Adsorbent packing for purification column, its preparation method and use

Abstract

The present application belongs to the field of chromatographic packing, discloses an adsorbing packing for purification column and its preparation method and use. A polyethylene oxide and clay composite material, the composite material comprises the following raw materials by weight: inorganic salt modified clay 4000-8000 parts, quaternary ammonium salt compound 50-100 parts, polyethylene oxide 1 part. The present application also provides an adsorbing packing for purification column, which can effectively and selectively adsorb protein, lipid and other impurities in the pretreatment extraction liquid for mycotoxin detection, has a small matrix effect, and has a high absolute recovery rate for several typical mycotoxin target objects.

Description

Technical Field

[0001] This invention relates to the field of chromatographic packing materials, and in particular to an adsorption packing material for purification columns, its preparation method, and its applications. Background Technology

[0002] The term "mycotoxin" originates from the Greek word "Mykes" and the Latin word "Toxicum," referring to secondary metabolites produced by toxin-producing fungi under suitable environmental conditions. Rice, wheat, and corn are the three most consumed grains in China, and these grains are highly susceptible to mycotoxin contamination during processing and storage, making fungal contamination a growing concern.

[0003] Aflatoxin is a toxic secondary metabolite produced by Aspergillus flavus and Aspergillus parasiticus under high temperature and humidity conditions. It is a class of extremely toxic substances. Besides aflatoxin, more than a dozen other fungal toxins that pose significant threats to humans have been extensively studied. These toxins generally exhibit both high toxicity and high contamination frequency, with deoxynivalenol (vomitoxin), zearalenone, and patulin being the most prominent. These four fungal toxins not only have carcinogenic, teratogenic, and mutagenic effects, but also hepatotoxicity, toxic nephropathy, reproductive disorders, and immunosuppression, posing a significant threat to human health. Fungal toxin contamination in food has become an issue that cannot be ignored. Therefore, establishing rapid, efficient, and sensitive detection methods, especially the simultaneous detection of multiple fungal toxins, is particularly important.

[0004] Currently, the main methods for detecting mycotoxins in food and agricultural products include thin-layer chromatography (TLC), enzyme-linked immunosorbent assay (ELISA), immunoaffinity column purification-fluorescence assay, immunoaffinity column purification-high performance liquid chromatography (HPLC), and HPLC-tandem mass spectrometry (HPLC-MS / MS). To reduce detection interference, improve method detection capabilities, and extend instrument lifespan, the sample extract needs to be purified before entering the instrument for analysis. This involves removing a large amount of non-target substances, such as fats, proteins, pigments, minerals, and cellulose. Commonly used purification methods include the following:

[0005] (1) Liquid-liquid extraction (LLE): Liquid-liquid extraction is based on the difference in solubility of impurities and analytes in different solvents to achieve extraction and purification. For example, weakly polar solvents such as n-hexane and petroleum ether can be used to remove slightly polar impurities such as oils and cholesterol from the extract, while the polar target analyte is retained. Liquid-liquid extraction is a simple method with low equipment requirements, fast operation, and wide application, but it has disadvantages such as long processing time, low efficiency, poor method specificity, and large solvent consumption.

[0006] (2) Solid phase extraction (SPE)

[0007] SPE (Separation Optimization) is very similar to column chromatography in terms of separation principle, stationary phase, and solvent selection. However, the particle size of SPE packing material (above 40 μm) is much larger than that of chromatographic column packing material, therefore it can only separate substances with significantly different properties. Commonly used packing materials for SPE columns are silica gel or chemically bonded packing materials, such as -OH, -CN, -C18, and -C6H5, which achieve adsorption of target analytes through bonds and functional groups. SPE can be used to: 1) remove matrix interferences; 2) enrich trace components; 3) change the sample solvent; and 4) perform in-situ derivatization and sample desalting. The general operation process of SPE can be described as follows: 1) Activation: Elute the SPE column with an appropriate solvent to remove any impurities that may be present in the column and to solvate the surface of the packing material; 2) Sample loading: Slowly pass the extract through the SPE column under negative pressure or gravity to achieve a process of sufficient contact and distribution equilibrium; 3) Eluting: Use a medium-strength solvent to elute interfering substances retained on the column, while the analyte remains; 4) Elution: Completely elute the analyte and collect it in the smallest possible fraction.

[0008] Currently, the SPE method has replaced the LLE method in many analytical methods and even national standards. Compared with the LLE method, SPE has the following advantages: less organic reagent is used, the operation is rapid; the method has good selectivity and high sensitivity; good reproducibility and easy automation; it can process large-volume samples and has concentration and enrichment functions. However, the SPE method also has some disadvantages: the column itself is prone to clogging, the selection range of packing materials is limited; column performance is affected by factors such as pH value, solvent type and ionic strength.

[0009] (3) Improved solid phase extraction method

[0010] The improved solid phase extraction method is similar to the traditional SPE method in principle, but there are still differences in the type of packing material and purification mechanism. It mainly includes two methods: Immunoaffinity column (IAC) and Multifunctional column (MFC).

[0011] Multifunctional purification columns (MFCs) have become increasingly popular in recent years, primarily operating on the principle of physical adsorption. They typically use polar, nonpolar, and ion exchangers as adsorbents, selectively adsorbing impurities such as proteins and lipids when the extract comes into contact with the packing material, while leaving the analyte toxins unretained. MFCs are faster than traditional SPE methods, eliminating the need for activation, rinsing, and elution processes. They offer high sample throughput, making them suitable for the simultaneous determination of multiple toxins. Furthermore, compared to IACs, MFCs have lower detection costs and higher experimental efficiency, making them suitable for large-scale sample determination. However, MFCs also have significant drawbacks: limited purification effectiveness in complex matrices, a significant matrix effect, and poor absolute recovery rates for some target analytes. Summary of the Invention

[0012] In view of the shortcomings of the prior art described above, the purpose of this invention is to provide an adsorption packing for a purification column, its preparation method and application, in order to solve the problems existing in the prior art.

[0013] To achieve the above objectives, the present invention specifically adopts the following technical solution.

[0014] The first aspect of this invention protects a composite material of polyethylene oxide and clay, said composite material comprising the following raw materials in parts by weight:

[0015] 4000-8000 parts of inorganic salt modified clay

[0016] 50-100 parts of quaternary ammonium salt compounds

[0017] One part of polyethylene oxide.

[0018] In some embodiments, the inorganic salt modified clay may be 4000-6000 parts by weight, 5000-7000 parts by weight, or 6000-8000 parts by weight. In a preferred embodiment, it is 6000 parts, 4000 parts, or 5000 parts by weight.

[0019] In some embodiments, the quaternary ammonium salt compound may be present in parts by weight of 50-110, 80-150, or 120-200. In a preferred embodiment, it may be present in parts by weight of 100, 50, or 70.

[0020] The inorganic salt-modified clay composite material of this invention increases the expansibility of the clay. By embedding the cations of quaternary ammonium compounds between the crystal layers of the inorganic salt-modified clay, an organic clay is obtained. Then, the polymerization of polyethylene oxide, which penetrates into the clay layers, is initiated between the crystal layers, successfully producing a composite material of polyethylene oxide and clay. The composite material of this invention has uniform particle size and can selectively adsorb proteins and lipids from fungal toxin extracts.

[0021] In some embodiments, the quaternary ammonium salt compound is selected from one or more of N,N,N-trimethyl-2-(2-methyl-1-oxo-2-propenyloxy)ethyl ammonium chloride-acrylamide copolymer, chlorinated 2-hydroxy-3-(trimethylamino)propyl polyoxyethylene cellulose ether, alkyl dimethyl benzyl ammonium halide, and dialkyl dimethyl ammonium halide.

[0022] Preferably, the N,N,N-trimethyl-2-(2-methyl-1-oxo-2-propenyloxy)ethylammonium chloride-acrylamide copolymer has a molecular weight of 200 to 500, specifically 278.78.

[0023] Preferably, the molecular weight of the chlorinated 2-hydroxy-3-(trimethylamino)propyl polyethylene oxide cellulose ether is 600 to 1000, specifically 656.11.

[0024] Preferably, the alkyl dimethyl benzyl ammonium halide is dodecyl dimethyl benzyl ammonium chloride with a molecular weight of 339.99.

[0025] Preferably, the dialkyldimethyl ammonium halide is selected from dodecyldimethylammonium bromide with a molecular weight of 462.63.

[0026] In some embodiments, the weight-average molecular weight to number-average molecular weight ratio of the polyoxyethylene is 17-20, the particle size is 300-400 mesh, and the dissolution temperature is 30-50°C.

[0027] In some embodiments, the inorganic salt modified clay is selected from one or more of sodium-modified clay, potassium-modified clay, and calcified clay.

[0028] Preferably, the inorganic salt modified clay is a mixture of sodium-modified clay, potassium-modified clay, and calcified clay. The cationic modified clay composed of sodium-modified clay, potassium-modified clay, and calcified clay in this invention can improve clay viscosity and lubricity, which is beneficial for making fillers. Polymers are less likely to adhere to the clay, and selective adsorption is good.

[0029] More preferably, the mass ratio of the sodium-modified clay, potash-modified clay, and calcified clay is (0.5–2):(0.5–2):1. Even more preferably, the mass ratio of the sodium-modified clay, potash-modified clay, and calcified clay can be (0.5–0.8):(0.5–2):1, (0.6–1.5):(0.5–2):1, or (1.2–2):(0.5–2):1. In a certain preferred embodiment, it is 1:1:1.

[0030] In some embodiments, the method for preparing the inorganic salt modified clay is as follows:

[0031] 1) Disperse the clay in water, sonicate, and centrifuge to obtain a suspension;

[0032] 2) Adjust the pH of the suspension with acid, and add an oxidant to carry out the reaction;

[0033] 3) Adjust the pH value with alkali, add inorganic salt, mix, centrifuge, and dry to obtain the inorganic salt modified clay.

[0034] In this invention, the clay is first pretreated by ultrasonication and centrifugation to remove impurity mineral particles, laying the foundation for increasing the contact area between the clay and polymer, and simultaneously increasing the interlayer spacing of the clay crystals, thus facilitating the entry of polymers into the clay crystal interlayers. Acidification and oxidation are then combined to increase the specific surface area of ​​the clay while removing organic matter. This removal of organic matter increases pore size, creating an environment conducive to subsequent hydration and expansion. Sodium carbonate is then added to ensure the solution becomes alkaline before adding salt. This step is to facilitate the insertion of cations and increase the clay's expansibility, both internally and externally, creating conditions for the subsequent entry of polymers into the clay crystal layers and facilitating the entry of quaternary ammonium salt compounds.

[0035] Preferably, in 1), the clay is selected from one or more of kaolinite, montmorillonite, serpentine, talc, and mica.

[0036] Preferably, in step 2), the pH value is 2 to 7. More preferably, the pH value can be 2 to 4, 3 to 6, or 5 to 7. In a certain preferred embodiment, it is 6.

[0037] Preferably, in step 2), the acid is selected from one or more of dilute hydrochloric acid, dilute nitric acid, and dilute sulfuric acid.

[0038] More preferably, the acid is dilute hydrochloric acid. Even more preferably, the concentration of the dilute hydrochloric acid is 1–10 mol / L. More preferably, the concentration of the dilute hydrochloric acid can be 1–5 mol / L, 4–8 mol / L, or 6–10 mol / L. In a certain preferred embodiment, it is 5 mol / L.

[0039] Preferably, in step 2), the oxidant is selected from one or more of hydrogen peroxide, peracetic acid, and nitric acid.

[0040] More preferably, the oxidant is hydrogen peroxide (H2O2).

[0041] Preferably, in step 3), the pH value is 8-10. More preferably, the pH value can be 8-8.8, 8.6-9.6, or 9.2-10. In a preferred embodiment, it is 10.

[0042] Preferably, in step 3), the alkali is selected from one or both of sodium carbonate and sodium bicarbonate.

[0043] More preferably, the alkali is sodium carbonate.

[0044] Preferably, in step 3), the inorganic salt is selected from one or more of sodium chloride, potassium chloride, and calcium chloride.

[0045] Preferably, the mass ratio of clay to inorganic salt is (5-7):(12-30).

[0046] Preferably, the mass ratio of clay to inorganic salt is 7:(1-4). In a preferred embodiment, it is 700:136.347.

[0047] Preferably, the mass ratio of clay to oxidant is 1:(2-20).

[0048] More preferably, the mass ratio of clay to oxidant can be 1:(2-10), 1:(6-15), or 1:(12-20). In a preferred embodiment, it is 1:12.

[0049] Preferably, the mass ratio of clay to oxidant is 700:(1-3). In a certain preferred embodiment, it is 700:1 or 700:1.5.

[0050] The second aspect of this invention protects the method for preparing the composite material described above as follows: inorganic salt modified clay and quaternary ammonium salt compound are reacted in a solvent, and then polymerized with polyethylene oxide to obtain the composite material.

[0051] In this invention, inorganic salt modified clay is placed in an aqueous solution of quaternary ammonium salt compound to ensure that the inorganic salt clay is modified from polar to nonpolar, creating conditions for subsequent coating with polyethylene oxide and increasing the adsorption of oils, proteins and lipids by the composite material of polyethylene oxide and clay.

[0052] In some embodiments, the solvent is water.

[0053] In some embodiments, the reaction temperature is 40–80°C.

[0054] Preferably, the reaction temperature can be 40–55°C, 50–75°C, or 60–80°C. In a preferred embodiment, it is 60°C.

[0055] In some embodiments, the reaction time is 1 to 10 hours.

[0056] Preferably, the reaction time can be 1–6 hours, 4–8 hours, or 6–10 hours. In a preferred embodiment, it is 5 hours.

[0057] In some embodiments, the polymerization reaction temperature is 20–40°C.

[0058] Preferably, the polymerization reaction temperature can be 20–28°C, 26–36°C, or 35–40°C. In a preferred embodiment, it is 25°C.

[0059] In some embodiments, the polymerization reaction time is 5 to 8 hours.

[0060] Preferably, the reaction time can be 5-6.2 hours, 5.8-7.2 hours, or 7.0-8 hours. In a preferred embodiment, it is 7 hours.

[0061] A third aspect of this invention protects the use of the aforementioned composite material as a raw material in adsorption packings.

[0062] A fourth aspect of the present invention protects an adsorption packing material for a purification column, wherein the adsorption packing material for the purification column comprises the composite material, activated silica gel and silane coupling agent described above.

[0063] In some embodiments, the adsorption packing material used in the purification column comprises the following parts by weight of raw materials:

[0064] 40-70 parts of composite material

[0065] 20-50 parts activated silica gel

[0066] 5-12 parts of silane coupling agent.

[0067] This application found that silicone and polymer composites can adsorb some grease, but also adsorb the target substance. However, the addition of composite materials can adsorb grease and other interfering substances to the greatest extent without adsorbing the target substance.

[0068] Preferably, the composite material can be 40-58 parts by weight, 48-62 parts by weight, or 55-70 parts by weight. In a preferred embodiment, it is 40 parts, 60 parts, or 70 parts by weight.

[0069] Preferably, the activated silica gel can be in the following weight proportions: 20-24 parts, 23-26 parts, or 25-30 parts. In a preferred embodiment, it is 50 parts, 30 parts, 20 parts, or 25 parts.

[0070] Preferably, the silane coupling agent can be 5-7 parts by weight, 6-10 parts by weight, or 9-12 parts by weight. In a preferred embodiment, it is 10 parts or 5 parts by weight.

[0071] In some embodiments, the silane coupling agent is selected from one or more of γ-aminopropyltriethoxysilane (KH-550), vinyltriethoxysilane (A151), N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (KH-792), and γ-aminoethylaminopropyltrimethoxysilane (KH-900).

[0072] In some embodiments, the activated silica gel is prepared by mixing silica gel powder with acid in a solvent and drying it to obtain the activated silica gel.

[0073] In some specific embodiments, the specific surface area of ​​the silica gel powder is 300–680 m². 2 / g.

[0074] In some specific embodiments, the pore size of the silica gel powder is 10-25 nm.

[0075] In some specific embodiments, the acid is selected from one or more of sulfuric acid, hydrochloric acid, nitric acid, and perchloric acid.

[0076] Preferably, the acid is sulfuric acid.

[0077] In some specific embodiments, the solvent is water.

[0078] In some specific embodiments, the mass-to-volume ratio of the silica gel powder to the acid is (1-8) g: 1 mL.

[0079] Preferably, the mass-to-volume ratio of the silica gel powder to the acid can be (1-5) g:1 mL, (3-7) g:1 mL, or (6-8) g:1 mL. In a preferred embodiment, it is 4 g:1 mL.

[0080] In some specific embodiments, the mixing temperature is 40–80°C.

[0081] Preferably, the mixing temperature can be 40–60°C, 50–70°C, or 60–80°C. In a preferred embodiment, it is 60°C.

[0082] In some specific embodiments, the mixing time is 2 to 8 hours.

[0083] Preferably, the mixing time can be 2-5 hours, 4-6 hours, or 5-8 hours. In a preferred embodiment, it is 4 hours.

[0084] In some specific embodiments, the drying temperature is 5 to 20 hours.

[0085] Preferably, the drying time can be 5-10 hours, 8-15 hours, or 12-20 hours. In a preferred embodiment, it is 10 hours.

[0086] The fifth aspect of the present invention protects a method for preparing adsorption packing material for purification columns as described above, comprising the following steps: mixing the raw material components, aging them, and obtaining the adsorption packing material for purification columns.

[0087] In some embodiments, the aging is carried out in an aqueous sodium hydroxide solution.

[0088] Preferably, the concentration of the sodium hydroxide aqueous solution is 0.1–1.0 mol / L. More preferably, the concentration can be 0.1–0.4 mol / L, 0.3–0.7 mol / L, or 0.6–1.0 mol / L. In a certain preferred embodiment, it is 0.8 mol / L.

[0089] In some embodiments, the aging time is 4 to 10 hours.

[0090] Preferably, the aging time can be 4-10 hours, or 4-10 hours, or 4-10 hours. In a preferred embodiment, it is 5 hours.

[0091] The sixth aspect of this invention protects the use of the adsorption packing material for purification columns as described above as a chromatographic material.

[0092] In some embodiments, the purification column is used as an adsorbent in the preparation of chromatographic materials for mycotoxins.

[0093] The adsorption packing material for the purification column of the present invention can effectively and selectively adsorb impurities such as proteins and lipids in the pretreatment extract of fungal toxins, thereby making the chromatographic analysis of trace or ultra-trace substances more accurate.

[0094] Compared with the prior art, the present invention has the following beneficial effects:

[0095] 1) The purification column of the present invention uses an adsorption packing material made by combining a composite material of polyethylene oxide and clay with activated silica gel through a silane coupling agent, which can effectively purify fungal toxins before pretreatment.

[0096] 2) The purification column adsorption packing material in this invention is very suitable for the detection of mycotoxins. It can effectively and selectively adsorb impurities such as proteins and lipids in the pretreatment extract, thereby making the chromatographic analysis of trace or ultra-trace substances more accurate. The determination of several mycotoxins can reach the content of the analyte in the mixture when the content is within 10. -6 ~10 -9 (mass ratio).

[0097] 3) The adsorption packing material of the purification column in this invention has a good purification effect on complex matrices, has a small matrix effect, and has a high absolute recovery rate for several typical fungal toxin targets.

[0098] 4) The adsorption packing material for the purification column in this invention exhibits uniformity and stability in both particle size distribution and pore size distribution. Attached Figure Description

[0099] Figure 1 The graphs show the solvent effect evaluation of aflatoxin B1, aflatoxin B2, aflatoxin G1, and aflatoxin G2 by the adsorption packing material of the purification column of Example 10 of the present invention, and the packing materials of Comparative Example 1 and Comparative Example 2, respectively.

[0100] Figure 2 Microscopic images of the adsorption packing material for the purification column of Example 10 of the present invention, and the packing materials of Comparative Example 1 and Comparative Example 2.

[0101] Figure 3 This diagram illustrates the batch stability effect of the adsorption packing material for the purification column in Example 10 of the present invention. Detailed Implementation

[0102] The following specific embodiments illustrate the implementation of the present invention. Those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification.

[0103] Before further describing specific embodiments of the present invention, it should be understood that the scope of protection of the present invention is not limited to the specific embodiments described below; it should also be understood that the terminology used in the embodiments of the present invention is for describing specific embodiments and not for limiting the scope of protection of the present invention. Test methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions or as recommended by the respective manufacturers.

[0104] When numerical ranges are given in the embodiments, it should be understood that, unless otherwise stated in the present invention, both endpoints of each numerical range and any value between the two endpoints may be selected. Unless otherwise defined, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art. In addition to the specific methods, apparatus, and materials used in the embodiments, based on the knowledge of the prior art possessed by one of ordinary skill in the art and the description of this invention, any prior art methods, apparatus, and materials similar to or equivalent to those described, apparatus, and materials in the embodiments of this invention may be used to implement the present invention.

[0105] The sources and parameters of each raw material component used in the following embodiments and comparative examples of this application are shown in Table 1.

[0106] Table 1. Raw Material Sources and Parameters

[0107]

[0108] Example 1

[0109] In this embodiment, a composite material of polyethylene oxide and clay, an adsorption packing for a purification column, and a method for preparing the same are provided, comprising the following steps.

[0110] The composite material formulation of polyethylene oxide and clay is as follows: 60g inorganic salt modified clay, 1g chlorinated 2-hydroxy-3-(trimethylamino)propyl polyethylene oxide cellulose ether and 10mg polyethylene oxide, wherein the inorganic salt modified clay includes 20g sodium modified clay, 20g potassium modified clay and 20g calcified modified clay.

[0111] A method for preparing a composite material of polyethylene oxide and clay includes the following steps:

[0112] 1) Disperse 700g of kaolinite in 2L of deionized water, stir at 7000rpm for 30min, then sonicate for 15min, and then centrifuge at 5000rpm for 80min to remove precipitate and other mineral particles to obtain a suspension.

[0113] 2) First, adjust the pH of the suspension to 2-7 with 5mol / L dilute hydrochloric acid, add 10mL of 10% H2O2 (1g H2O2), heat to 80℃ to decompose H2O2 to remove organic matter in kaolinite, and then adjust the pH to 9-10 with sodium carbonate.

[0114] 3) Add 300 mL of 3M NaCl (52.65 g NaCl), 300 mL of 3M KCl (67.05 g KCl), and 300 mL of 0.5 M CaCl2 (16.647 g CaCl2) respectively, stir at room temperature for 48 h to allow sufficient ion exchange, then centrifuge, collect the precipitate, wash the precipitate until there is no excess solution, dry and pulverize at 120 °C, and pass through a 500 mesh sieve to obtain sodium-modified kaolinite, potassium-modified kaolinite, and calcified modified kaolinite respectively.

[0115] 4) 20g each of sodium-modified kaolinite, potassium-modified kaolinite, and calcified kaolinite, along with 1g of chlorinated 2-hydroxy-3-(trimethylamino)propyl polyethylene oxide cellulose ether, were placed in 500mL of distilled water and reacted in a water bath at 60℃ for 5h. After the reaction was completed, the mixture was cooled to room temperature (25℃), and then 10mg of polyethylene oxide was added for polymerization for 7h. The mixture was ultrasonically stirred to obtain the reaction product. The reaction product was centrifuged, washed multiple times with distilled water, and dried under reduced pressure in a vacuum dryer at 70℃. The product was then ground through a 300-mesh sieve to obtain a composite material of polyethylene oxide and clay (referred to as composite kaolin polymer).

[0116] The formulation of the adsorption packing material for the purification column is: 40wt% of a composite material of polyethylene oxide and clay (referred to as composite kaolin polymer), 50wt% activated silica gel and 10wt% KH-550.

[0117] The preparation method of adsorption packing material for purification columns includes the following steps:

[0118] The composite kaolin polymer, activated silica gel, and silane coupling agent (KH-550) were stirred in a reactor for 2 hours using a magnetic stirrer at a speed of 100 r / min to obtain a mixture. 600 mL of the mixture was aged in 1000 mL of 0.5 mol / L sodium hydroxide solution for 5 hours to prepare microspheres. The microspheres were separated from the aged solution using a sieve, washed 5 times with a washing solution such as deionized water, and dried at 50–65 °C to obtain the adsorption packing material for the purification column, labeled as adsorption packing material 1#.

[0119] Activated silica gel is obtained through the following method:

[0120] Take a specific surface area of ​​300–680 m² 2 200g of silica gel with a pore size distribution of 10-25nm was mixed with 50mL of concentrated sulfuric acid and 200mL of distilled water in a 1000mL two-necked flask. The mixture was then soaked in a constant temperature water bath at 60℃ with magnetic stirring for 4h. After washing with distilled water and filtering until neutral, the mixture was dried in an oven at 75℃ for 10h and then cooled for later use.

[0121] Example 2

[0122] In this embodiment, a composite material of polyethylene oxide and clay, an adsorption packing for a purification column, and a method for preparing the same are provided, including the following:

[0123] The composite material formulation of polyethylene oxide and clay is as follows: 60g inorganic salt modified clay, 1g dodecyl dimethyl ammonium bromide and 10mg polyethylene oxide, wherein the inorganic salt modified clay includes 20g sodium modified clay, 20g potassium modified clay and 20g calcified modified clay.

[0124] A method for preparing a composite material of polyethylene oxide and clay includes the following steps:

[0125] 1) Disperse 700g of montmorillonite in 2L of deionized water, stir at 7000rpm for 30min, then sonicate for 15min, and then centrifuge at 5000rpm for 80min to remove precipitate and other mineral particles to obtain a suspension.

[0126] 2) First, adjust the pH of the suspension to 5 with 5 mol / L dilute hydrochloric acid, add 15 ml of 10% H2O2 (1.5 g H2O2), heat to 80℃ to decompose H2O2 to remove organic matter in montmorillonite, and then adjust the pH to 10 with sodium carbonate.

[0127] 3) Add 300 mL of 3M NaCl (52.65 g NaCl), 300 mL of 3M KCl (67.05 g KCl), and 300 mL of 0.5 M CaCl2 (16.647 g CaCl2) respectively, stir at room temperature for 48 h to allow sufficient ion exchange, then centrifuge, collect the precipitate, wash the precipitate until there is no excess solution, dry at 120 °C, pulverize, and pass through a 500 mesh sieve to obtain sodium-modified montmorillonite, potassium-modified montmorillonite, and calcified modified montmorillonite respectively.

[0128] 4) 20g each of sodium-modified montmorillonite, potassium-modified montmorillonite, and calcified montmorillonite, and 1g of dodecyl dimethyl ammonium bromide were placed in 500mL of distilled water and reacted in a water bath at 60℃ for 5h. After the reaction was completed, the mixture was cooled to room temperature (25℃), and then 10mg of polyethylene oxide was added. The mixture was ultrasonically stirred for 7h to carry out the polymerization reaction and obtain the reaction product. The reaction product was centrifuged, washed several times with distilled water, placed in a vacuum dryer at 70℃ and dried under reduced pressure, and ground through a 300-mesh sieve to obtain a composite material of polyethylene oxide and clay (referred to as composite montmorillonite polymer).

[0129] The formulation of the adsorption packing material for the purification column is: 40wt% of a composite material of polyethylene oxide and clay (referred to as composite montmorillonite polymer), 50wt% activated silica gel and 10wt% A151.

[0130] The preparation method of adsorption packing material for purification columns includes the following steps:

[0131] The composite montmorillonite polymer, activated silica gel, and silane coupling agent (A151) were stirred in a reactor for 2 hours using a magnetic stirrer at a speed of 100 r / min to obtain a mixture. The mixture was then aged in a 0.5 mol / L sodium hydroxide solution for 5 hours to prepare microspheres. The microspheres were separated from the solution, washed 5 times with a washing solution, and dried to obtain the adsorption packing material for the purification column, labeled as adsorption packing material 2#.

[0132] The preparation method of activated silica gel is the same as in Example 1.

[0133] Example 3

[0134] In this embodiment, a composite material of polyethylene oxide and clay, an adsorption packing for a purification column, and a method for preparing the same are provided, including the following:

[0135] The composite material formulation of polyethylene oxide and clay is as follows: 60g inorganic salt modified clay, 1g dodecyl dimethyl benzyl ammonium chloride and 10mg polyethylene oxide, wherein the inorganic salt modified clay includes 20g sodium modified clay, 20g potassium modified clay and 20g calcified modified clay.

[0136] A method for preparing a composite material of polyethylene oxide and clay includes the following steps:

[0137] 1) Disperse 700g of serpentine in 2L of deionized water, stir at 10000rpm for 50min, then sonicate for 15min, and then centrifuge at 8000rpm for 40min to remove precipitate and other mineral particles to obtain a suspension.

[0138] 2) First, adjust the pH of the suspension to 5 with 5 mol / L dilute hydrochloric acid, add 15 mL of 10% H2O2 (1.5 g H2O2), heat to 90℃ to decompose H2O2 to remove organic matter from the serpentine, and then adjust the pH to 10 with sodium carbonate.

[0139] 3) Add 300 mL of 3M NaCl (52.65 g NaCl), 300 mL of 3M KCl (67.05 g KCl), and 300 mL of 0.5 M CaCl2 (16.647 g CaCl2) to each solution. Stir at room temperature for 48 h to allow sufficient ion exchange. Then centrifuge, collect the precipitate, wash the precipitate until there is no excess solution, dry and pulverize at 120 °C, and pass through a 500 mesh sieve to obtain sodium-modified serpentine, potassium-modified serpentine, and calcified serpentine, respectively.

[0140] 4) 20g each of sodium-modified serpentine, potassium-modified serpentine, and calcified serpentine, and 1g of dodecyl dimethyl benzyl ammonium chloride were placed in 500mL of distilled water and reacted in a water bath at 60℃ for 5h. After the reaction was completed, the mixture was cooled to room temperature (25℃), and then 10mg of polyethylene oxide was added. The mixture was ultrasonically stirred for 7h to carry out the polymerization reaction and obtain the reaction product. The reaction product was centrifuged, washed several times with distilled water, placed in a vacuum dryer at 70℃ and dried under reduced pressure, and ground through a 300-mesh sieve to obtain a composite material of polyethylene oxide and clay (referred to as composite serpentine polymer).

[0141] The formulation of the adsorption packing material for the purification column is: 60wt% of a composite material of polyethylene oxide and clay (composite serpentine polymer), 30wt% activated silica gel and 10wt% A151.

[0142] The preparation method of adsorption packing material for purification columns includes the following steps:

[0143] The composite serpentine polymer, activated silica gel, and silane coupling agent (A151) were stirred in a reactor for 2 hours using a magnetic stirrer at a speed of 180 r / min to obtain a mixture. The mixture was then aged in a 0.5 mol / L sodium hydroxide solution for 4 hours to prepare microspheres. The microspheres were separated from the solution, washed 5 times with a washing solution, and dried to obtain the adsorption packing material for the purification column, labeled as adsorption packing material 3#.

[0144] The preparation method of activated silica gel is the same as in Example 1.

[0145] Example 4

[0146] In this embodiment, a composite material of polyethylene oxide and clay, an adsorption packing for a purification column, and a method for preparing the same are provided, including the following:

[0147] The composite material formulation of polyethylene oxide and clay is as follows: 60g inorganic salt modified clay, 1g chlorinated 2-hydroxy-3-(trimethylamino)propyl polyethylene oxide cellulose ether and 10mg polyethylene oxide, wherein the inorganic salt modified clay includes 20g sodium modified clay, 20g potassium modified clay and 20g calcified modified clay.

[0148] A method for preparing a composite material of polyethylene oxide and clay includes the following steps:

[0149] 1) Disperse 700g of talc in 2L of deionized water, stir at 10000rpm for 50min, then sonicate for 15min, and then centrifuge at 8000rpm for 40min to remove precipitate and other mineral particles to obtain a suspension.

[0150] 2) First, adjust the pH of the suspension to 5 with 5 mol / L dilute hydrochloric acid, add 15 mL of 10% H2O2 (1.5 g H2O2), heat to 90℃ to decompose H2O2 to remove organic matter from the talc, and then adjust the pH to 10 with sodium carbonate.

[0151] 3) Add 300 mL of 3M NaCl (52.65 g NaCl), 300 mL of 3M KCl (67.05 g KCl), and 300 mL of 0.5 M CaCl2 (16.647 g CaCl2) respectively. Stir at room temperature for 48 h to allow sufficient ion exchange. Then centrifuge, collect the precipitate, wash the precipitate until there is no excess solution, dry and pulverize at 120 °C, and pass through a 500 mesh sieve to obtain sodium-modified talc, potassium-modified talc, and calcified talc respectively.

[0152] 4) 20g each of sodium-modified talc, potassium-modified talc, and calcium-modified talc, and 1g of chloro-2-hydroxy-3-(trimethylamino)propyl polyethylene oxide cellulose ether were placed in 500mL of distilled water and reacted in a water bath at 60℃ for 5h. After the reaction was completed, the mixture was cooled to room temperature, and then 10mg of polyethylene oxide was added. The mixture was ultrasonically stirred for 7h to carry out the polymerization reaction and obtain the reaction product. The reaction product was centrifuged, washed several times with distilled water, placed in a vacuum dryer at 70℃ and dried under reduced pressure, and ground through a 300-mesh sieve to obtain a composite material of polyethylene oxide and clay (referred to as composite talc polymer).

[0153] The formulation of the adsorption packing material for the purification column is: 60wt% of a composite material of polyethylene oxide and clay (referred to as composite talc polymer), 30wt% activated silica gel and 10wt% A151.

[0154] The preparation method of adsorption packing material for purification columns includes the following steps:

[0155] The composite talc polymer, activated silica gel, and silane coupling agent (A151) were stirred in a reactor for 2 hours using a magnetic stirrer at a speed of 180 r / min to obtain a mixture. The mixture was then aged in a 0.5 mol / L sodium hydroxide solution for 4 hours to prepare microspheres. The microspheres were separated from the solution, washed 5 times with a washing solution, and dried to obtain the adsorption packing material for the purification column, labeled as adsorption packing material 4#.

[0156] The preparation method of activated silica gel is the same as in Example 1.

[0157] Example 5

[0158] In this embodiment, a composite material for adsorbing ethylene oxide and clay, a filler for a purification column, and a method for preparing the same are provided, including the following.

[0159] The composite material formulation of polyethylene oxide and clay is as follows: 60g inorganic salt modified clay, 1g chlorinated 2-hydroxy-3-(trimethylamino)propyl polyethylene oxide cellulose ether and 10mg polyethylene oxide, wherein the inorganic salt modified clay includes 20g sodium modified clay, 20g potassium modified clay and 20g calcified modified clay.

[0160] A method for preparing a composite material of polyethylene oxide and clay includes the following steps:

[0161] 1) Disperse 700g of mica in 2L of deionized water, stir at 10000rpm for 50min, then sonicate for 15min, and then centrifuge at 8000rpm for 40min to remove precipitate and other mineral particles to obtain a suspension.

[0162] 2) First, adjust the pH of the suspension to 5 with 5 mol / L dilute hydrochloric acid, add 15 mL of 10% H2O2 (1.5 g H2O2), heat to 90℃ to decompose H2O2 to remove organic matter from mica, and then adjust the pH to 10 with sodium carbonate.

[0163] 3) Add 300 mL of 3M NaCl (52.65 g NaCl), 300 mL of 3M KCl (67.05 g KCl), and 300 mL of 0.5 M CaCl2 (16.647 g CaCl2) respectively. Stir at room temperature for 48 h to allow sufficient ion exchange. Then centrifuge, collect the precipitate, wash the precipitate until there is no excess solution, dry and pulverize at 120 °C, and pass through a 500 mesh sieve to obtain sodium-modified mica, potassium-modified mica, and calcified mica, respectively.

[0164] 4) 20g each of sodium-modified mica, potassium-modified mica, and calcium-modified mica, along with 1g of chlorinated 2-hydroxy-3-(trimethylamino)propyl polyethylene oxide cellulose ether, were placed in 500mL of distilled water and reacted in a water bath at 60℃ for 5h. After the reaction was completed, the mixture was cooled to room temperature (25℃), and then 10mg of polyethylene oxide was added. The mixture was ultrasonically stirred for 7h to carry out the polymerization reaction and obtain the reaction product. The reaction product was centrifuged, washed several times with distilled water, and dried under reduced pressure in a vacuum dryer at 70℃. It was then ground through a 300-mesh sieve to obtain a composite material of polyethylene oxide and clay (referred to as composite mica polymer).

[0165] The formulation of the adsorption packing material for the purification column is: 60wt% of a composite material of polyethylene oxide and clay (referred to as composite mica polymer purification column), 30wt% activated silica gel and 10wt% A151.

[0166] The preparation method of adsorption packing material for purification columns includes the following steps:

[0167] The composite mica polymer, activated silica gel, and silane coupling agent (A151) were stirred in a reactor for 2 hours using a magnetic stirrer at a speed of 180 r / min to obtain a mixture. The mixture was then aged in a 0.5 mol / L sodium hydroxide solution for 4 hours to prepare microspheres. The microspheres were separated from the solution, washed 5 times with a washing solution, and dried to obtain the adsorption packing material for the purification column, labeled as adsorption packing material 5#.

[0168] The preparation method of activated silica gel is the same as in Example 1.

[0169] Example 6

[0170] In this embodiment, a composite material of polyethylene oxide and clay, an adsorption packing for a purification column, and a method for preparing the same are provided, including the following:

[0171] The composite material formulation of polyethylene oxide and clay is as follows: 60g inorganic salt modified clay, 1g chlorinated 2-hydroxy-3-(trimethylamino)propyl polyethylene oxide cellulose ether and 10mg polyethylene oxide, wherein the inorganic salt modified clay includes 20g sodium modified clay, 20g potassium modified clay and 20g calcified modified clay.

[0172] A method for preparing a composite material of polyethylene oxide and clay includes the following steps:

[0173] 1) Disperse 700g of kaolinite in 2L of deionized water, stir at 9000rpm for 50min, then sonicate for 15min, and then centrifuge at 6000rpm for 70min to remove precipitate and other mineral particles, and obtain a suspension.

[0174] 2) First, adjust the pH of the suspension to 6 with 5 mol / L dilute hydrochloric acid, add 15 mL of 10% H2O2 (1.5 g H2O2), heat to 95℃ to decompose H2O2 to remove organic matter from kaolinite, and then adjust the pH to 10 with sodium carbonate.

[0175] 3) Add 300 mL of 3M NaCl (52.65 g NaCl), 300 mL of 3M KCl (67.05 g KCl), and 300 mL of 0.5 M CaCl2 (16.647 g CaCl2) respectively. Stir at room temperature for 48 h to allow sufficient ion exchange. Then centrifuge, collect the precipitate, wash the precipitate until there is no excess solution, dry and pulverize at 120 °C, and pass through a 500 mesh sieve to obtain sodium-modified kaolinite, potassium-modified kaolinite, and calcified modified kaolinite, respectively.

[0176] 4) 20g each of sodium-modified kaolinite, potassium-modified kaolinite, and calcified kaolinite, along with 1g of chlorinated 2-hydroxy-3-(trimethylamino)propyl polyethylene oxide cellulose ether, were placed in 500mL of distilled water and reacted in a water bath at 60℃ for 5h. After the reaction was completed, the mixture was cooled to room temperature, and then 10mg of polyethylene oxide was added. The mixture was ultrasonically stirred for 7h to carry out the polymerization reaction and obtain the reaction product. The reaction product was centrifuged, washed several times with distilled water, and dried under reduced pressure in a vacuum dryer at 70℃. It was then ground through a 300-mesh sieve to obtain a composite material of polyethylene oxide and clay (referred to as composite kaolinite polymer).

[0177] The formulation of the adsorption packing material for the purification column is: 70wt% of a composite material of polyethylene oxide and clay (referred to as composite kaolinite polymer), 20wt% activated silica gel and 10wt% KH-792.

[0178] The preparation method of adsorption packing material for purification columns includes the following steps:

[0179] The composite kaolinite polymer, activated silica gel, and silane coupling agent (KH-792) were stirred in a reactor for 5 hours using a magnetic stirrer at a speed of 150 r / min to obtain a mixture. The mixture was then aged in 0.8 mol / L sodium hydroxide solution for 5 hours to prepare microspheres. The microspheres were separated from the solution, washed 5 times with washing solution, and dried to obtain the adsorption packing material for the purification column, labeled as adsorption packing material 6#.

[0180] The preparation method of activated silica gel is the same as in Example 1.

[0181] Example 7

[0182] In this embodiment, a composite material of polyethylene oxide and clay, an adsorption packing for a purification column, and a method for preparing the same are provided, including the following:

[0183] The composite material formulation of polyethylene oxide and clay is as follows: 60g inorganic salt modified clay, 1g chlorinated 2-hydroxy-3-(trimethylamino)propyl polyethylene oxide cellulose ether and 10mg polyethylene oxide, wherein the inorganic salt modified clay includes 20g sodium modified clay, 20g potassium modified clay and 20g calcified modified clay.

[0184] A method for preparing a composite material of polyethylene oxide and clay includes the following steps:

[0185] 1) Disperse 700g of mica in 2L of deionized water, stir at 9000rpm for 50min, then sonicate for 15min, and then centrifuge at 6000rpm for 70min to remove precipitate and other mineral particles to obtain a suspension.

[0186] 2) First, adjust the pH of the suspension to 5 with 5 mol / L (concentration) dilute hydrochloric acid, add 15 mL of 10% H2O2 (1.5 g H2O2), heat to 95℃ to decompose H2O2 to remove organic matter from mica, and then adjust the pH to 10 with sodium carbonate.

[0187] 3) Add 300 mL of 3M NaCl (52.65 g NaCl), 300 mL of 3M KCl (67.05 g KCl), and 300 mL of 0.5 M CaCl2 (16.647 g CaCl2) respectively. Stir at room temperature for 48 h to allow sufficient ion exchange. Then centrifuge, collect the precipitate, wash the precipitate until there is no excess solution, dry and pulverize at 120 °C, and pass through a 500 mesh sieve to obtain sodium-modified mica, potassium-modified mica, and calcified mica, respectively.

[0188] 4) 20g each of sodium-modified mica, potassium-modified mica, and calcium-modified mica, along with 1g of chlorinated 2-hydroxy-3-(trimethylamino)propyl polyethylene oxide cellulose ether, were placed in 500mL of distilled water and reacted in a water bath at 60℃ for 3h. After the reaction was completed, the mixture was cooled to room temperature (25℃), and then 10mg of polyethylene oxide was added. The mixture was ultrasonically stirred for 7h to carry out the polymerization reaction and obtain the reaction product. The reaction product was centrifuged, washed several times with distilled water, and dried under reduced pressure in a vacuum dryer at 70℃. It was then ground through a 300-mesh sieve to obtain a composite material of polyethylene oxide and clay (referred to as composite mica polymer).

[0189] The formulation of the adsorption packing material for the purification column is: 70wt% of a composite material of polyethylene oxide and clay (referred to as composite mica polymer), 25wt% activated silica gel and 5wt% KH-792.

[0190] The preparation method of adsorption packing material for purification columns includes the following steps:

[0191] The composite mica polymer, activated silica gel, and silane coupling agent (KH-792) were stirred in a reactor for 6 hours using a magnetic stirrer at a speed of 150 r / min to obtain a mixture. The mixture was then aged in a 0.5 mol / L sodium hydroxide solution for 4 hours to prepare microspheres. The microspheres were separated from the solution, washed 5 times with a washing solution, and dried to obtain the adsorption packing material for the purification column, labeled as adsorption packing material 7#.

[0192] The preparation method of activated silica gel is the same as in Example 1.

[0193] Example 8

[0194] In this embodiment, a composite material of polyethylene oxide and clay, an adsorption packing for a purification column, and a method for preparing the same are provided, including the following:

[0195] The composite material formulation of polyethylene oxide and clay is as follows: 60g inorganic salt modified clay, 1g chlorinated 2-hydroxy-3-(trimethylamino)propyl polyethylene oxide cellulose ether and 10mg polyethylene oxide, wherein the inorganic salt modified clay includes 20g sodium modified clay, 20g potassium modified clay and 20g calcified modified clay.

[0196] A method for preparing a composite material of polyethylene oxide and clay includes the following steps:

[0197] 1) Disperse 700g of serpentine in 2L of deionized water, stir at 9000rpm for 70min, then sonicate for 15min, and then centrifuge at 6000rpm for 70min to remove precipitate and other mineral particles, and obtain a suspension.

[0198] 2) First, adjust the pH of the suspension to 7 with 5 mol / L dilute hydrochloric acid, add 15 mL of 10% H2O2 (1.5 g H2O2), heat to 95℃ to decompose H2O2 to remove organic matter from the serpentine, and then adjust the pH to 10 with sodium carbonate.

[0199] 3) Add 300 mL of 3M NaCl (52.65 g NaCl), 300 mL of 3M KCl (67.05 g KCl), and 300 mL of 0.5 M CaCl2 (16.647 g CaCl2) respectively. Stir at room temperature for 48 h to allow sufficient ion exchange. Then centrifuge, collect the precipitate, wash the precipitate until there is no excess solution, dry and pulverize at 120 °C, and pass through a 500 mesh sieve to obtain sodium-modified serpentine, potassium-modified serpentine, and calcified serpentine, respectively.

[0200] 4) 20g each of sodium-modified serpentine, potassium-modified serpentine, and calcified serpentine, and 1g of chloro-2-hydroxy-3-(trimethylamino)propyl polyethylene oxide cellulose ether were placed in 500mL of distilled water and reacted in a water bath at 60℃ for 3h. After the reaction was completed, the mixture was cooled to room temperature (25℃), and then 10mg of polyethylene oxide was added. The mixture was ultrasonically stirred for 7h to carry out the polymerization reaction and obtain the reaction product. The reaction product was centrifuged, washed several times with distilled water, placed in a vacuum dryer at 70℃ and dried under reduced pressure, and ground through a 300-mesh sieve to obtain a composite material of polyethylene oxide and clay (referred to as composite serpentine polymer).

[0201] The formulation of the adsorption packing material for the purification column is: 70wt% of a composite material of polyethylene oxide and clay (referred to as composite serpentine polymer), 25wt% activated silica gel and 5wt% KH-792.

[0202] The preparation method of adsorption packing material for purification columns includes the following steps:

[0203] The composite serpentine polymer, activated silica gel, and silane coupling agent (KH-792) were stirred in a reactor for 6 hours using a magnetic stirrer at a speed of 150 r / min to obtain a mixture. The mixture was then aged in a 0.5 mol / L sodium hydroxide solution for 4 hours to prepare microspheres. The microspheres were separated from the solution, washed 5 times with a washing solution, and dried to obtain the adsorption packing material for the purification column, labeled as adsorption packing material 8#.

[0204] The preparation method of activated silica gel is the same as in Example 1.

[0205] Example 9

[0206] In this embodiment, a composite material of polyethylene oxide and clay, an adsorption packing for a purification column, and a method for preparing the same are provided, including the following:

[0207] The composite material formulation of polyethylene oxide and clay is as follows: 60g inorganic salt modified clay, 1g chlorinated 2-hydroxy-3-(trimethylamino)propyl polyethylene oxide cellulose ether and 10mg polyethylene oxide, wherein the inorganic salt modified clay includes 20g sodium modified clay, 20g potassium modified clay and 20g calcified modified clay.

[0208] A method for preparing a composite material of polyethylene oxide and clay includes the following steps:

[0209] 1) Disperse 700g of talc in 2L of deionized water, stir at 9000rpm for 70min, then sonicate for 15min, and then centrifuge at 6000rpm for 70min to remove precipitate and other mineral particles to obtain a suspension.

[0210] 2) First, adjust the pH of the suspension to 7 with 5 mol / L dilute hydrochloric acid, add 15 mL of 10% H2O2 (1.5 g H2O2), heat to 95℃ to decompose H2O2 to remove organic matter from the talc, and then adjust the pH to 10 with sodium carbonate.

[0211] 3) Add 300 mL of 3M NaCl (52.65 g NaCl), 300 mL of 3M KCl (67.05 g KCl), and 300 mL of 0.5 M CaCl2 (16.647 g CaCl2) to each solution. Stir at room temperature for 48 h to allow sufficient ion exchange. Then centrifuge, collect the precipitate, wash the precipitate until no excess solution remains, dry and pulverize at 120 °C, and pass through a 500-mesh sieve to obtain modified talc, potassium-modified talc, and calcified modified talc, respectively.

[0212] 4) 20g each of sodium-modified talc, potassium-modified talc, and calcium-modified talc, and 1g of chloro-2-hydroxy-3-(trimethylamino)propyl polyethylene oxide cellulose ether were placed in 500mL of distilled water and reacted in a water bath at 60℃ for 3h. After the reaction was completed, the mixture was cooled to room temperature (25℃), and then 10mg of polyethylene oxide was added. The mixture was ultrasonically stirred for 7h to carry out the polymerization reaction and obtain the reaction product. The reaction product was centrifuged, washed several times with distilled water, placed in a vacuum dryer at 70℃ and dried under reduced pressure, and ground through a 300-mesh sieve to obtain a composite material of polyethylene oxide and clay (referred to as composite talc polymer).

[0213] The formulation of the adsorption packing material for the purification column is: 70wt% of a composite material of polyethylene oxide and clay (referred to as composite talc polymer), 25wt% activated silica gel and 5wt% KH-900.

[0214] The preparation method of adsorption packing material for purification columns includes the following steps:

[0215] The composite talc polymer, activated silica gel, and silane coupling agent (KH-900) were stirred in a reactor for 6 hours using a magnetic stirrer at a speed of 150 r / min to obtain a mixture. The mixture was then aged in a 0.5 mol / L sodium hydroxide solution for 4 hours to prepare microspheres. The microspheres were separated from the solution, washed 5 times with a washing solution, and dried to obtain the adsorption packing material for the purification column, labeled as adsorption packing material 9#.

[0216] The preparation method of activated silica gel is the same as in Example 1.

[0217] Example 10

[0218] In this embodiment, a composite material of polyethylene oxide and clay, an adsorption packing for a purification column, and a method for preparing the same are provided, including the following:

[0219] The composite material formulation of polyethylene oxide and clay is as follows: 60g inorganic salt modified clay, 1g chlorinated 2-hydroxy-3-(trimethylamino)propyl polyethylene oxide cellulose ether and 10mg polyethylene oxide, wherein the inorganic salt modified clay includes 20g sodium modified clay, 20g potassium modified clay and 20g calcified modified clay.

[0220] A method for preparing a composite material of polyethylene oxide and clay includes the following steps:

[0221] 1) Disperse 700g of montmorillonite in 2L of deionized water, stir at 9000rpm for 70min, then sonicate for 15min, and then centrifuge at 6000rpm for 70min to remove precipitate and other mineral particles to obtain a suspension.

[0222] 2) First, adjust the pH of the suspension to 7 with 5 mol / L dilute hydrochloric acid, add 15 mL of 10% H2O2 (1.5 g H2O2) and react at 95 °C to decompose H2O2 and remove organic matter from montmorillonite. Then, adjust the pH to 10 with sodium carbonate.

[0223] 3) Add 300 mL of 3M NaCl (52.65 g NaCl), 300 mL of 3M KCl (67.05 g KCl), and 300 mL of 0.5 M CaCl2 (16.647 g CaCl2) respectively. Stir at room temperature for 48 h to allow sufficient ion exchange. Then centrifuge, collect the precipitate, wash the precipitate until there is no excess solution, dry and pulverize at 120 °C, and pass through a 500 mesh sieve to obtain sodium-modified montmorillonite, potassium-modified montmorillonite, and calcified modified montmorillonite, respectively.

[0224] 4) 20g each of sodium-modified montmorillonite, potassium-modified montmorillonite, and calcified montmorillonite, along with 1g of chloro-2-hydroxy-3-(trimethylamino)propylpolyethylene oxide cellulose ether, were placed in 500mL of distilled water and reacted in a water bath at 60℃ for 3h. After the reaction was completed, the mixture was cooled to room temperature (25℃), and then 10mg of polyethylene oxide was added. The mixture was ultrasonically stirred for 7h to carry out the polymerization reaction and obtain the reaction product. The reaction product was centrifuged, washed multiple times with distilled water, and dried under reduced pressure in a vacuum dryer at 70℃. It was then ground through a 300-mesh sieve to obtain a composite material of polyethylene oxide and clay (referred to as composite montmorillonite polymer).

[0225] The formulation of the adsorption packing material for the purification column is: 70wt% of a composite material of polyethylene oxide and clay (referred to as composite montmorillonite polymer), 25wt% activated silica gel and 5wt% KH-900.

[0226] The preparation method of adsorption packing material for purification columns includes the following steps:

[0227] The composite montmorillonite polymer, activated silica gel, and silane coupling agent (KH-900) were stirred in a reactor for 6 hours using a magnetic stirrer at a speed of 150 r / min to obtain a mixture. The mixture was then aged in a 0.5 mol / L sodium hydroxide solution for 4 hours to prepare microspheres. The microspheres were separated from the solution, washed 5 times with a washing solution, and dried to obtain the adsorption packing material for the purification column, labeled as adsorption packing material 10#.

[0228] The preparation method of activated silica gel is the same as in Example 1.

[0229] Example 11

[0230] The difference from Example 1 is that the inorganic salt modified clay in the composite material formulation is 40g, which is obtained by mixing sodium modified clay, potassium modified clay and calcified modified clay in a mass ratio of 1:1:1; the rest are the same as in Example 1.

[0231] Example 12

[0232] The difference from Example 1 is that the inorganic salt modified clay in the composite material formulation is 50g, which is obtained by mixing sodium modified clay, potassium modified clay and calcified modified clay in a mass ratio of 1:1:1; the rest are the same as in Example 1.

[0233] Example 13

[0234] The difference from Example 1 is that the composite material formulation contains 0.5g of chlorinated 2-hydroxy-3-(trimethylamino)propyl polyethylene oxide cellulose ether, which is obtained by mixing sodium-modified clay, potassium-modified clay and calcified clay in a mass ratio of 1:1:1; the rest are the same as in Example 1.

[0235] Example 14

[0236] The difference from Example 1 is that the composite material formulation contains 0.7g of chlorinated 2-hydroxy-3-(trimethylamino)propyl polyethylene oxide cellulose ether, which is obtained by mixing sodium-modified clay, potassium-modified clay and calcified clay in a mass ratio of 1:1:1; the rest are the same as in Example 1.

[0237] Comparative Example 1

[0238] The difference between Comparative Example 1 and Example 10 is that the inorganic salt modified clay formed by sodium-modified montmorillonite, potassium-modified montmorillonite and calcified montmorillonite obtained in step 3) of Example 10 in a mass ratio of 1:1:1 is directly used as filler.

[0239] Comparative Example 2

[0240] The difference between Comparative Example 2 and Example 10 is that the formulation of the adsorption packing for the purification column does not include the silane coupling agent KH-900, but is composed of 70wt% composite montmorillonite polymer and 30wt% activated silica gel. All other aspects are the same as the packing obtained in Example 10.

[0241] Comparative Example 3

[0242] The difference between Comparative Example 3 and Example 10 is that no polyethylene oxide is added in the preparation of the composite material; instead, inorganic salt modified clay is reacted with quaternary ammonium salt compounds and used directly as a filler.

[0243] Comparative Example 4

[0244] The difference between Comparative Example 4 and Example 10 is that no quaternary ammonium salt compound is added in the preparation of the composite material; instead, inorganic salt modified clay is reacted with polyethylene oxide and then directly used as a filler.

[0245] Performance testing

[0246] The purification columns of Examples 1-10, the packing material of Comparative Example 1, and the packing material of Comparative Example 2 were used to purify the matrix. The contents of various mycotoxins in the matrix were determined by ultra-high performance liquid chromatography-mass spectrometry, and the recovery rate was also determined.

[0247] The base ingredients include rice, vegetable oil, vinegar, chili sauce, soybeans, soy sauce, sunflower seeds, fermented black beans, hawthorn slices, apples, hawthorn juice, etc.

[0248] Various mycotoxins include aflatoxin B1 (AFB1), aflatoxin B2 (AFB2), aflatoxin G1 (AFG1), aflatoxin G2 (AFG2), zearalenone (ZEN), and patulin (PAT). (Based on national standards GB 5009.22-2016 "National Food Safety Standard - Determination of Aflatoxin B and G Groups in Food", GB 5009.209-2016 "National Food Safety Standard - Determination of Zearalenone in Food", and GB 5009.185-2016 "National Food Safety Standard - Determination of Patulin in Food".)

[0249] 1.1 Determination of the contents of aflatoxin B1, aflatoxin B2, aflatoxin G1 and aflatoxin G2

[0250] 1.1.1 Solution Preparation

[0251] Standard stock solution: Accurately weigh an appropriate amount of standard, dissolve it in acetonitrile, and prepare a standard stock solution of 100 μg / mL.

[0252] Mixed standard intermediate solution: Accurately transfer 100 μL of each standard stock solution and dilute to 10 mL with acetonitrile, with a concentration of 1 μg / mL.

[0253] Mixed standard working solution: Accurately transfer 0.1 mL of the mixed standard intermediate solution and dilute to 10 mL with acetonitrile, with a concentration of 100 ng / mL.

[0254] Acetonitrile-water solution (84+16): Take 840 mL of acetonitrile and add 160 mL of water, then mix well.

[0255] 1.1.2 Extraction Steps

[0256] Weigh 5g of the sample into a 50mL centrifuge tube, add 20mL of acetonitrile-water solution (84+16), vortex to mix, place in an ultrasonic / vortex oscillator or shaker and shake for 20min, centrifuge at 6000r / min for 10min, and take the supernatant as the sample extraction solution for later use.

[0257] 1.1.3. Purification Steps of a Multifunctional Purification Column

[0258] 1) Add 10 mL of the sample extract obtained in step 1.1.2 to a glass test tube.

[0259] 2) Insert the rubber head of the purification column containing the adsorption packing material of Examples 1-10, the packing material of Comparative Example 1, and the packing material of Comparative Example 2 into the test tube from the top of the test tube, and press the purification column down to the bottom of the test tube to purify the sample extract.

[0260] 3) Take the purified sample extract into a centrifuge tube to obtain the purified extract.

[0261] 4) Take 5 mL of purified extract, dry it with nitrogen, redissolve it with 1 mL of initial mobile phase (mobile phase conditions starting at 0 minutes, such as 68% A phase plus 32% B phase), vortex for 30 s to dissolve the residue, filter it through a microporous membrane and then analyze it on the instrument.

[0262] 1.1.4 Chromatographic-Mass Spectrometry Conditions

[0263] Ultra-high performance liquid chromatography (UPLC) conditions

[0264] Chromatographic column: Ultimate UHPLC XB-C18, 1.8μm, 2.1×100mm

[0265] Guard column core: Ultimate UHPLC XB-C18, ultra-high pressure column core: 2.1×5mm

[0266] Mobile phases: Phase A: 5 mmol / L ammonium acetate solution; Phase B: acetonitrile-methanol solution (50+50).

[0267] Column temperature: 40℃; Flow rate: 0.3 mL / min; Injection volume: 1 μL

[0268] Gradient elution procedure: see Table 1.

[0269] Table 1 Gradient elution program

[0270] Time / min Phase A / % Phase B / % 0.00 68 32 0.50 68 32 3.00 55 45 4.00 55 45 4.20 0 100 4.80 0 100 5.00 68 32 7.00 68 32

[0271] Mass spectrometry conditions

[0272] Liquid chromatography-mass spectrometry (LC-MS) instrument model: AB Sciex TRIPLE QUAD 4500

[0273] Ion source: Electrospray ionization (ESI);

[0274] Scanning method: positive ion scan;

[0275] Detection method: Multiple response monitoring (MRM) mode;

[0276] Ion spray voltage: 5500V; Ion source temperature: 500℃;

[0277] Curtain gas (CUR) 10psi; atomizing gas (GS1) 55psi; auxiliary gas (GS2) 50psi.

[0278] Other mass spectrometry parameters are shown in Table 2.

[0279] Table 2. Parameters of Multiple Reaction Monitoring (MRM) Mode

[0280]

[0281] 1.2 Determination of Zearalenone Content

[0282] 1.2.1 Solution Preparation

[0283] Standard stock solution: Accurately weigh an appropriate amount of standard, dissolve it in acetonitrile, and prepare a standard stock solution with a concentration of 100 μg / mL.

[0284] Standard working solution: Accurately transfer 100 μL of standard stock solution and dilute to 10 mL with acetonitrile, with a concentration of 1 μg / mL.

[0285] Acetonitrile-water solution (9+1): Take 900 mL of acetonitrile and add 100 mL of water, then mix well.

[0286] 1.2.2 Extraction Steps

[0287] Weigh 5g of the sample into a 50mL centrifuge tube, add 1g of sodium chloride, then add 20mL of acetonitrile-water solution (9+1), vortex for 15min, centrifuge at 6000r / min for 5min, and take the supernatant for later use.

[0288] 1.2.3. Purification Steps of a Multifunctional Purification Column

[0289] Same as step 1.1.3 in 1.1.

[0290] 1.2.4 Chromatographic-Mass Spectrometry Conditions

[0291] Ultra-high performance liquid chromatography (UPLC) conditions

[0292] Chromatographic column: Ultimate UHPLC XB-C18, 1.8μm, 2.1×100mm

[0293] Guard column core: Ultimate UHPLC XB-C18, ultra-high pressure column core: 2.1×5mm

[0294] Mobile phases: Phase A: Water; Phase B: Acetonitrile

[0295] Column temperature: 40℃; Flow rate: 0.2 mL / min; Injection volume: 1 μL

[0296] Gradient elution procedure: see Table 3.

[0297] Table 3 Gradient elution program

[0298] Time / min Phase A / % Phase B / % 0.00 75 25 5.00 30 70 6.00 30 70 9.00 75 25 11.00 75 25

[0299] Mass spectrometry conditions

[0300] Liquid chromatography-mass spectrometry (LC-MS) instrument model: AB Sciex TRIPLE QUAD 4500

[0301] Ion source: Electrospray ionization (ESI);

[0302] Scanning method: Negative ion scanning;

[0303] Detection method: Multiple response monitoring (MRM) mode;

[0304] Ion spray voltage: -4500V; Ion source temperature: 500℃;

[0305] Curtain gas (CUR) 10psi; atomizing gas (GS1) 55psi; auxiliary gas (GS2) 50psi.

[0306] Other mass spectrometry parameters are shown in Table 4.

[0307] Table 4. Parameters of Multiple Reaction Monitoring (MRM) Mode

[0308]

[0309] 1.3 Determination of Patrin Content

[0310] 1.3.1 Solution Preparation

[0311] Standard stock solution: Accurately weigh an appropriate amount of standard, dissolve it in acetonitrile, and prepare a standard stock solution with a concentration of 100 μg / mL.

[0312] Standard working solution: Accurately transfer 100 μL of standard stock solution and dilute to 10 mL with acetonitrile, with a concentration of 1 μg / mL.

[0313] 1.3.2 Extraction Steps

[0314] Weigh 4g of the sample into a 50mL centrifuge tube, add 20mL of acetonitrile, sonicate for 5min, centrifuge at 6000r / min for 5min, and take the supernatant as the sample extraction solution for later use.

[0315] 1.3.3. Purification Steps of a Multifunctional Purification Column

[0316] 1) Add 10 mL of the sample extract obtained in step 1.3.2 to a glass test tube, and then add 50 μL of acetic acid.

[0317] 2) Insert the rubber head of the purification column containing the adsorption packing material of Examples 1-10, the packing material of Comparative Example 1, and the packing material of Comparative Example 2 into the test tube from the top of the test tube, and press the purification column down to the bottom of the test tube to purify the sample extract.

[0318] 3) Take the purified sample extract from the top of the purification column into a centrifuge tube to obtain the purified extract.

[0319] 4) Take 5 mL of purified extract, add 20 μL of acetic acid, dry with nitrogen, redissolve with 1 mL of initial mobile phase (95% A phase and 5% B phase), vortex for 30 s to dissolve the residue, filter through a microporous membrane and then analyze.

[0320] 1.3.4 Chromatographic conditions

[0321] Ultra-high performance liquid chromatography (UPLC) conditions

[0322] Chromatographic column: Ultimate UHPLC AQ-C18, 1.8μm, 2.1×100mm

[0323] Guard column core: Ultimate UHPLC AQ-C18, ultra-high pressure column core: 2.1×5mm

[0324] Mobile phase: A: Water; B: Acetonitrile

[0325] Column temperature: 30℃; Flow rate: 0.3 mL / min; Injection volume: 1 μL

[0326] Gradient elution procedure: see Table 5.

[0327] Table 5 Gradient elution program

[0328] Time / min Phase A / % Phase B / % 0.00 95 5 7.00 95 5 7.20 0 100 9.00 0 100 9.20 95 5 13.00 95 5

[0329] Mass spectrometry conditions

[0330] Liquid chromatography-mass spectrometry (LC-MS) instrument model: AB Sciex TRIPLE QUAD 4500

[0331] Ion source: Electrospray ionization (ESI);

[0332] Scanning method: Negative ion scanning;

[0333] Detection method: Multiple response monitoring (MRM) mode;

[0334] Ion spray voltage: -4500V; Ion source temperature: 500℃;

[0335] Curtain gas (CUR) 10psi; atomizing gas (GS1) 55psi; auxiliary gas (GS2) 50psi.

[0336] Other mass spectrometry parameters are shown in Table 6.

[0337] Table 6. Parameters of Multiple Reaction Monitoring (MRM) Mode

[0338]

[0339] In addition to Comparative Example 1 and Comparative Example 2, a multi-functional purification column from a domestic commercial brand 1 and a multi-functional purification column from a domestic commercial brand 2 were added as controls.

[0340] The main components of the multifunctional purification column of a certain domestic commercial brand 1 are silica gel and anionic and cationic polymers; Reference 1, Reference 1 is: Zhang Chun'e, Liu Xinbao, Liao Ruoyu et al. Determination of vomitoxin content in whole wheat flour by high performance liquid chromatography [J]. Grain and Oil Food Science and Technology, 2018, 26(5): 53-57.

[0341] The main components of a multi-functional purification column from a domestic commercial brand are activated carbon, anionic and cationic polymers, and Copure228.

[0342] 1.6 Recovery rate and precision

[0343] Negative samples were weighed and subjected to a three-level, six-parallel spiking experiment. The purified columns were pretreated using the adsorption packing materials from Examples 1-10, Comparative Example 1, and Comparative Example 2, respectively. Multifunctional purified columns from domestic commercial brand 1 and a domestic commercial brand 2 were used as controls. In this application, the spiking experiment was a blank spiking experiment, meaning the initial mycotoxin content in each matrix was 0.

[0344] Recovery rate and precision are shown in Tables 7 to 11.

[0345] Table 7. Accuracy and precision results of Examples 8-10

[0346]

[0347]

[0348] Table 8. Accuracy and precision results of Examples 5-7

[0349]

[0350] Table 9. Accuracy and precision results of Examples 2-4

[0351]

[0352] Table 10 Recovery and precision results for Comparative Example 1 and Comparative Example 2

[0353]

[0354]

[0355] Table 11 Recovery and precision results of a domestic commercial brand 1, a domestic commercial brand 2, and Example 1.

[0356]

[0357]

[0358] As shown in Tables 7-11, the recovery rate of the adsorption packing material for the purification column using Example 10 is 77% to 120%, and the daytime precision is 1.2% to 5%, which is better than that of Comparative Example 1.

[0359] As shown in Tables 7 to 11, the adsorption packing materials used in the purification columns of Examples 1-10 exhibit good recovery rates and good generalizability for aflatoxin B1 (AFB1), aflatoxin B2 (AFB2) group, aflatoxin G1 (AFG1), aflatoxin G2 (AFG2), zearalenone (ZEN), and patulin (PAT). In contrast, Comparative Examples 1 and 2 show poor generalizability. The recovery rates and generalizability of commercial purification columns 1 and 2 are lower than those of the examples, although they exhibit greater adsorption for each fungal toxin.

[0360] 1.4 Evaluation of matrix effect

[0361] The evaluation is carried out by extraction and addition method, and the specific calculation method is shown in formula (1).

[0362]

[0363] If ME (%) < 100%, it indicates an inhibitory effect;

[0364] If ME (%) > 100%, it indicates an enhancing effect;

[0365] According to literature reports, when the ME value is between 80% and 120%, it indicates that there is no obvious matrix effect and its influence can be ignored.

[0366] The matrix effect is evaluated by converting the standard curve established using the external standard method.

[0367] Calculations showed that the ME values ​​of Examples 1-10 were between 80% and 120%. However, the ME values ​​of Comparative Examples 1 and 2, as well as some of the ME values ​​of a certain domestic commercial brand 1 and a certain domestic commercial brand 2, were not between 80% and 120%, indicating a significant matrix effect.

[0368] 1.5 Evaluation of Solvent Effect

[0369] The organic ratio of the reconstituted solvent (initial mobile phase) will produce different degrees of solvent effect on the analyte (fungal toxin).

[0370] Figure 1 The solvent effect evaluation diagrams for aflatoxin B1, aflatoxin B2, aflatoxin G1, and aflatoxin G2 were performed using the adsorption packing material of the purification column in Example 10, and the packing materials of Comparative Examples 1 and 2, respectively. (From left to right: aflatoxin B1, aflatoxin B2, aflatoxin G1, and aflatoxin G2)

[0371] from Figure 1 It can be seen that the solution purified by the adsorption packing material of the purification column in Example 10 has no obvious solvent effect, while Comparative Example 1, Comparative Example 2, and a certain domestic commercial brand 1 and a certain domestic commercial brand 2 have obvious solvent effect interference.

[0372] 1.7 Packing morphology test

[0373] Figure 2 Microscopic images of the adsorption packing material for the purification column in Example 10, the packing material in Comparative Example 1, the packing material in Comparative Example 2, the multifunctional purification column of a domestic commercial brand 1, the multifunctional purification column of a domestic commercial brand 2, and Comparative Examples 3 and 4.

[0374] from Figure 2 It can be seen that the microspheres of the adsorption packing material for the purification column in Example 10 are more uniformly distributed and have less impurity content (few irregularly shaped particles). The particle size of small particles is distributed between 3μm and 5μm, and the particle size of large particles is distributed between 10μm and 15μm.

[0375] 1.8 Batch reproducibility test of adsorption packing material for purification columns

[0376] Figure 3 This is the baseline spectrum after purifying and analyzing zearalenone using the adsorption packing material for the purification column prepared in Example 10, which synthesized six batches consecutively.

[0377] from Figure 3 It can be seen that the elution peaks of the adsorption packing materials used in the six batches of purification columns almost completely overlap.

[0378] The above results fully demonstrate that the adsorption material of the present invention has good batch stability, and further illustrate that the adsorption packing material for the purification column used in this study has excellent stability and reproducibility.

[0379] In summary, the adsorption packing material for the purification column in this invention has a uniform distribution of small and large-sized microspheres, resulting in minimal matrix and solvent interference, high recovery rate, low RSD, and high stability. It is particularly suitable for the detection of fungal toxins, such as aflatoxin B1, aflatoxin B2, aflatoxin G1, aflatoxin G2, zearalenone (ZEN), and patulin (PAT).

[0380] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept disclosed in the present invention should still be covered by the claims of the present invention.

Claims

1. A composite material of polyethylene oxide and clay used as raw materials in an adsorption packing, characterized in that, The composite material comprises the following raw materials in parts by weight: 4000-8000 parts of inorganic salt modified clay 50-100 parts of quaternary ammonium salt compounds 1 part of polyethylene oxide; The inorganic salt modified clay is a mixture of sodium-modified clay, potassium-modified clay and calcified clay; the mass ratio of sodium-modified clay, potassium-modified clay and calcified clay is (0.5~2):(0.5~2):1; The quaternary ammonium salt compound is selected from one or more of N,N,N-trimethyl-2-(2-methyl-1-oxo-2-propenyloxy)ethyl ammonium chloride-acrylamide copolymer, chlorinated 2-hydroxy-3-(trimethylamino)propyl polyoxyethylene cellulose ether, alkyl dimethyl benzyl ammonium halide and dialkyl dimethyl ammonium halide; The polyoxyethylene has a weight-average molecular weight to number-average molecular weight ratio of 17-20, a particle size of 300-400 mesh, and a dissolution temperature of 30-50℃. The composite material is obtained using a method comprising the following steps: Inorganic salt-modified clay and quaternary ammonium salt compounds are reacted in a solvent, and then polymerized with polyethylene oxide to obtain the composite material.

2. The composite material as described in claim 1, characterized in that, The method for preparing the inorganic salt modified clay is as follows: 1) Disperse the clay in water, sonicate, and centrifuge to obtain a suspension; 2) Adjust the pH of the suspension with acid, and add an oxidant to carry out the reaction; 3) Adjust the pH value with alkali, add inorganic salt, mix, centrifuge, and dry to obtain the inorganic salt modified clay.

3. The composite material as described in claim 2, characterized in that, Includes at least one of the following technical features: In 1), the clay is selected from one or more of kaolinite, montmorillonite, serpentine, talc, and mica; In step 2), the oxidant is selected from one or more of hydrogen peroxide, peracetic acid, and nitric acid; In step 2), the pH value is 2-7; In step 3), the pH value is 8-10; In step 3), the inorganic salt is selected from sodium chloride, potassium chloride, and calcium chloride; The mass ratio of clay to inorganic salt is 7:(1-4); The mass ratio of clay to oxidant is 700:(1-3).

4. The method for preparing the composite material according to any one of claims 1-3, characterized in that, Includes the following steps: Inorganic salt-modified clay and quaternary ammonium salt compounds are reacted in a solvent, and then polymerized with polyethylene oxide to obtain the composite material.

5. The method as described in claim 4, characterized in that, The reaction temperature is 40–80°C; And / or, the polymerization reaction temperature is 20–40°C; And / or, the solvent is selected from water.

6. Use of the composite material as a raw material in adsorption packing as described in any one of claims 1-3.

7. An adsorption packing material for a purification column, characterized in that, Includes the composite material, activated silica gel, and silane coupling agent as described in any one of claims 1-3.

8. The adsorption packing material for the purification column according to claim 7, characterized in that, The adsorption packing material for the purification column comprises the following raw materials in parts by weight: 40-70 parts of composite material 20-50 parts activated silica gel 5-12 parts of silane coupling agent.

9. The adsorption packing material for the purification column as described in claim 8, characterized in that, The silane coupling agent is selected from one or more of γ-aminopropyltriethoxysilane, vinyltriethoxysilane, N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, and γ-aminoethylaminopropyltrimethoxysilane; And / or, the method for preparing the activated silica gel is as follows: silica gel powder is mixed with acid and dried to obtain the activated silica gel.

10. The method for preparing adsorption packing material for purification columns according to any one of claims 7 to 9, characterized in that, Includes the following steps: The raw material components are mixed and aged to obtain the adsorption packing material for the purification column.

11. Use of the adsorption packing material for purification columns as described in any one of claims 7 to 9 as a chromatographic material.

Images