KR100933795B1 - Oligomeric / Halosite Complex and Manufacturing Method Thereof, and Hydrocarbon Adsorbent Using the Complex - Google Patents

Abstract

The present invention comprises the steps of adding and mixing the halosite powder to the oligomer / halosite complex material and the oligomer aqueous solution; Heating the mixture to expand air inside the halosite nanotubes; And cooling the mixture to room temperature to fill an aqueous oligomer solution inside the halosite nanotubes. The composite material according to the present invention can be used as a highly efficient nanoporous carrier that can control the dissolution rate of the functional material in order to improve the sustainability of the adsorbent and the adsorbed functional material having an efficient adsorption capacity for hydrocarbons. .

Amphoteric Oligomer / Halosite Complex, Hydrocarbon Adsorbent

Description

Oligomer / Haloisite complex and method for preparing the same, and hydrocarbon adsorbent using the complex `` OLIGOMER / HALLOYSITE COMPOSITE MATERIAL AND METHOD FOR PREPARING THE SAME, AND HYDROCARBON ADSORBENT USING THE SAME}

The present invention relates to oligomer / halosite composites and methods for their preparation, and adsorbents using the composites. More specifically, the present invention provides a composite material obtained by filling oligomers in a halosite nanotube, a method for preparing the same, and a slow release of a functional material obtained by effectively adsorbing and recovering or adsorbing various organic compounds including hydrocarbons. The present invention relates to an adsorbent using the composite material, which can be applied as a carrier capable of maximizing durability.

The present invention is derived from the research conducted as part of the basic project of the Ministry of Science and Technology [Task Management Number: GP2007-007, Task name: Development of natural nano-mineral utilization technology: Smart nano-container manufacturing].

Recently, research on nano-structured materials has been conducted in various angles across various fields. In particular, nano-porous materials can be used as adsorbents, catalysts, carriers, carriers, etc. in the electro-optic, fine chemical, medical, and bio fields. Efforts to apply in various fields are being activated.

The material having such pores is microporous having a size of less than 2 nm, mesoporous having a size of 2-50 nm, and macroporous having a size larger than 50 nm, depending on the size of the pores. Can be classified as a substance. Zeolite is most commonly used as a microporous material, and mesoporous silica is widely used as a molecular sieve as a mesoporous material.

Mesoporous silica is generally known as having a structure having a structure in which pores having a diameter of 1.5 to 10 nm are regularly arranged, and having a surface area of about 700 m 2 / g. Research is underway as nanomaterials. In general, mesoporous silica is chemically synthesized through hydrothermal reaction using a surfactant or an amphoteric polymer through a liquid crystal template path.

Compared to microporous materials, mesoporous materials such as mesoporous silica have a range of mesopores, and thus are applicable in adsorption, separation, and catalytic reaction of molecules having a larger size than micropores. In addition, the mesoporous material has a uniform pore size, a very large surface area, and thus is highly applicable as a carrier, and may be widely applied to conductive materials, fine chemistry and biotechnology, and electro-optics.

As the use of various pesticides and petrochemicals, including herbicides, has recently increased, the seriousness of environmental pollution problems has increased, and thus, carrier materials that can be used for adsorption of organic compounds including hydrocarbons to minimize contamination therefrom, and In order to improve the sustainability of the efficacy of the active compounds, research on a carrier material that can control the dissolution rate of the functional material is being actively conducted.

In view of this, many studies on mesoporous materials have been published as nanoporous carriers for maximizing the efficacy and sustainability of functional materials such as functional cosmetics and specialty medicines as well as hydrocarbons.

However, as yet, the results of research on such nanoporous materials are not satisfactory, and there is still a need for high-efficiency nanoporous materials with excellent carrier properties that can be suitably applied to various applications. In addition, there is a need for an adsorbent having physical and chemical stability capable of adsorbing organic materials such as hydrocarbons with better efficiency.

It is an object of the present invention to provide an oligomer / halogenite composite material formed by filling an oligomer in a nanotube of a halosite and a method of manufacturing the same.

The present invention also provides a novel functional hydrocarbon adsorbent using an oligomer / halogenite composite material prepared by filling an oligomer which exhibits excellent adsorption characteristics to hydrocarbons inside the halosite and a method for producing the same.

The present invention for achieving the above object is, adding and mixing the halosite powder to the aqueous oligomer solution; Heating the mixture to expand air inside the halosite nanotubes; And cooling the mixture to room temperature to fill an oligomer aqueous solution in the halosite nanotubes.

In addition, the present invention provides an oligomer / halosite composite material formed by filling the oligomer inside the halosite nanotubes.

The present invention also provides a hydrocarbon adsorbent comprising the oligomer / halosite composite material.

The oligomer / halosite composite material according to the present invention is formed by filling the pores of the halosite having a nanotube structure, that is, by filling oligomers having high adsorption capacity to organic materials including hydrocarbons in the nanotubes, thereby providing high efficiency to hydrocarbons. It can be used as an adsorbent having an adsorption capacity for.

In addition, the composite material according to the present invention can be used as a carrier that can maximize the sustainability of the effect by slowly releasing the adsorbed hydrocarbons, without causing problems to the environment or health by using the halosite excellent carrier capacity Do.

That is, the composite material according to the present invention can be used as an environmentally friendly hydrocarbon adsorbent and carrier, thereby minimizing the environmental pollution caused by the recent increase in the use of various pesticides and petrochemicals, including herbicides, In order to improve the sustainability, it can be utilized as a highly efficient carrier that can control the dissolution rate of the functional material.

Furthermore. By using these properties, it can be used as a nano-porous carrier for maximizing the efficacy and sustainability of functional materials such as functional cosmetics or specialty medicines.

The above objects, features, and advantages will become more apparent from the detailed description given hereinafter with reference to the accompanying drawings, and accordingly, those skilled in the art to which the present invention pertains may share the technical idea of the present invention. It will be easy to implement. In addition, in describing the present invention, when it is determined that the detailed description of the known technology related to the present invention may unnecessarily obscure the gist of the present invention, the detailed description thereof will be omitted. Hereinafter, with reference to the accompanying drawings will be described in detail with respect to the present invention.

The oligomer / halogenite composite material according to the present invention is formed by filling oligomers into the nanotubes using a halosite, which is a natural mineral having a nanotube structure.

The halosite used in the present invention is represented by the following Chemical Formula 1

Al ₂ Si ₂ O ₅ (OH) ₄ 2H ₂ O

A material represented by is an aluminum silicate clay mineral in which the ratio of aluminum to silicon is 1: 1. The halosite is a hollow nanotube structure, the inner diameter of the tube is about 40 ~ 250nm excellent carrier properties compared to conventional chemically synthesized mesoporous silica. In addition, since it is a natural mineral that is harmless to the human body, since there is no problem in environmental pollution or human hazards at the time of application, it has a very excellent utility as a carrier.

In the present invention, oligomers filled in the pores of the halosite, i.e., inside the nanotubes, can be used without limitation as long as they exhibit adsorption characteristics for organic materials such as hydrocarbons. Those skilled in the art may select and use an oligomer suitable for adsorption of organic materials such as hydrocarbons from known oligomers without any difficulty.

Particularly preferred are amphoteric oligomers, which together show hydrophilic properties, and thus can be easily filled in water-soluble conditions using water as a solvent when the oligomer is filled in the halosite. Such amphoteric oligomers can be selected and used appropriately, and as described above, any amphoteric oligomer can be used without limitation as long as it exhibits adsorption characteristics of organic substances such as hydrocarbons.

For example, the amphoteric oligomers which can be preferably used in the present invention include urethane / acrylate oligomers. Since the urethane / acrylate oligomer has a high hydrophilic propylene glycol functional group, it has both hydrophobicity and hydrophilicity, and this hydrophilic property can be filled in water-soluble conditions using water as a solvent when the oligomer is filled in the halosite. The manufacturing process may be easy.

Urethane / acrylate oligomers that can be used in the present invention is a mixture of polypropylene glycol (polypropylene glycol) and isophorone diisocyanate (isophorone diisocyanate) to proceed with the urethane reaction, 2-hydroxy ethyl acrylate to the reaction mixture (2-hydroxy ethylacryate) and polyethylene glycol (polyethylene glycol) may be prepared by the addition of the reaction, but is not limited thereto.

More specifically, 50 to 70% by weight of polypropylene glycol and 30 to 50% by weight of isophorone diisocyanate were mixed to perform a urethane reaction at 50 to 80 ° C. for 2 to 4 hours, and then the mixture was added to the mixture. Hydroxyethyl acrylate is added in an amount of 5 to 25% by weight based on the total weight of the polypropylene glycol and isophorone diisocyanate mixture and reacted with stirring for 2 to 4 hours at the same temperature. 25 to 45% by weight of polyethylene glycol relative to the total weight of the reaction mixture at the same temperature after the reaction, to the reaction mixture (reaction mixture reacted by adding 2-hydroxy ethyl acrylate to the mixture of polypropylene glycol and isophorone diisocyanate) By addition, amphoteric oligomers which can be suitably used in the present invention can be prepared by reacting with stirring for 2-4 hours.

Since the oligomer is generally very high in viscosity, it is preferable to dilute to about 4 to 6 times using distilled water, and it is particularly preferable to use an aqueous solution diluted with about 5 times distilled water.

In order to prepare the composite material according to the present invention, first, the halosite powder is added to the oligomer aqueous solution and mixed. At this time, it is preferable to mix and manufacture in 30 to 50 weight% of oligomer aqueous solution, and about 50 to 70 weight% of halosite powder. In addition, in the mixing step may be additionally mixed by adding distilled water.

Next, the mixture of the aqueous oligomer solution and the halosite powder is heated to expand the air inside the nanotubes of the halosite. The heating is preferably performed for 10 to 30 minutes at 50 ~ 100 ℃, it is particularly preferred to be made for about 20 minutes at 70 ℃. By heating, the air inside the nanotubes of the halosite is expanded so that some air is released to the outside, thereby forming an empty space.

When the heated mixture is gradually cooled to room temperature, the expanded air in the halosite nanotubes is condensed and the oligomer aqueous solution is filled in the empty space therein. In order to sufficiently fill the oligomer inside the halosite nanotube, the heated mixture is cooled to room temperature, and then stirred for about 5 to 30 minutes, preferably about 10 minutes.

When the oligomer filling is completed inside the halosite nanotubes, it is preferable to undergo a filtration and drying process according to a known method. Filtration and drying can be used by selecting a suitable method among known methods, and are not particularly limited. Drying can occur for example in air at 50-100 ° C., preferably about 70 ° C.

The oligomer / halosite composite material prepared according to the present invention is a nanotube-type porous material made by filling oligomers having strong adsorptivity to organic materials, especially hydrocarbons, in the halosite pores having excellent carrier properties. Therefore, it can be used as an adsorbent with high efficiency adsorption performance on organic materials including hydrocarbons, and also useful as a nano-porous carrier that can gradually release the adsorbed hydrocarbons to maximize the persistence of the effect. Can be.

Hereinafter, the present invention will be described in detail with reference to Examples.

However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited to the following examples.

Example  One: Oligomer  Produce

To obtain the oligomer 195.21 g of polypropylene glycol ([GP1000]) was mixed with 130.19 g of isophorone diisocyanate. The mixture was allowed to proceed with a urethane reaction at 55 ~ 60 ℃ for 2 hours, then maintained at 65 ℃ and stirred for 3 hours to react.

At this temperature, 45.34 g of 2-hydroxy ethyl acrylate ([2-HEA]) was further added and reacted with stirring for 2 hours. Again, 128.84 g of polyethylene glycol and 0.02 g of lauryltrimethyltin were added as a catalyst and stirred for 3 hours to continue the reaction to synthesize a urethane / acrylate oligomer.

Example  2: Oligomer Of Halloysite  Composite Material Manufacturing (1)

The oligomer prepared in Example 1 was diluted 1: 5 with distilled water. In order to fill the oligomer inside the halosite, a weight ratio of halosite: oligomer aqueous solution: distilled water was mixed at a ratio of 1: 1: 5. The mixture was heated at 70 ° C. for about 20 minutes to expand and expand the air in the halosite pores, and then gradually cooled to room temperature and continued stirring for about 10 minutes to allow the oligomer aqueous solution to condense into the halloysite. When the oligomer filling of the halosite into the nanotube was completed, the resultant was dried in air at 70 ° C. after filtration to prepare an oligomer / halosite composite material.

Example  3: Oligomer Of Halloysite  Composite Material Manufacturing (2)

The oligomer prepared in Example 1 was diluted 1: 5 with distilled water. In order to fill the oligomer inside the halosite, the weight ratio of halosite: oligomer aqueous solution: distilled water was mixed at 1: 2: 5. The mixture was heated at 70 ° C. for about 20 minutes to expand and expand the air in the halosite pores, and then gradually cooled to room temperature and continued stirring for about 10 minutes to allow the oligomer aqueous solution to condense into the halloysite. When the oligomer filling of the halosite into the nanotube was completed, the resultant was dried in air at 70 ° C. after filtration to prepare an oligomer / halosite composite material.

Example  4: Oligomer Of Halloysite  Composite Material Manufacturing (3)

The oligomer prepared in Example 1 was diluted 1: 5 with distilled water. In order to fill the oligomer prepared in Example 1 to the inside of the halosite, a weight ratio of a halosite: oligomer aqueous solution: distilled water was mixed at 1: 2: 1. The mixture was heated at 70 ° C. for about 20 minutes to expand and expand the air in the halosite pores, and then gradually cooled to room temperature and continued stirring for about 10 minutes to allow the oligomer aqueous solution to condense into the halloysite. When the oligomer filling of the halosite into the nanotube was completed, the resultant was dried in air at 70 ° C. after filtration to prepare an oligomer / halosite composite material.

The oligomer / halosite composite material prepared in Example 2 was observed with an electron-scan prescan microscope and a high-resolution electron microscope, respectively, in FIGS. 1A and 1B, respectively. 1 (a) and (b), the oligomer / halosite composite material according to the present invention can be seen that the oligomer is filled inside the halosite tube of the nanotube structure to form a complex.

In addition, the graph obtained by analyzing the oligomer / halosite composite material prepared in Example 2 with an X-ray diffractometer is shown in FIG. From the above results, it can be clearly confirmed that the oligomer / haloisite according to the present invention is a complex formed by filling oligomers inside the halosite of the nanotube structure.

The oligomer / halosite composite material according to the present invention prepared as described above uses a nanotube structure of halosite having excellent carrier properties and thus does not cause environmental pollution or human hazard problems, and has a high adsorption capacity for hydrocarbons. It can be used as a high efficiency selective adsorbent. Therefore, in line with the recently rising environmental pollution and health concerns, it can be very usefully applied as an adsorbent having high efficiency and selectivity, physical and chemical stability and durability while minimizing the pollution.

In addition, the composite material according to the present invention can be widely applied to various fields as an excellent nano-porous carrier that can improve the sustainability of the effect by adjusting the dissolution rate of the adsorbed functional material.

The present invention described above can be variously substituted, modified and changed within the scope without departing from the spirit of the present invention for those of ordinary skill in the art to which the present invention belongs, the above-described embodiment and the accompanying drawings It is not limited by.

Figure 1 is a photograph of the oligomer / halosite composite obtained in Example 2 of the present invention with an electron-scanning electron microscope (a) and a high-resolution electron microscope (b).

Figure 2 is a graph of the oligomer / halosite composite obtained in Example 2 of the present invention by an X-ray diffraction analyzer.

Claims (16)

Adding and mixing the halosite powder to the aqueous oligomer solution; Heating the mixture to expand air inside the halosite nanotubes; And Cooling the mixture to room temperature to fill an oligomer aqueous solution inside the halosite nanotubes Method for producing an oligomer / halosite composite material comprising a. The method of claim 1, The halosite is represented by Chemical Formula 1 [Formula 1] Al ₂ Si ₂ O ₅ (OH) ₄ 2H ₂ O Hollow nanotube structure, the inner diameter of the tube is 40 ~ 250nm Method for preparing oligomer / halosite composite material. The method of claim 1, The mixing step is performed by mixing 30 to 50% by weight of the oligomer aqueous solution having a volume ratio of oligomer: water of 1: 4 to 1: 6 and 50 to 70% by weight of halosite powder Method for preparing oligomer / halosite composite material. The method of claim 1, The heating is made for 10 to 30 minutes at 50 ~ 100 ℃ Method for preparing oligomer / halosite composite material. The method of claim 1, After the filling step, further comprising the step of filtration and drying Method for preparing oligomer / halosite composite material. The method of claim 5, The drying is made in air at 50 ~ 100 ℃ Method for preparing oligomer / halosite composite material. The method of claim 1, The oligomer is an amphoteric oligomer Method for preparing oligomer / halosite composite material. The method of claim 7, wherein The amphoteric oligomer is a urethane acrylate oligomer Method for preparing oligomer / halosite composite material. The method of claim 8, The amphoteric oligomer is a mixture of polypropylene glycol (polypropylene glycol) and isophorone diisocyanate to proceed with the urethane reaction, the mixture is 2-hydroxy ethyl acrylate (2-hydroxy ethylacryate) and polyethylene glycol prepared by adding (polyethylene glycol) Method for preparing amphoteric oligomer / halosite composites. The method of claim 9, The amphoteric oligomer is Iii) mixing 50 to 70% by weight of polypropylene glycol and 30 to 50% by weight of isophorone diisocyanate and reacting at 50 to 70 ° C. for 2 to 4 hours; Ii) adding 5 to 25% by weight of 2-hydroxy ethyl acrylate to the mixture of step iii) with respect to the total weight of the mixture and reacting with stirring at the same temperature for 2 to 4 hours; And Iii) at the same temperature after the reaction, by adding 25 to 45% by weight of polyethylene glycol to the reaction mixture of step ii) based on the total weight of the reaction mixture, stirring for 2 to 4 hours Method for preparing oligomer / halosite composite material. delete The method of claim 1, In the mixing step to further add distilled water to the mixture of the oligomer aqueous solution and the halosite powder to mix Method for preparing oligomer / halosite composite material. An oligomer / halogenite composite material formed by filling oligomers inside a halogenated nanotube. The method of claim 13, The oligomer is an amphoteric oligomer Oligomeric / Halosite Complex Materials. The method of claim 14, The amphoteric oligomer is a urethane acrylate oligomer Oligomeric / Halosite Complex Materials. Hydrocarbon adsorbent comprising the oligomer / halosite composite material according to any one of claims 13 to 15.

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