An ionic porous organic polymer based on fluoroboron fluoride, its preparation method and photocatalytic application

Abstract

The present invention discloses a fluoroborane-based ionic porous organic polymer, its preparation method, and photocatalytic application. The ionic porous organic polymer is prepared by a one-pot Friedel-Crafts alkylation reaction and salt formation reaction, followed by a one-step crosslinking of a fluoroborane derivative with a crosslinking agent. The resulting ionic porous organic polymer can be used for the photocatalytic degradation of organic pollutants in water. BPA, methyl orange, Congo red, methylene blue, and rhodamine B in water can be degraded in a very short time. For organic pollutants as high as 100 ppm, such as bisphenol A, the ionic porous organic polymer can completely remove it within 40 minutes, achieving the highest known efficiency.

Description

Technical Field

[0001] The present invention belongs to the technical field of photocatalytic materials, and in particular relates to an ionic porous organic polymer based on fluoroboron fluoride, a preparation method thereof, and photocatalytic applications. Background Art

[0002] Persistent pollutants refer to chemical substances that are difficult to decompose and eliminate in the environment and have the characteristics of long-term existence, such as some organic dyes and compounds such as bisphenol A. These substances can exist in the environment for a long time, posing potential risks to ecosystems and human health. In order to reduce the emission of persistent pollutants and alleviate their impact on the environment, people have developed a variety of treatment methods. These methods include biological adsorption degradation, non-biological adsorption degradation, chemical degradation, ultrasonic catalytic degradation, photocatalytic degradation, etc. However, traditional treatment methods may have some limitations, such as low removal efficiency, high cost, and easy to cause secondary pollution. Therefore, research and development of new technologies and methods to improve the treatment efficiency of persistent pollutants and seek more sustainable and economical solutions are current hot research directions.

[0003] Photocatalytic technology is a technology that uses light energy to accelerate chemical reactions. In this technology, photocatalysts (usually semiconductor materials) can absorb light energy under light conditions and carry out chemical reactions on the catalyst surface through the generated electron-hole pairs. Under light conditions, photocatalysts can transfer electrons from the valence band to the conduction band, forming free electrons and holes. These free electrons and holes can react with molecules adsorbed on the surface of the catalyst to produce useful chemicals or degrade harmful substances. Compared with traditional catalytic technology, photocatalytic technology has the advantages of high energy efficiency, environmental friendliness and strong selectivity. Therefore, photocatalytic technology has been widely used in the field of environmental protection, and is used to degrade organic pollutants, kill bacteria and viruses, remove harmful gases, etc.

[0004] However, photocatalytic technology also faces challenges, such as catalyst stability, cyclability, catalytic efficiency, and visible light absorption efficiency, which still require further research and improvement. Ionic porous polymers have high stability and cyclability, and can provide electrostatic effects for adsorption, thereby increasing the driving force for adsorption and accelerating mass transfer, thereby achieving a better match between the adsorption and photodegradation processes and improving the overall photocatalytic degradation efficiency. Summary of the Invention

[0005] The purpose of this section is to summarize some aspects of the embodiments of the present invention and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section and the abstract and title of this application to avoid obscuring the purpose of this section, the abstract and the title of the invention, and such simplifications or omissions should not be used to limit the scope of the present invention.

[0006] In view of the above problems and / or the problems existing in the prior art, the present invention is proposed.

[0007] Therefore, the purpose of the present invention is to overcome the deficiencies in the prior art and provide an ionic porous organic polymer based on fluoroborane.

[0008] In order to solve the above technical problems, the present invention provides the following technical solution: the ionic porous organic polymer is obtained by a cross-linking reaction between a fluoroboron fluoride derivative and an arylmethylene cross-linking agent;

[0009] in:

[0010] (i) The parent of the fluoroboron derivative is selected from one of the compounds represented by the structural formulas (I-1) to (I-3):

[0011]

[0012] The monomer of the cross-linking agent containing an arylmethylene group is selected from the structural formulas shown in formula (II-1) to formula (II-5).

[0013] (ii) the molar ratio of the fluoroborane derivative to the arylmethylene crosslinker monomer is 1:5 to 5:1;

[0014] (iii) The para-carbon of the benzene ring and the nitrogen on the pyridine group of the fluoroboron fluorine derivative mother body represented by any one of the structural formulas (I-1) to (I-3) are simultaneously connected to the aromatic methylene group connected to chlorine in the cross-linking agent monomer represented by any one of the structural formulas (II-1) to (II-5).

[0015] Another object of the present invention is to provide a method for preparing ionic porous organic polymers based on fluoroborane.

[0016] To solve the above technical problems, the present invention provides the following technical solution: a fluoroboron fluoride derivative precursor, a crosslinking agent monomer, and 1,2-dichloroethane are sequentially added to a reaction bottle, and ultrasonically mixed to obtain a reaction system I;

[0017] The reaction system I was nitrogen-purged three times, and ferric chloride was added in four batches under a nitrogen atmosphere and purged with nitrogen for 10 min. After the addition, nitrogen was continued to be purged for 5 to 10 min. The reaction was carried out in an oil bath for 3 to 5 days. After the reaction, the reaction was cooled to room temperature and filtered to obtain a solid product.

[0018] The solid product is dried and washed with a solvent, and then subjected to Soxhlet extraction with methanol. The extracted solid is vacuum dried to obtain a fluoroborane-based ionic porous organic polymer.

[0019] As a preferred solution of the method for preparing the ionic porous organic polymer based on fluoroborane according to the present invention, the reaction temperature of the oil bath reaction is 70-90°C.

[0020] As a preferred solution of the method for preparing the fluoroborane-based ionic porous organic polymer of the present invention, the molar ratio of the fluoroborane derivative matrix to the crosslinking agent monomer is 1:5 to 5:1.

[0021] As a preferred embodiment of the method for preparing the ionic porous organic polymer based on fluoroborane according to the present invention, the solid-liquid ratio of the reactants to the solvent 1,2-dichloroethane in the reaction system I is 1 to 10:30 g / ml.

[0022] As a preferred embodiment of the method for preparing the ionic porous organic polymer based on fluoroborane according to the present invention, the molar ratio of the reactants to ferric chloride in the reaction system I is 1:3 to 1:5.

[0023] As a preferred embodiment of the method for preparing the ionic porous organic polymer based on fluoroborane according to the present invention, the solid product is dried and then washed with a solvent, wherein the solvent comprises one of dichloromethane, tetrahydrofuran or methanol.

[0024] Another object of the present invention is to provide an ionic porous organic polymer based on fluoroborane as a catalyst for photocatalytic degradation of organic pollutants in water.

[0025] As a preferred solution for the application of the fluoroboron-based ionic porous organic polymer of the present invention in the photocatalytic degradation of organic pollutants in water, the organic pollutants include BPA, methyl orange, Congo red, methylene blue, rhodamine, and bisphenol A.

[0026] As a preferred solution for the application of the fluoroboron-based ionic porous organic polymer described in the present invention in the photocatalytic degradation of organic pollutants in water, when the organic pollutant is bisphenol A, the corresponding dosage of the ionic porous organic polymer is 0.1 to 1 mg / mL when the bisphenol A concentration in water is 10 to 200 ppm.

[0027] Beneficial effects of the present invention:

[0028] This invention, based on fluoroborane derivatives, uses a one-pot Friedel-Crafts alkylation reaction and salt formation reaction to crosslink the fluoroborane derivatives with a crosslinking agent to prepare an ionic porous organic polymer. The resulting ionic porous organic polymer can be used for the photocatalytic degradation of organic pollutants in water. It can degrade BPA, methyl orange, Congo red, methylene blue, and rhodamine B in water in a very short time. For organic pollutants as high as 100 ppm, such as bisphenol A, the ionic porous organic polymer can completely remove it within 40 minutes, achieving the highest known efficiency. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following briefly introduces the drawings required for describing the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be derived from these drawings without inventive effort. Among them:

[0030] Figure 1 This is the infrared spectrum of iBPyP (3:3) prepared in Example 1 of the present invention.

[0031] Figure 2 This is the IR spectrum of iBPyP (3:3) prepared in Example 1 of the present invention.

[0032] Figure 3 The iBPyP (3:3) prepared in Example 1 of the present invention 13 C-NMR spectrum.

[0033] Figure 4 This is a scanning electron microscope image of iBPyP (3:3) prepared in Example 1 of the present invention.

[0034] Figure 5 This is the N2 adsorption-desorption isotherm diagram of iBPyP (3:3) prepared in Example 1 of the present invention.

[0035] Figure 6 This is the thermogravimetric analysis diagram of iBPyP (3:3) prepared in Example 1 of the present invention.

[0036] Figure 7 This is the UV-visible diffuse reflectance spectrum of iBPyP (3:3) prepared in Example 1 of the present invention.

[0037] Figure 8 This is a curve diagram of the photodegradation of bisphenol A by iBPyP (3:3) prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0038] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the specific implementation methods of the present invention are described in detail below in conjunction with the embodiments of the specification.

[0039] In the following description, many specific details are set forth to facilitate a full understanding of the present invention. However, the present invention may also be implemented in other ways different from those described herein. Those skilled in the art may make similar generalizations without violating the connotation of the present invention. Therefore, the present invention is not limited to the specific embodiments disclosed below.

[0040] Secondly, the term "one embodiment" or "embodiment" herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in various places throughout this specification does not necessarily refer to the same embodiment, nor does it refer to a separate or selective embodiment that is mutually exclusive of other embodiments.

[0041] The reagents and instruments used in the present invention without manufacturer indication are all conventional products that can be purchased from the market.

[0042] Example 1 iBPyP (3:3)

[0043] This embodiment provides a method for preparing an ionic porous organic polymer iBPyP, the reaction process of which is shown in Formula (III-1):

[0044]

[0045] The specific preparation method is:

[0046] 1) In a 100 mL Schlenk flask, 30 mL of 1,2-dichloroethane, 4,4'-bis(chloromethyl)biphenyl (1.13 g, 4.50 mmol) and 5,5-difluoro-1,3,7,9-tetramethyl-10-phenyl-2,8-di(pyridin-4-yl)-5H-4λ were added in sequence. 4 ,5λ 5 ,-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborolane (1.43 g, 3.00 mmol), ultrasonically stirred for 20 min to uniformly disperse the mixture to obtain reaction system I;

[0047] 2) The Schlenk flask was filled with nitrogen, and the nitrogen in reaction system I was replaced three times. Ferric chloride (2.43 g, 15.00 mmol, added in four equal batches) was added sequentially under nitrogen. The mixture was reacted in an 80°C oil bath for 3 days. After cooling to room temperature, the product was isolated by filtration.

[0048] 3) The product was washed multiple times with 1,2-dichloroethane, N,N-dimethylformamide, tetrahydrofuran and methanol, and then Soxhlet extraction was performed with 1,2-dichloroethane, tetrahydrofuran, dichloromethane and methanol as solvents for two days. The obtained solid product was dried in a vacuum drying oven at 50°C for 24 hours to obtain fluoroboron fluoride-based ionic porous organic polymer iBPyP (3:3) (1.6 g) with a yield of 70%.

[0049] Figure 1 The infrared spectrum of iBPyP (3:3) prepared in this example shows that the wavelength of the IR spectrum at about 1400 cm -1 and 600-800cm -1 The peak at 1000-1300 cm-1 can be attributed to the connection between BODIPY and phenyl groups, which proves the successful synthesis of the polymer. -1 The nearby peaks belong to the CN vibration of BODIPY, indicating that the main structure has not changed.

[0050] Figure 2 is the IR spectrum of iBPyP(3:3), Figure 3 For iBPyP(3:3) 13 C-NMR spectrum, Figure 4 This is a scanning electron microscopy image (SEM image) of iBPyP (3:3), showing that it has a cluster-like morphology.

[0051] Figure 5 Figure 3 is the N2 adsorption-desorption isotherm of iBPyP(3:3), which shows that iBPyP(3:3) has type IV adsorption characteristics with adsorption / desorption hysteresis, indicating the existence of a mesoporous structure.

[0052] Figure 6 This is the thermogravimetric analysis (TGA) diagram of iBPyP (3:3), which shows that iBPyP (3:3) has good thermal stability and only loses less than 30% of its mass at 500°C.

[0053] Figure 7 The UV-visible diffuse reflectance spectrum of iBPyP(3:3) also shows that it has good absorption properties.

[0054] These characterization results indicate the successful synthesis of the iBPyP(3:3) polymer as well as its specific morphology, pore structure, thermal stability, and optical properties.

[0055] Example 2 iBPyP (3:4)

[0056] The difference between this embodiment and embodiment 1 is that the molar ratio of the reactants in step 1) is adjusted, and the amount of ferric chloride added in step 2) is adaptively adjusted. The monomer composition is shown in formula (III-2):

[0057]

[0058] The specific preparation method is:

[0059] 1) In a 100 mL Schlenk flask, 10 mL of 1,2-dichloroethane, 4,4'-bis(chloromethyl)biphenyl (0.35 g, 1.41 mmol) and 5,5-difluoro-1,3,7,9-tetramethyl-10-phenyl-2,8-di(pyridin-4-yl)-5H-4λ were added in sequence. 4 ,5λ 5 ,-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborolane (0.34 g, 0.70 mmol), ultrasonically stirred for 20 min to uniformly disperse the mixture to obtain reaction system I;

[0060] 2) The Schlenk flask was filled with nitrogen, and the nitrogen in reaction system I was replaced three times. Ferric chloride (0.57 g, 3.53 mmol, added in four equal batches) was added sequentially under nitrogen. The mixture was reacted in an 80°C oil bath for 3 days. After cooling to room temperature, the product was isolated by filtration.

[0061] The remaining steps and processes were the same as those in Example 1, and the ionic porous organic polymer iBPyP (3:4) (0.28 g) of this example was obtained with a yield of 41%.

[0062] Example 3 iBPyP (4:3)

[0063] The difference between this embodiment and embodiment 1 is that the molar ratio of the reactants in step 1) is adjusted, and the amount of ferric chloride added in step 2) is adaptively adjusted. The monomer composition is shown in formula (III-3):

[0064]

[0065] The specific preparation method is:

[0066] 1) In a 100 mL Schlenk flask, 10 mL of 1,2-dichloroethane, 4,4'-bis(chloromethyl)biphenyl (0.24 g, 0.97 mmol) and 5,5-difluoro-1,3,7,9-tetramethyl-10-phenyl-2,8-di(pyridin-4-yl)-5H-4λ were added in sequence. 4 ,5λ 5,-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborolane (0.41 g, 0.86 mmol), ultrasonically stirred for 20 min to uniformly disperse the mixture to obtain reaction system I;

[0067] 2) The Schlenk flask was filled with nitrogen, and the nitrogen in reaction system I was replaced three times. Ferric chloride (0.70 g, 4.31 mmol, added in four equal batches) was added sequentially under nitrogen. The mixture was reacted in an 80°C oil bath for 3 days. After cooling to room temperature, the product was isolated by filtration.

[0068] The remaining steps and processes were the same as those in Example 1, and the ionic porous organic polymer iBPyP (4:3) (0.39 g) of this example was obtained with a yield of 60%.

[0069] Example 4 iBPhP (3:3)

[0070] This embodiment provides a method for preparing an ionic porous organic polymer iBPyP, the reaction process of which is shown in Formula (IV-1):

[0071]

[0072] The specific preparation method is

[0073] 1) In a 100 mL Schlenk flask, 10 mL of 1,2-dichloroethane, 4,4'-bis(chloromethyl)biphenyl (0.39 g, 1.57 mmol) and 5,5-difluoro-1,3,7,9-tetramethyl-2,8,10-triphenyl-5H-4λ were added in sequence. 4 ,5λ 5 ,-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborolane (0.50 g, 1.04 mmol), ultrasonically stirred for 20 min to uniformly disperse the mixture to obtain reaction system I;

[0074] 2) The Schlenk flask was filled with nitrogen, and the nitrogen in reaction system I was replaced three times. Ferric chloride (0.85 g, 5.23 mmol) was added in four batches under nitrogen. The mixture was reacted in an 80°C oil bath for 3 days. After cooling to room temperature, the product was isolated by filtration.

[0075] 3) The product was washed several times with 1,2-dichloroethane, N,N-dimethylformamide, tetrahydrofuran and methanol, and then Soxhlet extraction was performed with 1,2-dichloroethane, tetrahydrofuran, dichloromethane and methanol as solvents for two days. The obtained solid product was dried in a vacuum drying oven at 50°C for 12 hours to obtain an ionic porous organic polymer iBPhP (3:3) (0.50 g) based on fluoroborane with a yield of 56%.

[0076] Example 5 iBPhP (3:4)

[0077] The difference between this embodiment and embodiment 4 is that the molar ratio of the reactants in step 1) is adjusted, and the monomer composition is shown in formula (IV-2):

[0078]

[0079] The specific preparation method is:

[0080] 1) In a 100 mL Schlenk flask, 10 mL of 1,2-dichloroethane, 4,4'-bis(chloromethyl)biphenyl (0.52 g, 2.08 mmol) and 5,5-difluoro-1,3,7,9-tetramethyl-2,8,10-triphenyl-5H-4λ were added in sequence. 4 ,5λ 5 ,-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborolane (0.50 g, 1.04 mmol), ultrasonically stirred for 20 min to uniformly disperse the mixture to obtain reaction system I;

[0081] The remaining steps and processes were the same as those in Example 4, and the ionic porous organic polymer iBPhP (3:4) (0.60 g) of this example was obtained with a yield of 59%.

[0082] Example 6 iBPhP (3:4)

[0083] The difference between this embodiment and embodiment 4 is that the molar ratio of the reactants in step 1) is adjusted, and the monomer composition is shown in formula (IV-3):

[0084]

[0085] The specific preparation method is:

[0086] 1) In a 100 mL Schlenk flask, 10 mL of 1,2-dichloroethane, 4,4'-bis(chloromethyl)biphenyl (0.29 g, 1.17 mmol) and 5,5-difluoro-1,3,7,9-tetramethyl-2,8,10-triphenyl-5H-4λ were added in sequence. 4 ,5λ 5 ,-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborolane (0.50 g, 1.04 mmol), ultrasonically stirred for 20 min to uniformly disperse the mixture to obtain reaction system I;

[0087] The remaining steps and processes were the same as those in Example 4, to obtain the ionic porous organic polymer iBPhP (4:3) (0.48 g) of this example, with a yield of 61%.

[0088] Example 7iBPyP-1

[0089] This embodiment provides a method for preparing an ionic porous organic polymer iBPyP, wherein the monomer composition is shown in formula (V-1):

[0090]

[0091] The specific preparation method is:

[0092] 1) In a 100 mL Schlenk flask, 10 mL of 1,2-dichloroethane, 4,4'-bis(chloromethyl)biphenyl (0.39 g, 1.56 mmol), and 5,5-difluoro-1,3,7,9-tetramethyl-2,8,10-tris(pyridin-4-yl)-5H-4,5-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborolane (0.50 g, 1.04 mmol) were added in sequence and stirred for 20 min to uniformly disperse the mixture to obtain Reaction System I;

[0093] 2) Nitrogen was introduced into the Schlenk flask, and ferric chloride (0.41 mg, 0.34 mmol, 0.21 g each) was added in four batches under nitrogen. The mixture was reacted in an 80°C oil bath for 3 days. After cooling to room temperature, the product was isolated by filtration.

[0094] 3) The product was washed several times with N,N-dimethylformamide, tetrahydrofuran and methanol, and then Soxhlet extraction was performed with 1,2-dichloroethane, tetrahydrofuran, dichloromethane and methanol as solvents for two days. The obtained solid product was dried in a vacuum drying oven at 50°C for 12 hours to obtain fluoroboron fluoride-based ionic porous organic polymer iBPyP-1 (1.6 g) with a yield of 70%.

[0095] Example 8 iBPyP-2

[0096] The difference between this embodiment and embodiment 7 is that the reactant 4,4'-bis(chloromethyl)biphenyl is adjusted to p-dichlorobenzyl, and the monomer composition is shown in formula (V-2):

[0097]

[0098] The specific preparation method is:

[0099] 1) In a 100 mL Schlenk flask, 10 mL of 1,2-dichloroethane, p-dichlorobenzyl (0.27 g, 1.56 mmol), and 5,5-difluoro-1,3,7,9-tetramethyl-2,8,10-tris(pyridin-4-yl)-5H-4,5-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborolane (0.50 g, 1.04 mmol) were added sequentially and stirred for 20 min to uniformly disperse the mixture to obtain Reaction System I;

[0100] The remaining steps and processes were the same as those in Example 7, and the ionic porous organic polymer iBPyP-2 (0.49 g) of this example was obtained with a yield of 61%.

[0101] Example 9iBPyP-3

[0102] The difference between this embodiment and embodiment 7 is that the reactant 4,4'-bis(chloromethyl)biphenyl is adjusted to 5,5'-bis(chloromethyl)-2,2'-bipyridine, and the monomer composition is shown in formula (V-3):

[0103]

[0104] The specific preparation method is:

[0105] 1) In a 100 mL Schlenk flask, 10 mL of 1,2-dichloroethane, 5,5'-bis(chloromethyl)-2,2'-bipyridine (0.39 g, 1.56 mmol), and 5,5-difluoro-1,3,7,9-tetramethyl-2,8,10-tris(pyridin-4-yl)-5H-4,5-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborolane (0.50 g, 1.04 mmol) were added in sequence and stirred for 20 min to uniformly disperse the mixture to obtain Reaction System I;

[0106] The remaining steps and processes were the same as those in Example 7, and the ionic porous organic polymer iBPyP-3 (0.64 g) of this example was obtained with a yield of 73%.

[0107] Example 10 iBPyP-4

[0108] The difference between this embodiment and embodiment 7 is that the reactant 4,4'-bis(chloromethyl)biphenyl is adjusted to 4,4'-bis(chloromethyl)-p-triphenyl, and the monomer composition is shown in formula (V-4):

[0109]

[0110] The specific preparation method is:

[0111] 1) In a 100 mL Schlenk flask, 10 mL of 1,2-dichloroethane, 4,4'-bis(chloromethyl)biphenyl, 4,4'-bis(chloromethyl)-p-triphenyl (0.51 g, 1.56 mmol), and 5,5-difluoro-1,3,7,9-tetramethyl-2,8,10-tris(pyridin-4-yl)-5H-4,5-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborolane (0.50 g, 1.04 mmol) were added in sequence and stirred for 20 min to uniformly disperse the mixture to obtain reaction system I;

[0112] The remaining steps and processes were the same as those in Example 7, and the ionic porous organic polymer iBPyP-4 (0.73 g) of this example was obtained with a yield of 81%.

[0113] Example 11iBPyP-5

[0114] The difference between this embodiment and embodiment 7 is that the reactant 4,4'-bis(chloromethyl)biphenyl is adjusted to 5,5'-bis(chloromethyl)-2,2'-bithiophene, and the monomer composition is shown in formula (V-5):

[0115]

[0116] The specific preparation method is:

[0117] 1) In a 100 mL Schlenk flask, 10 mL of 1,2-dichloroethane, 5,5'-bis(chloromethyl)-2,2'-bithiophene (0.41 g, 1.56 mmol), and 5,5-difluoro-1,3,7,9-tetramethyl-2,8,10-tris(pyridin-4-yl)-5H-4,5-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborolane (0.50 g, 1.04 mmol) were added in sequence and stirred for 20 min to uniformly disperse the mixture to obtain reaction system I;

[0118] The remaining steps and processes were the same as those in Example 7, and the ionic porous organic polymer iBPyP-5 (0.22 g) of this example was obtained with a yield of 24%.

[0119] Example 12 iBPyP-6

[0120] The difference between this embodiment and embodiment 7 is that the reactant 4,4'-bis(chloromethyl)biphenyl is adjusted to 2,7-bis(chloromethyl)-4,9-dihydropyrene, and the monomer composition is shown in formula (V-6):

[0121]

[0122] The specific preparation method is:

[0123] 1) In a 100 mL Schlenk flask, 10 mL of 1,2-dichloroethane, 2,7-bis(chloromethyl)-4,9-dihydropyrene (0.47 g, 1.56 mmol), and 5,5-difluoro-1,3,7,9-tetramethyl-2,8,10-tris(pyridin-4-yl)-5H-4,5-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborolane (0.50 g, 1.04 mmol) were added in sequence and stirred for 20 min to uniformly disperse the mixture to obtain Reaction System I;

[0124] The remaining steps and processes were the same as those in Example 7, and the ionic porous organic polymer iBPyP-6 (0.53 g) of this example was obtained with a yield of 55%.

[0125] Study on photodegradation of organic pollutant bisphenol A:

[0126] The products obtained in Examples 1 to 12 were used as photocatalysts to study the photodegradation of the organic pollutant bisphenol A. The specific steps were as follows:

[0127] Preparation of a phenolic organic solution: A bisphenol A solution with a solubility of 100 ppm was prepared. 5 mg of the ionic porous organic polymer obtained in Examples 1-12 was added to a sample bottle, followed by 10 ml of the prepared bisphenol A solution. The sample was placed in a constant temperature reactor, stirred, and subjected to a photodegradation experiment (using a 300 W xenon lamp to simulate sunlight). Samples were taken at 1 minute, 3 minutes, 5 minutes, 10 minutes, 20 minutes, 30 minutes, and 40 minutes, and the concentration of the bisphenol A solution was measured using liquid chromatography. The photodegradation ability of the porous organic polymer on the bisphenol A solution was calculated, and the bisphenol A removal rate at 40 minutes was measured. The results are shown in Table 1.

[0128] Table 1 Comparison of photodegradation effects of organic pollutant bisphenol A

[0129]

[0130]

[0131] Figure 8 2 is the curve of the photodegradation of bisphenol A by the catalyst of Example 1. It can be seen that the ionic porous organic polymer prepared by the method of the present invention can completely remove 100 ppm of bisphenol A within 40 minutes, and the degradation efficiency can reach up to 100%.

[0132] Comparative Example

[0133] This comparative example uses the degradation effect of existing photocatalysts on BPA (bisphenol A) as a comparison, see Table 2 for details:

[0134] Table 2 Degradation effect of different catalysts on BPA (bisphenol A)

[0135]

[0136]

[0137]

[0138] It can be seen that compared with other catalysts in the prior art, the iBPyP prepared by the present invention can completely remove bisphenol A, an organic pollutant with a high concentration of 100 ppm, within 20 minutes. This ionic porous organic polymer is the highest known efficiency.

[0139] Study on the photodegradation of organic pollutant methyl orange dye:

[0140] The products obtained in Examples 1 to 12 were used as photocatalysts to study the photodegradation of methyl orange dye, an organic pollutant. The specific steps were as follows:

[0141] Preparation of methyl orange dye solution: Prepare a methyl orange dye solution with a solubility of 100 ppm;

[0142] 5 mg of the ionic porous organic polymer obtained in Examples 1 to 12 was added to a sample bottle, and 10 ml of the prepared methyl orange dye solution was added. The sample was placed in a constant temperature reactor, stirred, and a photodegradation experiment was performed (300 W xenon lamp, simulating sunlight). Samples were taken at 1 min, 3 min, 5 min, 10 min, 20 min, 30 min, and 40 min, and the concentration of the methyl orange dye solution was measured using a UV-visible spectrophotometer. The photodegradation ability of the porous organic polymer on the methyl orange dye solution was calculated. The photodegradation ability of the methyl orange dye at 40 min of the reaction was measured. The results are shown in Table 3.

[0143] Table 3 Comparison of photodegradation effects of methyl orange dye

[0144]

[0145]

[0146] It can be seen that the ionic porous organic polymer prepared by the method of the present invention can achieve a degradation effect of more than 70% on methyl orange dye within 40 minutes.

[0147] Study on the photodegradation of organic pollutant Congo red dye:

[0148] The products obtained in Examples 1 to 12 were used as photocatalysts to study the photodegradation of Congo red dye, an organic pollutant. The specific steps were as follows:

[0149] Preparation of Congo red dye solution: Prepare a Congo red dye solution with a solubility of 100ppm

[0150] 5 mg of the ionic porous organic polymer obtained in Example 1-12 was added to a sample bottle, and 10 ml of the prepared Congo red dye solution was added. The sample was placed in a constant temperature reactor, stirred, and a photodegradation experiment was performed (300 W xenon lamp, simulating sunlight); samples were taken once at 1 min, 3 min, 5 min, 10 min, 20 min, 30 min, and 40 min, and the concentration of the Congo red dye solution was measured using a UV-visible spectrophotometer. The photodegradation ability of the porous organic polymer to the Congo red dye solution was calculated, and the photodegradation ability of the Congo red dye was measured at 40 min of the reaction. The results are shown in Table 4.

[0151] Table 4 Comparison of Congo red dye photodegradation effects

[0152]

[0153] It can be seen that the ionic porous organic polymer prepared by the method of the present invention can completely remove 100 ppm of methyl orange dye within 40 minutes, with a degradation efficiency of up to 100%.

[0154] Study on photodegradation of organic pollutant methylene blue dye:

[0155] The products obtained in Examples 1 to 12 were used as photocatalysts to study the photodegradation of methylene blue dye, an organic pollutant. The specific steps were as follows:

[0156] : 5 mg of the ionic porous organic polymer obtained in Examples 1-12 was added to a sample bottle, and 10 ml of the prepared methylene blue dye solution was added. The sample was placed in a thermostatic reactor, stirred, and a photodegradation experiment was performed (300 W xenon lamp, simulating sunlight); samples were taken at 1 min, 3 min, 5 min, 10 min, 20 min, 30 min, and 40 min, respectively. The concentration of the methylene blue dye solution was measured using a UV-visible spectrophotometer, and the photodegradation ability of the ionic porous organic polymer on the methylene blue dye solution was calculated. The photodegradation ability of the methylene blue dye at 40 min of the reaction was measured. The results are shown in Table 5.

[0157] Table 5 Comparison of photodegradation effects of methylene blue

[0158]

[0159] It can be seen that the ionic porous organic polymer prepared by the method of the present invention can achieve a degradation effect of more than 80% on methylene blue dye within 40 minutes.

[0160] Study on photodegradation of organic pollutant Rhodamine B:

[0161] The products obtained in Examples 1 to 12 were used as photocatalysts to study the photodegradation of the organic pollutant Rhodamine B. The specific steps were as follows:

[0162] Preparation of Rhodamine B dye solution: Prepare a Rhodamine B dye solution with a solubility of 100 ppm;

[0163] 5 mg of the ionic porous organic polymer obtained in Examples 1-12 was added to a sample vial, along with 10 ml of the prepared rhodamine B dye solution. The sample was stirred in a thermostatic reactor and subjected to a photodegradation experiment (using a 300W xenon lamp to simulate sunlight). Samples were taken at 1, 3, 5, 10, 20, 30, and 40 minutes, and the concentration of the rhodamine B dye solution was measured using a UV-visible spectrophotometer to evaluate the photodegradation ability of the ionic porous organic polymer. The photodegradation ability of methyl orange dye was also measured at 40 minutes, with the results shown in Table 6.

[0164] Table 6 Comparison of photodegradation effects of Rhodamine B

[0165]

[0166] It can be seen that the ionic porous organic polymer prepared by the method of the present invention can achieve a degradation effect of more than 80% on Rhodamine B within 40 minutes.

[0167] In summary, the ionic porous organic polymer based on fluoroboron prepared by the present invention has been shown to have efficient photocatalytic degradation of organic pollutants, and iBPyP (3:3) has the best effect. The material quickly produces oxygen active species under light irradiation, which can degrade BPA, methyl orange, Congo red, methylene blue and rhodamine B in water in a very short time. This ionic porous organic polymer is an efficient photocatalyst in a heterogeneous medium, and the construction of the photocatalyst is achieved using pure organic component materials. Through detailed structural analysis, it was found that different connecting units and synthesis ratios have a key influence on the photocatalytic performance. This study provides an in-depth understanding of the relationship between the synthesis, structure and performance of ionic porous organic polymers based on fluoroboron.

[0168] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present invention may be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present invention, which should all be included in the scope of the claims of the present invention.

Claims

1. An ionic porous organic polymer based on fluoroborane, characterized in that: The ionic porous organic polymer is obtained by cross-linking reaction between a fluoroboron derivative and a cross-linking agent containing an aromatic methylene group; in: (i) The fluoroborane derivative is selected from one of the compounds represented by formula (I-1) to formula (I-3): The monomer of the cross-linking agent containing an arylmethylene group is selected from one of the compounds represented by formula (II-1) to formula (II-5): (ii) the molar ratio of the fluoroborane derivative to the arylmethylene crosslinker monomer is 1:5 to 5:1; (iii) The para-carbon of the benzene ring and the nitrogen on the pyridine group of the fluoroboron fluorine derivative represented by any one of the structural formulas (I-1) to (I-3) are simultaneously connected to the aromatic methylene group connected to chlorine in the cross-linker monomer represented by any one of the structural formulas (II-1) to (II-5).

2. The method for preparing the ionic porous organic polymer based on fluoroborane as claimed in claim 1, Its characteristics are: include, Adding a fluoroborane derivative, a crosslinking agent monomer, and 1,2-dichloroethane to a reaction flask in sequence, and mixing by ultrasonication to obtain a reaction system I; The reaction system I was nitrogen-purged three times, and ferric chloride was added in four batches under a nitrogen atmosphere and purged with nitrogen for 10 min. After the addition, nitrogen was continued to be purged for 5 to 10 min. The reaction was carried out in an oil bath for 3 to 5 days. After the reaction, the reaction was cooled to room temperature and filtered to obtain a solid product. The solid product is dried and washed with a solvent, and then subjected to Soxhlet extraction with methanol. The extracted solid is vacuum dried to obtain a fluoroborane-based ionic porous organic polymer.

3. The method for preparing the ionic porous organic polymer based on fluoroborane as claimed in claim 2, Its characteristics are: The reaction temperature of the oil bath reaction is 70-90°C.

4. The method for preparing the ionic porous organic polymer based on fluoroborane as claimed in claim 3, characterized in that: The molar ratio of the fluoroboron fluoride derivative to the crosslinking agent monomer is 1:5 to 5:

1.

5. The method for preparing the ionic porous organic polymer based on fluoroborane as claimed in claim 3, characterized in that: The solid-to-liquid ratio of the reactants to the solvent 1,2-dichloroethane in the reaction system I is 1-10:30 g / ml.

6. The method for preparing the ionic porous organic polymer based on fluoroborane as claimed in claim 3, characterized in that: The molar ratio of the reactants to ferric chloride in the reaction system I is 1:3 to 1:

5.

7. The method for preparing the ionic porous organic polymer based on fluoroborane as claimed in claim 3, characterized in that: The solid product is dried and washed with a solvent, wherein the solvent comprises one of dichloromethane, tetrahydrofuran or methanol.

8. Use of the fluoroborane-based ionic porous organic polymer according to claim 1 as a catalyst in the photocatalytic degradation of organic pollutants in water.

9. The use of the ionic porous organic polymer according to claim 8, characterized in that: The organic pollutant includes one of methyl orange, Congo red, methylene blue, rhodamine or bisphenol A.

10. The use of the ionic porous organic polymer according to claim 8, characterized in that: When the organic pollutant is bisphenol A, the corresponding dosage of the ionic porous organic polymer is 0.1-1 mg / mL when the concentration of bisphenol A in water is 10-200 ppm.

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