CN117085657A - Preparation and application of modified magnetic microsphere - Google Patents

Preparation and application of modified magnetic microsphere Download PDF

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Publication number
CN117085657A
CN117085657A CN202311135079.4A CN202311135079A CN117085657A CN 117085657 A CN117085657 A CN 117085657A CN 202311135079 A CN202311135079 A CN 202311135079A CN 117085657 A CN117085657 A CN 117085657A
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modified magnetic
magnetic microsphere
swelling
solution
microsphere
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刘宝乾
楼绮睿
邸多隆
裴栋
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Lanzhou Institute of Chemical Physics LICP of CAS
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/26—Selective adsorption, e.g. chromatography characterised by the separation mechanism
    • B01D15/34—Size selective separation, e.g. size exclusion chromatography, gel filtration, permeation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28009—Magnetic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28016—Particle form
    • B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

The invention provides a preparation method and application of modified magnetic microspheres, and belongs to the technical field of preparation and application of natural product separation materials. Firstly, preparing a monodisperse polystyrene microsphere material by a seed swelling method, synthesizing a magnetic polymer material by a seed swelling technology, adding magnetic nanoparticles, a polymerizable monomer containing active hydrogen, a cross-linking agent, an initiator and a pore-forming agent in the swelling process, and finally modifying the magnetic microsphere by using the method; and the obtained material is used for enriching flavonoid compounds. The modified magnetic material synthesized by the invention has good spherical morphology, can be rapidly separated under an external magnetic field, has large adsorption capacity as an adsorbent, and is suitable for efficient enrichment of flavonoid compounds in a complex system.

Description

Preparation and application of modified magnetic microsphere
Technical Field
The invention belongs to the technical field of preparation and application of natural product adsorption separation materials, and particularly relates to a modified magnetic microsphere and a preparation method and application thereof.
Background
Flavonoid compounds such as rutin, quercetin, myricetin and the like are polyphenol compounds, have strong antioxidant capacity, and have the effects of reducing the incidence rate of cardiovascular diseases, resisting inflammation and the like. However, the flavonoid compounds in the actual sample are low in content, and complex matrix interference exists, so that direct analysis is not facilitated. Therefore, it is necessary to develop an effective method for sample pretreatment to extract and separate flavonoid compounds from complex sample matrices.
The traditional extraction method of flavone mainly comprises solvent extraction, solid phase extraction, ultrasonic assisted extraction, microwave assisted extraction, enzyme assisted extraction, supercritical fluid extraction, etc. However, most of these methods have the disadvantages of time consuming, tedious, not environment friendly, etc., thereby causing resource waste. The monodisperse porous polymer microsphere has the advantages of high specific surface area, uniform particle size, good mechanical strength and the like, and is widely applied to the fields of adsorption separation, ion exchange, sensors and the like. The polystyrene divinylbenzene (PS-DVB) microsphere has the advantages of good stability, high mechanical strength, high specific surface area, regular spherical morphology and the like, and is widely applied to adsorption separation of natural products. However, the adsorption selectivity and the adsorption capacity of the compound are poor, and the difficult problem of rapid enrichment and separation of total flavonoids from natural products cannot be solved.
Disclosure of Invention
The invention aims to provide a preparation method and application of a modified magnetic microsphere, namely a reaction modified magnetic microsphere which is simple to operate, easy to separate and capable of enriching and separating flavonoid compounds in natural products, and a preparation method and application thereof; the prepared modified magnetic microsphere can be used for adsorption separation of flavonoid compounds.
The preparation method of the modified magnetic microsphere provided by the invention comprises the following steps:
1) Dispersing ferric trichloride hexahydrate and ferrous sulfate in water, heating to 80 ℃, adding ammonia water and oleic acid, and washing the collected product after the reaction is finished to obtain oleic acid coated ferroferric oxide nano particles;
wherein oleic acid: ammonia water: ferrous sulfate: the mass ratio of the ferric trichloride hexahydrate is 1:1-5:1-5:1-5, wherein the reaction time is 1-10h, and the stirring rotation speed is 50-250rpm;
the washing is performed by washing with an organic solvent such as n-heptane, dichloromethane or n-octane after washing with water.
2) Suspending seed polymer particles in an aqueous solution containing a surfactant to form a seed solution;
adding a swelling agent into an aqueous solution containing a surfactant for emulsification to obtain an emulsion; then mixing the seed solution and the emulsion, and swelling to obtain a seed swelling solution;
the seed polymer particles are polystyrene microspheres, and one particle size of the seed polymer particles is 1-15 mu m.
The swelling agent is any one of ethanol, toluene, 1, 2-dichloroethane, N-dimethylformamide, 1-chlorododecane and dibutyl phthalate.
3) Emulsifying the oleic acid coated ferroferric oxide nano particles prepared in the step 1) by using the polymerizable monomer containing active hydrogen, the cross-linking agent and the initiator to prepare a solution, and then pouring the solution into a reactor after emulsifying the solution into the solution, and continuing swelling;
the active hydrogen-containing polymerizable monomers include, but are not limited to, acrylic acid, acrylamide, acrylic esters, N-vinyl pyrrolidone, and the like,
crosslinking agents include, but are not limited to, divinylbenzene, glycol dimethacrylate, tetra vinyl ammonium bromide and the like,
porogens include, but are not limited to, toluene, xylene, n-heptane, and the like;
the mass ratio of the oleic acid coated ferroferric oxide nano particles to the polymerizable monomer containing active hydrogen and the cross-linking agent is 1:1-5;
4) Adding an aqueous solution containing a stabilizer into the reaction liquid after the swelling treatment in the step 3) to polymerize after the swelling is finished, filtering after the polymerization is finished, washing the filtered substances with water and ethanol respectively, and performing Soxhlet extraction and vacuum drying to obtain the magnetic monodisperse porous microspheres;
the solvent for Soxhlet extraction is tetrahydrofuran, toluene, xylene, etc.
5) Dispersing the magnetic monodisperse porous microspheres obtained in the step 4) in a dispersing solvent, and condensing an aldehyde group-containing compound and an amino group-containing compound under an acidic condition to obtain reaction modified magnetic microspheres;
the dispersion solvent includes but is not limited to organic solvents such as ethanol, methylene chloride, toluene, N-dimethylformamide and the like,
the acidic condition is pH <5, the reaction temperature is 25-100 ℃, and the reaction time is 1-20h;
the aldehyde group compound comprises but is not limited to fatty aldehyde, aromatic aldehyde and the like, the amine group compound comprises but is not limited to primary amine, secondary amine and the like, and the mass ratio of the amine group compound to the primary amine is 1:1-10.
The reaction modified magnetic microsphere prepared by the invention is used for adsorbing flavonoid compounds such as rutin, myricetin, kaempferol and the like in aqueous solution and purifying total flavonoids in boxthorn leaves.
Compared with the prior art, the invention has the following advantages:
1. the preparation process of the modified magnetic microsphere is simple and clear, the operation is simple and convenient, the reaction is carried out on the surface of the microsphere to increase the amount of the nitrogen-containing functional groups, the hydrogen bonding effect can be enhanced, and the adsorption acting force of the magnetic microsphere on the target molecular flavonoid compound can be enhanced;
2. the modified magnetic microsphere prepared by the invention can be rapidly separated under an external magnetic field and can be regenerated and reused.
Drawings
Fig. 1: FT-IR diagram of modified magnetic microspheres;
fig. 2: XPS diagram of modified magnetic microsphere;
fig. 3: VSM profile of modified magnetic microspheres;
fig. 4: SEM image of modified magnetic microspheres.
Detailed Description
The preparation method of the modified magnetic microsphere provided by the invention comprises the following steps:
1) Dispersing ferric trichloride hexahydrate and ferrous sulfate in water, heating to 80 ℃, rapidly adding ammonia water and oleic acid, and collecting with the help of a magnet after the reaction is completed; washing the product to obtain oleic acid coated ferroferric oxide nano particles;
the reaction, oleic acid: ammonia water: ferrous sulfate: the mass ratio of the ferric trichloride hexahydrate is 1: (1-5): (1-5): (1-5), the reaction time is 1-10h, and the stirring speed is 50-250rpm.
The washing is carried out for 3-5 times by using organic solvents such as n-heptane, dichloromethane, n-octane and the like for 3 times.
2) Suspending seed polymer particles in an aqueous solution containing a surfactant to form a seed solution; adding a swelling agent into an aqueous solution containing a surfactant for emulsification to obtain an emulsion; then mixing the seed solution and the emulsion, and swelling to obtain a seed swelling solution;
the seed polymer particles are polystyrene microspheres, and the particle size of the seed polymer particles is 1-15 mu m.
The swelling agent is any one of ethanol, toluene, 1, 2-dichloroethane, N-dimethylformamide, 1-chlorododecane and dibutyl phthalate.
3) Preparing a solution from polymerizable monomers containing active hydrogen, a cross-linking agent, oleic acid coated ferroferric oxide nano particles, a pore-forming agent and an initiator, emulsifying in the solution containing a surfactant, pouring the solution into a reactor after emulsification, and continuing swelling;
the active hydrogen-containing polymerizable monomers comprise, but are not limited to, acrylic acid, acrylamide, acrylic esters, N-vinyl pyrrolidone and the like, the crosslinking agents comprise, but are not limited to, divinylbenzene, oxalic acid dimethacrylate, tetra-vinyl ammonium bromide and the like, and the pore-forming agents comprise, but are not limited to, toluene, xylene, N-heptane and the like;
the mass ratio of the oleic acid coated ferroferric oxide nano particles to the polymerizable monomer containing active hydrogen and the cross-linking agent is 1:1-5;
4) Adding an aqueous solution containing a stabilizer into the reaction liquid after the swelling treatment in the step 3) to polymerize after the swelling is finished, filtering after the polymerization is finished, washing the filtered substances with water and ethanol respectively, and performing Soxhlet extraction and vacuum drying to obtain the magnetic monodisperse porous microspheres;
the solvent for Soxhlet extraction is tetrahydrofuran, toluene, xylene, etc.
5) Dispersing the magnetic monodisperse porous microspheres obtained in the step 4) in a solvent, and condensing the magnetic monodisperse porous microspheres with an aldehyde group-containing compound and an amino group-containing compound under an acidic condition to obtain reaction modified magnetic microspheres;
the dispersion solvent comprises but is not limited to ethanol, dichloromethane, toluene, N-dimethylformamide and other organic solvents, the acidic condition is pH <5, the reaction temperature is 25-100 ℃, and the reaction time is 1-20h;
the aldehyde group compound comprises but is not limited to fatty aldehyde, aromatic aldehyde and the like, the amine group compound comprises but is not limited to primary amine, secondary amine and the like, and the mass ratio of the amine group compound to the primary amine is 1:1-10.
The modified magnetic microsphere prepared by the invention is used for adsorbing flavonoid compounds such as rutin, myricetin, kaempferol and the like in aqueous solution and purifying total flavonoids in boxthorn leaves.
The present invention will be described in detail below with reference to specific embodiments and accompanying drawings.
Example 1: synthesis of materials
(1) Dispersing 25g of ferric trichloride hexahydrate and 15g of ferrous sulfate in water, stirring at a rotation speed of 150rpm, heating to 80 ℃, rapidly adding 50mL of ammonia water and 10mL of oleic acid, reacting for 3 hours, and collecting with the help of a magnet; washing the product with water for 5 times and n-heptane for 3 times to obtain oleic acid coated ferroferric oxide nano particles;
(2) 2g of swellable monodisperse 5 mu m PS microspheres are weighed and added into 100mL of 0.25% sodium dodecyl sulfonate aqueous solution, ultrasonic dispersion is carried out for 2min, 2g of dibutyl phthalate is taken and emulsified in 100mL of 0.25% sodium dodecyl sulfonate aqueous solution, then the two solutions are mixed into a 500mL three-port round bottom flask, and swelling is carried out for 24h at 35 ℃ and 150 rpm;
(3) Weighing 3g N-vinyl pyrrolidone, 10g of divinylbenzene, 10g of dimethylbenzene and 0.25g of azodiisobutyronitrile, dispersing 7g of oleic acid coated ferroferric oxide nano particles to obtain a mixed solution, adding 100mL of 0.25% sodium dodecyl sulfate aqueous solution for emulsification, pouring the solution into a reactor, and continuously swelling for 24 hours at 35 ℃ and 150 rpm;
(4) 50mL of 1% polyvinyl alcohol aqueous solution is added, the temperature is raised to 75 ℃, and the reaction is carried out for 18 hours at 300 rpm; after the reaction is finished, filtering, repeatedly flushing with water and ethanol for a plurality of times, extracting with tetrahydrofuran for 12 hours to obtain magnetic monodisperse porous microspheres, filtering, and drying in vacuum to obtain regular spherical polymer MPM;
(5) Swelling 3g of magnetic monodisperse porous microspheres in 120mL of ethanol (pH is adjusted to be less than 4 by adding hydrochloric acid), mechanically stirring at 120rpm, adding a mixed solution of formaldehyde solution (2 mL) and hydrochloric acid (pH is less than 4), adding a mixed solution of dimethylamine (3.5 mL) and hydrochloric acid (pH is less than 4), heating to 80 ℃ for reaction for 6 hours, filtering, washing with 5% sodium hydroxide solution for 1 time, washing with ethanol for several times, and vacuum drying at 35 ℃ for 12 hours to obtain the reaction modified magnetic microspheres MPM-MR.
FT-IR characterization of MPM-MR of the prepared modified magnetic microsphere is shown in FIG. 1, 1272 and 1640cm -1 The characteristic peak of C-N stretching vibration and the absorption peak of carbonyl C=O stretching vibration in N-vinyl pyrrolidone are 579cm respectively -1 The characteristic peak of Fe-O is shown; meanwhile, the characterization by XPS (FIG. 2) showed that the MPM-MR nitrogen atom content increased from 0.38% to 1.14%, the above characterization demonstrated successful synthesis of MPM-MR.
FIG. 3 is a representation of a VSM, which shows that the magnetic properties of MPM are slightly reduced after the reaction modification, but the final MPM-MR can still achieve rapid and effective separation under an externally applied magnetic field. FIG. 4 is an SEM image of MPM-MR, from which it can be seen that the synthesized material is regular spherical and uniform in particle size.
Example 2: synthesis of materials
(1) Dispersing 25g of ferric trichloride hexahydrate and 12g of ferrous sulfate in water, stirring at a rotation speed of 120rpm, heating to 80 ℃, rapidly adding 50mL of ammonia water and 10mL of oleic acid, reacting for 3 hours, and collecting with the help of a magnet; washing the product with water for 5 times and with dichloromethane for 3 times to obtain oleic acid coated ferroferric oxide nano particles;
(2) 2g of swellable monodisperse 3 mu m PS microspheres are weighed and added into 100mL of 0.25% sodium dodecyl sulfonate aqueous solution, ultrasonic dispersion is carried out for 2min, 2g of o-1-chlorododecane is taken and emulsified in 100mL of 0.25% sodium dodecyl sulfonate aqueous solution, then the two solutions are mixed into a 500mL three-necked round bottom flask, and swelling is carried out for 24h at 35 ℃ and 150 rpm;
(3) 3g of methyl acrylate, 10g of divinylbenzene, 10g of dimethylbenzene and 0.25g of azobisisobutyronitrile are weighed, 10g of oleic acid coated ferroferric oxide nano particles are dispersed to obtain a mixed solution, 100mL of 0.25% sodium dodecyl sulfate aqueous solution is added for emulsification, and the solution is poured into a reactor for continuous swelling for 24 hours at 35 ℃ and 150 rpm;
(4) 50mL of 1% polyvinyl alcohol aqueous solution is added, the temperature is raised to 75 ℃, and the reaction is carried out for 18 hours at 300 rpm; after the reaction is finished, filtering, repeatedly flushing with water and ethanol for a plurality of times, extracting with tetrahydrofuran for 12 hours to obtain magnetic monodisperse porous microspheres, filtering, and drying in vacuum to obtain regular spherical polymer MPM;
(5) Swelling 3g of magnetic monodisperse porous microspheres in 120mL of ethanol (pH is adjusted to be less than 4 by adding hydrochloric acid), mechanically stirring at 120rpm, adding a mixture of benzaldehyde solution (2 mL) and hydrochloric acid (pH is less than 4), adding a mixture of dimethylamine (3.5 mL) and hydrochloric acid (pH is less than 4), heating to 80 ℃ for reaction for 6 hours, filtering, washing with 5% sodium hydroxide solution for 1 time, washing with ethanol for several times, and drying in vacuum at 35 ℃ for 12 hours to obtain the modified magnetic microspheres MPM-MR.
Example 3: synthesis of materials
(1) Dispersing 25g of ferric trichloride hexahydrate and 18g of ferrous sulfate in water, stirring at 200rpm, heating to 80 ℃, rapidly adding 50mL of ammonia water and 10mL of oleic acid, reacting for 3 hours, and collecting with the help of a magnet; washing the product with water for 5 times and with dichloromethane for 3 times to obtain oleic acid coated ferroferric oxide nano particles;
(2) 2g of swellable and monodisperse 10 mu m PS microspheres are weighed and added into 100mL of 0.25% sodium dodecyl sulfate aqueous solution, ultrasonic dispersion is carried out for 2min, 2g of toluene is taken and emulsified in 100mL of 0.25% sodium dodecyl sulfate aqueous solution, and then the two solutions are mixed into a 500mL three-neck round bottom flask to be swelled for 24h under the conditions of 35 ℃ and 150 rpm;
(3) 3g of acrylic acid, 10g of divinylbenzene, 10g of dimethylbenzene and 0.25g of azodiisobutyronitrile are weighed, 10g of oleic acid coated ferroferric oxide nano particles are dispersed to obtain a mixed solution, 100mL of 0.25% sodium dodecyl sulfate aqueous solution is added for emulsification, the solution is poured into a reactor, and swelling is continued for 24 hours at 35 ℃ and 150 rpm;
(4) 50mL of 1% polyvinyl alcohol aqueous solution is added, the temperature is raised to 75 ℃, and the reaction is carried out for 18 hours at 300 rpm; after the reaction is finished, filtering, repeatedly flushing with water and ethanol for a plurality of times, extracting with tetrahydrofuran for 12 hours to obtain magnetic monodisperse porous microspheres, filtering, and drying in vacuum to obtain regular spherical polymer MPM;
(5) Swelling 3g of magnetic monodisperse porous microspheres in 120mL of toluene (adding hydrochloric acid to adjust pH < 4), mechanically stirring at 150rpm, adding an acetaldehyde solution (2 mL) and hydrochloric acid mixed solution (pH < 4), adding aniline (3.5 g) and hydrochloric acid mixed solution (pH < 4), heating to 70 ℃ for reaction for 10 hours, filtering, washing with 5% sodium hydroxide solution for 1 time, washing with ethanol for several times, and vacuum drying at 35 ℃ for 12 hours to obtain the modified magnetic microspheres MPM-MR.
Example 4 application of materials
The prepared reaction modified magnetic microsphere is used for adsorbing flavonoid compounds such as rutin, quercetin, myricetin, kaempferol and naringenin, and is compared with unmodified magnetic microsphere. The compounds rutin, quercetin, myricetin, kaempferol and naringenin are prepared into the concentration of 0.1 mg.mL -1 Is prepared by preparing a solution of Lycium barbarum leaf extract to 4mg.mL -1 Is a solution of (a) and (b). 20mg of the reaction modified magnetic microsphere material was precisely weighed into a 50mL centrifuge tube, 25mL of the prepared solution was added, and the mixture was continuously shaken and adsorbed in a constant temperature shaker for 6 hours (25 ℃ C., 125 rpm) to reach adsorption equilibrium. The adsorption amount and adsorption rate were calculated, and the content of flavone in the purified lycium barbarum leaves was calculated (Table 1).
Table 1: adsorption capacity and adsorption rate of material to different flavonoid compounds
Example 5 enrichment of flavone from Lycium barbarum leaves
The prepared reaction modified magnetic microsphere is applied to the purification of the total flavone (the flavone content is 8.17%) of the lycium barbarum leaf extract, and the lycium barbarum leaf extract is prepared into 4 mg.mL -1 Is a solution of (a) and (b). 20mg of the reaction modified magnetic microsphere material was precisely weighed into a 50mL centrifuge tube, 40mL of the prepared solution was added, and the mixture was adsorbed by continuous shaking in a constant temperature shaker for 6 hours (25 ℃ C., 125 rpm). After the desorption is completed, the concentration of flavone in the desorption solution is measured by an ultraviolet spectrophotometer, and the content of flavone in the purified wolfberry leaves is calculated (table 2).
Table 2: enrichment of matrimony vine leaf flavone by reaction modified magnetic microsphere
The results show that the adsorption capacity of the modified magnetic microsphere provided by the invention to flavonoids is obviously improved, and the modified magnetic microsphere can be used for adsorbing flavonoids in water.

Claims (10)

1. The preparation method of the modified magnetic microsphere is characterized by comprising the following steps of:
1) Dispersing ferric trichloride hexahydrate and ferrous sulfate in water, heating to 80 ℃, adding ammonia water and oleic acid, and washing the collected product after the reaction is finished to obtain oleic acid coated ferroferric oxide nano particles;
2) Suspending seed polymer particles in an aqueous solution containing a surfactant to form a seed solution;
adding a swelling agent into an aqueous solution containing a surfactant for emulsification to obtain an emulsion; then mixing the seed solution and the emulsion, and swelling to obtain a seed swelling solution;
3) Emulsifying the oleic acid coated ferroferric oxide nano particles prepared in the step 1) by using the polymerizable monomer containing active hydrogen, the cross-linking agent and the initiator to prepare a solution, and then pouring the solution into a reactor after emulsifying the solution into the solution, and continuing swelling;
4) Adding an aqueous solution containing a stabilizer into the reaction liquid after the swelling treatment in the step 3) to polymerize after the swelling is finished, filtering after the polymerization is finished, washing the filtered substances with water and ethanol respectively, and performing Soxhlet extraction and vacuum drying to obtain the magnetic monodisperse porous microspheres;
5) Dispersing the magnetic monodisperse porous microsphere obtained in the step 4) in a dispersing solvent, and condensing the magnetic monodisperse porous microsphere with an aldehyde group-containing compound and an amino group-containing compound under an acidic condition to obtain the reaction modified magnetic microsphere.
2. The modified magnetic microsphere of claim 1, wherein the oleic acid in 1): ammonia water: ferrous sulfate: the mass ratio of the ferric trichloride hexahydrate is 1:1-5:1-5:1-5.
3. The modified magnetic microsphere of claim 1, wherein the washing of 1) is performed with n-heptane, dichloromethane or n-octane after washing with water.
4. The modified magnetic microsphere of claim 1, wherein the seed polymer particles of 2) are polystyrene microspheres.
5. The modified magnetic microsphere of claim 1, wherein the swelling agent in 2) is any one of ethanol, toluene, 1, 2-dichloroethane, N-dimethylformamide, 1-chlorododecane, and dibutyl phthalate.
6. The modified magnetic microsphere as defined in claim 1, wherein the polymerizable monomer containing active hydrogen in 3) is acrylic acid, acrylamide, acrylic acid esters or N-vinyl pyrrolidone,
the cross-linking agent is divinylbenzene, oxalic acid dimethacrylate or tetravinyl ammonium bromide;
the pore-forming agent is toluene, xylene or n-heptane, etc.
7. The modified magnetic microsphere of claim 1, wherein the solvent used in the soxhlet extraction of 4) is tetrahydrofuran, toluene or xylene.
8. The modified magnetic microsphere of claim 1, wherein the dispersion solvent in 5) is ethanol, dichloromethane, toluene or N, N-dimethylformamide;
the acidic condition is pH <5, the reaction temperature is 25-100 ℃, and the reaction time is 1-20h;
the aldehyde group compound is aliphatic aldehyde or aromatic aldehyde;
the amine-based compound is a primary amine or a secondary amine.
9. The use of the modified magnetic microsphere of claim 1 for adsorbing flavonoids in aqueous solutions.
10. A method for adsorbing a flavonoid compound in an aqueous solution, wherein the method is adsorption using the modified magnetic microsphere of claim 1.
CN202311135079.4A 2023-09-05 2023-09-05 Preparation and application of modified magnetic microsphere Pending CN117085657A (en)

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