Organic ion polymer carrier-supported Rh-X catalyst and preparation method and application thereof

Abstract

The present invention provides an organic ion polymer carrier-supported Rh-X catalyst and its preparation method and application, the Rh-X bimetallic catalyst includes an active component and a carrier, the active component is two components, component 1 is a Rh metal complex, component 2 is an X metal complex, X is one of Cr, Fe, and Ni, and the carrier is an ion polymer carrier; wherein Rh accounts for 0.01 to 5.0 wt% of the total mass of the catalyst, and X accounts for 0.01 to 5.0 wt% of the total mass of the catalyst; the ion polymer carrier is a polymer formed by polymerization of organic salt monomers containing a variety of vinyl groups including N or P, and the organic salt monomer is one or more of vinyl monomers containing imidazole salts, quaternary ammonium salts, and quaternary phosphonium salts, and / or divinylbenzene is used as a cross-linking agent. In a kettle reactor, under a certain temperature and pressure and the action of the Rh-X catalyst described in the present application, olefins and organic amines (including aromatic amines) are used as substrates, and under the action of CO, they can be converted into amide compounds with high activity and high selectivity.

Description

Technical Field

[0001] The invention belongs to the technical field of heterogeneous catalytic carbonylation, and particularly relates to an organic ion polymer carrier-supported Rh-X catalyst, a preparation method and an application thereof. Background Art

[0002] Amides are important organic intermediates in the chemical industry, possessing significant value in organic synthesis and life sciences. Therefore, efficient and highly selective construction of amide bonds is a key technology. In addition to the traditional condensation of carboxylic acids and amines, scientists have recently developed a one-step process for preparing amides using olefins as substrates instead of carboxylic acids, hydroamidating them with amines in the presence of CO.

[0003] Traditional hydroamidation techniques primarily rely on homogeneous Pd-catalyzed systems. In 2013, Beller et al. reported the palladium-catalyzed carbonylation of olefins with (hetero)aromatic amines to produce amides. The reaction exhibited high regioselectivity, high yields, and a broad substrate range, but was not suitable for aliphatic amines. Cole-Hamilton further improved the yields of amides by introducing 2-naphthol and sodium or potassium iodide. In 2014, Beller et al. reported the first hydroamidation of 1,3-butadiene compounds. The palladium-catalyzed reaction of 1,3-butadiene compounds with aromatic amines produced β,γ-unsaturated amides with high selectivity. However, this reaction was also unsuitable for aliphatic amines. It is generally believed that the strong basicity of amines hinders the formation of Pd-H bonds, thereby preventing the reaction from proceeding. Therefore, aromatic amines, due to their weaker basicity compared to aliphatic amines, are more susceptible to the corresponding amides. Therefore, Beller developed a Rh-based homogeneous catalyst for the low-hydrogen amidation activity of aliphatic amines, which is common in Pd systems. He found that using RhCl3 as a catalyst in the presence of CO can not only activate aromatic amines but also effectively activate aliphatic amines, thus obtaining aliphatic amide compounds with high selectivity. (Rh计算) ≈5h -1 .

[0004] At present, the research on hydroamidation is still at the basic research stage, and the following problems still exist: (1) Most of the reported systems are homogeneous systems, which make it difficult to separate and recover the catalyst and industrialize it; (2) Although the homogeneous system of Rh has solved the problem of the inability of aliphatic amines to undergo hydroacylation, its activity is too low and still needs to be further improved.

[0005] Therefore, how to heterogeneously immobilize Rh species, stably reduce separation costs and improve the activity of hydroacylation becomes a key technical challenge. Summary of the Invention

[0006] To address the problems existing in the prior art, the present invention provides an organic ionomer-supported Rh-X catalyst, its preparation method, and application. The Rh-X bimetallic catalyst comprises an active component and an ionomer support. The ionomer support is prepared by self-polymerization of organic salts containing various vinyl groups, such as N or P, using a solvothermal polymerization method or copolymerization with a crosslinker, divinylbenzene, followed by an initiator-induced polymerization reaction. This large-surface, multi-level porous organic ionomer serves as a carrier for the supported metal catalyst to support the active metal component. Furthermore, due to ionic bonding between the metal component and the cationic backbone salt in the ionomer, the Rh and X metal components are highly dispersed within the polymer support. In a tank reactor, under a certain temperature and pressure, and in the presence of the catalyst, olefins and organic amines (including aromatic amines) can be converted into amide compounds with high activity and selectivity under the action of CO.

[0007] The purpose of the present invention is achieved through the following technical solutions:

[0008] The first aspect of the present invention provides a Rh-X catalyst supported by an organic ion polymer carrier, wherein the Rh-X bimetallic catalyst comprises an active component and a carrier, wherein the active component is two components, component 1 is a Rh metal complex, component 2 is an X metal complex, X is one of Cr, Fe, and Ni, and the carrier is an ion polymer carrier;

[0009] Wherein, Rh accounts for 0.01 to 5.0 wt% of the total mass of the catalyst, preferably 0.1 to 4.0 wt% of the total mass of the catalyst; X accounts for 0.01 to 5.0 wt% of the total mass of the catalyst, preferably 0.1 to 4.0 wt% of the total mass of the catalyst; the ion polymer carrier is a polymer formed by polymerization of organic salt monomers containing multiple vinyl groups including N or P, the organic salt monomers are one or more vinyl monomers containing imidazole salts, quaternary ammonium salts, and quaternary phosphonium salts, and / or divinylbenzene is used as a cross-linking agent.

[0010] Furthermore, the ionomer comprises a multi-level pore structure of macropores, mesopores and micropores, wherein the proportions of macropores, mesopores and micropores of the ionomer are 5% to 20%, 40% to 70%, and 10% to 55% respectively, and the pore volume is 0.1 to 5.0 cm 3 / g, pore size distribution is 0.2~50.0nm, specific surface area is 100~3000m 2 / g.

[0011] Furthermore, the preparation method of the ionic polymer carrier comprises the following steps:

[0012] a) adding a free radical initiator to an organic solvent containing an organic salt monomer and / or divinylbenzene at 273-473 K under an inert gas atmosphere, wherein the weight ratio of the salt monomer to the free radical initiator is 5:1-100:1; and the weight ratio of divinylbenzene to the salt monomer is 0:1-5:1; and stirring the resulting mixture solution for 1-100 hours;

[0013] b) transferring the mixture solution in step a) to a hydrothermal reactor at 273-473 K under an inert gas atmosphere, and allowing it to stand for 1-100 hours under solvent thermal polymerization conditions at 373-523 K to carry out a polymerization reaction;

[0014] c) removing the solvent from the reaction mixture obtained in step b) under vacuum at room temperature, thereby obtaining an organic ion polymer carrier having a large surface area and a multi-level pore structure.

[0015] Furthermore, the organic solvent used in step a) is selected from one or more of ethanol, N,N-dimethylformamide and N-methylpyrrolidone; and the free radical initiator is selected from one of azobisisobutyronitrile and azobisisoheptanenitrile.

[0016] Furthermore, in step a), the organic salt monomer is one or more of the following structures AF;

[0017]

[0018] The second aspect of the present invention provides a method for preparing the organic ion polymer carrier-supported Rh-X catalyst, comprising the following steps:

[0019] a) adding an ionomer carrier to an organic solvent containing a Rh precursor and an X precursor at 273-473 K under an inert gas atmosphere, wherein the weight ratio of the Rh content, the X content, and the carrier is 0.01:0.01:1 to 0.2:0.2:1; and stirring the resulting mixture solution for 0.1-100 hours;

[0020] b) washing the reaction mixture obtained in step a) with the same solvent at room temperature, filtering, and then removing the solvent in vacuo to obtain the organic ion polymer carrier-supported Rh-X catalyst.

[0021] Furthermore, the organic solvent used in step a) is selected from one of ethanol, dimethyl sulfoxide and N,N-dimethylformamide; the Rh precursor is selected from one of RhCl3, Rh2(CO)4Cl2 and Rh(PPh3)3Cl; and the X precursor is selected from one of CrCl2, Cr(OAc)2, FeCl3, Fe(OAc)3, NiCl2 and Ni(OAc)2.

[0022] The third aspect of the present invention provides the use of the Rh-X catalyst in the heterogeneous hydroamidation of olefins to produce amides.

[0023] Furthermore, the material of the main reactor used is 316L; the reaction temperature is 50-250° C., and the reaction pressure is 0.5-10 MPa.

[0024] Furthermore, the substrate olefin is one of n-octene, n-nonene, and n-heptene; the substrate organic amine is one of n-hexylamine, n-pentylamine, and aniline; the molar ratio of the reaction substrate olefin to Rh is 3000:1 to 20:1; and the molar ratio of olefin to organic amine is 1:0.5 to 0.5:1.

[0025] The beneficial effects of the present invention compared to the prior art are:

[0026] 1. The Rh-X bimetallic catalyst of the present invention comprises an active component and an ionic polymer carrier. The organic ionic polymer carrier is prepared by self-polymerization or copolymerization of an organic salt containing a vinyl group or divinylbenzene using a solvent thermal polymerization method, followed by a polymerization reaction initiated by an initiator. The organic ionic polymer with a large surface area and a multi-level porous structure can serve as a carrier for the supported metal catalyst to support the active metal component. Furthermore, due to the strong ionic bonding between the Rh and X metal components and the organic salt cationic skeleton species in the polymer carrier skeleton, the Rh and X metal components are highly dispersed in the polymer carrier.

[0027] 2. Compared with existing homogeneous Rh-based catalysts, the heterogeneous Rh-X catalyst described in this invention can significantly reduce separation costs and simplify the production process in hydroamidation processes, thus promoting its industrialization. Furthermore, the catalyst exhibits significantly higher hydroamidation activity than homogeneous Rh systems. This catalyst not only exhibits high hydroamidation activity, high selectivity, and high stability in hydroamidation reactions, but also possesses universal compatibility with aliphatic amine substrates. DETAILED DESCRIPTION

[0028] In order to better understand the present invention, the present invention is further described in detail below so that those skilled in the art can implement it according to the description.

[0029] It should be noted that the experimental methods described in the following experiments, unless otherwise specified, are conventional methods, and the reagents and materials, unless otherwise specified, can be obtained from commercial channels.

[0030] Example 1

[0031] At 298K and a nitrogen atmosphere, 5.0g of monomer (A) (as described in claim 5) and 5g of divinylbenzene were added to 100.0ml of ethanol solvent. 0.25g of azobisisobutyronitrile (ABI) as a free radical initiator was added to the solution and stirred for 2 hours. The stirred solution was transferred to a hydrothermal reactor and polymerized at 373K under a nitrogen atmosphere for 24 hours using a solvent thermal polymerization method. After the polymerized solution was cooled to room temperature, the solvent was removed under vacuum at room temperature to obtain an organic ionomer support with a large surface area and a multi-level porous structure. Subsequently, at 298K and a nitrogen atmosphere, 0.095g of Rh(CO)Cl and 0.111g of Cr(OAc) were dissolved in 50ml of ethanol. 5g of the polymer was added and stirred at room temperature for 24 hours. After washing with CHCl and filtration, the solvent was removed under vacuum to obtain the organic ionomer support-supported rhodium-based Rh-Cr catalyst 1. The technical route of polymer carrier polymerization and metal Rh loading in this embodiment is as follows.

[0032]

[0033] Example 2

[0034] At 298K under a nitrogen atmosphere, 7.5g of monomer (B) (as described in claim 5) and 2.5g of divinylbenzene were added to 100.0ml of ethanol solvent. 0.25g of azobisisobutyronitrile (ABI) as a free radical initiator was added to the solution and stirred for 2 hours. The stirred solution was transferred to a hydrothermal reactor and polymerized for 24 hours at 373K under a nitrogen atmosphere using a solvothermal polymerization method. After the polymerized solution was cooled to room temperature, the solvent was removed under vacuum at room temperature to obtain a large surface area, multi-level porous structure organic ionomer support. Subsequently, at 298K under a nitrogen atmosphere, 0.095g of Rh(CO)Cl and 0.060g of CrCl were dissolved in 50ml of N,N-dimethylformamide. 5g of the polymer was added and stirred at room temperature for 24 hours. After washing with CHCl and filtration, the solvent was removed under vacuum to obtain the organic ionomer support-supported rhodium-based Rh-Cr catalyst 2. The technical route of polymer carrier polymerization and metal Rh loading in this embodiment is as follows.

[0035]

[0036] Example 3

[0037] At 298K under a nitrogen atmosphere, 10.0g of monomer (C) (as described in claim 5) was dissolved in 100.0ml of N,N-dimethylformamide solvent. 0.25g of azobisisobutyronitrile (ABI) as a free radical initiator was added to the solution and stirred for 2 hours. The stirred solution was transferred to a hydrothermal reactor and polymerized at 373K under a nitrogen atmosphere for 24 hours using a solvothermal polymerization method. After the polymerized solution was cooled to room temperature, the solvent was removed under vacuum at room temperature to obtain an organic ionomer support with a large surface area and a hierarchical porous structure. Subsequently, at 298K under a nitrogen atmosphere, 0.095g of Rh(CO)Cl and 0.086g of Ni(OAc) were dissolved in 50ml of N,N-dimethylformamide, and 5g of the polymer was added. The mixture was stirred at room temperature for 24 hours. After washing with CHCl and filtration, the solvent was removed under vacuum to obtain the organic ionomer support-supported rhodium-based Rh-Ni catalyst 3. The technical route of polymer carrier polymerization and metal Rh loading in this embodiment is as follows.

[0038]

[0039] Example 4

[0040] At 298K under a nitrogen atmosphere, 10.0g of monomer (D) (as described in claim 5) was dissolved in 100.0ml of N,N-dimethylformamide solvent. 0.25g of azobisisobutyronitrile (ABI) as a free radical initiator was added to the solution and stirred for 2 hours. The stirred solution was transferred to a hydrothermal reactor and polymerized at 373K under a nitrogen atmosphere for 24 hours using a solvothermal polymerization method. After the polymerized solution was cooled to room temperature, the solvent was removed under vacuum at room temperature to obtain an organic ionomer support with a large surface area and a hierarchical porous structure. Subsequently, at 298K under a nitrogen atmosphere, 0.095g of Rh(CO)Cl and 0.115g of NiCl were dissolved in 50ml of N,N-dimethylformamide, and 5g of the polymer was added. The mixture was stirred at room temperature for 24 hours. After washing with CHCl and filtration, the solvent was removed under vacuum to obtain the rhodium-based Rh-Ni catalyst 4 supported on the organic ionomer support. The technical route of polymer carrier polymerization and metal Rh loading in this embodiment is as follows.

[0041]

[0042] Example 5

[0043] At 298K under a nitrogen atmosphere, 10.0g of monomer (E) (as described in claim 5) was dissolved in 100.0ml of N-methylpyrrolidone. 0.25g of azobisisobutyronitrile (ABI) as a free radical initiator was added to the solution and stirred for 2 hours. The stirred solution was transferred to a hydrothermal reactor and polymerized at 373K under a nitrogen atmosphere for 24 hours using a solvothermal polymerization method. After the polymerized solution was cooled to room temperature, the solvent was removed under vacuum at room temperature to obtain an organic ionomer support with a large surface area and a hierarchical porous structure. Subsequently, at 298K under a nitrogen atmosphere, 0.449g of Rh(PPh3)3Cl and 0.094g of Fe(OH)(OAc)2 were dissolved in 50ml of dimethyl sulfoxide (DMSO). 5g of the polymer was added and stirred at room temperature for 24 hours. After washing with CH2Cl2 and filtration, the solvent was removed under vacuum to obtain the rhodium-based Rh-Fe catalyst 5 supported on the organic ionomer support. The technical route of polymer carrier polymerization and metal Rh loading in this embodiment is as follows.

[0044]

[0045] Example 6

[0046] At 298K and a nitrogen atmosphere, 10.0g of monomer (D) (as described in claim 5) was dissolved in 100.0ml of N-methylpyrrolidone solvent. 0.25g of azobisisobutyronitrile (DIBN) as a free radical initiator was added to the solution and stirred for 2 hours. The stirred solution was transferred to a hydrothermal reactor and polymerized at 373K under a nitrogen atmosphere for 24 hours using a solvent thermal polymerization method. After the polymerized solution was cooled to room temperature, the solvent was removed under vacuum at room temperature to obtain an organic ionomer support with a large surface area and a multi-level porous structure. Then, at 298K and a nitrogen atmosphere, 0.128g of RhCl3·3H2O and 0.079g of FeCl3 were dissolved in 50ml of ethanol, and 5g of the polymer was added. The mixture was stirred at room temperature for 24 hours, washed with CH2Cl2, filtered, and the solvent was removed under vacuum to obtain the organic ionomer support-supported rhodium-based Rh-Fe catalyst 6. The technical route for polymer support polymerization and metal Rh loading in this example is as follows.

[0047]

[0048] Example 7

[0049] At 298K under a nitrogen atmosphere, 10.0g of monomer (C) (as described in claim 5) was dissolved in 100.0ml of N,N-dimethylformamide solvent. 0.25g of azobisisobutyronitrile (ABI) as a free radical initiator was added to the solution and stirred for 2 hours. The stirred solution was transferred to a hydrothermal reactor and polymerized at 373K under a nitrogen atmosphere for 24 hours using a solvothermal polymerization method. After the polymerized solution was cooled to room temperature, the solvent was removed under vacuum at room temperature to obtain a large surface area, multi-level porous structure organic ionomer support. Subsequently, at 298K under a nitrogen atmosphere, 0.095g of Rh(CO)Cl and 0.172g of Ni(OAc) were dissolved in 50ml of N,N-dimethylformamide, and 5g of the polymer was added. The mixture was stirred at room temperature for 24 hours. After washing with CHCl and filtration, the solvent was removed under vacuum to obtain the organic ionomer support-supported rhodium-based Rh-Ni catalyst 7. The technical route of polymer carrier polymerization and metal Rh loading in this embodiment is as follows.

[0050]

[0051] Example 8

[0052] At 298K under a nitrogen atmosphere, 7.5g of monomer (B) (as described in claim 5) and 2.5g of divinylbenzene were added to 100.0ml of N,N-dimethylformamide solvent. 0.25g of azobisisobutyronitrile (ABI) as a free radical initiator was added to the solution and stirred for 2 hours. The stirred solution was transferred to a hydrothermal reactor and polymerized by solvothermal polymerization at 373K under a nitrogen atmosphere for 24 hours. After the solution was cooled to room temperature, the solvent was removed under vacuum at room temperature to obtain a high-surface-area, multi-level porous organic ionomer carrier. Then, at 298K and under a protective atmosphere of N2, 0.095g of Rh2(CO)4Cl2 and 0.172g of Ni(OAc)2 were dissolved in 50ml of N,N-dimethylformamide, and 5g of the polymer was added thereto. The mixture was stirred at room temperature for 24h, washed with CH2Cl2, and filtered. The solvent was then removed by vacuum to obtain a rhodium-based Rh-Ni catalyst 8 supported on an organic ion polymer carrier. The technical route for polymer support polymerization and metal Rh loading in this example is shown below.

[0053]

[0054] Comparative Example

[0055] At 298K and a protective atmosphere of N2, 10.0g of monomer (C) (as described in claim 5) was dissolved in 100.0ml of N,N-dimethylformamide solvent. 0.25g of azobisisobutyronitrile as a free radical initiator was added to the solution and stirred for 2 hours. The stirred solution was transferred to a hydrothermal reactor and polymerized using a solvent thermal polymerization method at 373K and a protective atmosphere of nitrogen for 24 hours. After the solution after the polymerization was cooled to room temperature, the solvent was removed under vacuum at room temperature to obtain an organic ion polymer carrier with a large surface area and a multi-level porous structure. Then, at 298K and a protective atmosphere of N2, 0.095g of Rh2(CO)4Cl2 was dissolved in 50ml of N,N-dimethylformamide, and 5g of the polymer was added thereto. The mixture was stirred at room temperature for 24 hours, washed with CH2Cl2, and filtered. The solvent was then removed under vacuum to obtain the organic ion polymer carrier-supported rhodium-based Rh catalyst 9. The technical route for polymer support polymerization and metal Rh loading in this comparative example is shown below.

[0056]

[0057] Application example: Application of Rh-X catalyst in the hydroamidation of olefins to produce amide compounds

[0058] The reaction conditions were: 120°C, 5.0 MPa CO, 2 mmol olefin, 2 mmol organic amine, olefin / organic amine molar ratio of 1:1, olefin / Rh molar ratio of 500:1, 10 ml toluene solvent, and a reaction time of 2 hours. After the reaction, the mixture was cooled to room temperature, and the product was filtered and analyzed using an Agilent 7890A GC with a DB-1701 capillary column and an FID detector.

[0059] The organic ion polymer carrier-supported Rh-X catalyst prepared in Example 1-8 was used to prepare amide compounds according to the above operation. The carbonylation TOF (calculated based on amide species) and the selectivity of the amide compound are shown in Table 1.

[0060] Table 1 Summary of hydroamidation reaction results of Examples / Comparative Examples (substrates are n-octene and n-hexylamine)

[0061]

[0062]

[0063] The substrate expansion experiment was carried out using the Rh-Ni catalyst 7 prepared in Example 7: the conditions were the same as above, and the results are shown in Table 2.

[0064] Table 2 Summary of substrate extension reaction results

[0065]

[0066] The results show that the hydroamidation activity of Rh-Ni catalyst is significantly higher than that of Rh catalyst, and it can catalyze not only aromatic amines but also aliphatic amines. The catalyst has excellent carbonylation activity, excellent selectivity and good stability.

[0067] Finally, it should be noted that the above is only used to illustrate the technical solution of the present invention and is not limiting. Although the present invention is described in detail with reference to the preferred arrangement scheme, ordinary technicians in this field should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the spirit and scope of the technical solution of the present invention.

Claims

1. An application of an organic ion polymer carrier-supported Rh-X catalyst in the heterogeneous hydroamidation of olefins to produce amides, characterized in that: The Rh-X bimetallic catalyst comprises an active component and a carrier, wherein the active component is two components, component 1 is a Rh metal complex, component 2 is an X metal complex, X is one of Cr, Fe, and Ni, and the carrier is an ion polymer carrier; Wherein, Rh accounts for 0.01-5.0wt% of the total mass of the catalyst, and X accounts for 0.01-5.0wt% of the total mass of the catalyst; the ion polymer carrier is a polymer formed by polymerization of organic salt monomers containing multiple vinyl groups including N or P, the organic salt monomers are one or more of the following structures AF, and / or divinylbenzene is used as a crosslinking agent; The structures AF are respectively:

2. The use according to claim 1, characterized in that: The ionic polymer comprises a multi-level pore structure of macropores, mesopores and micropores, and the pore volume is 0.1 to 5.0 cm 3 / g, pore size distribution is 0.2~50.0nm, specific surface area is 100~3000m 2 / g.

3. The use according to claim 1 or 2, characterized in that: The preparation method of the ionic polymer carrier comprises the following steps: a) adding a free radical initiator to an organic solvent containing an organic salt monomer and / or divinylbenzene at 273-473K and under inert gas atmosphere, wherein the weight ratio of the salt monomer to the free radical initiator is 5:1-100:1; the weight ratio of divinylbenzene to the salt monomer is 0:1-5:1; and stirring the obtained mixture solution for 1-100 hours; b) transferring the mixture solution in step a) to a hydrothermal autoclave at 273-473K and under inert gas atmosphere protection, and allowing to stand for 1-100 hours under solvent thermal polymerization conditions at 373-523K to carry out polymerization reaction; c) removing the solvent from the reaction mixture obtained in step b) under vacuum at room temperature, thereby obtaining an organic ion polymer carrier having a large surface area and a multi-level pore structure.

4. The use according to claim 3, characterized in that: The organic solvent used in step a) is selected from one or more of ethanol, N,N-dimethylformamide and N-methylpyrrolidone; the free radical initiator is selected from one of azobisisobutyronitrile and azobisisoheptanenitrile.

5. The use according to claim 1, characterized in that: The material of the main reactor is 316L; the reaction temperature is 50-250°C, and the reaction pressure is 0.5-10MPa.

6. The use according to claim 1, characterized in that: The substrate olefin is one of n-octene, n-nonene and n-heptene; the substrate organic amine is one of n-hexylamine, n-pentylamine and aniline; the molar ratio of the reaction substrate olefin to Rh is 3000:1-20:1; and the molar ratio of the olefin to the organic amine is 1:0.5-0.5:1.

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