KR100741381B1 - Organic-inorganic complex nano-hydrogel and preparing process thereof - Google Patents

Abstract

The present invention relates to an organic-inorganic hybrid nanohydrogel and a method for producing the same, and more particularly, to a silicate-based organic / inorganic hybrid nanohydrogel having improved water resistance, which is useful as a flame retardant, and a method for producing the same.

The organic-inorganic hybrid nanohydrogel according to the present invention is characterized in that a silicate-based inorganic aqueous solution is bonded to the surface of a porous nanoparticle of a polymer capable of forming an ionic bond in an ion-bonded form to form a skin-core structure, The surface area is dramatically increased by emulsifying the polymer solution dissolved in the solvent with a water-soluble polymer surfactant, rapidly removing the organic solvent from the micelles of the emulsion thus obtained to have a porous structure, and then adding a water- And adjusting the equilibrium so as to minimize the size of the micelle to the nanometer level, while at the same time inducing an organic or ionic bond cross-linking at the surface of the micelle or particle.

Organic, complex, silicate, nano, hydrogel, water resistant, cross-linked

Description

TECHNICAL FIELD [0001] The present invention relates to an organic-inorganic hybrid nano-hydrogel and an organic-inorganic hybrid nano-hydrogel,

1 is a scanning electron microscope (SEM) image of the organic / inorganic hybrid nanohydrogel prepared in Example 1 of the present invention.

The present invention relates to an organic-inorganic hybrid nanohydrogel and a method for producing the same, and more particularly, to a silicate-based organic / inorganic hybrid nanohydrogel having improved water resistance, which is useful as a flame retardant, and a method for producing the same.

The silicate-based water-soluble inorganic material has a property of improving the heat resistance, flame resistance, and flame retardancy of the inner substrate by forming a flame retardant film on the surface of the material, and is widely used for the flame retarding treatment of fiber and nonwoven products. However, since the silicate-based water-soluble inorganic material has a fatal disadvantage that it is weak in water, when it is used in a substrate such as fiber and nonwoven fabric, it causes cloudiness and dust generation due to moisture absorption and reconstruction in the air. Therefore, studies for improving the water resistance of silicate-based minerals have been actively carried out, but the results are not yet widely accepted.

Korean Patent Publication No. 0509705 discloses a method of forming an ionic complex with a silicate using a high-alcohol-based organic material and a polymer as a method for improving the water resistance of a silicate-based inorganic material, As a possible method, the achievement of structure control up to nano size has not been reported yet.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in order to solve the problems of the prior art as described above, and it is an object of the present invention to provide a flame retardant additive having an average particle size of several tens of nanometers and not dissolving in water Organic-inorganic hybrid nanohydrogels and a process for producing the same.

In order to accomplish the above object, the present invention provides an organic / inorganic hybrid nanohydrogel,

And a porous organic nanoparticle of a polymer capable of forming an ionic bond is formed on the surface of the porous nanoparticle by forming a skin-core structure by bonding a silicate-based inorganic aqueous solution in an ionic bond form.

The method for producing the organic / inorganic hybrid nanohydrogel according to the present invention as described above,

Dissolving a fat-soluble polymer capable of forming an ionic terminal group in an organic solvent;

Mixing a solution of the oil-soluble polymer with an aqueous solution containing a water-soluble surfactant;

Stirring the mixed solution to form micelles;

Adding water to the mixed solution in which the micelles are formed, and stirring the mixed solution to rapidly elute the organic solvent from the micelles, thereby preparing porous nanoparticles;

And adding an aqueous solution of a silicate-based inorganic material to the porous nanoparticle mixture to induce ionic bonding on the surface of the nanoparticles.

 In the process for producing an organic / inorganic hybrid nanohydrogel according to the present invention, the polymer capable of forming an ionic bond or the lipophilic polymer capable of forming an ionic terminal group may be, for example, polyacrylonitrile and a copolymer thereof, Terminal groups may dissociate under acidic or alkaline conditions such as polyethylene glycol and its copolymers, polypropylene glycol, polylactic acid and its copolymers, polyvinyl acetate and its copolymers, modified cellulose and its derivatives, And the like, and is not necessarily limited to these, and includes forms in which ionic terminal groups can be formed by other methods.

The average molecular weight of the polymer used herein is in the range of 100-1,000,000, preferably in the range of about 700-200,000. The above range is an experiential value obtained as a result of the experiment, but the present invention can not be practiced even if it deviates slightly from the above range.

According to the method of the present invention, the oil-soluble polymer forming the ionic terminal group is dissolved in a solvent which is a solvent, and the solution is mixed with an aqueous solution containing a water-soluble surfactant and stirred to form micelles.

Then, water is added thereto again and stirred to rapidly remove the organic solvent from the micelles, so that the polymer forms porous nanoparticles. In this case, it is preferable to use hot water having a temperature of about 40 to 90 ° C. The higher the temperature, the faster the elution of the organic solvent, the more the micropores are formed, the larger the surface area and the faster the reaction rate. However, when the temperature is too high, evaporation occurs, which is undesirable. When the temperature is low, the formation of micropores is small and the reaction rate is slow.

On the other hand, by adding a silicate-based inorganic aqueous solution to the mixed solution containing the polymer in which the porous nanoparticles are formed, the ionic bonding with the silicate material is performed on the surface of the porous nanoparticles of the polymer, A nanohydrogel is formed.

The aqueous solution of the silicate-based inorganic material is one in which one or more silicate materials such as sodium silicate, potassium silicate and sodium silicate potassium are dissolved in water at a content ratio of 0.5% by weight to 80% by weight.

In this process, the acidity of the solution is adjusted so that, for example, the polymer modified in the silicate-based inorganic aqueous solution has a tendency of binding to water and a tendency of bonding between the modified polymer and silicate rather than a tendency of the silicate to bond with water A water-resistant nanohydrogel having an average diameter of several tens nanometers to several hundreds of nanometers can be obtained.

The organic / inorganic hybrid nanohydrogels thus prepared can be applied variously according to the purpose of the final product such as a flame retarding agent. In this process, it is also possible to use, in the course of the process, a foaming agent, a nucleating agent, a lubricant, an antioxidant, a heat stabilizer, an ultraviolet stabilizer, a biostabilizer, a filler, a reinforcing agent, a plasticizer, a colorant, an impactor, a flame retardant, an antistatic agent, Other processing agents such as an electric conductivity imparting agent, a permeability adjusting agent, a magnetic property imparting agent, a surfactant, a stabilizer, an excipient, a medicine, a solvent, a hardener, a moisture absorber, a reinforcing agent, a perfume and an antibacterial agent may be added.

Example

Hereinafter, the present invention will be described in more detail with reference to preferred embodiments. The following examples are intended to illustrate the present invention, and the scope of the present invention is not limited by these examples.

Example  One

2 parts by weight of polyvinyl acetate was dissolved in 100 parts by weight of ethyl acetate as an organic solvent to form a homogeneous solution. Then, 2 parts by weight of polyvinyl alcohol as a surfactant was mixed with an aqueous solution of 100 parts by weight of water.

The mixed solution was mixed with a homogenizer for 10 minutes to form polyvinyl acetate micelles.

After adding the hot water at 80 ° C to the mixed solution to increase the porosity and surface area of the nanoparticles, the diluted acetic acid was added dropwise to the mixed solution to adjust the acidity of the solution to 3 to 4, and then the basic silicate- And the mixture was gradually stirred for 30 minutes.

Since the reaction-terminated solution is a state in which the organic-inorganic hybrid nanohydrogels of skin-core structure composed of polyvinyl acetate or saponified polyvinyl alcohol and silicate are dispersed, it is centrifuged and dried in vacuum for 1 day to produce solidified particles Respectively.

The dried particles were uniformly sprayed in water using an ultrasonic homogenizer, and the average particle size was measured using a particle size analyzer. As a result, a value of 193 nm was obtained.

FIG. 1 is a scanning electron microscope (SEM) image of the solidified organic / inorganic hybrid nanohydrogel thus obtained.

In order to evaluate the water resistance of the obtained organic / inorganic hybrid nanohydrogel, the solidified nanohydrogel was allowed to stand for 4 hours with gentle stirring at 60 ° C in hot water, and the weight recovery rate was measured to be 99% or more.

Example  2 to 24

Using the conditions shown in Table 1 below, the organic / inorganic hybrid nanohydrogels were prepared in the same manner as in Example 1, according to the method of the present invention.

division Polymer Organic solvent (high molecular weight per 100 weight parts of organic solvent) Surfactant (amount of surfactant per 100 parts by weight of water) Amount of silicate aqueous solution added (parts by weight) Average particle size Weight recovery rate (%) Example 2 PAN Dimethyl sulfoxide (2 parts by weight) PVA (1 part by weight) 100 310 97 Example 3 PAN Dimethyl sulfoxide (2 parts by weight) PVA (2 parts by weight) 100 213 84 Example 4 PAN Dimethyl sulfoxide (2 parts by weight) PVA (5 parts by weight) 100 196 79 Example 5 PAN Dimethyl sulfoxide (2 parts by weight) DMAB (2 parts by weight) 100 211 88 Example 6 PAN Dimethyl sulfoxide (5 parts by weight) PVA (2 parts by weight) 100 478 > 99 Example 7 PAN Dimethyl sulfoxide (5 parts by weight) DMAB (2 parts by weight) 100 452 > 99 Example 8 PAN Dimethyl sulfoxide (1 part by weight) PVA (2 parts by weight) 100 148 69 Example 9 PEG Ethyl acetate (2 parts by weight) PVA (2 parts by weight) 100 225 65 Example 10 PEG Ethyl acetate (2 parts by weight) DMAB (2 parts by weight) 100 210 62 Example 11 PEG Ethyl acetate (5 parts by weight) PVA (2 parts by weight) 100 578 71 Example 12 PEG Ethyl acetate (5 parts by weight) DMAB (2 parts by weight) 100 496 75 Example 13 PEG Ethyl acetate (1 part by weight) PVA (2 parts by weight) 100 170 58 Example 14 PVAc Ethyl acetate (2 parts by weight) DMAB (2 parts by weight) 100 86 92 Example 15 PVAc Ethyl acetate (5 parts by weight) PVA (2 parts by weight) 100 409 > 99 Example 16 PVAc Ethyl acetate (5 parts by weight) DMAB (2 parts by weight) 100 135 95 Example 17 PVAc Ethyl acetate (1 part by weight) PVA (2 parts by weight) 100 122 91 Example 18 PVAc Propylene carbonate (2 parts by weight) PVA (2 parts by weight) 100 341 87 Example 19 PVAc Propylene carbonate (1 part by weight) PVA (2 parts by weight) 100 302 90 Example 20 PLGA Ethyl acetate (2 parts by weight) PVA (2 parts by weight) 100 89 94 Example 21 PLGA Ethyl acetate (2 parts by weight) DMAB (2 parts by weight) 100 80 91 Example 22 PLGA Ethyl acetate (5 parts by weight) PVA (2 parts by weight) 100 105 > 99 Example 23 PLGA Ethyl acetate (5 parts by weight) DMAB (2 parts by weight) 100 100 98 Example 24 PLGA Ethyl acetate (1 part by weight) PVA (2 parts by weight) 100 45 88

According to the method of the present invention, an organic-inorganic hybrid nanohydrogel having a particle diameter of several tens to several hundreds of nanometers and not dissolving in water is obtained. Therefore, a functional preparation of fibers and resins requiring nano- And can be particularly useful for the production of a flame retardation treatment agent.

Claims (5)

Wherein the porous organic nanoparticle comprises an organic-inorganic hybrid material having a skin-core structure formed by binding an aqueous solution of a silicate-based inorganic material in ionic form to the surface of porous nanoparticles of a polymer capable of forming an ionic bond. Dissolving a fat-soluble polymer capable of forming an ionic terminal group in an organic solvent; Mixing a solution of the oil-soluble polymer with an aqueous solution containing a water-soluble surfactant; Stirring the mixed solution to form micelles; Adding water to the mixed solution in which the micelles are formed, and stirring the mixed solution to rapidly elute the organic solvent from the micelles, thereby preparing porous nanoparticles; And adding an aqueous solution of a silicate-based inorganic material to the porous nanoparticle mixture to induce ionic bonding on the surface of the nanoparticles. The method according to claim 2, wherein hot water in the range of 40 to 90 ° C is used in the step of preparing the porous nanoparticles.  The polymer according to claim 2, wherein the polymer capable of forming the ionic terminal group is selected from the group consisting of polyacrylonitrile and a copolymer thereof, polyethylene glycol and a copolymer thereof, polypropylene glycol, polylactic acid and a copolymer thereof, polyvinyl acetate and Wherein the polymer is selected from the group consisting of a copolymer, a modified cellulose, and a derivative thereof. The aqueous solution of the silicate-based inorganic material according to claim 2, wherein at least one silicate material selected from the group consisting of sodium silicate, potassium silicate and sodium silicate potassium is dissolved in water at a content ratio of 0.5% by weight to 80% by weight Wherein the method comprises the steps of:

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