1 to 10:1; the molar ratio of manganese to rhodium is 5:1 to 20:

1.

5. The catalytic system for olefin hydroformylation as described in claim 1, characterized in that, The method for synthesizing the fluorinated bisphosphonate ligand Ln includes the following steps: (1) At room temperature, the tetrahydrofuran solution of organic divalent bridged aromatic phenols is added dropwise to the tetrahydrofuran solution of sodium hydride to carry out the reaction and obtain a mixed solution; (2) The bis(o-fluorophenyl)phosphorus chloride intermediate was added dropwise to the mixed solution obtained in step (1), and the reaction was continued to be stirred at room temperature to obtain the reaction mixture; (3) Under an inert atmosphere, the reaction mixture obtained in step (2) is filtered through diatomaceous earth to obtain the filtrate; (4) Remove the solvent from the filtrate of step (3) by vacuum distillation to obtain a crude product containing the fluorinated bisphosphonate ligand Ln; (5) The crude product of the fluorinated bisphosphonate ligand Ln obtained in step (4) is purified to obtain the purified fluorinated bisphosphonate ligand Ln.

6. The catalytic system for olefin hydroformylation as described in claim 5, characterized in that, The molar ratio of the raw material organic divalent bridged arylphenol: sodium hydride: intermediate bis(o-fluorophenyl)phosphorus chloride is 1: 2.2:

2.

7. A method for the hydroformylation reaction of olefins using the catalytic system of claim 1, characterized in that, A catalyst system containing rhodium-manganese bimetallic compounds and fluorinated bisphosphonates (Ln) is used to catalyze the reaction of hydrogen, carbon monoxide, and olefins to produce aldehydes. The reaction temperature is 60–150°C, the total gas pressure is 1–5 MPa, the molar ratio of hydrogen, carbon monoxide, and olefins is 1:1:1, and the reaction is carried out in a solvent capable of dissolving the catalyst and reactants.

8. The method for using the catalytic system of claim 7 for the hydroformylation reaction of olefins, characterized in that, The solvent is toluene, and the product aldehyde is an autosolvent.

9. A method for using the catalytic system of claim 7 for the hydroformylation reaction of olefins, characterized in that, The mass concentration of metallic rhodium in the solvent in the catalytic system is 60~250 ppm.

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