Preparation and application of a polymer based on spirobifluorene structure

Abstract

The application discloses a preparation and application of a polymer based on a spirobifluorene structure, and a preparation method thereof, which comprises the following steps: dissolving spirobifluorene monomers and aromatic ring monomers as raw materials in an organic solvent to obtain a reaction solution; adding the reaction solution into a catalyst under an inert atmosphere and heating to react to obtain a product; washing the product to obtain a filter cake, and then washing and drying the filter cake 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 through a Sonogashira coupling reaction, and the operation is simple and has a high yield. The porous organic polymer prepared by the application has excellent photocatalytic performance, and can efficiently generate hydrogen peroxide under light conditions. The application provides a new idea and method for designing and synthesizing a novel photocatalyst, especially in the aspect of efficiently generating hydrogen peroxide through photocatalysis.

Description

Technical Field

[0001] The present invention relates to the preparation and application of an organic photocatalytic material, 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, suffer from severe pollution, high energy consumption, and difficulties in storage and transportation.

[0003] Photocatalytic technology, which converts light energy into chemical energy, boasts the advantages of high efficiency, gentleness, and sustainable green development. Porous organic polymer (POPs) photocatalysts offer advantages such as environmental friendliness, visible light responsiveness, and easily tunable structure. However, the rapid recombination of photogenerated charges, slow charge carrier migration, and sluggish reaction kinetics severely hinder the performance improvement and industrial application of POPs. Therefore, the development of efficient POPs photocatalysts to address these challenges is needed. Summary of the Invention

[0004] Objectives of the invention: The present invention provides a method for preparing a spirobifluorene-based polymer, thereby addressing the problem of how to prepare such polymers. Another objective of the present invention is to propose the use of spirobifluorene-based polymers in the photocatalytic production of hydrogen peroxide, thereby addressing the problem of how to prepare such polymers.

[0005] Technical solution: The method for preparing a polymer based on a spirobifluorene structure according to 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 the following;

[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 prepares POPs by polymerizing different spirobifluorene monomers and different aromatic ring monomers through a Sonogashira coupling reaction. 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 for increasing 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 eluting and drying the solid powder to obtain a polymer based on the 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, bistriphenylphosphine palladium dichloride, palladium acetate, and palladium tetrachloride; preferably, it is a mixture of cuprous iodide and tetrakis(triphenylphosphine)palladium.

[0019] The inert atmosphere is argon or nitrogen atmosphere; the heating reaction is 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; and the solid powder is eluted in a Soxhlet extractor using at least one of dichloromethane, methanol, tetrahydrofuran, acetone, and ether 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 includes the following steps:

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

[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 using a xenon lamp, and the constant temperature reaction method is a constant temperature 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 simple to operate, and has a high yield.

[0028] 2. The porous organic polymer produced by the present invention has excellent photocatalytic properties and can efficiently generate hydrogen peroxide under light conditions. This invention provides new ideas and methods for the design and synthesis of new photocatalysts, especially for 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 This is the infrared spectrum of the polymer TS-2,2-2Br prepared in Example 1;

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

[0032] Figure 4 This is a graph showing the photocatalytic hydrogen peroxide production rate 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 This is a graph showing the photocatalytic hydrogen peroxide production rate 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 will be further described below with reference to 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 to 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 FIG. Figure 1 、 2 , 3, 5, 7, Figure 1 The water contact angle was 115°, indicating that the material was hydrophobic. 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 654 nm. 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 to 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) 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 were added to a Shrek bottle equipped with a magnetic rod and stirred under a nitrogen atmosphere for 15-30 minutes;

[0053] (2) After the solids in step (1) are completely dissolved, cuprous iodide (171.4 mg, 0.90 mmol) and tetrakis(triphenylphosphine)palladium (520.0 mg, 0.45 mmol) are sequentially added to the above solution, 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, and the product is obtained by suction filtration to obtain a filter cake, which is sequentially washed with water, tetrahydrofuran, methanol, and dichloromethane;

[0055] (4) The filter cake obtained in step (3) is transferred to a Soxhlet extractor, and tetrahydrofuran, methanol, and dichloromethane are sequentially used for elution for 48 hours. The eluted filter cake is 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) 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 are added to a Schlenk bottle equipped with a magnetic stirrer, and stirred for 15-30 minutes under a nitrogen atmosphere;

[0059] (2) After the solids in step (1) are completely dissolved, cuprous iodide (228.5 mg, 1.20 mmol) and tetrakis(triphenylphosphine)palladium (693.3 mg, 0.60 mmol) are sequentially added to the above solution, 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, and the product is obtained by suction filtration to obtain a filter cake, which is sequentially washed with water, tetrahydrofuran, methanol, and dichloromethane;

[0061] (4) The filter cake obtained in step (3) is transferred to a Soxhlet extractor, and tetrahydrofuran, methanol, and dichloromethane are sequentially used for elution for 48 hours. The eluted filter cake is 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-tris(4-ethynylphenyl)benzene (1.26 g, 3.33 mmol), 160 mL of N,N-dimethylformamide, and 80 mL of diisopropylamine to 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-tris(4-ethynylphenyl)benzene (1.26 g, 3.33 mmol), 160 mL of N,N-dimethylformamide, and 80 mL of diisopropylamine to 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-tris(4-ethynylphenyl)benzene (1.89 g, 5 mmol), 160 mL of N,N-dimethylformamide, and 80 mL of diisopropylamine to 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) 2,2',7,7'-tetrabromo-9,9'-spirobifluorene (3.16 g, 5 mmol), 1,3,5-tris(4-ethynylphenyl)benzene (2.52 g, 6.66 mmol), 160 mL of N,N-dimethylformamide, and 80 mL of diisopropylamine were added to a Shrek bottle equipped with a magnetic rod and stirred 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), tris(4-ethynylphenyl)amine (1.06 g, 3.33 mmol), 160 mL of N,N-dimethylformamide, and 80 mL of diisopropylamine to a Shrek bottle equipped with a magnetic rod 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), tris(4-ethynylphenyl)amine (1.06 g, 3.33 mmol), 160 mL of N,N-dimethylformamide, and 80 mL of diisopropylamine to a Shrek bottle equipped with a magnetic rod and stir under a nitrogen atmosphere for 15-30 minutes;

[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) 2,2',7-Tribromo-9,9'-spirobi[fluorene] (2.77 g, 5 mmol), tris(4-ethynylphenyl)amine (1.59 g, 5 mmol), 160 mL of N,N-dimethylformamide, and 80 mL of diisopropylamine were added to a Shrek bottle equipped with a magnetic rod and stirred 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) 2,2',7,7'-tetrabromo-9,9'-spirobifluorene (3.16 g, 5 mmol), tris(4-ethynylphenyl)amine (2.11 g, 6.66 mmol), 160 mL of N,N-dimethylformamide, and 80 mL of diisopropylamine were added to a Shrek bottle equipped with a magnetic rod and stirred 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 structured porous organic polymers prepared in Examples 1-4, add them to 20 mL of pure water in a centrifuge tube, and 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 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 xenon lamp with a power of 300 watts 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 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 aqueous 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 in a continuous stirring state, and a xenon lamp with a power of 300 watts is used to continuously illuminate the reactor. After 60 minutes of illumination, take 2 mL of the reaction solution and filter it with 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 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: 5 mg of the spirobifluorene structured porous organic polymer prepared in Example 1 was added to a 20 mL centrifuge tube. After 5 to 10 minutes of ultrasonic dispersion, it was transferred to a constant temperature reactor. The reactor was kept in a continuous ventilation state using balloons filled with nitrogen, air, and oxygen, respectively. The temperature was controlled at 25°C by circulating water, the reactor was kept in a continuous stirring state, and a xenon lamp with a power of 300 watts was used to continuously illuminate the reactor. After 60 minutes of illumination, 2 mL of the reaction solution was taken and filtered using a 0.22 μm filter. 1.5 mL of the filtered liquid was placed in a centrifuge tube and 1 mL of 1 mol L -1 The potassium titanium oxalate aqueous solution was mixed and reacted for 5 minutes, and the 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 following; 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, wherein: 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, wherein: 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 eluting and drying the solid powder to obtain a polymer based on the 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, bistriphenylphosphine palladium dichloride, palladium acetate, and palladium tetrachloride; the inert atmosphere is argon or nitrogen; 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 with at least one of dichloromethane, methanol, ethanol, tetrahydrofuran, water, dilute hydrochloric acid, and acetone; and the solid powder is eluted in a Soxhlet extractor with at least one of dichloromethane, methanol, tetrahydrofuran, acetone, and ether 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-based polymer in water to obtain a raw material solution; (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 material-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 using a xenon lamp, and the constant temperature reaction method is a constant temperature reaction at room temperature in an oxygen-containing gas atmosphere for at least 60 minutes.

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