KR101766958B1 - Method for pickering emulsion-based manufacture of non-spherical amphiphilic dimeric nanoparticles reversibly changing the interfacial properties with temperatures - Google Patents
Method for pickering emulsion-based manufacture of non-spherical amphiphilic dimeric nanoparticles reversibly changing the interfacial properties with temperatures Download PDFInfo
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- KR101766958B1 KR101766958B1 KR1020150094438A KR20150094438A KR101766958B1 KR 101766958 B1 KR101766958 B1 KR 101766958B1 KR 1020150094438 A KR1020150094438 A KR 1020150094438A KR 20150094438 A KR20150094438 A KR 20150094438A KR 101766958 B1 KR101766958 B1 KR 101766958B1
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- particles
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- nanoparticles
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
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- 229920001600 hydrophobic polymer Polymers 0.000 claims description 7
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 6
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 claims description 6
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- 238000004132 cross linking Methods 0.000 claims description 3
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 3
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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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/12—Powdering or granulating
- C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/245—Differential crosslinking of one polymer with one crosslinking type, e.g. surface crosslinking
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Graft Or Block Polymers (AREA)
Abstract
The present invention relates to a method for preparing non-spherical amphiphilic dimeric nanoparticles based on a Pickering emulsion without the use of a surfactant. Since the present invention does not use a surfactant, it can remarkably reduce human stimulation and toxicity, and can control the swelling time to control the size and shape of the particles to adjust the hydrophilic and hydrophobic properties of the particle surface. Spherical amphiphilic dimer nanoparticles can be provided.
According to the present invention, as the hydrophilic and hydrophobic characteristics of the particle surface reversibly change according to temperature, non-spherical amphiphilic dimeric nanoparticles capable of reversibly controlling the interface characteristics between liquid-liquid or liquid- .
The non-spherical amphiphilic dimeric nanoparticles prepared according to the present invention can be usefully used in an emulsion composition for maximizing drug delivery in the field of pharmaceutical cosmetics. Further, the wettability of the liquid to the solid substrate can be controlled by utilizing the property that the interface property can be reversibly adjusted according to the temperature in the electronic industry, thereby maximizing the efficiency of the lithography process for manufacturing semiconductor chips . In addition, it is possible to maximize the coating efficiency on the surface of the printing paper having various surface properties and the surface of the printer paper by being used in the ink for printer and the ink liquid composition for printer in the paint industry.
Description
The present invention relates to a method for preparing non-spherical amphiphilic dimeric nanoparticles, and more particularly to a method for preparing non-spherical amphiphilic dimeric nanoparticles based on Pickering emulsion without the use of a surfactant. will be. The non-spherical amphiphilic dimeric nanoparticles prepared according to the present invention are capable of reversibly controlling the interfacial properties depending on the temperature at the aqueous-oil-oil-aqueous-solid interface.
In the field of pharmaceuticals and cosmetics, various surfactants are used to stably disperse the oil composition of an emulsion system composed of water-oil. When the emulsion system is applied to the skin, the oil has an occlusive effect, which is applied to the skin interface to prevent evaporation of water present in the skin, and at the same time, it transmits a physiologically active ingredient and a drug, which are mixed with the oil component, to the skin . Surfactants control the size of oil particles and control the degree of oil absorption by controlling the interfacial energy between water and oil, in addition to stabilizing the oil in water. However, when an excessive amount of surfactant is used, the surfactant is also transferred to the skin, causing skin irritation and damage. To solve this problem, a surfactant composed of polymer particles was introduced. However, since a polymer surfactant composed of a single chemical component is highly hydrophobic or hydrophilic, it is insufficient to stabilize the interface between water and oil and has irreversibility depending on temperature. When denaturing such as particle agglomeration, it can no longer serve as a surfactant, so that there is a problem that it is difficult to manage. Therefore, although many techniques have been proposed to solve this problem, more researches are needed.
In the lithography process, which is the first step for manufacturing a semiconductor chip in the electronic industry, a photolithography technique based on a photosensitizer capable of responding to a light stimulus such as ultraviolet rays is currently utilized . In recent years, methods of patterning a substrate using various methods have been applied, such as soft lithography, a pattern using a block copolymer or nanoparticles, etc. For this purpose, have. However, when a substrate is patterned using an aqueous solution, if the surface property is hydrophobic, wetting is not ensured, which makes the process difficult.
Therefore, it is necessary to develop nanoparticles capable of transferring the nanoparticles dispersed in the aqueous solution to the substrate while controlling the interface energy between the aqueous solution and the hydrophobic substrate. In addition, there is a need for a technique capable of effectively coating the surface of painted and print paper having various surface properties in the ink and paint industry for printers, and further, there is a need for a technique for reversibly controlling the surface properties of water and the substrate It is necessary to develop a technique for controlling the wettability by using the properties.
Non-Patent
In addition,
Therefore, it is possible to regulate the size of the emulsion by controlling the interfacial characteristics acting on the water-oil phase in a reversible manner depending on the temperature without using the surfactant, and to control the interface characteristics between the solid substrate and the liquid having various surface properties It is necessary to develop non-spherical particles capable of controlling the wettability of the liquid to the solid substrate.
Accordingly, the present invention is to provide a method for preparing non-spherical amphiphilic dimeric nanoparticles that can adjust the interface characteristics reversibly based on Pickering emulsion without using a surfactant.
In order to solve the above problems,
(a) preparing a solution in which seed particles are formed by adding a hydrophobic monomer, an ionic initiator and a crosslinking agent to an aqueous solution containing cyclodextrin;
(b) adding a solution in which the seed particles are formed to an aqueous solution containing a hydrophilic monomer and an ionic initiator to prepare a solution in which the first particles of the core-shell structure are formed;
(c) further adding a hydrophobic monomer to the solution in which the first particles are formed, followed by stirring to swell the first particles;
(d) re-swelling the first particles by heating and re-crosslinking at 25 to 100 ° C after step (c); And
(e) adding a radical initiator after the re-swelling to polymerize the hydrophobic monomer added in the step (c)
Wherein the hydrophobic monomer is polymerized to form a second particle protruding from a point of the first particle, wherein the second particle protrudes from one point of the first particle, and the interface energy of the non-spherical amphiphilic dimer is reversibly adjusted according to temperature. to provide.
The first particle of the core-shell structure includes a core made of a hydrophobic polymer and a hydrophilic polymer surrounding the core, wherein the surface property of the first particle is hydrophilic and the surface characteristic of the second particle is hydrophobic . Further, the interface energy between the surface of the first particle and water is reversibly increased or decreased depending on the temperature.
According to an embodiment of the present invention, the step (c) may be performed at 10 to 40 ° C for 10 to 30 hours.
According to another embodiment of the present invention, the size of the first particle increases and the size of the second particle decreases as the re-swelling time of step (d) increases.
According to another embodiment of the present invention, the hydrophobic monomer is selected from the group consisting of styrene, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl betacrylate, pentyl acrylate, pentyl methacrylate, Methyl methacrylate, and dile methacrylate.
According to another embodiment of the present invention, the hydrophilic monomer may be at least one selected from N-isopropylacrylamide, methacrylic acid, methacrylate, allylamine and ethylene glycol methacrylate.
According to another embodiment of the present invention, the cyclodextrin is selected from the group consisting of methyl-β-cyclo dextrin, β-cyclodextrin, 2,6-dimethyl-β-cyclodextrin Cyclodextrin, 2,6-dimethyl-β-cyclodextrin, and sodium sulphobutyl ether-β-cyclodextrin.
According to another embodiment of the present invention, the ionic initiator may be at least one selected from potassium peroxodisulfate (KPS), ammonium persulfate (APS) and sodium persulfate (SPS).
According to another embodiment of the present invention, the radical initiator is selected from the group consisting of 2,2-azobisisobutyronitrile (AIBN), 2,2-azobis (2-methylisobutyronitrile) (2,4-dimethylvaleronitrile), benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, t-butyl hydroperoxide, o-chlorobenzoyl peroxide, o- Benzoyl peroxide, t-butyl peroxy-2-ethyl hexanoate, t-butyl peroxyisobutyrate, and mixtures thereof.
The present invention can produce non-spherical amphiphilic dimeric nanoparticles without the use of a surfactant. As a result, it is possible to greatly reduce the human stimulation and toxicity, and to control the size and shape of particles by controlling the swelling time It is possible to provide non-spherical amphiphilic dimeric nanoparticles whose hydrophilicity and hydrophobic properties of the particle surface can be controlled. According to the present invention, as the hydrophilic and hydrophobic characteristics of the particle surface reversibly change according to temperature, non-spherical amphiphilic dimeric nanoparticles capable of reversibly controlling the interface characteristics between liquid-liquid or liquid- .
Thus, the non-spherical amphiphilic dimeric nanoparticles prepared according to the present invention can be usefully used in an emulsion composition for maximizing drug delivery in the field of pharmaceutical cosmetics. Further, the wettability of the liquid to the solid substrate can be controlled by utilizing the property that the interface property can be reversibly adjusted according to the temperature in the electronic industry, thereby maximizing the efficiency of the lithography process for manufacturing semiconductor chips . In addition, it is possible to maximize the coating efficiency on the surface of the printing paper having various surface properties and the surface of the printer paper by being used in the ink for printer and the ink liquid composition for printer in the paint industry.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1A is a cross-sectional view of non-spherical amphiphilic dimeric nanoparticles prepared according to the present invention. FIG.
FIG. 1B is a schematic view showing the process for preparing the non-spherical amphiphilic dimeric nanoparticles according to the present invention and the characteristics of the non-spherical amphiphilic dimeric nanoparticles.
2A is an SEM image of polystyrene seed particles (PS), and FIG. 2B is an SEM image of Pnipaam-co-MA-coated polystyrene nanoparticles (Core-shell).
FIG. 3 (a) is a graph showing changes in particle diameter (hydrodynamic diameter) according to temperature changes of polystyrene nanoparticles (PS) and hydrophilic polymer-coated polystyrene nanoparticles (core-shell) The graph shows the change in potential (zeta potential).
FIG. 4 is a schematic view showing a process of forming a Pickering emulsion by adding a polystyrene monomer to a solution in which a hydrophilic polymer-coated polystyrene nanoparticle (core-shell) is formed, and stirring the solution to form a Pickering emulsion. ).
FIG. 5 is a cross-sectional view schematically showing a process of forming a Pickering emulsion according to an embodiment of the present invention and a change in size of a pickling emulsion with stirring time. FIG.
FIG. 6 is a graph showing the size change of picking emulsion formed according to an embodiment of the present invention with agitation time. FIG.
7 is an optical microscope image showing the formation mechanism of the non-spherical amphiphilic dimeric nanoparticles according to the present invention, wherein ac is a hydrophilic polymer-coated polystyrene nanoparticle (Core-shell) dispersion (A: stirring at room temperature for 11 hours, b: heating at 80 占 폚, re-stirring and 10 minutes after the addition of AIBN, c: heating at 80 占 폚, re-stirring and AIBN input (D: heating immediately after homogenization at room temperature, e: heating at 80 DEG C, f: heating at 80 DEG C, re-stirring and injection of AIBN) 20 minutes after heating, g: heating at 80 DEG C, re-stirring, and 4 hours after injection of AIBN).
8 is an SEM image of non-spherical amphiphilic dimeric nanoparticles prepared according to the present invention.
FIG. 9 is a graph showing the swelling time (a: 0 h, b: 1 h, c: 2 h, d: 6 h, 24h) of the particles.
FIG. 10 is a graph showing changes in swelling time (a: 0 h, b: 1 h, c: 2 h, d: 6 h, 24h). Fig.
FIG. 11 is a graph showing the relationship between the non-spherical amphiphilic dimeric nanoparticles according to the present invention and the non-spherical amphiphilic dimeric nanoparticles synthesized after adsorbing the fluorescent dye to the first particles of the core- , An image taken with a Confocal microscope, and images taken with a confocal microscope after re-adsorption of fluorescent dyes after synthesis.
12A is a graph showing the results of measurement of the particle diameter of polystyrene nanoparticles (PS), polystyrene nanoparticles coated with a hydrophilic polymer (Core-shell), non-spherical amphiphilic dimeric nanoparticles (0h, 6h, 18h ) And poly (N-isopropylacrylamide) hydrated gel nanoparticles (FL Intensity).
Fig. 12B is a graph showing the results obtained by measuring the average particle diameter of polystyrene nanoparticles (PS), polystyrene nanoparticles coated with a hydrophilic polymer (Core-shell), non-spherical amphiphilic dimeric nanoparticles (0h, 1h, 2h (Diameter at room temperature (RT) - diameter at 50 占 폚) according to the temperature change of the particles (6h, 12h, 24h).
Fig. 12C is a graph showing the results of measurement of the particle size distribution of polystyrene nanoparticles (PS), polystyrene nanoparticles coated with a hydrophilic polymer (core-shell), non-spherical amphiphilic dimeric nanoparticles (0h, 1h, 2h (The zeta potential at room temperature (RT) - the zeta potential at 50 deg. C) according to the temperature change of the substrate, 6h, 12h, 24h.
FIG. 13 is a graph showing changes in the size of emulsion (a: room temperature (RT), b (b), and the like) of a solution prepared by mixing an unsulfurized amphiphilic dimeric nano- : 30 占 폚, c: 35 占 폚, d: 40 占 폚, and e: 45 占 폚 f: 50 占 폚) using an optical microscope.
FIG. 14 is a graph showing changes in emulsion size (a: room temperature (RT), b: volume average particle size) of a solution obtained by mixing an unsulfurized amphiphilic nanoparticle dispersed nanoparticle dispersion solution and
FIG. 15 is a graph showing changes in size of an emulsion during repeated cooling of a solution prepared by mixing a dispersion solution of non-spherical amphiphilic dimeric nanoparticles prepared according to an embodiment of the present invention and silicone oil (DC 200) Is photographed with an optical microscope.
16 is a graph showing a change in size of an emulsion due to repeated cooling of a solution prepared by mixing a dispersion solution of non-spherical amphiphilic dimeric nanoparticles prepared according to an embodiment of the present invention and silicone oil (DC 200) Fig.
17A is an image showing the contact angle of a non-spherical amphiphilic dimer nanoparticle (Dimer) dispersion solution prepared according to an embodiment of the present invention on a polystyrene film surface at room temperature (25 DEG C) and at 50 DEG C, to be.
FIG. 17B shows a cross-sectional view of an embodiment of the present invention in which water, polystyrene nanoparticles (PS), polystyrene nanoparticles coated with a hydrophilic polymer (Core-shell, CS) at room temperature (25 DEG C) 2 is a graph showing the contact angle of the non-spherical amphiphilic dimer nanoparticle (Dimer) dispersion solution with respect to the polystyrene film surface.
18A is a graph showing the results of a comparison of the surface of a polydimethylsiloxane (PDMS) film surface of a non-spherical amphiphilic dimer nanoparticle (Dimer) dispersion solution prepared according to an embodiment of the present invention, at room temperature (25 DEG C) And the contact angle with respect to the contact angle.
FIG. 18B shows a cross-sectional view of an embodiment of the present invention in which water, polystyrene nanoparticles (PS), polystyrene nanoparticles coated with a hydrophilic polymer (Core-shell, CS) at room temperature (25 DEG C) (PDMS) film surface of a non-spherical amphiphilic dimer nanoparticle (Dimer) dispersion solution.
Hereinafter, the present invention will be described in more detail.
In order to overcome various problems that may occur depending on the use of surfactants in an emulsion system comprising water-oil, attempts have been made to prepare emulsions using polymer particles. However, most of the polymer particles have hydrophobicity, The surfactant force of the surfactant is remarkably lowered.
Thus, in recent years, studies have been conducted to prepare dimer particles, impart hydrophilicity to one particle, and increase hydrophobicity to one particle to increase the surfactant activity.
However, the surfactant is inevitably used in the preparation of the dimer particles so far developed, and there is a fear that the toxicity may cause stimulation to the human body and the interface characteristics may be reduced. In addition, until now, the preparation of particles capable of controlling the size and oil function of oil dispersed in water has not been developed by reversibly adjusting the surfactant power between water and oil according to temperature, and has various surface properties There has been no development of a technique for controlling the wettability of the substrate or controlling the patterning of the particles on the substrate by using the particles capable of reversibly adjusting the surface properties of water and the substrate on the substrate with the temperature and properties thereof.
Accordingly, the present inventors have found that it is possible to effectively control interfacial characteristics such as interfacial energy or interfacial tension between a liquid and a liquid or between a liquid and a solid, and more particularly to a method of reversibly adjusting interfacial properties between water and oil, The size of the oil and the function of the oil can be controlled and the interfacial characteristics of the water and the substrate can be reversibly controlled according to the temperature so that the wettability of the substrate can be controlled or the shape of the patterning of the particles on the substrate can be controlled. To provide a method for producing amphiphilic dimeric nanoparticles.
In addition, the production method according to the present invention can produce non-spherical amphiphilic dimeric nanoparticles without using a surfactant, thereby greatly reducing the human stimulation and toxicity, and can also control the swelling time The hydrophilic and hydrophobic properties of the particle surface can be controlled by controlling the size and shape of the particles.
1A is a cross-sectional view of non-spherical amphiphilic dimeric nanoparticles prepared according to the present invention.
The non-spherical amphiphilic dimeric nanoparticle according to the present invention is composed of a first particle and a second particle, and is capable of reversibly adjusting the interfacial energy with water according to the temperature. Further, in the non-spherical amphiphilic dimeric nanoparticle according to the present invention, the first particle is a core-shell structure including a core made of a hydrophobic polymer and a shell made of a hydrophilic polymer surrounding the core And the second particle is formed by protruding a hydrophobic polymer constituting the core from a point of the first particle, and the second particle is partially in contact with the first particle at the one point. In addition, the first particle second particles which are in contact with each other are phase-separated without being mixed with each other.
In the non-spherical amphiphilic dimeric nanoparticles according to the present invention, the first particle has a surface property hydrophilic and the second particle has a surface property hydrophobic, so that an amphipatic characteristic is realized. Here, the surface of the first particle has a hydrophilic property, but the hydrophobic property changes as the temperature increases. Particularly, the change of the surface hydrophilic property and the hydrophobic property is reversible according to the temperature change.
As shown in FIG. 1B, the surface energy of the first particle of the non-spherical amphiphilic dimeric nanoparticle prepared according to the present invention at room temperature (RT) is low at the interface energy (γ pw ) with water, (Γ pw ) of the interface is increased, and this characteristic has a reversibility that the interface energy (γ pw ) with water is lowered when the temperature is further lowered to room temperature. That is, the interface energy between the surface of the first particle of the non-spherical amphiphilic dimeric nanoparticles prepared according to the present invention and water reversibly increases or decreases according to the temperature.
Hereinafter, a method of producing an amorphous amorphous dimer having the above-described characteristics will be described in more detail with reference to drawings and Examples.
FIG. 1B shows the method of preparing non-spherical amphiphilic dimeric nanoparticles according to the present invention and the method of preparing non-spherical amphiphilic dimeric nanoparticles according to the present invention. .
(a) preparing a solution in which seed particles are formed by adding a hydrophobic monomer, an ionic initiator and a crosslinking agent to an aqueous solution containing cyclodextrin;
(b) adding a solution in which the seed particles are formed to an aqueous solution containing a hydrophilic monomer and an ionic initiator to prepare a solution in which the first particles of the core-shell structure are formed;
(c) further adding a hydrophobic monomer to the solution in which the first particles are formed, followed by stirring to swell the first particles;
(d) re-swelling the first particles by heating and re-crosslinking at 25 to 100 ° C after step (c); And
(e) adding a radical initiator after the re-swelling to polymerize the hydrophobic monomer added in the step (c).
At this time, as the hydrophobic monomer added in the step (c) is polymerized, second particles protruding from one point of the first particles are formed, and non-spherical particles are formed as a whole.
First, in step (a), a hydrophobic monomer, an ionic initiator and a crosslinking agent are added to an aqueous solution containing cyclodextrin to prepare a solution in which seed particles are formed. Thereafter, in step (b), a solution in which the seed particles are formed and an ionic initiator are added to an aqueous solution containing the hydrophilic monomer to prepare a solution having the first particles of the core-shell structure.
Wherein the first particle of the core-shell structure comprises a core comprising a hydrophobic polymer and a hydrophilic polymer surrounding the core, wherein the surface characteristics of the first particle are hydrophilic and the surface characteristics of the second particle are hydrophobic . 2A is an SEM image of the polystyrene seed particles (PS) prepared in the step (a) according to an embodiment of the present invention, and FIG. 2B is a SEM image of the polystyrene seed particles (PS) prepared by the step (b) coated with Pnipaam- SEM image of polystyrene nanoparticles (Core-shell). As can be seen from FIGS. 3A and 3B, the polystyrene seed particles (PS) prepared through the step (a) have almost no change in particle diameter and zeta potential with temperature change, The Pnipaam-co-MA-coated polystyrene nanoparticles (core-shell) prepared by the above step are susceptible to solubility in water as the temperature increases due to the temperature sensitivity of Pnipaam-co-MA coated on the seed particles The phase separation causes the particle size to decrease through contraction, and the zeta potential and the negative property become higher.
Next, in the step (c), a hydrophobic monomer is further added to the solution in which the first particles are formed, followed by stirring to swell the first particles. At this time, according to a preferred embodiment of the present invention, the step (c) is preferably performed at 10 to 40 ° C for 10 to 30 hours. As shown in FIG. 5, when the hydrophobic monomer is added and then stirred to swell the first particles, the first particles of the core-shell structure surround the added hydrophobic monomer to form a picking emulsion As shown in FIGS. 4 and 6, it can be confirmed that the size of the pickling emulsion gradually decreases with agitation time. This is because when the first particles are swollen, the added hydrophobic monomers are dispersed in the first particles Or that the pickling emulsion splits to form a smaller sized pickling emulsion. The amount of the hydrophobic monomer to be added may be 5 to 15 times, preferably 7 to 11 times, based on the hydrophobic monomer used in the step (a).
Next, in the step (d), the step (c) is followed by heating and re-coating at 25 to 100 ° C to re-swell the first particles. At this time, as the re-swelling time of the first particle through the re-stirring is increased, the size of the first particle of the core-shell structure of the produced non-spherical amphiphilic dimeric nanoparticles is increased, while the size of the second particle is decreased (FIG. 9 and FIG. 10). In the present invention, the swelling time of the step (d) is controlled to adjust the size and shape of the particles, Lt; / RTI > and hydrophobic and hydrophobic properties thereof. In addition, the higher the temperature within the above-mentioned temperature range, the faster the size of the first particles of the core-shell structure becomes within a short time, and the re-swelling time for controlling the shape closer to spherical shape is relatively shortened On the other hand, the lower the temperature, the larger the size of the first particle of the core-shell structure becomes, and the more the swelling time is required to adjust to the shape close to the spherical shape.
Next, in the step (e), a radical initiator is added to polymerize the hydrophobic monomer added through the step (c). At this time, the added hydrophobic monomer is polymerized, The protruded second particles are formed, and the non-spherical amphiphilic dimer particles according to the present invention are formed as a whole.
According to a preferred embodiment of the present invention, the hydrophobic monomer is selected from the group consisting of styrene, methyl acrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl betacrylate, pentyl acrylate, pentyl methacrylate, glycidyl methacrylate It is preferable to use at least one member selected from the group consisting of acrylate and acrylate.
According to a preferred embodiment of the present invention, it is preferable that the hydrophilic monomer is at least one selected from N-isopropylacrylamide, methacrylic acid, methacrylate, allylamine and ethylene glycol methacrylate.
According to a preferred embodiment of the present invention, the cyclodextrin is selected from the group consisting of methyl- beta -cyclo dextrin, beta -cyclodextrin, 2,6-dimethyl- beta -
According to a preferred embodiment of the present invention, the ionic initiator is preferably at least one selected from potassium peroxodisulfate (KPS), ammonium persulfate (APS) and sodium persulfate (SPS).
According to a preferred embodiment of the present invention, the radical initiator is selected from the group consisting of 2,2-azobisisobutyronitrile (AIBN), 2,2-azobis (2-methylisobutyronitrile), 2,2-
Hereinafter, the present invention will be described in more detail with reference to preferred embodiments and the like. It will be apparent to those skilled in the art, however, that these examples are provided for further illustrating the present invention and that the scope of the present invention is not limited thereto.
<Examples>
Example 1.
(1) Preparation of polystyrene seed particle dispersion solution
A 250 ml flask was immersed in an oil reaction vessel at 80 ° C and an aqueous solution of 1 wt% methyl- beta -cyclodextrin (M- beta -CD) was added thereto while heating to 80 ° C, and potassium peroxodisulfate (KPS ) Initiator. 0.4 g of a crosslinking agent divinylbenzene (DVB) and 5.6 g of a styrene monomer were added to the flask at a constant rate for 2 hours through a syringe pump while stirring. After the crosslinking agent and the monomer were all put in, the solution was stirred for 1 hour and then cooled to prepare a solution in which polystyrene seed particles were dispersed.
(2) Coating of NIPAAm-co-MA copolymer high molecular material
A 250 ml flask was immersed in an oil reaction vessel at 80 ° C and a solution containing 90:10 mol% of N-isopropylacrylamide (NIPAAm) monomer and methacrylic acid (MA) monomer in 40 ml of distilled water I put it. Next, 15 ml of the polystyrene seed particles-dispersed solution was added and heated to 80 DEG C, followed by addition of potassium peroxodisulphate (KPS) initiator and reaction for 2 hours and 30 minutes to obtain NIPAAm and MA (First particles) dispersed in a solution of a polystyrene seed particle coated with a copolymer composed of the above-mentioned polystyrene seed particles (first particles).
(3) Production of non-spherical amphiphilic dimeric nanoparticles according to the present invention
3.5 ml of a dispersion of polystyrene seed particles (first particle) coated with a copolymer of NIPAAm and MA in the core-shell structure and 4 ml of distilled water were placed in a beaker, 50.4 g of styrene monomer was added, and 12 The swollen polystyrene seed particles coated with the copolymer consisting of NIPAAm and MA were swollen with stirring for a period of time. The beaker was immersed in an oil reaction vessel at 80 캜 and heated to 80 캜 and stirred again for 0 hours, 1 hour, 2 hours, 6 hours, 18 hours and 24 hours while the copolymer consisting of NIPAAm and MA was coated And the resulting polystyrene seed particles were re-swollen. Thereafter, an azobisisobutylonitrile (AIBN) initiator was added and reacted for 4 hours and 30 minutes to polymerize the styrene monomer, thereby preparing a solution in which the non-spherical amphiphilic dimer was dispersed.
<Experimental Example>
Experimental Example 1. Confirmation of formation mechanism of non-spherical amphiphilic dimeric nanoparticles
Experiments were conducted to confirm the formation mechanism of the non-spherical amphiphilic dimeric nanoparticles according to the present invention.
First, the change of the pickling emulsion after injecting styrene monomer into a polystyrene seed particle (first particle) dispersion solution coated with a copolymer of NIPAAm and MA in a core-shell structure was observed with an optical microscope, The results are shown in the ac of FIG. 7 (a: stirring at room temperature for 11 hours, b: heating at 80 占 폚, re-stirring and 10 minutes after the addition of AIBN, c: heating at 80 占 폚, Results after 20 minutes). Referring to FIG. 7, as the reaction progresses, it can be seen that the injected styrene monomer enters into the first particle of the swollen core-shell structure or the size of the emulsion gradually decreases as the pickering emulsion splits to form a smaller size emulsion This means that the non-spherical amphiphilic dimeric nanoparticles according to the present invention are formed. This means that the non-spherical amphiphilic dimeric nanoparticles can be prepared without using a surfactant according to the preparation method of the present invention. .
Next, the styrene monomer was injected into the distilled water and homogenized. The change of the emulsion was observed with an optical microscope. The results are shown in dg of FIG. 7 (d: immediately after homogenization at room temperature, e: f: heating at 80 占 폚, re-stirring and 20 minutes after the addition of AIBN, g: heating at 80 占 폚, re-stirring and 4 hours after the addition of AIBN). Referring to dg in FIG. 8, the size of the emulsion gradually decreases with the progress of the reaction, suggesting that polystyrene nanoparticles can be synthesized even without a surfactant.
Experimental Example 2. Confirmation of amphipathy of non-spherical amphotropic dimer particles
In order to confirm the amphipathic nature of the non-spherical amphiphilic dimeric nanoparticles according to the present invention, a polystyrene seed particle (first particle) coated with a core-shell structure copolymer of NIPAAm and MA was adsorbed with a fluorescent dye Then, the styrene monomer was added to proceed the reaction. The non-spherical amphiphilic dimeric nanoparticles were synthesized. SEM images, images obtained by confocal microscopy, and fluorescent dyes after synthesis were reabsorbed and then confocal microscopy (Confocal microscope). The results are shown in FIG. 11. FIG.
As shown in FIG. 11, it can be confirmed that non-spherical amphiphilic dimeric nanoparticles were formed through SEM images after synthesis. Immediately after the synthesis, the confocal microscope image showed circular fluorescence while the fluorescence dye adsorption showed non-spherical fluorescence, indicating that the copolymer composed of coated NIPAAm and MA was only present on the surface of the first particle As a result, the dimeric nanoparticles according to the present invention are characterized in that the first particles of the core-shell structure having the hydrophilic surface characteristics and the second particles of the core- Particles, that is, amphipathic characteristics.
Experimental Example 3. Measurement of particle size and morphological change according to the regeneration time, measurement of fluorescence intensity, change in particle size and zeta potential
(1) Observation of particle size and morphological change according to re-swelling time
B: 1h, c: 2h, d: 6h, e: 18h, h: 1h) in the process of re-swelling the first particles of the core-shell structure at 80 ° C according to the embodiment of the present invention. : 24h). The results are shown in FIG. 9 (SEM) and FIG. 10 (graph).
As shown in FIGS. 9 and 10, as the re-swelling time increases, the area of the first particle of the core-shell structure coated with the hydrophilic polymer increases, while the area of the second particle composed of the hydrophobic polymer decreases, , Which means that the hydrophilicity and the hydrophobic property of the particle surface, that is, the amphipathy can be controlled by controlling the size and shape of the particle by controlling the swelling time.
(2) Fluorescence intensity (FL intensity) measurement
In order to confirm the amphipathic nature of the non-spherical amphiphilic dimeric nanoparticles according to the present invention, it was confirmed that the amphiphilic nature of the nanoparticles of polystyrene nanoparticles (PS), core-shell structure of the core-shell structure, Methylene blue (MB) adsorbed on non-spherical amphiphilic dimeric nanoparticles (0h, 6h, 18h) and poly (N-isopropylacrylamide) The fluorescence intensity (FL Intensity) at the excitation wavelength was measured. The results are shown in FIG. 12A.
As can be seen from the results shown in FIG. 12A, it can be seen that the peak of polystyrene nanoparticles is the highest and the peak of poly (N-isopropylacrylamide) hydrated gel nanoparticles is the lowest. This is due to the physical properties of the polystyrene nanoparticles and poly (N-isopropylacrylamide), and the polystyrene nanoparticles have relatively hard properties so that the dye is adsorbed on the surface of the particles, Poly (N-isopropylacrylamide) has soft properties, so that the dye is adsorbed inside the particles and most of the light is transmitted A peak will appear. As the non-spherical amphiphilic dimeric nanoparticles according to the present invention show a decrease in peaks as the re-swelling time increases, it is considered that as the re-swelling time increases, the first particles of the core- While the area of the second particle composed of the hydrophobic polymer increases the reduced particle size. As a result, the non-spherical amphiphilic dimeric nanoparticles according to the present invention have an amphipathic characteristic and can control the hydrophilic and hydrophobic characteristics, i.e., the amphipathic nature, of the particle surface by controlling the size and shape of the particles by controlling the swelling time . It also implies that the amphipathic regulation can control the physicochemical properties of the particles, including the surface properties of the dimer, in particular the softness.
(3) Measurement of particle diameter and zeta potential change with temperature change
In order to confirm the amphipathic nature of the non-spherical amphiphilic dimeric nanoparticles according to the present invention, it was confirmed that the amphiphilic nature of the nanoparticles of polystyrene nanoparticles (PS), core-shell structure of the core-shell structure, The change in the hydrodynamic diameter with the temperature change of the non-spherical amphiphilic dimeric nanoparticles (0h, 1h, 2h, 6h, 12h, 24h) according to the invention (diameter at room temperature (RT) Diameter and zeta potential (zeta potential at room temperature (RT) - zeta potential at 50 deg. C) were measured. The results are shown in Figs. 12B and 12C.
As shown in FIG. 12A, the polystyrene nanoparticles have almost no difference in particle diameter and zeta potential according to the temperature change. On the other hand, in the case of the core-shell structure of the core-shell structure, The difference in diameters and zeta potentials was very large, which is a result of the temperature sensitivity of the copolymer consisting of coated hydrophilic polymers NIPAAm and MA. In addition, the non-spherical amphiphilic dimeric nanoparticles according to the present invention have intermediate values between the polystyrene nanoparticles and the core-shell, which indicates that the non-spherical amphiphilic dimeric nanoparticles according to the present invention have amphiphilic characteristics Which means that the size and shape may vary with temperature and thus the physicochemical properties of the particles change.
Experimental Example 4. Measurement of size of emulsion containing non-spherical amphiphilic dimer and determination of reversibility according to temperature change
13 to 16 are diagrams showing the results obtained by mixing the non-spherical amphiphilic dimeric nano-particle dispersion solution prepared according to the example of the present invention (re-swelling time is 0 h) and silicone oil (DC 200) at a volume ratio of 9.9: 0.1 An image and a graph showing changes in emulsion size with the temperature of the solution using an optical microscope.
As shown in FIGS. 13 to 14, when the temperature is increased from room temperature to 50 DEG C, the size of the emulsion is reduced from approximately 10 mu m to 4 mu m. This is because a smaller number of dimers emulsion To form a large number of small emulsions.
15 to 16, it can be seen that when the temperature is cooled to room temperature and the heating is repeated at 50 DEG C, the size of the emulsion reversibly increases and becomes smaller. As a result, it can be seen that the non- The amphiphilic dimer nanoparticles can change their physico-chemical properties depending on the temperature. As a result, the interface characteristics can be reversibly controlled according to the temperature, and it can be confirmed that the size of the emulsion can be reversibly changed according to the temperature.
Experimental Example 5. Contact Angle Measurement
The non-spherical amphiphilic dimer nanoparticle dispersion solution, water, polystyrene (PS) dispersion solution prepared according to the embodiment of the present invention (re-swelling time is 0 h), the first The contact angle with the temperature at the hydrophobic surface of the particles (CS) was measured.
17A is an image showing the contact angle of a non-spherical amphiphilic dimer nanoparticle (Dimer) dispersion solution prepared according to an embodiment of the present invention on a polystyrene film surface at room temperature (25 DEG C) and at 50 DEG C, 17B is a cross-sectional view of the core-shell (CS) coated with water, polystyrene nanoparticles (PS), hydrophilic polymer at room temperature (25 DEG C) and 50 DEG C, FIG. 5 is a graph showing the contact angle of the prepared non-spherical amphiphilic dimeric nanoparticle (Dimer) dispersion solution on the polystyrene film surface.
18A is a graph showing the results of a comparison of the surface of a polydimethylsiloxane (PDMS) film surface of a non-spherical amphiphilic dimer nanoparticle (Dimer) dispersion solution prepared according to an embodiment of the present invention, at room temperature (25 DEG C) FIG. 18B is an image showing the contact angle with respect to the contact angle with respect to water, water, polystyrene nanoparticles (PS), polystyrene nanoparticles coated with a hydrophilic polymer (Core-shell, CS) 2 is a graph showing the contact angle of a non-spherical amphiphilic dimeric nanoparticle (Dimer) dispersion solution prepared according to an embodiment of the present invention with respect to the surface of a polydimethylsiloxane (PDMS) film.
As shown in FIGS. 17A to 18B, it can be seen that the difference in the contact angle with temperature is large in the first particle (CS) of the core-shell structure and the non-spherical amphiphilic dimeric nanoparticle dispersion solution according to the present invention. This is because, unlike water molecules and polystyrene, the first particles (CS) of the core-shell structure and the non-spherical amphiphilic dimeric nanoparticles according to the present invention have a temperature-sensitive hydrophilic polymer surface, and the dimer of the present invention has a temperature Because they form emulsions of different sizes. Specifically, since a large number of dimers gather at a room temperature (RT) to form an emulsion, the contact angle with the interface becomes large as the size of the emulsion increases. On the other hand, at 50 ° C, a small number of dimers are gathered to form an emulsion. And the contact angle with the interface becomes smaller.
As a result, the non-spherical amphiphilic dimeric nanoparticles prepared according to the present invention change physico-chemical properties depending on the temperature, and consequently the interface characteristics can be reversibly controlled according to the temperature, Can be controlled.
Claims (10)
(b) adding a solution in which the seed particles are formed to an aqueous solution containing a hydrophilic monomer and an ionic initiator to prepare a solution in which the first particles of the core-shell structure are formed;
(c) further adding a hydrophobic monomer to the solution in which the first particles are formed, followed by stirring to swell the first particles;
(d) re-swelling the first particles by heating and re-crosslinking at 25 to 100 ° C after step (c); And
(e) adding a radical initiator after the re-swelling to polymerize the hydrophobic monomer added in the step (c)
Characterized in that the hydrophobic monomer is polymerized to form a second particle protruding from a point of the first particle,
Wherein the hydrophobic monomer is styrene,
Wherein the ionic initiator is at least one selected from potassium peroxodisulfate (KPS), ammonium persulfate (APS), and sodium persulfate (SPS)
Wherein the hydrophilic monomer is at least one selected from the group consisting of N-isopropylacrylamide, methacrylic acid, allylamine, and ethylene glycol methacrylate. The non-spherical amphipathic A method for producing dimeric nanoparticles.
Wherein the first particle of the core-shell structure comprises a core made of a hydrophobic polymer and a hydrophilic polymer surrounding the core,
Wherein the surface characteristics of the first particles are hydrophilic and the surface characteristics of the second particles are hydrophobic.
Wherein the interfacial energy between the first particle surface and water is reversibly increased or decreased according to the temperature of the nanoparticles.
Wherein the step (c) is performed at 10 to 40 ° C for 10 to 30 hours.
Wherein the size of the first particle is increased and the size of the second particle is decreased as the re-swelling time of the step (d) is increased.
The cyclodextrin may be selected from the group consisting of methyl-β-cyclo dextrin, β-cyclodextrin, 2,6-dimethyl-β-cyclodextrin, And sodium sulphobutyl ether -? - cyclodextrin. 2. The method of claim 1, wherein the non-spherical amphiphilic dimer nanoparticles are at least one selected from the group consisting of sodium sulfobutyl ether and? -Cyclodextrin.
The radical initiator may be selected from the group consisting of 2,2-azobisisobutyronitrile (AIBN), 2,2-azobis (2-methylisobutyronitrile), 2,2-azobis (2,4- dimethylvaleronitrile) , Benzoyl peroxide, lauryl peroxide, cumene hydroperoxide, methyl ethyl ketone peroxide, t-butyl hydroperoxide, o-chlorobenzoyl peroxide, o-methoxybenzoyl peroxide, t- - ethylhexanoate, t-butylperoxyisobutyrate, and mixtures thereof. The method for producing an amorphous amorphous nanoparticle according to claim 1,
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| KR1020150094438A KR101766958B1 (en) | 2015-07-02 | 2015-07-02 | Method for pickering emulsion-based manufacture of non-spherical amphiphilic dimeric nanoparticles reversibly changing the interfacial properties with temperatures |
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| Preparation of Stimuli-Responsive "Mushroom-Like" Janus Polymer Particles as Particulate Surfactant by Site-Selective Surface-Initiated AGET ATRP Langmuir 2014,30,7823-7832 |
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