Preparation method and application of porous organic polymer adsorbent

Abstract

The invention discloses a preparation method and application of a porous organic polymer adsorbent, and belongs to the technical field of porous organic polymers in high polymer materials. Comprising the following steps: carrying out acylating chlorination on a carbamate-bonded porous polymer through thionyl chloride to obtain an acylating chlorinated carbamate-bonded porous polymer, and carrying out esterification reaction on the acylating chlorinated carbamate-bonded porous polymer and a chelating agent to obtain the porous organic polymer adsorbent, wherein the carbamate bonded porous polymer is prepared from the following raw materials: a diisocyanate monomer, a triphenolic monomer and a carboxyl-containing diphenolic monomer. The preparation process is simple, raw materials are easy to obtain, the cost is low, and organic dye and heavy metal ion pollutants can be efficiently adsorbed and removed at the same time.

Description

Technical Field

[0001] The invention belongs to the technical field of porous organic polymers in polymer materials, and in particular relates to a preparation method and application of a porous organic polymer adsorbent. Background Art

[0002] With the development of science and technology and the expansion of industrial production, environmental pollution caused by pollutant emissions needs to be solved urgently, among which the impact caused by industrial and domestic sewage discharge is the most serious. Dyes and heavy metal pollution from papermaking, chemical production, printing, mining and other fields pose a great threat to human health and the survival of animals and plants. Dyes are usually organic compounds containing aromatic rings and functional groups such as nitrogen, sulfur, chlorine and amines, which are highly physiologically toxic and carcinogenic [Separation and Purification Technology, 2015, 150: 229-242.]. For example, methylene blue is a cationic dye widely used in the textile industry. It is often used for dyeing paper, cotton and wool because of its high chromaticity at low concentrations [Journal of Colloid Interface Science, 2019, 534: 408-419; Advances in Colloid and Interface Science, 2020, 282: 102198]. However, its wastewater discharge has caused serious pollution to the environment. Methylene blue wastewater not only has deep chromaticity and high organic matter content, but is also difficult to degrade. Therefore, it is particularly important to effectively treat methylene blue wastewater [Journal of Hazardous Materials, 2010, 177, 70-80]. Heavy metals usually refer to those with a density greater than 5g / cm 3 Most of the metals in the wastewater are toxic, mutagenic and carcinogenic. After entering the atmosphere, water and soil, they will accumulate, remain and even migrate through the food chain of the ecosystem, causing harm to the environment and human health [RSC Advances, 2023, 13(7): 4275-7302; Chemosphere, 2023, 328: 138508]. Currently, a large amount of industrial wastewater often contains organic dyes such as methylene blue and heavy metal ions such as lead, cadmium, chromium, copper and iron. Therefore, how to simultaneously remove dyes and heavy metal ions at low cost is crucial for wastewater purification and environmental governance.

[0003] Many technologies such as adsorption, membrane filtration, solvent extraction and biodegradation have been widely used in the clean treatment of various sewage. With its advantages of low cost, simple operation and low energy consumption, the adsorption method of removing various pollutants in sewage by using the adsorption properties of solid adsorbents has become an important treatment method in the field of sewage treatment, especially for the treatment of sewage containing bio-refractory organic pollutants and toxic heavy metal ions. It has irreplaceable important application value [npj Clean Water, 2021, 4, 36; Environmental Technology & Innovation, 2018, 11, 187-240; Science of The Total Environment, 2022, 822, 153555; Environmental Research, 2021, 201, 111534]. The key to treating sewage by adsorption lies in the research and development of low-cost, high-performance adsorbents. Porous organic frameworks (POPs) are a class of polymer materials connected by covalent bonds with advantages such as high specific surface area, adjustable pore size, chemical stability, and thermal stability. They have become the most important adsorbents and are increasingly widely used in sewage treatment [ACS Catalysis, 2011, 1(7): 819-835; Chemical Society Reviews, 2022, 51(6): 2031-2080]. However, the large-scale application of POPs still faces many challenges. First, the preparation of high-performance POPs often requires monomers with special structures and functions, and the synthesis process of these monomers is complicated or expensive. In addition, industrial wastewater and domestic wastewater may contain pollutants such as organic dyes and heavy metal ions at the same time. Research and development of adsorbents that can simultaneously remove multiple pollutants such as organic dyes and heavy metal ions in water is crucial to reducing the treatment cost of complex sewage and improving operating efficiency. Despite this, existing POPs as adsorbents are often only suitable for the adsorption and separation of organic dyes or heavy metal ions, and there are no reports on efficient adsorbents that can be used to remove organic dyes and heavy metal ion pollutants at the same time.

[0004] In short, complex wastewater containing pollutants such as organic dyes and heavy metal ions is increasing day by day, and the current traditional adsorbents cannot meet the performance requirements of such complex wastewater treatment. Therefore, researching and developing efficient adsorbents with simple preparation process, easy-to-obtain and low-cost raw materials, and the ability to simultaneously and efficiently adsorb and remove organic dyes and heavy metal ion pollutants has important research significance and application value for repairing environmental pollution problems caused by complex wastewater. Summary of the invention

[0005] In view of the above technical problems, the present invention proposes a preparation method and application of porous organic polymer adsorbent (POPs). The preparation process is simple, the raw materials are easily available and the cost is low, and it can simultaneously and efficiently adsorb and remove organic dyes and heavy metal ion pollutants.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] One of the technical objectives of the present invention is to provide a method for preparing a porous organic polymer adsorbent, comprising the following steps: chlorinating a porous polymer bonded with carbamate by sulfoxide chloride to obtain a porous polymer bonded with acyl chloride carbamate, and subjecting the porous polymer bonded with acyl chloride carbamate to an esterification reaction with a chelating agent to obtain the porous organic polymer adsorbent;

[0008] The urethane-bonded porous polymer is prepared using diisocyanate monomers, triphenol monomers and carboxyl-containing diphenol monomers as raw materials.

[0009] The present invention obtains a porous polymer bonded with carbamate by chlorinating the carboxyl groups on the porous polymer skeleton bonded with carbamate by thionyl chloride, and then grafts a chelating agent onto the skeleton of the porous polymer bonded with carbamate by esterification reaction, so as to obtain a multifunctional POPs adsorbent. The porous polymer has nanopores and a high specific surface area, and can adsorb cationic dyes and heavy metal ions in water by physical adsorption, and then the chelating agent forms a stable complex with the heavy metal ions by complexation reaction, and each raw material can exert its own adsorption and complexation functions, and is used for synchronous adsorption and removal of cationic dyes and heavy metal ions in water.

[0010] Furthermore, the specific preparation steps of the carbamate-bonded porous polymer include: mixing a diisocyanate monomer, a triphenol monomer and a carboxyl-containing diphenol monomer, dissolving the mixture in an organic solvent, and performing a condensation reaction under a nitrogen atmosphere.

[0011] Furthermore, the molar ratio of the diisocyanate monomer, the triphenol monomer and the carboxyl-containing diphenol monomer is 12:(4-6):(3-6); and / or

[0012] The mass ratio of the total mass of the diisocyanate monomer, the triphenol monomer and the carboxyl-containing diphenol monomer to the organic solvent is 1:(30-50); and / or

[0013] The diisocyanate monomer is p-phenylene diisocyanate; and / or

[0014] The triphenol-based monomer is phloroglucinol; and / or

[0015] The carboxyl-containing diphenol monomer is p-dihydroxybenzoic acid; and / or

[0016] The organic solvent is anhydrous dimethyl sulfoxide (DMSO); and / or

[0017] The parameters of the condensation reaction are: temperature 120-160° C., time 12-48 h.

[0018] Furthermore, the specific step of chlorinating the thionyl chloride comprises: dispersing the carbamate-bonded porous polymer in a mixed solvent of N,N-dimethylformamide (DMF) and thionyl chloride (SOCl2) for heating reaction to obtain a chlorinated carbamate-bonded porous polymer.

[0019] Furthermore, the mass ratio of the carbamate-bonded porous polymer to the mixed solvent is 1:(10-20); and / or

[0020] The volume ratio of N,N-dimethylformamide to thionyl chloride is 1:(1-5); and / or

[0021] The parameters of the heating reaction are: temperature 75-80°C, time 12-24h.

[0022] Furthermore, the chelating agent is N-β-hydroxyethylethylenediaminetriacetic acid (HEDTA).

[0023] Furthermore, the specific steps of the esterification reaction include: dissolving the acyl chloride carbamate bonded porous polymer and chelating agent in an organic solvent, adding an acid binding agent to carry out an esterification reaction, and obtaining a porous organic polymer adsorbent after precipitation, washing and drying.

[0024] Furthermore, the mass ratio of the porous polymer bonded with acyl chloride carbamate to the acid binding agent is (4-10):1; and / or

[0025] The mass ratio of the acyl chloride carbamate bonded porous polymer to the chelating agent is 1:(1-5); and / or

[0026] The mass ratio of the porous polymer bonded with acyl chloride carbamate to the organic solvent is 1:(30-50); and / or

[0027] The organic solvent is anhydrous dimethyl sulfoxide; and / or

[0028] The acid binding agent is triethanolamine (TEA), triethylamine or pyridine; and / or

[0029] The parameters of the esterification reaction are: temperature 60-80°C, time 12-24h.

[0030] The second technical purpose of the present invention is to provide a porous organic polymer adsorbent prepared by the above preparation method.

[0031] The third technical purpose of the present invention is to provide an application of a porous organic polymer adsorbent in the removal of cationic dyes and heavy metal ions.

[0032] Compared with the prior art, the present invention has the following advantages and technical effects:

[0033] 1. The raw materials and preparation process of the porous organic polymer adsorbent prepared by the present invention are characterized by low cost. The raw materials and reagents required in the synthesis process are all low-priced and widely commercialized industrial products, which are suitable for large-scale industrial production.

[0034] 2. The porous organic polymer adsorbent prepared by the present invention has a rich carboxyl group in its skeleton due to the introduction of a large amount of chelating agent molecules HEDTA. It not only has a porous structure and a high specific surface area, but also can electrostatically adsorb cationic pollutants in water, thereby achieving efficient and rapid adsorption.

[0035] 3. The porous organic polymer adsorbent prepared by the present invention has the performance advantages of both porous polymers and chelating agents, and has the ability to simultaneously adsorb organic pollutants such as methylene blue and Fe under neutral conditions. 3+ , Cu 2+ It has the ability to adsorb and remove heavy metal cation pollutants, and has good reusability, and can achieve efficient adsorption and removal of various pollutants in sewage. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] The accompanying drawings constituting a part of the present invention are used to provide a further understanding of the present invention. The exemplary embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the accompanying drawings:

[0037] Figure 1 The reaction flow chart of the present invention for preparing the porous organic polymer adsorbent;

[0038] Figure 2 A reaction flow chart for preparing a urethane-bonded porous polymer according to the present invention;

[0039] Figure 3 This is a scanning electron microscope image of the multifunctional POPs adsorbent prepared in Example 1;

[0040] Figure 4 This is the NMR spectrum of the multifunctional POPs adsorbent prepared in Example 1;

[0041] Figure 5The infrared spectrum of the multifunctional POPs adsorbent prepared in Example 1 and the infrared spectrum of the multifunctional POPs adsorbent after being soaked in an acid-base solution;

[0042] Figure 6 This is a nitrogen adsorption-desorption isotherm test spectrum of the multifunctional POPs adsorbent prepared in Example 1;

[0043] Figure 7 The pore size and pore size distribution of the multifunctional POPs adsorbent prepared in Example 1;

[0044] Figure 8 This is the thermogravimetric analysis test spectrum of the multifunctional POPs adsorbent prepared in Example 1. DETAILED DESCRIPTION

[0045] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as limiting the present invention, but should be understood as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0046] It should be understood that the terms described in the present invention are only for describing special embodiments and are not intended to limit the present invention. In addition, for the numerical range in the present invention, it should be understood that each intermediate value between the upper and lower limits of the scope is also specifically disclosed. Each smaller range between the intermediate value in any stated value or stated range and any other stated value or intermediate value in the described range is also included in the present invention. The upper and lower limits of these smaller ranges can be independently included or excluded in the scope.

[0047] Unless otherwise indicated, all technical and scientific terms used herein have the same meanings as those generally understood by those skilled in the art. Although the present invention describes only preferred methods and materials, any methods and materials similar or equivalent to those described herein may also be used in the implementation or testing of the present invention. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and / or materials associated with the documents. In the event of a conflict with any incorporated document, the content of this specification shall prevail.

[0048] It will be apparent to those skilled in the art that various modifications and variations may be made to the specific embodiments of the present invention description without departing from the scope or spirit of the present invention. Other embodiments derived from the present invention description will be apparent to those skilled in the art. The present invention description and examples are exemplary only.

[0049] The words “include,” “including,” “have,” “contain,” etc. used in this document are open-ended terms, meaning including but not limited to.

[0050] The present invention provides a porous organic polymer adsorbent, which is prepared by synergistically integrating a porous polymer bonded with carbamate having nanopores and a high specific surface area and a chelating agent capable of forming an efficient complexing function with heavy metal ions in water. The preparation method comprises the following steps: chlorinating the porous polymer bonded with carbamate by thionyl chloride to obtain a porous polymer bonded with carbamate chloride, and subjecting the porous polymer bonded with carbamate chloride to an esterification reaction with a chelating agent to obtain the porous organic polymer adsorbent; the specific principle is to chlorinate the carboxyl groups on the skeleton of the porous polymer bonded with carbamate by thionyl chloride to obtain a porous polymer bonded with carbamate chloride, and then graft the chelating agent onto the skeleton of the porous polymer bonded with carbamate chloride by an esterification reaction to obtain a multifunctional POPs adsorbent, and each raw material can exert its own adsorption and complexing functions, and is used to simultaneously adsorb and remove cationic dyes and heavy metal ions in water. Its typical reaction process is as follows: Figure 1 shown.

[0051] In some embodiments, the specific preparation steps of the carbamate-bonded porous polymer include: mixing diisocyanate monomers, triphenol monomers and carboxyl-containing diphenol monomers and dissolving them in an organic solvent, performing a condensation reaction under a nitrogen atmosphere, generating a carbamate-bonded porous polymer through a condensation reaction of isocyanate and phenolic hydroxyl groups, and washing with an organic solvent (such as acetone, tetrahydrofuran, ethanol or methanol) and vacuum drying to obtain a carbamate-bonded porous organic polymer powder. Its typical reaction process is as follows: Figure 2 shown.

[0052] The molar ratio of the diisocyanate monomer, the triphenol monomer and the carboxyl-containing diphenol monomer is 12:(4-6):(3-6). Exemplarily, in the following preferred embodiments of the present invention, the molar ratio of the diisocyanate monomer, the triphenol monomer and the carboxyl-containing diphenol monomer comprises 12:6:3, 12:4:6, 12:5:4.5 or any range between the foregoing ratios.

[0053] The mass ratio of the total mass of the diisocyanate monomer, the triphenol monomer and the diphenol monomer containing a carboxyl group to the organic solvent is 1: (30-50). Exemplarily, in the following preferred embodiments of the present invention, the mass ratio of the total mass of the diisocyanate monomer, the triphenol monomer and the diphenol monomer containing a carboxyl group to the organic solvent comprises 1: 35, 1: 56, 1: 44 or any range between the aforementioned ratios.

[0054] The diisocyanate monomer is p-phenylene diisocyanate, which is a phenyl compound containing two isocyanate groups; the triphenol monomer is phloroglucinol; the carboxyl-containing diphenol monomer is p-dihydroxybenzoic acid, which is a phenyl compound containing two phenolic hydroxyl groups and one carboxyl group. In the present invention, the ratio of the three monomers should meet the requirement that the molar ratio of isocyanate group to phenolic hydroxyl group is 1:1. These monomers are all simple, easy to obtain and low-cost industrial products.

[0055] The organic solvent is anhydrous dimethyl sulfoxide (DMSO).

[0056] The condensation reaction refers to a reaction at a temperature of 120-160°C for 12-48 hours. Exemplarily, in the following embodiments of the present invention, the temperature of the condensation reaction includes 120°C, 140°C, 150°C, 160°C or any value between the aforementioned ranges, and the reaction includes 12h, 24h, 32h, 48h or any value between the aforementioned ranges.

[0057] In some embodiments, the specific steps of the chlorination of thionyl chloride include: dispersing the porous polymer bonded to the carbamate in a mixed solvent of N,N-dimethylformamide (DMF) and thionyl chloride (SOCl2), in the presence of excess thionyl chloride, reflux reaction at 75-80°C for 12-24h, and then fully precipitating and washing with an organic solvent (acetone or tetrahydrofuran, etc.) and vacuum drying to obtain a porous polymer bonded to the chlorinated carbamate. Exemplarily, in the following embodiments of the present invention, the temperature of the reflux reaction includes 75°C, 80°C or any value between the aforementioned range values, and the reflux reaction time includes 12h, 24h or any value between the aforementioned range values.

[0058] The mass ratio of the carbamate-bonded porous polymer to the mixed solvent is 1:(10-20); illustratively, in the following embodiments of the present invention, the mass ratio of the carbamate-bonded porous polymer to the mixed solvent is 1:12, 1:16, 1:20 or any range between the aforementioned ratios.

[0059] The volume ratio of N,N-dimethylformamide to thionyl chloride is 1:(1-5). Exemplarily, in the following embodiments of the present invention, the volume ratio of N,N-dimethylformamide to thionyl chloride includes 1:1, 1:3, 1:5 or any value between the aforementioned ranges.

[0060] In some embodiments, a chelating agent having coordination and complexing ability for heavy metal ions is selected. For example, in the following embodiments of the present invention, the chelating agent is N-β-hydroxyethylethylenediaminetriacetic acid (HEDTA).

[0061] In some embodiments, the specific steps of the esterification reaction include: dissolving the porous polymer bonded with acyl chloride carbamate and an excess of chelating agent in an organic solvent, adding an acid binding agent, performing an esterification reaction after sufficient dissolution, precipitating with deionized water, and repeatedly washing the obtained powder with acetone and then vacuum drying to obtain a porous organic polymer adsorbent.

[0062] The mass ratio of the porous polymer bonded with acylated carbamate to the acid binding agent is (4-10):1; illustratively, in the following embodiments of the present invention, the mass ratio of the porous polymer bonded with acylated carbamate to the acid binding agent is 4:1, 5:1, 6:1, 10:1 or any range between the foregoing ratios.

[0063] The mass ratio of the porous polymer bonded with acylated carbamate to the chelating agent is 1:(1-5); illustratively, in the following embodiments of the present invention, the mass ratio of the porous polymer bonded with acylated carbamate to the chelating agent is 1:1, 1:5 or any range between the aforementioned ratios.

[0064] The mass ratio of the porous polymer bonded with acylated carbamate to the organic solvent is 1:(30-50); illustratively, in the following embodiments of the present invention, the mass ratio of the porous polymer bonded with acylated carbamate to the organic solvent is 1:33, 1:44 or any range between the aforementioned ratios.

[0065] The organic solvent is anhydrous dimethyl sulfoxide.

[0066] The acid binding agent is triethanolamine (TEA), triethylamine or pyridine.

[0067] The parameters of the esterification reaction are: temperature 60-80°C, time 12-24h. For example, in the following embodiments of the present invention, the temperature of the esterification reaction includes 60°C, 80°C or any value between the aforementioned ranges, and the time of the esterification reaction includes 12h, 24h or any value between the aforementioned ranges.

[0068] The porous organic polymer adsorbent is prepared by the above preparation method.

[0069] The porous organic polymer adsorbent prepared by the method of the present invention has a porous structure and thermal stability and chemical stability under common water treatment environments; and is rich in a large number of carboxyl groups, which can ionize carboxyl anions in water and then electrostatically adsorb cationic pollutants, and can adsorb dye pollutants such as methylene blue and rhodamine B and Fe under neutral conditions. 3+ , Cu 2+ It has excellent adsorption and removal capabilities for common heavy metal cation pollutants and has good reusability.

[0070] During the application process, the porous organic polymer adsorbent of the present invention is placed in wastewater containing dyes and heavy metal ions, and after being fully stirred until adsorption equilibrium, pollutants in the environment are effectively removed. The concentration range of dyes and heavy metal ions is between 5-100 mg / L. For example, in the following embodiments of the present invention, the concentration range of the dye includes 10 mg / L, 25 mg / L, 50 mg / L, 100 mg / L or any value between the aforementioned range values; the concentration of heavy metal ions includes 5 mg / L, 10 mg / L, 25 mg / L, 50 mg / L, 100 mg / L or any value between the aforementioned range values. At the same time, the dosage ratio of the porous organic polymer adsorbent to the wastewater is 10 mg: (40-50) mL. For example, in the following embodiments of the present invention, the dosage ratio of the porous organic polymer adsorbent to the wastewater includes 10 mg: 40 mL, 10 mg: 50 mL or any value between the aforementioned range values.

[0071] The porous organic polymer adsorbent after adsorption can be recovered after centrifugal separation. The specific method is: after washing the pollutants on the porous organic polymer adsorbent with ethanol or hydrochloric acid solution, it is vacuum dried, and the treated adsorbent still has adsorption performance.

[0072] The "room temperature" in the present invention refers to 20-30°C unless otherwise specified.

[0073] The raw materials used in the present invention are all purchased from the market.

[0074] The technical solution of the present invention is further illustrated by the following embodiments.

[0075] Example 1

[0076] Preparation of a porous organic polymer adsorbent:

[0077] (1) Preparation of urethane-bonded porous polymers

[0078] Disperse and dissolve p-phenylene diisocyanate (1.92 g, 12 mmol), phloroglucinol (0.756 g, 6.0 mmol), and p-dihydroxybenzoic acid (0.462 g, 3.0 mmol) in 100 mL of dimethyl sulfoxide, and completely dissolve them by ultrasonication at room temperature for 20 min to obtain a mixed solution; add the mixed solution into a 250 mL Schlenk tube, evacuate the air in the tube and fill it with nitrogen as a protective gas, heat it in an oil bath at 150° C. for 24 h, cool it naturally to room temperature after the reaction is completed, collect the product into a centrifuge tube, wash it with acetone until the upper liquid is clear, and dry it in a vacuum oven at room temperature to obtain a black powder, which is a porous polymer bonded with carbamate;

[0079] (2) Preparation of porous polymers bonded with urethane chloride

[0080] 0.5 g of the carbamate-bonded porous polymer powder obtained in step (1) is added to 10 g of a mixed solvent of N,N-dimethylformamide (DMF) and thionyl chloride (SOCl2) (the volume ratio of DMF to SOCl2 is 1:1) and stirred to disperse evenly, heated at 75°C for 24 h and stirred under reflux, after the reaction is completed, the product is precipitated with a large amount of acetone and N,N-dimethylformamide and unreacted thionyl chloride are repeatedly washed away, then filtered to obtain a solid powder product and placed it in a vacuum oven to dry at room temperature, and ground to obtain a black powder, which is the acyl chloride carbamate-bonded porous polymer;

[0081] (3) 1 g of N-β-hydroxyethylethylenediaminetriacetic acid was added to 30 mL of dimethyl sulfoxide and stirred at 60° C. to dissolve. Then 1 g of the acyl chloride carbamate-bonded porous polymer powder obtained in step (2) was added to the solution and stirred to disperse evenly. Finally, 0.2 mL of triethanolamine was added as an acid binder. The mixture was stirred and heated at 60° C. for 24 h. After the reaction was completed, the solid was collected by centrifugation, precipitated with water, and then washed with acetone until the upper solution was clear. The solid was placed in a vacuum oven for drying and ground to obtain the final product, a porous organic polymer adsorbent, i.e., a multifunctional POPs adsorbent (denoted as CPOP-HEDTA).

[0082] Figure 3 This is a scanning electron microscope image of the multifunctional POPs adsorbent prepared in Example 1. Figure 3 It can be seen that the multifunctional POPs adsorbent has uniform nanopores.

[0083] The group composition of the multifunctional POPs adsorbent sample prepared in Example 1 was tested by solid nuclear magnetic resonance. Figure 4 As shown in Figure 4, the characteristic peaks of the segment structure of the multifunctional POPs adsorbent can be seen, confirming that the multifunctional POPs adsorbent was successfully synthesized.

[0084] The group composition of the multifunctional POPs adsorbent sample prepared in Example 1 was tested by infrared spectroscopy. Figure 5 As shown, Figure 5 It was confirmed that the multifunctional POPs adsorbent was successfully synthesized.

[0085] At the same time, the multifunctional POPs adsorbent prepared by the present invention is immersed in common organic solvents and acid-base solutions for 24 hours, including 1 mol / L HCl solution, chloroform (CHCl3), N,N-dimethylformamide (DMF), dioxane, and 1 mol / L sodium hydroxide solution. The infrared spectrum of the 24-hour immersion is as follows: Figure 5As shown, the results show that the multifunctional POPs adsorbent has good chemical stability and there is no obvious structural change when immersed in common organic solvents and acid-base solutions for 24 hours.

[0086] The pore structure and pore size distribution of the multifunctional POPs adsorbent sample prepared in Example 1 were analyzed by nitrogen adsorption-desorption isotherm test. Figure 6 and Figure 7 As shown by Figure 6 and Figure 7 It can be seen that the multifunctional POPs adsorbent prepared in Example 1 has a mesoporous and macroporous structure, and the pore size is evenly distributed between 10nm and 100nm.

[0087] The thermal stability of the multifunctional POPs adsorbent sample prepared in Example 1 was tested by thermogravimetric analysis. Figure 8 As shown, from Figure 8 It can be seen that it has good thermal stability at normal water treatment working temperature.

[0088] Example 2

[0089] Preparation of a porous organic polymer adsorbent:

[0090] (1) Preparation of urethane-bonded porous polymers

[0091] Disperse and dissolve p-phenylene diisocyanate (1.92 g, 12 mmol), phloroglucinol (0.504 g, 4.0 mmol), and p-dihydroxybenzoic acid (0.924 g, 6.0 mmol) in 170 mL of dimethyl sulfoxide, and completely dissolve them by ultrasonication at room temperature for 20 min to obtain a mixed solution; add the mixed solution into a 250 mL Schlenk tube, evacuate the air in the tube and fill it with nitrogen as a protective gas, heat it in an oil bath at 120° C. for 48 h, cool it naturally to room temperature after the reaction, collect the product into a centrifuge tube, wash it with tetrahydrofuran until the upper liquid is clear, and dry it in a vacuum oven at room temperature to obtain a black powder, which is a porous polymer bonded with carbamate;

[0092] (2) Preparation of porous polymers bonded with urethane chloride

[0093] 0.5 g of the carbamate-bonded porous polymer powder obtained in step (1) is added to 10 g of a mixed solvent of N,N-dimethylformamide (DMF) and thionyl chloride (SOCl2) (the volume ratio of DMF to SOCl2 is 1:3) and stirred to disperse evenly, heated at 80°C for 12 h and stirred under reflux, after the reaction is completed, the product is precipitated with a large amount of acetone and N,N-dimethylformamide and unreacted thionyl chloride are repeatedly washed away, then filtered to obtain a solid powder product and placed it in a vacuum oven to dry at room temperature, and ground to obtain a black powder, which is the acyl chloride carbamate-bonded porous polymer;

[0094] (3) Add 5 g of N-β-hydroxyethylethylenediaminetriacetic acid to 30 mL of dimethyl sulfoxide and stir to dissolve at 60° C., then add 1 g of the acyl chloride carbamate-bonded porous polymer powder obtained in step (2) to the solution and stir to disperse evenly, finally add 0.2 mL of triethanolamine as an acid binder, stir and heat at 80° C. for 12 h, collect the solid by centrifugation after the reaction is completed, precipitate with water, and then wash with acetone until the upper solution is clear, place in a vacuum oven to dry, and grind to obtain the final product, a porous organic polymer adsorbent, i.e., a multifunctional POPs adsorbent.

[0095] Example 3

[0096] Preparation of a porous organic polymer adsorbent:

[0097] (1) Preparation of urethane-bonded porous polymers

[0098] Disperse and dissolve p-phenylene diisocyanate (1.92 g, 12 mmol), phloroglucinol (0.63 g, 5.0 mmol), and p-dihydroxybenzoic acid (0.693 g, 4.5 mmol) in 130 mL of dimethyl sulfoxide, and completely dissolve them by ultrasonication at room temperature for 20 min to obtain a mixed solution; add the mixed solution into a 250 mL Schlenk tube, evacuate the air in the tube and fill it with nitrogen as a protective gas, heat it in an oil bath at 160° C. for 12 h, cool it naturally to room temperature after the reaction, collect the product into a centrifuge tube, wash it with ethanol until the upper liquid is clear, and dry it in a vacuum oven at room temperature to obtain a black powder, which is a porous polymer bonded with carbamate;

[0099] (2) Preparation of porous polymers bonded with urethane chloride

[0100] 0.5 g of the carbamate-bonded porous polymer powder obtained in step (1) is added to 8 g of a mixed solvent of N,N-dimethylformamide (DMF) and thionyl chloride (SOCl2) (the volume ratio of DMF to SOCl2 is 1:5) and stirred to disperse evenly, heated at 80°C for 12 h and stirred under reflux, after the reaction is completed, the product is precipitated with a large amount of acetone and N,N-dimethylformamide and unreacted thionyl chloride are repeatedly washed away, then filtered to obtain a solid powder product and placed it in a vacuum oven to dry at room temperature, and ground to obtain a black powder, which is the acyl chloride carbamate-bonded porous polymer;

[0101] (3) Add 5 g of N-β-hydroxyethylethylenediaminetriacetic acid to 30 mL of dimethyl sulfoxide and stir to dissolve at 60° C., then add 1 g of the acyl chloride carbamate-bonded porous polymer powder obtained in step (2) to the solution and stir to disperse evenly, finally add 0.1 mL of pyridine as an acid binding agent, stir and heat at 80° C. for 12 h, collect the solid by centrifugation after the reaction is completed, precipitate with water, and then wash with acetone until the upper solution is clear, place in a vacuum oven to dry, and grind to obtain the final product, a porous organic polymer adsorbent, i.e., a multifunctional POPs adsorbent.

[0102] Example 4

[0103] Preparation of a porous organic polymer adsorbent:

[0104] (1) Preparation of urethane-bonded porous polymers

[0105] Disperse and dissolve p-phenylene diisocyanate (1.92 g, 12 mmol), phloroglucinol (0.756 g, 6.0 mmol), and p-dihydroxybenzoic acid (0.462 g, 3.0 mmol) in 100 mL of dimethyl sulfoxide, and completely dissolve them by ultrasonication at room temperature for 20 min to obtain a mixed solution; add the mixed solution into a 250 mL Schlenk tube, evacuate the air in the tube and fill it with nitrogen as a protective gas, heat it in an oil bath at 140° C. for 32 h, cool it naturally to room temperature after the reaction is completed, collect the product into a centrifuge tube, wash it with acetone until the upper liquid is clear, and dry it in a vacuum oven at room temperature to obtain a black powder, which is a porous polymer bonded with carbamate;

[0106] (2) Preparation of porous polymers bonded with urethane chloride

[0107] 0.5 g of the carbamate-bonded porous polymer powder obtained in step (1) is added to 6 g of a mixed solvent of N,N-dimethylformamide (DMF) and thionyl chloride (SOCl2) (the volume ratio of DMF to SOCl2 is 1:3) and stirred to disperse evenly, heated at 75°C for 24 h and stirred under reflux, after the reaction is completed, the product is precipitated with a large amount of acetone and N,N-dimethylformamide and unreacted thionyl chloride are repeatedly washed away, then filtered to obtain a solid powder product and placed it in a vacuum oven to dry at room temperature, and ground to obtain a black powder, which is the acyl chloride carbamate-bonded porous polymer;

[0108] (3) Add 1 g of N-β-hydroxyethylethylenediaminetriacetic acid to 40 mL of dimethyl sulfoxide and stir to dissolve at 60° C., then add 1 g of the acyl chloride carbamate-bonded porous polymer powder obtained in step (2) to the solution and stir to disperse evenly, finally add 0.15 mL of triethanolamine as an acid binder, stir and heat at 60° C. for 24 h, collect the solid by centrifugation after the reaction is completed, precipitate with water, and then wash with acetone until the upper solution is clear, place in a vacuum oven to dry, and grind to obtain the final product, a porous organic polymer adsorbent, i.e., a multifunctional POPs adsorbent.

[0109] Application Example 1

[0110] The multifunctional POPs adsorbent is tested for the adsorption of methylene blue by:

[0111] 1. Weigh 10 mg of the multifunctional POPs adsorbent prepared in Example 1, disperse it in 40 mL of an aqueous solution with a methylene blue concentration of 10 mg / L, stir it at room temperature until adsorption equilibrium, and test the remaining methylene blue concentration using an ultraviolet spectrophotometer. The methylene blue removal rate in water was calculated to be 99.8%.

[0112] 2. Weigh 10 mg of the multifunctional POPs adsorbent prepared in Example 2, disperse it in 40 mL of an aqueous solution with a methylene blue concentration of 25 mg / L, stir it at room temperature until adsorption equilibrium, and test the remaining methylene blue concentration using an ultraviolet spectrophotometer. The methylene blue removal rate in water was calculated to be 99.6%.

[0113] 3. Weigh 10 mg of the multifunctional POPs adsorbent prepared in Example 3, disperse it in 40 mL of an aqueous solution with a methylene blue concentration of 50 mg / L, stir it at room temperature until adsorption equilibrium, and test the remaining methylene blue concentration using an ultraviolet spectrophotometer. The methylene blue removal rate in water was calculated to be 97.2%.

[0114] 4. Weigh 10 mg of the multifunctional POPs adsorbent prepared in Example 4, disperse it in 40 mL of an aqueous solution with a methylene blue concentration of 100 mg / L, stir it at room temperature until adsorption equilibrium, and test the remaining methylene blue concentration using an ultraviolet spectrophotometer. The calculation shows that the methylene blue removal rate in water is about 90%.

[0115] Application Example 2

[0116] The test method for the adsorption of iron ions by the multifunctional POPs adsorbent is as follows:

[0117] 1. Weigh 10 mg of the multifunctional POPs adsorbent prepared in Example 1, disperse it in 40 mL of an aqueous solution with an iron ion concentration of 10 mg / L, stir it at room temperature until adsorption equilibrium is reached, and test the residual iron ion concentration using inductively coupled plasma emission spectroscopy. The adsorption amount of iron ions in water is calculated to be 33.26 mg / g.

[0118] 2. Weigh 10 mg of the multifunctional POPs adsorbent prepared in Example 2, disperse it in 50 mL of an aqueous solution with an iron ion concentration of 50 mg / L, stir it at room temperature until adsorption equilibrium is reached, and test the residual iron ion concentration using inductively coupled plasma emission spectroscopy. The calculated adsorption amount of iron ions in water is 32.42 mg / g.

[0119] Application Example 3

[0120] The test method for the adsorption of copper ions by the multifunctional POPs adsorbent is as follows:

[0121] 1. Weigh 10 mg of the adsorbent prepared in Example 3, disperse it in 40 mL of an aqueous solution with a copper ion concentration of 10 mg / L, stir it at room temperature until adsorption equilibrium, and test the residual iron ion concentration using inductively coupled plasma emission spectroscopy. The adsorption amount of copper ions in water is calculated to be 28.15 mg / g.

[0122] 2. Weigh 10 mg of the adsorbent prepared in Example 4, disperse it in 10 mL of an aqueous solution with a copper ion concentration of 100 mg / L, stir it at room temperature until adsorption equilibrium, and test the residual iron ion concentration by inductively coupled plasma emission spectroscopy. The adsorption amount of copper ions in water is calculated to be 26.65 mg / g.

[0123] Application Example 4

[0124] The multifunctional POPs adsorbent simultaneously adsorbs multiple heavy metal ions. The test method is:

[0125] Weigh 10 mg of the multifunctional POPs adsorbent prepared in Example 1 and disperse it in 40 mL of Fe 3+ , Cu 2+Mg 2+ Cr 3+ 、Zn 2+ , Ba 2+ The aqueous solution was stirred at room temperature until adsorption equilibrium, and the residual heavy metal ion concentration was tested by inductively coupled plasma emission spectroscopy. The adsorption amounts of heavy metal ions in water were calculated to be 16.36 mg / g, 11.54 mg / g, 1.92 mg / g, 8.74 mg / g, 10.76 mg / g, and 4.14 mg / g, respectively.

[0126] Application Example 5

[0127] The multifunctional POPs adsorbent simultaneously adsorbs methylene blue and iron ions. The test method is as follows:

[0128] 1. Weigh 10 mg of the multifunctional POPs adsorbent prepared in Example 1, disperse it in 40 mL of an aqueous solution in which the concentration of methylene blue and iron ions were both 10 mg / L, stir it at room temperature until adsorption equilibrium is reached, and test the remaining methylene blue and iron ion concentrations using an ultraviolet spectrophotometer and an inductively coupled plasma emission spectrometer, respectively. The calculation shows that the adsorption amounts of methylene blue and iron ions in water are 49.3 mg / g and 25.81 mg / g, respectively.

[0129] 2. Weigh 10 mg of the multifunctional POPs adsorbent prepared in Example 1, disperse it in 40 mL of an aqueous solution with a methylene blue and iron ion concentration of 25 mg / L, stir it at room temperature until adsorption equilibrium is reached, and test the remaining methylene blue and iron ion concentrations using an ultraviolet spectrophotometer and an inductively coupled plasma emission spectrometer, respectively. The calculation shows that the adsorption amounts of methylene blue and iron ions in water are 98.3 mg / g and 32.9 mg / g, respectively.

[0130] The above are only preferred specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A method for preparing a porous organic polymer adsorbent, characterized in that: The following steps are involved: Chlorination of the porous polymer bonded with carbamate by thionyl chloride to obtain a porous polymer bonded with acyl chloride carbamate, and esterification of the porous polymer bonded with acyl chloride carbamate with a chelating agent to obtain the porous organic polymer adsorbent; The urethane-bonded porous polymer is prepared using diisocyanate monomers, triphenol monomers and carboxyl-containing diphenol monomers as raw materials.

2. The method for preparing a porous organic polymer adsorbent according to claim 1, characterized in that: The specific preparation steps of the carbamate-bonded porous polymer include: mixing the diisocyanate monomer, the triphenol monomer and the carboxyl-containing diphenol monomer, dissolving the mixture in an organic solvent, and performing a condensation reaction under a nitrogen atmosphere.

3. The method for preparing a porous organic polymer adsorbent according to claim 2, characterized in that: The molar ratio of the diisocyanate monomer, the triphenol monomer and the carboxyl-containing diphenol monomer is 12:(4-6):(3-6); and / or The diisocyanate monomer is p-phenylene diisocyanate; and / or The triphenol-based monomer is phloroglucinol; and / or The carboxyl-containing diphenol monomer is p-dihydroxybenzoic acid; and / or The organic solvent is anhydrous dimethyl sulfoxide; and / or The conditions of the condensation reaction are: temperature 120-160° C., time 12-48 h.

4. The method for preparing a porous organic polymer adsorbent according to claim 1, characterized in that: The specific step of chlorinating the thionyl chloride comprises: dispersing the porous polymer bonded with carbamate in a mixed solvent of N,N-dimethylformamide and thionyl chloride for heating reaction to obtain the chlorinated porous polymer bonded with carbamate.

5. The method for preparing a porous organic polymer adsorbent according to claim 4, characterized in that: The mass ratio of the carbamate-bonded porous polymer to the mixed solvent is 1:(10-20); and / or The volume ratio of N,N-dimethylformamide to thionyl chloride is 1:(1-5); and / or The conditions of the heating reaction are: temperature 75-80°C, time 12-24h.

6. The method for preparing a porous organic polymer adsorbent according to claim 1, characterized in that: The chelating agent is N-β-hydroxyethylethylenediaminetriacetic acid.

7. The method for preparing a porous organic polymer adsorbent according to claim 1, characterized in that: The specific steps of the esterification reaction include: dissolving the porous polymer bonded with acyl chloride carbamate and the chelating agent in an organic solvent, adding an acid binding agent to carry out an esterification reaction, and obtaining a porous organic polymer adsorbent after precipitation, washing and drying.

8. The method for preparing a porous organic polymer adsorbent according to claim 7, characterized in that: The mass ratio of the porous polymer bonded with acyl chloride carbamate to the acid binding agent is (4-10):1; and / or The mass ratio of the acyl chloride carbamate bonded porous polymer to the chelating agent is 1:(1-5); and / or The mass ratio of the porous polymer bonded with acyl chloride carbamate to the organic solvent is 1:(30-50); and / or The organic solvent is anhydrous dimethyl sulfoxide; and / or The acid binding agent is triethanolamine, triethylamine or pyridine; and / or The conditions of the esterification reaction are: temperature 60-80°C, time 12-24h.

9. A porous organic polymer adsorbent prepared by the preparation method according to any one of claims 1 to 8.

10. Use of the porous organic polymer adsorbent as claimed in claim 9 in the removal of cationic dyes and heavy metal ions.

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