Functionalized super-crosslinked polymer efficient adsorbent as well as preparation method and application thereof

Abstract

The invention discloses a functional super-crosslinked polymer efficient adsorbent as well as a preparation method and application thereof, and belongs to the technical field of wastewater treatment. The method comprises the following steps: (1) adding a biphenyl benzyl chloride hyper-crosslinked polymer, a functional monomer and a catalyst into a solvent according to a certain proportion to obtain a reaction mixture; wherein the functional monomer is a chloromethyl aromatic carboxylic ester compound, and the catalyst is Lewis acid; (2) carrying out planetary ball milling treatment on the reaction mixture, and carrying out Friedel-Crafts alkylation reaction to obtain a crude product; and extracting a crude product and drying to obtain the functional super-crosslinked polymer efficient adsorbent. The method does not need a cross-linking agent, and has the advantages of being simple in process, environmentally friendly, high in synthesis speed and suitable for large-scale production. The prepared functionalized super-crosslinked polymer high-efficiency adsorbent can show excellent adsorption capacity and adsorption rate on various sulfonamide antibiotics, and has important application and popularization values.

Description

Technical Field

[0001] The present invention relates to the technical field of wastewater treatment, and in particular to a functionalized super-crosslinked polymer high-efficiency adsorbent, a preparation method thereof, and an application thereof. Background Art

[0002] Sulfonamide antibiotics are a general term for p-aminobenzenesulfonamide and its various derivatives. They are synthetic antibiotics. With the exception of sulfazoline, which is alkaline, the others are amphoteric. Their antibacterial activity primarily relies on the R2 group on the para-amino group (N4) of the sulfonamide group and the R1 group of the sulfonamide group on the parent nucleus. Their structure is stable and resistant to decomposition. Sulfonamide antibiotics are broad-spectrum antibiotics with excellent antibacterial activity against most Gram-positive and Gram-negative bacteria.

[0003] Sulfonamide antibiotics are widely used in human medicine, livestock and poultry farming, and aquaculture to prevent and treat bacterial infections. In the medical industry, sulfonamide antibiotics are in high demand and usage, resulting in significant discharge of wastewater containing sulfonamide antibiotics during pharmaceutical production. In the livestock and aquaculture industries, approximately 85% of antibiotics are not absorbed and are excreted in feces and urine as parent drug or metabolites. These antibiotics remain biologically active, altering the genetic characteristics of microbial systems and causing poisoning. Sulfonamide antibiotic concentrations can reach μg / L in domestic sewage and surface waters surrounding sewage treatment plants. Sulfonamide antibiotics can accumulate in the environment, posing long-term ecological risks. Therefore, effective methods are essential for removing sulfonamide antibiotics from water to ensure human health.

[0004] Methods for treating sulfonamide antibiotic contaminants include photocatalytic degradation, bioremediation, membrane separation, adsorption, and chemical oxidation. Adsorption is one of the most efficient and simple methods for removing sulfonamide antibiotics from wastewater. However, the adsorption efficiency of sulfonamide antibiotics on common porous materials is not ideal. Therefore, the search for highly efficient adsorbents is crucial.

[0005] The main reasons for the unsatisfactory adsorption efficiency of porous materials for sulfonamide antibiotics are as follows: the surface chemistry regulation of traditional adsorbents is relatively difficult, and the specific surface area is easily affected after modification, resulting in low adsorption capacity.

[0006] For example, Chinese invention patent publication number CN119463082A discloses a method for preparing and applying a covalent organic framework material capable of adsorbing sulfonamide antibiotics. This invention achieves an adsorption efficiency of over 80% for sulfonamide antibiotics at an initial concentration of only 10 μg / L, and optimally reaches 88.3%. However, the entire synthesis process is time-consuming and requires high temperatures. Chinese invention patent publication number CN112619593A provides an adsorption material for sulfonamide antibiotics in wastewater and its preparation method. The adsorption raw materials include nanosilica, nanocellulose, urea, a chemical dispersant, and a catalyst. The material achieves a maximum adsorption rate of 93.1% for sulfamethoxazole. The synthesis process is relatively long, requiring 25-28 hours of static aging. Chinese invention patent publication number CN117696006A provides a cubic bifunctional adsorption material, its preparation method, and its application. In actual applications, adsorption equilibrium is reached within 5 hours, and the removal efficiency of sulfonamide antibiotics reaches 90%. However, the preparation of cubic bifunctional adsorption materials requires heating the zeolite imidazole framework to above 800°C for calcination under inert gas. The basic raw materials are expensive and the cost is high, which greatly limits the application of this material.

[0007] Based on this, it is a technical problem that urgently needs to be solved to provide a sulfonamide antibiotic adsorbent and its preparation method that has a simple preparation method, is green and environmentally friendly, has a fast synthesis speed, is suitable for large-scale production, has a large specific surface area, rich pores, and a high adsorption rate, so as to achieve rapid and efficient treatment of wastewater containing sulfonamide antibiotics. Summary of the Invention

[0008] In view of the above-mentioned defects of the prior art, in the first aspect of the present invention, a method for preparing a functionalized hyper-cross-linked polymer high-efficiency adsorbent is provided, which is simple in process, environmentally friendly, has a fast synthesis speed, and is suitable for large-scale production, comprising the following steps: (1) adding biphenylbenzyl chloride hypercrosslinked polymer, functional monomer, and catalyst into a solvent according to a certain ratio to obtain a reaction mixture; wherein the functional monomer is a chloromethyl aromatic carboxylate compound and the catalyst is a Lewis acid; (2) The reaction mixture is subjected to planetary ball milling and a Friedel-Crafts alkylation reaction to obtain a crude product; the crude product is extracted and dried to obtain a functionalized hyper-cross-linked polymer high-efficiency adsorbent.

[0009] Preferably, in step (1), the functional monomer includes one of ethyl 3-(chloromethyl)benzoate, butyl 3-(chloromethyl)benzoate, and methyl 2-(chloromethyl)phenylacetate.

[0010] Preferably, in step (1), the catalyst includes at least one of aluminum trichloride, ferric trichloride, zinc chloride, and tin chloride.

[0011] Preferably, in step (1), the solvent includes at least one of chloroform, dichloromethane, and dichloroethane.

[0012] Preferably, in step (1), the mass ratio of the biphenylbenzyl chloride hypercrosslinked polymer to the functionalized monomer is 1:0.1-0.5; and the mass ratio of the total mass of the biphenylbenzyl chloride hypercrosslinked polymer and the functionalized monomer to the catalyst is 1:0.08-1.

[0013] Preferably, in step (1), the concentrations of the biphenylbenzyl chloride hyper-crosslinked polymer and the functionalized monomer in the solvent are independently 0.001-0.01 g / mL.

[0014] Preferably, in step (2), the grinding medium balls for planetary ball milling are a combination of one or more of 5 mm, 10 mm, and 15 mm; the grinding medium balls are made of at least one of alumina, agate, zirconium oxide, polytetrafluoroethylene, tungsten carbide, and stainless steel.

[0015] Preferably, in step (2), the rotation speed of the planetary ball milling treatment is 100-500 rpm, and the treatment time is 10-60 min.

[0016] Further preferably, the planetary ball milling process is controlled in stages, and is carried out in the form of forward rotation combined with reverse rotation to obtain a crude product.

[0017] Preferably, in step (2), the planetary ball milling treatment adopts wet milling; the solvent used for wet milling includes at least one of water, methanol, ethanol, acetone, and ethyl acetate; and the mass ratio of the solvent to the reaction mixture is 80-100:1.

[0018] Preferably, in step (2), the drying temperature is 60-200°C, and the drying time is 8-24 hours.

[0019] Biphenylbenzyl chloride hyper-crosslinked polymers are polymers formed by hyper-crosslinking 4,4'-biphenylbenzyl chloride. These can be prepared using existing or homemade products. For example, in a solution, 4,4'-biphenylbenzyl chloride undergoes a mechanochemical reaction under the action of ferric chloride to form a biphenylbenzyl chloride hyper-crosslinked polymer.

[0020] In the second aspect of the present invention, a functionalized super-cross-linked polymer high-efficiency adsorbent with large specific surface area, rich pores, high oxygen content and high adsorption rate is provided, which is prepared by the preparation method of the first aspect of the present invention.

[0021] In the third aspect of the present invention, there is provided an application of the functionalized hyper-crosslinked polymer high-efficiency adsorbent according to the second aspect of the present invention, specifically as an adsorption material for adsorbing sulfonamide antibiotics.

[0022] Based on the above technical solutions, the design concept and principle of the present invention are as follows: The raw materials selected in the present invention utilize chloromethyl aromatic carboxylic acid ester compounds as functional monomers for the cross-linking reaction. The functional monomers contain chloromethyl groups and ester functional groups. Sulfonamides contain sulfonamide and amino groups in their molecules. The hydrogen atoms of these groups can serve as hydrogen bond donors, forming hydrogen bonds with the oxygen atoms in the oxygen-containing functional groups. The oxygen-containing functional groups increase the polarity of the polymer, bonding with the polar sulfonamide groups of the sulfonamides through dipole-dipole interactions. This, combined with the hydrogen bonding between the aromatic rings of the sulfonamides and the oxygen-containing functional groups, simultaneously enhances adsorption performance.

[0023] This invention utilizes planetary ball milling in the synthesis of a functionalized hypercrosslinked polymer high-efficiency adsorbent. The milling process increases the contact area between reactants, reduces the particle size of the finished polymer, and increases the specific surface area, forming a hierarchical porous structure. The high porosity provides more exposed active sites, while the rough surface promotes molecular diffusion and interfacial contact. The energy input from ball milling triggers the breakage and recombination of covalent bonds. Consequently, the milling-induced porous structure (micropore-dominated, mesopore-assisted) significantly increases the specific surface area, providing numerous adsorption sites for sulfonamides. The oxygen-containing functional groups enhance adsorption through hydrogen bonding.

[0024] In summary, the present invention adopts a mechanochemical method for functionalization, which mainly relies on converting mechanical force into chemical energy to form covalent bonds between monomer molecules. Mechanical friction will generate instantaneous high temperature to accelerate the reaction dynamics. Mechanical force will force the monomer to be in close contact with other raw materials, thereby improving the reaction efficiency and shortening the reaction time. The functional monomer is used to provide oxygen elements and exert cross-linking functions, without the need to use other external cross-linking agents for cross-linking.

[0025] Compared with the prior art, the present invention has the following advantages and beneficial effects: The present invention provides a method for preparing a functionalized hyper-crosslinked polymer high-efficiency adsorbent. The method uses biphenylbenzyl chloride hyper-crosslinked polymer and functional monomers as raw materials, adopts a mechanochemical method (planetary ball milling treatment) for functionalization, and completes a Friedel-Crafts alkylation reaction without the need for a crosslinking agent. The method has the advantages of simple process, green environmental protection, fast synthesis speed, and suitability for large-scale production.

[0026] The present invention provides a functionalized hyper-cross-linked polymer high-efficiency adsorbent with a high specific surface area and a multi-level pore structure. The adsorbent has a high content of heteroatom oxygen and can exhibit excellent adsorption capacity and adsorption rate for a variety of sulfonamide antibiotics, thus having important application and promotion value.

[0027] The present invention provides an application of a functionalized super-crosslinked polymer high-efficiency adsorbent, which has broad application prospects in the field of adsorption treatment of sulfonamide antibiotics. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This is a scanning electron microscope (SEM) image of the functionalized hyper-cross-linked polymer high-efficiency adsorbent prepared in Example 2; Figure 2 The 303 K adsorption isotherm curves of the functionalized hyper-cross-linked polymer high-efficiency adsorbent prepared in Example 2 for desulphamethoxazole and sulfamethazine. DETAILED DESCRIPTION

[0029] The present invention is further illustrated by way of examples below, but the present invention is not limited to the scope of the examples. Experimental methods in the following examples where specific conditions are not specified were performed according to conventional methods and conditions, or selected according to the product specifications.

[0030] In the following examples, the biphenylbenzyl chloride hypercrosslinked polymer was prepared in-house, and the preparation steps were as follows: 4,4'-Biphenylbenzyl chloride (0.012 mol, 3.0026 g), anhydrous ferric chloride (FeCl3, 1.9745 g), and 1,2-dichloroethane (45.2524 mL) were weighed and premixed in a 250 mL planetary ball mill. Then, 100 5 mm diameter grinding balls, 20 10 mm grinding balls, and 10 15 mm grinding balls were added in sequence. The assembled ball mill was fixed to the slot of the planetary ball mill, and the speed of the planetary ball mill was set to 150 rpm. Ball milling was continued for 30 min to complete the mechanochemical reaction and obtain biphenylbenzyl chloride hyper-crosslinked polymer.

[0031] Example 1 The preparation method of the functionalized hyper-cross-linked polymer high-efficiency adsorbent comprises the following steps: (1) Take 0.6 g of biphenylbenzyl chloride hypercrosslinked polymer, 0.06 g of ethyl 3-(chloromethyl)benzoate, and 6 g of anhydrous ferric chloride and add them to 80 mL of dichloroethane to obtain a reaction mixture; (2) The reaction mixture was placed in a 300 mL grinding jar, and 60 5 mm, 20 10 mm, and 10 15 mm diameter zirconium oxide grinding balls were added. The ball mill was rotated forward at 100 rpm for 15 min and then reversed at 200 rpm for 15 min. The crude product was transferred with ethanol, filtered, washed with methanol, and extracted for 12 h. The crude product was then rotary evaporated at 60 °C for 8 h to obtain a functionalized hyper-cross-linked polymer high-efficiency adsorbent.

[0032] Example 2 The preparation method of the functionalized hyper-cross-linked polymer high-efficiency adsorbent comprises the following steps: (1) Take 0.6 g of biphenylbenzyl chloride hypercrosslinked polymer, 0.12 g of ethyl 3-(chloromethyl)benzoate, and 6 g of anhydrous ferric chloride and add them to 80 mL of dichloroethane to obtain a reaction mixture; (2) The reaction mixture was placed in a 300 mL grinding jar, and 60 5 mm, 20 10 mm, and 10 15 mm diameter zirconium oxide grinding balls were added. The ball mill was rotated forward at 100 rpm for 15 min and then reversed at 200 rpm for 15 min. The crude product was transferred with ethanol, filtered, washed with methanol, and extracted for 12 h. The crude product was then rotary evaporated at 60 °C for 8 h to obtain a functionalized hyper-cross-linked polymer high-efficiency adsorbent.

[0033] Example 3 The preparation method of the functionalized hyper-cross-linked polymer high-efficiency adsorbent comprises the following steps: (1) Take 0.6 g of biphenylbenzyl chloride hypercrosslinked polymer, 0.18 g of ethyl 3-(chloromethyl)benzoate, and 6 g of anhydrous ferric chloride and add them to 80 mL of dichloroethane to obtain a reaction mixture; (2) The reaction mixture was placed in a 300 mL grinding jar, and 60 5 mm, 20 10 mm, and 10 15 mm diameter zirconium oxide grinding balls were added. The ball mill was rotated forward at 100 rpm for 15 min and then reversed at 200 rpm for 15 min. The crude product was transferred with ethanol, filtered, washed with methanol, and extracted for 12 h. The crude product was then rotary evaporated at 60 °C for 8 h to obtain a functionalized hyper-cross-linked polymer high-efficiency adsorbent.

[0034] Example 4 The preparation method of the functionalized hyper-cross-linked polymer high-efficiency adsorbent comprises the following steps: (1) Take 0.6 g of biphenylbenzyl chloride hypercrosslinked polymer, 0.06 g of 3-(chloromethyl)butyl benzoate, and 4 g of anhydrous ferric chloride and add them to 100 mL of dichloroethane to obtain a reaction mixture; (2) The reaction mixture was placed in a 300 mL grinding jar, and 60 5 mm, 20 10 mm, and 10 15 mm diameter zirconium oxide grinding balls were added. The ball mill was rotated forward at 100 rpm for 15 min and then reversed at 200 rpm for 15 min. The crude product was transferred with ethanol, filtered, washed with methanol, and extracted for 12 h. The crude product was then rotary evaporated at 60 °C for 8 h to obtain a functionalized hyper-cross-linked polymer high-efficiency adsorbent.

[0035] Example 5 The preparation method of the functionalized hyper-cross-linked polymer high-efficiency adsorbent comprises the following steps: (1) Take 0.6 g of biphenylbenzyl chloride hypercrosslinked polymer, 0.12 g of 3-(chloromethyl)butyl benzoate, and 4 g of anhydrous ferric chloride and add them to 100 mL of dichloroethane to obtain a reaction mixture; (2) The reaction mixture was placed in a 300 mL grinding jar, and 60 5 mm, 20 10 mm, and 10 15 mm diameter zirconium oxide grinding balls were added. The ball mill was rotated forward at 100 rpm for 15 min and then reversed at 200 rpm for 15 min. The crude product was transferred with ethanol, filtered, washed with methanol, and extracted for 12 h. The crude product was then rotary evaporated at 60 °C for 8 h to obtain a functionalized hyper-cross-linked polymer high-efficiency adsorbent.

[0036] Example 6 The preparation method of the functionalized hyper-cross-linked polymer high-efficiency adsorbent comprises the following steps: (1) Take 0.6 g of biphenylbenzyl chloride hypercrosslinked polymer, 0.18 g of 3-(chloromethyl)butyl benzoate, and 4 g of anhydrous ferric chloride and add them to 80 mL of dichloroethane to obtain a reaction mixture; (2) The reaction mixture was placed in a 300 mL grinding jar, and 60 5 mm, 20 10 mm, and 10 15 mm diameter zirconium oxide grinding balls were added. The ball mill was rotated forward at 100 rpm for 15 min and then reversed at 200 rpm for 15 min. The crude product was transferred with ethanol, filtered, washed with methanol, and extracted for 12 h. The crude product was then rotary evaporated at 60 °C for 8 h to obtain a functionalized hyper-cross-linked polymer high-efficiency adsorbent.

[0037] Example 7 The preparation method of the functionalized hyper-cross-linked polymer high-efficiency adsorbent comprises the following steps: (1) Take 0.6 g of biphenylbenzyl chloride hypercrosslinked polymer, 0.06 g of methyl 2-(chloromethyl)phenylacetate, and 4 g of anhydrous ferric chloride and add them to 80 mL of dichloroethane to obtain a reaction mixture; (2) The reaction mixture was placed in a 300 mL grinding jar, and 60 5 mm, 20 10 mm, and 10 15 mm diameter zirconium oxide grinding balls were added. The ball mill was rotated forward at 100 rpm for 15 min and then reversed at 200 rpm for 15 min. The crude product was transferred with ethanol, filtered, washed with methanol, and extracted for 12 h. The crude product was then rotary evaporated at 60 °C for 8 h to obtain a functionalized hyper-cross-linked polymer high-efficiency adsorbent.

[0038] Example 8 The preparation method of the functionalized hyper-cross-linked polymer high-efficiency adsorbent comprises the following steps: (1) Take 0.6 g of biphenylbenzyl chloride hypercrosslinked polymer, 0.12 g of methyl 2-(chloromethyl)phenylacetate, and 4 g of anhydrous ferric chloride and add them to 80 mL of dichloroethane to obtain a reaction mixture; (2) The reaction mixture was placed in a 300 mL grinding jar, and 60 5 mm, 20 10 mm, and 10 15 mm diameter zirconium oxide grinding balls were added. The ball mill was rotated forward at 100 rpm for 15 min and then reversed at 200 rpm for 15 min. The crude product was transferred with ethanol, filtered, washed with methanol, and extracted for 12 h. The crude product was then rotary evaporated at 60 °C for 8 h to obtain a functionalized hyper-cross-linked polymer high-efficiency adsorbent.

[0039] Example 9 The preparation method of the functionalized hyper-cross-linked polymer high-efficiency adsorbent comprises the following steps: (1) Take 0.6 g of biphenylbenzyl chloride hypercrosslinked polymer, 0.18 g of methyl 2-(chloromethyl)phenylacetate, and 4 g of anhydrous ferric chloride and add them to 80 mL of dichloroethane to obtain a reaction mixture; (2) The reaction mixture was placed in a 300 mL grinding jar, and 60 5 mm, 20 10 mm, and 10 15 mm diameter zirconium oxide grinding balls were added. The ball mill was rotated forward at 100 rpm for 15 min and then reversed at 200 rpm for 15 min. The crude product was transferred with ethanol, filtered, washed with methanol, and extracted for 12 h. The crude product was then rotary evaporated at 60 °C for 8 h to obtain a functionalized hyper-cross-linked polymer high-efficiency adsorbent.

[0040] Example 10 The preparation method of the functionalized hyper-cross-linked polymer high-efficiency adsorbent comprises the following steps: (1) Take 0.6 g of biphenylbenzyl chloride hypercrosslinked polymer, 0.06 g of ethyl 3-(chloromethyl)benzoate, and 4 g of anhydrous ferric chloride and add them to 100 mL of dichloroethane to obtain a reaction mixture; (2) The reaction mixture was placed in a 300 mL grinding jar, and 60 5 mm, 20 10 mm, and 10 15 mm diameter zirconium oxide grinding balls were added. The ball mill was rotated forward at 100 rpm for 15 min and then reversed at 200 rpm for 15 min. The crude product was transferred with ethanol, filtered, washed with methanol, and extracted for 12 h. The crude product was then rotary evaporated at 60 °C for 8 h to obtain a functionalized hyper-cross-linked polymer high-efficiency adsorbent.

[0041] Example 11 This example studies the effect of functionalized hypercross-linked polymer high-efficiency adsorbents in practical applications and conducts performance tests on them. The functionalized hypercross-linked polymer high-efficiency adsorbents prepared in Examples 1 to 10 were added to sewage containing different types of sulfonamide antibiotics at a mass ratio of 0.001:1, and the concentration of sulfonamide antibiotics in the sewage was 300 mg / L. The adsorption temperature was controlled at 30°C, the adsorption time was 60 min, and the adsorption amount was calculated. The test results of the adsorption capacity of the functionalized hypercross-linked polymer high-efficiency adsorbents prepared in Examples 1 to 10 for sulfonamide antibiotics are shown in Table 1.

[0042] Table 1: Test results of the adsorption capacity of functionalized hypercross-linked polymer high-efficiency adsorbent for sulfonamide antibiotics

[0043] The adsorbents prepared in Examples 1 to 10 of the present invention have a high specific surface area, a multi-level pore structure, and abundant oxygen. Based on these advantages, the adsorbents have high adsorption capacity for various sulfonamide antibiotics and a fast adsorption rate. The total test time is 60 minutes, but the adsorbent of the present invention can reach adsorption equilibrium within 3 minutes, corresponding to an adsorption amount of 259 to 466 mg / g.

[0044] The best performance example 2 was used as a representative example, and its surface morphology was observed using a scanning electron microscope. The results are as follows: Figure 1 shown. Figure 1 The morphological characteristics of the material at 100 nm are displayed. The high-magnification image (100.00 KX) shows that the material presents a typical amorphous porous structure with a large number of nanoscale pores distributed on the surface, with a particle size of about 100~200 nm. This is consistent with the existence of mesopores (10~20 nm) in the nitrogen adsorption test, indicating that the material has a multi-level pore structure. This loose and porous structure is conducive to the diffusion and mass transfer of sulfonamide antibiotics.

[0045] The 303 K isothermal adsorption curves of the functionalized hypercrosslinked polymer high-efficiency adsorbent of Example 2 for desulfamethoxazole and sulfamethazine are as follows: Figure 2 shown. Figure 2The results showed that the functionalized hypercross-linked polymer adsorbent was added to wastewater containing different types of sulfonamide antibiotics at a mass ratio of 0.001:1, with the concentration of sulfonamide antibiotics in the wastewater at 350 mg / L. The adsorption capacity of the adsorbent for sulfonamide antibiotics was tested at a controlled temperature of 30°C and a time of 3 minutes. The results showed that the oxygen-containing polymer enhanced the adsorption of sulfonamide antibiotics through hydrogen bonding, with the adsorption capacity of sulfamethoxazole reaching 466 mg / g and sulfamethazine reaching 318 mg / g.

[0046] In summary, the method of the present invention uses a mechanochemical method to achieve functionalization, relying on the conversion of mechanical force into chemical energy to form covalent bonds between monomer molecules, accelerating the reaction kinetics through the instantaneous high temperature generated by mechanical friction, and utilizing mechanical force to force the monomers into close contact with other raw materials, thereby improving reaction efficiency and shortening reaction time. Functional monomers are used to provide oxygen elements while exerting cross-linking functions, without the need to use other external cross-linking agents for cross-linking. This method has the advantages of simple process, green environmental protection, fast synthesis speed, and applicability to large-scale production. The prepared functionalized super-cross-linked polymer high-efficiency adsorbent can show excellent adsorption capacity and adsorption rate for a variety of sulfonamide antibiotics, and has important application and promotion value.

[0047] The above describes in detail the preferred embodiments of the present invention. It should be understood that those skilled in the art can make numerous modifications and variations based on the concepts of the present invention without inventive effort. Therefore, any technical solutions that can be derived by those skilled in the art through logical analysis, reasoning, or limited experimentation based on the concepts of the present invention and the prior art should be within the scope of protection defined by the claims.

Claims

1. A method for preparing a functionalized hyper-crosslinked polymer high-efficiency adsorbent, characterized in that: The steps include: (1) adding biphenylbenzyl chloride hypercrosslinked polymer, functional monomer, and catalyst into a solvent according to a certain ratio to obtain a reaction mixture; wherein the functional monomer is a chloromethyl aromatic carboxylate compound and the catalyst is a Lewis acid; (2) The reaction mixture is subjected to planetary ball milling and a Friedel-Crafts alkylation reaction to obtain a crude product; the crude product is extracted and dried to obtain a functionalized hyper-cross-linked polymer high-efficiency adsorbent.

2. The method for preparing a functionalized hyper-crosslinked polymer high-efficiency adsorbent according to claim 1, wherein: In the step (1), the functional monomer includes one of ethyl 3-(chloromethyl)benzoate, butyl 3-(chloromethyl)benzoate, and methyl 2-(chloromethyl)phenylacetate; and the catalyst includes at least one of aluminum chloride, ferric chloride, zinc chloride, and tin chloride.

3. The method for preparing a functionalized hyper-crosslinked polymer high-efficiency adsorbent according to claim 1, wherein: In the step (1), the mass ratio of the biphenylbenzyl chloride hypercrosslinked polymer to the functionalized monomer is 1:0.1-0.5; and the mass ratio of the total mass of the biphenylbenzyl chloride hypercrosslinked polymer and the functionalized monomer to the catalyst is 1:0.08-1.

4. The method for preparing a functionalized hyper-crosslinked polymer high-efficiency adsorbent according to claim 1, wherein: In the step (1), the solvent includes at least one of chloroform, dichloromethane, and dichloroethane; and the concentrations of the biphenylbenzyl chloride hypercrosslinked polymer and the functionalized monomer in the solvent are independently 0.001-0.01 g / mL.

5. The method for preparing a functionalized hyper-crosslinked polymer high-efficiency adsorbent according to claim 1, wherein: In the step (2), the grinding medium balls treated by planetary ball milling are a combination of one or more of 5 mm, 10 mm, and 15 mm; the grinding medium balls are made of at least one of alumina, agate, zirconium oxide, polytetrafluoroethylene, tungsten carbide, and stainless steel.

6. The method for preparing a functionalized hyper-crosslinked polymer high-efficiency adsorbent according to claim 1, wherein: In the step (2), the rotation speed of the planetary ball milling treatment is 100-500 rpm, and the treatment time is 10-60 min; the planetary ball milling treatment is controlled in stages, and is carried out in the form of forward rotation combined with reverse rotation to obtain a crude product.

7. The method for preparing a functionalized hyper-crosslinked polymer high-efficiency adsorbent according to claim 1, wherein: In the step (2), the planetary ball milling treatment adopts wet milling; the solvent used for wet milling includes at least one of water, methanol, ethanol, acetone, and ethyl acetate; and the mass ratio of the solvent to the reaction mixture is 80-100:

1.

8. The method for preparing a functionalized hyper-crosslinked polymer high-efficiency adsorbent according to claim 1, wherein: In the step (2), the drying temperature is 60-200°C and the drying time is 8-24 hours.

9. A functionalized hyper-crosslinked polymer high-efficiency adsorbent, characterized by: The method is as described in any one of claims 1 to 8.

10. A use of the functionalized hyper-crosslinked polymer high-efficiency adsorbent according to claim 9, characterized in that: Used as adsorption material for sulfonamide antibiotics.

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