WO2014142378A1

WO2014142378A1 - Method for manufacturing magnetic nanoparticles and nanoparticles manufactured using same

Info

Publication number: WO2014142378A1
Application number: PCT/KR2013/002231
Authority: WO
Inventors: 현재호
Original assignee: 고센바이오비드 주식회사
Priority date: 2013-03-15
Filing date: 2013-03-19
Publication date: 2014-09-18
Also published as: KR20140122223A; KR101516345B1

Abstract

The present invention relates to a method for manufacturing magnetic nanoparticles and nanoparticles manufactured using the same. The present invention is characterized by comprising: a mixing step of mixing an iron precursor, a solvent, a ligand, and tertiary distilled water at room temperature, followed by a base reaction; a dispersing step of putting a polymeric material for enhancing dispersion force in the solution mixed in the mixing step, followed by mixing; a changing step of, while heating the solution mixed in the dispersing step to 150-300℃ and maintaining a reaction for a predetermined time, identifying the change in the color of the solution from yellow to black; and a separating step of separating magnetic nanoparticles from the solution, of which the color is changed to black in the changing step, using a centrifuge or magnetism. Further, the present invention is characterized by magnetic nanoparticles manufactured by the method. Therefore, the present invention has an effect of manufacturing magnetic nanoparticles having high stability, a uniform particle distribution, and improved magnetic characteristics, by mixing the iron precursor, solvent, ligand, and tertiary distilled water at room temperature to conduct a base reaction, mixing the polymeric material therewith to enhance the dispersion force, performing heating to achieve magnetization, and then separating the magnetic nanoparticles.

Description

[Correction 12.06.2013 by Rule 26] 방법 Magnetic Nanoparticles Manufacturing Method and Magnetic Nanoparticles Prepared Using the Same

The present invention relates to a method for producing magnetic nanoparticles and to magnetic nanoparticles prepared using the same, and more particularly, to make nanoparticles have high stability and uniform particle distribution, and to induce synthesis and effective dispersion of nanoparticles, The present invention relates to a method of manufacturing magnetic nanoparticles that can improve properties and facilitate mass production, and to magnetic nanoparticles prepared using the same.

In recent years, attention has been focused on nano-functional materials that can overcome the limitations of existing materials, technologies for effectively manufacturing them, and techniques for applying them.

Nanotechnology is not just an emerging technology due to the size of the object, but is one of the important technical fields because materials with sizes ranging from 1 to 1000 nm exhibit unique properties not found in materials with sizes larger than that. do.

In particular, in recent years, nano technology has been applied to a reflective display that is attracting attention. The core of the reflective display is a display light transmission control device, and magnetic nanoparticles manufactured by nano technology are used in the display light transmission control device. have. At this time, the display light transmission control device is an optical device that transmits or blocks the light emitted from the display device or the light incident from the outside, it is the magnetic nanoparticles to realize this.

In addition, the magnetic nanoparticles are raw materials such as bio-sensor for disease diagnosis, MRI contrast agents, hyperthermia, drug delivery systems, and the like, and can safely reduce side effects. In addition to providing a medical technology, it is possible to simultaneously solve the requirements of the medical technology, such as the acquisition of fast diagnosis and treatment results, high accuracy, and completeness, attracting attention in the bio and medical field recently. However, magnetic nanoparticles must meet some requirements in order to be applied in bio and medical fields.

First, each of the magnetic nanoparticles generates a uniform magnetic field, and in order to exhibit more accurate and uniform characteristics, the magnetic nanoparticles should not aggregate with each other, and have a particle size and spherical particle shape that may have superparamagnetism. It is important to do so.

In addition, in order for the magnetic nanoparticles to respond to external application or minute changes in the induced magnetic field, the magnetic nanoparticles must have improved saturation magnetization value and high susceptibility, and have high chemical stability.

In addition, the magnetic properties should be designed so as to maintain magnetic properties when the surface of the magnetic nanoparticles having affinity with a living cell or coated with a biocompatible material. That is, the nanoparticles must meet both the magnetic properties and biocompatibility to be finally applied to the bio and medical fields.

In relation to the production of the magnetic nanoparticles, researches on the iron oxide-based magnetic nanoparticles are active, mainly research on Fe3O4 and Fe2O3 (γ-Fe2O3, α-Fe2O3) [Ajay Kumar Gupta and Mona Gupta, Biomaterials, 26, 3995 (2005); Pedro Tartaj et al., J. Phys. D: Applied Phys., 36, R182 (2003); Ajay Kumar Gupta and Stephen Wells, IEEE Trans. on Nanobioscience, 3 (1), 6673 (2004)].

In addition, as a result of continuous research, nanoparticles having a size of several nanometers have been manufactured, see Shouheng Sun et al., J. Am. Chem. Soc. 126, 273 (2004)], and the results of successful studies on the production of plural ferrites are reported [Shouheng Sun and Hao Zeng, J. Am. Chem. Soc. 124, 8204 (2002).

However, most of the reported manufacturing methods require inert reaction environments such as nitrogen or argon, and therefore, there is a difficulty in preparing after completely separating and removing air or moisture. In addition, since surfactants are used to induce dispersion of the particles, magnetic properties such as saturation magnetization value and susceptibility are significantly lowered. However, if the surfactant is not used, it is difficult to obtain independent magnetic nanoparticles due to the aggregation phenomenon due to the surface magnetism between the nanoparticles.

Due to these technical limitations, magnetic nanoparticles have not been applied directly to the bio and medical fields.

In addition, there is a limit in confirming detailed and accurate physical properties in the magnetic and physical characterization of the previously reported nanoparticles. In order to prevent problems that may occur in bio and medical applications in advance, it is necessary to confirm the correct physical properties of the nanoparticles, and accurate physical property identification is necessary to properly cope with any problem.

In particular, magnetite (magnetite; Fe3O4) and maghemite (γ-Fe2O3), which are iron oxides, have a similar crystal structure and are limited in their classification by X-ray diffraction analysis (XRD) based on the crystal structure principle. The distinction is not clear even with the macroscopic magnetic properties of the vibration susceptibility meter (VSM) and the superconducting quantum interference magnetic measurement device (SQUID). Sang Won Lee and Chul Sung Kim, Sae Mulli, 50 (3), 147 (2005); M. Hanson, J. Magn. Magn. Mater. 96, 105 (1991)]

The method of manufacturing nanoparticles and magnetic nanoparticles, which have been developed so far, have yet to reach the magnetic properties necessary for practical application in the field of reflective display and bio and medical fields, and the magnetic nanoparticles are unstable and the particle distribution is uneven. There was this.

In order to solve the above problems, the present invention, the magnetic nanoparticles to have a high stability and uniform particle distribution and at the same time to improve the magnetic properties, it can be easily applied to the reflective display or bio fields The purpose of the present invention is to provide a method for manufacturing magnetic nanoparticles and magnetic nanoparticles prepared using the same.

In addition, the surface of the magnetic nanoparticles can be easily modified, and particles of various sizes can be easily manufactured, so that the magnetic nanoparticles can be easily applied to various applications as well as reflective displays or biofields.

Hereinafter, a method of manufacturing magnetic nanoparticles of the present invention and magnetic nanoparticles manufactured using the same will be described in detail with reference to the accompanying drawings.

1 is a flow chart showing one embodiment of the method of manufacturing magnetic nanoparticles of the present invention, Figure 2 is a flow chart showing another embodiment of the method of manufacturing magnetic nanoparticles of the present invention.

First, as shown in FIG. 1, the iron precursor, the solvent, the ligand, and the tertiary distilled water are mixed at room temperature to proceed with the mixing step (S1) where the basic reaction is performed, and to increase the dispersibility in the solution mixed in the mixing step (S1). In order to proceed with the dispersion step (S2) to add and mix the polymer material in order to, the solution mixed in the dispersion step (S2) to 150 ~ 300 ℃ to continue the reaction for a predetermined time while the color of the solution from yellow to black Proceed with the change step (S3) to identify the change to, and the separation step (S4) to separate the magnetic nanoparticles by using a centrifugal separator or a magnetic solution in the change step (S3) to sequentially The magnetic nanoparticles to be obtained by the present invention are prepared.

Meanwhile, as shown in FIG. 2, the iron precursor, the solvent, the ligand, the tertiary distilled water, and the polymer material are mixed and heated to 150 to 300 ° C. to maintain the reaction for a predetermined time while changing the color of the solution from yellow to black. Proceed to step (S10), even if the solution is changed to black in the mixing change step (S10) using a centrifuge or a magnetic separation step (S4) to separate the magnetic nanoparticles in sequence, the magnetic properties are Improved magnetic nanoparticles can be prepared.

At this time, it is preferable to further proceed to the washing step (S5) for washing the magnetic nanoparticles separated in the separation step (S4) with a polar solvent to prepare magnetic nanoparticles without impurities.

Here, the normal temperature means, but is not limited to, 20 to 30 ℃ that the operator can react most comfortably without raising or lowering the temperature in the present invention. That is, the temperature may be lower or higher depending on the surrounding conditions and environment.

In the mixing step (S1), the iron precursor, the solvent, the ligand, and the third distilled water are mixed at room temperature to perform a basic reaction.

The iron precursor is iron (II), iron (III), iron nitrate (II) [Fe (NO3) 2], iron nitrate hexahydrate as an additive material containing iron capable of obtaining magnetism in order to obtain magnetic nanoparticles. (II) [Fe (NO3) 2.6H2O], iron nitrate (III) [Fe (NO3) 3], iron nitrate hexahydrate (III) [Fe (NO3) 2.6H2O], iron (II) [FeSO4], Ferrous sulfate heptahydrate (II) [FeSO4.7H2O], ferrous sulfate (III) [Fe2 (SO4) 3], ferrous chloride (II) [FeCl2], ferrous chloride tetrahydrate (II) [FeCl2.4H2O], iron chloride (III) [FeCl3], ferric chloride hexahydrate [FeCl3.6H2O], iron iodide (II) [FeI2], iron iodide tetrahydrate (II) [FeI2.4H2O], iron iodide (III) [FeI3], iron (II) acetylacetonate Iron [Fe (acetylacetonate) 2], iron (III) acetylacetonate Iron [Fe (acetylacetonate) 3], iron (II) trifluoroacetylacetonate [Fe (tfac) 2], iron (III) trifluoro Acetylacetonate [Fe (tfac) 3], iron (II) acetate [Fe (ac) 2], iron (III) acetate [Fe (ac) 3], iron perchlorate [Fe (ClO4) 3], iron sulfamate [Fe (NH 2 SO 3) 2], iron pentacarbonyl [Fe (CO) 5], iron bromide (II) [FeBr 2], iron bromide (III) [FeBr 3], iron stearate (II) [ (CH3 (CH2) 16COO) 2Fe], iron stearate (III) [(CH3 (CH2) 16COO) 3Fe], iron oleate (II) [(CH3 (CH2) 7CHCH (CH2) 7COO) 2Fe], iron oleate (III) ) [(CH3 (CH2) 7CHCH (CH2) 7COO) 3Fe], iron laurate (II) [(CH3 (CH2) 10COO) 2Fe], iron laurate (III) [(CH3 (CH2) 10COO) 3Fe], Iron (II) acetate [Fe (OOCCH3) 2], pentacarbonyl iron [Fe (CO) 5], ennicarbonyl iron [Fe2 (CO) 9], disodium tetracarbonyl iron [Na2 (Fe (CO)) 4)], zinc chloride (II) [ZnCl 2], cobalt chloride (III) [CoCl 3], cobalt chloride (II) [CoCl 2], cobalt (II) nitrate [Co (NO 3) 2], nickel sulfate (II) [ NiSO 4], nickel chloride (II) [NiCl 2], nickel nitrate (II) [Ni (NO 3) 2], titanium tetrachloride [TiCl 4], zirconium tetrachloride [ZrCl 4], hexachloro platinum (IV) acid [H 2 PtCl 6], hexachloro Palladium (IV) acid [H2PdCl6], barium chloride [BaCl2], barium sulfate [BaSO4], strontium chloride [SrCl2], strontium sulfate [SrSO4], zinc acetate [Zn ( OOCH3) 2], manganese acetate [Mn (OOCH3) 2], cerium acetate (III) hydrate [(CH3COO) 3CexH2O], cerium bromide hydrate [CeBr3xH2O], cerium chloride (III) heptahydrate CeCl 3 · 7H 2 O], cerium carbonate hydrate [Ce 2 (CO 3) × H 2 O], cerium fluoride (III) hydrate [CeF 3 · xH 2 O], cerium (III) 2-ethylhexanoate [CH 3 (CH 2) 3 CH ( C2H5) CO2] 3Ce, cerium iodide (III) [CeI3], cerium nitrate (III) hexahydrate [Ce (NO3) 3.6H2O], cerium oxalate hydrate [Ce (C2O4) 3xH2O], cerium perchlorate (III) [Ce (ClO4) 3], cerium sulfate (III) hydrate [Ce2 (SO4) 3.xH2O], cobalt acetylacetonate [Co (acac) 3], nickel acetylacetonate [Ni (acac) 2] Copper acetylacetonate [Cu (acac) 2], barium acetylacetonate [Ba (acac) 2], strontium acetylacetonate [Sr (acac) 2], cerium (III) acetylacetonate hydrate [(acac) 3Ce XH2O], platinum acetylacetonate [Pt (acac) 2], palladium acetylacetonate [Pd (acac) 2], titanium tetraasof Width of the seed [Ti (OC3H7) 4] and zirconium tetrabutoxide [Zr (OC4H9) 4] is made by any one.

The solvent is an additive material for dissolving the iron precursor to liquefy, and may include a polymer solvent, an ionic liquid solvent, a halogen hydrocarbon solvent, an alcohol solvent, an aromatic solvent, a heterocyclic solvent, a sulfoxide solvent, an amide solvent, a hydrocarbon solvent, It consists of either an ether solvent or water.

In addition, the solvent is acetate, ethyl acetate, butyl acetate, ethylene glycol, ethylene glycol, diethylene glycol, triethylene glycol, Tetra ethylene glycol, ethanol, 2-butoxy ethanol, di propylene glycol, ketone, methyl isobutyl ketone , Ethyl methyl ketone, acetone, alcohol, alcohol, butanol, propanol, methanol, acetonitrile, acetonitrile, acetonitrile, chloroform (chloroform), ether, diethylehter, phenyl ether, octyl ether, decyl ether, benzyl ether, pyridine, die Methyl sulfoxide, N, N-di N, N-Dimethylformamide, Squalene, Tetrahydrofuran, Dichloromethane, Amine, Hexane, Hexadecane, Hexadecene hexadecene, octadecane, octadecene, octadecene, eicosane, eicosene, phenanthrene, pentacene, anthracene and biphenyl It may be made of any one or a plurality of selected.

The ligand is a substance added to the base reaction with the iron precursor, sodium acetate, ammonia water, ammonium hydroxide, sodium hexane sulfonate, sodium bicarbonate, sodium alginate, phosphine, diphosphine, triphenylphosphine, tri-o -Tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, tris (pentafluorophenyl) phosphine, tris (p-fluorophenyl) phosphine, tris (o-methoxyphenyl) Phosphine, tris (m-methoxyphenyl) phosphine, tris (p-methoxyphenyl) phosphine, tris (2,4,6-trimethoxyphenyl) phosphine, tri (m-chlorophenyl) phosphine , Tri (p-chlorophenyl) phosphine, tricyclohexylphosphine, tri-tert-butylphosphine, tri-n-butylphosphine, tri-2-furylphosphine, 2- (dicyclohexylphosphino) Biphenyl, 2- (di-tert-butylphosphino) biphenyl, 2-di-tert-butylphosphino-2'-methylbiphenyl, 2- (dicyclohexylphosphino-2 ', 6'-dime Oxy-1,1'-biphenyl, 2- ( Dicyclohexylphosphino) -2 '-(N, N-dimethylamino) biphenyl, 2-dicyclohexylphosphino-2'-methyl-biphenyl, 2- (dicyclohexylphosphino) -2', 4 ', 6'-Tri-isopropyl-1,1'-biphenyl, hydrazine, arsine, primary arsine, secondary arsine, tertiary arsine, quaternary arsonium, styrene, silane, disilane, tri Silane, germane, monogerman, igerman, digerman, trigerman, methane, ivory, sodium phosphate, disodium phosphate, sodium triphosphate, sodium hexametaphosphate, sodium thiosphosphate, dimethylamineborane and formaldehyde It is made of either.

The tertiary distilled water is added to adjust the size of the prepared magnetic nanoparticles to be a mixture having a desired viscosity, and the water having a pH and a conductivity value of 18.2 megaohms through the ultrafilter. use.

As described above, when the iron precursor, the solvent, the ligand, and the third distilled water are mixed in the mixing step (S1), a basic reaction occurs by reaction between the additive materials.

In this case, the iron precursor and the ligand are added at a ratio of 1: 0.1 to 1: 100, preferably at a ratio of 1: 1 to 1:10, and the solvent is preferably added to 10 to 100,000mL. .

And the third distilled water, it is preferable to add 10 to 50,000mL bar, since the size of the finally prepared magnetic nanoparticles can be adjusted according to the amount of the third distilled water, according to the size of the predetermined magnetic nanoparticles 3 It controls the amount of secondary distilled water and easily prepares magnetic nanoparticles of various sizes.

It is emphasized that the preferred addition ratio as described above is a result of analyzing data obtained through many experiments by adding in various ratios.

The dispersing step (S2) is a step of making a mixture containing the nanoparticles dispersed therein by increasing the dispersibility by adding a polymer material to the mixture is mixed in the mixing step (S1) and the base reaction is made, the polymer material As the polyvinyl pyrrolidone (PVP (polyvinyl pyrrolidone)) is used.

In this case, the iron precursor and the polymer material are added at a ratio of 1: 0.01 to 1:20, but preferably at a ratio of 1: 0.1 to 1: 5.

The polyvinyl pyrrolidone [PVP (polyvinyl pyrrolidone)], the molecular weight is 55K and uses a molecular weight of 1,000 to 1,500,000, polyvinyl pyrrolidone [PVP (polyvinyl) having an appropriate molecular weight according to the mol concentration of the mixture pyrrolidone)].

On the other hand, the polymer material, polyvinyl pyrrolidone [PVP (Polyvinyl Pyrrolidone)], alginic acid (Alginic Acid), chitosan (Chitosan), carboxy methyl cellulose [CMC (Carboxy Methyl Cellulose)], acrylamide (Acrylamide) alone And copolymers, polyacrylic acid [PAA (Polyacrylic Acid)], polyethylene oxide, polyvinyl alcohol, polyvinyl alcohol-polyvinyl acetate copolymer, poly (N-vinylpyrrolidone), Polyhydroxyethylacrylate, polyaspartic acid [PAA (Poly Aspartic Acid)], carbomer, polyalkylene glycol [PAG (Poly Alkylen Glycol)], polyethylene glycol [PEG (Polyethylen Glycol)], polyalkyl Ethylene oxide [PAO (Polyalkylene oxides)], polyoxyethylene [POE (polyoxyethylene)], gelatin (gelatin), carboxyl group-containing monomer unit, sulfonic acid group-containing monomer unit and phosphoric acid group-containing monomer unit is used.

In addition, the molecular weight is limited to 1,000 to 1,500,000 as described above, but is not limited thereto. However, the higher the molecular weight, the higher the dispersibility, but the use of a polymer material having a molecular weight that is too high compared to the mol concentration may result in adverse effects. It is preferable to use a polymer material having the same molecular weight between 1,000 and 1,500,000.

The changing step (S3), after heating the mixture to increase the dispersion force through the dispersing step (S2) to 150 ~ 300 ℃ using a heating mantle, watching the reaction for a predetermined time while the heated mixture color is yellow It is a step to visually identify whether the color is changed from black to black. In this case, the preset time is preferably about 1 to 24 hours, and may be 48 to 72 hours depending on other requirements.

At this time, the heating of the mixture is to heat the solvent to the boiling point to allow the mixture to react.

And when the reaction is observed after heating the mixture, the nanoparticles dispersed in the dispersion step (S2) is reacted by heat and magnetized (magnetite).

The magnetization means that the nanoparticles are magnetic, so that the color of the heated mixture is changed from the first yellow to black.

The separation step (S4) is a step of separating magnetic nanoparticles having magnetic properties from the mixture by using a centrifuge or magnetic in the mixture that has undergone the change step (S3).

At this time, the method for separating the magnetic nanoparticles using the centrifuge or the magnetic may be any one of methods that are commonly used, and a detailed description thereof will be omitted.

The washing step (S5), by removing the impurities by washing the magnetic nanoparticles separated in the separation step (S4) with a polar solvent, the magnetic nanoparticles have a high stability and uniform particle distribution. At this time, the polar solvent is to use ethanol.

That is, the polar solvent may be any one of ethanol, alcohol, liquid ammonia, acetone, methanol, chloroform, ethyl acetate, ether, tetrahydrofuran, potassium hydroxide, sodium hydroxide, dichloromethane and water.

And in the washing step (S5), it is preferable to wash three times with a polar solvent. In this case, the washing is not limited to three washings, but the washing may be performed once to several times, and all simple modifications to the number of washings will fall within the scope of the present invention.

On the other hand, although the magnetic nanoparticles may be prepared in a state in which the washing step (S5) is not performed, it is preferable to proceed with the washing step (S5) to have a high stability and uniform particle distribution as described above.

Since the method of washing the magnetic nanoparticles may be any one of methods that are commonly used, a detailed description thereof will be omitted.

At this time, the washing step (S5) may proceed to the method using a centrifuge which is one of the conventional methods, the separation of the magnetic nanoparticles in the separation step (S4) to complete the washing is within the scope of the present invention. something to do. This is because the separation step (S4) proceeds by dividing into primary, secondary, etc. and proceeds with the separation and washing together.

On the other hand, as described above, after the mixing step (S1), the dispersion step (S2) and the change step (S3) without proceeding only the mixing change step (S10), the separation step (S4) and washing step ( S5) may be prepared to produce magnetic nanoparticles (see FIG. 2).

That is, the iron precursor, the solvent, the ligand, the tertiary distilled water, and the polymer material are mixed, and the mixture is heated to 150 to 300 ° C. using a heating mantle to maintain the reaction for a predetermined time while the color of the solution is yellow to black. Proceed with the mixed change step (S10) to visually identify the change to. In this case, as described above, the preset time is preferably about 1 to 24 hours, and may be 48 to 72 hours depending on other requirements.

Then, the magnetic nanoparticles may be manufactured by performing the separation step (S4) and the washing step (S5).

In this case, the magnetic nanoparticles may be manufactured without performing the washing step (S5). Of course, the washing step (S5) may be performed to have a high stability and a uniform particle distribution as described above. desirable.

Magnetic nanoparticles prepared as described above, the diameter of the center is 1 ~ 1,000nm, has a superparamagnetic, paramagnetic, diamagnetic, ferromagnetic, antiferromagnetic, ferrimagnetic and hydrophilic, reflective display and bio and various applications It can be easily applied and used.

In this case, the superparamagnetism can be controlled by using a magnetic force and can be redispersed when the magnetic force is lost, and thus can be used in various fields requiring magnetic nanoparticles having the superparamagnetism.

In addition, the hydrophilic property can be used in the field of biotechnology that requires magnetic nanoparticles having hydrophilic properties by dissolving in water.

Hereinafter, various embodiments of the present invention will be described, and these embodiments are only for describing the present invention, and it is obvious to those skilled in the art that the scope of the present invention is not limited to these embodiments.

Example 1

Into a 1L round cedar container, add 0.02 mol of acetylacetonate iron [Fe (acetylacetonate) 3] and 0.49 mol of sodium acetate (CH3COONa), and add 500 mL of diethylene glycol and 50 mL of tertiary distilled water. The mixture was mixed at room temperature for 30 minutes using a stirrer. (S1)

And 0.55mmol of polyvinyl pyrrolidone [PVP (polyvinyl pyrrolidone)] (molecular weight 55K) was added in order to increase the dispersibility, and the mixture was mixed at room temperature for 30 minutes using a stirrer (S2).

In addition, the reaction was carried out for 3 hours after raising the temperature to 220 ℃ while maintaining the stirring. At this time, it was confirmed that the color of the solution was changed from yellow to black, and that the change was completely black, the reaction was completed by the heat and the magnetite was changed (S3).

After the temperature was lowered, the magnetic nanoparticles and the solution were separated using a centrifuge (S4), and the separated magnetic nanoparticles were washed three times with ethanol, a polar solvent (S5), to provide high stability and uniform particle distribution. Magnetic nanoparticles having improved magnetic properties.

Example 2

Into a 1L round cedar container, add 0.02 mol of acetylacetonate iron [Fe (acetylacetonate) 3] and 1.14 mol of ammonia water (NH3H2O), add 500 mL of diethylene glycol and 50 mL of tertiary distilled water. The mixture was mixed at room temperature for 30 minutes. (S1)

After the temperature was reduced, the magnetic nanoparticles and the solution were separated using a centrifuge (S4), and the separated magnetic nanoparticles were washed three times with ethanol (S5) to have high stability and uniform particle distribution and magnetic properties. Magnetic nanoparticles with improved properties were prepared.

Example 3

Into a 1L round cedar container, add 0.04 mol of ferric chloride hexahydrate [FeCl3.6H2O] and 0.49 mol of sodium acetate (CH3COONa), add 500 mL of diethylene glycol and 50 mL of tertiary distilled water, and then use a stirrer. Mix for 30 minutes at room temperature. (S1)

Example 4

Into a 1L round cedar container, add 0.04 mol of ferric chloride hexahydrate [FeCl3.6H2O] and 1.14 mol of ammonia water (NH3H2O), and add 500 mL of diethylene glycol and 50 mL of tertiary distilled water. Mix for 30 minutes at room temperature. (S1)

Therefore, the method of manufacturing the magnetic nanoparticles of the present invention and the magnetic nanoparticles prepared by using the same, cause a basic reaction by mixing an iron precursor, a solvent, a ligand, and tertiary distilled water, increase the dispersibility by mixing a polymer material, and then heat and magnetize the magnetic nanoparticles. By separating the particles, it is possible to produce magnetic nanoparticles having high stability and uniform particle distribution and improved magnetic properties.

In addition, by easily modifying the surface of the magnetic nanoparticles and easily preparing particles of various sizes, not only can be easily applied to the reflective display or bio field, but also can be mass-produced to be easily applied to various applications. There is also an effect that can be used.

1 is a flow chart showing an embodiment of the present invention method for manufacturing magnetic nanoparticles

Figure 2 is a flow chart showing another embodiment of the method of manufacturing magnetic nanoparticles of the present invention

In order to achieve the above object, the present invention provides a method for preparing magnetic nanoparticles, a mixing step of mixing an iron precursor, a solvent, a ligand, and tertiary distilled water at room temperature for a basic reaction; And, in the solution mixed in the mixing step, the dispersion step of mixing the polymer material to increase the dispersion force; And, changing the step of identifying that the color of the solution is changed from yellow to black while continuing the reaction for a predetermined time by heating the solution mixed in the dispersion step to 150 ~ 300 ℃; And a separation step of separating the magnetic nanoparticles using a centrifugal separator or a magnet from the solution changed to black in the changing step. Characterized in that comprises a.

And mixing the iron precursor, the solvent, the ligand, the tertiary distilled water, and the polymer material, and heating to 150 to 300 ° C. to continue the reaction for a predetermined time while changing the color of the solution from yellow to black; And a separation step of separating the magnetic nanoparticles using a centrifugal separator or a magnet from the solution changed to black in the mixing change step. Characterized in that comprises a.

At this time, the washing step of washing the magnetic nanoparticles separated in the separation step with a polar solvent; It is preferable that further comprises.

On the other hand, the polar solvent is made of any one of ethanol, alcohol, liquid ammonia, acetone, methanol, chloroform, ethyl acetate, ether, tetrahydrofuran, potassium hydroxide, sodium hydroxide, dichloromethane and water.

The iron precursor is iron (II), iron (III), iron nitrate (II), iron nitrate hexahydrate (II), iron nitrate (III), iron nitrate hexahydrate (III), iron sulfate (II), sulfuric acid Iron lactate (II), iron sulfate (III), iron chloride (II), iron chloride tetrahydrate (II), iron chloride (III), iron chloride hexahydrate, iron iodide (II), iron iodide tetrahydrate (II), iron iodide ( III), iron (II) acetylacetonate iron, iron (III) acetylacetonate iron, iron (II) trifluoroacetylacetonate, iron (III) trifluoroacetylacetonate, iron (II) acetate, iron (III) acetate, iron perchlorate, iron sulfamate, iron pentacarbonyl, iron bromide (II), iron bromide (III), iron stearate (II), iron stearate (III), iron oleate (II), iron oleate ( (III), iron laurate (II), iron laurate (III), iron acetate (II), pentacarbonyl iron, enicarbonyl iron, disodium tetracarbonyl iron, zinc chloride ( Ⅱ), cobalt chloride (III), cobalt chloride (II), cobalt nitrate (II), nickel sulfate (II), nickel chloride (II), nickel nitrate (II), titanium tetrachloride, zirconium tetrachloride, hexachloro platinum (IV) Acid, hexachloropalladium (IV) acid, barium chloride, barium sulfate, strontium chloride, strontium sulfate, zinc acetate, manganese acetate, cerium (III) hydrate, cerium bromide (III) hydrate, cerium (III) heptahydrate , Cerium (III) hydrate, cerium (III) fluoride, cerium (III) 2-ethylhexanoate, cerium iodide, cerium (III) hexahydrate, cerium oxalate (III) hydrate, cerium perchlorate (III), cerium sulfate (III) hydrate, cobalt acetylacetonate, nickel acetylacetonate, copper acetylacetonate, barium acetylacetonate, strontium acetylacetonate, cerium (III) acetylacetonate hydrate, platinum acetylacetonate, Palladium acetyla Of soil carbonate, titanium tetra-Aso-propoxide and zirconium tetrabutoxide is made by any one.

The solvent may be any one of a polymer solvent, an ionic liquid solvent, a halogen hydrocarbon solvent, an alcohol solvent, an aromatic solvent, a heterocyclic solvent, a sulfoxide solvent, an amide solvent, a hydrocarbon solvent, an ether solvent, and water. Is done.

Wherein the solvent is acetate, ethyl acetate, butyl acetate, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, ethanol, 2-butoxy ethanol, dipropylene glycol, ketone, methyl isobutyl ketone, ethyl methyl Ketones, acetone, alcohols, butanol, propanol, methanol, acetonitrile, acetonitrile, chloroform, ether, diethyl ether, phenyl ether, octyl ether, decyl ether, benzyl ether, pyridine, dimethyl sulfoxide, N, N Any of dimethylformamide, squalene, tetrahydrofuran, dichloromethane, amine, hexane, hexadecane, hexadecene, octadecane, octadecene, icosane, icocene, phenanthrene, pentacene, anthracene and biphenyl It consists of one or a plurality of selected ones.

And the ligand is sodium acetate, ammonia water, ammonium hydroxide, sodium hexane sulfonate, sodium bicarbonate, sodium alginate, phosphine, diphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, Tri-p-tolylphosphine, tris (pentafluorophenyl) phosphine, tris (p-fluorophenyl) phosphine, tris (o-methoxyphenyl) phosphine, tris (m-methoxyphenyl) phosphine , Tris (p-methoxyphenyl) phosphine, tris (2,4,6-trimethoxyphenyl) phosphine, tri (m-chlorophenyl) phosphine, tri (p-chlorophenyl) phosphine, tricyclo Hexylphosphine, tri-tert-butylphosphine, tri-n-butylphosphine, tri-2-furylphosphine, 2- (dicyclohexylphosphino) biphenyl, 2- (di-tert-butylphosphino Biphenyl, 2-di-tert-butylphosphino-2'-methylbiphenyl, 2- (dicyclohexylphosphino-2 ', 6'-dimethoxy-1,1'-biphenyl, 2- ( Dicyclohexylphosphino) -2 '-(N, N-dimethylamino) biphenyl, 2-di Clohexylphosphino-2'-methyl-biphenyl, 2- (dicyclohexylphosphino) -2 ', 4', 6'-tri-isopropyl-1,1'-biphenyl, hydrazine, arsine, Primary arsine, secondary arsine, tertiary arsine, quaternary arsonium, stibin, silane, disilane, trisilane, germane, monogerman, igerman, digerman, trigerman, methane, ivoran, sodium phosphate , Sodium diphosphate, sodium triphosphate, sodium hexametaphosphate, sodium phosphate, dimethylamine borane and formaldehyde.

In addition, the polymer material may be polyvinyl pyrrolidone, alginic acid, chitosan, carboxymethyl cellulose, homopolymer and copolymer of acrylamide, polyacrylic acid, polyethylene oxide, polyvinyl alcohol, polyvinyl alcohol-polyvinyl acetate copolymer, Poly (N-vinylpyrrolidone), polyhydroxyethylacrylate, polyaspartic acid, carbomer, polyalkylene glycol, polyethylene glycol, polyalkylene oxide, polyoxyethylene, gelatin, carboxyl group-containing monomer unit, sulfonic acid It consists of either a group containing monomer unit and a phosphoric acid group containing monomer unit.

At this time, the polymer material, it is preferable to use a polymer of 1,000 to 1,500,000 in order to increase the initial dispersion.

On the other hand, it is preferable that the iron precursor and the ligand are added at a ratio of 1: 0.1 to 1: 100, and the iron precursor and the polymer are added at a ratio of 1: 0.01 to 1:20.

In addition, the tertiary distilled water may adjust the amount of mixing to control the size of the magnetic nanoparticles.

On the other hand, the magnetic nanoparticles of the present invention, the iron precursor, the solvent, the ligand, the tertiary distilled water by mixing at room temperature mixing step of the base reaction; And, in the solution mixed in the mixing step, the dispersion step of mixing the polymer material to increase the dispersion force; And, changing the step of identifying that the color of the solution is changed from yellow to black while continuing the reaction for a predetermined time by heating the solution mixed in the dispersion step to 150 ~ 300 ℃; And a separation step of separating the magnetic nanoparticles using a centrifugal separator or a magnet from the solution changed to black in the changing step. Manufactured in progress,

Mixing the iron precursor, a solvent, a ligand, a tertiary distilled water, and a polymer material, changing the color of the solution from yellow to black while maintaining the reaction for a predetermined time by heating to 150 to 300 ° C .; And a separation step of separating the magnetic nanoparticles using a centrifugal separator or a magnet from the solution changed to black in the mixing change step. It is characterized in that it is manufactured by proceeding.

The magnetic nanoparticles preferably have a central diameter of 1 to 1,000 nm and have superparamagnetic, paramagnetic, diamagnetic, ferromagnetic, antiferromagnetic and ferrimagnetic properties and hydrophilicity dispersed in a polar solvent.

Claims

Mixing the iron precursor, the solvent, the ligand, and the tertiary distilled water at room temperature to perform a basic reaction (S1); Wow,

Dispersion step (S2) for putting the polymer material in the solution mixed in the mixing step (S1), in order to increase the dispersing power; Wow,

A change step (S3) of identifying that the color of the solution changes from yellow to black while continuing the reaction for a predetermined time by heating the mixed solution in the dispersing step (S2) to 150 to 300 ° C .; And,

A separation step (S4) of separating the magnetic nanoparticles using a centrifugal separator or a magnet from the solution changed to black in the changing step (S3); Magnetic nanoparticles manufacturing method comprising a.
Mixing the iron precursor, a solvent, a ligand, a tertiary distilled water, and a polymer material, and heating the solution at 150 to 300 ° C. to maintain the reaction for a predetermined time, wherein the color of the solution is changed from yellow to black (S10); And,

A separation step (S4) of separating the magnetic nanoparticles using a centrifugal separator or a magnet from the solution changed to black in the mixing change step (S10); Magnetic nanoparticles manufacturing method comprising a.
The method according to claim 1 or 2,

A washing step (S5) of washing the magnetic nanoparticles separated in the separating step (S4) with a polar solvent; Magnetic nanoparticles manufacturing method characterized in that it further comprises.
The method of claim 3, wherein

The polar solvent,

Method of producing magnetic nanoparticles, characterized in that any one of ethanol, alcohol, liquid ammonia, acetone, methanol, chloroform, ethyl acetate, ether, tetrahydrofuran, potassium hydroxide, sodium hydroxide, dichloromethane and water.
The method according to claim 1 or 2,

The iron precursor is,

Iron (II), iron (III), iron nitrate (II), iron nitrate hexahydrate (II), iron nitrate (III), iron nitrate hexahydrate (III), iron sulfate (II), iron sulfate heptahydrate (II) ), Iron sulfate (III), iron chloride (II), iron chloride tetrahydrate (II), iron chloride (III), iron chloride hexahydrate, iron iodide (II), iron iodide tetrahydrate (II), iron iodide (III), iron ( II) acetylacetonate iron, iron (III) acetylacetonate iron, iron (II) trifluoroacetylacetonate, iron (III) trifluoroacetylacetonate, iron (II) acetate, iron (III) acetate, Iron perchlorate, iron sulfamate, iron pentacarbonyl, iron bromide (II), iron bromide (III), iron stearate (II), iron stearate (III), iron oleate (II), iron oleate (III), lauric Ferric iron (II), iron laurate (III), iron acetate (II), pentacarbonyl iron, ennicarbonyl iron, disodium tetracarbonyl iron, zinc chloride (II), cobalt chloride (III) ), Cobalt (II) chloride, cobalt (II) nitrate, nickel sulfate (II), nickel chloride (II), nickel nitrate (II), titanium tetrachloride, zirconium tetrachloride, hexachloroplatinum (IV) acid, hexachloropalladium ( IV, acid, barium chloride, barium sulfate, strontium chloride, strontium sulfate, zinc acetate, manganese acetate, cerium (III) hydrate, cerium bromide (III) hydrate, cerium (III) heptahydrate, cerium (III) hydrate , Cerium fluoride (III) hydrate, cerium (III) 2-ethylhexanoate, cerium iodide (III), cerium (III) hexahydrate, cerium oxalate (III) hydrate, cerium perchlorate (III), cerium sulfate ( III) hydrate, cobalt acetylacetonate, nickel acetylacetonate, copper acetylacetonate, barium acetylacetonate, strontium acetylacetonate, cerium (III) acetylacetonate hydrate, platinum acetylacetonate, palladium acetylacetonate, titanium A method for producing magnetic nanoparticles, comprising one of tetrasopropoxide and zirconium tetrabutoxide.
The method according to claim 1 or 2,

The solvent,

Magnetic, characterized in that it comprises one of a polymer solvent, an ionic liquid solvent, a halogen hydrocarbon solvent, an alcohol solvent, an aromatic solvent, a heterocyclic solvent, a sulfoxide solvent, an amide solvent, a hydrocarbon solvent, an ether solvent, and water. Nanoparticles manufacturing method.
The method according to claim 1 or 2,

The solvent,

Acetate, ethyl acetate, butyl acetate, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, ethanol, 2-butoxy ethanol, dipropylene glycol, ketone, methyl isobutyl ketone, ethyl methyl ketone, acetone, alcohol , Butanol, propanol, methanol, acetonitrile, acetonitrile, chloroform, ether, diethyl ether, phenyl ether, octyl ether, decyl ether, benzyl ether, pyridine, dimethyl sulfoxide, N, N-dimethylformamide, Any one or selected of squalene, tetrahydrofuran, dichloromethane, amine, hexane, hexadecane, hexadecene, octadecane, octadecene, icosan, icocene, phenanthrene, pentacene, anthracene and biphenyl Magnetic nanoparticles manufacturing method characterized in that made.
The method according to claim 1 or 2,

The ligand is,

Sodium acetate, ammonia water, ammonium hydroxide, sodium hexane sulfonate, sodium bicarbonate, sodium alginate, phosphine, diphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolyl Phosphine, tris (pentafluorophenyl) phosphine, tris (p-fluorophenyl) phosphine, tris (o-methoxyphenyl) phosphine, tris (m-methoxyphenyl) phosphine, tris (p- Methoxyphenyl) phosphine, tris (2,4,6-trimethoxyphenyl) phosphine, tri (m-chlorophenyl) phosphine, tri (p-chlorophenyl) phosphine, tricyclohexylphosphine, tri -tert-butylphosphine, tri-n-butylphosphine, tri-2-furylphosphine, 2- (dicyclohexylphosphino) biphenyl, 2- (di-tert-butylphosphino) biphenyl, 2 -Di-tert-butylphosphino-2'-methylbiphenyl, 2- (dicyclohexylphosphino-2 ', 6'-dimethoxy-1,1'-biphenyl, 2- (dicyclohexylphosphino ) -2 '-(N, N-dimethylamino) biphenyl, 2-dicyclohexylphosphino-2'- Til-biphenyl, 2- (dicyclohexylphosphino) -2 ', 4', 6'-tri-isopropyl-1,1'-biphenyl, hydrazine, arsine, primary arsine, secondary arsine, Tertiary arsine, quaternary arsonium, styrene, silane, disilane, trisilane, germane, monogerman, igerman, digerman, trigerman, methane, ivoran, sodium phosphate, dibasic sodium phosphate, tertiary A method for producing magnetic nanoparticles, comprising any one of sodium phosphate, sodium hexametaphosphate, sodium thiophosphate, dimethylamine borane and formaldehyde.
The method according to claim 1 or 2,

The polymer material,

Polyvinyl pyrrolidone, alginic acid, chitosan, carboxy methyl cellulose, acrylamide alone and copolymers, polyacrylic acid, polyethylene oxide, polyvinyl alcohol, polyvinyl alcohol-polyvinyl acetate copolymers, poly (N-vinylpyrrolidone) Pig), polyhydroxyethyl acrylate, polyaspartic acid, carbomer, polyalkylene glycol, polyethylene glycol, polyalkylene oxide, polyoxyethylene, gelatin, carboxyl group-containing monomer unit, sulfonic acid group-containing monomer unit and phosphoric acid group-containing Magnetic nanoparticles manufacturing method comprising any one of the monomer units.
The method according to claim 1 or 2,

The polymer material is a method for producing magnetic nanoparticles, characterized in that for using the polymer in the range of 1,000 to 1,500,000 to increase the initial dispersion.
The method according to claim 1 or 2,

The iron precursor and the ligand, magnetic nanoparticles manufacturing method characterized in that the addition of a ratio of 1: 0.1 to 1: 100.
The method according to claim 1 or 2,

The iron precursor and the polymer, magnetic nanoparticles manufacturing method characterized in that the addition of a ratio of 1: 0.01 to 1: 20.
The method according to claim 1 or 2,

The third distilled water, the magnetic nanoparticles manufacturing method characterized in that for adjusting the amount of mixing to control the size of the magnetic nanoparticles.
Magnetic nanoparticles, characterized in that produced by the method of any one of claims 1 or 2.
The method of claim 14,

The magnetic nanoparticles are magnetic nanoparticles, characterized in that the central diameter is 1 ~ 1,000nm.
The method of claim 14,

The magnetic nanoparticles are magnetic nanoparticles, characterized in that the superparamagnetic, paramagnetic, diamagnetic, ferromagnetic, antiferromagnetic, ferrimagnetic.