KR20210030009A - Pickering emulsion including alginate hydrogel particles coated with chitosan and manufacturing method by the same - Google Patents

Abstract

The present invention relates to a pickering emulsion including alginate hydrogel particles coated with chitosan and a method for preparing the same. The method for preparing a pickering emulsion including alginate hydrogel particles coated with chitosan includes the steps of: introducing alginate liquid droplets formed in a first humidifier by a first carrier gas to a reaction glass tube; introducing divalent cation liquid droplets formed in a second humidifier by a second carrier gas to the reaction glass tube; crosslinking the alginate liquid droplets with the divalent cation liquid droplets in the reaction glass tube to form alginate hydrogel particles; collecting the alginate hydrogel particles in a collection container including a coating solution containing chitosan; agitating the alginate hydrogel particles and the coating solution received in the collection container so that the surfaces of the alginate hydrogel particles may be coated with chitosan; and mixing the aqueous phase material including the alginate hydrogel particles coated with chitosan with an oil phase material to obtain a pickering emulsion.

Description

Pickering emulsion containing chitosan-coated alginate hydrogel particles and its manufacturing method {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 the excessive use of surfactants that are harmful to human health and the environment.

In order to solve this problem, pickering emulsions prepared using solid particles replacing surfactants have emerged.

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

Therefore, Pickering Emulsion shows potential applications in various fields such as drug delivery, food industry, cosmetics, agriculture, road construction industry, and paint companies.

Pickering emulsion 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 fall into four categories, including polysaccharides, proteins, nucleic acids and lipids.

Natural polymers can be used in various applications because they have properties such as reproducibility, biodegradability, biocompatibility and non-toxicity, and most natural polymers are inexpensive because they are obtained from nature.

Natural polymers have various surface reactors capable of surface modification, and thus can be used in various applications.

Among the natural polymer polysaccharides, alginate is a naturally occurring anionic polymer that is widely found in brown algae, and has proven its excellent utility in biomedical fields for encapsulation in the food industry, pharmaceuticals, arts and crafts industries.

Nevertheless, there are few studies used to stabilize emulsions due to alginate particles 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, this has a problem of using again an existing surfactant that is harmful to the human body and the environment in order to prepare an emulsion containing alginate particles.

Korean Patent Laid-Open Publication No. 10-2011-0100857, "HH sensitive microcapsules containing fine alginate particles and fine calcium carbonate particles and a method for manufacturing the same" Republic of Korea Patent Registration No. 10-0919508, "Alginate particles containing calcium carbonate in the matrix and its manufacturing method"

In an embodiment of the present invention, by obtaining the alginate hydrogel particles in a collection container containing the chitosan solution, it is possible to coat the surface of the alginate hydrogel particles at the same time as obtaining the alginate hydrogel particles, so that the mass production of alginate hydrogel particles coated with chitosan And it is intended to provide a pickering emulsion containing alginate hydrogel particles coated with chitosan capable of continuous production, and a method for producing the same.

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

An embodiment of the present invention relates to a pickering emulsion comprising alginate hydrogel particles coated with chitosan that can adjust 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. I want to provide.

An embodiment of the present invention is a pickering emulsion containing alginate hydrogel particles coated with chitosan that can control the hydrophobicity of alginate hydrogel particles coated with chitosan according to the stirring time of the coating solution and the alginate hydrogel particles, and a method for preparing the same. I want to provide.

An embodiment of the present invention is to provide a pickering emulsion containing alginate hydrogel particles coated with chitosan that can stabilize the pickering emulsion for a long time by using the hydrophilicity and hydrophobicity of the alginate hydrogel particles coated with chitosan and a method for preparing the same. do.

An embodiment of the present invention is that the alginate hydrogel particles coated with chitosan further include a magnetic material, and alginate hydrogel particles coated with chitosan for easy recovery of the alginate hydrogel particles coated with chitosan in the Pickering emulsion by a magnetic field. It is intended to provide a pickering emulsion comprising a and a method for producing the same.

The method for producing a pickering emulsion comprising alginate hydrogel particles coated with chitosan according to the present invention comprises: injecting alginate droplets formed in a first humidifier by a first carrier gas into a reaction glass tube; Injecting a divalent cation droplet formed in a second humidifier by a second carrier gas into the reaction glass tube; Crosslinking the alginate droplets and the divalent cation droplets 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; 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; And it characterized in that it comprises the step of preparing a pickering emulsion by mixing the water phase material and the oily material containing the alginate hydrogel particles coated with chitosan.

According to the method for producing a pickering emulsion including alginate hydrogel particles coated with chitosan according to an embodiment of the present invention, the chitosan may be contained in an amount of 0.7% to 1.4% by weight based on the total weight of the coating solution.

According to the method for preparing a pickering emulsion including 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 producing a pickering emulsion containing alginate hydrogel particles coated with chitosan according to an embodiment of the present invention, the stirring may be performed for 1 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, and metal nanoparticles. And metal-organic frameworks (MOF) composite nanoparticles.

Pickering emulsion comprising alginate hydrogel particles coated with chitosan according to the present invention includes an oily substance; Waterborne substances; And alginate hydrogel particles formed by crosslinking the alginate droplets and the divalent cation droplets, and having a surface coated with chitosan.

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

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

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

According to the Pickering emulsion containing 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- It may further include at least one of the organic framework (MOF, metal organic frameworks) composite nanoparticles.

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 of the alginate hydrogel particles at the same time as obtaining the alginate hydrogel particles. Mass production and serial 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 may 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 may 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 that the alginate hydrogel particles coated with chitosan in the Pickering emulsion can be easily recovered 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.
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.
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.
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 a binding relationship between alginate hydrogel particles and chitosan according to an embodiment of the present invention.
6 is a flow chart showing a method of manufacturing a pickering emulsion including alginate hydrogel particles coated with chitosan according to an embodiment of the present invention.
7 is a graph showing the FT-IR spectrum of alginate hydrogel particles according to Examples and Comparative Examples of the present invention.
8 is a graph showing a contact angle of a pickering emulsion including 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 preparation of a 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 preparation of a Pickering emulsion containing chitosan-coated alginate hydrogel particles and styrene according to an embodiment of the present invention.
11A to 11C are optical microscopes showing the recovery of the pickering emulsion containing chitosan-coated alginate hydrogel particles, magnetic materials, and styrene by a magnet according to an embodiment of the present invention, and immediately after and 3 days after manufacture. It is an image.

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

The terms used in the present specification are for describing exemplary embodiments and are not intended to limit the present invention. In this specification, the singular form also includes the plural form unless specifically stated in the phrase. As used in the specification, “comprises” and/or “comprising” do not exclude the presence or addition of one or more other elements or steps to the mentioned elements or steps.

As used herein, "an embodiment", "example", "side", "example", etc. should be construed as having any aspect or design described better than or having an advantage over other aspects or designs. It is not.

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

In addition, the singular expression ("a" or "an") used in this specification and claims generally means "one or more" unless otherwise stated or unless it is clear from the context that it relates to the singular form. Should be interpreted as.

The terms used in the description below have been 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, terms used in the following description should not be understood as limiting the technical idea, but should be understood as illustrative terms for describing embodiments.

In addition, in certain cases, there are terms arbitrarily selected by the applicant, and in this case, detailed meanings will be described in the corresponding description. Therefore, terms used in the following description should be understood based on the meaning of the term and the contents throughout the specification, not just the name of the term.

Unless otherwise defined, all terms (including technical and scientific terms) used in the present specification may be used with meanings that can be 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 interpreted ideally or excessively unless explicitly defined specifically.

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 subject matter of the present invention, a detailed description thereof will be omitted. In addition, terms used in the present specification are terms used to properly express an embodiment of the present invention, which may vary depending on the intention of users or operators, or customs in the field to which the present invention belongs. Therefore, definitions of these terms should be made based on the contents throughout the present specification.

The method for preparing a pickering emulsion comprising alginate hydrogel particles coated with chitosan according to the present invention relates to a method of 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 containing the alginate hydrogel particles coated with chitosan, a description of the apparatus for producing the chitosan-coated alginate hydrogel particles and the method for manufacturing the same will be described in FIGS. 1 to 1 below. 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.

Referring to FIG. 1, a structure in which a first humidifier 110 is formed on an upper portion and a second humidifier 120 is formed on a lower portion is illustrated, 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 comprises a first humidifier 110 for injecting alginate droplets using a first carrier gas, and divalent cation droplets using a second carrier gas. A reaction glass tube 130 formed between the injected second humidifier 120, the first humidifier 110 and the second humidifier 120, and in which alginate droplets and divalent cation droplets are crosslinked to form alginate hydrogel particles, and And a collection container 140 from which alginate hydrogel particles are obtained.

The collection container 140 may include a coating solution containing chitosan and 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 the first humidifier 110 and the second humidifier 120 to mass-produce alginate hydrogel particles in the size of hundreds of nanometers to tens of microns. It can be produced and serially produced.

The first humidifier 110 is for injecting alginate droplets into the reaction glass tube 130, and the first humidifier 110 may include an alginate aqueous 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 contain 1% to 10% by weight of the alginate compound, and when the amount of the alginate compound is out of the above-described range, the viscosity of the alginate aqueous solution increases and sprays through the first humidifier 110 There is a problem that does not work.

According to an embodiment, 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 framework (MOF) composite nanoparticles, but is not limited thereto.

The magnetic metal nanoparticles are 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) , Currency 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 It may contain at least one of elements (Pt, Pd, etc.).

The magnetic metal oxide nanoparticles are 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 ), currency 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 containing at least one or more of platinum group elements (Pt, Pd, etc.).

The alginate hydrogel particles coated with chitosan can further include a magnetic material to produce alginate hydrogel particles that react to a magnetic field, so that it is easy to recover the alginate hydrogel particles coated with chitosan, and use this to achieve a small size. It is possible to manufacture a magnetic bar (magnetic bar).

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

The metal-organic skeletal structure complex nanoparticle may be a complex in which various central metal ions are combined with an organic ligand.

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

The organic ligands include benzoimidazole, 2,5-dihydroxyterephthalic acid (DOT; 2,5-dihydroxyterephthalic acid), carboxylate, phosphonate, amine, and Zide, thionite, squaryl, heteroatom, monocarboxylic acid, dicarboxylic acid, tricarboxylic acid , Tetracarboxylic acid, imidazole, formic acid, acetic acid, oxalic acid, propanoic acid, butanedioic 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-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, 2,5-dihydro 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'-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 any one of 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 in that the power is too weak to spray an aqueous solution of alginate 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 a dotted box portion of FIG. 1. In addition, although FIG. 2 illustrates the first humidifier 110, the first humidifier 110 and the second humidifier may include the same components except that the types of aqueous solutions contained in the humidifier are different. It is not limited.

The first humidifier 110 has an ultrasonic vibrator disposed under a container for accommodating an aqueous alginate 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, a first connection tube 161 through which alginate droplets are moved is connected.

Therefore, when the first humidifier 110 vibrates the alginate aqueous solution using an ultrasonic vibrator disposed under the container containing the alginate aqueous solution, the alginate droplet 111 is fined by ultrasonic waves, and the generated alginate droplet 111 ) 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 alginate droplets, and may include, for example, at least one of air, nitrogen, argon, and helium.

The alginate droplet 111 can be injected into the reaction glass tube 130 only by the first humidifier 110, but the first humidifier 110 can further improve the movement of the alginate droplet 111 by flowing the first carrier gas. have.

Therefore, the apparatus for producing alginate hydrogel particles coated with chitosan according to an embodiment of the present invention uses the first carrier gas 122 to improve the spray amount and movement speed of the alginate droplet 111, and further react It is possible to increase the crosslinking reaction ratio 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, an 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 ), and strontium chloride. (strontium chloride, SrCl ₂ ), calcium acetate, calcium lactate, and calcium gluconate.

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

When the concentration of the aqueous divalent cation solution increases, a 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% to 10% by weight of a divalent cation compound.

When the amount of the divalent cation compound contained in the aqueous divalent cation solution has the above-described range, since the crosslinking reaction proceeds sufficiently quickly, the amount of the divalent cation solution does not need to exceed the above-described range.

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 in the second humidifier 120 rather than a divalent cation aqueous solution, and a trivalent cation 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 that the power is too weak to spray the aqueous divalent cation solution.

In the second humidifier 120, an ultrasonic vibrator is disposed under the container for accommodating a divalent cation aqueous solution, a second carrier gas pump for injecting a second carrier gas is disposed on the side, and the second humidifier 120 A second connection pipe 162 through which divalent cation droplets and alginate hydrogel particles are moved is connected between the reaction glass tube 130, and divalent cation droplets are connected between the second humidifier 120 and the collection container 140. And a third connection pipe 163 through which alginate hydrogel particles are moved.

Therefore, the second humidifier 120 vibrates the divalent cation aqueous solution using an ultrasonic vibrator disposed under the container containing the divalent cation aqueous solution, and generates micronized divalent cation droplets by ultrasonic waves, and the generated 2 The positive cation droplet 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 only with the second humidifier 120, but the second humidifier 120 may improve the movement of the divalent cation droplet by flowing a second carrier gas.

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 further, the reaction glass tube 130 It is possible to increase the crosslinking reaction rate of the alginate droplets and the divalent cation droplets within.

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

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

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

The second connector 162 and the third connector 163 integrally formed are in the direction of the collection container 140 so that the alginate hydrogel particles formed in the reaction glass tube 130 can be dispersed as a solution in the collection container 140. The end of the formed third connection 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 such that the end of the third connecting pipe 163 is buried in the solution in the collection container 140, so that the alginate droplets and 2 Alginate hydrogel particles may be prepared by secondary reaction of the cation droplets in the collection container 140.

In addition, the end of the third connecting pipe 163 formed in the direction of the collecting container 140 may be formed to have a sharp inclination, and the end of the third connecting pipe formed in the direction of the collecting container 140 may have an inclination. By being formed, the speed of the first carrier gas and the second carrier gas increases while passing through the third connecting pipe whose end is narrowed, so that gas flow may be smooth.

The reaction glass tube 130 includes the first humidifier 110 and agent so that the alginate droplet injected from the first humidifier 110 and the divalent cation droplet injected from the second humidifier 120 crosslink to generate alginate hydrogel particles. 2 It may be disposed between the humidifier 120.

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

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 As soon as the positive cation droplet 121 collides, alginate hydrogel particles 131 may be generated by a crosslinking reaction.

More specifically, 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 each containing an aqueous solution of alginate and an aqueous solution of divalent cation. Alginate droplets 111 and divalent cation droplets 121 are sprayed into a reaction glass tube 130 vertically erected between the first humidifier 110 and the second humidifier 120, and the alginate droplets ( 111) and the divalent cation droplet 121 may crosslink each other to generate alginate hydrogel particles 131.

At this time, in the reaction glass tube 130, the divalent cations included in the divalent cation droplet 121 cross-link the alginate polymer chain included in the alginate droplet 111, so that the alginate droplet 111 and the divalent cation droplet 121 As soon as) collides, a crosslinking reaction may occur to generate solid alginate hydrogel particles 131.

Referring back to FIG. 1, an 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 container 140 installed at the lower end of the reaction glass tube 130 formed in a vertical direction.

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

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

For example, to make a pickering emulsion that stabilizes the emulsion by adsorbing alginate hydrogel particles at the water-oil interface, it must have adequate hydrophilicity and lipophilicity, but alginate hydrogel particles are very hydrophilic, so they cannot be adsorbed at the water-oil interface. Does not.

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

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

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

A detailed description of the coating principle of alginate hydrogel particles and chitosan will be described in more detail in FIG. 5 to be described later, and a 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's deal with it.

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

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

In the apparatus for producing alginate hydrogel particles coated with chitosan according to an embodiment of the present invention, the alginate hydrogel particles are collected in the collection container 140 containing the coating solution, and the alginate hydrogel particles coated with chitosan are collected in bulk/continuously. Can be produced.

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 a first humidifier into a collection container to produce alginate hydrogel particles, and the collection container The coating solution contained in may further include a divalent cationic compound as a crosslinking agent, and alginate hydrogel particles coated with chitosan may be prepared.

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

The obtained alginate droplet crosslinks the divalent cation compound contained in the coating solution, and chitosan is incorporated therein to prepare alginate hydrogel particles containing chitosan in the collection container.

Hereinafter, in the description of the present invention, all of the alginate hydrogel particles containing chitosan will be expressed as alginate hydrogel particles coated with chitosan.

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

4, the alginate compound is ionized in the alginate aqueous 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 the alginate aqueous solution.

Therefore, alginate droplets including sodium (Na ⁺ ) and alginate chains are injected into the reaction glass tube by the first carrier gas, and sodium (Na ⁺ ) and alginate chains are included in the reaction glass tube. When the alginate droplet collides with the divalent cation droplet including the divalent cation, the alginate chain ionized around the divalent cation is entangled by a crosslinking reaction, thereby generating alginate hydrogel particles immediately.

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

5, the carboxyl group (-COOH) included in the alginate hydrogel particles (Alginate) and the amine group (-NH ₂ ) included in chitosan are changed to ^-COO- and -NH ³⁺ in an aqueous solution. Strong hydrogen bonds occur between the two functional groups.

The chitosan is coated on the surface of the alginate hydrogel particles based on the hydrogen bonds of ^-COO- and -NH ^{3+, so that the alginate hydrogel particles coated with chitosan can be prepared.}

Hereinafter, a method of preparing a pickering emulsion using alginate hydrogel particles coated with chitosan will be described in detail through FIG. 6.

6 is a flow chart showing a method of manufacturing a pickering emulsion including alginate hydrogel particles coated with chitosan according to an embodiment of the present invention.

6, the step of injecting the alginate droplet formed in the first humidifier by the first carrier gas into the reaction glass tube (S110), the divalent cation droplet formed in the second humidifier by the second carrier gas into the reaction glass tube Injecting (S120), in which the alginate droplets and the divalent cation droplets are crosslinked in the reaction glass tube to prepare alginate hydrogel particles (S130), including a coating solution containing chitosan for the alginate hydrogel particles 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 And a step (S160) of preparing a Pickering emulsion by mixing an aqueous phase material including hydrogel particles and an oily material.

Since the method for preparing the pickering emulsion according to the embodiment of the present invention includes the same components as the apparatus for producing 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 power is too weak to spray the alginate aqueous solution.

In addition, the amount of humidification 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 speed of the first carrier gas is out of the above-described range, the speed is too high, and thus alginate droplets and divalent cation droplets are not sufficiently reacted 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 including the alginate hydrogel particles coated with chitosan may have magnetic properties, and thus the pickering emulsion may be easily recovered using a magnet.

According to an 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 that the power is too weak to spray the aqueous divalent cation solution.

In addition, the amount of humidification 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-described range, the speed is too high, and there is a problem in that the alginate droplet and the divalent cation droplet are not sufficiently reacted in the reaction glass tube.

Step S130 can produce alginate hydrogel particles in a reaction glass tube, so mass production and continuous production of alginate hydrogel particles are possible.

Step S140 is primarily to obtain alginate hydrogel particles prepared in a reaction glass tube.

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

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, so that the hydrophobicity of the alginate hydrogel particles coated with chitosan may be improved.

According to an embodiment, the chitosan may be included in the coating solution in an amount of 0.7% to 1.4% by weight 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 because it is coated on the surface of the alginate hydrogel particles, and when it is included in more than 1.4% by weight, the viscosity is excessively high, and the alginate hydrogel particles are coated with There is a problem in that the solution is not stirred well.

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 decreases, and when the pH of the coating solution is 6 to 7 neutral, the coating solution is coated with chitosan. The hydrophobicity of the alginate hydrogel particles may be strong.

Specifically, when the pH is less than 4, the carboxyl group of the alginate hydrogel particles is mainly intended to remain -COOH because it is acidic, and the amine group of chitosan is mainly _{changed to -NH 3} ⁺ and the chitosan hydrogen bonds with the alginate hydrogel particles. The number decreases.

When the pH is greater than 7, the carboxyl group of the alginate hydrogel particle is mainly -COO ^- and the amine group of the chitosan _{remains mainly -NH 2} because the alginate hydrogel particle is basic, and the hydrogen bond between the alginate hydrogel particle and the chitosan is weakened.

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, chitosan may be coated 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 an embodiment, step S150 may be performed by stirring the obtained alginate hydrogel particles and the coating solution to coat the surface of the alginate hydrogel particles with chitosan.

Step S150 may adjust 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 chitosan increases, so that the hydrophobicity may become stronger.

Depending on the embodiment, the agitation may be performed for 1 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 chitosan coated on the alginate hydrogel particles may be 10 nm to 200 nm.

When the thickness of the chitosan coated on the alginate hydrogel particles is out of the thickness range, there is a problem 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 may be further included on the inside or the surface of the alginate hydrogel particles coated with chitosan.

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

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

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

In step S160, an oily substance and an aqueous phase substance may be mixed to prepare a pickering emulsion.

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

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

Specifically, the water phase material may be an aqueous solution including alginate hydrogel particles having an alginate droplet and a divalent cation droplet crosslinking and having a surface coated with chitosan.

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

According to an embodiment, the alginate hydrogel particles coated with chitosan may further include a magnetic material to have magnetic properties.

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

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

In the step of drying the chitosan-coated alginate hydrogel particles, the chitosan-coated alginate hydrogel particles may be freeze-dried.

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, a pickering emulsion prepared by a method for producing a pickering emulsion according to an embodiment of the present invention will be described.

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

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

The oily material is a material having lipophilicity, and may include n-decane or styrene, but is not limited thereto.

The water-phase material may be water depending on the embodiment, but the material is not limited to the material as long as it has hydrophilicity.

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 chitosan may be adsorbed to the interface between the oily material and the aqueous material to stabilize the interface.

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

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

According to an embodiment, the alginate hydrogel particles coated with chitosan may further include a magnetic material to have magnetic properties.

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

In the pickering emulsion according to an embodiment of the present invention, the oily substance and the water phase substance may have a volume ratio of 1:0.5 to 1:10.

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

If the alginate hydrogel particles coated with chitosan are contained in an amount of less than 0.005 g/mL, there are too few particles and it is difficult to stabilize the interface of the pickering emulsion.

When the alginate hydrogel particles coated with chitosan exceed 0.1 g/mL, the alginate hydrogel particles coated with chitosan on the water phase material become excessively large, making it difficult to stabilize the pickering emulsion.

The alginate hydrogel particles coated with chitosan may have not only hydrophilicity but also hydrophobicity due to chitosan.

Therefore, the alginate hydrogel particles coated with chitosan can stabilize the pickering emulsion by mixing the oily substance and the aqueous phase substance of the pickering emulsion well due to the hydrophilicity and hydrophobicity of the alginate hydrogel particles coated with chitosan.

Pickering emulsion according to an embodiment of the present invention, including alginate, is excellent in 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, foods, pharmaceuticals, detergents and shampoos. Compared with, the tactile feel may be better.

Hereinafter, the alginate hydrogel particles coated with chitosan according to an embodiment of the present invention were prepared according to the Preparation Example, and then the characteristics and effects of the Pickering emulsion according to the Example 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, while continuously stirring under heating, sodium alginate was dispersed in distilled water to prepare an alginate aqueous solution.

After the alginate aqueous solution was transferred to a first humidifier stored in an ultrasonic chamber, 1.0% by weight of an aqueous barium acetate 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 a glass tube of a vertical tube to form alginate hydrogel particles.

The formed alginate hydrogel particles were obtained in a collection container 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

1.4 g of chitosan was dispersed in a 0.1 M acetic acid solution to prepare a homogeneous coating solution.

Then, the solution in which the alginate hydrogel particles were dispersed and the coating solution were mixed in a 1:1 ratio to prepare a dispersion.

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

3. Preparation of Pickering Emulsion

A dispersion of chitosan-coated alginate hydrogel particles and n-decane or styrene were mixed in a 1:1 volume ratio and then stirred for 2 minutes to prepare a Pickering emulsion.

[Example 2]

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

[Example 3]

1% by weight of barium acetate was further added to the neutral coating solution, and 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 the alginate hydrocoated with chitosan. A Pickering emulsion containing gel particles was prepared. (Hereinafter, CDAP)

[Example 4]

A Pickering emulsion including 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]

Including alginate hydrogel particles coated with chitosan in the same manner as in [Example 4], except that 0.05 g/mL _{of iron oxide (Fe 2} O ₃ ), which is a magnetic nanoparticle, was further added to the coating solution to the alginate aqueous solution. A Pickering emulsion was prepared. (Hereinafter, CDAP-MNP)

[Comparative Example]

Pickering emulsion containing the alginate hydrogel particles of [Example 1]. (Hereinafter, AP)

Property evaluation

1. Whether alginate hydrogel particles are coated with chitosan

7 is a graph showing the FT-IR spectrum 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 around 3424 cm -1} , which is due to the hydroxyl group and 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 seen that the alginate hydrogel particles coated with chitosan of Examples 1 to 5 have both a peak due to alginate and a peak characteristic 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 the fifth embodiment has magnetism by the magnetic material.

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

2. Wetability evaluation of alginate hydrogel particles

8 is a graph showing a contact angle of a pickering emulsion including 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 example by chitosan.

Accordingly, since Examples 1 to 5 have properties in which hydrophilicity and hydrophobicity are properly mixed, a stabilized Pickering emulsion can be prepared.

3. Stabilization evaluation of pickering emulsion

9A and 9B are optical microscope images showing the appearance immediately after and 4 days after preparation of a 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 of the Pickering emulsions of Examples 1 to 3 is smaller than that of the Pickering emulsions of Comparative Examples in the case of immediately after preparation of the Pickering emulsion.

This is because the alginate hydrogel particles coated with chitosan acted as a stabilizer for the pickering emulsion so that n-decane, an oily substance, and an aqueous phase substance were well mixed.

These results can be seen that even when the Pickering emulsion was observed 4 days later, the Pickering emulsions of Examples 1 to 3 had smaller emulsion droplets than the Pickering emulsion of the Comparative Example.

It can be seen that the size of the emulsion droplets increased after 4 days of the pickering emulsion of the comparative example compared to immediately after preparation.

This shows that it is difficult to stabilize the pickering emulsion with only alginate hydrogel particles.

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

This is because, due to the hydrophilicity and hydrophobicity of the alginate hydrogel particles coated with chitosan, the pickering emulsion containing an oily substance and an aqueous phase substance is easily emulsified to enable stabilization.

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 preparation of a Pickering emulsion containing chitosan-coated alginate hydrogel particles and styrene according to an embodiment of the present invention.

Referring to FIGS. 10A and 10B, it can be seen that in the pickering emulsion of the comparative example, when the oily substance is styrene, the oily substance and the aqueous phase substance are hardly emulsified immediately after preparation.

In addition, in the pickering emulsion of the comparative example, it can be confirmed that the oily substance and the aqueous phase substance are completely separated 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 substance and the aqueous phase substance well while forming droplets of the emulsion having a small size immediately after preparation, as in the case where the oily substance is n-decane.

In addition, it can be seen that the pickering emulsions of Examples 1 to 3 maintain the emulsion droplets of almost the same size as immediately after preparation even after 4 days from the time of preparation.

Accordingly, the pickering emulsion according to an embodiment of the present invention can be stabilized by maintaining an 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 of the pickering emulsion containing chitosan-coated alginate hydrogel particles, magnetic material, and styrene by a magnet according to an embodiment of the present invention, and immediately after and 3 days after manufacture. It is an image.

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

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

Accordingly, it can be seen that the alginate hydrogel particles prepared according to Example 5 have magnetic properties due to the magnetic material.

Referring to FIGS. 11B and 11C, it can be seen that the pickering emulsion of Example 5 forms emulsion droplets of small size immediately after preparation.

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

In addition, it can be seen that the pickering emulsion of Example 5 maintains almost the same droplets of the emulsion as immediately after preparation even after 3 days from the time of preparation.

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

As described above, although the present invention has been described by limited embodiments and drawings, the present invention is not limited to the above embodiments, and various modifications and variations from these descriptions are those of ordinary skill in the field to which the present invention pertains. This is possible. Therefore, the scope of the present invention is limited to the described embodiments and should not be defined, but should be defined by the claims to be described later as well as those equivalent to the claims.

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

Claims (11)

Injecting the alginate droplets formed in the first humidifier by the first carrier gas into the reaction glass tube;
Injecting a divalent cation droplet formed in a second humidifier by a second carrier gas into the reaction glass tube;
Crosslinking the alginate droplets and the divalent cation droplets 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;
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; And
Preparing a pickering emulsion by mixing an aqueous phase material and an oily material including the alginate hydrogel particles coated with chitosan
Method for producing a pickering emulsion, characterized in that it comprises a.
The method of claim 1,
The chitosan is a method for producing a pickering emulsion, characterized in that contained in an amount of 0.7% to 1.4% by weight based on the total weight of the coating solution.
The method of claim 1,
The method for producing a pickering emulsion, characterized in that the pH of the coating solution is 4 to 7.
The method of claim 1,
The stirring is a method for producing a pickering emulsion, characterized in that carried out for 1 to 40 hours.
The method of 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. Method for producing a pickering emulsion.
Oily substances;
Waterborne substances; And
Alginate hydrogel particles formed by crosslinking alginate droplets and divalent cation droplets, and coated with chitosan on the surface
Pickering emulsion comprising a.
The method of claim 6,
Pickering emulsion, characterized in that the thickness of the chitosan coated on the alginate hydrogel particles is 10nm to 200nm.
The method of claim 6,
The oily substances include hexadecane, mineral oil, dodecane, octane, toluene, xylene, benzene, phenol, and chloroform. Pickering emulsion comprising at least one of (chloroform), dichloromethane, n-decane and styrene.
The method of claim 6,
Pickering emulsion, characterized in that the oily material and the water-phase material are contained in a volume ratio of 1:0.5 to 1:10.
The method of claim 6,
Pickering emulsion, characterized in that the alginate hydrogel particles coated with chitosan are contained in the pickering emulsion at 0.005g/mL to 0.1g/mL.
The method of claim 6,
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. Pickering emulsion.

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