A phosphine-containing porous organic polymer supported ruthenium catalyst and a method for preparing the same

Abstract

This invention discloses a ruthenium catalyst supported on a phosphine-containing porous organic polymer and its preparation method. The phosphine-containing porous organic polymer serves as both a support and a solid ligand. The phosphine-containing porous organic polymer ligand is a random copolymer, and its structure can be represented by general formula I. The ruthenium catalyst supported on the phosphine-containing porous organic polymer according to this invention has a large specific surface area and contains a hierarchical porous structure, enabling efficient direct preparation of alcohols from olefins via reductive hydroformylation, and is easily recyclable. It exhibits excellent activity and regioselectivity in the direct preparation of alcohols from olefins via reductive hydroformylation, with an alcohol selectivity of nearly 90% and a high ratio of straight-chain alcohols to branched-chain alcohols.

Description

Technical Field

[0001] This invention belongs to the field of catalysis and fine chemicals, and specifically relates to a method for preparing a class of ruthenium catalysts supported on porous organic polymers containing phosphine. Background Technology

[0002] Porous organic polymers (POPs) are a class of porous network materials with two-dimensional or three-dimensional structures. They have advantages such as large specific surface area, porous structure, and high thermal stability, and are widely used in various fields such as gas storage, gas separation, heterogeneous catalysis, and optoelectronic materials. In recent years, the construction of phosphine-containing organic porous polymers by polymerizing functionalized phosphine ligand monomers has attracted widespread attention in the research of olefin hydroformylation. Compared with traditional supports, phosphine-containing organic porous polymers have the following advantages as catalyst supports: (1) Higher specific surface area (500~2000 m² / m²). 2 · g -1(1) It facilitates the high dispersion and exposure of the metal active center; (2) The rich multi-level porous structure facilitates the contact between the reactants and the catalytic active site and the diffusion and transfer of the product, thereby improving the catalytic activity; (3) It can be used as a "solid" ligand to play a role similar to "host-guest chemistry". The "built-in" phosphine ligand unit ("host") in the polymer provides "anchoring" sites for the metal active center ("guest") and coordinates to form a catalyst of "quasi-homogeneous metal complex", which is conducive to stabilizing the metal center and preventing aggregation and loss; (4) The "built-in" phosphine ligand structure in the polymer has strong modulatory properties and can be designed and synthesized according to the reaction characteristics and needs. Domestically, Xiao Fengshou et al. (Catalysis Today, 2017, 298: 40-45; J. Am. Chem. Soc., 2015, 137(15): 5204-5209; Chem. Commun., 2014, (50): 11844-11847.), Ding Yunjie et al. (Microporous and Mesoporous Materials, 2022, 329: 111508; Applied Catalysis A:General, 2018, 551: 98-105; Journal of Catalysis, 2017, 353: 123-132.), and Shi Feng et al. (Journal of Catalysis, 2021, 401: 321-330; Chem. Commun., 2022, 58(58):8093-8096.), Li Fuwei et al. (Journal of catalysis, 2020, 387: 196-206) have made many outstanding contributions to the hydroformylation of olefins using rhodium catalysts supported on phosphine-containing organic porous polymers. They have developed phosphine-containing porous organic polymers containing monodentate phosphine ligands (such as PPh3 and PPh3 substituted at different positions on the benzene ring) and bidentate phosphine ligands (such as Xantphos, BINAP, dppe, etc.). They have also used these polymers as supports to prepare Rh nanoparticle-supported catalysts and Rh single atom catalysts (SACs) for the hydroformylation of ethylene, propylene, and long-chain olefins, achieving high efficiency and high stability.The inventors' research group of this application has also developed a variety of novel phosphorus-containing porous polymer-supported rhodium catalysts, which have achieved highly efficient and selective hydroformylation reactions of long-chain α-olefins (such as 1-hexene, 1-octene, etc.) under solvent-free conditions. The TON can reach up to 20,000, and the positive-to-isomeric ratio of aldehydes in the product is as high as 175, which is much higher than that of phosphorus ligand monomer homogeneous catalysts. Moreover, the catalysts can be recycled multiple times (ACS Applied Materials & Interfaces, 2020, 12(47): 53141-53149; RSC Adv., 2020, (10): 29263–29267).

[0003] As mentioned above, phosphine-containing porous organic polymers, as supports and "solid" ligands, exhibit excellent performance in stabilizing and improving the activity and selectivity of Rh-catalyzed olefin hydroformylation reactions, showing great promise for applications. However, current research mainly focuses on the preparation of aldehydes from olefin hydroformylation reactions, while the direct preparation of alcohols from the challenging olefin reductive hydroformylation reaction remains unreported. Given that alcohols have a higher added value than aldehydes, there is still a need to develop heterogeneous catalysts for the direct preparation of alcohols from olefin reductive hydroformylation reactions, resulting in a more economical and environmentally friendly process. Summary of the Invention

[0004] To address the problems in the prior art, this application successfully developed a ruthenium catalyst supported on a phosphine-containing porous organic polymer. This catalyst not only efficiently catalyzes the reductive hydroformylation of olefins to directly produce higher-value-added straight-chain alcohols, but also allows for recycling and reuse after the reaction, exhibiting excellent cyclic catalytic performance and significantly reducing production costs. The catalyst according to this invention demonstrates excellent activity and site selectivity in the direct preparation of alcohols from the reductive hydroformylation of olefins, with an alcohol selectivity of nearly 90% and a straight-chain to branched-chain alcohol ratio as high as 31, laying the foundation for the industrialization of the direct preparation of alcohols from the reductive hydroformylation of olefins.

[0005] According to one aspect of the present invention, one object of the present invention is to provide a ruthenium catalyst supported on a phosphine-containing porous organic polymer, the catalyst being prepared by impregnation of a Ru precursor and a phosphine-containing porous organic polymer ligand, wherein the Ru loading has a mass fraction of 0.1%-10%. The Ru precursor may be selected from Ru3(CO). 12 , RuH2(CO)(PPh3)3, RuCl2(PPh3)3, Ru2Cl4(CO)6, [CpRu(CO)2]2, RuCl3, [Ru(COD)Cl2] n One or more of Ru(methylallyl)2(COD) and [Ru(COD)2]BF4, preferably Ru3(CO) 12The phosphine-containing porous organic polymer ligand is a random copolymer, and its structure can be represented by general formula I:

[0006] General Formula I

[0007] in

[0008] R is selected from , , , , and One or more of them, where * indicates the location of the aggregated link.

[0009] R 1 and R 2 Each is independently selected from hydrogen, C1-C6 alkyl, C1-C6 alkoxy, C3-C14 cycloalkyl, C6-C14 aryl, or 3-10 heteroaryl containing 1 to 3 heteroatoms selected from N, O, and S.

[0010] Preferably, R 1 and R 2 Each is independently selected from hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C3-C10 cycloalkyl, C6-C10 aryl, or 5-10 heteroaryl containing one or two heteroatoms selected from N and O.

[0011] More preferably, R 1 and R 2 Each of the following is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, cyclopentyl, cyclohexyl, 1-adamantyl, phenyl, 1-naphthyl, 2-furanyl, 2-pyrrolyl, pyranyl, and pyridyl.

[0012] R 3 and R 4 Each is independently selected from hydrogen, halogen, cyano, amino, C1-C6 alkyl, and C1-C6 alkoxy.

[0013] Preferably, R 3 and R 4 Each is independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkyl, and C1-C4 alkoxy.

[0014] More preferably, R 3 and R 4 Each is independently selected from hydrogen, fluorine, chlorine, methyl, ethyl, propyl, cyano, etc.

[0015] R 5 R 6 R 7and R 8 Each is independently selected from hydrogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylamino, and cyano.

[0016] Preferably, R 5 R 6 R 7 and R 8 Each is independently selected from hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylamino, and cyano.

[0017] More preferably, R 5 R 6 R 7 and R 8 Each is independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, dimethylamino, cyano, etc.

[0018] Preferably, in general formula I, the subscript m represents the molar content of the phosphine-containing polymeric monomer, the subscript n represents the molar content of the comonomer, and m:n is 1:0 to 1:100. However, the subscripts m and n do not represent the linkage order of the monomers. The linkage order of the monomers can be unfixed and is a random polymer.

[0019] Preferably, m:n is 1:1 to 1:20.

[0020] According to another aspect of the present invention, another object of the present invention is to provide a method for preparing the ruthenium catalyst supported on a phosphine-containing porous organic polymer, the method being carried out as follows: under inert gas protection, a certain amount of Ru precursor and phosphine-containing porous organic polymer ligand are taken in proportion, stirred in a solvent at a certain temperature for a certain time to allow the Ru precursor to be coordinated and anchored on the phosphine-containing porous organic polymer ligand, and then the solvent is removed under reduced pressure to obtain the catalyst.

[0021] Preferably, the Ru precursor can be selected from Ru3(CO). 12 , RuH2(CO)(PPh3)3, RuCl2(PPh3)3, Ru2Cl4(CO)6, [CpRu(CO)2]2, RuCl3, [Ru(COD)Cl2] n One or more of Ru(methylallyl)2(COD) and [Rh(COD)2]BF4, preferably Ru3(CO) 12 .

[0022] Preferably, based on the weight of the final catalyst, the mass fraction of Ru loading is 0.1%-10%, more preferably 1%-10%, calculated according to the amount of element Ru.

[0023] Preferably, the solvent is selected from hexane, dichloromethane, ethyl acetate, tetrahydrofuran, benzene, and toluene, and more preferably tetrahydrofuran and toluene.

[0024] Preferably, the temperature is 0 o C-100 o C, preferably 10 o C-50 o C.

[0025] Preferably, the stirring time is 2-48 hours, and more preferably 12-36 hours.

[0026] Preferably, the inert gas is argon or nitrogen, with argon being more preferred.

[0027] According to another aspect of the present invention, another object of the present invention is to provide a method for preparing the phosphine-containing porous organic polymer ligand, the method being carried out as follows: under inert gas protection, a certain amount of vinyl-functionalized phosphine-containing polymer monomer ( A certain amount of comonomer based on substituent R is dissolved in tetrahydrofuran, and a certain amount of free radical initiator azobisisobutyronitrile is added. The mixture is stirred and reacted at a certain temperature for 24-48 hours.

[0028] Preferably, the molar ratio of the phosphine-containing polymeric monomer to the comonomer based on the substituent R is 1:0-1:100, more preferably 1:5-1:20.

[0029] Preferably, the amount of initiator azobisisobutyronitrile is 0.1%-5% of the molar amount of vinyl groups in the raw material.

[0030] Preferably, the comonomer based on substituent R is selected from... , , , , and One or more of them.

[0031] Preferably, the reaction temperature is 60°C. o C-150 o C, preferably 80 o C-100 o C.

[0032] Preferably, the inert gas is argon or nitrogen, with argon being more preferred.

[0033] The method for preparing the vinyl-functionalized phosphine-containing polymeric monomer is as follows:

[0034]

[0035] The definitions of substituents R1 to R8 are the same as in general formula I.

[0036] Step 1: Add compound 1, trimethyl orthoformate, and tetrabutylammonium tribromide to the reactor, dissolve in methanol, and add 80... o The reaction was stirred for 3 hours, the solvent was removed under reduced pressure, and compound 2 was obtained by column chromatography.

[0037] Step 2: Add sodium hydride and DMF to the reactor, and add imidazole compounds in batches. Stir the reaction at room temperature for half an hour, then add copper powder and compound 2, 150 o The reaction was stirred at C for 3 hours, cooled, quenched with water, extracted with ethyl acetate, and purified by column chromatography to obtain compound 3.

[0038] Step 3: Under inert gas protection, compound 3 is added to the reactor, dissolved in tetrahydrofuran, and cooled to -78°C. o C, add n-butyllithium dropwise, -78 o C. Stir the reaction for 1 hour, then add phosphine chloride compounds. The reaction was carried out at room temperature for 1 hour, and then dilute hydrochloric acid was added to continue the reaction for 2 hours. Sodium bicarbonate was added to dissolve the compound and adjust the pH to weakly alkaline. The mixture was extracted with ethyl acetate and separated by column chromatography to obtain compound 4.

[0039] Step 4: Under inert gas protection, methyltriphenylphosphine bromide was added to a reaction flask, dispersed with tetrahydrofuran, and potassium tert-butoxide was added in portions. The mixture was stirred at room temperature for half an hour, then compound 4 was added, and the mixture was stirred at room temperature for 3 hours. The reaction was quenched with water, extracted with ethyl acetate, and compound 5, separated by column chromatography, was the vinyl-functionalized phosphine-containing polymer monomer.

[0040] Beneficial effects

[0041] The ruthenium-supported phosphorus-containing porous organic polymer catalyst of the present invention has a large specific surface area and a hierarchical porous structure, enabling efficient direct preparation of alcohols from olefins via reductive hydroformylation, and is easily recyclable. It exhibits excellent activity and site selectivity in the direct preparation of alcohols from olefins via reductive hydroformylation, with an alcohol selectivity of nearly 90% and a straight-chain to branched-chain alcohol ratio as high as 31, laying the foundation for the industrialization of direct alcohol preparation from olefins via reductive hydroformylation. Attached Figure Description

[0042] Figure 1 The BET spectra are those of the phosphine-containing porous organic polymer PL2 prepared in Example 3 and the phosphine-containing porous organic polymer supported on the ruthenium catalyst Ru@PL2 prepared in Example 6.

[0043] Figure 2The pore size distribution maps are those of the phosphine-containing porous organic polymer PL2 prepared in Example 3 and the phosphine-containing porous organic polymer supported on the ruthenium catalyst Ru@PL2 prepared in Example 6.

[0044] Figure 3 The image shows the infrared spectrum of PL2, a phosphine-containing porous organic polymer prepared in Example 3.

[0045] Figure 4 The image shows the scanning electron microscope (SEM) spectrum of PL2, a phosphine-containing porous organic polymer prepared in Example 3. Detailed Implementation

[0046] The present invention will now be described in detail. Before proceeding with the description, it should be understood that the terminology used in this specification and the appended claims should not be construed as limited to its general or dictionary meaning, but rather should be interpreted according to the meaning and concept corresponding to the technical aspects of the invention, based on the principle that the inventors are allowed to appropriately define the terms for the best interpretation. Therefore, the description presented herein is merely a preferred example for illustrative purposes and is not intended to limit the scope of the invention. It should be understood that other equivalents or modifications can be obtained from it without departing from the spirit and scope of the invention.

[0047] definition

[0048] In this application, the term "cycloalkyl" refers to a non-aromatic cyclic hydrocarbon group, for example, having 3 to 14 cyclic carbon atoms ("C3-14 cycloalkyl") and zero heteroatoms in a non-aromatic ring system. The cycloalkyl group can be monocyclic ("monocyclic cycloalkyl") or comprise a fused, bridged, or spirocyclic system, such as a bicyclic system ("bicyclic cycloalkyl"), and can be saturated or partially unsaturated. "Cycloalkyl" also includes ring systems in which the carbon ring as defined above is fused with one or more aryl or heteroaryl groups, wherein the bonding point is on the cycloalkyl ring, and in this case, the carbon number continues to indicate the number of carbon atoms in the cycloalkyl ring system. Non-limiting exemplary cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornyl, decahydronaphthalene, adamantyl, cyclopentenyl, and cyclohexenyl. In a preferred embodiment, the term "cycloalkyl" refers to a monocyclic saturated group having 3 to 10, more preferably 3 to 6 cyclic carbon atoms.

[0049] "Heterocyclic alkyl" refers to a group having a 3- to 10-membered non-aromatic ring system having a ring carbon atom and 1 to 4 ring heteroatoms, wherein each heteroatom is independently selected from N, O, and S ("3–10-membered heterocyclic group"). In heterocyclic groups containing one or more nitrogen atoms, the linkage can be a carbon or nitrogen atom, where the valence allows. Heterocyclic groups can be monocyclic ("monocyclic heterocyclic group") or fused, bridged, or spirocyclic systems, such as bicyclic systems ("bicyclic heterocyclic group"), and can be saturated or partially unsaturated. A heterocyclic bicyclic system may contain one or more heteroatoms in one or both rings. "Heterocyclic group" also includes ring systems in which the heterocycle defined above is fused with one or more cycloalkyl groups, wherein the linkage is on the cycloalkyl or heterocycle, or ring systems in which the heterocycle defined above is fused with one or more aryl or heteroaryl groups, wherein the linkage is on the heterocycle, in which case the number of ring members continues to indicate the number of ring members in the heterocyclic system.

[0050] In this document, all features or conditions defined in the form of numerical ranges or percentage ranges are for the sake of brevity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered as covering and specifically disclosing all possible secondary ranges and individual values ​​within those ranges, particularly integer values. For example, a range description of "1 to 8" should be considered as specifically disclosing all secondary ranges such as 1 to 7, 2 to 8, 2 to 6, 3 to 6, 4 to 8, 3 to 8, etc., particularly secondary ranges defined by all integer values, and should be considered as specifically disclosing individual values ​​within those ranges such as 1, 2, 3, 4, 5, 6, 7, 8, etc. Unless otherwise specified, the foregoing interpretation applies to all content throughout this invention, regardless of its scope.

[0051] If a quantity or other numerical value or parameter is expressed as a range, a preferred range, or a series of upper and lower limits, it should be understood that this document has specifically disclosed all ranges consisting of any upper or preferred value of that range and the lower or preferred value of that range, regardless of whether such ranges are separately disclosed. Furthermore, when a range of numerical values ​​is mentioned herein, unless otherwise stated, the range shall include its endpoints and all integers and fractions within the range.

[0052] In this document, numerical values ​​are to be understood as having a precision with significant digits, provided that the purpose of the invention can be achieved. For example, the number 40.0 should be understood to cover a range from 39.50 to 40.49.

[0053] In the phosphine-containing porous organic polymer-supported ruthenium catalyst according to the present invention, the mass fraction of Ru loading is 0.1%-10%. If the loading is too low, it will lead to the waste of a large number of active sites in the solid ligand, and more catalyst will be used during the catalytic process, which is inconvenient to operate; if the loading is too high, there will be relatively fewer active sites, Ru metal will be easily lost, and the catalyst stability will be poor. Experiments have shown that a Ru loading mass fraction between 0.1% and 10% is more ideal.

[0054] The phosphine-containing porous organic polymer ligand is a random copolymer, and its structure can be represented by general formula I:

[0055] General Formula I

[0056] In general formula I, the subscript m represents the molar content of the phosphine-containing polymeric monomer, and the subscript n represents the molar content of the comonomer, with m:n ranging from 1:0 to 1:100, preferably from 1:1 to 1:20. When m:n is 1:0, it indicates that no comonomer is needed, and polymerization can proceed solely from the phosphine-containing polymeric monomer. The subscripts m and n do not indicate the linkage order of the monomers; the linkage order of the monomers is not fixed, resulting in a random polymer.

[0057] In the ruthenium catalyst supported by the phosphine-containing porous organic polymer according to the present invention, the phosphine-containing porous organic polymer is used as a support and also as a ligand for metal Ru. The phosphine in the polymer coordinates with Ru, anchoring Ru to the solid support. This not only makes it more robust and reduces metal loss, but the phosphine ligand can also donate electrons to Ru, thereby enhancing the catalytic activity of Ru.

[0058] IR measurements were performed using a Thermo Fisher Nicolet 6700 infrared spectrometer (USA); specific surface area and pore structure were measured using a Micron ASAP 2460 physical adsorption spectrometer (USA); and surface morphology was observed using a Hitachi S-4800 cold field emission scanning electron microscope (Japan). Gas chromatography was performed using a Shimadzu GC-2030.

[0059] For the phosphine-containing porous organic polymer-supported ruthenium catalyst of the present invention, the catalytic activity and selectivity are affected by many factors, among which the choice of support is one of the most important factors.

[0060] Compared with traditional supports, phosphine-containing organic porous polymers have the following advantages as catalyst supports: (1) higher specific surface area, which is conducive to the high dispersion and exposure of metal active centers; (2) rich multi-level porous structure, which is conducive to the contact between reactants and catalytic active sites and the diffusion and transfer of products, thereby improving catalytic activity; (3) it can act as a "solid" ligand, playing a role similar to "host-guest chemistry". The "built-in" phosphine-containing ligand units ("host") in the polymer provide "anchoring" sites for the metal active centers ("guests") and coordinate to form a catalyst of "quasi-homogeneous metal complex", which is conducive to stabilizing the metal centers and preventing aggregation and loss; (4) the "built-in" phosphine ligand structure in the polymer has strong modulatory properties and can be designed and synthesized according to the reaction characteristics and needs. Therefore, the choice of support is crucial to the activity and selectivity of the phosphine-containing porous organic polymer-supported ruthenium catalyst of the present invention.

[0061] The following embodiments are merely examples illustrating implementations of the present invention and do not constitute any limitation on the present invention. Those skilled in the art will understand that modifications made without departing from the spirit and concept of the present invention fall within the protection scope of the present invention. Unless otherwise specified, the reagents and instruments used in the following embodiments are commercially available products.

[0062] Example 1: Preparation of vinyl-functionalized phosphine-containing polymeric monomers

[0063] Step 1: Preparation of compound 2a

[0064]

[0065] Add 10 g of compound 1a, 6.9 g of trimethyl orthoformate, and 1.3 g of tetrabutylammonium tribromide to a reaction flask, dissolve in 20 mL of methanol, and 80 o The reaction mixture was stirred at C for 3 hours, the solvent was removed under reduced pressure, and 12.57 g of compound 2a was obtained by column chromatography. The NMR data are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.49 (d, J = 8.3 Hz, 2H), 7.32 (d, J = 8.4Hz, 2H), 5.35 (s, 1H), 3.30 (s, 6H).

[0066] Step 2: Preparation of compound 3a

[0067]

[0068] Add 4.4 g of sodium hydride and 38 mL of DMF to a reaction flask, then add 7.4 g of imidazole in portions. Stir the mixture at room temperature for half an hour, then add 0.69 g of copper powder and 12.57 g of compound 2a. Add 150 mL of DMF. oThe reaction was stirred at C for 3 hours. After cooling, the mixture was quenched with water, extracted with ethyl acetate, and purified by column chromatography to give 7 g of compound 3a. The NMR data are as follows: 1 H NMR (400 MHz, DMSO) δ8.30 (s, 1H), 7.78 (s, 1H), 7.73 – 7.64 (m, 2H), 7.52 (d, J = 8.4 Hz, 2H), 7.14 (s, 1H), 5.45 (s, 1H), 3.28 (s, 6H).

[0069] Step 3: Preparation of compound 4a

[0070]

[0071] Under argon protection, 5 g of compound 3a was added to a reaction flask, dissolved in 50 mL of tetrahydrofuran, and cooled to -78°C. o C, add 10 mL of 1.6 mol / L n-butyllithium, -78 o The mixture was stirred at C for 1 hour, then 5.32 g of dicyclohexylphosphine chloride was added, and the reaction was continued at room temperature for 1 hour. Then, 25 mL of 2.4 mol / L dilute hydrochloric acid was added, and the reaction was continued for 2 hours. The pH was adjusted to weakly alkaline with sodium bicarbonate solution, and the mixture was extracted with ethyl acetate and separated by column chromatography to obtain 2 g of compound 4a. The NMR data are as follows: 1 H NMR (400 MHz, CDCl3) δ 10.08(s, 1H), 7.99 (d, J = 8.3 Hz, 2H), 7.53 (d, J = 8.2 Hz, 2H), 7.39 (d, J = 1.0Hz, 1H), 7.24 – 7.20 (m, 1H), 2.15 (dd, J = 16.9, 6.6 Hz, 2H), 1.77 – 1.54 (m, 10H), 1.35 – 0.92 (m, 10H). 31 P NMR (162 MHz, CDCl3) δ -23.37.

[0072] Step 4: Preparation of compound 5a

[0073]

[0074] Under argon protection, 4.4 g of methyltriphenylphosphine bromide was added to a reaction flask, dispersed in 40 ml of tetrahydrofuran, and then 1.4 g of potassium tert-butoxide was added in portions. The mixture was stirred at room temperature for half an hour, followed by the addition of 2 g of compound 4a. The reaction was then stirred at room temperature for 3 hours. The mixture was quenched with water, extracted with ethyl acetate, and 1.9 g of compound 5a, the vinyl-functionalized phosphine-containing polymer monomer, was separated by column chromatography. The NMR data are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.48 (d, J = 8.4 Hz, 2H), 7.35 (d, J = 0.8Hz, 1H), 7.26 (d, J = 7.5 Hz, 3H), 7.16 (dd, J = 2.2, 1.1 Hz, 1H), 6.75 (dd,J = 17.6, 10.9 Hz, 1H), 5.80 (d, J = 17.6 Hz, 1H), 5.33 (d, J = 11.0 Hz, 1H), 2.13 (dd, J = 17.0, 6.4 Hz, 2H), 1.75 – 1.54 (m, 10H), 1.31 – 0.98 (m, 10H). 31 P NMR (162 MHz, CDCl3) δ -24.03.

[0075] Example 2: Preparation of phosphine-containing porous organic polymer PL1 (m:n=1:5)

[0076]

[0077] Under argon protection, 1 g of compound 5a obtained in Example 1, 1.77 g of divinylbenzene, and 49 mg of azobisisobutyronitrile (AIBN) were added to a reaction flask, dissolved in 30 ml of THF, stirred at room temperature for half an hour, transferred to a hydrothermal reactor, and reacted at 100°C for 24 h. After cooling to room temperature, methanol was added for dispersion, centrifuged, and washed three times with methanol to obtain 2.7 g of a phosphine-containing porous organic polymer (PL1). This polymer has a BET specific surface area of ​​350 m². 2 / g, mainly exists in the form of micropores and mesopores.

[0078] Example 3: Preparation of phosphine-containing porous organic polymer PL2 (m:n=1:10)

[0079] Under argon protection, 1 g of compound 5 obtained in Example 1, 3.54 g of divinylbenzene, and 94 mg of AIBN were added to a reaction flask, dissolved in 50 ml of THF, stirred at room temperature for half an hour, transferred to a hydrothermal reactor, and reacted at 100°C for 24 h. After cooling to room temperature, methanol was added for dispersion, centrifugation was performed, and the mixture was washed three times with methanol to obtain 4.5 g of a phosphine-containing porous organic polymer (PL2). This polymer has a BET specific surface area of ​​480 m². 2 / g, mainly exists in the form of micropores and mesopores.

[0080] Example 4: Preparation of phosphine-containing porous organic polymer PL3 (m:n=1:20)

[0081] Under argon protection, 1 g of compound 5 obtained in Example 1, 7.09 g of divinylbenzene, and 184 mg of AIBN were added to a reaction flask, dissolved in 80 ml of THF, stirred at room temperature for half an hour, transferred to a hydrothermal reactor, and reacted at 100°C for 24 h. After cooling to room temperature, methanol was added for dispersion, centrifugation was performed, and the mixture was washed three times with methanol to obtain 7.9 g of a phosphine-containing porous organic polymer (PL3). The BET specific surface area of ​​this polymer is 760 m². 2 / g, mainly exists in the form of micropores and mesopores.

[0082] Example 5: Preparation of Ruthenium catalyst Ru@PL1 supported on phosphine-containing porous organic polymer

[0083] Under argon protection, 500 mg of phosphine-containing porous organic polymer PL1 was dispersed in 30 ml of tetrahydrofuran, and 52.5 mg of Ru3(CO) was added. 12 The mixture was stirred at room temperature for 24 h, and the solvent was removed under reduced pressure to obtain 500 mg of ruthenium-based catalyst (Ru@PL1) supported on a phosphine-containing porous organic polymer. The polymer has a BET specific surface area of ​​330 m². 2 / g, mainly exists in the form of micropores and mesopores.

[0084] Example 6: Preparation of Ruthenium catalyst Ru@PL2 supported on phosphine-containing porous organic polymer

[0085] Under argon protection, 500 mg of the phosphine-containing porous organic polymer PL2 was dispersed in 30 ml of tetrahydrofuran, and 32 mg of Ru3(CO) was added. 12 The mixture was stirred at room temperature for 24 h, and the solvent was removed under reduced pressure to obtain 500 mg of ruthenium-based catalyst (Ru@PL2) supported on a phosphine-containing porous organic polymer. The polymer has a BET specific surface area of ​​470 m². 2 / g, mainly exists in the form of micropores and mesopores.

[0086] Example 7: Preparation of Ruthenium catalyst Ru@PL3-1 supported on phosphine-containing porous organic polymer

[0087] Under argon protection, 500 mg of phosphine-containing porous organic polymer PL3 was dispersed in 30 ml of tetrahydrofuran, and 72 mg of Ru3(CO) was added. 12 The mixture was stirred at room temperature for 24 h, and the solvent was removed under reduced pressure to obtain 500 mg of ruthenium-based catalyst (Ru@PL3-1) supported on a phosphine-containing porous organic polymer. The polymer has a BET specific surface area of ​​720 m². 2 / g, mainly exists in the form of micropores and mesopores.

[0088] Example 8: Preparation of Ruthenium catalyst Ru@PL3-2 supported on phosphine-containing porous organic polymer

[0089] Under argon protection, 500 mg of the phosphine-containing porous organic polymer PL3 was dispersed in 30 ml of tetrahydrofuran, and 36 mg of Ru3(CO) was added. 12 The mixture was stirred at room temperature for 24 h, and the solvent was removed under reduced pressure to obtain 500 mg of ruthenium-based catalyst (Ru@PL3-2) supported on a phosphine-containing porous organic polymer. The polymer has a BET specific surface area of ​​750 m². 2 / g, mainly exists in the form of micropores and mesopores.

[0090] Example 9: Preparation of Ruthenium catalyst Ru@PL3-3 supported on phosphine-containing porous organic polymer

[0091] Under argon protection, 500 mg of the phosphine-containing porous organic polymer PL3 was dispersed in 30 ml of tetrahydrofuran, and 18 mg of Ru3(CO) was added. 12 The mixture was stirred at room temperature for 24 h, and the solvent was removed under reduced pressure to obtain 500 mg of ruthenium-based catalyst (Ru@PL3-3) supported on a phosphine-containing porous organic polymer. The polymer has a BET specific surface area of ​​760 m². 2 / g, mainly exists in the form of micropores and mesopores.

[0092] Example 10: Preparation of Ruthenium catalyst Ru@PL3-4 supported on phosphine-containing porous organic polymer

[0093] Under argon protection, 500 mg of the phosphine-containing porous organic polymer PL3 was dispersed in 30 ml of tetrahydrofuran, and 9 mg of Ru3(CO) was added. 12 The mixture was stirred at room temperature for 24 h, and the solvent was removed under reduced pressure to obtain 500 mg of ruthenium-based catalyst (Ru@PL3-4) supported on a phosphine-containing porous organic polymer. The polymer has a BET specific surface area of ​​760 m². 2 / g, mainly exists in the form of micropores and mesopores.

[0094] Some test examples are as follows:

[0095] Test Example 1

[0096] Under argon protection, 57 mg of ruthenium-based catalyst (Ru@PL1) supported on a phosphine-containing porous organic polymer was added to an autoclave, along with 5 mmol of 1-hexene and 3 ml of toluene. The autoclave was sealed, and 1 MPa of carbon monoxide and 5 MPa of hydrogen were introduced. The reaction was stirred at 80 °C for 24 h, followed by a reaction at 150 °C for 24 h. After cooling to room temperature, 1.25 mmol of n-decane was added. Gas chromatography analysis showed a conversion rate of 99%, a selectivity of 83% for heptanol, and a linear to branched heptanol (l / b) ratio of 24.

[0097] Test Example 2

[0098] Under argon protection, 100 mg of ruthenium-based catalyst (Ru@PL2) supported on a phosphine-containing porous organic polymer was added to an autoclave, along with 5 mmol of 1-hexene and 3 ml of toluene. The autoclave was sealed, and 1 MPa of carbon monoxide and 5 MPa of hydrogen were introduced. The reaction was stirred at 80 °C for 24 h, followed by a reaction at 150 °C for 24 h. After cooling to room temperature, 1.25 mmol of n-decane was added. Gas chromatography analysis showed a conversion rate of 99%, a selectivity of 88% for heptanol, and a linear-chain to branched-chain heptanol (l / b) ratio of 26.

[0099] Test Example 3

[0100] Under argon protection, 48 mg of ruthenium-based catalyst (Ru@PL3-1) supported on a phosphine-containing porous organic polymer was added to an autoclave, along with 5 mmol of 1-hexene and 3 ml of toluene. The autoclave was sealed, and 1 MPa of carbon monoxide and 5 MPa of hydrogen were introduced. The reaction was stirred at 80 °C for 24 h, followed by a reaction at 150 °C for 24 h. After cooling to room temperature, 1.25 mmol of n-decane was added. Gas chromatography analysis showed a conversion rate of 99%, a selectivity of 62% for heptanol, and a linear to branched heptanol (l / b) ratio of 18.

[0101] Test Example 4

[0102] Under argon protection, 83 mg of ruthenium-based catalyst (Ru@PL3-2) supported on a phosphine-containing porous organic polymer was added to an autoclave, along with 5 mmol of 1-hexene and 3 ml of toluene. The autoclave was sealed, and 1 MPa of carbon monoxide and 5 MPa of hydrogen were introduced. The reaction was stirred at 80 °C for 24 h, followed by a reaction at 150 °C for 24 h. After cooling to room temperature, 1.25 mmol of n-decane was added. Gas chromatography analysis showed a conversion rate of 99%, a selectivity of 89% for heptanol, and a linear-chain to branched-chain heptanol (l / b) ratio of 23.

[0103] Test Example 5

[0104] Under argon protection, 166 mg of ruthenium-based catalyst (Ru@PL3-3) supported on a phosphine-containing porous organic polymer was added to an autoclave, along with 5 mmol of 1-hexene and 3 ml of toluene. The autoclave was sealed, and 1 MPa of carbon monoxide and 5 MPa of hydrogen were introduced. The reaction was stirred at 80 °C for 24 h, followed by a reaction at 150 °C for 24 h. After cooling to room temperature, 1.25 mmol of n-decane was added. Gas chromatography analysis showed a conversion rate of 99%, a selectivity of 70% for heptanol, and a linear to branched heptanol (l / b) ratio of 31.

[0105] The above description is merely a specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A ruthenium catalyst supported on a phosphine-containing porous organic polymer, wherein the catalyst is prepared by impregnation of a Ru precursor and a phosphine-containing porous organic polymer ligand, wherein the Ru loading has a mass fraction of 0.1%-10%; wherein the Ru precursor is selected from Ru3(CO). 12 One or more of the following: RuH2(CO)(PPh3)3, RuCl2(PPh3)3, Ru2Cl4(CO)6, [CpRu(CO)2]2, RuCl3, Ru(methylallyl)2(COD), and [Ru(COD)2]BF4; wherein the phosphine-containing porous organic polymer ligand is a random copolymer, the structure of which is represented by general formula I: General Formula I in R is selected from , , , , and One or more of them, where * indicates the location of the aggregated link; R 1 and R 2 Each is independently selected from hydrogen, C1-C6 alkyl, C1-C6 alkoxy, C3-C14 cycloalkyl, C6-C14 aryl, and 3-10 heteroaryl groups containing 1 to 3 heteroatoms selected from N, O and S; R 3 and R 4 Each is independently selected from hydrogen, halogen, cyano, amino, C1-C6 alkyl, and C1-C6 alkoxy. R 5 R 6 R 7 and R 8 Each is independently selected from hydrogen, C1-C6 alkyl, C1-C6 alkoxy, C1-C6 alkylamino, and cyano; The subscript m indicates the molar content of the phosphine-containing polymeric monomer, and the subscript n indicates the molar content of the comonomer, with m:n ranging from 1:5 to 1:

20.

2. The ruthenium catalyst supported on a phosphine-containing porous organic polymer according to claim 1, characterized in that, The Ru precursor is Ru3(CO). 12 .

3. The ruthenium catalyst supported on a phosphine-containing porous organic polymer according to claim 1, characterized in that, R 1 and R 2 Each is independently selected from hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C3-C10 cycloalkyl, C6-C10 aryl, and 5-10 heteroaryl containing 1 or 2 heteroatoms selected from N and O; R 3 and R 4 Each is independently selected from hydrogen, halogen, cyano, amino, C1-C4 alkyl, and C1-C4 alkoxy. R 5 R 6 R 7 and R 8 Each is independently selected from hydrogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylamino, and cyano.

4. The ruthenium catalyst supported on a phosphine-containing porous organic polymer according to claim 1, characterized in that, R 1 and R 2 Each of the following is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, cyclopentyl, cyclohexyl, phenyl, 1-naphthyl, 2-furanyl, 2-pyrrolyl, pyranyl, and pyridyl; R 3 and R 4 Each is independently selected from hydrogen, fluorine, chlorine, methyl, ethyl, propyl, and cyano; R 5 R 6 R 7 and R 8 Each is independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, methoxy, ethoxy, dimethylamino, and cyano.

5. The method for preparing the ruthenium catalyst supported on a phosphine-containing porous organic polymer according to claim 1, wherein the method is carried out as follows: under inert gas protection, a certain amount of Ru precursor and phosphine-containing porous organic polymer ligand are taken in proportion, stirred in a solvent at a certain temperature for a certain time to allow the Ru precursor to be coordinated and anchored on the phosphine-containing porous organic polymer ligand, and then the solvent is removed under reduced pressure to obtain the catalyst.

6. The preparation method according to claim 5, characterized in that, Based on the weight of the final catalyst, the mass fraction of Ru loading is 0.1%-10% according to the amount of element Ru.

7. The preparation method according to claim 5, characterized in that, Based on the weight of the final catalyst, the mass fraction of Ru loading is 1%-10% according to the amount of element Ru.

8. The preparation method according to claim 5, characterized in that, The solvent is selected from n-hexane, dichloromethane, ethyl acetate, tetrahydrofuran, benzene, and toluene; Temperature is 0 o C-100 o C; The stirring time is 2-48 hours; The inert gas is argon or nitrogen.

9. The preparation method according to claim 8, characterized in that, The solvent is selected from tetrahydrofuran and toluene; The temperature is 10 o C-50 o C; The stirring time is 12-36 hours; The inert gas is argon.

10. The preparation method according to claim 5, characterized in that, The preparation method of the phosphine-containing porous organic polymer ligand is as follows: Under inert gas protection, a certain amount of vinyl-functionalized phosphine-containing polymer monomer is taken in proportion. A certain amount of comonomer based on substituent R is dissolved in tetrahydrofuran, and a certain amount of free radical initiator azobisisobutyronitrile is added. The mixture is stirred and reacted at a certain temperature for 24-48 hours, wherein the substituents R, R1 to R8 are defined as in claim 1.

11. The preparation method according to claim 10, characterized in that, The molar ratio of the phosphine-containing polymeric monomer to the comonomer based on substituent R is 1:5-1:20; The amount of initiator azobisisobutyronitrile (AIBN) used is 0.1%-5% of the molar amount of vinyl groups in the raw material; The comonomer based on substituent R is selected from... , , , , and One or more of the following; The reaction temperature is 60°C. o C-150 o C; The inert gas is argon or nitrogen.

12. The preparation method according to claim 10, characterized in that, The reaction temperature is 80°C. o C-100 o C; The inert gas is argon.

13. The preparation method according to claim 10, characterized in that, The method for preparing the vinyl-functionalized phosphine-containing polymeric monomer is as follows: The definitions of substituents R1 to R8 are the same as in claim 1; Step 1: Add compound 1, trimethyl orthoformate, and tetrabutylammonium tribromide to the reactor, dissolve in methanol, and add 80... o C. Stir the reaction for 3 hours, remove the solvent under reduced pressure, and separate by column chromatography to obtain compound 2; Step 2: Add sodium hydride and DMF to the reactor, and add imidazole compounds in batches. Stir the reaction at room temperature for half an hour, then add copper powder and compound 2, 150 o The reaction was stirred for 3 hours, cooled, quenched with water, extracted with ethyl acetate, and purified by column chromatography to obtain compound 3. Step 3: Under inert gas protection, compound 3 is added to the reactor, dissolved in tetrahydrofuran, and cooled to -78°C. o C, add n-butyllithium dropwise, -78 o C. Stir the reaction for 1 hour, then add phosphine chloride compounds. The reaction was carried out at room temperature for 1 hour, and then dilute hydrochloric acid was added to continue the reaction for 2 hours. Sodium bicarbonate was added to dissolve and adjust the pH to weakly alkaline. The mixture was extracted with ethyl acetate and separated by column chromatography to obtain compound 4. Step 4: Under inert gas protection, add methyltriphenylphosphine bromide to the reaction flask, add tetrahydrofuran for dispersion, add potassium tert-butoxide in batches, stir at room temperature for half an hour, add compound 4, stir at room temperature for 3 hours, quench with water, extract with ethyl acetate, and separate compound 5 by column chromatography, which is the vinyl-functionalized phosphine-containing polymer monomer.

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