KR101852066B1 - Magnetic nanoparticles with enhanced dispersion property in a fluorous solvent and a preparation method thereof - Google Patents
Magnetic nanoparticles with enhanced dispersion property in a fluorous solvent and a preparation method thereof Download PDFInfo
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- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
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- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
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- 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
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Abstract
The present invention relates to magnetic nanoparticles having improved dispersibility in a fluorinated solvent, a method for producing the same, and a nanocolloid system comprising the same.
Description
The present invention relates to magnetic nanoparticles having improved dispersibility in a fluorinated solvent, a method for producing the same, and a nanocolloid system comprising the same.
In general, colloidal inorganic nanoparticles are composed of a core and a ligand shell made of nanocrystals. The ligand includes a functional group (carboxylic acid, thiol, amine, etc.) It is a major factor in determining the dispersion characteristics of the particles (dispersible solvent type and dispersion stability). Therefore, the method of substituting a given nanoparticle surface with a specific ligand is one of important techniques for providing nanocrystalline colloids stably dispersed in a solvent as required.
The perfluorinated materials are widely used for ultrasound imaging, coatings on organic-based film lamination, and working fluids for the organic Rankine cycle. In general, it is advantageous when used in a liquid phase, especially because of its high chemical and / or thermal stability, low vaporization heat, low refractive index and low viscosity compared to hydrocarbon materials. In this regard, fluorinated colloid systems composed of inorganic nanoparticles and perfluorinated solvents are being studied. For example, in addition to using quantum dots having a composition of CdSe / ZnS and InGaP / ZnS as a multimodal bioimaging contrast agent in combination with a water-dispersed perfluorocarbon emulsion droplet, fluoride colloids based on gold and iron oxide nanoparticles Are also reported.
In developing a nanocolloid system, uniform dispersion and colloidal stability are essential to ensure size-driven material properties. A common, simple way to prepare fluorinated nanoparticle colloids is to introduce perfluorocarbon-containing ligands into the surface of the particles. For example, conventional fluorinated nanoparticle colloids were prepared by replacing conventional hydrocarbon-based ligands with perfluorocarbon-containing ligands. On the other hand, the use of dispersions in which these fluorinated nanoparticles are dispersed in a fluorine-based solvent has not been exploited by itself, and therefore research on this has not yet been made.
The present inventors have made intensive studies to discover magnetic nanoparticles excellent in dispersibility and stability against fluorine-based solvents usable for power generation using waste heat and a method for producing the same. As a result, it has been found that the magnetic nanoparticles coated with fatty acid, The magnetic nanoparticles having a fluorocarbon-based or fluorocarbon-based carboxylic acid-containing ligand shell brought into contact with a fluorine-based solvent containing a hydrocarbon-based or fluorocarbon-based carboxylic acid and having excellent dispersibility in a fluorine-based solvent Further, the present inventors have completed the present invention by confirming that the use of a fluorinated solvent having a reduced amount of dissolved oxygen during the ligand replacement reaction can increase the dispersibility of the magnetic nanoparticles prepared from the magnetic nanoparticles to a fluorinated solvent.
One object of the present invention is to provide a magnetic nanoparticle core comprising a ligand shell comprising a fluorocarbon-based or fluorocarbon-based carboxylic acid represented by the formula of a core of a magnetic nanoparticle and CF 3 - (CF 2 ) x - (CH 2 ) y -COOH, And to provide a magnetic nanoparticle soluble in a fluorine-based solvent.
Another object of the invention is a solution to disperse the magnetic nanoparticles coated with the first fatty acid in an organic solvent CF 3 - (CF 2) x - (CH 2) y fluorinated hydrocarbon or fluorocarbon represented by the general formula of -COOH Based carboxylic acid represented by the general formula of CF 3 - (CF 2 ) x - (CH 2 ) y -COOH and a fluorocarbon-based carboxylic acid represented by the formula CF 3 - A first step of preparing a magnetic second nanoparticle including a ligand shell; And a second step of recovering the magnetic second nanoparticles migrated to the fluorine-based solvent layer. The present invention also provides a method for producing the fluorine-based solvent-soluble magnetic nanoparticle.
Another object of the present invention is to provide a fluorine-based solvent; And a nanocolloid system including the magnetic nanoparticles dispersed in the fluorine-based solvent.
A first aspect of the present invention is a magnetic nanocrystal core comprising a magnetic nanocrystalline core and a ligand shell comprising a fluorocarbon-based or fluorocarbon-based carboxylic acid represented by the formula CF 3 - (CF 2 ) x - (CH 2 ) y -COOH. And to provide a magnetic nanoparticle soluble in a fluorine-based solvent.
In a second aspect of the present invention, there is provided a method for preparing a fluorine-containing fluorine-based or fluorine-containing fluorine-based fluorine-containing or fluorine-containing fluorine-containing compound represented by the formula CF 3 - (CF 2 ) x - (CH 2 ) y -COOH in a solution prepared by dispersing magnetic first nanoparticles coated with fatty acid in an organic solvent Based carboxylic acid represented by the general formula of CF 3 - (CF 2 ) x - (CH 2 ) y -COOH and a fluorocarbon-based solvent containing carbon-based carboxylic acid to react A first step of preparing a magnetic second nanoparticle comprising a ligand shell to be formed; And a second step of recovering the magnetic second nanoparticles migrated to the fluorine-based solvent layer. The present invention also provides a method for producing the fluorine-based solvent-soluble magnetic nanoparticle.
A third aspect of the present invention is a fluorine-containing resin composition comprising: a fluorine-based solvent; And a nanocolloid system comprising the magnetic nanoparticle according to the first aspect of the present invention dispersed in the fluorine-based solvent.
Hereinafter, the present invention will be described in more detail.
The present invention relates to a magnetic nanoparticle coated with a fatty acid by fluorinating the magnetic nanoparticle coated with a fatty acid through a ligand substitution reaction in an organic solvent by bringing it into contact with a fluorinated solvent containing fluorinated hydrocarbon or fluorocarbon carboxylic acid, Based on the discovery that particles can be produced. Particularly, the inventors of the present invention have found for the first time that the amount of dissolved oxygen in the fluorine-based solvent used in the ligand-substitution reaction step is an important factor for determining the dispersibility of the fluorinated magnetic nanoparticles to be produced in the fluorine-based solvent.
The present invention relates to a magnetic nanoparticle core comprising a magnetic nanoparticle core and a ligand shell containing a fluorocarbon-based or fluorocarbon-based carboxylic acid represented by the formula CF 3 - (CF 2 ) x - (CH 2 ) y -COOH, Nanoparticles can be provided. Here, x is an integer of 0 to 10, y is an integer of 0 to 4, and x? Y.
For example, the magnetic nanoparticles may be a magnetic element selected from the group consisting of iron, nickel, and cobalt, or a ferromagnetic particle composed of a compound containing the magnetic element. Specifically, the magnetic nanoparticles are nanoparticles of a ferromagnetic material such as iron oxide (Fe 2 O 3 , Fe 3 O 4 ), silicon iron (CoFe 2 O 4 , MnFe 2 O 4 ), alloys (FePt, CoPt) But is not limited thereto.
For example, as the fluorohydrocarbon-based or fluorocarbon-based carboxylic acid, 2H, 2H, 3H, 3H-heptadecafluorodecanoic acid or heptadecafluorononanoic acid, but is not limited thereto.
The term " fluorine-based solvent soluble "as used herein means the property of particles that are uniformly dispersed upon being added to a fluorine-based solvent to be phase-separated or precipitated or agglomerated with the solvent, . ≪ / RTI >
The magnetic nanoparticle core of the present invention and a magnetic nanoparticle including a ligand shell containing a fluorocarbon-based or fluorocarbon-based carboxylic acid represented by the formula CF 3 - (CF 2 ) x - (CH 2 ) y -COOH Non-limiting examples of phosphorus-based solvents include fluorine-containing aromatic solvents, fluorine-containing cyclic carbonate solvents, fluorine-containing linear carbonate solvents, fluorine-containing ester solvents, fluorine-containing ether solvents, fluorine-containing nitrile solvents, (sulfur) based solvent, or a mixture thereof.
For example, the fluorine-containing aromatic solvent may be fluorobenzene, 1,2-difluorobenzene, 1,2,3-trifluorobenzene, 1,2,3,4-tetrafluorobenzene, pentafluorobenzene , Hexafluorobenzene, 2-fluorotoluene, alpha, alpha, alpha -trifluorotoluene, 3-fluorotoluene, 4-fluorotoluene, 2,3-difluorotoluene, Fluoro-o-xylene, 2-fluoro-m-xylene, 4-fluoro-m-xylene, and 2-fluoro-o- -Fluoro-p-xylene, or a mixture of two or more thereof.
For example, the fluorine-containing cyclic carbonate solvent may be at least one selected from the group consisting of fluoroethylene carbonate, difluoroethylene carbonate, trifluoroethylene carbonate, tetrafluoroethylene carbonate, 3,3,3-trifluoropropylene carbonate, and 1-fluoro Propylene carbonate, or a mixture of two or more thereof.
For example, the fluorine-containing linear carbonate solvent includes di (2,2,2-trifluoroethyl) carbonate, 2,2,2-trifluoroethyl methyl carbonate, fluoromethyl methyl carbonate, difluoromethyl methyl carbonate , Trifluoromethyl methyl carbonate, fluoromethyl ethyl carbonate, difluoromethyl ethyl carbonate, trifluoromethyl ethyl carbonate, and 1-fluoroethyl methyl carbonate, or two or more kinds selected from the group consisting of Lt; / RTI >
For example, the fluorine-containing ester-based solvent may be at least one selected from the group consisting of? -Fluoro-? -Butyrolactone,? -Fluoro-gamma -butyrolactone,?,? -Difluoro- Fluoro-gamma -valerolactone, alpha-alpha-difluoro-gamma -valerolactone, alpha -fluoro-gamma -valerolactone, δ-valerolactone, and β-fluoro-δ-valerolactone, or a mixture of two or more thereof.
Specifically, the fluorinated solvent may be at least one selected from the group consisting of polyfluoropolyether, hydrofluoroether, hydrofluorocarbon, and perfluorocarbon, but is not limited thereto. More specifically, hydrofluoroether, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4- (trifluoromethyl) pentane, or purple But are not limited to, peroxodisulfuron, peroxodisulfuron, peroxodisulfuron, peroxodisulfuron, peroxodisulfuron,
As described above, the magnetic nanoparticles are uniformly dispersed in a fluorine-based solvent and are not phase-separated or agglomerated, and the average particle size of the dispersed phase is maintained.
The fluorine-based solvent-soluble magnetic nanoparticles according to the present invention are prepared by dissolving a magnetic first nanoparticle coated with a fatty acid in an organic solvent and adding a fluorine-containing compound represented by the formula CF 3 - (CF 2 ) x - (CH 2 ) y -COOH A fluorine-based solvent containing a hydrocarbon-based or fluorocarbon-based carboxylic acid is added and reacted to produce a magnetic nanoparticle core and a fluorocarbon-based or fluorocarbon-based fluorocarbon represented by the formula CF 3 - (CF 2 ) x - (CH 2 ) y -COOH A first step of preparing a magnetic second nanoparticle comprising a ligand shell containing a carboxylic acid; And a second step of recovering the magnetic second nanoparticles transferred to the fluorine-based solvent layer. As described above, x is an integer of 0 to 10, y is an integer of 0 to 4, and x? Y.
For example, in the production method of the present invention, the first step may be carried out by additionally including a tertiary amine compound as a base molecule, but is not limited thereto. The base molecule can facilitate ligand substitution by deprotonating a fluorocarbon-based or fluorocarbon-based carboxylic acid acting as a ligand. The tertiary amine compound as the base molecule may be used in an amount of 0.5 to 5 times the molar amount of the fluorinated hydrocarbon-based or fluorinated carboxylic acid used as the ligand, but is not limited thereto. On the other hand, in the case of primary and secondary amines, the base molecule is preferably a tertiary amine since it adsorbs on the crystal surface and may interfere with the ligand substitution.
For example, in the manufacturing method of the present invention, non-limiting examples of the fatty acid coated on the magnetic first nanoparticle coated with the fatty acid in the first step include oleic acid, elaidic acid, eicosanic acid, erucic acid, nerubic acid, , Linoleic acid, gamma-linolenic acid, dihomo-gamma-linolenic acid, arachidonic acid, alpha-linolenic acid, eicosapentaenoic acid and docosahexaenoic acid Unsaturated fatty acids; But are not limited to, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, feraric acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, And saturated fatty acids such as acetic acid, citric acid, and the like.
For example, in the process of the present invention, the organic solvent used in the first step may be selected from the group consisting of chloroform, dichloromethane, C 1-4 alcohol, acetone, C 6-20 alkane, toluene, N, ≪ / RTI > and mixtures thereof.
In the production method of the present invention, the solvents exemplified in the first embodiment can be used without limitation as the fluorinated solvents.
For example, as the fluorinated solvent in the first step, those treated so as to reduce the amount of dissolved oxygen may be used.
The fluorinated solvent treated to reduce the amount of dissolved oxygen in the first stage may be prepared by bubbling an ordinary fluorinated solvent with an inert gas such as nitrogen or argon, but is not limited thereto.
For example, the magnetic second nanoparticles obtained from the second step have a particle size distribution similar to that of the magnetic first nanoparticles used as the reactant in the dispersion phase, that is, an average particle size within 15%, more preferably within 10% Lt; / RTI > This indicates that each individual nanoparticle is uniformly dispersed throughout the solvent.
For example, the magnetic second nanoparticles obtained from the second step may exhibit a change of 30% or less with respect to the average particle size immediately after preparation even after 100 days of storage as a dispersed phase. Generally, particles having low dispersibility with respect to a solvent may be phase-separated with a solvent over time in the solvent, aggregated between particles, and then precipitated. Therefore, the average particle size change in the solvent can serve as a measure of the dispersibility of the particles to the solvent. Therefore, even after 100 days of storage in a fluorine-based solvent such as 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4- (trifluoromethyl) Since the average particle size immediately after production is maintained, the production method according to the present invention can be utilized for producing magnetic nanoparticles having excellent dispersibility to fluorinated solvents.
In a specific embodiment of the present invention, the magnetic nanoparticles according to the present invention are dissolved in a fluorine-based solvent such as 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4- ( (Trifluoromethyl) pentane, it was confirmed that the particle size distribution was maintained at a level similar to that immediately after the preparation even after storage for 100 days or longer (FIGS. 4 and 5).
Particularly, the particles (Table 1) in which the original consumption of fluorine and carbon were remarkably increased with respect to iron by preparing a fluorine-based solvent with nitrogen bubbling during the first step of the ligand substitution reaction showed an average particle size and a dispersion state immediately after preparation It could last for more than 100 days at almost the same level.
Further, the present invention relates to a fluorine-based solvent; And a nanocolloid system including the magnetic nanoparticles according to the first aspect of the present invention dispersed in the fluorine-based solvent.
For example, the magnetic nanoparticles may be produced by a manufacturing method according to the second aspect of the present invention, but are not limited thereto.
The fluorinated solvent may be at least one selected from the group consisting of a fluorine-containing aromatic solvent, a fluorine-containing cyclic carbonate solvent, a fluorine-containing linear carbonate solvent, a fluorine-containing ester solvent, a fluorine-containing ether solvent, a fluorine-containing nitrile solvent, Can be used daily. Specific examples of the fluorine-based solvent are as described above.
In the nanocolloid system of the present invention, the change rate of the average particle size may be within 30% even after more than 100 days have elapsed.
For example, since the nanocolloid system of the present invention includes a nonflammable fluorinated solvent, it can be used for power generation using waste heat, but its application field is not limited thereto.
INDUSTRIAL APPLICABILITY The method for producing a fluorinated solvent-soluble magnetic nanoparticle of the present invention can remarkably improve the dispersibility and stability of a magnetic nanoparticle finally produced by a simple method using a fluorinated solvent in which the amount of dissolved oxygen is reduced in a ligand substitution reaction have.
FIG. 1 is a graph showing a method for preparing iron oxide nanoparticles having improved dispersibility in a fluorine-based solvent by ligand substitution according to the present invention and a phase transition behavior thereof. 2H, 2H, 3H, 3H-heptadecafluorodecanoic acid was used as an example of the ligand.
Fig. 2 is a diagram showing morphologies (A and B) and X-ray diffraction patterns (C) observed with TEM of the iron oxide nanoparticles before and after the ligand substitution. In FIG. 2C, OA-NCs represents iron oxide nanoparticles coated with oleic acid before substitution (Example 1), pF-NCs represents 2H2, 2H, 3H, 3H-heptadecafluorodecanoic acid Nanoparticles (Example 2).
Fig. 3 shows FT-IR spectra of iron oxide nanoparticles before and after ligand replacement. Fig.
FIG. 4 is a graph showing the average particle size of the finally prepared iron oxide nanoparticles according to the storage time of (A) the amount of dissolved oxygen in the fluorine-based solvent used for ligand replacement and (B) the dispersion state after 7 days of storage. The average particle size was measured using a dynamic light scattering method.
Fig. 5 is a graph showing the results of (A) iron oxide nanoparticles before ligand replacement dispersed in toluene; (B) immediately after the ligand substitution using a fluorine-based solvent in which the amount of dissolved oxygen is reduced by bubbling with nitrogen, and (C) 100 days after the storage of the iron oxide nanoparticles dispersed in the fluorine-based solvent.
FIG. 6 is a graph showing the results of the binding of iron oxide nanoparticles (B, N 2 -pF-NCs and C, air-pF-NCs) after ligand substitution (A, OA-NCs) and a ligand substitution using a fluorinated solvent bubbled with nitrogen or air, respectively FIG. 4 is a diagram showing the XPS O 1s spectrum of the oxygen and the binding energy and the component ratio of the constituent oxygen analyzed therefrom.
FIG. 7 is a graph showing the results of the measurement of iron oxide nanoparticles (B, N 2 -pF-NCs and C, air-pF-NCs) after ligand substitution (A, OA-NCs) and a fluorine-based solvent bubbled with nitrogen or air, respectively the XPS Fe 2p 3/2 is a diagram showing a binding energy and the component ratio of a configuration iron spectrometry and therefrom.
FIG. 8 shows a method for producing fluorine-based solvent-soluble iron oxide nanoparticles by ligand substitution using heptadecafluorononanoic acid as a ligand and a phase transition behavior therefor.
Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are for further illustrating the present invention, and the scope of the present invention is not limited by these examples.
Example 1: Iron oxide coated with oleic acid ( Fe 3 O 4 ) Preparation of nanoparticles
1.0 mmol of ion (III) oxide, hydrated, FeO (OH) and Sigma-Aldrich Inc.), 4.0 mmol of oleic acid (Sigma-Aldrich Inc.) octadecene, Sigma-Aldrich Inc.) and then replaced with an inert atmosphere. The reaction solution was heated to 320 ° C and reacted for 1 hour. The reaction solution was extracted with a chloroform / methanol mixed solvent (1: 1, v / v), excess acetone was added and centrifuged to precipitate iron oxide nanoparticles coated with oleic acid Respectively. The above chloroform / acetone mixed solvent was added and centrifugation was repeated three times to obtain iron oxide nanoparticles coated with purified oleic acid.
Example 2: 2H, 2H, 3H, 3H - To heptadecafluorodecanoic acid Preparation of Iron Oxide Nanoparticles Improved in Dispersion to Fluorine-Based Solvent by Ideal Ligand Substitution Reaction
The iron oxide nanoparticles coated with oleic acid prepared in Example 1 were dispersed in 5 mL of toluene at a concentration of 10 mg / mL, and 200 mg of 2H, 2H, 3H, 3H-heptadecafluorodecanoic acid (2H, 3 mL of perfluorodecalin (PFD, Alfa Aesar) mixed with 0.2 mL of triethylamine (Sigma-Aldrich Inc.) was added to a solution of 2-mercaptoethanol, 2H, 3H, 3H-heptadecafluoroundecanoic acid, Tokyo Chemical Industry Co., Lt; / RTI > The mixed solution was visually observed while stirring at 60 DEG C for 2 hours, and it was confirmed that the iron oxide nanoparticles dispersed in the initial toluene layer migrate to the perfluorodecalin layer (FIG. 1). Subsequently, the supernatant (toluene) was removed, and the permanent magnet was placed adjacent to the reactor to obtain iron oxide nanoparticles which were ligand-substituted with 2H, 2H, 3H, 3H-heptadecafluorodecanoic acid from the perfluorodecalin layer. The obtained iron oxide nanoparticles were purified by washing several times with toluene and perfluorodecalin to obtain 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4 - (trifluoromethyl) pentane (1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4- (trifluoromethyl) pentane, available from Tokyo Chemical Industry Co., Ltd. ) To prepare iron oxide nanoparticles dispersed in a fluorine-based solvent. The characteristics of the iron oxide nanoparticles as the reactant coated with oleic acid and the iron oxide nanoparticles substituted with 2H, 2H, 3H, 3H-heptadecafluorodecanoic acid were analyzed by TEM, XRD and FT-IR. 2 and 3. As shown in the TEM image of FIGS. 2A and 2B and the XRD pattern of FIG. 2C, it was confirmed that the crystal form and the crystal structure of the iron oxide nanoparticles before and after the ligand replacement remained unchanged. On the other hand, in the FT-IR spectra of the iron oxide nanoparticles after ligand substitution, as shown in Fig. 3, before that is a ligand substituted, hydrocarbon shown in the nano-particles coated with oleic acid peak (v as @ 2921 cm -1, v s @ 2850 cm - 1 ) showed the disappearance and absence of perfluorocarbon peaks (v as @ 1237 cm -1 and 1203 cm -1 , v s @ 1148 cm - 1 ).
Example 3: Preparation of Iron Oxide Nanoparticles Using Dissolved Oxygen Controlled Fluorinated Solvent
In order to confirm the effect of the dissolved oxygen amount in the fluorine-based solvent on the dispersibility of iron oxide nanoparticles coated with oleic acid and ligand substituted with 2H, 2H, 3H, 3H-heptadecafluorodecanoic acid, Two kinds of iron oxide nanoparticles were prepared by performing ligand substitution using perfluorodecalin bubbled in air as the fluorinated solvent of Example 2, respectively.
Example 4: Dispersion stability and surface element analysis according to dissolved oxygen amount in fluorinated solvent
In order to confirm the dispersion stability of the iron oxide nanoparticles having improved dispersibility with respect to the two kinds of fluorinated solvents obtained in Example 3, the average particle size was measured according to the storage time at room temperature using a dynamic light scattering method , And the results are shown in Fig. Specifically, the nanoparticle dispersed phase was prepared at a concentration of 10 mg / mL and diluted 10 times with the same solvent at the time of particle size measurement. The average particle size was measured every day for the first three days from the day immediately after manufacture (day 0) to one day (seven days), and from day to day afterwards, and the change was confirmed. As shown in FIG. 4, the iron oxide nanoparticles prepared by substituting the ligand with a nitrogen-bubbling fluorinated solvent having a relatively small amount of dissolved oxygen had an average particle size similar to that immediately after preparation even after storage for 7 days However, in the case of iron oxide nanoparticles prepared by substituting the ligand with an air-bubbling fluorinated solvent, not only the average particle size was large at the initial stage of storage but also the measured particle size deviations were very large. The average particle size increased accordingly. This indicates that the iron oxide nanoparticles prepared by ligand substitution in a fluorinating solvent containing a relatively large amount of dissolved oxygen may be unstably dispersed in the fluorinated solvent and agglomeration among the particles may occur over time. On the other hand, the iron oxide nanoparticles prepared using the nitrogen bubbling fluorinated solvent showed an average particle size and particle size distribution similar to that immediately after the preparation even after storage for 100 days after the production (FIG. 5).
Further, the surface iron consumption and the composition ratio of oxygen and iron were analyzed by X-ray photoelectron spectroscopy (XPS) on the iron oxide nanoparticles prepared by ligand substitution in the two fluorination solvents described in Example 3 The results are shown in Figs. 6 and 7 and Table 1 below.
† The irradiated areas are F 1s, Fe 2p, C 1s and O 1s, respectively.
‡ The N 2 / air ratio corresponds to the value of N 2 -pF-NCs divided by the value of air-pF-NCs.
The XPS analysis was carried out using an X-ray source of 24.5 W / 15 kV with a monochromator Al Ka (1486.6 eV) anode, and the spectrum was the C 1s binding energy of adventitious carbon (284.6 eV).
Example 5: To heptadecafluorononanoic acid Preparation of Iron Oxide Nanoparticles Improved in Dispersion to Fluorine-Based Solvent by Ideal Ligand Substitution Reaction
4 mL of N, N-dimethylformamide mixed with 2 g of heptadecafluorononanoic acid was bubbled with nitrogen in an ice water bath for 1 hour, and then an aqueous solution of an iron oxide nanoparticle dispersion solution coated with oleic acid (EFH-1, Ferrotec Corporation, USA) was added and reacted at 100 ° C for 24 hours. Then, 2 mL of 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4- (trifluoromethyl) pentane was added to the reaction solution to obtain a ligand It was confirmed that the substituted nanoparticles were dispersed in the added solvent layer and transitioned to phase (Fig. 8). The supernatant was separated from the layered reaction product, and the fluoric solvent layer was washed with N, N-dimethylformamide several times to obtain iron oxide nanoparticles substituted with heptadecafluorononanoic acid for ligand.
Claims (20)
X is an integer of 0 to 10, y is an integer of 0 to 4,
x < RTI ID = 0.0 > y. < / RTI >
Wherein the magnetic nanoparticles are ferromagnetic particles comprising a magnetic element selected from the group consisting of iron, nickel, and cobalt, or a compound containing the magnetic element.
The fluorohydrocarbon-based or fluorocarbon-based carboxylic acid 2H, 2H, 3H, 3H-heptadecafluorodecanoic acid or heptadecafluorononanoic acid.
The fluorinated solvent may be at least one selected from the group consisting of a fluorine-containing aromatic solvent, a fluorine-containing cyclic carbonate solvent, a fluorine-containing linear carbonate solvent, a fluorine-containing ester solvent, a fluorine-containing ether solvent, a fluorine-containing nitrile solvent, ≪ / RTI > and mixtures thereof.
Wherein the fluorine-based solvent is at least one selected from the group consisting of polyfluoropolyether, hydrofluoroether, hydrofluorocarbon, and perfluorocarbon.
Wherein the magnetic nanoparticles are uniformly dispersed in a fluorine-based solvent, are not phase-separated or aggregated, and maintain an average particle size in a dispersed phase.
And a second step of recovering the magnetic second nanoparticles moved to the fluorine-based solvent layer, the method comprising the steps of:
X is an integer of 0 to 10, y is an integer of 0 to 4,
x? y.
Wherein said first step is carried out further comprising a tertiary amine compound as a base molecule.
Wherein the organic solvent is selected from the group consisting of chloroform, dichloromethane, C 1-4 alcohol, acetone, C 6-20 alkane, toluene, N, N-dimethylformamide, and mixtures thereof.
The fluorinated solvent may be at least one selected from the group consisting of a fluorine-containing aromatic solvent, a fluorine-containing cyclic carbonate solvent, a fluorine-containing linear carbonate solvent, a fluorine-containing ester solvent, a fluorine-containing ether solvent, a fluorine-containing nitrile solvent, ≪ / RTI > and mixtures thereof.
Wherein the fluorine-based solvent is at least one selected from the group consisting of polyfluoropolyether, hydrofluoroether, hydrofluorocarbon, and perfluorocarbon.
Wherein the fluorinated solvent in the first step is treated so as to reduce the dissolved oxygen amount.
Wherein the fluorinated solvent in the first step is prepared by bubbling with an inert gas.
Wherein the magnetic second nanoparticles obtained from the second step have an average particle size varied within 15% with respect to the average particle size of the dispersed phase of the magnetic first nanoparticles in the dispersion phase.
Wherein the magnetic second nanoparticles obtained from the second step exhibit a change of 30% or less with respect to the average particle size immediately after preparation even after being stored in the dispersed phase for 100 days.
Wherein the magnetic nanoparticles are prepared according to any one of claims 7 to 15. 17. The nanocolloid system of claim 16,
The fluorinated solvent may be at least one selected from the group consisting of a fluorine-containing aromatic solvent, a fluorine-containing cyclic carbonate solvent, a fluorine-containing linear carbonate solvent, a fluorine-containing ester solvent, a fluorine-containing ether solvent, a fluorine-containing nitrile solvent, ≪ / RTI > and mixtures thereof.
Wherein the nanocolloid system has a change rate of an average particle size within 30% even after 100 days or more has elapsed.
Wherein the nanocolloid system is for power generation.
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| PCT/KR2017/003275 WO2018048048A1 (en) | 2016-09-09 | 2017-03-27 | Magnetic nano-particle having improved dispersibility in fluorine-based solvent and method for producing same |
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