Immobilized organic base catalyst as well as preparation method and application thereof

Abstract

The invention discloses an immobilized organic base catalyst and a preparation method and application thereof, the immobilized organic base catalyst comprises functionalized activated carbon, the functionalized activated carbon has a Bronsted base site comprising an organic Bronsted base molecular structure, the organic Bronsted alkali molecular structure is connected to the surface of the functionalized activated carbon through a covalent bond. The immobilized organic base catalyst is a heterogeneous active carbon-based immobilized organic # imgabs0 # base catalyst, and has the advantages of low preparation cost, high reaction activity, good stability and the like.

Description

Technical Field

[0001] This application belongs to the technical field of reaction engineering, and particularly relates to a supported organic base catalyst, a preparation method thereof, and an application thereof. Background Art

[0002] A class of carbon-carbon bond formation reactions catalyzed by bases play an important role in the chemical industry and are widely used in the production of bulk chemicals and fine chemicals. At present, a large number of homogeneous base catalysts have been developed by researchers, which have the advantages of high catalytic efficiency, mild reaction conditions, and compatibility with a variety of substrate molecules, and are well-developed. However, the homogeneous system faces many challenges in the process of refining products. Since the substrate molecules are mainly aldehydes and ketones, they have high reactivity and are prone to oxidation, condensation, and disproportionation reactions. Therefore, in the process of separating raw materials, products, and catalysts, the separation energy consumption is high, the catalyst is difficult to reuse, and side reactions are likely to occur, resulting in a decrease in product quality. The reaction process is generally complex and cumbersome, the cost increases, which is not conducive to sustainable development.

[0003] Heterogeneous catalysts have advantages in simplifying the separation process and reducing energy consumption, and are an important means to achieve green chemistry. Realizing heterogeneous catalysis by loading organic bases on the surfaces of different carriers is an important development direction in the field of base catalysis. However, the selection of carriers for existing solid organic base catalysts mainly focuses on resin polymers and silica materials, and the obtained catalysts generally have problems such as insufficient catalyst activity, low reaction yield, and harsh reaction conditions; moreover, the swelling problem of resin-based catalysts is significant, and the hydrothermal stability of silica-based materials is poor and prone to hydrolysis over a long time, and the shortcomings of the two materials are obvious. Summary of the Invention

[0004] This application aims to solve at least one of the technical problems in the related art to some extent. To this end, the purpose of this application is to propose a supported organic base catalyst, a preparation method thereof, and an application thereof. The supported organic base catalyst of this application is a heterogeneous activated carbon-based supported organic base catalyst, which has the advantages of low preparation cost, high reaction activity, and good stability.

[0005] In one aspect of this application, this application proposes a supported organic base catalyst. According to the embodiments of this application, the supported organic base catalyst includes:

[0006] Functionalized activated carbon, the functionalized activated carbon has Bronsted base sites including an organic Bronsted base molecular structure, and the organic Bronsted base molecular structure is covalently bonded to the surface of the functionalized activated carbon.

[0007] The supported organic base catalyst according to the embodiments of the present application. First, the supported organic base catalyst of the present application belongs to a heterogeneous catalyst. Compared with the traditional homogeneous organic base catalysis process, this heterogeneous catalyst immobilizes the organic base on the surface of the support, and the catalyst can be quickly and simply separated from the system by filtration or dense filling in the reactor, which can effectively reduce the separation energy consumption and is convenient for multiple recycling and reuse. Second, the support of the present application is taken from commercial activated carbon particles, which are economically cheap and easily available, reducing the preparation cost of the catalyst, and having good chemical stability, hydrothermal stability and high mechanical strength, and can maintain long-term stability in the base catalysis system. Third, the activated carbon-supported organic Brønsted base (i.e., base) catalyst can efficiently catalyze a series of aldol condensation reactions, Knoevenagel reactions and Henry reactions in both batch reactor mode and continuous flow mode. Using this type of catalyst, the highest product yield of 99.0% can be achieved in both batch mode and continuous flow mode, and the catalyst and product can be quickly separated only by simple filtration or catalyst confinement. Fourth, the supported organic base catalyst of the present application exhibits better catalytic stability. The conversion rates of a series of aldol condensation reactions, Knoevenagel reactions and Henry reactions of substrates can reach up to 100.0%, and the selectivity can reach up to 99.0%. Excellent stability is maintained after 6 cycles in batch mode; in continuous flow mode, consistent yields are maintained during long-term continuous catalysis for 24 h, which is of great significance for guiding the development of supported organic base catalysts and new processes for such base-catalyzed reactions.

[0008] In addition, the supported organic base catalyst according to the above embodiments of the present application may further have the following additional technical features:

[0009] In some embodiments of the present application, the organic Brønsted base molecule includes at least one of ethylenediamine, diethylenetriamine, tetraethylenepentamine, N-methylethylenediamine, ethanolamine, 1,4-butanediamine, 1,6-hexanediamine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene.

[0010] In some embodiments of the present application, the supported organic base catalyst includes at least one of the compounds shown in Formulas 1 to 9, where the black spheres represent activated carbon particles:

[0011]

[0012] In the second aspect of the present application, the present application proposes a method for preparing a supported organic base catalyst. According to the embodiments of the present application, the method includes:

[0013] (1) Treat activated carbon with a functionalizing reagent to obtain an intermediate activated carbon with active groups;

[0014] (2) Mix the intermediate activated carbon, an organic Bronsted base molecule, and a first solvent, and react to obtain a supported organic base catalyst.

[0015] According to the method for preparing a supported organic base catalyst according to the embodiments of the present application, first, this method uses commercially available activated carbon particles with excellent chemical stability and not easily swelling as the catalyst support, which is economically cheap and easy to obtain, reducing the cost of catalyst preparation. Moreover, the commercially available activated carbon particles have good chemical stability, hydrothermal stability, and high mechanical strength, enabling the prepared supported organic base catalyst to maintain long-term stability in the base-catalyzed system. The activated carbon particles of the present application are subjected to one-step or multi-step simple functionalization treatment (i.e., surface modification technology), and then an organic base is loaded on the activated carbon by covalent grafting, which can further achieve covalent grafting and fixation of the organic base to synthesize a heterogeneous solid organic base catalyst. The whole process is simple to operate and has a low cost. Second, the activated carbon-supported organic base catalyst prepared by this method can efficiently catalyze a series of aldol condensation reactions, Knoevenagel reactions, and Henry reactions in both batch reactor mode and continuous flow mode. Higher reaction rates can be achieved under milder conditions. The conversion rates of a series of substrates in aldol condensation reactions, Knoevenagel reactions, and Henry reactions can reach up to 100%, and the selectivities can reach up to 99%. It maintains excellent stability after being recycled 6 times in batch mode and maintains a stable yield for at least 24 h in continuous mode.

[0016] In addition, the method for preparing a supported organic base catalyst according to the above embodiments of the present application may further have the following additional technical features:

[0017] In some embodiments of the present application, in step (1), the temperature for treating the activated carbon with the functionalizing reagent is 25°C to 150°C, and the time is 2 h to 200 h; and / or, in step (1), the mass ratio of the activated carbon to the functionalizing reagent is 1:4 to 1:100; and / or, in step (1), the functionalizing reagent includes at least one of an ozone / oxygen mixed gas, a nitric acid solution, a maleic anhydride solution, a sodium hydroxide solution, a potassium hydroxide solution, a thionyl chloride solution, and a cis-1,4-dichloro-2-butene solution.

[0018] In some embodiments of the present application, the mass concentration of ozone in the ozone / oxygen mixed gas is 5 mg / L to 200 mg / L; and / or, the mass concentration of the nitric acid solution is 5 wt% to 50 wt%; and / or, the mass concentration of the maleic anhydride solution is 60 wt% to 99 wt%; and / or, the mass concentration of the sodium hydroxide solution is 2 wt% to 30 wt%; and / or, the mass concentration of the potassium hydroxide solution is 2 wt% to 30 wt%; and / or, the mass concentration of the thionyl chloride solution is 60 wt% to 99 wt%; and / or, the mass concentration of the cis-1,4-dichloro-2-butene solution is 60 wt% to 99 wt%.

[0019] In some embodiments of the present application, in step (2), the reaction temperature is 50 °C to 110 °C, and the reaction time is 4 h to 24 h; and / or, in step (2), the mass ratio of the intermediate activated carbon to the organic Brønsted base molecule is 100:1 to 100:50; and / or, in step (2), the organic Brønsted base molecule includes at least one of ethylenediamine, diethylenetriamine, tetraethylenepentamine, N-methylethylenediamine, ethanolamine, 1,4-butanediamine, 1,6-hexanediamine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1,8-diazabicyclo[5.4.0]undec-7-ene; and / or, in step (2), the first solvent includes at least one of ethanol, 1,4-dioxane, acetonitrile, toluene, tetrahydrofuran, N,N-dimethylformamide.

[0020] In the third aspect of the present application, the present application proposes an application of the supported organic base catalyst as described in the above embodiments or the supported organic base catalyst prepared by the method as described in the above embodiments in the catalytic carbon-carbon bond formation reaction. Thus, the activated carbon supported organic Brønsted base of the present application (i.e., The (base) catalyst can efficiently catalyze a series of aldol condensation reactions, Knoevenagel reactions, and Henry reactions in both batch reactor mode and continuous flow mode. Using this type of catalyst, a series of aldol condensation reactions, Knoevenagel reactions, and Henry reactions can be efficiently catalyzed in both batch reactor mode and continuous flow mode. With this type of catalyst, a product yield of up to 99.0% can be achieved in both batch mode and continuous flow mode, and the catalyst can be rapidly separated from the product simply by filtration or catalyst confinement. At the same time, the supported organic base catalyst of this application exhibits better catalytic stability. The conversion rates of a series of aldol condensation reactions, Knoevenagel reactions, and Henry reactions of substrates can reach up to 100.0%, and the selectivities can reach up to 99.0%. It maintains excellent stability after being recycled 6 times in batch mode; in continuous flow mode, maintaining a consistent yield during continuous catalysis for 24 hours is of great significance for guiding the development of supported organic base catalysts and the development of new processes for such base-catalyzed reactions.

[0021] In some embodiments of this application, the carbon-carbon bond formation reaction includes at least one of aldol condensation reaction, Knoevenagel reaction, and Henry reaction; and / or, the specific operation mode of the carbon-carbon bond formation reaction includes at least one of batch reactor mode and continuous flow mode.

[0022] In some embodiments of this application, the batch reactor mode includes: uniformly mixing the supported organic base catalyst, reaction substrates, and a second solvent in a reactor, stirring until the reaction is complete; and / or, the continuous flow mode includes: densely packing the supported organic base catalyst in a reactor, using a pump to feed a homogeneous reactant solution into the reactor, and the outlet is the resulting product solution.

[0023] Additional aspects and advantages of this application will be given in part in the following description, become apparent in part from the following description, or be learned through the practice of this application. Description of the Drawings

[0024] The above and / or additional aspects and advantages of this application will become apparent and easy to understand from the description of the embodiments in conjunction with the following drawings, where:

[0025] Figure 1 Fourier transform infrared spectrum of the activated carbon supported TBD base catalyst synthesized in Example 7.

[0026] Figure 2 77K nitrogen adsorption-desorption curve of the activated carbon supported TBD base catalyst synthesized in Example 7.

[0027] Figure 3Pore size distribution diagram obtained by using the Density Functional Theory (DFT) model for the activated carbon-supported TBD base catalyst synthesized in Example 7. Detailed implementation manners

[0028] The embodiments of the present application are described in detail below. The following described embodiments are exemplary and are intended to explain the present application, and should not be construed as a limitation to the present application.

[0029] The present application is proposed by the inventors based on the following problems:

[0030] Currently, for base-catalyzed reactions (such as aldol condensation reaction, Knoevenagel reaction, Henry reaction, etc.), homogeneous organic base catalysts (such as trimethylamine, triethylamine, pyridine, etc.) are widely used, which have advantages such as high catalytic efficiency and mild reaction conditions. However, in the homogeneous system, the catalyst is not easy to recycle and reuse, the energy consumption required for product purification is high, and common aldehyde and ketone reactants are easily oxidized by oxygen, and side reactions are likely to occur during the separation process, resulting in a decrease in product quality.

[0031] In view of this, in one aspect of the present application, the present application proposes a supported organic base catalyst. According to an embodiment of the present application, the supported organic base catalyst includes: functionalized activated carbon, and the functionalized activated carbon has Bronsted base (i.e., base) sites including the molecular structure of organic Bronsted base (i.e., base), and the molecular structure of organic Bronsted base (i.e., base) is covalently bonded to the surface of the functionalized activated carbon.

[0032] The beneficial effects that the supported organic base catalyst proposed by the present application can achieve are described in detail below:

[0033] First, the supported organic base catalyst of the present application belongs to a heterogeneous catalyst. Compared with the traditional homogeneous organic base catalysis process, this heterogeneous catalyst realizes the fixation of the organic base on the surface of the carrier, and the catalyst can be quickly and simply separated from the system by filtration or dense filling in the reactor, which can effectively reduce the separation energy consumption and is convenient for multiple recycling and reuse.

[0034] Second, the carrier of the present application is taken from commercial activated carbon particles, which are economically cheap and easy to obtain, reducing the preparation cost of the catalyst, and having good chemical stability, hydrothermal stability and high mechanical strength, and can maintain long-term stability in the base catalysis system.

[0035] Third, the activated carbon-supported organic Bronsted base (i.e., The (base) catalyst can efficiently catalyze a series of aldol condensation reactions, Knoevenagel reactions, and Henry reactions in both batch reactor mode and continuous flow mode. Using this type of catalyst, product yields of up to 99.0% can be achieved in both batch mode and continuous flow mode.

[0036] Fourth, the supported organic base catalyst of the present application exhibits better catalytic stability. The conversion rates of aldol condensation reactions, Knoevenagel reactions, and Henry reactions of a series of substrates can reach up to 100.0%, and the selectivities can reach up to 99.0%. Excellent stability is maintained after 6 cycles in batch mode; in continuous flow mode, consistent yields are maintained during continuous catalysis for 24 h, which is of great significance for guiding the development of supported organic base catalysts and new processes for such base-catalyzed reactions.

[0037] According to some specific embodiments of the present application, the organic Brønsted base molecules include but are not limited to at least one of ethylenediamine, diethylenetriamine, tetraethylenepentamine, N-methylethylenediamine, ethanolamine, 1,4-butanediamine, 1,6-hexanediamine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and other aliphatic primary amines, aliphatic secondary amines, aliphatic tertiary amines, and organic superbases not mentioned above. The above organic Brønsted base molecules are covalently bonded to the surface of activated carbon by reacting with the intermediate activated carbon to form basic sites.

[0038] According to still some other specific embodiments of the present application, the supported organic base catalyst includes at least one of the compounds shown in Formulas 1 to 9, where the black spheres represent activated carbon particles:

[0039]

[0040] In the second aspect of the present application, the present application proposes a method for preparing the above-mentioned supported organic base catalyst. According to the embodiments of the present application, the method includes the following steps:

[0041] S100: Treat activated carbon with a functionalizing reagent to obtain an intermediate activated carbon with an activating group;

[0042] In this step, a certain concentration of the functionalizing reagent can be first prepared, and the activated carbon is pretreated with the functionalizing reagent to obtain an intermediate activated carbon with an activating group.

[0043] According to some specific embodiments of the present application, in step S100, the temperature for treating the activated carbon with the functionalizing reagent is 25°C to 150°C (for example, it can be 25°C, 30°C, 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C), and the time is 2 h to 200 h (for example, it can be 2 h, 10 h, 25 h, 50 h, 75 h, 100 h, 125 h, 150 h, 175 h, 200 h, etc.). Thus, it can be further ensured that the activated carbon is pretreated with the functionalizing reagent to obtain an intermediate activated carbon with activating groups.

[0044] According to still some specific embodiments of the present application, in step S100, the mass ratio of the activated carbon to the functionalizing reagent is 1:4 to 1:100, for example, it can be 1:4, 1:10, 1:20, 1:40, 1:60, 1:80, 1:100, etc. Thus, it can be further ensured that the activated carbon is pretreated with the functionalizing reagent to obtain an intermediate activated carbon with activating groups. Preferably, it is 1:4 to 1:20.

[0045] In the embodiments of the present application, the specific type of the above-mentioned functionalizing reagent is not particularly limited. As some specific embodiments, the above-mentioned functionalizing reagent includes at least one of an ozone / oxygen mixed gas, a nitric acid solution, a maleic anhydride solution, a sodium hydroxide solution, a potassium hydroxide solution, a thionyl chloride solution, and a cis-1,4-dichloro-2-butene solution. The above-mentioned functionalizing reagent can effectively perform a simple functionalization treatment on the activated carbon to obtain an intermediate activated carbon with activating groups.

[0046] According to some further specific embodiments of the present application, the mass concentration of ozone in the ozone / oxygen mixed gas is 5 mg / L to 200 mg / L (for example, it can be 5 mg / L, 10 mg / L, 50 mg / L, 100 mg / L, 150 mg / L, 200 mg / L, etc.); and / or, the mass concentration of the nitric acid solution is 5 wt% to 50 wt% (for example, it can be 5 wt%, 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, etc.); and / or, the mass concentration of the maleic anhydride solution is 60 wt% to 99 wt% (for example, it can be 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, 99 wt%, etc.); and / or, the mass concentration of the sodium hydroxide solution is 2 wt% to 30 wt% (for example, it can be 2 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, etc.); and / or, the mass concentration of the potassium hydroxide solution is 2 wt% to 30 wt% (for example, it can be 2 wt%, 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, etc.); and / or, the mass concentration of the thionyl chloride solution is 60 wt% to 99 wt% (for example, it can be 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, 99 wt%, etc.); and / or, the mass concentration of the cis-1,4-dichloro-2-butene solution is 60 wt% to 99 wt% (for example, it can be 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt%, 85 wt%, 90 wt%, 95 wt%, 99 wt%, etc.). Thus, it can be further ensured that the above functionalizing reagents effectively perform a simple surface modification treatment on the activated carbon to obtain an intermediate activated carbon with activated groups.

[0047] In the embodiments of the present application, the above commercial activated carbon is any commercially purchased activated carbon particles used as a catalyst support, without special limitations.

[0048] In the embodiments of the present application, the solvent used in the above functionalization treatment can be one or a mixture of deionized water, toluene, and tetrahydrofuran.

[0049] S200: Mix the functionalized activated carbon, the organic Bronsted base molecule, and the first solvent, and react to obtain a supported organic base catalyst.

[0050] In this step, the above intermediate activated carbon can be dispersed in the first solvent, and then mixed with the corresponding target organic Bronsted base (i.e., base) molecule to graft the organic base in the form of a covalent bond to obtain the corresponding grafted supported organic base catalyst.

[0051] According to some specific embodiments of the present application, in step S200, the reaction temperature is 50°C to 110°C (for example, it can be 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, etc.), and the reaction time is 4h to 24h (for example, it can be 4h, 6h, 8h, 10h, 12h, 15h, 18h, 20h, 22h, 24h, etc.). Thus, it can be further ensured that the target organic Brønsted base (i.e., base) molecules are grafted onto the organic base in the form of forming covalent bonds to obtain the corresponding grafted type of supported organic base catalyst.

[0052] According to still some other specific embodiments of the present application, in step S200, the mass ratio of the functionalized activated carbon to the organic Brønsted base molecules is 100:1 to 100:50. For example, it can be 100:1, 100:5, 100:10, 100:20, 100:30, 100:40, 100:50, etc. Thus, it can be further ensured that the target organic Brønsted base (i.e., base) molecules are grafted onto the organic base in the form of forming covalent bonds to obtain the corresponding grafted type of supported organic base catalyst. Preferably, it is 100:1 to 100:20.

[0053] According to yet some other specific embodiments of the present application, the above-mentioned organic Brønsted base molecules include but are not limited to at least one of ethylenediamine, diethylenetriamine, tetraethylenepentamine, N-methylethylenediamine, ethanolamine, 1,4-butanediamine, 1,6-hexanediamine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), and other aliphatic primary amines, aliphatic secondary amines, aliphatic tertiary amines, and organic super bases not mentioned above. The above-mentioned organic Brønsted base molecules are covalently bonded to the surface of the activated carbon through reaction with the functionalized activated carbon to form base sites.

[0054] In the embodiments of the present application, the above-mentioned first solvent includes at least one of ethanol, 1,4-dioxane, acetonitrile, toluene, tetrahydrofuran, and N,N-dimethylformamide.

[0055] Furthermore, the above method further includes:

[0056] S300: Separating the grafted type of solid base catalyst and washing it with a small amount of solvent multiple times, and drying it in an oven to obtain the target catalyst.

[0057] The method for preparing a supported organic base catalyst according to the embodiments of the present application has at least one of the following advantages:

[0058] First, the method uses commercially available activated carbon particles with excellent chemical stability and low swelling tendency as the catalyst support. These particles are inexpensive, readily available, and can reduce the cost of catalyst preparation. Moreover, the commercially available activated carbon particles have good chemical and hydrothermal stability as well as high mechanical strength, enabling the prepared supported organic base catalyst to maintain long-term stability in the base-catalyzed system. After one-step or multi-step simple functionalization treatment (i.e., surface modification technology) of the activated carbon particles in this application, organic bases are loaded onto the functionalized activated carbon by covalent grafting, further realizing the covalent grafting and fixation of organic bases to synthesize heterogeneous solid organic base catalysts. The entire process is simple and low-cost.

[0059] Second, the supported organic base catalyst prepared by this method can efficiently and stably catalyze a series of aldol condensation reactions, Knoevenagel reactions, and Henry reactions in both batch reactor mode and continuous flow mode. In terms of catalytic activity, higher reaction rates can be achieved under milder conditions. The conversion rates of a series of aldol condensation reactions, Knoevenagel reactions, and Henry reactions of substrates can reach up to 100%, and the selectivities can reach up to 99%. At the same time, in terms of catalytic stability, excellent stability is maintained after 6 cycles in batch mode, and a stable yield is maintained for at least 24 h in continuous mode.

[0060] In the third aspect of this application, this application proposes an application of a supported organic base catalyst as in the above embodiments or a supported organic base catalyst prepared by the method as in the above embodiments in the catalytic carbon-carbon bond formation reaction. Thus, the supported organic Brønsted base (i.e., base) catalyst of this application can efficiently catalyze a series of aldol condensation reactions, Knoevenagel reactions, and Henry reactions in both batch reactor mode and continuous flow mode. Using this type of catalyst, a product yield of up to 99.0% can be achieved in both batch mode and continuous flow mode, and the catalyst and product can be rapidly separated only by simple filtration or catalyst confinement. At the same time, the supported organic base catalyst of this application exhibits better catalytic stability. The conversion rates of a series of aldol condensation reactions, Knoevenagel reactions, and Henry reactions of substrates can reach up to 100.0%, and the selectivities can reach up to 99.0%. Excellent stability is maintained after 6 cycles in batch mode; in continuous flow mode, a consistent yield is maintained during long-term continuous catalysis for 24 h, which is of great significance for guiding the development of supported organic base catalysts and new processes for such base-catalyzed reactions.

[0061] According to some specific embodiments of the present application, the specific operation mode of the above-mentioned carbon-carbon bond formation reaction includes at least one of an intermittent reactor mode and a continuous flow mode. Among them, the intermittent reactor mode is to add the above-mentioned solid base catalyst, reaction substrate and suitable solvent into the reactor, fill with a certain pressure of air or nitrogen to avoid the volatilization of aldehydes and ketones with lower boiling points, and then heat at a constant temperature, and stir the reaction at a certain speed until the reaction is completed. The continuous flow mode is to densely fill the catalyst in the reactor, use a pump to send a uniform reactant solution into the reactor to flow through the catalyst, and obtain the product solution at the outlet of the reactor.

[0062] According to some further specific embodiments of the present application, the carbon-carbon bond forming reaction comprises at least one of an aldol condensation reaction, a Knoevenagel reaction and a Henry reaction; the aldol condensation reaction comprises the reaction of formaldehyde and isobutyraldehyde to obtain 2,2-dimethyl-3-hydroxypropanal, the condensation reaction of acetone and furfural to obtain 4-(2-furanyl)-3-butene-2-one and 4-(2-furanyl)-4-hydroxy-2-ketobutene, the self-condensation of acetone to obtain 4-hydroxy-4-methyl-2-pentanone, the condensation of p-nitrobenzaldehyde and acetone to obtain 4-hydroxy-4-(4-nitrophenyl)-2-pentanone. Butan-2-one and 4-(4-nitrophenyl)-3-buten-2-one, n-butyraldehyde self-condenses to obtain 2-ethyl-3-hydroxyhexanal and 2-ethylhex-2-enal; Knoevenagel reaction belongs to the condensation reaction of aldehydes and active methylene compounds, aldehydes include benzaldehyde, p-nitrobenzaldehyde, p-methylbenzaldehyde, n-heptylaldehyde, furfural, active methylene compounds include malononitrile, ethyl cyanoacetate, ethyl acetoacetate; Henry reaction includes the condensation reaction of aldehydes and nitromethane, aldehydes include benzaldehyde, p-methoxybenzaldehyde, p-methylbenzaldehyde, p-chlorobenzaldehyde, furfural.

[0063] According to some other specific embodiments of the present application, the above-mentioned reaction substrate can be dissolved in an organic solvent with a mass concentration of 2wt% to 20wt%, and the organic solvent includes a mixture of one or more of toluene, ethanol, acetonitrile, N,N-dimethylformamide, dimethyl sulfoxide, deionized water, 1,2-dichloroethane, acetone, and isopropanol.

[0064] According to some further specific embodiments of the present application, the reaction temperature of the above carbon-carbon bond forming reaction can be 25°C to 100°C (preferably 40°C to 70°C), and the pressure can be 0 to 1.0 MPa (preferably 0.3 MPa to 0.8 MPa).

[0065] Embodiments of the present application will be described in detail below. It should be noted that the embodiments described below are exemplary and are only used to explain the present application, and should not be construed as a limitation to the present application. Additionally, if not explicitly stated, all reagents used in the following embodiments are commercially available or can be synthesized according to methods described herein or known methods. Reaction conditions not listed are also easily obtainable by those skilled in the art.

[0066] Example 1

[0067] Weigh 5.0 g of commercial activated carbon particles and disperse them evenly in 30.0 g of deionized water. Continuously introduce an ozone / oxygen mixed gas into the system at room temperature for 10 hours at a flow rate of 200 mL / min. The mass concentration of ozone in the ozone / oxygen mixed gas is 80 mg / L. After the reaction is completed, wash it with deionized water multiple times and dry it to a constant weight in a vacuum drying oven to obtain intermediate activated carbon.

[0068] Disperse the intermediate activated carbon in acetonitrile, add 2.0 g of ethylenediamine and 0.20 g of NaBH 3 CN. The mass ratio of the intermediate activated carbon to ethylenediamine is 5:2. Stir at 40 °C for 96 hours. After filtration, wash the solid clean with a small amount of acetonitrile multiple times, and place the solid in a vacuum drying oven to dry overnight to obtain the activated carbon-supported ethylenediamine catalyst.

[0069] To verify the catalytic effect of the activated carbon-supported ethylenediamine catalyst prepared in Example 1 on the aldol condensation reaction, use the batch reactor mode to evaluate the catalyst and obtain the reaction conversion rate and selectivity.

[0070] Add 1.0 g of the activated carbon-supported ethylenediamine catalyst, 10.0 mL of 0.8 mol L -1 aqueous formaldehyde solution and 10 mL of 0.8 mol L -1 isopropyl alcohol solution of isobutyraldehyde into the reactor. Fill the reactor with nitrogen until the pressure rises to 0.4 MPa, stir at 70 °C for 2 hours. After the reaction is completed, filter out the catalyst and quickly cool the solution to room temperature. Take a sample for analysis. The conversion rate of isobutyraldehyde reaches 90%, and the yield of 2,2-dimethyl-3-hydroxypropanal obtained can reach 85%.

[0071] Example 2

[0072] Weigh a certain mass of activated carbon and a nitric acid aqueous solution with a mass fraction of 40.0 wt% according to a mass ratio of 1:20, disperse them evenly in a round-bottom flask, react at 80 °C for 6 hours, filter after cooling to room temperature, wash thoroughly with a large amount of deionized water until the pH of the washing liquid reaches about 7.0, and dry in a forced-air drying oven for 8 hours. Further, mix the solid and thionyl chloride evenly according to a mass ratio of 1:20, react at 80 °C for 8 hours, filter after cooling to room temperature, and finally dry in a forced-air drying oven for 8 hours to obtain the intermediate activated carbon.

[0073] Using 1,4-dioxane as the solvent, add the intermediate activated carbon and diethylenetriamine in a mass ratio of 100:20, stir well and mix evenly, stir at a constant temperature of 80 °C for 24 hours, filter the obtained solid, wash it with 1,4-dioxane and acetonitrile, and dry for more than 12 hours to obtain the activated carbon-supported diethylenetriamine catalyst.

[0074] To verify the catalytic effect of the activated carbon-supported diethylenetriamine catalyst prepared in Example 2 on the aldol condensation reaction, use the continuous flow reaction mode to evaluate the catalyst and obtain the reaction conversion rate and selectivity.

[0075] Using a mixture of acetone and toluene as the solvent, prepare a 5.0 wt% furfural solution. Pack 1.0 g of the activated carbon-supported diethylenetriamine catalyst in a micro-packed bed reactor to catalyze the aldol condensation reaction of acetone and furfural. The homogeneous substrate solution flows through the catalyst bed, control the bed temperature at 50 °C, the reaction pressure at 0.5 MPa, and the residence time at 300 seconds. Collect the product at the outlet of the bed and analyze it. The furfural conversion rate reaches 100%, and the total yield of the products 4-(2-furyl)-3-buten-2-one and 4-(2-furyl)-4-hydroxy-2-oxo-butene reaches 86.5%.

[0076] Example 3

[0077] In a round-bottom flask, add activated carbon, maleic anhydride and the solvent toluene in a ratio of 1:10:100 in sequence, react at a constant temperature of 100 °C for 120 hours under reflux conditions, quickly cool to room temperature after the reaction, filter, and wash thoroughly with toluene and water in small amounts multiple times. The obtained solid is dried in a vacuum drying oven for at least 24 hours. Further, mix the solid and thionyl chloride evenly according to a mass ratio of 1:20, react at 70 °C for 15 hours, filter after cooling to room temperature, and finally dry in a drying oven for 8 hours to obtain the intermediate activated carbon.

[0078] Using 1,4-dioxane as solvent, add intermediate activated carbon, N-methylethylenediamine and ethanolamine in a ratio of 100:10:10, and react at a constant temperature of 90°C for 24 hours. After the reaction is completed, filter and wash with toluene and 1,4-dioxane several times. The obtained solid is placed in a vacuum drying oven and fully dried to constant weight to obtain an activated carbon-supported composite organic base catalyst.

[0079] In order to verify the catalytic activity of the activated carbon-supported composite organic base catalyst for the aldol condensation reaction in Example 3, an evaluation was performed in an intermittent reactor mode. An acetone solution of 5.0 wt% p-nitrobenzaldehyde was prepared, 20.0 g of the above solution was added to a round-bottom flask, and then 1.0 g of the activated carbon-supported composite organic base catalyst was added and stirred continuously until the mixture was uniformly mixed, and the mixture was reacted at a constant temperature of 50°C for 3 hours. After the catalyst was filtered hot, the solution was quickly cooled to room temperature, and the sample was tested and analyzed to obtain a conversion rate of p-nitrobenzaldehyde of 95%, and the total yield of the monocondensation products of acetone and p-nitrobenzaldehyde, 4-hydroxy-4-(4-nitrophenyl)butan-2-one and 4-(4-nitrophenyl)-3-butene-2-one, reached 84.3%.

[0080] Example 4

[0081] Prepare 100.0g of sodium hydroxide aqueous solution with a mass fraction of 10.0wt%, add 5.0g of activated carbon particles washed with deionized water, react at a constant temperature of 150°C for 4 hours under reflux, filter after the reaction, wash with a large amount of deionized water until the pH of the washing liquid reaches about 7.0, and then vacuum dry. The above solid is further mixed with thionyl chloride, dispersed in toluene, reacted at 80°C for 6 hours, filtered, washed with tetrahydrofuran in small amounts and multiple times, and finally placed in a vacuum drying oven to dry until constant weight, to obtain intermediate activated carbon.

[0082] The intermediate activated carbon and tetraethylenepentamine are mixed in a mass ratio of 100:40, 1,4-dioxane is added for dispersion, and the mixture is stirred and reacted at 90°C for 24 hours, then quickly cooled to room temperature, and a solid is obtained by filtration. The solid is fully washed with 1,4-dioxane and ethanol, and the solid is placed in a vacuum drying oven and dried overnight to obtain an activated carbon-supported tetraethylenepentamine catalyst.

[0083] In order to verify the catalytic activity of the activated carbon-supported tetraethylenepentamine catalyst for the aldol condensation reaction in Example 4, the catalyst was evaluated in a continuous flow mode to obtain the reaction conversion rate and selectivity.

[0084] Prepare an acetonitrile solution of acetone with a mass concentration of 4.0 wt%. Confine 1.0 g of activated carbon supported tetraethylenepentamine catalyst in a micro-packed bed reactor. Use an injection pump to pump the raw material liquid into the system at a constant flow rate to fully contact the catalyst. Control the bed temperature at 60 °C, the reaction pressure at 0.6 MPa, and the residence time at 360 seconds. Collect the product at the bed outlet and analyze it. The conversion rate of acetone reaches 70.5%, and the selectivity of the self-condensation product 4-hydroxy-4-methyl-2-pentanone can reach 96%.

[0085] Example 5

[0086] Mix equal masses of an aqueous sodium hydroxide solution with a mass fraction of 20.0 wt% and an aqueous potassium hydroxide solution with a mass fraction of 20.0 wt% to obtain 100.0 g of a homogeneous solution. Then add 5.0 g of activated carbon washed clean with deionized water and react at a constant temperature of 150 °C for 4 hours under reflux conditions. After the reaction, wash it clean with a large amount of deionized water until the pH of the washing liquid reaches about 7.0, and then dry it in a vacuum drying oven. Mix the above solid with 20.0 g of thionyl chloride, add toluene for dilution and dispersion, react at a constant temperature of 80 °C for 6 hours, filter to obtain the solid, and wash it clean with tetrahydrofuran in multiple times, and place it in a vacuum drying oven to dry to constant weight, that is, obtain the intermediate activated carbon.

[0087] Add the intermediate activated carbon and 1,4-butanediamine in a mass ratio of 100:50, and add the solvent 1,4-dioxane to promote uniform dispersion in the system. After the mixture is continuously stirred at 90 °C for 12 hours, filter out the solid, and wash it with a mixed solvent of 1,4-dioxane and ethanol in multiple times. Finally, dry the solid in a vacuum drying oven to constant weight, that is, obtain the activated carbon supported butanediamine catalyst.

[0088] To verify the catalytic activity of the activated carbon supported butanediamine catalyst in the aldol condensation reaction in Example 5, evaluate the catalyst in a continuous flow mode to obtain the reaction conversion rate and selectivity.

[0089] Prepare a mixed solution of n-butyraldehyde in acetonitrile / water with a mass fraction of 4.0 wt%. Then confine 1.0 g of activated carbon supported butanediamine catalyst in a micro-packed bed reactor. Use an injection pump to pump the raw material liquid into the system at a constant flow rate to fully contact the catalyst. Control the bed temperature at 70 °C, the reaction pressure at 0.5 MPa, and the residence time at 240 seconds. Collect the product at the bed outlet and analyze it. The conversion rate of n-butyraldehyde reaches 82.3%, and the total yield of the self-condensation products 2-ethyl-3-hydroxyhexanal and 2-ethylhex-2-enal can reach 78.4%.

[0090] Example 6

[0091] cis-1,4-Dichloro-2-butene and toluene were completely mixed in a mass ratio of 1:4 to form 30.0 g of a homogeneous solution. Then, 5.0 g of activated carbon that had been thoroughly washed with deionized water and dried was added thereto, and the reaction was carried out at a constant temperature of 150 °C for 120 hours. After the reaction was completed, it was quickly cooled to room temperature. The filtered solid was further washed thoroughly with the solvent toluene to remove the residual cis-1,4-dichloro-2-butene, and then placed in a drying oven to be dried at a constant temperature to remove the residual toluene, thus obtaining the intermediate activated carbon.

[0092] The intermediate activated carbon and 1,6-hexanediamine were mixed in a mass ratio of 100:50. Then, the solvent acetonitrile was added to promote the dispersion of the system, and the reaction was stirred at 90 °C for 15 hours. Then, the solid was filtered out and washed repeatedly with pure solvent acetonitrile. Finally, it was placed in a vacuum drying oven and dried to a constant weight, thus obtaining the activated carbon-supported hexanediamine catalyst.

[0093] To verify the catalytic activity of the activated carbon-supported hexanediamine catalyst for the Knoevenagel reaction in Example 6, the catalyst was evaluated in a batch reactor mode to obtain the reaction conversion rate and selectivity.

[0094] In a round-bottom flask, a 0.5 mol / L -1 p-nitrobenzaldehyde and 0.5 mol / L -1 malononitrile were prepared with a total volume of 20.0 mL, using acetonitrile as the solvent. Then, 1.0 g of the activated carbon-supported hexanediamine catalyst was added. Air was filled into the reactor until the pressure rose to 0.4 MPa, and the temperature was heated to 50 °C and kept constant for reaction for 50 minutes. After the reaction was completed, it was quickly cooled to room temperature using an ice-water bath, and then the solid was filtered out and sampled for testing. The conversion rate of p-nitrobenzaldehyde reached 100.0%, and the product selectivity reached 99.0%. The filtered solid catalyst was washed with the solvents acetonitrile and ethanol in small amounts multiple times and placed in a vacuum drying oven to be dried for 6 hours. The obtained catalyst was reused without other treatment in the batch reactor mode, and the reaction was catalyzed in the same manner. During the continuous recycling of the catalyst for 6 times, the conversion rate of p-nitrobenzaldehyde remained constant at 100.0%, and the product selectivity decreased from 99.0% to 95.0%, indicating good stability of the catalyst.

[0095] Example 7

[0096] A 35.0 g homogeneous toluene solution of cis-1,4-dichloro-2-butene with a mass fraction of 20.0 wt% was prepared, and then 5.0 g of activated carbon that had been washed clean with deionized water and dried completely in advance was added. Then, it was introduced into a reflux system, and the reaction was carried out at a constant temperature of 150 °C for 180 hours. After the reaction was completed, it was quickly cooled to room temperature. The filtered solid was further washed thoroughly with toluene, and then placed in a vacuum drying oven to be dried overnight to remove the residual toluene, thus obtaining the intermediate activated carbon.

[0097] The intermediate activated carbon and 1,5,7-triazabicyclo[4.4.0]dec-5-ene were mixed in a mass ratio of 100:40, and then 30.0 g of the solvent acetonitrile was added to promote the uniform mixing of the activated carbon and the organic base. After heating to 85 °C, the mixture was continuously stirred and reacted for 12 hours. Then, it was filtered, and washed thoroughly with pure solvent acetonitrile to remove the physically adsorbed 1,5,7-triazabicyclo[4.4.0]dec-5-ene remaining on the surface. Finally, it was placed in a vacuum drying oven and dried for at least 24 hours to obtain the activated carbon-supported TBD base catalyst.

[0098] As Figure 1 shown, the Fourier transform infrared spectra of the initial activated carbon, intermediate activated carbon, and activated carbon-supported TBD base catalyst of Example 7 were comparatively analyzed. The peak at 725 cm -1 representing the vibration of the C-Cl bond was significantly enhanced in the intermediate activated carbon compared with the initial activated carbon, proving that the activated carbon was successfully chloromethylated. This peak was significantly reduced or even disappeared in the activated carbon-supported TBD base catalyst, indicating that the chlorine atom had been nucleophilically substituted and left the solid system. The peak at 1570 cm -1 representing the vibration of the C-N bond was significantly enhanced in the activated carbon-supported TBD base catalyst, proving the newly formed C-N bond and indicating that TBD was loaded in a grafted form. The peak at 1380 cm -1 representing the vibration of the C=N bond was found to be enhanced in the spectrum of the activated carbon-supported TBD base catalyst, which was closely related to the C=N structure existing in the TBD structure, fully proving the introduction of TBD. It can be seen that the signals of the C-N and C=N bonds were both significantly distributed in the initial activated carbon, which was related to the fact that the activated carbon itself contained a certain amount of N element.

[0099] As Figure 2 shown, the 77K nitrogen adsorption-desorption isotherm curves of the initial activated carbon, intermediate activated carbon, and activated carbon-supported TBD base catalyst of Example 7 were presented; as Figure 3 shown, the pore size distribution diagrams of the initial activated carbon, intermediate activated carbon, and activated carbon-supported TBD base catalyst of Example 7 were presented. The curve shapes of all samples were similar, and the adsorption amount increased rapidly in the low-pressure region, which was attributed to micropore filling; at P / P 0When it is greater than 0.90, the curves all show steep adsorption, indicating that there are a certain number of macropores in the material. These conclusions are confirmed in the pore size distribution diagram. The material mainly includes micropores less than 2 nm and mesopores and macropores above 30 nm with a wide distribution. It can be seen that after the initial activated carbon undergoes surface functionalization, the specific surface area and pore volume decrease significantly, and the introduction of chloromethyl groups causes the micropore size to shrink. After grafting the organic base TBD, the specific surface area and pore volume of the material further decrease. Due to the relatively large size of the TBD molecule, a part of the small-sized micropores will be occupied and blocked during the grafting process. When the pore size in the carrier is greater than 1 nm, the blocking phenomenon significantly decreases, especially in the mesopore and macropore regions above 30 nm, where the pore density significantly decreases, proving that grafting a higher density of TBD in this region is beneficial for the substrate to diffuse and contact the basic sites to occur reactions.

[0100] To verify the catalytic activity of the activated carbon-supported TBD base catalyst in the Knoevenagel reaction in Example 7, the catalyst was evaluated in a continuous flow mode to obtain the reaction conversion rate and selectivity.

[0101] In a beaker, using N,N-dimethylformamide as a solvent, a homogeneous mixed raw material solution of 1.0 mol L -1 of benzaldehyde and 1.0 mol L -1 of malononitrile was prepared. Accurately weigh 1.0 g of the activated carbon-supported TBD base catalyst and densely pack it in a micro-packed bed reactor. The raw material solution was pumped into the reactor at a stable flow rate by a plunger pump and brought into full contact with the catalyst. The reactor was vertically placed in a constant-temperature electric heating jacket to maintain a constant temperature of 50 °C, and the back pressure valve was adjusted to keep the system pressure at 0.5 MPa. A small amount of product solution was collected at the tail of the reactor for composition analysis. At a residence time of 180 seconds, the conversion rate of benzaldehyde reached 100.0%, and the selectivity of the product benzylidene malononitrile reached 99.0%. Further, while continuously pumping the raw material solution into the system at a constant flow rate, a consistent product yield higher than 90% was obtained within at least 24 h, proving the stability of the catalyst.

[0102] Example 8

[0103] Prepare a 1,4-dioxane solution of 50.0 g of cis-1,4-dichloro-2-butene with a mass fraction of 15.0 wt%. Then add 10.0 g of washed and dried activated carbon, and introduce it into a reflux system. React at a constant temperature of 120 °C for 150 hours. After the reaction is completed, quickly cool it to room temperature. The filtered solid is further washed thoroughly with toluene and 1,4-dioxane, and dried overnight in a vacuum drying oven to obtain the intermediate activated carbon.

[0104] The intermediate activated carbon and 1,8-diazabicyclo[5.4.0]undec-7-ene were mixed in a mass ratio of 100:30, and then 50.0 g of the solvent acetonitrile was added. The mixture was continuously stirred and reacted at 80 °C for 24 hours. Then, it was filtered using a Buchner funnel and successively washed thoroughly with pure solvent acetonitrile, 1.0 mol L -1 of sodium hydroxide solution and deionized water to remove the physically adsorbed 1,8-diazabicyclo[5.4.0]undec-7-ene remaining on the surface. Finally, it was placed in a vacuum drying oven and dried overnight to obtain the activated carbon-supported DBU base catalyst.

[0105] To verify the catalytic activity of the activated carbon-supported DBU base catalyst in the Henry reaction in Example 8, the catalyst was evaluated in a continuous flow mode to obtain the reaction conversion and selectivity.

[0106] In a round-bottom flask, using dimethyl sulfoxide as the solvent, a homogeneous mixed feed solution of 0.8 mol L -1 of furfural and 0.8 mol L -1 of nitromethane was prepared. 1.0 g of the activated carbon-supported DBU base catalyst was accurately weighed and filled in a micro-packed bed reactor. The feed solution was pumped into the reactor at a stable flow rate by a plunger pump and brought into full contact with the catalyst. The reactor was placed in an oil bath and maintained at a constant temperature of 50 °C. The system pressure was adjusted to 0.8 MPa by a back pressure valve. A small amount of product solution was collected at the tail of the reactor for composition analysis. At a residence time of 120 seconds, the conversion of furfural reached 100.0% and the product selectivity reached 99.0%.

[0107] In the description of this specification, the description with reference to terms such as "one embodiment", "some embodiments", "examples", "specific examples", or "some examples" means that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described can be combined in a suitable manner in any one or more embodiments or examples. In addition, without contradiction, those skilled in the art can combine and combine the different embodiments or examples described in this specification and the features of different embodiments or examples.

[0108] Although the embodiments of the present application have been shown and described above, it can be understood that the above embodiments are exemplary and should not be construed as limiting the present application. Those of ordinary skill in the art can make changes, modifications, substitutions, and variations to the above embodiments within the scope of the present application.

Claims

1. A supported organic base catalyst, characterized in that: include: Functionalized activated carbon, wherein the functionalized activated carbon has a Bronsted base site comprising an organic Bronsted base molecular structure, wherein the organic Bronsted base molecular structure is connected to the surface of the functionalized activated carbon through a covalent bond.

2. The immobilized organic base catalyst according to claim 1, characterized in that The organic Bronsted base molecule includes at least one of ethylenediamine, diethylenetriamine, tetraethylenepentamine, N-methylethylenediamine, ethanolamine, 1,4-butanediamine, 1,6-hexanediamine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and 1,8-diazabicyclo[5.4.0]undec-7-ene.

3. The immobilized organic base catalyst according to claim 1 or 2, characterized in that: The solid-supported organic base catalyst includes at least one of the compounds shown in Formula 1 to Formula 9:

4. A method for preparing the immobilized organic base catalyst according to any one of claims 1 to 3, characterized in that: include: (1) treating activated carbon with a functionalizing agent to obtain an intermediate activated carbon having an activated group; (2) mixing the intermediate activated carbon, the organic Bronsted base molecule and the first solvent, and reacting them to obtain a solid-supported organic base catalyst.

5. The method for preparing a supported organic base catalyst according to claim 4, characterized in that: In step (1), the temperature of treating the activated carbon with the functionalizing agent is 25°C to 150°C and the time is 2h to 200h; and / or, in step (1), the mass ratio of the activated carbon to the functionalizing agent is 1:4 to 1:100; And / or, in step (1), the functionalizing agent includes at least one of ozone / oxygen mixed gas, nitric acid solution, maleic anhydride solution, sodium hydroxide solution, potassium hydroxide solution, thionyl chloride solution, and cis-1,4-dichloro-2-butene solution.

6. The method for preparing a supported organic base catalyst according to claim 5, characterized in that: The mass concentration of ozone in the ozone / oxygen mixed gas is 5 mg / L to 200 mg / L; And / or, the mass concentration of the nitric acid solution is 5wt% to 50wt%; And / or, the mass concentration of the maleic anhydride solution is 60wt% to 99wt%; And / or, the mass concentration of the sodium hydroxide solution is 2wt% to 30wt%; And / or, the mass concentration of the potassium hydroxide solution is 2wt% to 30wt%; And / or, the mass concentration of the thionyl chloride solution is 60wt% to 99wt%; And / or, the mass concentration of the cis-1,4-dichloro-2-butene solution is 60wt% to 99wt%.

7. The method for preparing a supported organic base catalyst according to any one of claims 4 to 6, characterized in that: In step (2), the reaction temperature is 50°C to 110°C, and the reaction time is 4h to 24h; and / or, in step (2), the mass ratio of the intermediate activated carbon to the organic Brønsted base molecule is 100:1 to 100:50; and / or, in step (2), the organic Bronsted base molecule comprises at least one of ethylenediamine, diethylenetriamine, tetraethylenepentamine, N-methylethylenediamine, ethanolamine, 1,4-butanediamine, 1,6-hexanediamine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and 1,8-diazabicyclo[5.4.0]undec-7-ene; And / or, in step (2), the first solvent includes at least one of ethanol, 1,4-dioxane, acetonitrile, toluene, tetrahydrofuran, and N,N-dimethylformamide.

8. Use of the immobilized organic base catalyst according to any one of claims 1 to 3 or the immobilized organic base catalyst prepared by the method according to any one of claims 4 to 7 in catalyzing a carbon-carbon bond forming reaction.

9. The use according to claim 8, characterized in that: The carbon-carbon bond forming reaction comprises at least one of an aldol condensation reaction, a Knoevenagel reaction and a Henry reaction; And / or, the specific operation mode of the carbon-carbon bond forming reaction includes at least one of a batch reactor mode and a continuous flow mode.

10. The use according to claim 9, characterized in that: The intermittent reactor mode comprises: uniformly mixing the immobilized organic base catalyst, the reaction substrate and the second solvent in a reactor, and stirring until the reaction is completed; And / or, the continuous flow mode includes: densely filling the immobilized organic base catalyst in a reactor, using a pump to deliver a uniform reactant solution into the reactor, and the outlet is the obtained product solution.

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