Macroporous resin material and preparation method thereof

By combining modified acrylate polymerized monomers with pore-generating agents and crosslinking agents, macroporous resin materials are prepared through suspension polymerization, which solves the problems of insufficient performance of existing materials and environmental and health threats during the preparation process, and achieves macroporous resin materials with high specific surface area and stability.

CN120098190APending Publication Date: 2025-06-06BEIHUA UNIV
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Patent Information

Application Number
CN202510341454.3
Authority / Receiving Office
CN · China
Patent Type
Applications(China)
Current Assignee / Owner
Filing Date
2025-03-21
Publication Date
2025-06-06

AI Technical Summary

Technical Problem

When faced with complex separation tasks, existing macroporous resin materials are difficult to accurately control the pore structure and chemical composition, and their performance is insufficient, and the organic solvents and toxic chemicals used in the preparation process pose a threat to the environment and human health.

Method used

The macroporous resin material is obtained by reacting acrylic chloride with quercetin and methyl vanillic acid to form a modified acrylate polymerized monomer and mixed with a pore-generating agent, a crosslinking agent and a dispersing agent.

Benefits of technology

The prepared macroporous resin material has a high specific surface area and pore structure, which improves adsorption performance and mechanical and chemical stability, is suitable for reuse, and reduces the threat to the environment and human health.

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Abstract

The invention discloses a macroporous resin material and a preparation method thereof, and macroporous resin with high specific surface area and excellent adsorption performance is obtained through a specific modified acrylate polymeric monomer and a preparation method of the macroporous resin material. The method comprises the following steps: reacting quercetin, methyl vanillate and acryloyl chloride to prepare a modified acrylate polymeric monomer, mixing the modified acrylate polymeric monomer with polyvinyl alcohol, ethylene glycol dimethacrylate, dodecanol, benzoyl peroxide and the like, and carrying out suspension polymerization to prepare the macroporous resin material. The prepared macroporous resin material has excellent performance in the aspects of pore structure, polarity and the like, can be widely applied to the related fields of adsorption separation and the like, and provides a new thought and method for research and development of the macroporous resin material.
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Description

Technical Field

[0001] The invention belongs to the technical field of macroporous resins, and in particular relates to a macroporous resin material and a preparation method thereof. Background Art

[0002] As an important polymer material, macroporous resin can selectively adsorb target substances based on differences in molecular size, polarity, etc. due to its unique pore structure and rich surface functional groups, effectively improving separation efficiency and reducing production costs. It is widely used in many fields such as adsorption separation and catalysis.

[0003] However, existing macroporous resin materials still have certain limitations when facing increasingly complex separation and adsorption tasks. It is difficult to accurately control the pore structure and chemical composition of the resin, and it is difficult to meet the growing demand in terms of performance. The adsorption capacity of some macroporous resins is limited, and the efficiency is low when processing high-concentration or large-scale samples; the adsorption selectivity needs to be further improved, and it is difficult to meet the high-purity separation requirements of certain specific substances; the physical and chemical stability is insufficient, and the performance is easily affected in different use environments, and the service life is greatly shortened, which increases the cost of use. In addition, the organic solvents and toxic chemicals used in the preparation process of traditional resins pose a threat to the environment and the health of operators.

[0004] Therefore, it is of great significance to develop a macroporous resin material with improved structure and performance. The present invention aims to provide a macroporous resin material and a preparation method thereof to overcome the shortcomings of the prior art and meet the demand for improved performance of macroporous resins in related fields such as synthesis and analysis. Summary of the invention

[0005] The purpose of the present invention is to provide a macroporous resin material and a preparation method thereof. The macroporous resin material prepared by the method has the characteristics of large specific surface area and good adsorption performance, improves mechanical and chemical stability, and is conducive to repeated use.

[0006] The technical solution adopted by the present invention to achieve the above-mentioned purpose is: A macroporous resin material and a preparation method thereof, comprising: Reacting acryloyl chloride with a modifier to obtain a modified acrylate polymerization monomer, wherein the modifier includes quercetin and / or methyl vanillate, and the modified acrylate polymerization monomer includes methyl vanillate modified acrylate and / or quercetin modified acrylate; The modified acrylic ester polymerization monomer, porogen, crosslinking agent and dispersant are mixed, and a macroporous resin material is obtained by suspension polymerization; the porogen is dodecanol, the crosslinking agent is ethylene glycol dimethacrylate, the dispersant is polyvinyl alcohol, and the initiator is benzoyl peroxide.

[0007] Vanillic acid methyl ester modified acrylate and quercetin modified acrylate can form amphiphilic synergy in the resin, that is, the synergistic effect of the hydrophobic skeleton and the polar group, so that the prepared macroporous resin material has a higher specific surface area and pore structure, increases the number of adsorption sites, and improves the adsorption capacity of substances; at the same time, stable chemical bonds can be formed in the resin skeleton, so that the resin can maintain structural integrity under different chemical environments, improves the mechanical and chemical stability of the macroporous resin, and is conducive to repeated use.

[0008] Preferably, the volume mass ratio of acryloyl chloride to quercetin is 1.3-8 mL:1-6 g.

[0009] Preferably, the volume mass ratio of acryloyl chloride to methyl vanillate is 1-8 mL:2.2-18.2 g.

[0010] Preferably, the mass ratio of vanillic acid methyl ester modified acrylate to quercetin modified acrylate is 3-15:1-5.

[0011] Preferably, the mass ratio of dodecanol to methyl vanillate-modified acrylate is 10-150:1-15.

[0012] Preferably, the mass ratio of ethylene glycol dimethacrylate to methyl vanillate-modified acrylate is 20-300:1-15.

[0013] Preferably, the mass ratio of polyvinyl alcohol to methyl vanillate modified acrylate is 1-10:1.5-15.

[0014] Preferably, the mass ratio of benzoyl peroxide to methyl vanillate-modified acrylate is 1-10:1.5-15.

[0015] Preferably, the heating temperature of the suspension polymerization is 75-85° C. for 3-5 h, 80-90° C. for 1-3 h, or 85-95° C. for 0.5-2 h.

[0016] More preferably, trimethylolpropane trimethacrylate can also be added to the cross-linking agent, and the mass ratio of trimethylolpropane trimethacrylate to ethylene glycol dimethacrylate is 10-100:10-100. Trimethylolpropane trimethacrylate can form co-crosslinking with ethylene glycol dimethacrylate to form a denser and more complex cross-linking network structure during the polymerization process, thereby increasing the number of cross-linking points inside the resin, improving the mechanical strength of the resin and the stability of the pore structure, improving the chemical stability and thermal stability of the resin, and ensuring the effective diffusion of substances in the pores and the smooth progress of the adsorption-desorption process, thereby improving the adsorption kinetics and adsorption capacity of the resin.

[0017] The present invention provides a method for preparing quercetin modified acrylate, comprising: Dissolve quercetin in anhydrous dichloromethane, add acid-binding agent triethylamine, stir to fully dissolve, add acryloyl chloride under 0-4°C ice-water bath conditions and nitrogen protection, stir to react for 5-7 hours, let stand to separate the liquid to obtain an organic phase, wash with deionized water, rotary evaporate to obtain a crude product, wash with toluene and vacuum dry to obtain quercetin modified acrylate.

[0018] Preferably, the mass volume ratio of quercetin to anhydrous dichloromethane is 1-6g:80-500mL.

[0019] Preferably, the volume mass ratio of triethylamine to quercetin is 1.25-7 mL:1-6 g.

[0020] Preferably, the volume mass ratio of acryloyl chloride to quercetin is 1.3-8 mL:1-6 g.

[0021] Preferably, the rotary evaporation temperature is 35-45° C., the rotation speed is 80-120 rpm, and the pressure is 30-50 mbar.

[0022] The present invention provides a method for preparing methyl vanillate modified acrylate, comprising: Dissolve methyl vanillate in anhydrous dichloromethane, add acid-binding agent triethylamine, stir to fully dissolve, add acryloyl chloride in an ice-water bath at 0-4°C and under nitrogen protection, stir to react for 5-7 hours, let stand to separate the liquid to obtain an organic phase, wash with deionized water, rotary evaporate to obtain a crude product, wash with toluene and vacuum dry to obtain methyl vanillate modified acrylate.

[0023] Preferably, the mass volume ratio of methyl vanillate to anhydrous dichloromethane is 1-18.2 g:25-500 mL.

[0024] Preferably, the volume mass ratio of triethylamine to methyl vanillate is 1-7.5 mL:2.4-18.2 g.

[0025] Preferably, the volume mass ratio of acryloyl chloride to methyl vanillate is 1-8 mL:2.2-18.2 g.

[0026] Preferably, the rotary evaporation temperature is 35-45° C., the rotation speed is 80-120 rpm, and the pressure is 30-50 mbar.

[0027] The present invention provides a method for preparing a macroporous resin material, comprising: Dissolve polyvinyl alcohol in deionized water, stir at 70-90° C. to completely dissolve it, and obtain an aqueous phase.

[0028] Preferably, the mass volume ratio of polyvinyl alcohol to deionized water is 1-10g:200-2000mL.

[0029] The quercetin-modified acrylate and the vanillic acid methyl ester-modified acrylate are dissolved in ethylene glycol dimethacrylate, and dodecanol and benzoyl peroxide are added and stirred evenly to obtain an oil phase.

[0030] Preferably, the mass ratio of vanillic acid methyl ester modified acrylate to quercetin modified acrylate is 3-15:1-5.

[0031] Preferably, the mass ratio of ethylene glycol dimethacrylate to methyl vanillate-modified acrylate is 20-300:1-15.

[0032] Preferably, the mass ratio of dodecanol to methyl vanillate-modified acrylate is 10-150:1-15.

[0033] Preferably, the mass ratio of benzoyl peroxide to methyl vanillate-modified acrylate is 1-10:1.5-15.

[0034] Under stirring conditions and nitrogen protection, add the oil phase to the water phase to evenly disperse the oil phase in the water phase, heat to 75-85°C for 3-5h, heat to 80-90°C for 1-3h, heat to 85-95°C for 0.5-2h, filter when the system is cooled to 35-45°C, wash alternately with deionized water and anhydrous ethanol, and vacuum dry at 50-60°C for 10-18h to obtain a macroporous resin material.

[0035] Preferably, the water phase is measured by the mass of the polyvinyl alcohol therein, and the oil phase is measured by the mass of the methyl vanillate-modified acrylate therein, and the mass ratio of the water phase to the oil phase is 1-10:1.5-15.

[0036] The invention adopts vanillic acid methyl ester, quercetin and acryloyl chloride to generate vanillic acid methyl ester modified acrylate and quercetin modified acrylate polymerization monomers, which are mixed with dodecanol, ethylene glycol dimethacrylate, polyvinyl alcohol and benzoyl peroxide, and macroporous resin material is obtained by suspension polymerization, so it has the following beneficial effects: the macroporous resin material has a high specific surface area and pore structure, has a large number of adsorption sites, has enhanced adsorption capacity for substances, has good mechanical stability and chemical stability, can maintain structural integrity under different chemical environments, and is conducive to repeated use. Therefore, the invention is a macroporous resin material with high specific surface area and excellent adsorption performance and a preparation method thereof. BRIEF DESCRIPTION OF THE DRAWINGS

[0037] Figure 1 Schematic diagram of the infrared absorption spectrum of macroporous resin material.

[0038] Figure 2 Schematic diagram of the specific surface area test results of macroporous resin materials.

[0039] Figure 3 Schematic diagram of the recovery rate of chlorogenic acid in honeysuckle using macroporous resin material. DETAILED DESCRIPTION

[0040] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0041] The following first describes the concepts involved in the present application in conjunction with the accompanying drawings. It should be noted that the following description of each concept is only to make the content of the present application easier to understand, and does not limit the scope of protection of the present application; at the same time, the embodiments and features in the embodiments of the present application can be combined with each other in the absence of conflict. The present application will be described in detail with reference to the accompanying drawings and in conjunction with the embodiments.

[0042] Embodiment 1: Preparation of quercetin modified acrylate: quercetin was dissolved in anhydrous dichloromethane, acid-binding agent triethylamine was added, and the mixture was stirred to fully dissolve. Acryloyl chloride was added under nitrogen protection at 2°C ice-water bath conditions, and the mixture was stirred for reaction for 6 hours. The organic phase was allowed to stand for separation, and the crude product was washed with deionized water and rotary evaporated to obtain a crude product. The crude product was washed with toluene and then vacuum dried to obtain quercetin modified acrylate. The mass volume ratio of quercetin to anhydrous dichloromethane was 1.2 g:100 mL, the volume mass ratio of triethylamine to quercetin was 1.5 mL:1.2 g, the volume mass ratio of acryloyl chloride to quercetin was 1.6 mL:1.2 g, the rotary evaporation temperature was 40°C, the rotation speed was 100 rpm, and the pressure was 40 mbar.

[0043] Preparation of vanillic acid methyl ester modified acrylate: vanillic acid methyl ester is dissolved in anhydrous dichloromethane, acid binding agent triethylamine is added, and stirred to fully dissolve. Acryloyl chloride is added under 2°C ice-water bath conditions and nitrogen protection. After stirring and reacting for 6 hours, the organic phase is allowed to stand for separation to obtain the organic phase, which is washed with deionized water, and a crude product is obtained by rotary evaporation. The crude product is washed with toluene and then vacuum dried to obtain vanillic acid methyl ester modified acrylate; the mass volume ratio of vanillic acid methyl ester to anhydrous dichloromethane is 3.64g:100mL, the volume mass ratio of triethylamine to vanillic acid methyl ester is 1.5mL:3.64g, the mass ratio of acryloyl chloride to vanillic acid methyl ester is 1.6mL:3.64g, the rotary evaporation temperature is 40°C, the rotation speed is 100rpm, and the pressure is 40mbar.

[0044] Preparation of the aqueous phase: polyvinyl alcohol was dissolved in deionized water, and stirred at 80° C. to completely dissolve the polyvinyl alcohol to obtain an aqueous phase; the mass volume ratio of polyvinyl alcohol to deionized water was 2 g:400 mL.

[0045] Preparation of oil phase: dissolve vanillic acid methyl ester modified acrylate and quercetin modified acrylate in ethylene glycol dimethacrylate, add dodecanol and benzoyl peroxide, stir evenly to obtain oil phase; the mass ratio of quercetin modified acrylate to vanillic acid methyl ester modified acrylate is 1:3, the mass ratio of ethylene glycol dimethacrylate to vanillic acid methyl ester modified acrylate is 60:3, the mass ratio of dodecanol to vanillic acid methyl ester modified acrylate is 30:3, and the mass ratio of benzoyl peroxide to vanillic acid methyl ester modified acrylate is 2:3.

[0046] Preparation of macroporous resin material: Under stirring conditions and nitrogen protection, the oil phase is added to the water phase to make the oil phase uniformly dispersed in the water phase, heated to 80°C for 4 hours, heated to 85°C for 2 hours, heated to 90°C for 1 hour, and the system is filtered when it is cooled to 40°C, washed alternately with deionized water and anhydrous ethanol, and vacuum dried at 55°C for 12 hours to obtain a macroporous resin material; the water phase is measured by the mass of the polyvinyl alcohol therein, the oil phase is measured by the mass of the vanillic acid methyl ester-modified acrylate therein, and the mass ratio of the water phase to the oil phase is 2:3.

[0047] Example 2: The difference between this example and Example 1 is only the preparation of the oil phase.

[0048] Preparation of oil phase: dissolve vanillic acid methyl ester modified acrylate and quercetin modified acrylate in ethylene glycol dimethacrylate, add dodecanol and benzoyl peroxide, stir evenly to obtain oil phase; the mass ratio of quercetin modified acrylate to vanillic acid methyl ester modified acrylate is 1.5:3, the mass ratio of ethylene glycol dimethacrylate to vanillic acid methyl ester modified acrylate is 60:3, the mass ratio of dodecanol to vanillic acid methyl ester modified acrylate is 30:3, and the mass ratio of benzoyl peroxide to vanillic acid methyl ester modified acrylate is 2:3.

[0049] Example 3: The difference between this example and Example 1 is only the preparation of the oil phase.

[0050] Preparation of oil phase: dissolving vanillic acid methyl ester modified acrylate and quercetin modified acrylate in ethylene glycol dimethacrylate, adding trimethylolpropane trimethacrylate, dodecanol and benzoyl peroxide, stirring evenly to obtain an oil phase; the mass ratio of quercetin modified acrylate to vanillic acid methyl ester modified acrylate is 1.5:3, the mass ratio of ethylene glycol dimethacrylate to vanillic acid methyl ester modified acrylate is 60:3, the mass ratio of trimethylolpropane trimethacrylate to ethylene glycol dimethacrylate is 30:30, the mass ratio of dodecanol to vanillic acid methyl ester modified acrylate is 30:3, and the mass ratio of benzoyl peroxide to vanillic acid methyl ester modified acrylate is 2:3.

[0051] Example 4: The difference between this example and Example 1 is only the preparation of the oil phase.

[0052] Preparation of oil phase: dissolving vanillic acid methyl ester modified acrylate and quercetin modified acrylate in ethylene glycol dimethacrylate, adding trimethylolpropane trimethacrylate, dodecanol and benzoyl peroxide, stirring evenly to obtain an oil phase; the mass ratio of quercetin modified acrylate to vanillic acid methyl ester modified acrylate is 1.5:3, the mass ratio of ethylene glycol dimethacrylate to vanillic acid methyl ester modified acrylate is 60:3, the mass ratio of trimethylolpropane trimethacrylate to ethylene glycol dimethacrylate is 40:30, the mass ratio of dodecanol to vanillic acid methyl ester modified acrylate is 30:3, and the mass ratio of benzoyl peroxide to vanillic acid methyl ester modified acrylate is 2:3.

[0053] Comparative Example 1: This comparative example is different from Example 1 only in the preparation of the oil phase.

[0054] Preparation of oil phase: dissolving quercetin modified acrylate in ethylene glycol dimethacrylate, adding dodecanol and benzoyl peroxide, stirring evenly to obtain an oil phase; the mass ratio of quercetin modified acrylate to ethylene glycol dimethacrylate is 1:60, the mass ratio of dodecanol to quercetin modified acrylate is 30:1, and the mass ratio of benzoyl peroxide to quercetin modified acrylate is 2:1.

[0055] Comparative Example 2: This comparative example is different from Example 1 only in the preparation of the oil phase.

[0056] Preparation of oil phase: dissolve vanillic acid methyl ester modified acrylate in ethylene glycol dimethacrylate, add dodecanol and benzoyl peroxide, stir evenly to obtain oil phase; the mass ratio of vanillic acid methyl ester modified acrylate to ethylene glycol dimethacrylate is 3:60, the mass ratio of dodecanol to vanillic acid methyl ester modified acrylate is 30:3, and the mass ratio of benzoyl peroxide to vanillic acid methyl ester modified acrylate is 2:3.

[0057] Comparative Example 3: This comparative example is different from Example 1 only in the preparation of the oil phase.

[0058] Preparation of oil phase: dissolve methyl acrylate in ethylene glycol dimethacrylate, add dodecanol and benzoyl peroxide, stir evenly to obtain an oil phase; the mass ratio of methyl acrylate to ethylene glycol dimethacrylate is 4:60, the mass ratio of dodecanol to methyl acrylate is 30:4, and the mass ratio of benzoyl peroxide to methyl acrylate is 2:4.

[0059] Test Example 1: Infrared absorption spectrum of macroporous resin material.

[0060] Test sample: macroporous resin material prepared in Example 1.

[0061] Test method: The macroporous resin material prepared in Example 1 was dried at 80°C for 5 h, mixed and ground with dried potassium bromide powder, pressed into thin sheets and heated at 400-4000 cm -1 The infrared absorption of macroporous resin is detected within a range of .

[0062] The infrared absorption spectrum of the macroporous resin material prepared by the present invention is as follows: Figure 1 As shown in the figure, it can be seen that at 3500-3200cm -1 There is a broad absorption peak of OH stretching vibration near 3000-2800cm -1 There is an absorption peak of CH stretching vibration nearby, at 1750-1735cm -1 There is an absorption peak of C=O stretching vibration in the range of 1600-1500cm -1 There is an absorption peak of aromatic ring skeleton stretching vibration in the range of 1150cm -1 The absorption peak of CO stretching vibration appeared, indicating that vanillic acid methyl ester-modified acrylate and quercetin-modified acrylate have been successfully fixed into the macroporous resin.

[0063] Test Example 2: Specific surface area test of macroporous resin material.

[0064] Test sample: macroporous resin material prepared by the methods of various embodiments and comparative examples.

[0065] Test method: The prepared macroporous resin material was dried at 150°C for 5h, cooled to liquid nitrogen temperature of -196.15°C, and the amount of nitrogen adsorbed on the surface of the macroporous resin material was measured. After saturation, the temperature was raised to measure the amount of desorbed nitrogen, and the specific surface area of ​​the macroporous resin material was obtained according to the BET equation.

[0066] The specific surface area test results of the macroporous resin material prepared by the present invention are as follows: Figure 2 As shown, the specific surface area of ​​Example 1 is 652.6 m2 / g, the specific surface area of ​​Example 2 is 676.2m 2 / g, the specific surface area of ​​Example 3 is 698.3m 2 / g, the specific surface area of ​​Example 4 is 719.0m 2 / g. From Examples 1-4, it can be seen that the macroporous resin material prepared by modifying the acrylic ester polymerization monomer has a high specific surface area, and with the introduction of trimethylolpropane trimethacrylate in the crosslinking agent, the specific surface area is further increased, indicating that quercetin and methyl vanillate can optimize the microstructure of the resin during the polymerization process, promote the formation of more pores or more reasonable pore distribution, and thus increase the specific surface area. At the same time, trimethylolpropane trimethacrylate and ethylene glycol dimethacrylate form a co-crosslinking, so that the resin is formed inside. The pore structure is more conducive to increasing the specific surface area, providing more surface sites for material adsorption. The specific surface area of ​​comparative example 1 is 494.7.m 2 / g, the specific surface area of ​​comparative example 2 is 502.2m 2 / g, the specific surface area of ​​comparative example 3 is 409.3m 2 / g, indicating that the lack of methyl vanillate-modified acrylate or quercetin-modified acrylate makes it impossible to form an efficient porous structure inside the resin, resulting in a significant decrease in the specific surface area.

[0067] Experimental Example 3: Isolation and purification test of chlorogenic acid in honeysuckle.

[0068] Test sample: macroporous resin material prepared by the methods of various embodiments and comparative examples.

[0069] Test method: Pre-treat the macroporous resin material, soak it in ethanol for 24 hours, and load it into a glass column with a diameter of 0.8 cm after it is fully swollen. Rinse it with deionized water until the effluent is clear and there is no ethanol residue. Rinse it with 5% hydrochloric acid and sodium hydroxide solution respectively, and finally rinse it with deionized water until it is neutral, and vacuum dry it for use. Crush the honeysuckle, extract it with 60% ethanol by ultrasonic extraction, and obtain the honeysuckle extract after filtration. The honeysuckle is adsorbed through the macroporous resin at a flow rate of 1 mL / min, and the resin column is rinsed with deionized water. 40% ethanol aqueous solution is used as the eluent, and eluted at a flow rate of 1 mL / min. The eluates of the macroporous resin materials are collected respectively, and the content of chlorogenic acid in the eluate is determined, and the recovery rate of chlorogenic acid is calculated.

[0070] The recovery rate of chlorogenic acid in honeysuckle by the macroporous resin material prepared in the present invention is as follows: Figure 3As shown, it can be seen from Examples 1-4 that the macroporous resin material synthesized by a specific modified acrylic ester polymerization monomer and a cross-linking agent has a highly efficient adsorption and separation effect on chlorogenic acid, reduces the adsorption of other impurities, and improves the enrichment of chlorogenic acid on the macroporous resin. Optimizing the ratio of the modified acrylic ester polymerization monomer and the ratio of the cross-linking agent can make the adsorption of chlorogenic acid on the macroporous resin more compact and specific, and it is easier to separate from impurities during the elution process, thereby improving the recovery rate. It can be seen from Comparative Examples 1-2 that the lack of one of the modified acrylic ester polymerization monomers will change the polarity and structure of the macroporous resin, significantly reduce the adsorption capacity of chlorogenic acid, and cannot effectively enrich chlorogenic acid from plant extracts, and the recovery rate is reduced. Comparative Example 3 does not use a modified acrylic ester polymerization monomer but uses methyl acrylate to prepare a macroporous resin with extremely weak adsorption of chlorogenic acid. Most of the chlorogenic acid directly penetrates the resin column, and effective separation and extraction of chlorogenic acid cannot be achieved.

[0071] The embodiments and / or implementation methods described above are only used to illustrate the preferred embodiments and / or implementation methods for realizing the technology of the present invention, and are not intended to limit the implementation methods of the technology of the present invention in any form. Any technical personnel in this field may make slight changes or modifications to other equivalent embodiments without departing from the scope of the technical means disclosed in the content of the present invention, but they should still be regarded as technologies or embodiments that are essentially the same as the present invention.

[0072] This article uses specific examples to illustrate the principles and implementation methods of this application. The description of the above embodiments is only used to help understand the method and its core ideas of this application. The above is only the preferred implementation method of this application. It should be pointed out that due to the limitations of textual expression and the objective existence of infinite specific structures, ordinary technicians in this technical field can make several improvements, modifications or changes without departing from the principles of this application, and can also combine the above technical features in an appropriate manner; these improvements, modifications, changes or combinations, or the direct application of the concept and technical solution of the invention to other occasions without improvement, should be regarded as the scope of protection of this application.

Claims

1. A method for preparing a macroporous resin material, comprising: Reacting acryloyl chloride with a modifier to obtain a modified acrylate polymerization monomer, wherein the modifier includes quercetin and / or methyl vanillate, and the modified acrylate polymerization monomer includes methyl vanillate modified acrylate and / or quercetin modified acrylate; The modified acrylic ester polymerization monomer, porogen, crosslinking agent and dispersant are mixed, and a macroporous resin material is obtained by suspension polymerization; the porogen is dodecanol, the crosslinking agent is ethylene glycol dimethacrylate, the dispersant is polyvinyl alcohol, and the initiator is benzoyl peroxide.

2. The method for preparing a macroporous resin material according to claim 1, characterized in that: The volume mass ratio of the acryloyl chloride to quercetin is 1.3-8 mL:1-6 g.

3. The method for preparing a macroporous resin material according to claim 1, characterized in that: The volume mass ratio of the acryloyl chloride to methyl vanillate is 1-8 mL:2.2-18.2 g.

4. The method for preparing a macroporous resin material according to claim 1, characterized in that: The mass ratio of the vanillic acid methyl ester modified acrylate to the quercetin modified acrylate is 3-15:1-5.

5. The method for preparing a macroporous resin material according to claim 1, characterized in that: The mass ratio of the dodecanol to the vanillic acid methyl ester modified acrylate is 10-150:1-15.

6. The method for preparing a macroporous resin material according to claim 1, characterized in that: The mass ratio of the ethylene glycol dimethacrylate to the methyl vanillate modified acrylate is 20-300:1-15.

7. The method for preparing a macroporous resin material according to claim 1, characterized in that: The mass ratio of the polyvinyl alcohol to the methyl vanillate modified acrylate is 1-10:1.5-15.

8. The method for preparing a macroporous resin material according to claim 1, characterized in that: The mass ratio of the benzoyl peroxide to the methyl vanillate modified acrylate is 1-10:1.5-15.

9. The macroporous resin material prepared by the method of claims 1-8.

10. Use of the macroporous resin material according to claim 9 in the separation and purification of substances, wherein the substances include but are not limited to proteins, flavonoid natural medicines, and alkaloid natural medicines.

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