Preparation and application of polymer based on spirobifluorene structure

Abstract

The invention discloses preparation and application of a polymer based on a spirobifluorene structure. A preparation method comprises the following steps: dissolving a spirobifluorene monomer and an aromatic ring monomer serving as raw materials in an organic solvent to obtain a reaction solution; adding a catalyst into the reaction liquid in an inert atmosphere, and heating to react to obtain a product; and washing a filter cake obtained by filtering the product to obtain solid powder, and eluting and drying the solid powder to obtain the polymer based on the spirobifluorene structure. The polymer can be applied to photocatalytic production of hydrogen peroxide. The porous organic polymer containing the spirobifluorene structure is synthesized in one step through the Sonogashira coupling reaction, the operation is simple and convenient, and the yield is relatively high. The prepared porous organic polymer has excellent photocatalytic performance, and hydrogen peroxide can be efficiently generated under the illumination condition. The invention provides a new thought and method for designing and synthesizing a novel photocatalyst, especially in the aspect of high-efficiency photocatalytic generation of hydrogen peroxide.

Description

Technical Field

[0001] The invention relates to the preparation and application of an organic photocatalytic material, and in particular to the preparation of a polymer based on a spirobifluorene structure and the application of the polymer in photocatalytic production of hydrogen peroxide. Background Art

[0002] Hydrogen peroxide (H2O2) is widely used in industries such as pulp and textile bleaching, hydrometallurgy, and electronic equipment factories. However, traditional H2O2 production methods, such as the anthraquinone process, have problems such as severe pollution, high energy consumption, and difficulty in storage and transportation.

[0003] Photocatalytic technology uses light energy to convert into chemical energy, and has the advantages of high efficiency, mildness, and green sustainability. Porous organic polymer (POPs) photocatalysts have the advantages of being environmentally friendly, responsive to visible light, and easy to control in structure. However, the rapid recombination of photogenerated charges, slow charge carrier migration, and slow reaction kinetics seriously hinder the improvement of POPs performance and its industrial application. Therefore, it is necessary to develop efficient POPs photocatalysts to address the above problems. Summary of the invention

[0004] Purpose of the invention: The purpose of the present invention is to provide a method for preparing a polymer based on a spirobifluorene structure, thereby solving the problem of how to prepare a polymer based on a spirobifluorene structure. Another purpose of the present invention is to propose the use of a polymer based on a spirobifluorene structure in the photocatalytic preparation of hydrogen peroxide, thereby solving the problem of how to photocatalytically prepare hydrogen peroxide.

[0005] Technical solution: The method for preparing a polymer based on a spirobifluorene structure described in the present invention comprises any one of the following steps:

[0006]

[0007]

[0008] wherein R1, R2, R3, and R4 are independently selected from H or halogen, and at least two of R1, R2, R3, and R4 are halogen, and R is selected from N, One of;

[0009] The halogen group in the monomer I or the monomer II undergoes a Sonogashira coupling reaction with the alkynyl group in the monomer III.

[0010] The present invention uses a Sonogashira coupling reaction to polymerize different spirobifluorene monomers and different aromatic ring monomers to prepare POPs, and the formed donor-π connection-acceptor (D-π-A) structure reduces the exciton binding energy, reduces the recombination of photogenerated carriers, and improves the efficient separation and transmission efficiency of electrons, which is of great significance to the improvement of the yield of hydrogen peroxide produced by POPs photocatalysis.

[0011] Preferably, the halogen is at least one of Br, F, Cl, and I.

[0012] Preferably, the above reaction specifically comprises the following steps:

[0013] (1) dissolving monomer I and monomer III as raw materials or monomer II and monomer III as raw materials in an organic solvent to obtain a reaction solution;

[0014] (2) adding a catalyst to the reaction solution under an inert atmosphere and heating the reaction solution to obtain a product;

[0015] (3) washing the filter cake after filtering the product to obtain a solid powder, and then washing and drying the solid powder to obtain a polymer based on a spirobifluorene structure.

[0016] Preferably, in step (1), the molar ratio of the monomer I to the monomer III is 5:3-7; the molar ratio of the monomer II to the monomer III is 5:3-7.

[0017] Preferably, in step (1), the organic solvent comprises at least one of chloroform, N,N-dimethylformamide, 1,4-dioxane, diisopropylamine, N,N-diisopropylethylamine, tetrahydrofuran, methanol and ethanol, preferably a mixture of diisopropylamine and N,N-dimethylformamide.

[0018] Preferably, in step (2), the catalyst comprises cuprous iodide and at least one of tetrakis(triphenylphosphine)palladium, bis(triphenylphosphine)palladium dichloride, palladium acetate, and palladium tetrachloride; preferably, it is a mixture of cuprous iodide and tetrakis(triphenylphosphine)palladium.

[0019] The inert atmosphere is an argon or nitrogen atmosphere; the heating reaction is a reflux reaction at 100-120° C. for 48-96 hours.

[0020] Preferably, in step (3), the filter cake is washed using at least one of dichloromethane, methanol, ethanol, tetrahydrofuran, water, dilute hydrochloric acid and acetone; the solid powder is eluted using at least one of dichloromethane, methanol, tetrahydrofuran, acetone and ether in a Soxhlet extractor for 12-48 hours.

[0021] Another aspect of the present invention discloses the use of the spirobifluorene structure-based polymer obtained by the above preparation method in the photocatalytic production of hydrogen peroxide.

[0022] The above-mentioned application of the spirobifluorene structure-based polymer photocatalytic production of hydrogen peroxide comprises the following steps:

[0023] (1) dispersing a spirobifluorene structure-based polymer in water to obtain a raw material liquid;

[0024] (2) The raw material liquid is reacted at a constant temperature under light conditions to obtain hydrogen peroxide.

[0025] Preferably, in step (1), the source of the water body includes at least one of pure water, surface water, seawater, and urban tap water, and the solid-liquid ratio of the polymer based on the spirobifluorene structure to the water body is 2.5-10 mg: 20 mL. In step (2), the lighting condition is continuous illumination by a xenon lamp, and the isothermal reaction method is a isothermal reaction at room temperature in an oxygen-containing gas atmosphere for at least 60 minutes.

[0026] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages:

[0027] 1. The present invention synthesizes a porous organic polymer containing a spirobifluorene structure in one step through a Sonogashira coupling reaction. This method utilizes spirobifluorene and its derivatives to react with aromatic ring monomers, is easy to operate and has a high yield.

[0028] 2. The porous organic polymer prepared by the present invention has excellent photocatalytic performance and can efficiently generate hydrogen peroxide under light conditions. The present invention provides new ideas and methods for designing and synthesizing new photocatalysts, especially in the efficient photocatalytic generation of hydrogen peroxide. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 1 is the water contact angle of the polymer TS-2,2-2Br prepared in Example 1;

[0030] Figure 2 is the infrared spectrum of the polymer TS-2,2-2Br prepared in Example 1;

[0031] Figure 3 is the Mott-Schottky spectrum of the polymer TS-2,2-2Br prepared in Example 1;

[0032] Figure 4 The photocatalytic hydrogen peroxide production rate diagram of the polymer TS-2,2-2Br prepared in Example 1 under different water sources;

[0033] Figure 5 This is the solid UV spectrum of the polymer TS-2,2-2Br prepared in Example 1;

[0034] Figure 6 The photocatalytic hydrogen peroxide production rate diagram of the polymer TS-2,2-2Br prepared in Example 1 under different atmospheres;

[0035] Figure 7 This is the photocurrent spectrum of the polymer TS-2,2-2Br prepared in Example 1;

[0036] Figure 8 This is a graph showing the photocatalytic hydrogen peroxide production rate of the polymer TS-2,2-2Br prepared in Example 1 at different contents. DETAILED DESCRIPTION

[0037] The technical solution of the present invention is further described below in conjunction with the accompanying drawings.

[0038] Example 1: A method for preparing a polymer based on a spirobifluorene structure is as follows:

[0039]

[0040] (1) Add 2,2'-dibromo-9,9'-spirobifluorene (2.37 g, 5 mmol), 2,4,6-tris(4-ethynylphenyl)-1,3,5-triazine (1.27 g, 3.33 mmol), 160 mL of N,N-dimethylformamide, and 80 mL of diisopropylamine into a Shrek bottle equipped with a magnetic rod, and stir under a nitrogen atmosphere for 15-30 minutes;

[0041] (2) After the solid in step (1) is completely dissolved, cuprous iodide (114.3 mg, 0.60 mmol) and tetrakis(triphenylphosphine)palladium (346.7 mg, 0.30 mmol) are added to the above solution in sequence, and the mixed solution is heated to 110° C. and refluxed for 72 hours;

[0042] (3) After the reaction is completed, the reaction system is cooled to room temperature, the product is filtered to obtain a filter cake, and the obtained filter cake is washed with water, tetrahydrofuran, methanol, and dichloromethane in sequence;

[0043] (4) The filter cake obtained in step (3) was transferred to a Soxhlet extractor and eluted with tetrahydrofuran, methanol, and dichloromethane in sequence for 48 hours. The eluted filter cake was placed in a vacuum oven and vacuum dried at 50° C. for 24 hours to obtain a porous organic polymer TS-2,2-2Br based on a spirobifluorene structure with a yield of 92%. The characterization test results of TS-2,2-2Br are shown in Figure 1 , 2 , 3, 5, 7, Figure 1 The water contact angle was shown to be 115°, indicating a hydrophobic material. Figure 2 Display 515-690cm-1 The stretching vibration peak of C-Br disappeared, proving that the material was successfully synthesized. Figure 3 The conduction band (CB) was shown to be -0.6V. Figure 5 The maximum absorption wavelength is shown to be 654nm. Figure 7 The display material has a strong photocurrent response.

[0044] Example 2: A method for preparing a polymer based on a spirobifluorene structure is as follows:

[0045]

[0046] (1) Add 2,7-dibromo-9,9-spirobifluorene (2.37 g, 5 mmol), 2,4,6-tris(4-ethynylphenyl)-1,3,5-triazine (1.27 g, 3.33 mmol), 160 mL of N,N-dimethylformamide, and 80 mL of diisopropylamine into a Shrek bottle equipped with a magnetic rod, and stir under a nitrogen atmosphere for 15-30 minutes;

[0047] (2) After the solid in step (1) is completely dissolved, cuprous iodide (114.3 mg, 0.60 mmol) and tetrakis(triphenylphosphine)palladium (346.7 mg, 0.30 mmol) are added to the above solution in sequence, and the mixed solution is heated to 110° C. and refluxed for 72 hours;

[0048] (3) After the reaction is completed, the reaction system is cooled to room temperature, the product is filtered to obtain a filter cake, and the obtained filter cake is washed with water, tetrahydrofuran, methanol, and dichloromethane in sequence;

[0049] (4) The filter cake obtained in step (3) was transferred to a Soxhlet extractor and eluted with tetrahydrofuran, methanol and dichloromethane in sequence for 48 hours. The eluted filter cake was placed in a vacuum oven and vacuum dried at 50° C. for 24 hours to obtain a porous organic polymer TS-2,7-2Br based on a spirobifluorene structure with a yield of 93%.

[0050] Example 3: A method for preparing a polymer based on a spirobifluorene structure is as follows:

[0051]

[0052] (1) Add 2,2',7-tribromo-9,9'-spirobi[fluorene] (2.77 g, 5 mmol), 2,4,6-tris(4-ethynylphenyl)-1,3,5-triazine (1.91 g, 5 mmol), 160 mL of N,N-dimethylformamide, and 80 mL of diisopropylamine into a Shrek bottle equipped with a magnetic rod, and stir under a nitrogen atmosphere for 15-30 minutes;

[0053] (2) After the solid in step (1) is completely dissolved, cuprous iodide (171.4 mg, 0.90 mmol) and tetrakis(triphenylphosphine)palladium (520.0 mg, 0.45 mmol) are added to the above solution in sequence, and the mixed solution is heated to 110° C. and refluxed for 72 hours;

[0054] (3) After the reaction is completed, the reaction system is cooled to room temperature, the product is filtered to obtain a filter cake, and the obtained filter cake is washed with water, tetrahydrofuran, methanol, and dichloromethane in sequence;

[0055] (4) The filter cake obtained in step (3) was transferred to a Soxhlet extractor and eluted with tetrahydrofuran, methanol and dichloromethane in sequence for 48 hours. The eluted filter cake was placed in a vacuum oven and vacuum dried at 50° C. for 24 hours to obtain a porous organic polymer TS-3Br based on a spirobifluorene structure with a yield of 92%.

[0056] Example 4: A method for preparing a polymer based on a spirobifluorene structure is as follows:

[0057]

[0058] (1) Add 2,2',7,7'-tetrabromo-9,9'-spirobifluorene (3.16 g, 5 mmol), 2,4,6-tris(4-ethynylphenyl)-1,3,5-triazine (2.54 g, 6.66 mmol), 160 mL of N,N-dimethylformamide, and 80 mL of diisopropylamine into a Shrek bottle equipped with a magnetic rod, and stir under a nitrogen atmosphere for 15-30 minutes;

[0059] (2) After the solid in step (1) is completely dissolved, cuprous iodide (228.5 mg, 1.20 mmol) and tetrakis(triphenylphosphine)palladium (693.3 mg, 0.60 mmol) are added to the above solution in sequence, and the mixed solution is heated to 110° C. and refluxed for 72 hours;

[0060] (3) After the reaction is completed, the reaction system is cooled to room temperature, the product is filtered to obtain a filter cake, and the obtained filter cake is washed with water, tetrahydrofuran, methanol, and dichloromethane in sequence;

[0061] (4) The filter cake obtained in step (3) was transferred to a Soxhlet extractor and eluted with tetrahydrofuran, methanol and dichloromethane in sequence for 48 hours. The eluted filter cake was placed in a vacuum oven and vacuum dried at 50° C. for 24 hours to obtain a porous organic polymer TS-4Br based on a spirobifluorene structure with a yield of 95%.

[0062] Example 5: A method for preparing a polymer based on a spirobifluorene structure is as follows:

[0063]

[0064] (1) Add 2,2'-dibromo-9,9'-spirobifluorene (2.37 g, 5 mmol), 1,3,5-tri(4-ethynylphenyl)benzene (1.26 g, 3.33 mmol), 160 mL of N,N-dimethylformamide, and 80 mL of diisopropylamine into a Shrek bottle equipped with a magnetic rod, and stir under a nitrogen atmosphere for 15-30 minutes;

[0065] (2) After the solid in step (1) is completely dissolved, cuprous iodide (114.3 mg, 0.60 mmol) and tetrakis(triphenylphosphine)palladium (346.7 mg, 0.30 mmol) are added to the above solution in sequence, and the mixed solution is heated to 110° C. and refluxed for 72 hours;

[0066] (3) After the reaction is completed, the reaction system is cooled to room temperature, the product is filtered to obtain a filter cake, and the obtained filter cake is washed with water, tetrahydrofuran, methanol, and dichloromethane in sequence;

[0067] (4) The filter cake obtained in step (3) was transferred to a Soxhlet extractor and eluted with tetrahydrofuran, methanol and dichloromethane in sequence for 48 hours. The eluted filter cake was placed in a vacuum oven and vacuum dried at 50° C. for 24 hours to obtain a porous organic polymer TB-2,2-2Br based on a spirobifluorene structure with a yield of 92%.

[0068] Example 6: A method for preparing a polymer based on a spirobifluorene structure is as follows:

[0069]

[0070] (1) Add 2,7-dibromo-9,9-spirobifluorene (2.37 g, 5 mmol), 1,3,5-tri(4-ethynylphenyl)benzene (1.26 g, 3.33 mmol), 160 mL of N,N-dimethylformamide, and 80 mL of diisopropylamine into a Shrek bottle equipped with a magnetic rod, and stir under a nitrogen atmosphere for 15-30 minutes;

[0071] (2) After the solid in step (1) is completely dissolved, cuprous iodide (114.3 mg, 0.60 mmol) and tetrakis(triphenylphosphine)palladium (346.7 mg, 0.30 mmol) are added to the above solution in sequence, and the mixed solution is heated to 110° C. and refluxed for 72 hours;

[0072] (3) After the reaction is completed, the reaction system is cooled to room temperature, the product is filtered to obtain a filter cake, and the obtained filter cake is washed with water, tetrahydrofuran, methanol, and dichloromethane in sequence;

[0073] (4) The filter cake obtained in step (3) was transferred to a Soxhlet extractor and eluted with tetrahydrofuran, methanol and dichloromethane in sequence for 48 hours. The eluted filter cake was placed in a vacuum oven and vacuum dried at 50° C. for 24 hours to obtain a porous organic polymer TB-2,7-2Br based on a spirobifluorene structure with a yield of 93%.

[0074] Example 7: A method for preparing a polymer based on a spirobifluorene structure is as follows:

[0075]

[0076] (1) Add 2,2',7-tribromo-9,9'-spirobi[fluorene] (2.77 g, 5 mmol), 1,3,5-tri(4-ethynylphenyl)benzene (1.89 g, 5 mmol), 160 mL of N,N-dimethylformamide, and 80 mL of diisopropylamine into a Shrek bottle equipped with a magnetic rod, and stir under a nitrogen atmosphere for 15-30 minutes;

[0077] (2) After the solid in step (1) is completely dissolved, cuprous iodide (171.4 mg, 0.90 mmol) and tetrakis(triphenylphosphine)palladium (520.0 mg, 0.45 mmol) are added to the above solution in sequence, and the mixed solution is heated to 110° C. and refluxed for 72 hours;

[0078] (3) After the reaction is completed, the reaction system is cooled to room temperature, the product is filtered to obtain a filter cake, and the obtained filter cake is washed with water, tetrahydrofuran, methanol, and dichloromethane in sequence;

[0079] (4) The filter cake obtained in step (3) was transferred to a Soxhlet extractor and eluted with tetrahydrofuran, methanol and dichloromethane in sequence for 48 hours. The eluted filter cake was placed in a vacuum oven and vacuum dried at 50° C. for 24 hours to obtain a porous organic polymer TB-3Br based on a spirobifluorene structure with a yield of 94%.

[0080] Example 8: A method for preparing a polymer based on a spirobifluorene structure is as follows:

[0081]

[0082] (1) Add 2,2',7,7'-tetrabromo-9,9'-spirobifluorene (3.16 g, 5 mmol), 1,3,5-tri(4-ethynylphenyl)benzene (2.52 g, 6.66 mmol), 160 mL of N,N-dimethylformamide, and 80 mL of diisopropylamine into a Shrek bottle equipped with a magnetic rod, and stir under a nitrogen atmosphere for 15-30 minutes;

[0083] (2) After the solid in step (1) is completely dissolved, cuprous iodide (228.5 mg, 1.20 mmol) and tetrakis(triphenylphosphine)palladium (693.3 mg, 0.60 mmol) are added to the above solution in sequence, and the mixed solution is heated to 110° C. and refluxed for 72 hours;

[0084] (3) After the reaction is completed, the reaction system is cooled to room temperature, the product is filtered to obtain a filter cake, and the obtained filter cake is washed with water, tetrahydrofuran, methanol, and dichloromethane in sequence;

[0085] (4) The filter cake obtained in step (3) was transferred to a Soxhlet extractor and eluted with tetrahydrofuran, methanol and dichloromethane in sequence for 48 hours. The eluted filter cake was placed in a vacuum oven and vacuum dried at 50° C. for 24 hours to obtain a porous organic polymer TB-4Br based on a spirobifluorene structure with a yield of 96%.

[0086] Example 9: A method for preparing a polymer based on a spirobifluorene structure is as follows:

[0087]

[0088] (1) Add 2,2'-dibromo-9,9'-spirobifluorene (2.37 g, 5 mmol), tri(4-ethynylphenyl)amine (1.06 g, 3.33 mmol), 160 mL of N,N-dimethylformamide, and 80 mL of diisopropylamine into a Shrek bottle equipped with a magnetic bar, and stir under a nitrogen atmosphere for 15-30 minutes;

[0089] (2) After the solid in step (1) is completely dissolved, cuprous iodide (114.3 mg, 0.60 mmol) and tetrakis(triphenylphosphine)palladium (346.7 mg, 0.30 mmol) are added to the above solution in sequence, and the mixed solution is heated to 110° C. and refluxed for 72 hours;

[0090] (3) After the reaction is completed, the reaction system is cooled to room temperature, the product is filtered to obtain a filter cake, and the obtained filter cake is washed with water, tetrahydrofuran, methanol, and dichloromethane in sequence;

[0091] (4) The filter cake obtained in step (3) was transferred to a Soxhlet extractor and eluted with tetrahydrofuran, methanol and dichloromethane in sequence for 48 hours. The eluted filter cake was placed in a vacuum oven and vacuum dried at 50° C. for 24 hours to obtain a porous organic polymer TN-2,2-2Br based on a spirobifluorene structure with a yield of 91%.

[0092] Example 10: A method for preparing a polymer based on a spirobifluorene structure is as follows:

[0093]

[0094] (1) Add 2,7-dibromo-9,9-spirobifluorene (2.37 g, 5 mmol), tri(4-ethynylphenyl)amine (1.06 g, 3.33 mmol), 160 mL of N,N-dimethylformamide, and 80 mL of diisopropylamine into a Shrek bottle equipped with a magnetic bar and stir for 15-30 minutes under a nitrogen atmosphere;

[0095] (2) After the solid in step (1) is completely dissolved, cuprous iodide (114.3 mg, 0.60 mmol) and tetrakis(triphenylphosphine)palladium (346.7 mg, 0.30 mmol) are added to the above solution in sequence, and the mixed solution is heated to 110° C. and refluxed for 72 hours;

[0096] (3) After the reaction is completed, the reaction system is cooled to room temperature, the product is filtered to obtain a filter cake, and the obtained filter cake is washed with water, tetrahydrofuran, methanol, and dichloromethane in sequence;

[0097] (4) The filter cake obtained in step (3) was transferred to a Soxhlet extractor and eluted with tetrahydrofuran, methanol and dichloromethane in sequence for 48 hours. The eluted filter cake was placed in a vacuum oven and vacuum dried at 50° C. for 24 hours to obtain a porous organic polymer TN-2,7-2Br based on a spirobifluorene structure with a yield of 94%.

[0098] Example 11: A method for preparing a polymer based on a spirobifluorene structure is as follows:

[0099]

[0100] (1) Add 2,2',7-tribromo-9,9'-spirobi[fluorene] (2.77 g, 5 mmol), tri(4-ethynylphenyl)amine (1.59 g, 5 mmol), 160 mL of N,N-dimethylformamide, and 80 mL of diisopropylamine into a Shrek bottle equipped with a magnetic bar, and stir under a nitrogen atmosphere for 15-30 minutes;

[0101] (2) After the solid in step (1) is completely dissolved, cuprous iodide (171.4 mg, 0.90 mmol) and tetrakis(triphenylphosphine)palladium (520.0 mg, 0.45 mmol) are added to the above solution in sequence, and the mixed solution is heated to 110° C. and refluxed for 72 hours;

[0102] (3) After the reaction is completed, the reaction system is cooled to room temperature, the product is filtered to obtain a filter cake, and the obtained filter cake is washed with water, tetrahydrofuran, methanol, and dichloromethane in sequence;

[0103] (4) The filter cake obtained in step (3) was transferred to a Soxhlet extractor and eluted with tetrahydrofuran, methanol and dichloromethane in sequence for 48 hours. The eluted filter cake was placed in a vacuum oven and vacuum dried at 50° C. for 24 hours to obtain a porous organic polymer TN-3Br based on a spirobifluorene structure with a yield of 94%.

[0104] Example 12: A method for preparing a polymer based on a spirobifluorene structure is as follows:

[0105]

[0106] (1) Add 2,2',7,7'-tetrabromo-9,9'-spirobifluorene (3.16 g, 5 mmol), tri(4-ethynylphenyl)amine (2.11 g, 6.66 mmol), 160 mL of N,N-dimethylformamide, and 80 mL of diisopropylamine into a Shrek bottle equipped with a magnetic bar, and stir under a nitrogen atmosphere for 15-30 minutes;

[0107] (2) After the solid in step (1) is completely dissolved, cuprous iodide (228.5 mg, 1.20 mmol) and tetrakis(triphenylphosphine)palladium (693.3 mg, 0.60 mmol) are added to the above solution in sequence, and the mixed solution is heated to 110° C. and refluxed for 72 hours;

[0108] (3) After the reaction is completed, the reaction system is cooled to room temperature, the product is filtered to obtain a filter cake, and the obtained filter cake is washed with water, tetrahydrofuran, methanol, and dichloromethane in sequence;

[0109] (4) The filter cake obtained in step (3) was transferred to a Soxhlet extractor and eluted with tetrahydrofuran, methanol and dichloromethane in sequence for 48 hours. The eluted filter cake was placed in a vacuum oven and vacuum dried at 50° C. for 24 hours to obtain a porous organic polymer TN-4Br based on a spirobifluorene structure with a yield of 98%.

[0110] Example 13: The porous organic polymer based on spirobifluorene structure obtained in Example 1, Example 2, Example 3 and Example 4 was used to study the photocatalytic production of hydrogen peroxide;

[0111] Experimental method: Take 5 mg of each of the spirobifluorene structure porous organic polymers prepared in Examples 1-4, add them to centrifuge tubes containing 20 mL of pure water, and transfer them to a constant temperature reactor after 5 to 10 minutes of ultrasonic dispersion. The temperature is controlled at 25°C by circulating water, the reactor is kept in a continuous stirring state, and a 300-watt xenon lamp is used to continuously illuminate the reactor. After 60 minutes of illumination, take 2 mL of the reaction solution and filter it using a 0.22 μm filter. Place 1.5 mL of the filtered liquid in a centrifuge tube and add 1 mL of 1 mol L-1 The potassium titanium oxalate aqueous solution was mixed and reacted for 5 minutes, the absorbance was measured by a UV-visible spectrophotometer, and the concentration of hydrogen peroxide was determined according to the standard curve. The results are shown in Table 1.

[0112] Table 1 Performance test results of different porous organic polymers for photocatalytic production of hydrogen peroxide

[0113]

[0114] Example 14: The porous organic polymer based on spirobifluorene structure obtained in Example 1 was used to study the photocatalytic production of hydrogen peroxide at different catalyst concentrations.

[0115] Experimental method: Take 2.5 mg, 5 mg, and 10 mg of the spirobifluorene structure porous organic polymer prepared in Example 1 and add them to a centrifuge tube containing 20 mL of pure water. After 5 to 10 minutes of ultrasonic dispersion, transfer them to a constant temperature reactor. The temperature is controlled at 25°C by circulating water, the reactor is kept in a continuous stirring state, and a 300-watt xenon lamp is used to continuously illuminate the reactor. After 60 minutes of illumination, take 2 mL of the reaction solution and filter it using a 0.22 μm filter. Place 1.5 mL of the filtered liquid in a centrifuge tube and add 1 mL of 1 mol L -1 The potassium titanium oxalate aqueous solution was mixed and reacted for 5 minutes, the absorbance was measured by a UV-visible spectrophotometer, and the concentration of hydrogen peroxide was determined according to the standard curve. The results are shown in Table 2.

[0116] Table 2 Effect of the concentration of porous organic polymer on the production of hydrogen peroxide

[0117]

[0118] Example 15: The porous organic polymer based on spirobifluorene structure obtained in Example 1 was used to study the photocatalytic production of hydrogen peroxide in different water substrates.

[0119] Experimental method: Take 5 mg of the spirobifluorene structure porous organic polymer prepared in Example 1 and add it to 20 mL of pure water, river water, tap water, sea water, and Yangtze River water in a centrifuge tube. After 5 to 10 minutes of ultrasonic dispersion, transfer it to a constant temperature reactor. The temperature is controlled at 25°C by circulating water, the reactor is kept in a continuous stirring state, and a 300-watt xenon lamp is used to continuously illuminate the reactor. After 60 minutes of illumination, take 2 mL of the reaction solution and filter it using a 0.22 μm filter. Place 1.5 mL of the filtered liquid in a centrifuge tube and add 1 mL of 1 mol L -1The potassium titanium oxalate aqueous solution was mixed and reacted for 5 minutes, the absorbance was measured by a UV-visible spectrophotometer, and the concentration of hydrogen peroxide was determined according to the standard curve. The results are shown in Table 3.

[0120] Table 3 Effects of different water sources on the photocatalytic performance of porous organic polymers

[0121]

[0122] Example 16: The porous organic polymer based on spirobifluorene structure obtained in Example 1 was used to study the photocatalytic production of hydrogen peroxide under different atmospheric conditions.

[0123] Experimental method: Take 5 mg of the spirobifluorene structure porous organic polymer prepared in Example 1 and add it to a 20 mL centrifuge tube. After 5 to 10 minutes of ultrasonic dispersion, transfer it to a constant temperature reactor. Use balloons filled with nitrogen, air, and oxygen to keep the reactor in a continuous ventilation state. The temperature is controlled at 25°C by circulating water, the reactor is kept in a continuous stirring state, and a 300-watt xenon lamp is used to continuously illuminate the reactor. After 60 minutes of illumination, take 2 mL of the reaction solution and filter it using a 0.22 μm filter. Place 1.5 mL of the filtered liquid in a centrifuge tube and add 1 mL of 1 mol L -1 The potassium titanium oxalate aqueous solution was mixed and reacted for 5 minutes, and its absorbance was measured by UV-visible spectrophotometer, and the concentration of hydrogen peroxide was determined according to the standard curve. The results are shown in Table 4:

[0124] Table 4 Effects of different atmospheres on the photocatalytic performance of porous organic polymers

[0125]

[0126] As can be seen from Table 4, the amount of photocatalytic products generated by porous organic polymers under aerobic conditions is significantly higher than that under anaerobic conditions. Therefore, in order to improve the photocatalytic performance of the polymer, it is necessary to provide a gas atmosphere containing oxygen for the reaction system.

Claims

1. A method for preparing a polymer based on a spirobifluorene structure, characterized in that: Include any of the following steps: wherein R1, R2, R3, and R4 are independently selected from H or halogen, and at least two of R1, R2, R3, and R4 are halogen, and R is selected from N, One of; The halogen group in the monomer I or the monomer II undergoes a Sonogashira coupling reaction with the alkynyl group in the monomer III.

2. The method for preparing a polymer based on a spirobifluorene structure according to claim 1, characterized in that: The halogen is at least one of Br, F, Cl and I.

3. The method for preparing a polymer based on a spirobifluorene structure according to claim 1, characterized in that: The steps include: (1) dissolving monomer I and monomer III as raw materials or monomer II and monomer III as raw materials in an organic solvent to obtain a reaction solution; (2) adding a catalyst to the reaction solution under an inert atmosphere and heating the reaction solution to obtain a product; (3) washing the filter cake after filtering the product to obtain a solid powder, and then washing and drying the solid powder to obtain a polymer based on a spirobifluorene structure.

4. The method for preparing a polymer based on a spirobifluorene structure according to claim 3, characterized in that: In step (1), the molar ratio of the monomer I to the monomer III is 5:3-7; the molar ratio of the monomer II to the monomer III is 5:3-7.

5. The method for preparing a polymer based on a spirobifluorene structure according to claim 3, characterized in that: In step (1), the organic solvent includes at least one of chloroform, N,N-dimethylformamide, 1,4-dioxane, diisopropylamine, N,N-diisopropylethylamine, tetrahydrofuran, methanol and ethanol.

6. The method for preparing a polymer based on a spirobifluorene structure according to claim 3, characterized in that: In step (2), the catalyst includes cuprous iodide and at least one of tetrakis(triphenylphosphine)palladium, bis(triphenylphosphine)palladium dichloride, palladium acetate, and palladium tetrachloride; the inert atmosphere is argon or nitrogen atmosphere; and the heating reaction is a reflux reaction at 100-120° C. for 48-96 hours.

7. The method for preparing a polymer based on a spirobifluorene structure according to claim 3, characterized in that: In step (3), the filter cake is washed using at least one of dichloromethane, methanol, ethanol, tetrahydrofuran, water, dilute hydrochloric acid, and acetone; the solid powder is eluted using at least one of dichloromethane, methanol, tetrahydrofuran, acetone, and ether in a Soxhlet extractor for 12-48 hours.

8. Use of the spirobifluorene structure-based polymer obtained by the preparation method according to any one of claims 1 to 7 in the photocatalytic production of hydrogen peroxide.

9. The use according to claim 8, characterized in that: The steps include: (1) dispersing a spirobifluorene structure-based polymer in water to obtain a raw material liquid; (2) The raw material liquid is reacted at a constant temperature under light conditions to obtain hydrogen peroxide.

10. The use according to claim 9, characterized in that: In step (1), the source of the water body includes at least one of pure water, surface water, seawater, and urban tap water, and the solid-liquid ratio of the polymer based on the spirobifluorene structure to the water body is 2.5-10 mg: 20 mL. In step (2), the lighting condition is continuous lighting using a xenon lamp, and the isothermal reaction method is a isothermal reaction at room temperature in an oxygen-containing gas atmosphere for at least 60 minutes.

Images