CN107993784B - Magnetic particles with various shapes and preparation method and application thereof - Google Patents
Magnetic particles with various shapes and preparation method and application thereof Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/06—Coating with compositions not containing macromolecular substances
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
- H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/01—Magnetic additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
Abstract
The invention discloses magnetic particles with various shapes, a preparation method and application thereof. The preparation method of the magnetic particles comprises the following steps: heating a system consisting of iron salt, a template agent, a shape maintaining agent and a solvent for reaction to obtain the magnetic particles; the form maintaining agent is sodium acetate, potassium acetate, sodium hydroxide, potassium hydroxide, urea or oleylamine; the template agent is polyethylene glycol, hexadecyl triethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, sodium dodecyl sulfate or sodium dodecyl benzene sulfonate. Compared with other synthesis methods of magnetic particles with special shapes, such as a hydrothermal method, a solvothermal method, a thermal decomposition method, a sol-gel method and the like, the method can synthesize the magnetic particles with different shapes by adjusting the reaction temperature and the reaction time in a raw material system, the particle size of the product is in a micron level, the preparation method and the steps are simple, the raw materials are easy to obtain, the cost is low, the reaction temperature is low, the method does not need to be carried out under a high-pressure environment, and the method is suitable for industrial large-scale production.
Description
Technical Field
The invention relates to the technical field of preparation and surface modification of magnetic particles, in particular to magnetic particles with various shapes and a preparation method and application thereof.
Background
The performance of a material depends not only on its chemical composition, but also is closely related to its fine structure and morphology. The structural and morphological control of particles is therefore of increasing interest to researchers. In particular the control of magnetic particles. Zijian Zhou et al, ACS Nano 2014, 8 vol 7976-7985, reported that a Nano Fe with two flat hexagonal basal planes was synthesized by thermal decomposition of iron oleate in a system of oleic acid, sodium oleate and benzyl ether3O4A magnetic disk. The large number of exposed (111) crystal faces enables the imaging effect of T1 to be excellent, and the anisotropic morphology of the nano disk enables the imaging effect of T2 to be enhanced. This opens up new raw materials for high performance MRI contrast agents for biomedicine. Genban Sun et al, Chemistry of Materials 2011 23 vol 1587-15933[Fe(CN)6]Dissolving in deionized water to obtain 0.1mol/L solutionThen pouring the mixture into a stainless steel reaction kettle for high-temperature high-pressure reaction for two days to obtain the branched α -Fe2O3Then in air, H2Or oxidizing or reducing at high temperature in Ar atmosphere to obtain dendritic Fe3O4、γ-Fe2O3And Fe. These dendrites have excellent absorption ability for microwaves of medium and low frequencies (2-9 GHz). Xun-Liang Cheng et al in The Journal of physical chemistry C2014 118 12588-12598 hydrazine hydrate, water, Fe (acac)3Oleic acid and toluene as raw materials are mixed in a stainless steel reaction kettle to form a two-phase reaction system, and rhombic dodecahedron-shaped Fe is prepared by high-temperature high-pressure reaction3O4. The product has peroxidase-like activity and can rapidly catalyze H2O2Oxidation of TMB (3,3',5,5' -tetramethylbenzidine) or catalysis of H2O2The methyl blue is degraded, and the performance is excellent in the lithium battery test. Fei-Xiang Ma et al reported a Fe (NO) solution on volume 27 of Advanced Materials 2015, 4097-3)3·6H2Using O as iron source, using glycerin, isopropanol and small quantity of deionized water as solvent, using hydrothermal method to prepare hollow iron alkoxide precursor whose diameter is about 650nm, and said precursor is formed from interconnected flakes, then placing the precursor in N2The hollow multilevel structure Fe is prepared by heat treatment for 3h at 350 ℃ in the atmosphere3O4Fe of such a hollow multi-stage structure3O4The lithium ion battery shows excellent electron transmission rate, high capacity and high cycle number, and is a potential anode material. Zhang Hui et al in invention patent CN103145535B disclose diethylene glycol ferrous alkoxide with three-dimensional pattern multi-level structure and preparation method thereof, specifically FeCl3·6H2O and CH3COONa·3H2O is used as a raw material, EG is used as a solvent, diethylene glycol ferrous alkoxide with a three-dimensional pattern multi-stage structure is thermally synthesized in a Teflon stainless steel reaction kettle by a high-temperature high-pressure solvent, and the flower-shaped particle size is 7-8 mu m.
However, the preparation methods of the magnetic particles with various morphologies in the above reports generally require high pressure environment, and one system can generally only obtain products with one dimension (0-dimensional, 1-dimensional, 2-dimensional, 3-dimensional or three-dimensional hierarchical structure, etc.). The methods have complex reaction process and higher synthesis cost, and are not beneficial to large-scale production and application.
Disclosure of Invention
The invention aims to provide magnetic particles with various shapes and a preparation method and application thereof, the adopted raw materials are cheap and easy to obtain, a high-pressure environment is not needed, and one reaction system can be used for preparing the magnetic particles with different shapes by adjusting different reaction temperatures and reaction times.
The preparation method of the magnetic particles provided by the invention comprises the following steps: heating a system consisting of iron salt, a template agent, a shape maintaining agent and a solvent for reaction to obtain the magnetic particles;
the template agent is polyethylene glycol, hexadecyl triethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate;
the form maintaining agent is sodium acetate, potassium acetate, sodium hydroxide, potassium hydroxide, urea or oleylamine;
the solvent is glycol, glycerol, ethanol or a mixed solvent of any one of the glycol, the glycerol and the ethanol and water.
In the above preparation method, the iron salt may be FeCl3、Fe(NO3)3、Fe2(SO4)3、FeNH4(SO4)2、Fe(acac)3Or a hydrate thereof.
The molecular weight of the polyethylene glycol can be 200-20000, and particularly, 600-1000, such as 800, can be preferred.
In the preparation method, the system consists of a solution A and a solution B; the solution A consists of the morphology-maintaining agent and the solvent; the solution B consists of the iron salt, the template and the solvent.
The volume ratio of the solution A to the solution B can be 4: 1-1: 4, preferably can be 2: 1-1: 2, as shown in 8: 7.
in the solution A, the mass-to-volume ratio of the morphology maintaining agent to the solvent can be (5-20) g: 80mL, and particularly preferably (13 to 16) g: 80mL, such as 14.4 g: 80 mL.
In the solution B, the mass-to-volume ratio of the ferric salt to the template to the solvent can be (1-10) g: (1-10) g: (50-100) mL, more preferably (3-6) g: 70mL, such as 5.4 g: 4.0 g: 70 mL.
In the preparation method, the preparation steps of the system are as follows: preparing a solution to obtain a solution A and a solution B; and adding the solution A into the solution B, and mixing to obtain the mixed solution.
The preparation temperature can be 25-60 ℃, and specifically can be 50 ℃.
The preparation can be carried out under the condition of mechanical stirring, and the rotating speed of the mechanical stirring can be 200-400 r/min, and specifically can be 300 r/min; the time can be 15-60 min, specifically 30 min.
In the mixing step, the temperature may be 25 to 60 ℃, specifically 50 ℃.
The mixing can be carried out under the condition of mechanical stirring, and the rotating speed of the mechanical stirring can be 200-400 r/min, and specifically can be 300 r/min; the time can be 5-60 min, specifically 5 min.
In the preparation method, the heating temperature can be 120-200 ℃, and the time can be 15-60 hours; specifically, the heating can be carried out at 140 ℃, 160 ℃ or 170 ℃ for 52h, 180 ℃ for 52h, 190 ℃ for 52h, at 140-170 ℃ (such as 160 ℃) for 15h, and at 180-190 ℃ (such as 180 ℃) for 2-20 h (such as 20 h).
The reaction can be carried out under the condition of mechanical stirring, and the rotating speed of the mechanical stirring can be 50-800 r/min, specifically 200-400 r/min and 300 r/min.
In the above production method, the method further comprises, after the heating, a step of separating a magnetic product from the reacted system; the separation can be centrifugal separation or magnetic adsorption separation.
The invention further provides the magnetic particles prepared by the preparation method.
The magnetic particles are Fe3O4Magnetic particles or ferrialkoxide magnetic particles.
The particle size of the magnetic particles is micron-sized.
The shape of the magnetic particles can be sheet, block or flower.
In the invention, magnetic particles with different morphologies can be prepared by controlling the heating temperature and the heating time, which are as follows:
the heating temperature is 140-185 ℃, the heating time is more than 10h (such as 52h), and the magnetic particles are flaky;
the heating temperature is 190-198 ℃, the heating time is more than 10 hours (such as 52 hours), and the shape of the magnetic particles is blocky;
the heating is carried out for 15 hours at the temperature of 140-170 ℃, and then the temperature is increased to 180-190 ℃ for 2-20 hours; the shape of the magnetic particles is flower-shaped.
Specifically, the sheet shape may be a smooth sheet shape or a rough sheet shape;
the heating temperature is 140-170 ℃, the heating time is more than 10h (such as 52h), and the magnetic particles are smooth and flaky;
the heating temperature is 175-185 ℃, the heating time is more than 10 hours (such as 52 hours), and the shape of the magnetic particles is rough and flaky.
In the invention, the block is a non-spherical and non-sheet solid structure (such as a cube, a cuboid or an irregular shape); the flower shape is a structure formed by the crossed or radial arrangement of flaky or needle-shaped particles. The smooth sheet shape means that the surface of the sheet-shaped object is uniform and smooth; the rough sheet is a sheet with irregular bulges on the surface or a large sheet with grooves on the surface formed by mutually interpenetrating smaller sheets.
The invention also provides application of the flower-shaped magnetic particles prepared by the preparation method in preparation of super-hydrophilic surface modified resin. The resin can be at least one of polypropylene resin, polystyrene resin, phenolic resin and epoxy resin.
In the above application, the preparation of the resin with super-hydrophilic surface modification comprises the following steps: and spin-coating the dispersion liquid of the flower-shaped magnetic particles on the surface of the incompletely cured resin, and drying to obtain the resin with the super-hydrophilic surface modification.
Due to the adoption of the technical scheme, the invention has the following advantages:
compared with other synthesis methods of magnetic particles with special shapes, such as a hydrothermal method, a solvothermal method, a thermal decomposition method, a sol-gel method and the like, the method can synthesize the magnetic particles with different shapes by adjusting the reaction temperature and the reaction time in a raw material system, the particle size of the product is in a micron level, the preparation method and the steps are simple, the raw materials are easy to obtain, the cost is low, the reaction temperature is low, the method does not need to be carried out under a high-pressure environment, and the method is suitable for industrial large-scale production.
Drawings
Fig. 1 is a result of characterization of smooth flaky magnetic particles of example 1 of the present invention, in which fig. 1(a) is a scanning electron micrograph; FIG. 1(B) is a magnetization curve; FIG. 1(C) is an XRD spectrum.
Fig. 2 is a result of characterization of the coarse magnetic particles of example 2 of the present invention, wherein fig. 2(a) is a scanning electron micrograph; FIG. 2(B) is a magnetization curve; FIG. 2(C) is an XRD spectrum.
Fig. 3 is a result of characterization of bulk magnetic particles of example 3 of the present invention, in which fig. 3(a) is a scanning electron micrograph; FIG. 3(B) is a magnetization curve; FIG. 3(C) is an XRD spectrum.
FIG. 4 is a result of characterization of flower-like magnetic particles of example 4 of the present invention, wherein FIG. 4(A) is a scanning electron micrograph; FIG. 4(B) is a magnetization curve; FIG. 4(C) is an XRD spectrum.
FIG. 5 is a normal-temperature water contact angle chart of the flower-like magnetic particle-modified resin of example 4 of the present invention.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1 preparation of micron-sized smooth flaky magnetic particles
The method for preparing the smooth flaky magnetic particles by adopting a one-pot method under normal pressure comprises the following specific steps:
14.4g of NaAc was dissolved in 80mL EG at 50 ℃. 5.4g of FeCl was taken3·6H2O and 4.0g PEG-800 were dissolved in 70mL EG at 50 ℃. The dissolution time of the two solutions is 30min, and the magnetic stirring speed is 300 r/min. And mechanically stirring and uniformly mixing the two solutions at 50 ℃, setting the rotating speed to be 300r/min, and mixing for 5min to obtain a reddish brown solution. And (3) reacting the reddish brown solution at 160 ℃ for 52 hours under normal pressure at the rotating speed of 300 r/min. After the reaction, the product was collected with a magnet, and cleaned and dried with absolute ethanol and deionized water to obtain micron-sized smooth flaky particles (iron alkoxide). The scanning electron micrograph, the result of magnetic analysis and the XRD spectrum are shown in FIG. 1.
Example 2 preparation of micron-sized coarse flaky magnetic particles
The method is characterized in that the rough flaky magnetic particles are prepared by a one-pot method under normal pressure, and the method comprises the following specific steps:
14.4g NaAc was dissolved in 80mL EG at 50 ℃. 5.4g of FeCl was taken3·6H2O and 4.0g PEG-800 were dissolved in 70mL EG at 50 ℃. The dissolution time of the two solutions is 30min, and the magnetic stirring speed is 300 r/min. And mechanically stirring and uniformly mixing the two solutions at 50 ℃, setting the rotating speed to be 300r/min, and mixing for 5min to obtain a reddish brown solution. And (3) reacting the reddish brown solution at 180 ℃ for 52 hours under normal pressure at the rotating speed of 300 r/min. And (3) collecting the reaction product by using a magnet after the reaction is finished, and cleaning and drying the product by using absolute ethyl alcohol and deionized water to obtain the micron-sized rough flaky magnetic particles (iron alkoxide). The scanning electron micrograph, the result of magnetic analysis and the XRD spectrum are shown in FIG. 2.
Example 3 preparation of micron-sized bulk magnetic particles
Under normal pressure, a one-pot method is adopted to prepare the blocky magnetic particles, and the method comprises the following specific steps:
14.4g of NaAc was dissolved in 80mL EG at 50 ℃. 5.4g of FeCl was taken3·6H2O and 4.0g PEG-800 were dissolved in 70mL EG at 50 ℃. The dissolution time of the two solutions is 30min, and the magnetic stirring speed is 300 r/min. Mechanically stirring the two solutions at 50 deg.C, and mixing at a set rotation speedAt 300r/min, the mixing time was 5min to obtain a reddish brown solution. And (3) reacting the reddish brown solution at 190 ℃ for 52h under normal pressure at the rotating speed of 300 r/min. Collecting the reaction product with magnet after the reaction is finished, and cleaning and drying with anhydrous ethanol and deionized water to obtain micron-sized block-shaped magnetic particles (Fe)3O4). The scanning electron micrograph, the result of magnetic analysis and the XRD spectrum are shown in FIG. 3.
Example 4 preparation of micron-sized flower-like magnetic particles
The flower-shaped magnetic particles are prepared by a one-pot method under normal pressure, and the method comprises the following specific steps:
14.4g of NaAc was dissolved in 80mL EG at 50 ℃. 5.4g of FeCl was taken3·6H2O and 4.0g PEG-800 were dissolved in 70mL EG at 50 ℃. The dissolution time of the two solutions is 30min, and the magnetic stirring speed is 300 r/min. And mechanically stirring and uniformly mixing the two solutions at 50 ℃, setting the rotating speed to be 300r/min, and mixing for 5min to obtain a reddish brown solution. And (3) reacting the reddish brown solution at 160 ℃ for 15h under normal pressure, heating to 180 ℃ and reacting at normal pressure for 20h at the rotating speed of 300 r/min. And (3) after the reaction is finished, collecting the reaction product by using a magnet, and cleaning and drying by using absolute ethyl alcohol and deionized water to obtain the micron-sized flower-shaped magnetic particles (iron alkoxide). The scanning electron micrograph, the result of magnetic analysis and the XRD spectrum are shown in FIG. 4.
Example 5 preparation of flower-like magnetic particles super hydrophilic surface
The micron-sized flower-like magnetic particles prepared in the above example 4 are dispersed in a small amount of deionized water to prepare a dispersion solution with a concentration of 1g/mL, the dispersion solution is spin-coated on the surface of the incompletely cured resin, and the resin surface is dried at 120 ℃ for 12 hours to obtain a super-hydrophilic surface. The contact angle of water at normal temperature is shown in fig. 5, the test result is that theta is less than 5 degrees within 0.5s, and the result shows that the surface hydrophilicity of the flower-shaped magnetic particles can be effectively improved, so that the super-hydrophilic effect is achieved.
Wherein the incompletely cured resin surface is prepared by the following steps. According to the following phenol: formaldehyde 1: 1.5, reacting at 90 ℃ for 5 hours to obtain red liquid phenolic resin, and then, mixing the red liquid phenolic resin with a curing agent according to a mass ratio of 10: 1 adding hexamethylene tetramine serving as a curing agent, increasing the viscosity after 1 hour, and coating the obtained viscous phenolic resin on glass to obtain the incompletely cured resin surface.
Claims (9)
1. A preparation method for controlling the morphology of magnetic particles comprises the following steps: heating a system consisting of iron salt, a template agent, a shape maintaining agent and a solvent for reaction to obtain the magnetic particles;
the preparation method comprises the steps of preparing magnetic particles with different shapes in the same reaction system by adjusting the reaction temperature and the reaction time;
when the heating temperature is 140-185 ℃ and the heating time is more than 10 hours, the prepared magnetic particles are flaky;
when the heating temperature is 190-198 ℃ and the heating time is more than 10 hours, the prepared magnetic particles are blocky;
when the heating is performed for 15 hours at the temperature of 140-170 ℃, and then the temperature is increased to 180-190 ℃ for 2-20 hours, the prepared magnetic particles are flower-shaped;
the template agent is polyethylene glycol, hexadecyl triethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate;
the form maintaining agent is sodium acetate, potassium acetate, sodium hydroxide, potassium hydroxide, urea or oleylamine;
the solvent is glycol, glycerol, ethanol or a mixed solvent of any one of the glycol, the glycerol and the ethanol and water.
2. The method of claim 1, wherein: the iron salt is FeCl3、Fe(NO3)3、Fe2(SO4)3、FeNH4(SO4)2、Fe(acac)3Or a hydrate thereof; and/or the presence of a gas in the gas,
the molecular weight of the polyethylene glycol is 200-20000.
3. The production method according to claim 1 or 2, characterized in that: the system consists of a solution A and a solution B;
the solution A consists of the morphology-maintaining agent and the solvent;
the solution B consists of the ferric salt, the template and the solvent;
the volume ratio of the solution A to the solution B is 4: 1-1: 4;
in the solution A, the mass-to-volume ratio of the morphology maintaining agent to the solvent is (5-20) g: 80 mL;
in the solution B, the mass-to-volume ratio of the ferric salt to the template to the solvent is (1-10) g: (1-10) g: (50-100) mL.
4. The production method according to claim 1 or 2, characterized in that: the reaction is carried out under the condition of mechanical stirring, and the rotating speed of the mechanical stirring is 50-800 r/min.
5. The production method according to claim 1 or 2, characterized in that: the method further comprises, after the heating, the step of separating the magnetic product from the reacted system; the separation adopts centrifugal separation or magnetic adsorption separation.
6. The production method according to claim 1 or 2, characterized in that: the magnetic particles are Fe3O4Magnetic particles or ferrialkoxide magnetic particles.
7. The production method according to claim 1 or 2, characterized in that: the magnetic particles are in the micron order.
8. The production method according to claim 1 or 2, characterized in that: the sheet shape is a smooth sheet shape or a rough sheet shape;
the heating temperature is 140-170 ℃, the heating time is more than 10 hours, and the magnetic particles are smooth and flaky;
the heating temperature is 175-185 ℃, the heating time is more than 10 hours, and the shape of the magnetic particles is rough and flaky.
9. Use of the magnetic particles prepared by the method of any one of claims 1 to 8 for preparing a resin having a superhydrophilic surface modification.
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| CN112011176A (en) * | 2019-05-29 | 2020-12-01 | 北京服装学院 | Magnetic polyamide, preparation method thereof and magnetic fiber obtained by using magnetic polyamide |
| CN112011035A (en) * | 2019-05-29 | 2020-12-01 | 北京服装学院 | Magnetic polyester, preparation method thereof and magnetic fiber obtained by using magnetic polyester |
| CN110721655A (en) * | 2019-08-23 | 2020-01-24 | 河南长兴实业有限公司 | Preparation method of heavy metal adsorbent based on red mud |
| CN110697790B (en) * | 2019-10-18 | 2023-03-28 | 临沂大学 | Chapped sheet iron oxide nano material and preparation method thereof |
| CN112090430A (en) * | 2020-09-11 | 2020-12-18 | 浙江理工大学 | Fe3O4@MoS2Magnetic composite structure and preparation method thereof |
| CN112090431A (en) * | 2020-09-11 | 2020-12-18 | 浙江理工大学 | Gamma-Fe2O3@MoS2Magnetic composite material and preparation method thereof |
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