KR102595698B1 - Complex compound comprising metal-organic hybrid nano framework and synthetic resin - Google Patents

Abstract

According to one embodiment of the present invention, an organic-inorganic hybrid nanoporous body (metal-organic framework; MOF); and a miscible synthetic resin, wherein the organic-inorganic hybrid nanoporous body and the synthetic resin are provided in the form of a mixture, and a gap is provided between the organic-inorganic hybrid nanoporous body and the synthetic resin within the mixture, and the organic-inorganic hybrid nanoporous body is provided in the form of a mixture. A composite compound is provided in which the nanoporous body is in contact with the synthetic resin only on some sides, and the mixture is mixed with the raw materials of the product and used when molding the product.

Description

Composite compound containing organic-inorganic hybrid nanoporous body and synthetic resin {COMPLEX COMPOUND COMPRISING METAL-ORGANIC HYBRID NANO FRAMEWORK AND SYNTHETIC RESIN}

The present invention relates to a composite compound containing an organic-inorganic hybrid nanoporous body and a synthetic resin.

When a metal precursor and an organic ligand are placed in a specific solvent and reacted through hydrothermal synthesis, a porous material with a repeated arrangement of metal blocks and organic ligands is formed. The organic-inorganic hybrid nanoporous body formed in this way has a very large specific surface area including micropores and/or mesopores, and is attracting attention as a gas storage material due to the advantage of this large specific surface area. In addition, in the case of organic-inorganic hybrid nanoporous materials, the combination of metal precursors and organic ligands is very free, and tens of thousands of organic-inorganic hybrid nanoporous materials have been reported to date.

In addition, in the early days of the synthesis of organic-inorganic hybrid nanoporous materials, a single metal and a single organic ligand were used to synthesize them, and recently, various synthesis methods, such as using mixed metals or mixed organic ligands to control the pore size or secure the required performance, have been used. It is being reported.

Organic-inorganic hybrid nanoporous materials have various pore structures, pore sizes, and pore volumes depending on the type, and chemical properties can be imparted through functionalization to metal sites or organic ligands of the organic-inorganic hybrid nanoporous materials depending on their structural properties. Due to these physicochemical properties, organic-inorganic hybrid nanoporous materials can be applied to adsorbents for gas or liquid separation, materials for gas storage, sensors, membranes, functional thin films, drug delivery materials, filter materials, catalysts, and catalyst carriers.

In recent years, the outstanding properties of organic-inorganic hybrid nanoporous structures (MOFs), whose infinite design patterns originate from the combination of organic and inorganic building blocks, have sparked research activities in industry. Recent issues related to MOFs focus on securing various application fields in addition to improving the performance of MOFs. For example, securing diversity in product form in order to apply MOF to actual industrial fields and combining it for improved performance and stability have recently emerged as important tasks.

Patent Document 0001. Korean Patent Publication No. 10-0967631

The purpose of the present invention is to provide raw materials that can impart functions or characteristics resulting from MOF to the final product when producing products by processing and molding raw materials of synthetic resins containing polymer compounds or plastics through extrusion or injection. .

According to one embodiment of the present invention, an organic-inorganic hybrid nanoporous body (metal-organic framework; MOF); and a miscible synthetic resin, wherein the organic-inorganic hybrid nanoporous body and the synthetic resin are provided in the form of a mixture, the mixture is a masterbatch, and the final product manufactured from the masterbatch has additional functions due to the organic-inorganic hybrid nanoporous body. A composite compound is provided, wherein the mixture is mixed with the raw materials of the product and used during molding of the product.

According to one embodiment of the present invention, in a product manufactured by molding the composite compound, a gap is provided between the organic-inorganic hybrid nanoporous body and the synthetic resin, so that the organic-inorganic hybrid nanoporous body is separated from the synthetic resin only on some surfaces. A complex compound is provided, which is in contact with.

According to one embodiment of the present invention, a composite compound is provided in which the organic-inorganic hybrid nanoporous body is contained in an amount of 0.1% by weight to 50% by weight based on the total weight of the composite compound.

According to one embodiment of the present invention, a composite compound containing a synthetic resin containing at least one selected from the group consisting of thermosetting resin, thermoplastic resin, biodegradable plastic, rubber, and bioplastic is provided.

According to one embodiment of the present invention, the composite compound is provided, having at least one shape selected from the group consisting of a pellet, tablet, sphere, ellipse, hemisphere, flake, rectangular parallelepiped, and cube.

According to one embodiment of the present invention, the complex compound is provided, which includes an organic-inorganic hybrid nanoporous body composed of a central metal ion and an organic ligand that binds to the central metal ion.

According to one embodiment of the present invention, a carboxyl group (-COOH), a carboxylic acid anion group (-COO-), an amine group (-NH ₂ ) and an imino group (=NH), a nitro group (-NO ₂ ), and a hydroxy group. (-OH) _{, halogen} group ( _{- 2} -), a composite compound is provided, comprising an organic-inorganic hybrid nanoporous body composed of an organic ligand containing a compound having at least one functional group selected from the group consisting of a pyridine group and a pyrazine group, or a mixture thereof.

According to one embodiment of the present invention, a composite compound containing an organic-inorganic hybrid nanoporous body having a porous structure is provided.

According to one embodiment of the present invention, a composite compound including the organic-inorganic hybrid nanoporous body having a stable structure at the glass transition temperature of the synthetic resin is provided.

According to one embodiment of the present invention, a composite compound is provided, further comprising a gaseous compound or vapor provided in the pores.

According to one embodiment of the present invention, a synthetic resin product manufactured by molding any of the above-described composite compounds is provided.

According to one embodiment of the present invention, it is possible to provide a composite compound for the production of products containing resin, such as polymer compounds or plastic raw materials, and thereby easily impart functions/characteristics resulting from the organic-inorganic hybrid nanoporous body to the product. You can.

Figure 1 is a photograph showing the form of a complex compound according to an embodiment of the present invention.
Figure 2 is an enlarged photograph showing the form of a composite compound according to an embodiment of the present invention.
Figure 3 is an enlarged cross-sectional view showing the form of the complex compound provided according to an embodiment of the present invention.
Figure 4 is a photograph showing mapping using a scanning electron microscope and a Quantax FlatQUAD Energy Dispersive
Figure 5 is a photograph showing a scanning electron microscope image of a synthetic resin product manufactured using the composite compound according to Example 2 of the present invention.

Since the present invention can be subject to various changes and have various forms, specific embodiments will be illustrated in the drawings and described in detail in the text. However, this is not intended to limit the present invention to a specific disclosed form, and should be understood to include all changes, equivalents, and substitutes included in the spirit and technical scope of the present invention.

Figures 1 and 2 are photographs showing the form of a MOF-composite compound according to an embodiment of the present invention.

The composite compound may include an organic-inorganic hybrid nanoporous body (metal-organic framework (MOF)) and a synthetic resin.

Organic-inorganic hybrid nanoporous material (MOF) is a porous organic-inorganic polymer compound formed by combining a central metal ion with an organic ligand through molecular coordination. It contains both organic and inorganic substances within the skeletal structure and has molecular or nano-sized pores. It is a crystalline compound with a structure. Organic ligands are also called linkers, and can be any organic compound with a functional group that can coordinate. For example, the organic ligands include carboxyl group (-COOH), carboxylic acid anion group (-COO-), and amine. group (-NH ₂ ) and imino group (=NH), nitro group (-NO ₂ ), hydroxy group (-OH), halogen group (-X) and sulfonic acid group (-SO ₃ H), sulfonic acid anion group (-SO A compound or a mixture thereof having one or more functional groups selected from the group consisting of ₃ -), methanedithioic acid group (-CS ₂ H), methanedithioic acid ion group (-CS ₂ -), pyridine group, and pyrazine group may be used. . This organic-inorganic hybrid nanoporous body may have the structure of an organic-inorganic hybrid nanoporous body.

The framework of a MOF is formed by covalent bonds between a metal cluster, which is a secondary building unit (SBU), and organic ligands, and the metal cluster can become a node in the framework of the MOF. MOFs are composed of various coordination geometries, polytopic linkers, and ancillary ligands (F-, OH-, H ₂ O among others). Therefore, MOF design begins with selecting an appropriate metal ion and an appropriate organic ligand. For example, when metal ions (e.g., Zn ²⁺ ) react with various acetates, Zn ₄ O(CH ₃ COO) ₆ clusters are created, and when these clusters are combined with organic ligands, a MOF structure is created. At this time, the organic ligand part of the benzene structure can be a spacer, and the Zn ₄ O(CH ₃ COO) ₆ cluster part can be a node.

The mixable synthetic resin may include at least one selected from the group consisting of thermosetting resin, thermoplastic resin, biodegradable plastic, and rubber. Thermoplastic resins include polyolefin resin, polystyrene resin, acrylonitrile-butadiene-styrene copolymer resin, acrylonitrile-styrene copolymer resin, methacrylic acid-styrene copolymer resin, methacrylic resin, butadiene-styrene copolymer resin, polycarbonate resin, poly Amide resin, polyarylate resin, polysulfone resin, polyallylsulfone resin, polyethersulfone resin, polyetherimide resin, polyimide resin, polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polylactic acid, etc. It may include at least one of the group consisting of polyester resin, polyester carbonate resin, polyester ether resin, polyurethane resin, and bioplastic.

The organic-inorganic hybrid nanoporous body may have a porous structure. The porous structure can contribute to the organic-inorganic hybrid nanoporous material showing excellent adsorption performance.

The organic-inorganic hybrid nanoporous body and the synthetic resin may be provided in the form of a liquid or solid mixture.

Organic-inorganic hybrid nanoporous materials and synthetic resins can be mixed through melt compounding, in-situ polymerization, solution mixing, etc.

When performing the melt mixing method, the synthetic resin and the organic-inorganic hybrid nanoporous body can be mixed at a process temperature higher than the glass transition temperature of the synthetic resin. Therefore, in order to easily mix the synthetic resin and the organic-inorganic hybrid nanoporous body and use it in subsequent extrusion and injection processes, the organic-inorganic hybrid nanoporous body can have thermal stability. Specifically, the organic-inorganic hybrid nanoporous body may be a stable material that does not have structural changes at the glass transition temperature of synthetic resin.

The composite compound may have at least one shape selected from the group consisting of a pellet, tablet, sphere, ellipse, hemisphere, flake, cuboid, and cube.

The complex compound can be used as a master batch. Specifically, as a raw material for manufacturing synthetic resin products, it can be used in processes such as extrusion and injection, as described above. By using composite compounds, synthetic resin products can be produced more easily. In particular, when the raw materials for producing synthetic resin products are provided as solid composite compounds, it is very easy to transport, store, and input the raw materials into the process.

The term “composite compound” used herein may mean that a high concentration of additives is dispersed in advance when manufacturing a resin composition. At this time, the additive may be an organic-inorganic hybrid nanoporous body. Through the production of such a composite compound, the dispersibility of the organic-inorganic hybrid nanoporous body within the product can be improved, and thus the properties/functions of the organic-inorganic hybrid nanoporous body can be uniformly imparted to the product.

For example, when an organic-inorganic hybrid nanoporous material has adsorption performance, a product manufactured by adding a composite compound containing the organic-inorganic hybrid nanoporous material can also exhibit excellent adsorption performance.

When mixing organic-inorganic hybrid nanoporous bodies in the form of a composite compound, the composite compound can be easily used in injection and extrusion processes to manufacture products. Specifically, by mixing a composite compound in the form of a pellet or the like with raw materials for making a product, the organic-inorganic hybrid nanoporous body can be easily applied to the product. In particular, as the composite compound has a solid shape, the organic-inorganic hybrid nanoporous body can be uniformly dispersed within the polymer raw material just by mixing it with the polymer raw material and then stirring.

The organic-inorganic hybrid nanoporous body may be included in an amount of about 0.1% by weight to about 50% by weight based on the total weight of the composite compound. In some cases, the organic-inorganic hybrid nanoporous body may be included in an amount of about 1% by weight to about 15% by weight based on the total weight of the composite compound.

If the organic-inorganic hybrid nanoporous body is contained in an amount of less than about 0.1% by weight based on the total weight of the composite compound, the amount of the organic-inorganic hybrid nanoporous body is relatively insufficient, so the function/property of the organic-inorganic hybrid nanoporous body is not used in the product. It may not appear. On the other hand, when the organic-inorganic hybrid nanoporous body is included in more than about 20% by weight based on the total weight of the composite compound, moldability may be reduced when molding a product using the composite compound.

Figure 3 is an enlarged cross-sectional view showing the shape of a product manufactured by molding a composite compound according to an embodiment of the present invention.

According to Figure 3, products made from composite compounds are provided with voids. Specifically, voids are provided between the organic-inorganic hybrid nanoporous body and the synthetic resin. Accordingly, as can be seen in the drawing, the organic-inorganic hybrid nanoporous body is provided to contact the synthetic resin only on some surfaces.

The void provided between the organic-inorganic hybrid nanoporous body and the synthetic resin may, in some cases, have the same shape as a part of a pore. For example, the synthetic resin includes a plurality of pores, the mixture is provided in the form of an organic-inorganic hybrid nanoporous material inserted into each pore, and some surfaces of the organic-inorganic hybrid nanoporous body are in contact with some surfaces within the pores. It can be provided in the form However, the above is only an exemplary form, and the shape of the pores may vary depending on the type of synthetic resin and the type of organic-inorganic hybrid nanoporous body.

By providing a gap between the organic-inorganic hybrid nanoporous body and the synthetic resin, the uniformity of the mixture can be further improved and the moldability of the composite compound can be improved. Specifically, because the organic-inorganic hybrid nanoporous material has a certain fluidity within a volume equivalent to the pore, the organic-inorganic hybrid nanoporous material can be prevented from being concentrated only in a specific area. Accordingly, the organic-inorganic hybrid nanoporous body and the synthetic resin can be mixed more uniformly. In addition, when molding a composite compound, the synthetic resin forming the surface of the pore is in a glass transition state, so that the composite compound can be molded quickly at a lower temperature.

Additionally, the material can contact the organic-inorganic hybrid nanoporous body provided between the synthetic resins through the corresponding pores. Accordingly, the functions exhibited by the organic-inorganic hybrid nanoporous material can appear in products manufactured from the masterbatch.

A gaseous compound may be further provided in the pores provided between the organic-inorganic hybrid nanoporous body and the synthetic resin. Gas compounds can be of various types, such as hydrocarbons, water vapor, and hydrogen. Gas compounds can be used to improve the physical properties of products made from composite compounds by melting into the product during the molding process.

In particular, the size and shape of these pores can be controlled when manufacturing products by molding the masterbatch.

Films containing organic-inorganic hybrid nanoporous bodies can be used for various purposes. For example, using the gas adsorption capacity of organic-inorganic hybrid nanoporous materials, films can be used as packaging materials to monitor the freshness of food. Specifically, a food packaging film capable of monitoring the freshness of food can be provided by adsorbing the gas generated when food oxidizes into the organic-inorganic hybrid nanoporous body within the packaging film and exhibiting a color change due to gas adsorption. In addition to the examples described above, films containing organic-inorganic hybrid nanoporous bodies can be used in various fields.

In addition to the examples above, products containing plastic raw materials can take various forms. Products can be a variety of things, including fibers, packaging materials, storage containers, and filters. In addition, in the present invention, the term “product” may refer to all or part of the final product.

The product may be an article made of moldable resin, such as thermoplastic resin or thermosetting resin. At this time, the product referred to in the present invention may be made of a polymer compound, a mixture of a polymer compound and another material such as metal, etc., and there is no limitation as long as it is made of a material that can be molded.

Since users can easily mix complex compounds with desired polymer raw materials and produce products using processes such as injection and extrusion, there are no restrictions on the form and use of the product. In particular, the process can be easily performed because the organic-inorganic hybrid nanoporous material contained in the composite compound is stable at the glass transition temperature of the polymer raw material.

Therefore, by using the composite compound according to an embodiment of the present invention, organic-inorganic hybrid nanoporous bodies with various functions can be used to manufacture products of various shapes and purposes.

Below, the present invention will be described in more detail through examples. However, the following examples are intended to illustrate the present invention in more detail, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.

An organic-inorganic hybrid nanoporous body (metal-organic framework; MOF) according to an embodiment of the present invention; Prior to manufacturing a composite compound (or master batch) containing a miscible synthetic resin, an organic-inorganic hybrid nanoporous body suitable for forming a composite compound was first prepared as disclosed in Preparation Examples 1 to 5.

Preparation Example 1: Preparation of organic-inorganic hybrid nanoporous body (KRICT F100)

에서 12시간 내지 15시간 동안 가열하여 Fe-BTC 흡착제를 합성하였다.To prepare Fe-BTC (Fe-benzene-1,3,5-tricarboxylate), 23.0 g of double distilled water, 10.54 g of Fe(NO ₃ ) ₃ ·9H ₂ O and 3.79 g of 1,3 in a round bottom flask. , 5-Benzenetricarboxylic acid was mixed and stirred at room temperature for 30 minutes. Afterwards, the reflux cooler is installed and the temperature is 100 to 120 degrees Celsius using an oil bath.

The Fe-BTC adsorbent was synthesized by heating for 12 to 15 hours.

오븐에서 건조하여 흡착제 분말을 수득하였다.After completion of the reaction, the reaction solution was cooled, washed once with double distilled water, and three times with ethanol. The produced Fe-BTC crystals were recovered by filtration, and 100

Adsorbent powder was obtained by drying in an oven.

Preparation Example 2: Preparation of organic-inorganic hybrid nanoporous body (KRICT F300)

The organic-inorganic hybrid nanoporous Al-FMA (Al-Fumaric Acid) was synthesized as follows.

A metal precursor solution was prepared by dissolving 21.514 g of Al ₂ (SO ₄ ) ₃ ·18H ₂ O in 70 g of double distilled water. A ligand precursor solution was prepared by dissolving 7.34 g of fumaric acid and 7.593 g of caustic soda in 70 g of double distilled water.

로 각각 가열한 후, 금속 전구체 용액을 리간드 전구체 용액에 서서히 첨가하면서 교반하여 혼합하였다. 두 용액의 혼합이 종료된 후, 혼합 용액을 60

내지 80

의 온도에서 30분 내지 2시간 동안 반응시켜 Al-FMA 흡착제를 합성하였다. The two solutions prepared above were mixed at 60

After each heating, the metal precursor solution was slowly added to the ligand precursor solution and mixed with stirring. After mixing of the two solutions is completed, the mixed solution is

to 80

Al-FMA adsorbent was synthesized by reacting at a temperature for 30 minutes to 2 hours.

오븐에서 건조하여 흡착제 분말을 수득하였다.After completion of the reaction, the resulting reaction solution was filtered to recover Al-FMA crystals, washed with double distilled water and ethanol, and washed with 100% distilled water and ethanol.

Adsorbent powder was obtained by drying in an oven.

Preparation Example 3: Preparation of organic-inorganic hybrid nanoporous body (KRICT F400)

The organic-inorganic hybrid nanoporous body Al-FDC (Al-2,5-furandicarboxylate) was synthesized as follows.

로 가열하면서 24시간 동안 환류 교반하였다. 그런 다음 결과된 반응 용액을 상온으로 냉각시킨 후, 증류수와 에탄올을 이용하여 정제한 후 원심 분리하여 생성물을 회수하였다. First, add 4.683 g of 2,5-furandicarboxylic acid, 7.243 g of AlCl ₃ ·6H ₂ O, 1.20 g of NaOH, and 60 g of distilled water into a 100 mL round bottom flask, and leave at room temperature for 3 hours. After mixing by stirring, 100

It was refluxed and stirred for 24 hours while heating. Then, the resulting reaction solution was cooled to room temperature, purified using distilled water and ethanol, and then centrifuged to recover the product.

Preparation Example 4: Preparation of organic-inorganic hybrid nanoporous body (KRICT F600)

To prepare Al-IPA (Al-isophthalic acid), 16.4 g of Al ₂ (SO ₄ ) ₃ ·18H ₂ O was dissolved in 35 g of double distilled water to prepare a metal precursor solution. A ligand precursor solution was prepared by dissolving 8.45 g of isophthalic acid, 5.41 g of caustic soda, and 1.32 g of sodium aluminate in 110 g of double distilled water.

에서 6시간 동안 반응하여 Al-IPA 결정을 형성시켰다. The prepared metal precursor solution was slowly added to the prepared ligand precursor solution to prepare a mixed solution. The mixed solution was placed in a round bottom flask equipped with a reflux condenser, and 120

Al-IPA crystals were formed by reacting for 6 hours.

오븐에서 건조하여 흡착제 분말을 수득하였다.After completion of the reaction, the resulting reaction solution was cooled, washed twice with double distilled water, and then filtered under reduced pressure to recover Al-IPA crystals.

Adsorbent powder was obtained by drying in an oven.

Preparation Example 5: Preparation of organic-inorganic hybrid nanoporous body (KRICT P300 LP)

The organic-inorganic hybrid nanoporous material Al-TMA (Al-benzene-1,3,5-tricarboxylic acid) was synthesized as follows.

A metal precursor solution was prepared by dissolving 30.36 g of Al ₂ (SO ₄ ) ₃ ·18H ₂ O in 120 g of double distilled water. A ligand precursor solution was prepared by dissolving 18.95 g of trimellitic acid (1,2,4-benzenedicarboxylic acid) and 7.14 g of caustic soda in double distilled water.

에서 12시간 동안 반응하여 Al-TMA 결정을 형성시켰다. The prepared metal precursor solution was slowly added to the prepared ligand precursor solution to prepare a mixed solution. The mixed solution was placed in a round bottom flask equipped with a reflux condenser, and 130

Al-TMA crystals were formed by reacting for 12 hours.

오븐에서 건조하여 흡착제 분말을 수득하였다.After completion of the reaction, the resulting reaction solution was cooled, washed twice with double distilled water, and then filtered under reduced pressure to recover Al-TMA crystals,

Adsorbent powder was obtained by drying in an oven.

Next, a composite compound, that is, a masterbatch chip, was manufactured using the organic-inorganic hybrid nanoporous body obtained in Preparation Examples 1 to 5 above.

Example 1: Preparation of masterbatch chip containing organic-inorganic hybrid nanoporous body

Masterbatch chips with various content ratios were manufactured using the organic-inorganic hybrid nanoporous powder obtained in Preparation Example 1 and Preparation Example 5 as an adsorbent.

100 g of chip-shaped polypropylene and a trace amount of antioxidant and UV stabilizer were added to a T-die extruder and melted, and then the organic-inorganic hybrid nanoporous powder obtained in Preparation Examples 1 to 5 was added at a content ratio of 1 to 1. 25 g was added and dispersed, then extruded through an extrusion molder nozzle and cooled to prepare a masterbatch.

Figures 1 and 2 are product photos of the master batch chip obtained in Example 1, each containing 20 wt % of organic-inorganic hybrid nanoporous material.

Figure 3 shows a schematic diagram of a product manufactured from a masterbatch containing the organic-inorganic hybrid nanoporous body obtained in Example 1.

In the case of Figure 4, the electron microscope analysis results of a product manufactured by molding a master batch chip manufactured by adjusting the content ratio of the Fe-BTC organic-inorganic hybrid nanoporous body obtained in Preparation Example 1 and the distribution of elements using EDS mapping are shown. This is the result of analysis. At this time, the content of Fe-BTC contained in the master batch chip was 3, 10, and 15% by weight, respectively.

As shown in Figure 3, in the case of the Fe-BTC organic-inorganic hybrid nanoporous material, it exists in a dispersed form in the product manufactured from the master batch, and it can be confirmed that a certain level of pores is formed at the contact surface between polypropylene and the organic-inorganic nanoporous material. Similar results were observed in products manufactured by molding masterbatch chips containing 3, 10, and 15% by weight.

As can be seen in the drawing, the organic-inorganic hybrid nanoporous body formed based on the central metal (Fe) in the masterbatch contacts the polymer compound in some areas. Because not all surfaces of the organic-inorganic hybrid nanoporous body are covered by the polymer compound, pores exist between the organic-inorganic hybrid nanoporous body and the polymer compound. Through these pores, materials can enter and exit the masterbatch, and the materials that enter can meet the organic-inorganic hybrid nanoporous body.

Therefore, by providing a specific organic-inorganic hybrid nanoporous body in an appropriate amount, the organic-inorganic hybrid nanoporous body can be provided in a masterbatch form that is easy to form, while still utilizing the excellent physical properties exhibited by the organic-inorganic hybrid nanoporous body. However, as can be seen in the rightmost drawing of FIG. 4, when the content of the organic-inorganic hybrid nanoporous body is 15 wt%, it can be seen that the exposed area of the organic-inorganic hybrid nanoporous body within the pore is reduced. Therefore, when the content of the organic-inorganic hybrid nanoporous body increases above a certain level, the adhesion area between the polymer compound and the organic-inorganic hybrid nanoporous body expands, and it can be seen that the pores exposing the organic-inorganic hybrid nanoporous body in the master batch gradually decrease. . In this case, there is a problem that the possibility of the material flowing into the masterbatch and meeting the organic-inorganic hybrid nanoporous body is reduced.

On the contrary, referring to the leftmost drawing of FIG. 4, when the content of the organic-inorganic hybrid nanoporous body is less than 3 wt%, it can be seen that the effect of improving the physical properties through the organic-inorganic hybrid nanoporous body content is too small. there is.

Example 2: Preparation of composite film from masterbatch chip containing organic-inorganic hybrid nanoporous body

Polypropylene films containing 1% by weight and 3% by weight of Fe-BTC were prepared from the masterbatch chip containing 20% by weight of the Fe-BTC organic-inorganic hybrid nanoporous body prepared in Example 1.

First, 95 g of chip-shaped polypropylene and 5 g of masterbatch chips are melted by adding a small amount of antioxidant and UV stabilizer to a T-die extruder, heated to the melting point temperature to maintain the molten state, and then extruded with coolant. A composite film containing 1% by weight of Fe-BTC organic-inorganic hybrid nanoporous body was obtained by uniformly adjusting the thickness of the film to 0.1 mm or less using a metal roll.

Similarly, 85 g of polypropylene chips and 15 g of masterbatch chips were prepared in the same manner as above to obtain a composite film containing 3% by weight of Fe-BTC organic-inorganic hybrid nanoporous body.

Figure 5 shows the results of analyzing the surface of the composite film obtained in Example 2 using a scanning electron microscope. Additionally, the surface of the polypropylene film without the composite was compared with the surface of the composite film containing 1 or 3 weight % of Fe-BTC. As a result, it was confirmed that a uniformly smooth surface without pores was formed on the surface of the polypropylene film, and in the case of the composite film containing 1 to 3% by weight of Fe-BTC, it was confirmed that pores were developed on the contact surface. You can.

Although the present invention has been described above with reference to preferred embodiments, those skilled in the art or have ordinary knowledge in the relevant technical field should not deviate from the spirit and technical scope of the present invention as set forth in the claims to be described later. It will be understood that the present invention can be modified and changed in various ways within the scope of the present invention.

Therefore, the technical scope of the present invention should not be limited to what is described in the detailed description of the specification, but should be defined by the scope of the patent claims.

Claims (12)

Organic-inorganic hybrid nanoporous body (metal-organic framework; MOF); and
Contains miscible synthetic resins,
The organic-inorganic hybrid nanoporous body and the synthetic resin are provided in a mixture form,
The mixture is a masterbatch, and the final product manufactured from the masterbatch contains additional functions due to the organic-inorganic hybrid nanoporous body,
The mixture is used by mixing with the raw materials of the product when molding the product,
In a product manufactured by molding the mixture, a gap is provided between the organic-inorganic hybrid nanoporous body and the synthetic resin, so that the organic-inorganic hybrid nanoporous body contacts the synthetic resin only on some surfaces,
The organic-inorganic hybrid nanoporous body is contained in a ratio of 1% by weight to 20% by weight based on the total weight of the mixture of the organic-inorganic hybrid nanoporous body and the synthetic resin. delete delete According to paragraph 1,
A composite comprising the synthetic resin containing at least one selected from the group consisting of thermosetting resin, thermoplastic resin, biodegradable plastic, rubber, and bioplastic. According to paragraph 1,
The composite has the shape of at least one of a pellet, tablet, sphere, ellipse, hemisphere, flake, cuboid, and cube. According to paragraph 1,
The complex is
A composite comprising an organic-inorganic hybrid nanoporous body composed of a central metal ion and an organic ligand that binds to the central metal ion. According to clause 5,
Carboxyl group (-COOH), carboxylic acid anion group (-COO-), amine group (-NH ₂ ) and imino group (=NH), nitro group (-NO ₂ ), hydroxy group (-OH), halogen group (- _{( _ _ _} A composite comprising the organic-inorganic hybrid nanoporous body composed of an organic ligand that is a compound or a mixture thereof having one or more functional groups selected from the group consisting of. According to paragraph 1,
A composite comprising the organic-inorganic hybrid nanoporous body having a porous structure. According to paragraph 1,
A composite comprising the organic-inorganic hybrid nanoporous body having a stable structure at the glass transition temperature of the synthetic resin. According to paragraph 1,
The mixture has a liquid state or a solid state. According to paragraph 1,
The composite further comprising a gaseous compound or vapor provided within the pores. A synthetic resin product manufactured by molding the composite according to any one of claims 1 and 4 to 11.