Porous organic polymer based on benzyl alcohol structure as well as preparation method and application of porous organic polymer

Abstract

The invention discloses a porous organic polymer based on a benzyl alcohol structure and a preparation method and application thereof, and relates to the field of organic photocatalytic materials.The preparation method comprises the following steps that a monomer I and a monomer II are dissolved in a solvent I; after dissolving, in an inert gas atmosphere, adding a catalyst, and heating for reaction; after the reaction is finished, filtering, and washing a filter cake with a solvent II; the obtained solid powder is eluted in a Soxhlet extractor, vacuum drying is conducted, and then the porous organic polymer based on the benzyl alcohol structure is obtained.The benzyl alcohol and derivatives thereof and the chloromethyl arene are subjected to the Friedel-Crafts reaction to synthesize the porous organic polymer containing the benzyl alcohol structure in one step, the synthesis method is simple, and the yield is high; the prepared porous organic polymer has good photocatalytic performance, and hydrogen peroxide can be efficiently produced under the photocatalytic condition; the invention provides a novel method and a novel idea which are simple to operate, effective and feasible for design and research and development of photocatalysts.

Description

Technical Field

[0001] The invention relates to the field of organic photocatalytic materials, and in particular to a porous organic polymer based on a benzyl alcohol structure, and a preparation method and application thereof. Background Art

[0002] Hydrogen peroxide is an important chemical reagent, often used as a green oxidant, disinfectant, bleaching agent and energy carrier. However, the current mainstream industrial method for producing hydrogen peroxide is the anthraquinone method. This energy-intensive method has many disadvantages, including high production costs and huge hidden dangers in production safety and environmental protection. Therefore, it is imperative to develop a low-cost, low-energy, and environmentally friendly hydrogen peroxide production process. At present, the sustainable production of hydrogen peroxide using photosynthesis is an effective alternative.

[0003] So far, various semiconductor materials have been used for photocatalytic production of hydrogen peroxide, such as g-C3N4, metal organic frameworks (MOFs), and porous organic polymers (POPs). Among them, POPs have received extensive attention in the field of photocatalysis due to their high specific surface area, low density, good stability, and uniform pore size.

[0004] However, the concentration of hydrogen peroxide produced by photocatalysis using POPs is still at the μM level, which cannot meet the requirements of industrial production. Therefore, it is urgent to develop an efficient photocatalyst. According to research, the two-phase system of benzyl alcohol and water has the performance of efficient production of hydrogen peroxide under photocatalytic conditions, but the two-phase system of benzyl alcohol and water will produce by-products such as benzaldehyde and benzoic acid under light, which is not conducive to its recovery. POPs have the advantages of strong stability and easy recovery. Combining the performance of benzyl alcohol in efficient production of hydrogen peroxide with the characteristics of strong stability and easy recovery of POPs is the main challenge currently faced. Summary of the invention

[0005] In order to provide a low-cost, low-energy, and environmentally friendly hydrogen peroxide production process without producing byproducts such as benzaldehyde and benzoic acid, and solve the problem that the byproduct benzoic acid produced by small molecule benzyl alcohol under photocatalytic conditions affects the purity of hydrogen peroxide, the present invention provides the following technical solutions:

[0006] Porous organic polymer based on benzyl alcohol structure, the structural formula is as follows:

[0007]

[0008] Among them, n=1, 2.

[0009] Porous organic polymer based on benzyl alcohol structure, the synthesis reaction formula is as follows:

[0010]

[0011] Among them, in the structure shown in monomer I: R1, R2, R3 are independently selected from H or CH2OH; in the structure shown in monomer II, n=1, 2; X is halogen.

[0012] The present invention also discloses a method for preparing a porous organic polymer based on a benzyl alcohol structure, comprising the following steps:

[0013] S1, dissolving monomer I and monomer II in a solvent;

[0014] S2, under an inert gas atmosphere, adding a catalyst and heating to react to obtain a first product;

[0015] S3, filtering the first product to obtain a filter cake;

[0016] S4, washing the filter cake and eluting it in a Soxhlet extractor, and drying it to obtain a porous organic polymer based on a benzyl alcohol structure.

[0017] Preferably, the molar ratio of monomer I to monomer II in S1 is: 0.2-2 g, 2-10 mmol: 0.2-2.5 g, 2-10 mmol.

[0018] Preferably, in S1, the solvent is at least one of chloroform, N,N-dimethylformamide, diisopropylamine, tetrahydrofuran, methanol, ethanol, 1,4-dioxane, acetonitrile and toluene.

[0019] Preferably, in S2, the catalyst is at least one of aluminum chloride, ferric chloride, and boron trifluoride etherate, and the amount of the catalyst is: 3-6g, 30-50mmol; the inert gas is argon or nitrogen, and the method of heating the reaction is to heat the temperature to 50-100°C and react for no less than 72 hours.

[0020] Preferably, in S4, the filter cake is washed using at least one of dichloromethane, methanol, tetrahydrofuran, water, dilute hydrochloric acid, acetone, ether, and N,N-dimethylformamide.

[0021] Preferably, in S4, the elution method is: eluting with at least one of dichloromethane, methanol, tetrahydrofuran, water, dilute hydrochloric acid, acetone, ether, and N,N-dimethylformamide in a Soxhlet extractor for 12 to 48 hours, and the drying method is: vacuum drying at 40 to 60° C. for not less than 24 hours.

[0022] The present invention also applies the porous organic polymer based on the benzyl alcohol structure to the photocatalytic production of hydrogen peroxide.

[0023] The present invention also discloses the application of a porous organic polymer based on a benzyl alcohol structure, comprising the following steps:

[0024] Weigh 2.5-10 mg of a porous organic polymer based on a benzyl alcohol structure and 20 mL of a feed solution, add them into a centrifuge tube, and ultrasonically disperse them for 5-10 minutes. Then transfer them to a constant temperature reactor, circulate water to keep it in a state of continuous stirring at 25°C, and continuously illuminate the reactor with a 300-watt xenon lamp. Take 2 mL of the reaction solution every 60 minutes and filter it with a 0.22 μm filter.

[0025] Beneficial effects of the present invention: The present invention uses benzyl alcohol and its derivatives and chloromethyl aromatic hydrocarbons to synthesize a porous organic polymer containing a benzyl alcohol structure in one step through a Friedel-Crafts reaction. The synthesis method is simple and has a high yield. The prepared porous organic polymer has good photocatalytic performance and can efficiently produce hydrogen peroxide under photocatalytic conditions.

[0026] The exposed benzyl alcohol functional group in the present invention not only retains its performance of producing hydrogen peroxide, but also solves the problem that the byproduct benzoic acid produced by small molecule benzyl alcohol under photocatalytic conditions affects the purity of hydrogen peroxide. The present invention provides a new method and new idea that is simple to operate, effective and feasible for the design and development of photocatalysts, which is of great significance to the improvement of the yield of hydrogen peroxide produced by POPs photocatalysis. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] Figure 1 The water contact angle of the porous organic polymer PBA2B-31 based on the benzyl alcohol structure prepared in Example 10;

[0028] Figure 2a The infrared spectrum of the porous organic polymer based on benzyl alcohol structure prepared in Example 1-4;

[0029] Figure 2b The infrared spectrum of the porous organic polymer based on benzyl alcohol structure prepared in Examples 5-8;

[0030] Figure 2c The infrared spectra of the porous organic polymer based on benzyl alcohol structure prepared in Examples 9-13;

[0031] Figure 3 The X-ray diffraction pattern of the porous organic polymer PBA2B-31 based on the benzyl alcohol structure prepared in Example 10;

[0032] Figure 4 X-ray photoelectron spectrum of the porous organic polymer PBA2B-31 based on benzyl alcohol structure prepared in Example 10;

[0033] Figure 5 The electrochemical impedance of the porous organic polymer PBA2B-31 based on the benzyl alcohol structure prepared in Example 10;

[0034] Figure 6This is a photocurrent diagram of the porous organic polymer PBA2B-31 based on the benzyl alcohol structure prepared in Example 10;

[0035] Figure 7 This is a graph showing the photocatalytic hydrogen peroxide production rate of the porous organic polymer PBA2B-31 based on the benzyl alcohol structure prepared in Example 10 at different catalyst concentrations;

[0036] Figure 8 This is a graph showing the photocatalytic hydrogen peroxide production rate of the porous organic polymer PBA2B-31 based on benzyl alcohol structure prepared in Example 10 under different atmospheres. DETAILED DESCRIPTION

[0037] In order to make the technical means, creative features, objectives and effects achieved by the present invention easy to understand, the present invention is further explained below in conjunction with specific implementation methods.

[0038] Example 1: A porous organic polymer BAB based on a benzyl alcohol structure, the structural formula of which is as follows:

[0039]

[0040] The synthesis method of the above polymer is as follows:

[0041]

[0042] (1) Add benzyl alcohol (1.78 g, 16 mmol), p-dichlorobenzyl (1.4 g, 8 mmol), and 50 mL of chloroform into a three-necked flask equipped with a magnetic rod, and stir for 15-30 minutes under a nitrogen atmosphere;

[0043] (2) After the solid in step (1) is completely dissolved, anhydrous aluminum chloride (5.3 g, 40 mmol) is added to the above solution in small amounts and in multiple times. After dispersion under a nitrogen atmosphere, the mixed solution is heated to 70° C. and refluxed for 72 hours;

[0044] (3) After the reaction is completed, the reaction system is cooled to room temperature and poured into ice water. A filter cake is obtained by suction filtration, and the obtained filter cake is washed with water, dilute hydrochloric acid, methanol, and dichloromethane in sequence;

[0045] (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 BAB based on a benzyl alcohol structure with a yield of 83%.

[0046] Example 2: A porous organic polymer PBAB based on a benzyl alcohol structure, the structural formula of which is as follows:

[0047]

[0048] The synthesis method of the above polymer is as follows:

[0049]

[0050] (1) Add p-benzhydrol (1.38 g, 10 mmol), p-dichlorobenzyl (900 mg, 5 mmol), and 50 mL of chloroform into a three-necked flask equipped with a magnetic rod, and stir under a nitrogen atmosphere for 15-30 minutes;

[0051] (2) After the solid in step (1) is completely dissolved, anhydrous aluminum chloride (4 g, 30 mmol) is added to the above solution in small amounts and in multiple times. After dispersion under a nitrogen atmosphere, the mixed solution is heated to 70° C. and refluxed for 72 hours;

[0052] (3) After the reaction is completed, the reaction system is cooled to room temperature and poured into ice water. A filter cake is obtained by suction filtration, and the obtained filter cake is washed with water, dilute hydrochloric acid, methanol, and dichloromethane in sequence;

[0053] (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 PBAB based on a benzyl alcohol structure with a yield of 84%.

[0054] Example 3: A porous organic polymer OBAB based on a benzyl alcohol structure, the structural formula of which is as follows:

[0055]

[0056] The synthesis method of the above polymer is as follows:

[0057]

[0058] (1) Add o-benzyl alcohol (1.38 g, 10 mmol), p-dichlorobenzyl (900 mg, 5 mmol), and 50 mL of chloroform into a three-necked flask 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, anhydrous aluminum chloride (4 g, 30 mmol) is added to the above solution in small amounts and in multiple times. After dispersion under a nitrogen atmosphere, the mixed solution is heated to 70° C. and refluxed for 72 hours;

[0060] (3) After the reaction is completed, the reaction system is cooled to room temperature and poured into ice water. A filter cake is obtained by suction filtration, and the obtained filter cake is washed with water, dilute hydrochloric acid, 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 OBAB based on a benzyl alcohol structure with a yield of 83%.

[0062] Example 4: A porous organic polymer MBAB based on a benzyl alcohol structure, the structural formula of which is as follows:

[0063]

[0064] The synthesis method of the above polymer is as follows:

[0065]

[0066] (1) Add s-tribenzyl alcohol (168 mg, 1 mmol), p-dichlorobenzyl (88 mg, 0.5 mmol), and 10 mL of chloroform into a three-necked flask equipped with a magnetic rod, and stir for 15-30 minutes under a nitrogen atmosphere;

[0067] (2) After the solid in step (1) is completely dissolved, anhydrous aluminum chloride (400 mg, 3 mmol) is added to the above solution in small amounts and several times, dispersed under a nitrogen atmosphere, and the mixed solution is heated to 70° C. and refluxed for 72 hours;

[0068] (3) After the reaction is completed, the reaction system is cooled to room temperature and poured into ice water. A filter cake is obtained by suction filtration, and the obtained filter cake is washed with water, dilute hydrochloric acid, methanol, and dichloromethane in sequence;

[0069] (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 MBAB based on a benzyl alcohol structure with a yield of 86%.

[0070] Example 5: A porous organic polymer BA2B based on a benzyl alcohol structure, the structural formula of which is as follows:

[0071]

[0072] The synthesis method of the above polymer is as follows:

[0073]

[0074] (1) Add benzyl alcohol (1.73 g, 16 mmol), biphenyl dichlorobenzyl (2.01 g, 8 mmol), and 50 mL of chloroform into a three-necked flask equipped with a magnetic rod, and stir for 15-30 minutes under a nitrogen atmosphere;

[0075] (2) After the solid in step (1) is completely dissolved, anhydrous aluminum chloride (5.3 g, 40 mmol) is added to the above solution in small amounts and in multiple times. After dispersion under a nitrogen atmosphere, the mixed solution is heated to 70° C. and refluxed for 72 hours;

[0076] (3) After the reaction is completed, the reaction system is cooled to room temperature and poured into ice water. A filter cake is obtained by suction filtration, and the obtained filter cake is washed with water, dilute hydrochloric acid, methanol, and dichloromethane in sequence;

[0077] (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 BA2B based on a benzyl alcohol structure with a yield of 84%.

[0078] Example 6: A porous organic polymer PBA2B based on a benzyl alcohol structure, the structural formula of which is as follows:

[0079]

[0080] The synthesis method of the above polymer is as follows:

[0081]

[0082] (1) Add benzhydrol (1.38 g, 10 mmol), diphenylbenzyl chloride (1.3 g, 10 mmol), and 50 mL of chloroform into a three-necked flask 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, anhydrous aluminum chloride (4 g, 30 mmol) is added to the above solution in small amounts and in multiple times. After dispersion under a nitrogen atmosphere, the mixed solution is heated to 70° C. and refluxed for 72 hours;

[0084] (3) After the reaction is completed, the reaction system is cooled to room temperature and poured into ice water. A filter cake is obtained by suction filtration, and the obtained filter cake is washed with water, dilute hydrochloric acid, 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 PBA2B based on a benzyl alcohol structure with a yield of 82%.

[0086] Example 7: A porous organic polymer OBA2B based on a benzyl alcohol structure, the structural formula of which is as follows:

[0087]

[0088] The synthesis method of the above polymer is as follows:

[0089]

[0090] (1) Add o-benzyl alcohol (1.38 g, 10 mmol), biphenyl dichlorobenzyl (1.3 g, 5 mmol), and 50 mL of chloroform into a three-necked flask equipped with a magnetic rod, and stir for 15-30 minutes under a nitrogen atmosphere;

[0091] (2) After the solid in step (1) is completely dissolved, anhydrous aluminum chloride (4 g, 30 mmol) is added to the above solution in small amounts and in multiple times. After dispersion under a nitrogen atmosphere, the mixed solution is heated to 70° C. and refluxed for 72 hours;

[0092] (3) After the reaction is completed, the reaction system is cooled to room temperature and poured into ice water. A filter cake is obtained by suction filtration, and the obtained filter cake is washed with water, dilute hydrochloric acid, methanol, and dichloromethane in sequence;

[0093] (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 OBA2B based on a benzyl alcohol structure with a yield of 83%.

[0094] Example 8: A porous organic polymer MBA2B based on a benzyl alcohol structure, the structural formula of which is as follows:

[0095]

[0096] The synthesis method of the above polymer is as follows:

[0097]

[0098] (1) Add s-tribenzyl alcohol (168 mg, 1 mmol), biphenyl dichlorobenzyl (125 mg, 0.5 mmol), and 10 mL of chloroform into a three-necked flask equipped with a magnetic rod, and stir for 15-30 minutes under a nitrogen atmosphere;

[0099] (2) After the solid in step (1) is completely dissolved, anhydrous aluminum chloride (400 mg, 3 mmol) is added to the above solution in small amounts and several times, dispersed under a nitrogen atmosphere, and the mixed solution is heated to 70° C. and refluxed for 72 hours;

[0100] (3) After the reaction is completed, the reaction system is cooled to room temperature and poured into ice water. A filter cake is obtained by suction filtration, and the obtained filter cake is washed with water, dilute hydrochloric acid, methanol, and dichloromethane in sequence;

[0101] (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 MBA2B based on a benzyl alcohol structure with a yield of 86%.

[0102] Example 9: A porous organic polymer PBA2B-51 based on a benzyl alcohol structure, the structural formula of which is as follows:

[0103]

[0104] The synthesis method of the above polymer is as follows:

[0105]

[0106] (1) Add benzhydrol (1.65 g, 12 mmol), diphenylbenzyl chloride (600 mg, 2.4 mmol), and 50 mL of chloroform into a three-necked flask equipped with a magnetic rod, and stir under a nitrogen atmosphere for 15-30 minutes;

[0107] (2) After the solid in step (1) is completely dissolved, anhydrous aluminum chloride (4 g, 30 mmol) is added to the above solution in small amounts and in multiple times. After dispersion under a nitrogen atmosphere, the mixed solution is heated to 70° C. and refluxed for 72 hours;

[0108] (3) After the reaction is completed, the reaction system is cooled to room temperature and poured into ice water. A filter cake is obtained by suction filtration, and the obtained filter cake is washed with water, dilute hydrochloric acid, 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 PBA2B-51 based on a benzyl alcohol structure with a yield of 88%.

[0110] Example 10: A porous organic polymer PBA2B-31 based on a benzyl alcohol structure, the structural formula of which is as follows:

[0111]

[0112] The synthesis method of the above polymer is as follows:

[0113]

[0114] (1) Add p-benzhydrol (1.24 g, 9 mmol), biphenyl dichlorobenzyl (750 mg, 3 mmol), and 50 mL of chloroform into a three-necked flask equipped with a magnetic rod, and stir for 15-30 minutes under a nitrogen atmosphere;

[0115] (2) After the solid in step (1) is completely dissolved, anhydrous aluminum chloride (4 g, 30 mmol) is added to the above solution in small amounts and in multiple times. After dispersion under a nitrogen atmosphere, the mixed solution is heated to 70° C. and refluxed for 72 hours;

[0116] (3) After the reaction is completed, the reaction system is cooled to room temperature and poured into ice water. A filter cake is obtained by suction filtration, and the obtained filter cake is washed with water, dilute hydrochloric acid, methanol, and dichloromethane in sequence;

[0117] (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 PBA2B-31 based on a benzyl alcohol structure with a yield of 84%.

[0118] Example 11: A porous organic polymer PBA2B-11 based on a benzyl alcohol structure, the structural formula of which is as follows:

[0119]

[0120] The synthesis method of the above polymer is as follows:

[0121]

[0122] (1) Add p-benzhydrol (828 mg, 6 mmol), biphenyl dichlorobenzyl (1.5 g, 6 mmol), and 50 mL of chloroform into a three-necked flask equipped with a magnetic rod, and stir under a nitrogen atmosphere for 15-30 minutes;

[0123] (2) After the solid in step (1) is completely dissolved, anhydrous aluminum chloride (4 g, 30 mmol) is added to the above solution in small amounts and in multiple times. After dispersion under a nitrogen atmosphere, the mixed solution is heated to 70° C. and refluxed for 72 hours;

[0124] (3) After the reaction is completed, the reaction system is cooled to room temperature and poured into ice water. A filter cake is obtained by suction filtration, and the obtained filter cake is washed with water, dilute hydrochloric acid, methanol, and dichloromethane in sequence;

[0125] (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 PBA2B-11 based on a benzyl alcohol structure with a yield of 85%.

[0126] Example 12: A porous organic polymer PBA2B-13 based on a benzyl alcohol structure, the structural formula of which is as follows:

[0127]

[0128] The synthesis method of the above polymer is as follows:

[0129]

[0130] (1) Add benzhydrol (414 mg, 3 mmol), diphenylbenzyl chloride (2.3 g, 9 mmol), and 50 mL of chloroform into a three-necked flask equipped with a magnetic rod, and stir under a nitrogen atmosphere for 15-30 minutes;

[0131] (2) After the solid in step (1) is completely dissolved, anhydrous aluminum chloride (4 g, 30 mmol) is added to the above solution in small amounts and in multiple times. After dispersion under a nitrogen atmosphere, the mixed solution is heated to 70° C. and refluxed for 72 hours;

[0132] (3) After the reaction is completed, the reaction system is cooled to room temperature and poured into ice water. A filter cake is obtained by suction filtration, and the obtained filter cake is washed with water, dilute hydrochloric acid, methanol, and dichloromethane in sequence;

[0133] (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 PBA2B-13 based on a benzyl alcohol structure with a yield of 82%.

[0134] Example 13: A porous organic polymer PBA2B-15 based on a benzyl alcohol structure, the structural formula of which is as follows:

[0135]

[0136] The synthesis method of the above polymer is as follows:

[0137]

[0138] (1) Add benzhydrol (276 mg, 2 mmol), diphenylbenzyl chloride (2.5 g, 10 mmol), and 50 mL of chloroform into a three-necked flask equipped with a magnetic rod, and stir for 15-30 minutes under a nitrogen atmosphere;

[0139] (2) After the solid in step (1) is completely dissolved, anhydrous aluminum chloride (4 g, 30 mmol) is added to the above solution in small amounts and in multiple times. After dispersion under a nitrogen atmosphere, the mixed solution is heated to 70° C. and refluxed for 72 hours;

[0140] (3) After the reaction is completed, the reaction system is cooled to room temperature and poured into ice water. A filter cake is obtained by suction filtration, and the obtained filter cake is washed with water, dilute hydrochloric acid, methanol, and dichloromethane in sequence;

[0141] (4) The filter cake obtained in step (3) was transferred to a Soxhlet extractor and eluted with tetrahydrofuran, methanol and dichloromethane for 48 hours in sequence. 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 PBA2B-15 based on a benzyl alcohol structure with a yield of 83%. Study on the photocatalytic production of hydrogen peroxide by different porous organic polymers:

[0142] The porous organic polymer based on the benzyl alcohol structure obtained in Examples 1-8 was used to study the photocatalytic production of hydrogen peroxide;

[0143] Test method: Weigh 5 mg of the benzyl alcohol structure porous organic polymer prepared in Examples 1-8 above and 20 mL of pure water, add them to a centrifuge tube for ultrasonic dispersion for 5-10 minutes, transfer them to a constant temperature reactor, circulate water to keep it in a state of continuous stirring at 25°C, and use a 300-watt xenon lamp to continuously illuminate the reactor. Take 2 mL of the reaction solution after 60 minutes and filter it using a 0.22 μm filter. After taking 1.5 mL of the filtrate into a centrifuge tube, add 1 mL of 1 mol L -1 The potassium titanium oxalate aqueous solution was mixed and reacted for 5 minutes, and then the absorbance was measured by a UV-visible spectrophotometer. The concentration of hydrogen peroxide was determined according to the standard curve, as shown in Table 1.

[0144] Table 1

[0145]

[0146]

[0147] Study on photocatalytic production of hydrogen peroxide under different catalyst concentrations:

[0148] The porous organic polymer based on benzyl alcohol structure obtained in Example 10 was used to study the photocatalytic production of hydrogen peroxide at different catalyst concentrations.

[0149] Test method: Weigh 2.5 mg, 5 mg, and 10 mg of the benzyl alcohol structure porous organic polymer prepared in Example 10 above and 20 mL of pure water, add them to a centrifuge tube for ultrasonic dispersion for 5-10 minutes, transfer them to a constant temperature reactor, circulate water to keep it in a state of continuous stirring at 25°C, and use a 300-watt xenon lamp to continuously illuminate the reactor. Take 2 mL of the reaction solution at 60 minutes and filter it using a 0.22 μm filter. After absorbing 1.5 mL of the obtained filtrate into a centrifuge tube, add 1 mL of a 1 mol / L potassium titanium oxalate aqueous solution, mix and react for 5 minutes, measure the absorbance by a UV-visible spectrophotometer, and determine the concentration of hydrogen peroxide according to the standard curve, as shown in Table 2

[0150] Table 2

[0151] <![CDATA[Catalyst concentration (mg mL -1 )]]> <![CDATA[Hydrogen peroxide production (mmol g -1 h -1 )]]> 1.25 3.72 2.5 3.94 5 2.93

[0152] Study on photocatalytic production of hydrogen peroxide under different water sources:

[0153] The porous organic polymer based on benzyl alcohol structure obtained in Example 10 was used to study the photocatalytic production of hydrogen peroxide under different water sources.

[0154] Test method: Weigh 5 mg of the benzyl alcohol structure porous organic polymer prepared in Example 10 above and add 20 mL of pure water, river water, tap water, seawater, and Yangtze River water to a centrifuge tube for ultrasonic dispersion for 5-10 minutes, then transfer to a constant temperature reactor, circulate water to keep it in a state of continuous stirring at 25°C, and use a 300-watt xenon lamp to continuously illuminate the reactor. Take 2 mL of the reaction solution at 60 minutes and filter it using a 0.22 μm filter. After absorbing 1.5 mL of the obtained filtrate into a centrifuge tube, add 1 mL of a 1 mol / L potassium titanium oxalate aqueous solution, mix and react for 5 minutes, measure the absorbance by a UV-visible spectrophotometer, and determine the concentration of hydrogen peroxide according to the standard curve, as shown in Table 3

[0155] Table 3

[0156] Water Source <![CDATA[Hydrogen peroxide production (mmol g -1 h -1 )]]> Pure water 3.94 Yangtze River Water 4.50 River Water 4.70 seawater 4.01 Tap water 3.91

[0157] Study on photocatalytic production of hydrogen peroxide at different pH:

[0158] The porous organic polymer based on benzyl alcohol structure obtained in Example 10 was used to study the photocatalytic production of hydrogen peroxide under different pH conditions.

[0159] Test method: Weigh 5 mg of the benzyl alcohol structure porous organic polymer prepared in Example 10 above and add 20 mL of pH=3, pH=5, pH=7, pH=9, and pH=11 solution into a centrifuge tube for ultrasonic dispersion for 5-10 minutes, then transfer to a constant temperature reactor, circulate water to keep it in a state of continuous stirring at 25°C, and use a 300-watt xenon lamp to continuously illuminate the reactor. Take 2 mL of the reaction solution at 60 minutes and filter it using a 0.22 μm filter. After absorbing 1.5 mL of the obtained filtrate into a centrifuge tube, add 1 mL of 1 mol / L potassium titanium oxalate aqueous solution, mix and react for 5 minutes, measure the absorbance by a UV-visible spectrophotometer, and determine the concentration of hydrogen peroxide according to the standard curve, as shown in Table 4.

[0160] Table 4

[0161] pH <![CDATA[Hydrogen peroxide production (mmol g -1 h -1 )]]> 3 4.01 5 3.77 7 3.94 9 4.50 11 4.14

[0162] Study on long-term cumulative photocatalytic production of hydrogen peroxide:

[0163] The porous organic polymer based on the benzyl alcohol structure obtained in Example 10 was subjected to a long-term cumulative photocatalytic oxidation in an air atmosphere to produce hydrogen peroxide;

[0164] Experimental method: 5 mg of the benzyl alcohol structure porous organic polymer prepared in Example 10 above and 20 mL of pure water were weighed and added to a centrifuge tube for ultrasonic dispersion for 5-10 minutes, and then transferred to a constant temperature reactor, and circulating water was passed to keep it in a state of continuous stirring at 25°C, and the reactor was continuously illuminated by a 300-watt xenon lamp. 2 mL of the reaction solution was taken every 60 minutes and filtered using a 0.22 μm filter, 1.5 mL of the obtained filtrate was taken into a centrifuge tube, and 1 mL of 1 mol / L potassium titanium oxalate aqueous solution was added. After mixing and reacting 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, as shown in Table 5.

[0165] Table 5

[0166] Lighting time (h) <![CDATA[Hydrogen peroxide production (mmol g -1 h -1 )]]> 0 0 1 3.72 2 6.36 3 7.60 4 8.85 5 10.19 6 11.55 7 12.58

[0167] It is known from common technical knowledge that the present invention can be implemented by other embodiments that do not deviate from its spirit or essential features. Therefore, the above disclosed embodiments are only illustrative in all respects and are not exclusive. All changes within the scope of the present invention or within the scope equivalent to the present invention are included in the present invention.

Claims

1. A porous organic polymer based on a benzyl alcohol structure, characterized in that: The structural formula is as follows: Among them, n=1, 2.

2. The porous organic polymer based on benzyl alcohol structure according to claim 1, characterized in that: The synthetic reaction formula is as follows: Among them, in the structure shown in monomer I: R1, R2, R3 are independently selected from H or CH2OH; in the structure shown in monomer II, n=1, 2; X is halogen.

3. The method for preparing a porous organic polymer based on a benzyl alcohol structure according to claim 2, characterized in that: The steps include: S1, dissolving monomer I and monomer II in a solvent; S2, under an inert gas atmosphere, adding a catalyst and heating to react to obtain a first product; S3, filtering the first product to obtain a filter cake; S4, washing the filter cake and eluting it in a Soxhlet extractor, and drying it to obtain a porous organic polymer based on a benzyl alcohol structure.

4. The method for preparing a porous organic polymer based on a benzyl alcohol structure according to claim 3, characterized in that: The molar ratio of monomer I to monomer II in S1 is: 0.2-2g, 2-10mmol: 0.2-2.5g, 2-10mmol.

5. The method for preparing a porous organic polymer based on a benzyl alcohol structure according to claim 3, characterized in that: In S1, the solvent is at least one of chloroform, N,N-dimethylformamide, diisopropylamine, tetrahydrofuran, methanol, ethanol, 1,4-dioxane, acetonitrile, and toluene.

6. The method for preparing a porous organic polymer based on a benzyl alcohol structure according to claim 3, characterized in that: In S2, the catalyst is at least one of aluminum chloride, ferric chloride, and boron trifluoride etherate, and the amount of the catalyst is: 3-6g, 30-50mmol; the inert gas is argon or nitrogen, and the method of heating the reaction is to heat the temperature to 50-100°C and react for no less than 72 hours.

7. The method for preparing a porous organic polymer based on a benzyl alcohol structure according to claim 3, characterized in that: In S4, the filter cake is washed by using at least one of dichloromethane, methanol, tetrahydrofuran, water, dilute hydrochloric acid, acetone, ether, and N,N-dimethylformamide.

8. The method for preparing a porous organic polymer based on a benzyl alcohol structure according to claim 3, characterized in that: In S4, the elution method is: eluting with at least one of dichloromethane, methanol, tetrahydrofuran, water, dilute hydrochloric acid, acetone, ether, and N,N-dimethylformamide in a Soxhlet extractor for 12 to 48 hours, and the drying method is: vacuum drying at 40 to 60° C. for not less than 24 hours.

9. Use of the porous organic polymer based on benzyl alcohol structure according to claim 1 or 2 in photocatalytic production of hydrogen peroxide.

10. The use according to claim 9, characterized in that: The steps include: Weigh 2.5-10 mg of a porous organic polymer based on a benzyl alcohol structure and 20 mL of a feed solution, add them into a centrifuge tube, and ultrasonically disperse them for 5-10 minutes. Then transfer them to a constant temperature reactor, circulate water to keep it in a state of continuous stirring at 25°C, and continuously illuminate the reactor with a 300-watt xenon lamp. Take 2 mL of the reaction solution every 60 minutes and filter it with a 0.22 μm filter.

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