Hydroxyl functionalized ionic super-crosslinked polymer as well as preparation method and application thereof

Abstract

The invention provides a hydroxyl-functionalized ionic super-crosslinked polymer and a preparation method and application thereof.The hydroxyl-functionalized ionic super-crosslinked polymer is obtained by mixing benzyl dimethyl (2-ethoxyl) ammonium chloride and 4, 4 '-bis (chloromethyl) biphenyl for reaction, and results show that the hydroxyl-functionalized ionic super-crosslinked polymer has the advantages that the hydroxyl-functionalized ionic super-crosslinked polymer is high in molecular weight and high in molecular weight; the hydroxyl functionalized ionic super-crosslinked polymer is applied to pretreatment of a sample containing phenolic pollutants, can realize determination of trace phenolic pollutants in the sample, is high in accuracy and can be repeatedly used.

Description

Technical Field

[0001] The present invention relates to the field of polymer technology, and in particular to a hydroxyl-functionalized ionic hyper-crosslinked polymer and a preparation method and application thereof. Background Art

[0002] Phenolic pollutants are widespread and pose serious environmental risks. Typical examples include bisphenol A (BPA), bisphenol F (BPF), bisphenol B (BPB), and para-tert-butylphenol (PTBP). Industrial production is the primary source: BPA is widely used in the production of polycarbonate plastics and epoxy resins, while BPF and BPB are key raw materials in the synthesis of resins and chemicals. These substances can enter the aquatic environment through industrial wastewater. PTBP, an antioxidant in rubber and plastics, can easily migrate and release from products under conditions of high temperature, high humidity, or strong light. These pollutants pose a significant threat to ecology and health. Even low concentrations of phenols can inhibit the growth, reproduction, and metabolic functions of aquatic organisms, disrupting aquatic ecological balance and amplifying risks through the food chain. For humans, phenols have the potential to cause carcinogenesis, teratogenesis, and mutagenesis. Long-term exposure can damage the nervous, immune, and reproductive systems, leading to diseases such as neurasthenia, leukemia, and reproductive disorders. Given their environmental persistence, bioaccumulation and high toxicity, accurate monitoring of phenol residues in the environment is of urgent significance for ecological protection and public health.

[0003] Currently, the detection of phenolic pollutants mainly adopts high-performance liquid chromatography (HPLC) because it does not require derivatization, has high separation efficiency, good selectivity and excellent sensitivity. However, interferences and trace targets (below the detection limit) in complex environmental matrices require sample pretreatment. Among the commonly used pretreatment methods, solid phase extraction (SPE) was selected as the core technology due to its significant advantages: compared with liquid-liquid extraction, SPE has higher enrichment multiples, less organic solvent consumption, easy automation, efficient removal of matrix interference, and is suitable for a variety of samples such as water / soil / biological samples.

[0004] The core of SPE performance depends on the performance of the adsorbent. Although commercial adsorbents (such as reversed-phase C18, HLB, ion exchange SAX / SCX, mixed-mode MCX / MAX) are of various types, they still have defects such as insufficient adsorption capacity and poor stability under special conditions such as extreme pH. As a new adsorption material, hypercrosslinked polymers (HCPs) have significantly improved the capture efficiency and adsorption capacity of phenolic pollutants due to their high specific surface area, developed pore structure and abundant adsorption sites. This material has excellent rigidity and stability, and can still maintain structural integrity and reliable performance in complex wastewater environments such as temperature and pH fluctuations. By introducing specific functional groups through chemical modification, its selective adsorption capacity for phenolic pollutants can be further enhanced, providing an innovative solution for the efficient detection of phenolic pollutants in the environment. For example, the hypercrosslinked β-cyclodextrin polyurethane (CDPU-HCP) prepared by Zhou et al. has a stable and efficient adsorption effect on bisphenol A in wastewater. Wang et al. synthesized acetylamino-functionalized HCP through two consecutive Friedel-Crafts reactions. Song et al. synthesized HCP-COOH, a carboxyl-rich compound, from phenylmaleic anhydride and 1,4-dichlorobenzyl. By introducing amino and carboxyl groups, the compound formed special interactions with phenolic pollutants, such as hydrogen bonding and electrostatic interactions, enhancing adsorption.

[0005] Ionic hypercrosslinked polymers, based on their ability to effectively treat phenolic pollutants, further demonstrate unique advantages. The ionic groups in ionic hypercrosslinked polymers can generate strong electrostatic interactions with phenolic pollutants. Phenolic pollutants typically exist in water as ions or partially ionized forms, and the ionic groups of ionic hypercrosslinked polymers can effectively capture these phenolic ions through electrostatic attraction, significantly improving the selectivity and efficiency of adsorption. This electrostatic interaction can operate over a wide pH range, enabling ionic hypercrosslinked polymers to maintain good adsorption performance under varying water quality conditions. For example, Cai et al. prepared an imidazoline-linked cationic covalent triazine framework (IM-iCTF). Zhao et al. synthesized a cyanide-functionalized hypercrosslinked ionic polymer (CN-HIP) using (2-benzimidazole)acetonitrile as a cationic monomer through a hypercrosslinking strategy. Yuan et al. synthesized triazine-containing ionic hypercrosslinked polymers by quaternizing polyhalogenated hydrocarbons with pyridines bearing triazine functional groups. Li et al. designed a positively charged hypercrosslinked polymer based on pyridine. Although ionic hypercross-linked polymers have made some progress, their application in exploring the adsorption of phenolic pollutants by ionic hypercross-linked polymers is still limited.

[0006] Therefore, it is of great significance to develop new high-performance adsorption materials to improve the detection ability of phenolic pollutants. Summary of the Invention

[0007] In view of this, the technical problem to be solved by the present invention is to provide a hydroxyl-functionalized ionic hypercross-linked polymer and its preparation method and application. The polymer provided by the present invention is used for the pretreatment of phenolic pollutants and can realize the determination of the residual phenolic pollutant content in shrimp and environmental water with a low detection limit and high accuracy.

[0008] Compared with the prior art, the present invention provides a hydroxyl-functionalized ionic hyper-crosslinked polymer, which is obtained by mixing and reacting benzyldimethyl (2-hydroxyethyl) ammonium chloride with 4,4′-bis(chloromethyl) biphenyl. Experimental results show that the hydroxyl-functionalized ionic hyper-crosslinked polymer provided by the present invention can be used for the pretreatment of samples containing phenolic pollutants by selecting specific monomers for reaction, and can realize the determination of trace phenolic pollutants in the samples with high accuracy and reusability. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] Figure 1 Schematic diagram of the preparation of NN-HCP, BC-HCP and PB-HCP;

[0010] Figure 2 The infrared chromatograms of NN-HCP, BC-HCP and PB-HCP;

[0011] Figure 3 Thermogravimetric test graphs of NN-HCP, BC-HCP and PB-HCP;

[0012] Figure 4 Zeta potential test results of NN-HCP, BC-HCP and PB-HCP;

[0013] Figure 5 is the SEM image of NN-HCP;

[0014] Figure 6 is the SEM image of BC-HCP;

[0015] Figure 7 is the SEM image of PB-HCP;

[0016] Figure 8 The figure is a comparison of the adsorption capacity of NN-HCP and five commercial adsorbents;

[0017] Figure 9 Comparison of the adsorption capacity of NN-HCP and BC-HCP;

[0018] Figure 10 Comparison of the adsorption capacity of NN-HCP and PB-HCP;

[0019] Figure 11 is the homogeneity test result of NN-HCP;

[0020] Figure 12 The stability test results of NN-HCP;

[0021] Figure 13 This is the reproducibility test result of NN-HCP. DETAILED DESCRIPTION

[0022] The present invention provides a hydroxyl-functionalized ionic hyper-crosslinked polymer, which is obtained by mixing benzyldimethyl (2-hydroxyethyl) ammonium chloride (Formula (I)) and 4,4'-bis (chloromethyl) biphenyl (Formula (II)) to obtain a hydroxyl-functionalized ionic hyper-crosslinked polymer (Formula (III)), wherein the molar ratio of benzyldimethyl (2-hydroxyethyl) ammonium chloride to 4,4'-bis (chloromethyl) biphenyl is 1: (1 to 1.5), preferably 1: (1 to 1.2).

[0023]

[0024] In the present invention, the catalyst of the reaction is preferably anhydrous ferric chloride, anhydrous aluminum chloride or anhydrous tin tetrachloride, more preferably ferric chloride; the molar ratio of the benzyldimethyl (2-hydroxyethyl) ammonium chloride to the catalyst is preferably 1: (2.5-3.5), more preferably 1: (3-3.2). The solvent of the reaction is preferably dichloromethane, dichloroethane or chloroform, more preferably dichloroethane (DCE). The amount ratio of the benzyldimethyl (2-hydroxyethyl) ammonium chloride to the solvent is preferably 1 mol: (10-15) mL, more preferably 1 mol: (13-14) mL. The temperature of the reaction is preferably 75°C to 85°C, more preferably 80°C. The reaction time is preferably 20-30 hours, more preferably 24-28 hours.

[0025] The present invention also provides a method for preparing a hydroxyl-functionalized ionic hyper-crosslinked polymer, comprising reacting benzyldimethyl (2-hydroxyethyl) ammonium chloride with 4,4'-bis (chloromethyl) biphenyl to obtain a hydroxyl-functionalized ionic hyper-crosslinked polymer.

[0026] The molar ratio of benzyldimethyl (2-hydroxyethyl) ammonium chloride to 4,4'-bis (chloromethyl) biphenyl is 1: (1 to 1.5). In this preparation method, the amount of each reaction raw material, the type and amount of catalyst and solvent, and the reaction conditions are the same as those in the aforementioned product.

[0027] In the present invention, the present invention preferably first reacts benzyldimethyl (2-hydroxyethyl) ammonium chloride with 4,4′-bis(chloromethyl) biphenyl, a solvent and a catalyst. After the reaction is completed, a crude product of a hydroxyl-functionalized ionic hyper-crosslinked polymer is obtained. The crude product is further purified by Soxhlet extraction and dried to obtain a pure product of a hydroxyl-functionalized ionic hyper-crosslinked polymer; the extraction solvent is preferably methanol.

[0028] The present invention also provides a method for detecting phenolic pollutant residues, including pretreatment and detection.

[0029] The pretreatment is to use solid phase extraction to pretreat the sample to be tested; the extraction agent used for solid phase extraction is the hydroxyl functionalized ionic hyper-cross-linked polymer described in the present invention; the detection is preferably HPLC-UV method, HPLC-MS / MS method, UHPLC method or LC-MS / MS method.

[0030] The present invention provides a hydroxyl-functionalized ionic hyper-crosslinked polymer, which is obtained by reacting benzyldimethyl (2-hydroxyethyl) ammonium chloride with 4,4′-bis(chloromethyl) biphenyl. It is found that the hydroxyl-functionalized ionic hyper-crosslinked polymer provided by the present invention can be used for the pretreatment of samples containing phenolic pollutants by selecting specific monomers for reaction, and can realize the determination of trace phenolic pollutants in the samples with high accuracy and is reusable.

[0031] The following will be a clear and complete description of the technical solutions of the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of them. All other embodiments obtained by ordinary technicians in this field based on the embodiments of the present invention without making any creative efforts shall fall within the scope of protection of the present invention.

[0032] Example

[0033] 1. Synthesis of hydroxyl-functionalized ionic hypercrosslinked polymer (NN-HCP)

[0034] Benzyldimethyl(2-hydroxyethyl)ammonium chloride (NNC) (3 mmol) and 4,4′-bis(chloromethyl)biphenyl (3 mmol) were accurately weighed and transferred to a round-bottom flask. DCE (40 mL) and anhydrous FeCl3 (3 mmol) were then added. The reaction was carried out in an 80°C constant temperature oil bath for 24 h to complete the Friedel-Crafts alkylation reaction. After the reaction was completed, the crude product was filtered to obtain a brown solid NN-HCP. The obtained NN-HCP was further purified by Soxhlet extraction using methanol as the solvent until the solvent became transparent. Finally, the purified product was dried in an oven at 60°C to obtain NN-HCP.

[0035] 2. Synthesis of BC-HCP and PB-HCP

[0036] In order to study the effect of different monomers on the properties of the prepared polymer materials, benzyltrimethylammonium chloride (BTAC) was used to replace NNC to synthesize the polymer BC-HCP; 4-phenyl-1-butanol (PB) was used to replace NNC to prepare the non-ionic analogue PB-HCP; the preparation diagram of the three polymers is shown in the figure. Figure 1 As shown, Figure 1 Schematic diagram of the preparation of NN-HCP, BC-HCP and PB-HCP.

[0037] 3. Characterize the structure of the obtained polymer. Figures 2 to 7 ,

[0038] Figure 2 The infrared chromatograms of NN-HCP, BC-HCP and PB-HCP are shown in Figure 2. Figure 2 It can be seen that the molecular structures of NN-HCP, BC-HCP and PB-HCP were successfully verified by FT-IR characterization analysis. The experimental data showed that the molecular structure of NN-HCP at 2919 cm -1 The characteristic peak at 1610 cm is derived from the asymmetric stretching vibration of methylene. -1 and 1432cm -1 Aromatic ring skeleton vibration at 1492 cm -1 The strong absorption peak at 37° corresponds to the stretching vibration mode of the C-N+ bond in the quaternary ammonium salt structure. The collective presence of these diagnostic spectral features provides conclusive evidence for the successful synthesis of the target compound.

[0039] In order to evaluate the thermal stability of the material, the temperature was raised at a rate of 10 °C min -1 Thermogravimetric analysis was performed in an air atmosphere at a temperature ranging from room temperature to 900 °C. Figure 3 , Figure 3 The thermogravimetric test diagrams of NN-HCP, BC-HCP and PB-HCP show that NN-HCP exhibits excellent thermal stability and only shows 10% mass loss below 380°C.

[0040] The obtained polymer was subjected to Zeta potential analysis, and the results are shown in Figure 4 , Figure 4 The Zeta potential test results for NN-HCP, BC-HCP, and PB-HCP show that NN-HCP and BC-HCP maintain a consistent positive surface potential over a wide pH range (2-12), confirming the permanent cationic nature of the quaternary ammonium groups within their frameworks. Bisphenol A becomes negatively charged under alkaline conditions due to the deprotonation of its phenolic hydroxyl groups.

[0041] The obtained polymer was scanned by electron microscope. Figures 5 to 7 , Figure 5 is the SEM image of NN-HCP; Figure 6 is the SEM image of BC-HCP; Figure 7 is the SEM image of PB-HCP; SEM analysis shows that NN-HCP, BC-HCP and PB-HCP are composed of irregular block-shaped particle aggregates.

[0042] 4. Adsorption application

[0043] The adsorption effect of NN-HCP on phenolic pollutants was systematically evaluated. In the experimental scheme, 30 mg of adsorbent was loaded into the solid phase extraction column, and 100 mL of 6 μg mL -1 Aqueous solutions of phenolic pollutants were prepared. 20 μL of the eluate was quantitatively analyzed by high-performance liquid chromatography and compared with five commercial adsorbents: polyphenylacetic acid anion exchange resin (PXA), octadecylsilane (C18), activated carbon (AC), graphitized carbon black (GCB), and carbon nanotubes (CNTs), as well as homemade polymers BC-HCP and PB-HCP.

[0044] See the results Figures 8 to 10 , Figure 8 The figure is a comparison of the adsorption capacity of NN-HCP and five commercial adsorbents; Figure 9 Comparison of the adsorption capacity of NN-HCP and BC-HCP; Figure 10 The figure shows a comparison of the adsorption capacities of NN-HCP and PB-HCP. As can be seen from the figure, NN-HCP exhibits superior adsorption performance, with an extraction recovery significantly higher than that of all standard substances, and better adsorption capacity and effect than the comparison materials, thus confirming its potential as an advanced adsorbent for the efficient removal of phenolic pollutants.

[0045] In order to achieve satisfactory SPE performance, the main influencing parameters were optimized, including eluent type, eluent volume, sample solution flow rate, sample solution volume and pH. In the optimization experiment, 100 mL of 50 ng mL -1 An aqueous solution of phenolic contaminants was passed through an SPE column loaded with 30 mg of NN-HCP. This study used a single-factor optimization approach to optimize SPE conditions. Three replicates were performed under each condition.

[0046] The results showed that the optimal conditions were: sample solution pH: no adjustment of sample pH; sample solution flow rate: 4 mL min -1 ; Sample solution volume: 100 mL; Desorption conditions: 0.3 mL 1% acidic methanol.

[0047] Reusability of NN-HCP

[0048] To verify the reproducibility and reusability of NN-HCP, the extraction efficiency of NN-HCP from the same batch and different batches was compared. The solid phase extraction conditions were: NN-HCP dosage was 30 mg, phenolic contaminant concentration was 50 ng mL -1 , the sample solution was 100 mL, the sample pH was 7, and the flow rate was 4 mL min -1 The eluent was 300 μL 1% acidic methanol.

[0049] By filling the same batch of NN-HCP into different solid phase extraction columns, the extraction efficiency is highly consistent. Figure 11 As shown, Figure 11 This is the homogeneity test result of NN-HCP, which strongly confirms that this batch of materials has excellent uniformity;

[0050] When the extraction column filled with NN-HCP was reused for more than 30 times, the extraction efficiency of phenolic pollutants did not decrease significantly. Figure 12 As shown, Figure 12 This is the stability test result of NN-HCP. It can be seen from the figure that the material has good stability during repeated use.

[0051] Three different batches of NN-HCP were tested and the results were as follows: Figure 13 As shown, Figure 13 The results of the reproducibility test of NN-HCP are shown in the figure. As can be seen from the figure, there is no significant difference in the extraction efficiency of the target substance between different batches of polymer. This result fully demonstrates the good reproducibility of the preparation process of NN-HCP and the inherent ultra-stability of the material itself.

[0052] In order to reduce the influence of the matrix, a matrix-matched calibration curve was established. The results are shown in Table 1. Table 1 shows the analytical data of the current method for detecting phenolic pollutants (n=5). It can be seen from Table 1 that both water and shrimp samples showed good linear relationships, and the determination coefficient R 2 The values ​​were all above 0.99 (Table 1). Limits of detection (LODs) were defined as the contaminant concentration at which the signal-to-noise ratio (S / N) was 3. Limits of quantification (LOQs) were defined as the lowest concentration of the analyte that could be quantified. The LODs for water samples ranged from 0.005 to 0.020 ng mL -1 LOQs ranged from 0.015 to 0.060 ng mL -1 The LODs and LOQs of shrimp samples were 1.13-4.17 ng g -1 and 3.00-12.5 ng g -1 .

[0053] Through 5 repeated experiments on the same day (river water 50ng mL -1, shrimp 200ng g -1 The intraday relative standard deviation (RSD) was estimated using a 3.5-μm HPLC-MS / MS / MS, and the interday RSD was determined using five replicates over five days. The method demonstrated excellent reproducibility, with an intraday RSD <5.9% and an intraday RSD <8.2%. This reliability ensures the effective determination of phenolic contaminants in shrimp and water samples.

[0054] Enrichment factors (EFs) were calculated as the ratio of the phenolic contaminant concentration in 300 μL of eluate after SPE to the phenolic contaminant concentration in 100 mL of the initial sample solution before SPE. The results showed that the enrichment efficiencies for red shrimp ranged from 133 to 193, for freshwater shrimp from 140 to 180, and for water samples from 313 to 326.

[0055] Table 1 Analytical data of phenolic pollutants detected by current method (n=5)

[0056]

[0057] Note: The unit of concentration of phenolic pollutants in shrimp is ngg -1 The concentration of phenolic pollutants in water is in ngmL -1 .

[0058] Comparison with other literature methods

[0059] The present research method shows multiple advantages compared with the existing phenol pollutant analysis technology. The results are shown in Table 2. Table 2 shows the comparison between the method provided by the present invention and other existing technologies. [1-6] As can be seen from the table, in terms of sensitivity, its LOD / LOQ value is lower than that of most methods reported in the literature, especially for shrimp samples. [4,5] Compared with Yuan et al. [1] The hydrophilic magnetic amino-functional MOF material developed by this method reduces the amount of adsorbent and does not require complex modification. At the same time, it maintains stable extraction performance in the pH range of 2-12, breaking through the environmental limitations of the original material. The extraction time is shortened to 30 minutes, which is much faster than the dual-template molecularly imprinted polymer coated stirring rod. [3] The 90-min extraction efficiency is significantly improved. [2] The operation is similar, but the detection sensitivity is significantly improved. [6] While achieving a lower LOD, the tedious pH adjustment step compromises operational reproducibility. In practical applications, this method maintains high recovery while keeping the eluent dosage within 300 μL and shortening the detection time to 13 minutes. This method successfully achieves an optimal balance between detection sensitivity, operational efficiency, and environmental performance, providing a superior solution for the detection of trace pollutants in complex matrices.

[0060] Table 2 Comparison of this method with other methods

[0061]

[0062] Note: The unit of contaminant concentration in meat is ng g -1 The unit of water pollutant concentration is ngmL -1 .

[0063] [1] Yuan Y, Zheng X, Lin H, et al. Development of a hydrophilic magneticamino-functionalized metal-organic framework for the highly efficient enrichment of trace bisphenols in river water samples [J]. Talanta, 2020, 211: 120713.

[0064] [2]Li Y, Yang C, Ning J, et al. Cloud point extraction for the determination of bisphenol A, bisphenol AF and tetrabromobisphenol A in riverwater samples by high-performance liquid chromatography[J]. Anal Methods, 2014, 6(10): 3285-3290.

[0065] [3]Xu Z, Yang Z, Liu Z. Development of dual-templates molecularlyimprinted stir bar sorbtive extraction and its application for the analysis of environmental estrogens in water and plastic samples[J]. Journal of ChromatographyA, 2014,1358:52-59.

[0066] [4]Cai Z, Zhao B, Hao L, et al. Fabrication of imidazoline-linkedcationic covalent triazine framework for enrichment of environmental estrogens[J]. Talanta, 2024,272:125750.

[0067] [5]Li N,Wu D,Liu J,et al.Magnetic covalent organic frameworks based on magnetic solid phase extraction for determination of six steroidal andphenolic endocrine disrupting chemicals in food samples[J].MicrochemicalJournal,2018,143:350-358.

[0068] [6]Xu J, Li W, Sun M, et al. Magnetic cationic covalent organic framework for efficient enrichment and detection of phenolic endocrine disruptors infoodstuffs[J]. Journal of Chromatography A, 2025,1748:465827.

[0069] The above embodiments are only intended to help understand the method and core concept of the present invention. It should be noted that, without departing from the principles of the present invention, a number of improvements and modifications may be made to the present invention by those skilled in the art, and such improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims

1. A hydroxyl-functionalized ionic hyper-crosslinked polymer, obtained by reacting benzyldimethyl (2-hydroxyethyl) ammonium chloride with 4,4′-bis (chloromethyl) biphenyl. in, The molar ratio of the benzyldimethyl (2-hydroxyethyl) ammonium chloride to 4,4'-bis (chloromethyl) biphenyl is 1: (1-1.5).

2. The hydroxyl-functionalized ionic hypercrosslinked polymer according to claim 1, wherein The catalyst for the reaction is anhydrous ferric chloride, anhydrous aluminum chloride or anhydrous tin tetrachloride.

3. The hydroxyl-functionalized ionic hypercrosslinked polymer according to claim 2, wherein The molar ratio of the benzyldimethyl (2-hydroxyethyl) ammonium chloride to the catalyst is 1: (2.5-3.5).

4. The hydroxyl-functionalized ionic hypercrosslinked polymer according to claim 1, wherein The solvent for the reaction is dichloromethane, dichloroethane or chloroform.

5. The hydroxyl-functionalized ionic hypercrosslinked polymer according to claim 4, characterized in that The usage ratio of the benzyldimethyl (2-hydroxyethyl) ammonium chloride to the solvent is 1 mol: (10-15) mL.

6. The hydroxyl-functionalized ionic hypercrosslinked polymer according to claim 1, characterized in that The reaction temperature is 75°C to 85°C.

7. The hydroxyl-functionalized ionic hypercrosslinked polymer according to claim 1, characterized in that The reaction time is 20 to 30 hours.

8. A method for preparing a hydroxyl-functionalized ionic hypercrosslinked polymer, comprising reacting benzyldimethyl (2-hydroxyethyl) ammonium chloride with 4,4′-bis (chloromethyl) biphenyl to obtain a hydroxyl-functionalized ionic hypercrosslinked polymer. in, The molar ratio of the benzyldimethyl (2-hydroxyethyl) ammonium chloride to 4,4'-bis (chloromethyl) biphenyl is 1: (1-1.5).

9. A method for detecting phenolic pollutant residues, comprising pretreatment and detection, The pretreatment is to use solid phase extraction to pretreat the sample to be tested; the extractant for solid phase extraction is the hydroxyl functionalized ionic hypercrosslinked polymer according to any one of claims 1 to 7 or the hydroxyl functionalized ionic hypercrosslinked polymer prepared by the preparation method according to claim 8.

10. The detection method according to claim 9, characterized in that: The detection is HPLC-UV method, HPLC-MS / MS method, UHPLC method or LC-MS / MS method.

Images