KR102269249B1 - Pickering emulsion including alginate hydrogel particles coated with chitosan and manufacturing method by the same - Google Patents

Abstract

The present invention discloses a Pickering emulsion comprising alginate hydrogel particles coated with chitosan and a method for preparing the same. A method for producing a Pickering emulsion comprising alginate hydrogel particles coated with chitosan according to an embodiment of the present invention comprises: injecting alginate droplets formed in a first humidifier by a first carrier gas into a reaction glass tube; Injecting divalent cation droplets formed in a second humidifier by a second carrier gas into the reaction glass tube; The alginate droplet and the divalent cation droplet are crosslinked in the reaction glass tube to prepare alginate hydrogel particles; obtaining the alginate hydrogel particles in a collection container containing a coating solution containing chitosan; Coating the surface of the alginate hydrogel particles with chitosan by stirring the alginate hydrogel particles obtained in the collection container and the coating solution; And it characterized in that it comprises the step of preparing a Pickering emulsion by mixing the aqueous phase material and the oil phase material comprising the alginate hydrogel particles coated with the chitosan.

Description

Pickering emulsion comprising alginate hydrogel particles coated with chitosan and method for preparing the same {PICKERING EMULSION INCLUDING ALGINATE HYDROGEL PARTICLES COATED WITH CHITOSAN AND MANUFACTURING METHOD BY THE SAME}

The present invention relates to a Pickering emulsion comprising alginate hydrogel particles coated with chitosan and a method for preparing the same.

Conventional emulsions are generally stabilized by surfactants, but the main limitation of conventional emulsions is excessive use of surfactants that are harmful to human health and the environment.

To solve this problem, Pickering emulsions prepared using solid particles to replace surfactants have emerged.

The Pickering emulsion has the advantage of low toxicity and long-lasting stability.

Therefore, Pickering emulsion is showing potential applications in various fields such as drug delivery, food industry, cosmetics, agriculture, road construction industry, paint company, etc.

Pickering emulsions can be stabilized by solid particles such as silica, titania, zirconia, CaCO ₃ nanoparticles, clay, graphene oxide, zein, latex particles and biopolymer-based particles.

Natural polymers are classified into four categories, including polysaccharides, proteins, nucleic acids and lipids.

Since natural polymers have properties such as renewability, biodegradability, biocompatibility and non-toxicity, they can be used in a variety of applications, and most natural polymers are inexpensive because they are readily available from nature.

Natural polymers have a variety of surface reactive groups capable of surface modification, and thus can be used in a variety of applications.

Among the natural macromolecular polysaccharides, alginate is a naturally occurring anionic polymer widely found in brown seaweed, which has demonstrated excellent utility in biomedical applications for encapsulation in the food industry, pharmaceuticals, arts and crafts industries, etc.

Nevertheless, alginate particles have little research used to stabilize emulsions due to their hydrophilicity.

Therefore, in order to solve this problem, a study was conducted to prepare a Pickering emulsion containing alginate particles by adding span-80, a conventional surfactant.

However, there is a problem of using the existing surfactants that are harmful to the human body and the environment again to prepare an emulsion containing alginate particles.

Korean Patent Laid-Open No. 10-2011-0100857, "H-sensitive microcapsules containing alginate micro-particles and calcium carbonate micro-particles and a manufacturing method therefor" Republic of Korea Patent Registration No. 10-0919508, "Alginate particles containing calcium carbonate in matrix and manufacturing method thereof"

In an embodiment of the present invention, by obtaining alginate hydrogel particles in a collection container containing a chitosan solution, chitosan can be coated on the surface at the same time as the alginate hydrogel particles are obtained, so the mass production of alginate hydrogel particles coated with chitosan And to provide a Pickering emulsion comprising alginate hydrogel particles coated with chitosan capable of continuous production and a method for preparing the same.

An embodiment of the present invention is to provide a Pickering emulsion comprising alginate hydrogel particles coated with chitosan so that the alginate hydrogel particles can have both hydrophilicity and hydrophobicity by coating the alginate hydrogel particles with chitosan and a method for preparing the same .

An embodiment of the present invention is a Pickering emulsion comprising alginate hydrogel particles coated with chitosan, which can control the hydrophobicity of alginate hydrogel particles coated with chitosan according to the concentration and pH of the coating solution containing chitosan, and a method for preparing the same would like to provide

An embodiment of the present invention is a Pickering emulsion comprising alginate hydrogel particles coated with chitosan, which can control the hydrophobicity of alginate hydrogel particles coated with chitosan according to the stirring time of the coating solution and alginate hydrogel particles, and a method for preparing the same would like to provide

An embodiment of the present invention is to provide a Pickering emulsion comprising alginate hydrogel particles coated with chitosan and a method for preparing the same, wherein the Pickering emulsion can be stabilized for a long time using the hydrophilicity and hydrophobicity of the alginate hydrogel particles coated with chitosan do.

In an embodiment of the present invention, the alginate hydrogel particles coated with chitosan further include a magnetic material, so that the recovery of the alginate hydrogel particles coated with chitosan in the Pickering emulsion by a magnetic field is easy. Chitosan-coated alginate hydrogel particles An object of the present invention is to provide a Pickering emulsion comprising a and a method for preparing the same.

The method for producing a Pickering emulsion comprising alginate hydrogel particles coated with chitosan according to the present invention comprises the steps of injecting alginate droplets formed in a first humidifier by a first carrier gas into a reaction glass tube; Injecting divalent cation droplets formed in a second humidifier by a second carrier gas into the reaction glass tube; The alginate droplet and the divalent cation droplet are crosslinked in the reaction glass tube to prepare alginate hydrogel particles; obtaining the alginate hydrogel particles in a collection container containing a coating solution containing chitosan; Coating the surface of the alginate hydrogel particles with chitosan by stirring the alginate hydrogel particles obtained in the collection container and the coating solution; And it characterized in that it comprises the step of preparing a Pickering emulsion by mixing the aqueous phase material and the oil phase material comprising the alginate hydrogel particles coated with the chitosan.

According to the method for producing a Pickering emulsion comprising alginate hydrogel particles coated with chitosan according to an embodiment of the present invention, the chitosan may be included in an amount of 0.7% to 1.4% by weight relative to the total weight of the coating solution.

According to the method for preparing a Pickering emulsion comprising alginate hydrogel particles coated with chitosan according to an embodiment of the present invention, the pH of the coating solution may be 4 to 7.

According to the method for preparing a Pickering emulsion comprising alginate hydrogel particles coated with chitosan according to an embodiment of the present invention, the stirring may be performed for 1 hour to 40 hours.

According to the method for producing a Pickering emulsion comprising alginate hydrogel particles coated with chitosan according to an embodiment of the present invention, the alginate hydrogel particles coated with chitosan are magnetic metal nanoparticles, magnetic metal oxide nanoparticles, metal nanoparticles and at least one of metal-organic frameworks (MOF) composite nanoparticles.

A Pickering emulsion comprising alginate hydrogel particles coated with chitosan according to the present invention is an oily substance; aquatic substances; and alginate hydrogel particles formed by crosslinking alginate droplets and divalent cation droplets, the surface of which is coated with chitosan.

According to the Pickering emulsion comprising alginate hydrogel particles coated with chitosan according to an embodiment of the present invention, the thickness of the chitosan coated on the alginate hydrogel particles may be 10 nm to 200 nm.

According to the Pickering emulsion comprising alginate hydrogel particles coated with chitosan according to an embodiment of the present invention, the oily material is hexadecane, mineral oil, dodecane, octane , at least one of toluene, xylene, benzene, phenol, chloroform, dichloromethane, n-decane, and styrene may include.

According to the Pickering emulsion comprising alginate hydrogel particles coated with chitosan according to an embodiment of the present invention, the oily material and the water phase material may be included in a volume ratio of 1:0.5 to 1:10.

According to the Pickering emulsion comprising alginate hydrogel particles coated with chitosan according to an embodiment of the present invention, the alginate hydrogel particles coated with chitosan may be included in the Pickering emulsion at 0.005 g/mL to 0.1 g/mL. .

According to the Pickering emulsion comprising alginate hydrogel particles coated with chitosan according to an embodiment of the present invention, the alginate hydrogel particles coated with chitosan are magnetic metal nanoparticles, magnetic metal oxide nanoparticles, metal nanoparticles and metal- At least one of metal organic frameworks (MOF) composite nanoparticles may be further included.

According to an embodiment of the present invention, by obtaining alginate hydrogel particles in a collection container containing a chitosan solution, chitosan can be coated on the surface at the same time as obtaining alginate hydrogel particles, so that the alginate hydrogel particles coated with chitosan Mass production and continuous production are possible.

According to an embodiment of the present invention, the alginate hydrogel particles are coated with chitosan so that the alginate hydrogel particles can have both hydrophilicity and hydrophobicity.

According to an embodiment of the present invention, the hydrophobicity of the alginate hydrogel particles coated with chitosan can be adjusted according to the concentration and pH of the coating solution containing chitosan.

According to an embodiment of the present invention, the hydrophobicity of the alginate hydrogel particles coated with chitosan can be adjusted according to the stirring time of the coating solution and the alginate hydrogel particles.

According to an embodiment of the present invention, the Pickering emulsion can be stabilized for a long time by using the hydrophilicity and hydrophobicity of the alginate hydrogel particles coated with chitosan.

According to an embodiment of the present invention, the alginate hydrogel particles coated with chitosan further include a magnetic material, so it is easy to recover the alginate hydrogel particles coated with chitosan in the Pickering emulsion by a magnetic field.

1 is a schematic diagram showing an apparatus for producing alginate hydrogel particles coated with chitosan according to an embodiment of the present invention.
Figure 2 is a schematic diagram showing a first humidifier included in the apparatus for producing alginate hydrogel particles coated with chitosan according to an embodiment of the present invention.
Figure 3 is a schematic diagram showing a reaction glass tube included in the apparatus for producing alginate hydrogel particles coated with chitosan according to an embodiment of the present invention.
Figure 4 is a schematic diagram showing the reaction of alginate hydrogel particles coated with chitosan according to an embodiment of the present invention.
5 is a schematic diagram showing the binding relationship between alginate hydrogel particles and chitosan according to an embodiment of the present invention.
6 is a flowchart illustrating a method for preparing a Pickering emulsion comprising alginate hydrogel particles coated with chitosan according to an embodiment of the present invention.
7 is a graph showing FT-IR spectra of alginate hydrogel particles according to Examples and Comparative Examples of the present invention.
8 is a graph showing the contact angle of a Pickering emulsion comprising alginate hydrogel particles coated with chitosan according to an embodiment of the present invention.
9a and 9b are optical microscope images showing the appearance immediately after and 4 days after the preparation of the Pickering emulsion containing alginate hydrogel particles and n-decane coated with chitosan according to an embodiment of the present invention.
10a and 10b are optical microscope images showing the appearance immediately after and 4 days after the preparation of the Pickering emulsion containing alginate hydrogel particles and styrene coated with chitosan according to an embodiment of the present invention.
11a to 11c are optical microscopes showing the recovery by the magnet of the Pickering emulsion containing chitosan-coated alginate hydrogel particles, magnetic material and styrene according to an embodiment of the present invention, and immediately after and 3 days after preparation It is an image.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings and the contents described in the accompanying drawings, but the present invention is not limited or limited by the embodiments.

The terminology used herein is for the purpose of describing the embodiments and is not intended to limit the present invention. As used herein, the singular also includes the plural unless specifically stated otherwise in the phrase. As used herein, "comprises" and/or "comprising" does not exclude the presence or addition of one or more other elements, steps, or steps mentioned.

As used herein, “embodiment”, “example”, “aspect”, “exemplary”, etc. are to be construed as advantageous in which any aspect or design described is preferred or advantageous over other aspects or designs. it is not doing

Also, the term 'or' means 'inclusive or' rather than 'exclusive or'. That is, unless stated otherwise or clear from context, the expression 'x employs a or b' means any one of natural inclusive permutations.

Also, as used herein and in the claims, the singular expression "a" or "an" generally means "one or more" unless stated otherwise or clear from the context that it relates to the singular form. should be interpreted as

The terms used in the description below are selected as general and universal in the related technical field, but there may be other terms depending on the development and/or change of technology, customs, preferences of technicians, and the like. Therefore, the terms used in the description below should not be understood as limiting the technical idea, but should be understood as exemplary terms for describing the embodiments.

In addition, in specific cases, there are also terms arbitrarily selected by the applicant, and in this case, the meaning will be described in detail in the corresponding description. Therefore, the terms used in the description below should be understood based on the meaning of the term and the content throughout the specification, not the simple name of the term.

Unless otherwise defined, all terms (including technical and scientific terms) used herein may be used with the meaning commonly understood by those of ordinary skill in the art to which the present invention belongs. In addition, terms defined in a commonly used dictionary are not to be interpreted ideally or excessively unless clearly defined in particular.

Meanwhile, in the description of the present invention, if it is determined that a detailed description of a related known function or configuration may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted. And, the terms (terminology) used in this specification are terms used to properly express the embodiment of the present invention, which may vary according to the intention of the user or operator, or customs in the field to which the present invention belongs. Accordingly, definitions of these terms should be made based on the content throughout this specification.

The method for preparing a Pickering emulsion comprising alginate hydrogel particles coated with chitosan according to the present invention relates to a method for preparing a Pickering emulsion using the alginate hydrogel particles after coating with chitosan.

Accordingly, prior to the description of the method for preparing the Pickering emulsion comprising the alginate hydrogel particles coated with chitosan, the apparatus for preparing the chitosan-coated alginate hydrogel particles and the description of the method for preparing the same are shown in FIGS. It will be described with reference to FIG. 4 .

1 is a schematic diagram showing an apparatus for producing alginate hydrogel particles coated with chitosan according to an embodiment of the present invention.

1, the first humidifier 110 is formed on the upper portion, and the second humidifier 120 is shown in the structure formed in the lower portion, but is not limited thereto, and the first humidifier 110 and the second humidifier ( 110) can be freely changed.

The apparatus for producing alginate hydrogel particles coated with chitosan according to an embodiment of the present invention is a first humidifier 110 for injecting alginate droplets using a first carrier gas, a divalent cation droplet using a second carrier gas A reaction glass tube 130 that is formed between the injected second humidifier 120, the first humidifier 110 and the second humidifier 120, and alginate droplets and divalent cation droplets are crosslinked to form alginate hydrogel particles; and and a collection vessel 140 in which the alginate hydrogel particles are obtained.

The collection container 140 may include a coating solution containing chitosan to coat the surface of the alginate hydrogel particles with chitosan. A detailed description of the configuration of coating the alginate hydrogel particles with chitosan will be described in detail with reference to FIGS. 5 and 6 to be described later.

The apparatus for producing alginate hydrogel particles coated with chitosan according to an embodiment of the present invention uses a first humidifier 110 and a second humidifier 120 to mass alginate hydrogel particles having a size of several hundred nanometers to several tens of micrometers. production and continuous production.

The first humidifier 110 is for injecting alginate droplets into the reaction glass tube 130 , and the first humidifier 110 may include an aqueous alginate solution for forming alginate droplets.

The alginate aqueous solution includes an alginate compound, and the alginate compound may include sodium alginate, but is not limited thereto.

In addition, the amount of alginate droplets sprayed through the first humidifier 110 may be controlled according to the concentration of the alginate aqueous solution.

Preferably, the alginate aqueous solution may include 1 wt% to 10 wt% of the alginate compound, and when the amount of the alginate compound is out of the above range, the viscosity of the alginate aqueous solution increases and sprays through the first humidifier 110 There is a problem that doesn't work.

According to embodiments, the alginate aqueous solution may further include a magnetic material.

The magnetic material may be at least one of magnetic metal nanoparticles, magnetic metal oxide nanoparticles, metal nanoparticles, and metal-organic frameworks (MOF) composite nanoparticles, but is not limited thereto.

The magnetic metal nanoparticles include iron group metal elements (Fe, Ni, Co), rare earth elements (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu) , money metal elements (Cu, Ag, Au), zinc group elements (Zn, Cd, Hg), aluminum group elements (Al, Ga, In, Tl), alkaline earth metal elements (Ca, Sr, Ba, Ra) and platinum group elements It may include at least one of elements (Pt, Pd, etc.).

The magnetic metal oxide nanoparticles include iron group metal elements (Fe, Ni, Co), rare earth elements (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu ), money metal elements (Cu, Ag, Au), zinc group elements (Zn, Cd, Hg), aluminum group elements (Al, Ga, In, Tl), alkaline earth metal elements (Ca, Sr, Ba, Ra) and It may be an oxide of a metal including at least one of platinum group elements (Pt, Pd, etc.).

The alginate hydrogel particles coated with chitosan can prepare alginate hydrogel particles that respond to a magnetic field by further including a magnetic material, so it is easy to recover the alginate hydrogel particles coated with chitosan, and using this, a small size It is possible to manufacture a magnetic bar having a (magnetic bar).

The metal nanoparticles are gold (Au) silver (Ag), copper (Cu), platinum (Pt), palladium (Pd), nickel (Ni), bismuth (Bi), lead (Pb), indium (In), tin It may include at least one of (Sn), zinc (Zn), titanium (Ti), aluminum (Al), cobalt (Co), molybdenum (Mo), and antimony (Sb).

The metal-organic framework complex nanoparticles may be complexes in which various central metal ions are bound to organic ligands.

The metal ions are zinc (Zn), copper (Cu), nickel (Ni), cobalt (Co), iron (Fe), manganese (Mn), chromium (Cr), cadmium (Cd), magnesium (Mg), calcium (Ca), zirconium (Zr), chromium (Cr), vanadium (V), molybdenum (Mo), aluminum (Al), palladium (Pd), platinum (Pt), gold (Au), silver (Ag), ruthenium It may include at least one of (Ru), gadolinium (Gd), europium (Eu), and terbium (Tb).

The organic ligand is benzimidazole, 2,5-dihydroxyterephthalic acid (DOT; 2,5-dihydroxyterephthalic acid), carboxylate, phosphonate, amine, amine Zide, cyanide, squaryl, heteroatom, monocarboxylic acid, dicarboxylic acid, tricarboxylic acid , tetracarboxylic acid, imidazole, formic acid, acetic acid, oxalic acid, propanoic acid, butanedioic acid, ( E)-butenedioic acid ((E)-butenedioic acid), terephthalic acid (benzene-1,4-dicarboxylic acid), isophthalic acid (benzene-1,3-dicarboxylic acid), trimesic acid (benzene-1,3,5) -tricarboxylic acid), 2-amino-1,4-benzenedicarboxylic acid (2-amino-1,4-benzenedicarboxylic acid), 2-bromo-1,4-benzenedicarboxylic acid (2-bromo- 1,4-benzenedicarboxylic acid), biphenyl-4,4'-dicarboxylic acid, biphenyl-3,3',5,5'-tetracarboxylic acid ( biphenyl-3,3',5,5'-tetracarboxylic acid), biphenyl-3,4',5-tricarboxylic acid (biphenyl-3,4',5-tricarboxylic acid), 2,5-dihydr Roxy-1,4-benzenedicarboxylic acid (2,5-dihydroxy-1,4-benzenedicarboxylic acid), 1,3,5-tris (4-carboxylphenyl) benzene (1,3,5-tris ( 4-ca rboxyphenyl)benzene), (2E,4E)-hexa-2,4-dienoic acid ((2E,4E)-hexa-2,4-dienedioic acid), 1,4-naphthalenedicarboxylic acid (1,4- naphthalenedicarboxylic), naphthalene-2,6-dicarboxylate, pyrene-2,7-dicarboxylic acid, 4,5,9, 10-tetrahydropyrene-2,7-dicarboxylic acid (4,5,9,10-tetrahydropyrene-2,7-dicarboxylic acid), aspartic acid, glutamic acid, adenine ), 4,4'-bipyridine (4,4'-bypiridine), pyrimidine, pyrazine, 1,4-diazabicyclo[2.2.2]octane (1,4-diazabicyclo[2.2) .2] octane), pyridine-4-carboxylic acid, pyridine-3-carboxylic acid, imidazole, 1H-benzoimidazole (1H-benzimidazole), 2-methyl-1H-imidazole (2-methyl-1H-imidazole), and 4-methyl-5- imidazole carboxaldehyde (4-methyl-5-imidazolecarboxaldehyde) containing at least one can do.

In addition, the power of the first humidifier 110 may be 200W or more.

If the power of the first humidifier 110 is less than 200W, there is a problem that the power is too weak to spray the alginate aqueous solution having a high viscosity.

The first humidifier 110 included in the apparatus for producing alginate hydrogel particles coated with chitosan according to an embodiment of the present invention will be described in more detail with reference to FIG. 2 .

2 is a schematic diagram showing a first humidifier included in the apparatus for producing alginate hydrogel particles according to an embodiment of the present invention.

FIG. 2 is an enlarged view of the dotted line box of FIG. 1 . In addition, although FIG. 2 describes the first humidifier 110, the first humidifier 110 and the second humidifier may include the same components, except that the type of aqueous solution contained in the humidifier is different. Not limited.

The first humidifier 110 has an ultrasonic vibrator disposed at the bottom of the container for accommodating the alginate aqueous solution, and a first carrier gas pump for injecting the first carrier gas 122 is disposed on the side, and the first humidifier 110 ) and the reaction glass tube 130 is connected to a first connecting tube 161 through which the alginate droplet moves.

Accordingly, when the first humidifier 110 vibrates the alginate aqueous solution using an ultrasonic vibrator disposed at the bottom of the container for accommodating the alginate aqueous solution, the alginate droplets 111 are micronized by ultrasonic waves, and the alginate droplets 111 are generated. ) may be injected into the reaction glass tube 130 by the first carrier gas 122 flowing from the first carrier gas pump connected to the first humidifier 110 .

The first carrier gas 122 is a gas for transporting the alginate droplets, and may include, for example, at least one of air, nitrogen, argon, and helium.

The alginate droplet 111 may be injected into the reaction glass tube 130 only with the first humidifier 110, but the first humidifier 110 flows the first carrier gas to further improve the movement of the alginate droplet 111. have.

Therefore, the apparatus for producing alginate hydrogel particles coated with chitosan according to an embodiment of the present invention can improve the spray amount and movement speed of the alginate droplet 111 by using the first carrier gas 122, and further react It is possible to increase the crosslinking reaction rate of the alginate droplet 111 and the divalent cation droplet in the glass tube 130 .

In addition, the pressure of the first carrier gas 122 may be adjusted by the power of the first humidifier 110 .

Referring back to FIG. 1 , the apparatus for producing alginate hydrogel particles coated with chitosan according to an embodiment of the present invention includes a second humidifier 120 .

The second humidifier 120 is for injecting divalent cation droplets into the reaction glass tube 130 , and may include a divalent cation aqueous solution for forming divalent cation droplets.

The divalent cation aqueous solution is an aqueous solution containing a divalent cation compound, and the divalent cation compound is barium chloride (BaCl ₂ ), barium acetate, calcium chloride (CaCl ₂ ), strontium chloride. (strontium chloride, SrCl ₂ ), calcium acetate (Calcium acetate), calcium lactate (Calcium lactate), and may include at least one of calcium gluconate (Calcium gluconate).

In addition, the crosslinking reaction of alginate may be controlled according to the concentration of the divalent cation aqueous solution.

When the concentration of the divalent cation aqueous solution is increased, the crosslinking reaction of alginate may be rapidly generated, and further crosslinking strength may be increased.

According to an embodiment, the divalent cation aqueous solution may contain 1 wt% to 10 wt% of the divalent cation compound.

When the amount of the divalent cation compound contained in the divalent cation aqueous solution is within the above-mentioned range, the amount of the divalent cation aqueous solution does not need to exceed the above-mentioned range because the crosslinking reaction already proceeds sufficiently quickly.

According to an embodiment, the apparatus for producing alginate hydrogel particles coated with chitosan according to an embodiment of the present invention may include a trivalent cation aqueous solution rather than a divalent cation aqueous solution in the second humidifier 120, and trivalent cations The aqueous solution may contain a trivalent cationic compound.

The power of the second humidifier 120 may be 30W to 200W or more.

If the power of the second humidifier 120 is less than 30W, there is a problem in that the power is too weak to spray the divalent cation aqueous solution.

The second humidifier 120 has an ultrasonic vibrator disposed at the bottom of the container for accommodating the divalent cation aqueous solution, and a second carrier gas pump for injecting the second carrier gas is disposed on the side thereof, and the second humidifier 120 . A second connecting tube 162 through which divalent cation droplets and alginate hydrogel particles are moved is connected between the reaction glass tube 130 and the divalent cation droplet between the second humidifier 120 and the collecting vessel 140 . And a third connecting pipe 163 to which the alginate hydrogel particles are moved is connected.

Therefore, when the second humidifier 120 vibrates the divalent cation aqueous solution using an ultrasonic vibrator disposed at the bottom of the container for accommodating the divalent cation aqueous solution, the divalent cation aqueous solution is micronized by ultrasonic waves, and the generated 2 The false positive ion droplets may be injected into the reaction glass tube 130 by the second carrier gas flowing from the second carrier gas pump connected to the second humidifier 120 .

The second carrier gas is a gas for transporting divalent cation droplets, and may include, for example, at least one of air, nitrogen, argon, and helium.

The divalent cation droplet may be injected into the reaction glass tube 130 with only the second humidifier 120 , but the second humidifier 120 may flow the second carrier gas to improve the movement of the divalent cation droplet.

Therefore, the apparatus for producing alginate hydrogel particles coated with chitosan according to an embodiment of the present invention can improve the spraying amount and movement speed of divalent cation droplets by using the second carrier gas, and furthermore, the reaction glass tube 130 It can increase the crosslinking reaction rate of alginate droplets and divalent cation droplets in the

In addition, the pressure of the second carrier gas may be adjusted by the power of the second humidifier 120 .

The second connector 162 and the third connector 163 formed in the second humidifier 120 may be integrally formed, and the second connector 162 and the third connector 163 are integrally formed. ) may have a "ㅓ" shape. Accordingly, the divalent cation droplet may be moved to the reaction glass tube 130 through the second connection tube 162 by the second carrier gas, and may be moved to the collection vessel 140 through the third connection tube 163 . .

In addition, the vertical portion V of the integrally formed second connector 162 and the third connector 163 is disposed to connect the reaction glass tube 130 and the collection vessel 140 , and in the reaction glass tube 130 . The formed alginate hydrogel particles may be moved to a collection container (140).

The second connector 162 and the third connector 163 integrally formed in the collection container 140 direction so that the alginate hydrogel particles formed in the reaction glass tube 130 can be dispersed as a solution in the collection container 140 . An end of the formed third connecting pipe 163 is embedded in the solution in the collection container 140 .

The apparatus for producing alginate hydrogel particles coated with chitosan according to an embodiment of the present invention is formed so that the end of the third connector 163 is buried in the solution in the collection container 140, so that the alginate droplets and 2 The alginate hydrogel particles may be prepared by secondary reaction of the false cation droplets in the collection container 140 .

In addition, the end of the third connection pipe 163 formed in the direction of the collection vessel 140 may be formed to have a sharply inclined end, and the end of the third connection pipe formed in the direction of the collection vessel 140 may have an inclination. By being formed, the speed of the first carrier gas and the second carrier gas may be increased while passing through the third connecting pipe having a narrow end, so that the gas flow may be smooth.

The reaction glass tube 130 is a first humidifier 110 and a second humidifier so that the alginate droplets injected from the first humidifier 110 and the divalent cation droplets injected from the second humidifier 120 cross-link to generate alginate hydrogel particles. It may be disposed between the two humidifiers (120).

The reaction glass tube 130 will be described in more detail with reference to FIG. 3 .

Figure 3 is a schematic diagram showing a reaction glass tube included in the apparatus for producing alginate hydrogel particles coated with chitosan according to an embodiment of the present invention.

In the reaction glass tube 130, the alginate droplet 111 injected from the first humidifier 110 and the divalent cation droplet 121 injected from the second humidifier 120 collide, and the alginate droplet 111 and 2 When the false cation droplet 121 collides, alginate hydrogel particles 131 may be generated by a crosslinking reaction immediately.

More specifically, the apparatus for producing alginate hydrogel particles coated with chitosan according to an embodiment of the present invention is a first humidifier 110 and a second humidifier 120 comprising an alginate aqueous solution and a divalent cation aqueous solution, respectively. Alginate droplets 111 and divalent cation droplets 121 are sprayed into the reaction glass tube 130 erected vertically between the first humidifier 110 and the second humidifier 120, and the alginate droplets ( 111) and the divalent cation droplet 121 may cross-react with each other to produce alginate hydrogel particles 131.

At this time, inside the reaction glass tube 130, the divalent cations contained in the divalent cation droplet 121 cross-link the alginate polymer chain contained in the alginate droplet 111, so that the alginate droplet 111 and the divalent cation droplet 121 ), a crosslinking reaction may occur immediately upon collision to generate solid alginate hydrogel particles 131 .

Referring back to FIG. 1 , the apparatus for producing alginate hydrogel particles coated with chitosan according to an embodiment of the present invention includes a collection container 140 .

The alginate hydrogel particles 131 generated in the reaction glass tube 130 may be collected in the collection vessel 140 installed at the lower end of the reaction glass tube 130 formed in the vertical direction.

The collection container 140 may include a coating solution containing various functional materials capable of coating the surface of the alginate hydrogel particles, and the coating solution may be an aqueous solution containing chitosan.

Because alginate hydrogel particles are very hydrophilic, their use may be limited if the alginate hydrogel particles need to be hydrophobic.

For example, in order to make a Pickering emulsion that stabilizes the emulsion by adsorbing alginate hydrogel particles to the water-oil interface, it should have appropriate hydrophilicity and lipophilicity. However, the alginate hydrogel particles are very hydrophilic, so they cannot be adsorbed on the water-oil interface. does not

However, the apparatus for producing chitosan-coated alginate hydrogel particles according to an embodiment of the present invention can prepare alginate hydrogel particles coated with chitosan using a coating solution, and the degree of lipophilicity and hydrophilicity of the alginate hydrogel particles It can be used as a Pickering emulsion by adjusting the

According to the embodiment, the apparatus for producing chitosan-coated alginate hydrogel particles according to an embodiment of the present invention repeats the coating using a coating solution containing chitosan, so that the lipophilicity of the surface of the alginate hydrogel particles and The hydrophilicity can be controlled.

Specifically, the lipophilicity and hydrophilicity of the surface of the alginate hydrogel particles can be adjusted according to the concentration and pH of the coating solution, and the reaction time of the alginate hydrogel particles and the coating solution.

A detailed description of the coating principle of alginate hydrogel particles and chitosan will be dealt with in more detail in FIG. 5 to be described later, and the method of preparing a Pickering emulsion using alginate hydrogel particles coated with chitosan will be described in more detail in FIG. 6 to be described later. let it be dealt with

The apparatus for producing alginate hydrogel particles coated with chitosan according to an embodiment of the present invention may include an exhaust unit 150 formed in the collection container 140 .

The exhaust unit 150 discharges the first carrier gas and the second carrier gas carrying the alginate droplet and the divalent cation droplet to the reaction glass tube 130 .

The apparatus for producing alginate hydrogel particles coated with chitosan according to an embodiment of the present invention is collected in a collection container 140 in which alginate hydrogel particles contain a coating solution, and alginate hydrogel particles coated with chitosan are mass/continuous can be produced with

According to an embodiment, the apparatus for producing alginate hydrogel particles coated with chitosan according to an embodiment of the present invention directly obtains alginate droplets sprayed from the first humidifier in a collection container to prepare alginate hydrogel particles, and the collection container The coating solution contained in may further include a divalent cationic compound as a crosslinking agent, to prepare alginate hydrogel particles coated with chitosan.

Specifically, after a coating solution containing chitosan and a divalent cation compound is prepared in advance in the collection container, the alginate droplets sprayed from the first humidifier can be directly obtained in the collection container.

The obtained alginate droplets cross-link the divalent cation compound contained in the coating solution, and at the same time chitosan is incorporated therein, so that alginate hydrogel particles containing chitosan can be prepared in the collection container.

Hereinafter, in the description of the present invention, including the case of alginate hydrogel particles containing chitosan, all are expressed as alginate hydrogel particles coated with chitosan.

Figure 4 is a schematic diagram showing the reaction of alginate hydrogel particles according to an embodiment of the present invention.

Referring to FIG. 4 , the alginate compound is ionized in an aqueous alginate solution prepared by dissolving the alginate compound in water.

For example, when sodium alginate is used as the alginate compound, sodium alginate ^{is ionized into sodium (Na +} ) and alginate chains in an aqueous alginate solution.

Accordingly, sodium (Na ⁺ ) and alginate droplets containing alginate chains (alginate chains) are injected into the reaction glass tube by the first carrier gas, and sodium (Na ⁺ ) and alginate chains (alginate chains) are injected into the reaction glass tube in the reaction glass tube. When alginate droplets collide with divalent cation droplets containing divalent cations, ionized alginate chains centered on divalent cations by a crosslinking reaction may agglomerate to produce alginate hydrogel particles immediately.

5 is a schematic diagram showing the binding relationship between alginate hydrogel particles and chitosan according to an embodiment of the present invention.

Referring to Figure 5, the carboxyl group (-COOH) contained in the alginate hydrogel particles (Alginate) and the amine group (-NH ₂ ^{) contained in the chitosan (Chitosan) is -COO -} and -NH ³⁺ in the aqueous solution is changed to A strong hydrogen bond occurs between the two functional groups.

The -COO ^- and this is the chitosan coating on the surface of the alginate hydrogel particles based on the hydrogen bonding of the -NH ^3+, a chitosan-coated alginate hydrogel particles can be produced.

Hereinafter, a method for preparing a Pickering emulsion using alginate hydrogel particles coated with chitosan through FIG. 6 will be dealt with in detail.

6 is a flowchart illustrating a method for preparing a Pickering emulsion comprising alginate hydrogel particles coated with chitosan according to an embodiment of the present invention.

Referring to FIG. 6, the step of injecting alginate droplets formed in the first humidifier by the first carrier gas into the reaction glass tube (S110), the divalent cation droplets formed in the second humidifier by the second carrier gas into the reaction glass tube The step of injecting (S120), the step of crosslinking the alginate droplet and the divalent cation droplet in the reaction glass tube to produce alginate hydrogel particles (S130), the alginate hydrogel particles comprising a coating solution containing chitosan Obtaining in a collection container (S140), stirring the alginate hydrogel particles obtained in the collection container and the coating solution to coat the surface of the alginate hydrogel particles with chitosan (S150) and alginate coated with chitosan It includes a step (S160) of preparing a Pickering emulsion by mixing an aqueous phase material and an oil phase material containing hydrogel particles.

Since the manufacturing method of the Pickering emulsion according to an embodiment of the present invention includes the same components as the apparatus for manufacturing alginate hydrogel particles coated with chitosan, the same components will be omitted.

In step S110, the power of the first humidifier may be 200W or more.

If the power of the first humidifier is less than 200W, there is a problem that the alginate aqueous solution cannot be sprayed because the power is too weak.

In addition, the humidification amount of the first humidifier in step S110 may be 250g/hr to 3kg/hr.

In addition, the speed of the first carrier gas in step S110 may be 1L/min to 10L/min.

If the velocity of the first carrier gas is out of the above range, there is a problem in that the velocity is too high to sufficiently react the alginate droplet and the divalent cation droplet in the reaction glass tube.

According to an embodiment, the alginate aqueous solution sprayed through the first humidifier in step S110 may further include a magnetic material.

Accordingly, the Pickering emulsion containing the alginate hydrogel particles coated with the chitosan may have a magnetism, and it may be easy to recover the Pickering emulsion using a magnet.

According to the embodiment, the power of the second humidifier in step S120 may be 30W or more.

If the power of the second humidifier is less than 30W, there is a problem in that the power is too weak to spray the divalent cation aqueous solution.

In addition, the humidification amount of the second humidifier in step S120 may be 250g/hr to 3kg/hr.

In addition, the speed of the second carrier gas in step S120 may be 1L/min to 10L/min.

If the speed of the second carrier gas is out of the above range, there is a problem in that the alginate droplet and the divalent cation droplet cannot sufficiently react in the reaction glass tube because the speed is too high.

Step S130 can produce alginate hydrogel particles in the reaction glass tube, mass production and continuous production of alginate hydrogel particles is possible.

Step S140 primarily obtains alginate hydrogel particles prepared in a reaction glass tube.

According to an embodiment, in step S140, alginate hydrogel particles can be prepared by secondary reaction in a collection container using unreacted droplets, so that alginate hydrogel particles can be mass-produced in a simple way.

Step S140 may adjust the hydrophilicity and hydrophobicity of the alginate hydrogel particles coated with chitosan according to the concentration of the coating solution or the pH condition of the coating solution.

Specifically, as the concentration of the coating solution increases, the thickness of the chitosan coated on the surface of the alginate hydrogel particles increases, thereby improving the hydrophobicity of the alginate hydrogel particles coated with chitosan.

Depending on the embodiment, the chitosan may be included in the coating solution in an amount of 0.7 wt% to 1.4 wt% based on the total weight of the coating solution.

When the chitosan is included in the coating solution in an amount lower than 0.7% by weight, the amount of chitosan is insufficient to be coated on the surface of the alginate hydrogel particles, and when it is included in excess of 1.4% by weight, the viscosity is excessively high and the alginate hydrogel particles and coating There is a problem that the solution is not well stirred.

In addition, when the pH of the coating solution is acidic, specifically, when the pH of the coating solution is 4 to 5, the hydrophobicity of the alginate hydrogel particles coated with chitosan is weakened, and when the pH of the coating solution is neutral of 6 to 7, it is coated with chitosan The hydrophobicity of the alginate hydrogel particles can be strengthened.

Specifically, when the pH is less than 4, the carboxyl group of the alginate hydrogel particles mainly tries to remain -COOH because it is acidic, and the amine group of chitosan mainly changes to -NH ₃ ⁺ of the alginate hydrogel particles and hydrogen bonding of chitosan. the number decreases

If the pH is greater than 7, since the carboxyl group of the basic alginate hydrogel particles mainly -COO ^-, the amine groups of the chitosan weakens the hydrogen bond mainly it remains -NH ₂ between the alginate hydrogel particles and chitosan.

Therefore, in order to properly control the hydrophobicity and hydrophilicity of the alginate hydrogel particles coated with chitosan according to an embodiment of the present invention, the pH of the coating solution may be 4 to 7.

In step S150, the alginate hydrogel particles may be coated with chitosan on the surface of the alginate hydrogel particles by chemical bonding between the alginate hydrogel particles and chitosan in the collection container in which the alginate hydrogel particles are obtained.

According to the embodiment, in step S150, chitosan may be coated on the surface of the alginate hydrogel particles by stirring the obtained alginate hydrogel particles and the coating solution.

Step S150 can control the hydrophilicity and hydrophobicity of the alginate hydrogel particles coated with chitosan by adjusting the stirring time of the alginate hydrogel particles and the coating solution.

Specifically, as the stirring time increases, the reaction time between the alginate hydrogel particles and the chitosan may increase, thereby increasing the hydrophobicity.

Depending on the embodiment, the stirring may be performed for 1 hour to 40 hours.

Step S150 may prepare alginate hydrogel particles coated with chitosan having a diameter of 100 nm to 10 μm.

The thickness of the chitosan coated on the alginate hydrogel particles may be 10nm to 200nm.

When the thickness of the chitosan coated on the alginate hydrogel particles is out of the thickness range, there is a problem in that the alginate hydrogel particles and the chitosan do not hydrogen bond.

According to an embodiment, a magnetic material including magnetic metal nanoparticles and magnetic metal oxide nanoparticles and metal nanoparticles on the inside or surface of the alginate hydrogel particles coated with chitosan may be further included.

According to an embodiment, the inside or surface of the alginate hydrogel particles coated with chitosan and metal-organic frameworks (MOF) may further include at least one of composite nanoparticles,

Accordingly, the Pickering emulsion containing the alginate hydrogel particles coated with the chitosan can be collected by applying a magnetic field or can be efficiently collected by stirring in a magnetic stirrer, so it can be used in many biosensor and assay experiments.

In step S150, the surface of the alginate hydrogel particles may be coated with chitosan in the collection container, and the chitosan coating process of the alginate hydrogel particles may be performed in the same manufacturing apparatus.

In step S160, an oil phase material and an aqueous phase material may be mixed to prepare a Pickering emulsion.

According to an embodiment, the oily material is hexadecane, mineral oil, dodecane, octane, toluene, xylene, benzene, phenol. (phenol), chloroform (chloroform), dichloromethane (dichloromethane), n- decane (n-decane), and may include at least one of styrene (styrene).

The aqueous material may be an aqueous solution containing alginate hydrogel particles coated with chitosan prepared by steps S110 to S150.

Specifically, the aqueous material may be an aqueous solution comprising alginate hydrogel particles formed by crosslinking alginate droplets and divalent cation droplets, and the surface of which is coated with chitosan.

In step S160, a Pickering emulsion may be prepared by mixing the oil phase material and the aqueous phase material in a volume ratio of 1:0.5 to 1:10.

According to an embodiment, the alginate hydrogel particles coated with chitosan may have magnetism by further including a magnetic material.

Accordingly, the Pickering emulsion containing the alginate hydrogel particles coated with the chitosan can be collected by applying a magnetic field or can be efficiently collected by stirring in a magnetic stirrer, so it can be used in many biosensor and assay experiments.

According to an embodiment, between step S150 and step S160 may further include drying the alginate hydrogel particles coated with chitosan.

Drying the alginate hydrogel particles coated with chitosan may be freeze-drying the alginate hydrogel particles coated with chitosan.

According to an embodiment, the freeze-drying may be performed for 20 hours to 4 days at a temperature of -100°C to 10°C and a pressure of 3 Torr to 8 Torr.

Hereinafter, the Pickering emulsion prepared by the method for preparing the Pickering emulsion according to an embodiment of the present invention will be described.

Since the Pickering emulsion according to an embodiment of the present invention includes the same components as the manufacturing method of the Pickering emulsion described with reference to FIG. 6 , a redundant description will be omitted.

The Pickering emulsion according to an embodiment of the present invention is formed by crosslinking an oily material, an aqueous material, and alginate droplets and divalent cation droplets, and includes alginate hydrogel particles whose surface is coated with chitosan.

The oily material is a lipophilic material, and may include n-decane or styrene according to an embodiment, but is not limited thereto.

The water phase material may be water according to an embodiment, but is not limited to the material as long as it has a hydrophilic property.

The alginate hydrogel particles coated with chitosan serve as a Pickering emulsion stabilizer to stabilize the Pickering emulsion according to an embodiment of the present invention.

The alginate hydrogel particles coated with the chitosan may be adsorbed to the interface of the oil phase material and the water phase material to stabilize the interface.

The alginate hydrogel particles may have a diameter of 100 nm to 10 μm.

The thickness of the chitosan coated on the alginate hydrogel particles may be 10nm to 200nm.

According to an embodiment, the alginate hydrogel particles coated with chitosan may have magnetism by further including a magnetic material.

Accordingly, the Pickering emulsion containing the alginate hydrogel particles coated with the chitosan can be collected by applying a magnetic field or can be efficiently collected by stirring in a magnetic stirrer, so it can be used in many biosensor and assay experiments.

In the Pickering emulsion according to an embodiment of the present invention, the oil phase material and the aqueous phase material may have a volume ratio of 1:0.5 to 1:10.

The chitosan-coated alginate hydrogel particles may be included in the Pickering emulsion at 0.005 g/mL to 0.1 g/mL.

If the alginate hydrogel particles coated with chitosan are contained in less than 0.005 g/mL, the particles are too small to stabilize the interface of the Pickering emulsion.

When the alginate hydrogel particles coated with chitosan are included in excess of 0.1 g/mL, the alginate hydrogel particles coated with chitosan on the aqueous material become excessively large, so stabilization of the Pickering emulsion may be difficult.

The alginate hydrogel particles coated with chitosan may have hydrophobicity as well as hydrophilicity by chitosan.

Therefore, the alginate hydrogel particles coated with chitosan are well mixed with the oil phase material and the water phase material of the Pickering emulsion due to the hydrophilicity and hydrophobicity of the alginate hydrogel particles coated with chitosan, thereby stabilizing the Pickering emulsion.

Pickering emulsion according to an embodiment of the present invention, including alginate, has excellent biocompatibility, is eco-friendly, and has a low manufacturing cost.

Therefore, the Pickering emulsion according to an embodiment of the present invention can replace products containing existing surfactants such as cosmetics, food, pharmaceuticals, detergents and shampoos, and in particular, when the Pickering emulsion is used in cosmetics, cosmetics consisting of the existing emulsion The tactile feel may be better as compared to

Hereinafter, after preparing the alginate hydrogel particles coated with chitosan according to an embodiment of the present invention according to the preparation example, the characteristics and effects of the Pickering emulsion according to the embodiment were evaluated as follows.

Example

[Example 1]

1. Preparation of Alginate Hydrogel Particles

After mixing 1.0 g of sodium alginate and 100 mL of distilled water, sodium alginate was dispersed in distilled water while continuously stirring under heating to prepare an aqueous alginate solution.

After the alginate aqueous solution was transferred to the first humidifier stored in the ultrasonic chamber, 1.0% by weight of the barium acetate aqueous solution was added to the second humidifier.

Alginate droplets and barium ion droplets formed by spraying from the first humidifier and the second humidifier passed through the glass tube of the vertical tube to form alginate hydrogel particles.

The formed alginate hydrogel particles were collected in a collection vessel and stirred for one day.

The obtained alginate hydrogel particles were washed three times with distilled water to remove excess barium ions.

2. Preparation of Alginate Hydrogel Particles Coated with Chitosan

A homogeneous coating solution was prepared by dispersing 1.4 g of chitosan in a 0.1 M acetic acid solution.

Then, a dispersion was prepared by mixing a solution in which the alginate hydrogel particles were dispersed and the coating solution in a 1:1 ratio.

The prepared dispersion was stirred for 1 hour to prepare alginate hydrogel particles coated with chitosan. (hereinafter referred to as CAP-1h)

3. Preparation of Pickering Emulsion

A Pickering emulsion was prepared by mixing a dispersion of chitosan-coated alginate hydrogel particles with n-decane or styrene in a 1:1 volume ratio and stirring for 2 minutes.

[Example 2]

A Pickering emulsion comprising alginate hydrogel particles coated with chitosan was prepared in the same manner as in [Example 1] above, except that the solution in which the alginate hydrogel particles were dispersed and the coating solution were mixed and stirred for 20 hours. did. (hereinafter referred to as CAP-20h)

[Example 3]

1% by weight of barium acetate was further added to the neutral coating solution, and the alginate droplets sprayed from the first humidifier were immediately obtained in a collection container, and then stirred with the coating solution to which barium acetate and chitosan were added, and alginate hydrocoated with chitosan. A Pickering emulsion containing gel particles was prepared. (hereinafter referred to as CDAP)

[Example 4]

A Pickering emulsion comprising alginate hydrogel particles coated with chitosan was prepared in the same manner as in [Example 3], except that the pH of the coating solution was acidic.

[Example 5]

The alginate hydrogel particles coated with chitosan were included in the same manner as in [Example 4], except that 0.05 g/mL of magnetic nanoparticles (Fe ₂ O _{3 ) were further added to the coating solution in the alginate aqueous solution.} A Pickering emulsion was prepared. (hereinafter referred to as CDAP-MNP)

[Comparative example]

Pickering emulsion comprising the alginate hydrogel particles of [Example 1]. (hereinafter referred to as AP)

characterization

1. Whether alginate hydrogel particles are coated with chitosan

7 is a graph showing FT-IR spectra of alginate hydrogel particles according to Examples and Comparative Examples of the present invention.

Referring to FIG. 7 , it can be seen that the alginate hydrogel particles of the comparative example ^{have peaks at 1539 cm -1} and 1406 cm ^{-1 .}

This is due to the C=O stretching of the carboxyl groups in the alginate hydrogel particles.

In addition, the alginate hydrogel particles of Examples 1 to 5 have a ^{broad peak in the vicinity of about 3424 cm -1} , which is due to the hydroxyl group and the amine group of the alginate hydrogel particles.

It can be seen that the alginate hydrogel particles coated with chitosan of Examples 1 to 6 have a peak at ^{1656 cm -1 due to the C = O stretch of the secondary amide.}

Also, 1151cm ^-1, a peak at 1019cm ^-1 and 888cm ^-1 is due to the glue nose pyrano agarose ring of chitosan.

That is, it can be confirmed that the alginate hydrogel particles coated with chitosan of Examples 1 to 5 have both peak characteristics due to alginate and peak characteristics due to chitosan.

Accordingly, it can be seen that the alginate hydrogel particles coated with chitosan prepared according to Examples 1 to 5 are coated with chitosan on the surface of the alginate hydrogel particles.

Further, the iron oxide (MNP) is a magnetic material I of a peak at 636cm ^-1 and 549cm ^-1, it can be confirmed that such a peak characteristic is shown in Example 5.

Accordingly, it can be seen that Example 5 has magnetism due to the magnetic material.

Hereinafter, in order to evaluate the wettability of the alginate hydrogel particles, the contact angle of the alginate hydrogel particles of the Examples and Comparative Examples was measured.

2. Evaluation of wettability of alginate hydrogel particles

8 is a graph showing the contact angle of a Pickering emulsion comprising alginate hydrogel particles coated with chitosan according to an embodiment of the present invention.

Referring to FIG. 8 , it can be seen that the Pickering emulsions of Examples 1 to 5 have a larger contact angle than the Comparative Example.

That is, it can be seen that the alginate hydrogel particles coated with chitosan included in Examples 1 to 5 have more hydrophobicity than the Comparative Examples by chitosan.

Therefore, Examples 1 to 5 can prepare a stabilized Pickering emulsion because they have a property of appropriately mixing hydrophilicity and hydrophobicity.

3. Stabilization evaluation of Pickering emulsion

9a and 9b are optical microscope images showing the appearance immediately after and 4 days after the preparation of the Pickering emulsion containing alginate hydrogel particles and n-decane coated with chitosan according to an embodiment of the present invention.

Referring to FIGS. 9A and 9B , it can be seen that the size of the emulsion droplets is smaller in the Pickering emulsion of Examples 1 to 3 immediately after preparation of the Pickering emulsion compared to the Pickering emulsion of the comparative example.

This is because the alginate hydrogel particles coated with chitosan acted as a stabilizer of the Pickering emulsion so that the oily material n-decane and the water phase material were mixed well.

These results confirm that even when the Pickering emulsion was observed after 4 days, the Pickering emulsion of Examples 1 to 3 had smaller drops of the emulsion than the Pickering emulsion of the Comparative Example.

After 4 days of the Pickering emulsion of the comparative example, it can be confirmed that the size of the emulsion droplet increases compared to immediately after preparation.

This shows that it is difficult to stabilize the Pickering emulsion with alginate hydrogel particles alone.

On the other hand, it can be seen that the Pickering emulsions of Examples 1 to 3 have almost the same size of emulsion droplets even after 4 days.

This is because, due to the hydrophilicity and hydrophobicity of the alginate hydrogel particles coated with chitosan, emulsification of the Pickering emulsion including the oil phase material and the water phase material occurs well and stabilization is possible.

Therefore, the Pickering emulsion according to an embodiment of the present invention may have excellent stability due to the alginate hydrogel particles coated with chitosan.

10a and 10b are optical microscope images showing the appearance immediately after and 4 days after the preparation of the Pickering emulsion containing alginate hydrogel particles and styrene coated with chitosan according to an embodiment of the present invention.

Referring to FIGS. 10A and 10B , in the case of the Pickering emulsion of Comparative Example, when the oily material is styrene, it can be confirmed that the oily material and the water phase material are hardly emulsified immediately after preparation.

In addition, it can be confirmed that the Pickering emulsion of the comparative example is completely separated from the oily material and the water phase material after 4 days from the time of manufacture.

However, it can be seen that the Pickering emulsions of Examples 1 to 3 emulsify the oily material and the water phase material well while forming small-sized emulsion droplets immediately after preparation, similarly to the case where the oily material is n-decane.

In addition, it can be seen that the Pickering emulsion of Examples 1 to 3 maintains almost the same size of emulsion droplets as immediately after production even after 4 days from the time of manufacture.

Therefore, the Pickering emulsion according to an embodiment of the present invention can be stabilized by maintaining the emulsified state for a long period of time due to the alginate hydrogel particles coated with chitosan.

11a to 11c are optical microscopes showing the recovery by the magnet of the Pickering emulsion containing chitosan-coated alginate hydrogel particles, magnetic material and styrene according to an embodiment of the present invention, and immediately after and 3 days after preparation It is an image.

First, referring to FIG. 11a, in the Pickering emulsion of Example 5, it can be seen that the alginate hydrogel particles including the magnetic material of Example 5 are recovered in the direction of the neodymium magnet by the neodymium magnet.

In addition, when the neodymium magnet is removed, it can be seen that the alginate hydrogel particles of Example 5 are mixed with the Pickering emulsion again.

Therefore, it can be seen that the alginate hydrogel particles prepared according to Example 5 have magnetism by a magnetic material.

11B and 11C, it can be seen that the Pickering emulsion of Example 5 forms small-sized emulsion droplets immediately after preparation.

This means that the Pickering emulsion can be sufficiently stabilized even if a magnetic material is added during the preparation of alginate hydrogel particles.

In addition, it can be seen that the Pickering emulsion of Example 5 maintains almost the same drops of the emulsion as immediately after production even after 3 days from the time of manufacture.

Therefore, the Pickering emulsion according to an embodiment of the present invention can be stabilized by maintaining the emulsified state for a long period of time in the oily material and the water phase material even if a magnetic material is added to the alginate hydrogel particles coated with chitosan.

As described above, although the present invention has been described with reference to limited embodiments and drawings, the present invention is not limited to the above embodiments, and various modifications and variations from these descriptions are provided by those skilled in the art to which the present invention pertains. This is possible. Therefore, the scope of the present invention should not be limited to the described embodiments, but should be defined by the following claims as well as the claims and equivalents.

110: first humidifier 111: alginate droplets
112: first carrier gas 120: second humidifier
121: divalent cation droplet 130: reaction glass tube
131: alginate hydrogel particles 140: collection container
150: exhaust unit 161: first connection pipe
162: second connector 163: third connector

Claims (11)

alginate droplets formed in the first humidifier by the first carrier gas are injected into the reaction glass tube;
Injecting divalent cation droplets formed in a second humidifier by a second carrier gas into the reaction glass tube;
The alginate droplet and the divalent cation droplet are crosslinked in the reaction glass tube to prepare alginate hydrogel particles;
obtaining the alginate hydrogel particles in a collection container containing a coating solution containing chitosan;
Coating the surface of the alginate hydrogel particles with chitosan by stirring the alginate hydrogel particles obtained in the collection container and the coating solution; and
Comprising the step of preparing a Pickering emulsion by mixing an aqueous phase material and an oil phase material containing the alginate hydrogel particles coated with the chitosan,
The speed of the first carrier gas is 1 L / min to 10 L / min,
The speed of the second carrier gas is 1 L / min to 10 L / min,
The step of obtaining the alginate hydrogel particles in a collection vessel containing a coating solution containing chitosan is characterized in that the alginate hydrogel particles are prepared by secondary reaction in the collection vessel using unreacted droplets in the reaction glass tube. A method for producing a Pickering emulsion.
According to claim 1,
The method for producing a Pickering emulsion, characterized in that the chitosan is contained in 0.7% to 1.4% by weight relative to the total weight of the coating solution.
According to claim 1,
The method for producing a Pickering emulsion, characterized in that the pH of the coating solution is 4 to 7.
According to claim 1,
The stirring is a method for producing a Pickering emulsion, characterized in that it is carried out for 1 hour to 40 hours.
According to claim 1,
The alginate hydrogel particles coated with chitosan further include at least one of magnetic metal nanoparticles, magnetic metal oxide nanoparticles, metal nanoparticles, and metal-organic frameworks (MOF) composite nanoparticles. A method for producing a Pickering emulsion.
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