KR101816284B1 - Semipermeable Microcapsules by polymerization-induced phase separation and Method of preparing the same - Google Patents
Semipermeable Microcapsules by polymerization-induced phase separation and Method of preparing the same Download PDFInfo
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- KR101816284B1 KR101816284B1 KR1020150146497A KR20150146497A KR101816284B1 KR 101816284 B1 KR101816284 B1 KR 101816284B1 KR 1020150146497 A KR1020150146497 A KR 1020150146497A KR 20150146497 A KR20150146497 A KR 20150146497A KR 101816284 B1 KR101816284 B1 KR 101816284B1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
- B01J13/06—Making microcapsules or microballoons by phase separation
- B01J13/14—Polymerisation; cross-linking
- B01J13/16—Interfacial polymerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/02—Making microcapsules or microballoons
Abstract
TECHNICAL FIELD The present invention relates to a polymer semipermeable microcapsule using photopolymerization induced phase separation and a method for producing the same. More particularly, the present invention relates to a polymer semipermeable microcapsule, which polymerizes a monomer by adding ultraviolet rays to a double liquid droplet in which a photopolymerizable monomer and a porogen form a mesophase, The present invention relates to a polymer semipermeable microcapsule using a phase separation phenomenon with a porogen and a method for preparing the same.
The present invention can form pores uniformly in the shell and can be controlled in size, by using porogen type, concentration, and phase separation characteristics between polymer monomers.
The present invention forms a shell by polymerizing a photopolymerizable monomer so that it is possible to provide a microcapsule which is chemically stable and has excellent mechanical properties because it is hardly affected by a specific solvent or pH condition.
The microcapsule of the present invention has hundreds of nano pores at a few nanometers and can control the material flow into and out of the capsule.
Description
TECHNICAL FIELD The present invention relates to a polymer semipermeable microcapsule using photopolymerization induced phase separation phenomenon, and more particularly, to a polymer semipermeable microcapsule using photopolymerization induction phase separation phenomenon, and more particularly, to a polymer semipermeable microcapsule which is formed by polymerizing a monomer by applying ultraviolet rays to a double liquid droplet in which a photopolymerizable monomer and a porogen form a mesophase, To a polymer semipermeable microcapsule using a phase separation phenomenon between a polymer and a porogen, and a method for producing the same.
Microcapsules are not only very efficient in delivering active ingredients, such as pigments, drugs, cells, to specific locations, but also can stably differentiate or store these active ingredients.
Various methods for making such microcapsules have been proposed in the literature. Emulsion drops can be used as a template for capsule manufacturing and form a shell using particle adsorption or interfacial polymerization at the interface to store the internal active material. For example by dispersing the hydrophobic liquid droplets in an aqueous medium containing melamine formaldehyde pre-condensate and reducing the pH of the aqueous medium to produce an impermeable aminoplast resin surrounding the hydrophobic liquid as a shell, It is known to encapsulate liquids.
Recently, double-emulsion drops have been used as a template for producing microcapsules of core-shell structure. Japanese Patent Laid-Open No. 10-965839 discloses a method for producing a polymer capsule using a double droplet.
There is a demand for a technique of manufacturing a microcapsule in which a substance is stored in a stable state, or a substance is flowed out and introduced selectively, in order to utilize it for various purposes such as a drug delivery system, a micro reactor, and a sensor for surface enhancement Raman scattering marking. For this purpose, attempts have been made to form pores in microcapsules, but until now there has been no technique to control pore size and uniformity, membrane durability and stability. In addition, a method for effectively forming pores in microcapsules using a simple process is still required.
SUMMARY OF THE INVENTION The present invention provides a method of forming pores in capsules that are uniform and size controllable.
The present invention provides a microcapsule capable of selective permeation or release by controlling pore size.
The present invention provides a microcapsule which can be used for a drug, a physiologically active substance delivery material, a micro-reactor, a sensor for surface enhancement Raman scattering marking, and the like.
The microcapsules of the present invention have very high physical, chemical stability and semi-permeability properties and can be applied to various fields such as chemical processes and biomedical fields.
In one aspect,
A second fluid comprising a porogen (pore-forming derivative), a hydrophilic third fluid comprising a surfactant in a continuous phase, a second fluid comprising a second polymer comprising a second polymer, To form a double droplet;
Applying ultraviolet light to the double droplet; And
And removing the porogen to form pores. The present invention also relates to a process for preparing a polymer semipermeable microcapsule.
In another aspect,
A core containing a storage material; And
The present invention relates to a polymer semipermeable microcapsule formed by removing a porogen that is phase-separated from a polymer formed in a photopolymerization process, wherein the pores surround the core and have uniform pores.
The present invention makes it possible to form pores uniformly in the shell and capable of size control by using the type and concentration of the porogen and the phase separation characteristics between the porogen and the polymer monomer.
The present invention forms a polymer shell by polymerizing a photopolymerizable monomer, and thus it is possible to provide a microcapsule which is chemically stable and has excellent mechanical properties because it is hardly affected by a specific solvent or pH condition.
The microcapsule of the present invention has a pore size of several nanometers to several nanometers and can control the material flow into and out of the capsule.
1 shows a process for producing a polymer semipermeable microcapsule using a microfluidic device
FIG. 2 is a schematic view showing a semipermeable microcapsule forming process of the present invention. FIG.
3 is a transmission micrograph and a scanning electron microscope (SEM) photograph of the microcapsules prepared in Example 1. Fig.
Fig. 4 is a SEM micrograph and an average pore size of the microcapsules prepared in Examples 2 to 4 and Comparative Example 1. Fig.
5 is a photograph showing the permeability of Example 3 and the impermeability of Comparative Example 1, and an optical microscope photograph and a confocal microscope photograph.
6 shows the change in fluorescence intensity (I (t) / I max ) with time in the microcapsule in
7A to 7C are optical microscope photographs and scanning electron microscopic photographs of the microcapsules prepared in Example 5, and FIGS. 7D to 7F are schematic and confocal microscopic photographs showing the results of Experiment 3.
The present invention relates to a polymer semipermeable microcapsule using photopolymerization induced phase separation and a method for producing the same.
FIG. 1 shows a method for producing a polymer semipermeable microcapsule using a microfluidic device. FIG. 2 is a schematic view showing a semipermeable microcapsule forming process of the present invention. FIG. The method for producing a microcapsule of the present invention includes a step of forming a double droplet, a step of applying ultraviolet rays, and a step of forming a pore.
The double droplet is a w / o / w (water / oil / water) structure. The present invention is not limited to the method of forming the double droplet. For example, a double droplet can be formed without using the microfluidic device of Fig. That is, the present invention can prepare a double droplet by dripping a first fluid containing a storage material into a hydrophobic second fluid and hardening it.
In addition, a double droplet can also be prepared by a bulk emulsification method in which a single droplet of water / oil phase is formed through the first bulk emulsification and then continuously emulsified (second bulk emulsification) to the second hydrophilic fluid.
A specific method of forming a double droplet will be described in detail with reference to Fig. First, in the step of forming the double droplet, a hydrophilic first fluid containing a storage material is injected in an inner phase, an oleophilic second fluid containing a polymerizable polymer monomer and porogen is injected as an intermediate phase, A hydrophilic third fluid containing an activator is injected into the continuous phase to form a double droplet.
The hydrophilic first fluid may include a storage material to form an internal phase, and a material in which a storage material is dissolved in water may be used. At this time, a water-soluble surfactant such as polyvinyl alcohol (PVA) may be contained to stabilize the interface.
The storage material can be any material that is soluble or dispersible in water. For example, the storage material may be metal nanoparticles, water soluble drugs or proteins, physiologically active substances, water soluble polymers, microorganisms or cells.
More specifically, the metal nanoparticles can be any metal capable of causing surface enhanced Raman scattering, for example, silver nanoparticles or gold nanoparticles having biocompatibility.
The size of the metal nanoparticles can be as large as that of the surface-enhanced Raman scattering. For example, the metal nanoparticles may have a diameter of 3 to 1,000 nm, preferably 5 to 500 nm, and preferably 20 to 100 nm.
In addition, the storage material may be magnetic nanoparticles. In this case, the capsule containing the magnetic nanoparticles may react with external magnetic force. On the other hand, the magnetic nanoparticles may be mixed with a lipophilic fluid and injected. In this case, the magnetic nanoparticles may have a lipophilic property and are dispersed in the shell.
The storage material may be a drug, cosmetic, catalyst, nutrient or yeast cell or a cell of a mammal.
In addition, materials such as non-water-soluble particles dispersed in water as the storage material may be used without limitation.
There is no particular limitation on the content of the storage material. For example, 1 to 20% by weight of the storage material may be dissolved or dispersed in the first fluid.
The second fluid includes a first polymeric monomer, a second polymeric monomer, and a porogen that are polymerizable in an intermediate phase.
The first polymeric monomer may be a monovinylic monomer having an acrylate or methacrylate functional group. The first polymeric monomer may be selected from the group consisting of glycidyl methacrylate (GMA), ethyl acrylate, butyl acrylate, 2-hydroxyethylmethacrylate, 2 , 3-epithiopropyl methacrylate, ethylene glycol methyl ether acrylate, methyl methacrylate, acrylamide, phenyl methacrylate, N-isopropylacrylamide, hydroxyethyl methacrylate, and the like.
The second fluid may include a second polymer monomer having a larger number of vinyl groups than the first polymer monomer. The second polymeric monomer is selected from the group consisting of ethoxylated trimethylolpropane triacrylate (ETPTA), ethyleneglycol dimethacrylate, divinylbenzene, 2-hydroxypropylene dimethacrylate Acrylate, 2-hydroxypropylene dimethacrylate, triethyleneglycol dimethacrylate, N, N'-methylene (bis) acrylamide.
The porogen is a pore generator, which can dissolve the first polymer monomer and the second polymer monomer, and may be an inert small molecular organic material that does not undergo chemical denaturation during polymer polymerization.
The porogen may be a low-molecular-weight oil.
The porogen may be an alcohol having 5 to 20 carbon atoms, an alkane having 5 to 20 carbon atoms, toluene, an acetate having 4 to 6 carbon atoms, for example, butylacetate.
The porogen may be contained in the second fluid in an amount of less than 30% by weight, preferably 20% by weight or less. When the content of the porogen is 30 wt% or more, shell formation may be difficult.
The second polymeric monomer may be included in an amount of 0 to 300 parts by weight based on 100 parts by weight of the first polymeric monomer.
The second fluid may include a photoinitiator for polymerization. The photoinitiator may include an α-hydroxy ketone type, an α-amino ketone type, a benzionalkyether, a benzophenone, a benzyldimethylketal, a 1,1-dichloroacetophenone, a 2-chlorothioxanthone, 2-hydroxy-2-methylpropiophenone, but is not limited thereto.
When a photoinitiator is further used, 0.1 to 5% by weight, preferably 0.1 to 1% by weight, based on the mixture of the second fluid may be used.
The present invention can use water as a continuous phase (third fluid), preferably water containing a surfactant.
Referring to FIG. 1, the dual droplet forming apparatus includes an
In the present invention, the first fluid is injected into the inner
The first fluid and the second fluid are separated from each other in the
Referring to FIG. 2, the core-shell type microcapsules can be prepared by applying ultraviolet rays to the double droplets.
When ultraviolet rays are applied to the second fluid, which is an intermediate phase of the double droplet, the monomer is photopolymerized to form a polymer membrane (shell). The thickness of the polymer shell may be 20 to 5000 nm, preferably 20 to 1000 nm.
When ultraviolet rays are applied to the double droplet, the weight of the polymer and the mixing energy increase as the first polymer monomer and the second polymer monomer are polymerized. When the degree of polymerization of the first polymer and the second polymer gradually increases and exceeds the gel point, solidification occurs, resulting in phase separation between the first polymer or the second polymer solidified and the porogen. Further, when the polymerization is further performed, the solidified first polymer or the second polymer forms a polymer shell having a single structure.
Since the polymerization of the polymer by ultraviolet light is performed in a very short time in a few seconds, phase separation also occurs in a very short time, and as a result local phase separation occurs throughout the shell, Size uniformly dispersed throughout the shell.
In FIG. 2, a UV irradiator is disposed at the downstream of the dual droplet forming apparatus to emit ultraviolet rays immediately after the double droplet is formed. However, the present invention is not limited to that shown in FIG. And then irradiating and curing it.
Referring to FIGS. 1 and 2, the step of forming pores in the microcapsule is a step of removing porogen that is present in the shell.
The step of removing the porogen may include washing the ultraviolet cured double droplets with an organic solvent or water.
The porogen can be removed from the shell using methanol, acetone, or water. Using methanol or acetone can remove the porogen in a short time. When water alone is used, it may take some time to remove the porogen, but it is easy to maintain the physiological activity when the cell is carried inside. The pores are areas where the porogen is removed.
The method may control the type and content of the porogen or the pore size by controlling the phase separation characteristic between the porogen and the first polymer monomer or the second polymer monomer.
As the type of porogen, especially the molecular weight of porogen, increases, the pore size may increase.
In addition, as the content of the porogen added in the second fluid increases, the pore size increases. For example, the pore size is larger when the content of porogen in the second fluid is 20 wt% than that of 10 wt%.
The phase separation characteristics may be determined by an interaction parameter between the polymer and the porogen, a molecular weight of the polymer, a thickness of the polymer membrane, and the like.
When the affinity between the polymer and the porogen is high, the phase separation rate is relatively low and the resulting pore size is small. For example, when ETPTA is used as the monomer, butyl acetate has a higher affinity for ETPTA (with a lower interaction parameter value) than 1-decanol, resulting in a smaller pore size than 1-decanol.
The present invention forms a shell by polymerizing a photopolymerizable monomer, so that it is possible to provide chemically stable microcapsules that are hardly affected by specific solvents or pH conditions. For example, a polymer capsule produced by volatilizing a double-droplet solvent having a polymer solution as an intermediate phase is easily dissolved in a polar solvent because the molecular weight is low. However, since the present polymer capsule has a relatively high molecular weight single polymer membrane, Stability.
As described later, the microcapsule of the present invention is excellent in flexibility, mechanical strength and durability because it can be selected from a single membrane and a polymer having excellent elasticity.
The present invention can control the pore size to be smaller than the cell size. The microcapsules of the present invention can selectively transmit only a target material smaller than the pore size. That is, the microcapsule of the present invention can prevent the foreign matter larger than the pore from flowing into the capsule, and the target material can be selectively introduced into the capsule according to the size.
The microcapsules may be used as a cell culture device capable of storing, transporting and culturing cells.
When microcapsules containing cells are placed in a solution containing nutrients or nutrients in microcapsule-loaded solutions, nutrients can enter the microcapsules through the pores.
As the cell, yeast, monocellular organisms such as E. coli , or animal cells such as beta cells of the islet is used.
In another aspect, the present invention relates to a polymeric semipermeable microcapsule having pores formed therein. The microcapsule comprising a core containing a storage material; And a shell surrounding the core and formed with uniform pores, wherein the pores are formed by removing the porogen, which is present in a phase separated from the polymer formed in the photopolymerization process, from the polymer.
The size of the pores is smaller than the size of the storage material, so that the storage material may be carried on the inside of the microcapsule and may not flow out.
The microcapsule may selectively transmit only a target material smaller than the pore size.
The storage material may be a cell, a drug, a cosmetic, a nutrient, a catalyst, or a metal nanomaterial.
The microcapsules may have a size ranging from 10 to 1000 탆, preferably from 10 to 500 탆.
The pores may have a size ranging from 1 nm to 10 탆, preferably from 1 to 1000 nm.
The thickness of the shell may be 20 to 5000 nm.
The shell is a semipermeable polymer membrane.
The aforementioned microcapsules can be referred to above.
Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example One
Microcapsules were prepared using the apparatus of Fig.
(GMA, Sigma-Aldrich), ethoxylated trimethylolpropane triacrylate (ETPTA, Sigma-Aldrich), and a 10-wt% polyvinyl alcohol aqueous solution (molecular weight 13,000 to 23,000) decanol (Sigma-Aldrich) (weight ratio of GMA: ETPTA: 1-decanol = 51: 34: 15). 1 wt% of 2,2-dimethoxy-1,2-diphenylethanone was added thereto as a photoinitiator. GMA: ETPTA was adjusted to a weight ratio of about 3: 2. At the downstream of the collecting capillary, the double droplets were collected in a solution of 2 wt% PVA and 40 mM NaCl, and the liquid was irradiated with UV at 2 W /
Example 2 to 4, Comparative Example One
In Example 1, the weight ratio of GMA: ETPTA was maintained at 3: 2 and the weight of 1-decanol was adjusted to 0% (Comparative Example 1), 10% (Example 2), 15% Example 4). ≪ tb > < TABLE >
Example 5
The procedure of Example 1 was repeated except that 1-decanol was replaced with butyl acetate (15 wt%) as a porogen.
The microcapsules obtained in Example 3 (containing 15% by weight of porogen) were dispersed in dextran (molecular weight 2,000,000 g / mol) coated with 217 nm PS (coated with red dye) and green fluorescence isothiocyanate (FITC) ) Was left in the dispersed solution for one day and observed with a confocal microscope, and this is shown in Figs. 5 (a) to (c).
In addition, the microcapsules obtained in Comparative Example 1 (porogen-containing 0) were placed in a solution in which rhodamine 6G (Mw 479.02 g / mol) was dispersed for one day, and then observed with a transmission microscope and a confocal microscope. 5 d to f.
The microcapsules obtained in Example 3 (containing 15% by weight of porogen) were dissolved in dextran (molecular weight 20,000 g / mol, 70,000 g / mol, 150,000 g / mol, 500,000 g / mol, 2,000,000 g / mol) was left in the solution for one day and observed with a confocal microscope.
Experiment 3
The microcapsules obtained in Example 5 were dissolved in dextran (molecular weight of 500,000 g / mol, particle size of about 30 nm) and rhodamine B isothiocyanate (RITC) -dextran (molecular weight of 10,000 g) with fluorescein isothiocyanate (FITC) / mol, particle size of about 4, 4 nm, red) was left for about one day and observed with a confocal microscope, which is shown in Fig. 7 (d to f).
3 (a) is a transmission microscope photograph of the microcapsules prepared in Example 1, and FIGS. 3 (b) and 3 (c) are scanning electron microscopic (SEM) photographs of drying the microcapsules prepared in Example 1, And Fig. 3 (d) is a cross-sectional SEM image of the microcapsules prepared in Example 1. Fig.
Referring to Fig. 3 (a), a large amount of uniform microcapsules were produced. 3 (b) and 3 (c) show that the microcapsules are completely shrunk due to the evaporation of the internal moisture, but the membrane (shell) is maintained without being destroyed. This shows that the microcapsules prepared in Example 1 are mechanically very stable and very flexible. Figure 3 (d) shows that the pores have a uniform size and shape throughout the shell, showing that the pores communicate the inside and the outside of the shell.
Fig. 4 shows the average pore size of the microcapsules prepared in Examples 2 to 4 and Comparative Example 1. Fig. 4, almost no pores are generated in Comparative Example 1, and pore sizes of 160 nm, 205 nm, and 295 nm in Examples 2 to 4, respectively. FIG. 4 shows that as the weight% of porogen increases, the pore size increases.
5 compares the transmittances of Example 3 and Comparative Example 1. Referring to FIGS. 5D to 5F, in Comparative Example 1, rhodamine 6G having a diameter of 1 nm was not diffused into the capsule, showing that pores were not formed in the microcapsule film of Comparative Example 1. On the other hand, referring to FIGS. 5A to 5C, in Example 1, PS (red) having a particle size of 217 nm was not diffused into the capsule, whereas dextran particles (green) having a size of about 60 nm were diffused therein. That is, these experimental results show that the pore size of the microcapsules prepared in Example 3 is in the range of 60 to 217 nm.
6 shows the fluorescence intensities (I (t) / I max ) inside the microcapsules in time according to
7 (a) is a transmission microscope photograph of the microcapsules prepared in Example 5, and FIGS. 7 (b) and 7 (c) are scanning electron microscope (SEM) photographs of drying the microcapsules prepared in Example 5, Lt; / RTI > 7D to 7F are SEM images of the results of Experiment 3. Referring to Figs. 7 (b) and 7 (c), it is difficult to confirm the pore in the SEM image. 7, dextran (30 nm) with fluorescein isothiocyanate (FITC) was not diffused into the capsule, but dextran (4,4 nm) with red fluorescent dye was not diffused into the capsule. Is diffused into the capsule. That is, the pore size of the microcapsules prepared in Example 5 is expected to be in the range of 4.4 nm to 30 nm.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments.
Claims (14)
Applying ultraviolet light to the double droplet; And
Removing the porogen to form pores,
Wherein the second fluid comprises a second polymeric monomer having a greater or lesser number of vinyl groups than the first polymeric monomer.
Wherein the pores are formed by removing a porogen that is phase-separated from a polymer formed in a photopolymerization process,
The polymer is formed by polymerizing a second polymer monomer having a greater or lesser number of vinyl groups than the first polymer monomer and the first polymer monomer,
Wherein the pores include pores corresponding to the phase separation of the porogen and the first polymer monomers and pores corresponding to phase separation of the porogen and the second polymer monomers.
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KR102648911B1 (en) * | 2021-11-12 | 2024-03-20 | 충남대학교산학협력단 | Method of manufacturing capsul and manufacturing apparatus for capsul |
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