A supported salen ligand coordinated metal rh catalyst, its preparation method and application

Abstract

The application belongs to the technical field of supported catalysts, and discloses a supported Salen ligand coordinated metal Rh catalyst, a preparation method and application thereof.The supported Salen ligand coordinated metal Rh catalyst is formed by supporting a homogeneous Salen ligand coordinated metal Rh catalyst on a suitable porous carrier, and can realize efficient hydroformylation of long-chain alkenes, and exhibits high alkene conversion rate and selectivity of corresponding aldehydes.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of supported catalysts, in particular to a supported Salen ligand coordinated metal Rh catalyst, a preparation method and application thereof. BACKGROUND

[0002] The rapid development of hydroformylation technology is mainly driven by petroleum and coal chemical industry. Petroleum cracking produces a large amount of olefinic substances and a large amount of olefin raw materials through Fischer-Tropsch process, which provides an important material basis for the development of hydroformylation. Among them, the aldehyde prepared by hydroformylation reaction as a chemical intermediate can synthesize esters, carboxylic acids and fatty amines, etc., and its hydrogenation product alcohol can be widely used in fine chemical industry as a surfactant, plasticizer, etc., and has very broad application value.

[0003] Hydroformylation reaction is a green chemical process, which belongs to atom economic reaction and will not produce waste and harmful substances to the environment, has high selectivity, high catalyst activity and can realize recycling, etc. It is a representative of green process and is also an important development field of chemical industry at home and abroad. Hydroformylation reaction is a representative reaction of transition metal as active component of catalyst selectivity and activity. Because the reactivity of long-chain olefins is not as good as that of short-chain olefins, it is very meaningful to study the hydroformylation reaction of C6 and above long-chain olefins.

[0004] The activity of hydroformylation reaction depends largely on the selected catalyst. At present, the ligand of olefin hydroformylation catalyst is mainly phosphine ligand. Due to the influence of electronic and steric effect of phosphine ligand, the activity of olefin hydroformylation reaction is low and the selectivity is poor, and the preparation cost is high, which is not suitable for industrial large-scale application. The use of phosphorus compounds will also pollute the natural environment. The reaction conditions of homogeneous catalyst for olefin hydroformylation are mild, and the pressure and temperature requirements of the reaction are not high, which has the advantages of easy control, less side reaction, etc. However, homogeneous catalyst still has some shortcomings, such as complex molecular structure, difficult synthesis, poor thermal stability, large loss, difficult recovery and separation, etc., which limits its industrial application. In order to realize the efficient hydroformylation of long-chain olefins, suitable ligand should be selected to construct efficient catalyst for olefin hydroformylation. Compared with homogeneous catalyst, heterogeneous catalyst has lower selectivity and activity, but it has the advantages of convenient preparation process and easy separation from solvent. The supported catalyst not only has high catalytic activity, but also the active component is not easy to be inactivated, and the catalyst after reaction is easy to separate and recycle. SUMMARY

[0005] The present application aims to overcome the deficiencies of the prior art and provide a supported Salen ligand coordinated metal Rh catalyst, a preparation method and application thereof.

[0006] To achieve the above-mentioned object, the technical scheme adopted by the present application is as follows:

[0007] In a first aspect, the present application provides a supported Salen ligand coordinated metal Rh catalyst, comprising a porous carrier and a compound represented by formula (2);

[0008]

[0009] In the formula, the dotted line is a coordination bond; R1 is selected from any one of a hydrogen atom, a linear alkyl group, a branched alkyl group, a heteroalkyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a substituted aryl group and a derivative group thereof; R2 and R3 are selected from any one of a hydrogen atom, a linear alkyl group, a branched alkyl group, a heteroalkyl group, a cycloalkyl group, a heterocycloalkyl group, a hydroxyl group, an aryl group, a substituted aryl group and a derivative group thereof; M is a bridging group, preferably selected from any one of a carbon-hydrogen group, an imine group containing N atoms, a carbon group containing at least one heteroatom, and a carbon-hydrogen group containing at least one heteroatom.

[0010] The supported Salen ligand coordinated metal Rh catalyst of the present application is formed by immobilizing a homogeneous Salen ligand coordinated metal Rh catalyst on a suitable porous carrier, and can realize efficient hydroformylation of long-chain alkenes, showing high olefin conversion rate and selectivity for generating corresponding aldehydes.

[0011] As a preferred embodiment of the supported Salen ligand coordinated metal Rh catalyst of the present application, the supported Salen ligand coordinated metal Rh catalyst further comprises an auxiliary agent, which is an alkaline substance; preferably, the auxiliary agent is selected from at least one of a group IIA metal hydroxide, a group IIA metal amine-based compound, an inorganic carbonate, a metal salt of an organic phenol, a metal salt of an organic alcohol, and a metal salt of an organic carboxylic acid;

[0012] The porous carrier is selected from at least one of silica, alumina, diatomite, titanium oxide, zirconium oxide, cerium oxide, molybdenum oxide, tungsten oxide, magnesium oxide, zinc oxide, vanadium oxide, activated carbon, activated clay, montmorillonite, molecular sieve, cyclodextrin, polyethylene, polystyrene, polyvinyl alcohol, mesoporous silica gel fiber, metal organic framework, and covalent organic framework;

[0013] The mass ratio of the porous carrier to the compound represented by formula (2) is (1000-10):1, calculated based on the metal Rh; and the molar ratio of the auxiliary agent to the compound represented by formula (2) is (0.8-1.2):1.

[0014] In a second aspect, the application provides a preparation method of the supported Salen ligand coordinated metal Rh catalyst, comprising the following steps:

[0015] The compound shown in the formula (2) and an auxiliary agent are mixed and dispersed in a solvent under an inert atmosphere; the porous carrier is added for supporting; and the solvent is removed, thereby obtaining the supported Salen ligand coordinated metal Rh catalyst.

[0016] The preparation process of the supported catalyst is simple, the use of phosphorus ligands which are high in cost and easy to cause pollution is avoided, the active components in the supported catalyst are not easy to be lost and deactivated, and the supported catalyst can be simply and effectively separated after the reaction is completed and recycled.

[0017] As a preferred embodiment of the preparation method, the porous carrier is subjected to a calcination treatment before the addition; the calcination temperature is 100-600 DEG C, and the time is 0.5-15 h; the supporting mode is at least one selected from impregnation, stirring and stirring reflux; the reaction temperature of the supporting is 30-150 DEG C, and the reaction time is 1-10 h.

[0018] As a preferred embodiment of the preparation method, the mass ratio of the porous carrier to the compound shown in the formula (2) is (1000-10):1, preferably (200-50):1, based on the metal Rh; the solvent is an organic solvent, preferably at least one selected from cyclohexane, benzene, toluene, diethyl ether and tetrahydrofuran; and the molar ratio of the auxiliary agent to the compound shown in the formula (2) is (0.8-1.2):1.

[0019] As a preferred embodiment of the preparation method, the compound shown in the formula (2) is obtained by reacting a Salen ligand and a rhodium carbonyl compound under an inert atmosphere.

[0020] The structural formula of the Salen ligand is shown in the formula (1):

[0021]

[0022] In the formula, R1 is selected from any one of a hydrogen atom, a linear alkyl group, a branched alkyl group, a heteroalkyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a substituted aryl group and a derivative group thereof; R2 and R3 are selected from any one of a hydrogen atom, a linear alkyl group, a branched alkyl group, a heteroalkyl group, a cycloalkyl group, a heterocycloalkyl group, a hydroxyl group, an aryl group, a substituted aryl group and a derivative group thereof; and M is a bridging group, preferably any one of a carbon hydrogen group, an imine group containing N atoms, a carbon group containing at least one heteroatom and a carbon hydrogen group containing at least one heteroatom.

[0023] As a preferred embodiment of the preparation method of the present application, the carbonyl rhodium compound is at least one selected from [Rh(CO)2Cl]2, ([Rh(CO)2(acac)]2 and dicarbonyl (pentamethylcyclopentadienyl) rhodium; the reaction is carried out in an organic solvent, which is at least one of cyclohexane, benzene, toluene; the reaction temperature is 10-120℃, and the reaction time is 6-18h; the molar ratio of the Salen ligand and the carbonyl rhodium compound, calculated based on the metal Rh, is (0.8-1.2):1.

[0024] In a third aspect, the present application applies the supported Salen ligand coordinated metal Rh catalyst in olefin hydroformylation reaction.

[0025] As a preferred embodiment of the application of the present application, the olefin is at least one selected from C6-C8 linear olefin or branched olefin.

[0026] As a preferred embodiment of the application of the present application, the reaction method is as follows: the supported Salen ligand coordinated metal Rh catalyst is added to a high-pressure reaction kettle, the olefin is added, and the synthesis gas is added; the reaction is carried out under stirring, after the reaction is completed, the pressure is released, the kettle is opened, and the liquid product is extracted and treated for detection and analysis by gas chromatography.

[0027] The molar ratio of the supported Salen ligand coordinated metal Rh catalyst and the olefin, calculated based on the metal Rh, is 1:(50-2000), preferably 1:(100-1000); the synthesis gas is CO and H2 in a molar ratio of 1:(1-1.1); the reaction pressure is 0.2-8MPa, preferably 0.5-6MPa, the temperature is 30-180℃, preferably 60-120℃, the time is 1-24h, preferably 3-18h; the stirring rate is 200-1000rpm, preferably 500-800rpm.

[0028] Compared with the prior art, the present application has the following beneficial effects:

[0029] The present application first synthesizes a metal Rh catalyst coordinated with a Salen ligand, then immobilizes the catalyst with an alkaline substance on a porous carrier to form a supported metal Rh catalyst coordinated with a Salen ligand, and finally uses the supported catalyst for the hydroformylation of olefins. The supported metal Rh catalyst coordinated with a Salen ligand prepared by the present application is formed by immobilizing a homogeneous metal Rh catalyst coordinated with a Salen ligand on a suitable porous carrier, and can realize efficient hydroformylation of long-chain olefins, showing high olefin conversion rate and selectivity for the formation of corresponding aldehydes. Meanwhile, the preparation process of the supported catalyst proposed by the present application is simple, avoids the use of phosphorus ligands which are high in cost and easy to pollute, the active components in the supported catalyst are not easy to be lost and deactivated, and the supported catalyst can be simply and effectively separated after the reaction is completed and recycled. DETAILED DESCRIPTION

[0030] To better illustrate the purposes, technical solutions and advantages of the present application, the present application will be further described below in combination with specific examples. Those skilled in the art should understand that the specific examples described herein are only used to explain the present application, and are not used to limit the present application.

[0031] The reaction method used in the examples is a conventional method unless otherwise specified; the materials, reagents, etc. used are commercially available unless otherwise specified. The inert atmosphere can be at least one of nitrogen, argon and helium, and argon is used as the inert atmosphere in the following examples.

[0032] Example 1

[0033] Under an inert atmosphere, equimolar amounts of a Salen ligand as shown in formula (3) and a rhodium carbonyl compound [Rh(CO)2Cl]2 (calculated as metal Rh) were dispersed in toluene solvent in a Schlenk flask, and the above solution was stirred at room temperature for 10 h. After the reaction was completed, the solvent toluene was removed under reduced pressure to obtain a compound as shown in formula (4), denoted as Rh-A. Under an inert atmosphere, the prepared Rh-A (2 mmol) and KOH (2 mmol) were dispersed in toluene (100 mL), 100 g of activated carbon calcined in a muffle furnace at 100°C for 1 h was added, and the above mixture was continuously stirred at 60°C in an oil bath for 2 h, then filtered, and the solid was washed with toluene, and dried to obtain a supported catalyst S-A.

[0034]

[0035] Example 2

[0036] Under inert atmosphere, equimolar amount of Salen ligand as shown in formula (5) and rhodium carbonyl compound [Rh(CO)2Cl]2 (in terms of metal Rh) were dispersed in toluene solvent in a Schlenk flask, the above solution was stirred at room temperature for 10 h. After the reaction was completed, the solvent toluene was removed under reduced pressure, to obtain a compound as shown in formula (6), denoted as Rh-B. Under inert atmosphere, prepared Rh-B (2 mmol) and KOH (2 mmol) were dispersed in toluene (100 mL), 100 g of activated carbon calcined at 100 °C in a muffle furnace for 1 h was added, the above mixture was continuously stirred at 60 °C oil bath reflux for 2 h, then filtered, and the solid was washed with toluene, and dried to obtain a supported catalyst S-B.

[0037]

[0038] Example 3

[0039] Under inert atmosphere, equimolar amount of Salen ligand as shown in formula (7) and rhodium carbonyl compound [Rh(CO)2Cl]2 (in terms of metal Rh) were dispersed in toluene solvent in a Schlenk flask, the above solution was stirred at room temperature for 10 h. After the reaction was completed, the solvent toluene was removed under reduced pressure, to obtain a compound as shown in formula (8), denoted as Rh-C. Under inert atmosphere, prepared Rh-C (2 mmol) and KOH (2 mmol) were dispersed in toluene (100 mL), 100 g of activated carbon calcined at 100 °C in a muffle furnace for 1 h was added, the above mixture was continuously stirred at 60 °C oil bath reflux for 2 h, then filtered, and the solid was washed with toluene, and dried to obtain a supported catalyst S-C.

[0040]

[0041]

[0042] Example 4

[0043] Under inert atmosphere, equimolar amounts of Salen ligand (2-OH-3,5-iPr2C6H2)CH=NC6H4N=CH(2-OH-3,5-iPr2C6H2) and rhodium carbonyl compound [Rh(CO)2Cl]2 (in terms of metal Rh) were dispersed in toluene solvent in a Schlenk flask, and the solution was stirred at room temperature for 10 h. After the reaction was completed, the solvent toluene was removed under reduced pressure to obtain compound [(2-O-3,5-iPr2C6H2)CH=NC6H4N=CH(2-O-3,5-iPr2C6H2)]Rh(CO), denoted as Rh-D. Under inert atmosphere, prepared Rh-D (2 mmol) and KOH (2 mmol) were dispersed in toluene (100 mL), and 100 g of activated carbon calcined at 100 °C in a muffle furnace for 1 h was added. The mixture was continuously stirred at 60 °C in an oil bath for 2 h under reflux, then filtered, and the solid was washed with toluene, and dried to obtain the supported catalyst S-D.

[0044] Example 5

[0045] Under inert atmosphere, equimolar amounts of Salen ligand (2-OH-3,5-iPr2C6H2)CH=NC6H4N=CH(2-OH-3,5-iPr2C6H2) and rhodium carbonyl compound [Rh(CO)2Cl]2 (in terms of metal Rh) were dispersed in toluene solvent in a Schlenk flask, and the solution was stirred at room temperature for 10 h. After the reaction was completed, the solvent toluene was removed under reduced pressure to obtain compound [(2-O-3,5-iPr2C6H2)CH=NC6H4N=CH(2-O-3,5-iPr2C6H2)]Rh(CO), denoted as Rh-D. Under inert atmosphere, prepared Rh-D (2 mmol) and KOH (2 mmol) were dispersed in toluene (100 mL), and 100 g of activated carbon calcined at 100 °C in a muffle furnace for 1 h was added. The mixture was continuously stirred at 60 °C in an oil bath for 2 h under reflux, then filtered, and the solid was washed with toluene, and dried to obtain the supported catalyst S-D.

[0046] Example 6

[0047] Under inert atmosphere, equimolar amount of Salen ligand (2-OH-3-tBu2C6H2)CH=N-cyclo-C6H4and carbonyl rhodium compound [Rh(CO)2Cl]2(metal Rh basis) were dispersed in toluene solvent in a Schlenk flask, the above solution was stirred at room temperature for 10 h. After the reaction was completed, the solvent toluene was removed under reduced pressure, to obtain compound [(2-O-3-tBu2C6H2)CH=N-cyclo-C6H4]Rh(CO), noted as Rh-G. Under inert atmosphere, prepared Rh-G (2 mmol) and KOH (2 mmol) were dispersed in toluene (100 mL), 100 g of activated carbon calcined at 100 °C in a muffle for 1 h was added, the above mixture was continuously stirred at reflux at 60 °C oil bath for 2 h, then filtered, and the solid was washed with toluene, and dried to obtain supported catalyst S-G.

[0048]

[0049] Example 7

[0050] Under inert atmosphere, equimolar amount of Salen ligand (2-OH-3-tBu2C6H2)CH=N-cyclo-C6H 10 -N=CH(2-OH-3-tBu2C6H2) and carbonyl rhodium compound [Rh(CO)2Cl]2(metal Rh basis) were dispersed in toluene solvent in a Schlenk flask, the above solution was stirred at room temperature for 10 h. After the reaction was completed, the solvent toluene was removed under reduced pressure, to obtain compound [(2-O-3-tBu2C6H2)CH=N-cyclo-C6H 10 -N=CH(2-O-3-tBu2C6H2)]Rh(CO), noted as Rh-G. Under inert atmosphere, prepared Rh-G (2 mmol) and KOH (2 mmol) were dispersed in toluene (100 mL), 100 g of activated carbon calcined at 100 °C in a muffle for 1 h was added, the above mixture was continuously stirred at reflux at 60 °C oil bath for 2 h, then filtered, and the solid was washed with toluene, and dried to obtain supported catalyst S-G.

[0051] Example 8

[0052] Under inert atmosphere, equimolar amount of Salen ligand (2-OH-3-tBu2C6H2)CH=N-cyclo-C6H 10 -N=CH(2-OH-3-tBu2C6H2) and carbonyl rhodium compound [Rh(CO)2Cl]2(metal Rh basis) were dispersed in toluene solvent in a Schlenk flask, the above solution was stirred at room temperature for 10 h. After the reaction was completed, the solvent toluene was removed under reduced pressure, to obtain compound [(2-O-3-tBu2C6H2)CH=N-cyclo-C6H 10- N = C(CH3)(2-O-3-tBuC6H3)]Rh(CO), denoted as Rh-H. Under inert atmosphere, prepared Rh-H (2 mmol) was dispersed with KOH (2 mmol) in toluene (100 mL), and activated carbon (100 g) calcined at 100 °C in a muffle for 1 h was added. The mixture was stirred at reflux at 60 °C for 2 h in an oil bath, then filtered, and the solid was washed with toluene. The supported catalyst S-H was obtained after drying.

[0053] Example 9

[0054] Under inert atmosphere, equimolar amounts of the Salen ligand (2-OH-3,5-tBu2C6H2)CH=NC6H4N=CH(2-OH-3,5-tBu2C6H2) and the rhodium carbonyl compound [Rh(CO)2Cl]2 (in terms of the metal Rh) were dispersed in toluene in a Schlenk flask, and the solution was stirred at room temperature for 10 h. Once the reaction was complete, the solvent toluene was removed under reduced pressure, obtaining the compound [(2-O-3,5-tBu2C6H2)CH=NC6H4N=CH(2-O-3,5-tBu2C6H2)]Rh(CO), denoted as Rh-I. Under inert atmosphere, prepared Rh-I (2 mmol) was dispersed with KOH (2 mmol) in toluene (100 mL), and silica (100 g) calcined at 100 °C in a muffle for 1 h was added. The mixture was stirred at reflux at 60 °C for 2 h in an oil bath, then filtered, and the solid was washed with toluene. The supported catalyst S-I was obtained after drying.

[0055] Example 10

[0056] Under inert atmosphere, equimolar amounts of the Salen ligand (2-OH-3,5-tBu2C6H2)CH=NC6H4N=CH(2-OH-3,5-tBu2C6H2) and the rhodium carbonyl compound [Rh(CO)2Cl]2 (in terms of the metal Rh) were dispersed in toluene in a Schlenk flask, and the solution was stirred at room temperature for 10 h. Once the reaction was complete, the solvent toluene was removed under reduced pressure, obtaining the compound [(2-O-3,5-tBu2C6H2)CH=NC6H4N=CH(2-O-3,5-tBu2C6H2)]Rh(CO), denoted as Rh-J. Under inert atmosphere, prepared Rh-J (2 mmol) was dispersed with KOH (2 mmol) in toluene (100 mL), and alumina (100 g) calcined at 100 °C in a muffle for 1 h was added. The mixture was stirred at reflux at 60 °C for 2 h in an oil bath, then filtered, and the solid was washed with toluene. The supported catalyst S-J was obtained after drying.

[0057] Example 11

[0058] Under inert atmosphere, equimolar amount of Salen ligand (2-OH-3,5-tBu2C6H2)CH=NC6H4N=CH(2-OH-3,5-tBu2C6H2) and rhodium carbonyl compound [Rh(CO)2Cl]2 (1 mmol in terms of metal Rh) were dispersed in toluene solvent in a Schlenk flask, the above solution was stirred at room temperature for 10 h. After the reaction was completed, the solvent toluene was removed under reduced pressure, to obtain compound [(2-O-3,5-tBu2C6H2)CH=NC6H4N=CH(2-O-3,5-tBu2C6H2)]Rh(CO), noted as Rh-K. Under inert atmosphere, prepared Rh-K (2 mmol) and KOH (2 mmol) were dispersed in toluene (100 mL), added MCM-41 molecular sieve 100 g which was calcined at 100 °C in a muffle furnace for 1 h, the above mixture was continuously stirred at 60 °C oil bath reflux for 2 h, then filtered, and the solid was washed with toluene, and dried to obtain supported catalyst S-K.

[0059] Comparative Example 1

[0060] Under inert atmosphere, equimolar amount of Salen ligand (2-OH-3,5-tBu2C6H2)CH=NC6H4N=CH(2-OH-3,5-tBu2C6H2) and rhodium carbonyl compound [Rh(CO)2Cl]2 (1 mmol in terms of metal Rh) were dispersed in toluene solvent in a Schlenk flask, the above solution was stirred at room temperature for 10 h. After the reaction was completed, the solvent toluene was removed under reduced pressure, to obtain compound [(2-O-3,5-tBu2C6H2)CH=NC6H4N=CH(2-O-3,5-tBu2C6H2)]Rh(CO), noted as Rh-X. Under inert atmosphere, prepared Rh-X (2 mmol) was dispersed in toluene (100 mL), added activated carbon 100 g which was calcined at 100 °C in a muffle furnace for 1 h, the above mixture was continuously stirred at 60 °C oil bath reflux for 2 h, then filtered, and the solid was washed with toluene, and dried to obtain supported catalyst S-X.

[0061] Comparative Example 2

[0062] Under inert atmosphere, rhodium carbonyl compound [Rh(CO)2Cl]2 (1 mmol) and KOH (2 mmol) were dispersed in toluene (100 mL), added activated carbon 100 g which was calcined at 100 °C in a muffle furnace for 1 h, the above mixture was continuously stirred at 60 °C oil bath reflux for 2 h, then filtered, and the solid was washed with toluene, and dried to obtain supported catalyst S-Y.

[0063] Application Example

[0064] The supported catalysts prepared in Examples 1-11 and Comparative Examples 1-2 were used in the hydroformylation of olefins, wherein the olefins were at least one of C6-C8 linear olefins or branched olefins. The prepared supported catalysts were added to a high-pressure reaction kettle, and hexene or octene was added, wherein the molar ratio of the supported catalyst (calculated as Rh metal) to the olefins was 1:500, and a synthesis gas with a molar ratio of 1:1 of CO and H2 was added, and the pressure was 4 MPa, and then the reaction was carried out under stirring at a stirring rate of 600 rpm, the reaction temperature was 90°C, and the reaction time was 8 h. After the reaction was completed, the reaction kettle was cooled, depressurized, and opened, and the liquid phase product was extracted, treated, and then analyzed by gas chromatography. The performance results of the hydroformylation of olefins using different supported catalysts are shown in Table 1.

[0065] Table 1 Performance of different supported catalysts in the hydroformylation of olefins

[0066]

[0067] According to the performance of different supported catalysts in the hydroformylation of olefins in Table 1, it can be found that the conversion rate of the olefins in the hydroformylation of olefins using the supported catalysts prepared in Examples 1-11 is basically above 90%, and the selectivity of the aldehyde products is also basically above 90%. Among them, the conversion rate of the supported catalyst S-F prepared in Example 6 in the hydroformylation of octene reached 95.9%, and the selectivity of the aldehyde products reached 95.3%; the conversion rate and the selectivity of the aldehyde products of the supported catalyst S-C prepared in Example 3 in the hydroformylation of hexene reached 96.1% and 95.5%, respectively. The above test results show that the supported Salen ligand coordinated metal Rh catalyst prepared in the present application can realize the efficient hydroformylation of long-chain olefins, and has high conversion rate and selectivity of the corresponding aldehyde products. Through further comparison with the comparative examples, it can be found that the Salen ligand coordinated metal Rh catalyst is the main catalytically active component, and the presence of the alkaline adjuvant can significantly improve the efficiency of the hydroformylation of olefins.

[0068] The present application immobilizes the high-activity Salen ligand coordinated metal Rh catalyst on a porous carrier to obtain a supported catalyst, and the preparation process is simple, which not only avoids the use of high-priced phosphine ligands and the pollution to the environment, but also realizes the simple and effective separation and reuse of the supported catalyst after the reaction is completed, and the supported catalyst used in the hydroformylation of long-chain olefins shows high activity.

[0069] Finally, it should be noted that the above examples are merely intended to illustrate the technical solutions of the present application and not to limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or equivalently replaced without departing from the essence and scope of the technical solutions of the present application.

Claims

1. Use of a supported Salen ligand-coordinated metal Rh catalyst in an olefin hydroformylation reaction, characterized in that, The supported Salen ligand coordinated metal Rh catalyst comprises a porous carrier and a compound shown in formula (2); Formula (2) In the formula, the dotted line is a coordination bond; R1 is selected from any one of a hydrogen atom, a linear alkyl, a branched alkyl, a heteroalkyl, a cycloalkyl, a heterocycloalkyl, an aryl, a substituted aryl and a derivative thereof; R2 and R3 are selected from any one of a hydrogen atom, a linear alkyl, a branched alkyl, a heteroalkyl, a cycloalkyl, a heterocycloalkyl, a hydroxyl, an aryl, a substituted aryl and a derivative thereof; and M is a bridging group selected from any one of a carbon-hydrogen group, an imine group containing N atoms, a carbon group containing at least one heteroatom, and a carbon-hydrogen group containing at least one heteroatom.

2. Use according to claim 1, characterized in that, The supported Salen ligand coordinated metal Rh catalyst further comprises an auxiliary agent which is an alkaline substance; and the porous carrier is selected from at least one of silica, alumina, diatomite, titanium oxide, zirconium oxide, cerium oxide, molybdenum oxide, tungsten oxide, magnesium oxide, zinc oxide, vanadium oxide, activated carbon, activated clay, montmorillonite, molecular sieve, cyclodextrin, polyethylene, polystyrene, polyvinyl alcohol, mesoporous silica gel fiber, metal organic framework, and covalent organic framework. The mass ratio of the porous carrier to the compound shown in formula (2) is (1000-10):1, and the molar ratio of the auxiliary agent to the compound shown in formula (2) is (0.8-1.2):1, both based on the metal Rh.

3. Use according to claim 1, characterized in that, The olefin is selected from at least one of C6-C8 linear olefin or branched olefin.

4. Use according to claim 1, characterized in that, The method of the reaction is: the supported Salen ligand coordinated metal Rh catalyst is added to a high-pressure reaction kettle, the olefin is added, and synthesis gas is added; the reaction is carried out under stirring, after the reaction is completed, the pressure is released and the kettle is opened, and the liquid product is extracted, treated and detected and analyzed by gas chromatography; The molar ratio of the supported Salen ligand coordinated metal Rh catalyst to the olefin is 1:(50-2000) based on the metal Rh; the synthesis gas is CO and H2 in a molar ratio of 1:(1-1.1); the reaction pressure is 0.2 MPa-8 MPa, the temperature is 30°C-180°C, and the time is 1 h-24 h; and the stirring rate is 200 rpm-1000 rpm.

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