KR102037478B1 - REACTIVE FIBERS COMPRISING (metal-organic framework NANOPARTICLES, METHODS OF MAKING THE SAME, AND ARTICLES MADE THEREFROM - Google Patents

Abstract

The present invention relates to: a reactive fiber comprising reactive nanoparticles, a method for manufacturing the same; and an article manufactured therefrom. More specifically, the present invention relates to: the reactive fiber comprising a polymer fiber and reactive nanoparticles dispersed and bound in the polymer fiber, wherein the reactive nanoparticles comprise at least one selected from a group consisting of a metal organic framework (MOF) and a surface-modified MOF, and the reactive nanoparticles is surface-treated with a compound containing a hydrophobic chain and a hydrophilic functional group formed at the end of the hydrophobic chain; the method for manufacturing the same; and the article manufactured from the same. Manufactured fibers can realize fabrics for adsorption and decomposition of chemical agents.

Description

REACTIVE FIBERS COMPRISING (metal-organic framework NANOPARTICLES, METHODS OF MAKING THE SAME, AND ARTICLES MADE THEREFROM)

FIELD OF THE INVENTION The present invention relates to reactive fibers comprising metal-organic framework nanoparticles, methods for their preparation and articles made therefrom, in particular UiO-66 (Zr ₆ O ₄ (OH) ₄ (BDC) ₆ ) and UiO- 66-NH ₂ (Zr ₆ O ₄ (OH) ₄ (BDC-NH ₂ ) ₆ ) Reactive fibers comprising metal-organic framework (MOF) nanoparticles, methods for their preparation and articles made therefrom.

Commonly known chemicals that can be used in war or terror include neurochemical agents sarin (GB), mannose (GD), and VX (O-ethyl S- (2-diisopropylamino) ethyl methylphosphonothioate) and blisters on skin There is a mustard gas (HD). Persons at risk of contact with these chemicals should be protected from these by wearing appropriate protective clothing or by appropriate protective materials.

The method of protecting body parts from chemical agents or industrial toxic gases is carried out by wearing NBC protective clothing or industrial protective clothing, which prevents toxic gases from entering the body parts from outside of the protection to prevent contact with the body and toxic gases. The method is mainly used. This protective material uses a permeable and impermeable protective material, which is a cotton / polyester blend material that has a water / oil repellent function to block aerosols and fine liquid particles, and a toxic gas that penetrates inside. And it is equipped with the inner shell of the activated carbon material to remove the chemical agent by adsorption, and has the property that air is permeable well. Impervious protective materials are membrane materials or self-contained breathing apparatus (SCBA), which are selective permeable membranes that selectively release sweat and steam. Polymer material of impermeable properties is used.

Chemical agent protective garments used for military use, etc., are made of a laminated structure of functional fibers of several tens to hundreds of micrometers in size. Activated carbon contained in the existing protective clothing acts as a simple adsorbent, and thus cannot be used repeatedly and can be used only once. Also, once the protective clothing is exposed to the chemical agent, the chemical agent is adsorbed on the activated carbon, so the simple disposal is impossible. In order to add some catalytic functionality to the activated carbon, a catalyst component may be added, but since most heavy metal components are included, there is still concern about toxicity and / or contamination.

On the other hand, organic-inorganic hybrid nanoporous bodies, so-called metal-organic frameworks (MOFs), are also commonly referred to as "porous coordination polymers" or "porous organic-inorganic hybrids." The metal-organic framework has recently been newly developed by incorporating molecular coordination bonds and material science, and the metal-organic framework has high surface area and molecular size or nano-sized pores, so that the adsorbent, gas storage material In addition to its application in sensors, membranes, functional thin films, drug delivery materials, catalysts and catalyst carriers, it can also be used to capture guest molecules smaller than pore sizes or to separate molecules according to their size using pores. Therefore, it has been actively studied recently. In addition, since the metal-organic framework has a nano-sized pores and thus has a high surface area, the metal-organic framework is mainly used for the adsorption of materials or the delivery of a composition in pores.

In particular, UiO-66 (Zr ₆ O ₄ (OH) ₄ (BDC) ₆ ) and UiO-66-NH ₂ (Zr ₆ O ₄ (OH) ₄ (BDC-NH ₂ ) ₆ ) MOF It is known that it possesses many Zr-OH groups and thus has excellent properties of hydrolysis reaction and can be used to decompose chemical agent materials. However, as described above, the UiO-66 and UiO-66-NH ₂ MOF contain hydrophilic functional groups such as -OH groups on the surface thereof, so that the UiO-66 and UiO-66-NH ₂ MOF have poor compatibility with the polymer, thereby producing a fiber including the MOF uniformly. There is no problem.

The present invention is to solve the above problems, an object of the present invention, to provide a reactive fiber comprising at least 40% by weight of the reactive nanoparticles, such as UiO-66 and UiO-66-NH ₂ of the reactive fibers will be.

In addition, by improving the miscibility of the reactive nanoparticles, to prepare a polymer solution containing more than 40% by weight of MOF, to provide a method for producing a reactive fiber through this.

In addition, to provide a fabric for the adsorption and decomposition of the chemical agent made of the reactive fiber.

In addition, to provide an article made of a fabric for the adsorption and decomposition of the chemical agent.

However, the problem to be solved by the present invention is not limited to those mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

Reactive fiber according to an embodiment of the present invention, the polymer fiber; And reactive nanoparticles dispersed and bound to the polymer fibers, wherein the reactive nanoparticles include at least one selected from the group consisting of UiO-66 and UiO-66-NH ₂ , and the reactive nanoparticles. The particles are surface treated with a compound containing a hydrophobic chain and a hydrophilic functional group formed at the end of the hydrophobic chain.

According to one aspect, in the reactive fiber, the reactive nanoparticles may be from 40% by weight to 75% by weight.

According to one aspect, the compound comprising a hydrophobic chain and a hydrophilic functional group formed at the end of the hydrophobic chain may be oleic acid.

According to one aspect, the average diameter of the reactive nanoparticles may be from 100 nm to 200 nm.

According to one aspect, the reactivity may be at least one degradation reactivity selected from the group consisting of neurological agents, blisters, industrial toxicants and toxic gases.

According to one aspect, the polymer fiber is a polymer fiber capable of electrospinning, it may be a polyacrylonitrile fiber (polyacrylonitrile fiber).

Method for producing a reactive fiber according to an embodiment of the present invention, preparing at least one reactive nanoparticles selected from the group consisting of UiO-66 and UiO-66-NH ₂ ; Preparing the surface-treated reactive nanoparticles by treating the prepared reactive nanoparticle surface with a compound including a hydrophobic chain and a hydrophilic functional group formed at the end of the hydrophobic chain; Preparing a mixed solution by mixing the surface treated reactive nanoparticles and polymer fibers; And electrospinning the mixed solution.

According to one aspect, the step of preparing the reactive nanoparticles, it may be to prepare a reactive nanoparticle having an average diameter of 100 nm to 200 nm through an accelerator.

According to one aspect, the promoter may be at least one selected from the group consisting of benzoic acid and acetic acid.

According to one aspect, the step of preparing the surface-treated reactive nanoparticles, it may be performed by mixing the reactive nanoparticles, the compound and the solvent in a weight ratio of 1: 0.8 to 1.2: 5 to 10 and stirred. .

According to one aspect, the compound comprising a hydrophobic chain and a hydrophilic functional group formed at the end of the hydrophobic chain may be oleic acid.

According to one aspect, the mixed solution may include 40 wt% to 75 wt% of the reactive nanoparticles.

Fabric for adsorption and decomposition of the chemical agent according to an embodiment of the present invention, weaving with a reactive fiber prepared through a reactive fiber according to an embodiment of the present invention or a method for producing a reactive fiber according to an embodiment of the present invention It is.

According to one aspect, at least one selected from the group consisting of water and oil repellent (천 水 撥 油) cloth and activated carbon fiber (Activated Carbon Fiber); may be further included.

According to one aspect, the reactive fiber, the water and oil repellent cloth and the activated carbon fiber (Activated Carbon Fiber), may be in the form of a multi-layer composite fabric laminated in the order or otherwise. .

An article according to one embodiment of the invention is made of a fabric for adsorption and decomposition of a chemical agent according to one embodiment of the invention.

According to one aspect, it may include at least one selected from the group consisting of a protective, gas mask, purifier, combat suit, field tent and camouflage film.

According to the present invention, by treating the reactive nanoparticles with a compound containing a hydrophobic chain and a hydrophilic functional group formed at the end of the hydrophobic chain, a reactive fiber including 40 wt% or more of the reactive nanoparticles can be realized.

In addition, MOF nanoparticles such as UiO-66 and UiO-66-NH ₂ , which have very high hydrophilicity, and polymers can be realized in a very uniformly distributed composite fiber, and the prepared fiber can simultaneously disintegrate nerve agent and blister agent. Therefore, it is possible to implement a fabric for adsorption and decomposition of chemical agents.

1 shows XRD crystallinity analysis results of surface treated MOF nanoparticles and untreated MOF nanoparticles.
2 shows the results of FT-IR analysis of surface treated MOF nanoparticles and unsurfaced MOF nanoparticles.
Figure 3 is a SEM image of a reactive fiber made of a reactive fiber and oleic acid prepared in the UiO-66-NH ₂ MOF nanoparticles surface treated with oleic acid via UiO-66-NH ₂ MOF nanoparticles are not surface-treated.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. In describing the present invention, when it is determined that detailed descriptions of related known functions or configurations may unnecessarily obscure the subject matter of the present invention, the detailed description thereof will be omitted. In addition, terms used in the present specification are terms used to properly express preferred embodiments of the present invention, which may vary according to user's or operator's intention or customs in the field to which the present invention belongs. Therefore, the definitions of the terms should be made based on the contents throughout the specification. Like reference numerals in the drawings denote like elements.

Throughout the specification, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member is present between the two members.

Throughout the specification, when a part is said to "include" a certain component, it means that it may further include other components, not to exclude other components.

Hereinafter, a reactive fiber including the reactive nanoparticles of the present invention, a method for preparing the same, and an article prepared through the same will be described in detail with reference to Examples and drawings. However, the present invention is not limited to these embodiments and drawings.

Reactive fiber according to an embodiment of the present invention, the polymer fiber; And reactive nanoparticles dispersed and bound in the polymer fiber, wherein the reactive nanoparticles include at least one selected from the group consisting of a metal organic framework (MOF) and a surface-modified metal organic earpiece. The reactive nanoparticles are surface treated with a compound containing a hydrophobic chain and a hydrophilic functional group formed at the end of the hydrophobic chain.

The present invention begins with the object of applying a metal organic framework (MOF) known to be capable of adsorbing and degrading chemical agents, including nerve agents and blisters, to the protective clothing, and when making them into fibers, hydrophilic surface properties. Due to this, it is difficult to be mixed with the polymer and the MOF nanoparticles are agglomerated and mixed unevenly or the nozzle is clogged during the manufacturing process of the fiber. It is therefore designed to overcome the disadvantages of developing products of higher dimensions, such as fabrics and even garments made therefrom.

According to one aspect, in the reactive fiber, the reactive nanoparticles may be from 40% by weight to 75% by weight.

According to the present invention, by surface-treating the reactive nanoparticles having hydrophilic surface properties with a compound containing a hydrophobic chain and a hydrophilic functional group formed at the end of the hydrophobic chain, the dispersibility of the reactive nanoparticles is greatly improved, thereby the reactive nanoparticles It can be implemented a reactive fiber comprising at least 40 wt%, 75 wt% or less.

According to one aspect, the compound comprising a hydrophobic chain and a hydrophilic functional group formed at the end of the hydrophobic chain may be oleic acid.

Oleic acid is composed of a hydrophobic long chain and a carboxyl group having an acidic pKa value. That is, it includes a hydrophobic chain and a carboxyl group formed at the end of the hydrophobic chain. By surface treatment of the MOF nanoparticles with the oleic acid, it is possible to implement a reactive fiber including the MOF nanoparticles evenly dispersed.

According to an aspect, the reactive nanoparticles may include at least one selected from the group consisting of UiO-66 and UiO-66-NH ₂ .

The UiO-66 and UiO-66-NH ₂ MOF are materials containing zirconium as a main metal and terephthalic acid as a ligand in the basic structure, as well as adsorbing carbon dioxide or methane gas, as well as adsorbing a chemical agent as a powder to hydrolyze it. It is known that it can be decomposed by, and it has been disclosed that it can be applied to the purifier of gas masks, but due to its hydrophilicity was poor in miscibility with the polymer, it was difficult to fiberize, especially containing a high content of more than 40% by weight Fibers have not been produced, and only the form in which the MOF particles are bonded to the surface of the polymer fiber has been studied, rather than the composite fiber of the polymer and the MOF.

Specifically, since the UiO-66 and UiO-66-NH ₂ MOF include a Zr-O / Zr-OH structure in the central metal, it is difficult to disperse the polymer in organic materials having hydrophilicity. Therefore, even if radiated by electrospinning, only the MOF nanoparticles are agglomerated and do not mix uniformly with the polymer. As a result, problems such as clogging of the nozzle occur, making it difficult to manufacture a woven fabric of sufficient size (mat, mat). .

On the other hand, according to the present invention, by treating the MOF nanoparticles with a compound containing a hydrophobic chain and a hydrophilic functional group formed at the end of the hydrophobic chain, it is possible to realize a reactive fiber in which nanoparticles and polymers are uniformly mixed, It can be manufactured from a woven fabric.

According to one aspect, the average diameter of the reactive nanoparticles may be from 100 nm to 200 nm. If the average particle diameter of the reactive nanoparticles is less than 100 nm, problems may occur that are difficult to exhibit activity as a catalyst. If the average particle size of the reactive nanoparticles is larger than 200 nm, it may be difficult to maintain the fiber form itself or decrease the elasticity of the fiber. Therefore, problems may occur that exhibit poor properties such as being easily broken even at low stimuli.

According to one aspect, the reactivity may be at least one degradation reactivity selected from the group consisting of neurological agents, blisters, industrial toxicants and toxic gases. As described above, the reactive fibers of the present invention can decompose chemical agents, and are not limited thereto and can decompose at least one selected from the group consisting of industrial toxic substances and toxic gases.

According to one aspect, the polymer fiber is a polymer fiber capable of electrospinning, it may be a polyacrylonitrile fiber (polyacrylonitrile fiber). However, the present invention is not limited thereto and may be applied without limitation as long as the polymer fiber is mixed with the reactive nanoparticles to enable electrospinning.

Method for producing a reactive fiber according to an embodiment of the present invention comprises the steps of preparing at least one reactive nanoparticles selected from the group consisting of metal organic framework (MOF) and surface-modified metal organic dog; Preparing the surface-treated reactive nanoparticles by treating the prepared reactive nanoparticle surface with a compound including a hydrophobic chain and a hydrophilic functional group formed at the end of the hydrophobic chain; Preparing a mixed solution by mixing the surface treated reactive nanoparticles and polymer fibers; And electrospinning the mixed solution.

According to the present invention, by treating the surface of the reactive nanoparticles with a compound containing a hydrophobic chain and a hydrophilic functional group formed at the end of the hydrophobic chain, to prepare a surface-treated reactive nanoparticles, thereby uniformly dispersed in the molten polymer In this case, the phenomenon of aggregation of MOF particles is greatly improved, and a reactive fiber including MOF nanoparticles evenly dispersed through a conventional electrospinning method can be manufactured.

According to one aspect, the step of preparing the reactive nanoparticles, it may be to prepare a reactive nanoparticle having an average diameter of 100 nm to 200 nm through an accelerator.

According to one aspect, the promoter may be at least one selected from the group consisting of benzoic acid and acetic acid.

By applying a kind of modulator to the original reflux synthesis method, it is possible to produce nanoparticles of uniform size satisfying an average diameter of 100 nm to 200 nm, which is high even when compared to the synthesis results produced on a lab scale. It is possible to produce uniform nanoparticles with crystallinity.

According to one aspect, the step of preparing the surface-treated reactive nanoparticles, it may be performed by mixing the reactive nanoparticles, the compound and the solvent in a weight ratio of 1: 0.8 to 1.2: 5 to 10 and stirred. .

According to one aspect, the compound comprising a hydrophobic chain and a hydrophilic functional group formed at the end of the hydrophobic chain may be oleic acid.

According to an aspect, the reactive nanoparticles may include at least one selected from the group consisting of UiO-66 and UiO-66-NH ₂ .

According to one aspect, the mixed solution may include 40 wt% to 75 wt% of the reactive nanoparticles.

Fabric for adsorption and decomposition of the chemical agent according to an embodiment of the present invention, weaving with a reactive fiber prepared through a reactive fiber according to an embodiment of the present invention or a method for producing a reactive fiber according to an embodiment of the present invention It is.

The present invention provides a woven fabric for chemical agent adsorption and decomposition, which is woven from a reactive fiber according to an embodiment of the present invention or a reactive fiber produced through the method for producing a reactive fiber according to an embodiment of the present invention. For example, the reactive fiber according to the present invention contains UiO-66 and UiO-66-NH ₂ MOF in a high content of 40% by weight or more of the entire polymer, but does not entangle or separate the MOF particles from each other, Since it can be uniformly distributed in the form of a general fiber, UiO-66 and UiO-66-NH ₂ MOF can be produced in a uniformly distributed fabric by electrospinning.

According to one aspect, at least one selected from the group consisting of water and oil repellent (천 水 撥 油) cloth and activated carbon fiber (Activated Carbon Fiber); may be further included.

According to one aspect, the reactive fiber, the water and oil repellent cloth and the activated carbon fiber (Activated Carbon Fiber), may be in the form of a multi-layer composite fabric laminated in the order or otherwise. .

According to one aspect, it may be to include a reactive fiber, water and oil repellent (외 水 撥 油) functional sheath, activated carbon fiber and cotton material.

The water- and oil-repellent (撥 油水 기능) functional sheath is composed of the outer shell of the composite protective fabric, it can serve to fundamentally prevent the penetration of chemical agents.

The reactive fiber includes reactive nanoparticles and may serve to decompose the penetrating chemical agent.

The activated carbon fiber may be removed by adsorbing residual gas that may occur in the process of decomposing the chemical agent.

The cotton material may be laminated on the endothelium to protect the skin.

That is, the fabric for adsorption and decomposition of the chemical agent according to the present invention may be in the form of a multi-layer, it can effectively protect the body from chemical agents and harmful gases.

According to one aspect, in order to more effectively block the aerosol and fine liquid particles can be used by laminating a cotton, polyester blend material having a water and oil repellent (撥 水 撥 油) function.

According to one aspect, in order to more effectively absorb and remove toxic gases and chemical agents that penetrate into the inside can be used by stacking activated carbon fibers (Activated Carbon Fiber).

According to one aspect, a membrane material or a self-contained breathing apparatus (SCBA), which is a selective permeable membrane through which sweat, steam, etc. are selectively discharged, may be stacked and used.

An article according to one embodiment of the invention is made of a fabric for adsorption and decomposition of a chemical agent according to one embodiment of the invention.

According to one aspect, it may include at least one selected from the group consisting of a protective, gas mask, purifier, combat suit, field tent and camouflage film. However, it is not limited thereto. For example, the protective clothing currently in use is in the form of adsorption using a simple adsorbent, and has a limitation of being a disposable fiber material that is difficult to recycle after adsorption. However, the reactive nanoparticles in the present invention, as described above, are not simple adsorbents, and have the advantage of being reusable because they act as chemical decomposition catalysts at the same time as adsorption.

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

However, the following examples are only for illustrating the present invention, and the contents of the present invention are not limited to the following examples.

In a specific embodiment of the present invention, through the Swatch test, the fabric woven from polymer fibers containing UiO-66 and UiO-66-NH ₂ MOF nanoparticles according to an embodiment of the present invention includes a conventional adsorbent It was confirmed that it has an excellent resolution for the neurological and blistering agents which are actually known chemical agents as compared to the protective clothing.

Example

<Zr-MOF Nanoparticles Manufacturing (UiO-66, UiO-66-NH ₂ )>

UiO-66 Manufacturing

14 mol of ZrOCl ₂ · 8H ₂ O and 14 mol of terephthalic acid (H2BDC) were added to a 50 L plastic container, followed by 11.84 kg of N, N'-dimethylformamide (DMF) solvent. It was. 780 g of 37% HCl aqueous solution and 2.01 kg of water were further added to the mixture, and the reaction mixture was mixed with stirring at 50 rpm for 20 minutes at room temperature.

The reactant was transferred to a 50 L glass reactor capable of reflux reaction and raised to a temperature increase rate of 5 ° C. per minute from room temperature to 90 ° C. to form an organic gel, where the viscosity of the gel solution reached 300 cps at this temperature. The stirring speed was reduced and maintained for 3 hours while stirring. Then, the reaction product was raised to 120 ° C. again and held for 12 hours to carry out a crystallization reaction, and then cooled to room temperature at a cooling rate of 1 ° C. or less per minute.

After synthesis, the slurry solution containing the porous organic-inorganic hybrid was once filtered through a pressure filter at room temperature, and washed with a N, N'-dimethylformamide solvent. The filtered porous organic-inorganic hybrid powder was added to a reactor made of SUS 316 containing N, N'-dimethylformamide solvent and stirred at 70 ° C for 3 hours to dissolve unreacted organic acid ligands and ions contained in the powder. And filtered in a pressure filter. The N, N'-dimethylformamide solvent used at this time was used in a 10 molar ratio compared to the powder. Methanol was added to the filtered powder and the unreacted metal precursors and ions were washed with stirring at 60 ° C. for 3 hours and then dried in a drying oven at 70-100 ° C. for 12 hours to obtain zirconium-based UiO-66 MOF nanoparticles.

UiO-66-NH ₂  Produce

To prepare UiO-66-NH ₂ , using 10 mmol of 2-aminoterephthalic acid in UiO-66, the reaction conditions were stirred at 155 ° C. for 28 hours. The resulting solid powder was filtered, washed well with dichloromethane, and then dried at 75 ° C. in a vacuum of 10 mmHg for 14 hours to obtain UiO-66-NH ₂ .

<Preparation of Surface-treated MOF Nanoparticles by Addition of Oleic Acid>

UiO-66-NH ₂ MOF nanoparticles prepared as described above, oleic acid (oleic acid) and ethanol were mixed and mixed in a ratio of 1: 1: 5 ~ 10 by mass ratio. The mixture was dispersed in 2 volumes of water, centrifuged and washed to obtain UiO-66-NH ₂ MOF nanoparticles modified with oleic acid.

For MOF nanoparticles surface-treated by the method described above, XRD crystallinity analysis and FT-IR analysis before and after treatment were performed.

1 shows XRD crystallinity analysis results of surface treated MOF nanoparticles and untreated MOF nanoparticles.

2 shows the results of FT-IR analysis of surface treated MOF nanoparticles and unsurfaced MOF nanoparticles.

Referring to Figure 1, there was no difference in the XRD pattern before and after the addition of oleic acid, it can be seen that it maintains the same crystal structure as the untreated UiO-66-NH ₂ even after surface treatment with oleic acid.

Referring to FIG. 2. From the FT-IR pattern change of MOF nanoparticles before and after the addition of oleic acid, it can be confirmed that oleic acid is mixed with the MOF nanoparticles. Specifically, the spectrum of the MOF after the addition of oleic acid showed a peak corresponding to CH at 2926 cm ⁻¹ and 2851 cm ⁻¹ and an additional peak corresponding to ^C═O at 1700 cm ⁻¹ (FIG. 2 (b)).

Preparation of Reactive Fibers by Electrospinning

UiO-66-NH ₂ MOF nanoparticles surface-treated with polyacrylonitrile and the oleic acid were mixed and introduced into a spinning device at a constant rate to obtain reactive fibers in which the MOF nanoparticles were evenly dispersed in the polymer by electrospinning.

Comparative example

Reactive fibers were prepared in the same manner as in Example through UiO-66-NH ₂ MOF nanoparticles not surface-treated with oleic acid for comparison.

Figure 3 is a SEM image of a reactive fiber made of a reactive fiber and oleic acid prepared in the UiO-66-NH ₂ MOF nanoparticles surface treated with oleic acid via UiO-66-NH ₂ MOF nanoparticles are not surface-treated.

Specifically, (a) of FIG. 3 is an SEM image of a reactive fiber prepared through UiO-66-NH ₂ MOF nanoparticles not surface-treated with oleic acid, and FIG. 3 (b) shows UiO-66- surface-treated with oleic acid. SEM image of reactive fibers made through NH ₂ MOF nanoparticles.

Referring to FIG. 3, fibers prepared from a polymer solution containing MOF not surface-treated with oleic acid are aggregated with each other without uniformly distributing MOF particles throughout the fiber (FIG. 3 (a)). Thus, the fiber prepared by using the MOF with improved miscibility can be seen that evenly distributed and adsorbed MOF particles throughout the fiber (Fig. 3 (b)).

Evaluation example

According to the US Department of Defense's Permeation Testing of Materials With Chemical Agents or Simulants (Swatch Testing) protocol, the performance of protective clothing prepared from the fabric for adsorption and decomposition of the chemical agent of the present invention against the existing adsorbent protective clothing was compared and evaluated. The results are shown in Table 1 below.

sample Nerve agent
(μg / cm ² ) usage Blister
(μg / cm ² ) usage Comparative example 1.25 0.50 4.00 0.50 Example 0.41 0.15 1.58 0.50

The results of the performance evaluation means that the less the amount of use and performance value is superior, the fiber of the embodiment prepared using MOF improved surface miscibility by surface treatment with oleic acid according to the present invention through Table 1 is a conventional adsorbent protective fiber It can be seen that it has a remarkably good adsorption and / or degradation performance for neuro- and blisters compared to.

Although the embodiments have been described by the limited embodiments and the drawings as described above, various modifications and variations are possible to those skilled in the art from the above description. For example, the techniques described may be performed in a different order than the described method, and / or the components described may be combined or combined in a different form than the described method, or replaced or substituted by other components or equivalents. Appropriate results can be achieved. Therefore, other implementations, other embodiments, and equivalents to the claims are within the scope of the claims which follow.

Claims (17)

Polymer fibers; And
Reactive nanoparticles dispersed and bound in the polymer fibers;
As a reactive fiber containing,
The reactive nanoparticles include at least one selected from the group consisting of UiO-66 and UiO-66-NH ₂ ,
The reactive nanoparticles are surface treated with a compound containing a hydrophobic chain and a hydrophilic functional group formed at the end of the hydrophobic chain,
The compound containing a hydrophobic chain and a hydrophilic functional group formed at the end of the hydrophobic chain is oleic acid,
Among the reactive fibers, the reactive nanoparticles are 40 wt% to 75 wt%,
The average diameter of the reactive nanoparticles is 100 nm to 200 nm,
Reactive fibers, for fabrics for adsorption and decomposition of chemical agents.
delete delete delete The method of claim 1,
The reactivity is at least one decomposition reactivity that is selected from the group consisting of neurological agents, blisters, industrial toxicants and toxic gases,
Reactive fiber.
The method of claim 1,
The polymer fiber is a polymer fiber capable of electrospinning,
It is a polyacrylonitrile fiber,
Reactive fiber.
Preparing at least one reactive nanoparticle selected from the group consisting of UiO-66 and UiO-66-NH ₂ ;
Preparing the surface-treated reactive nanoparticles by treating the prepared reactive nanoparticle surface with a compound including a hydrophobic chain and a hydrophilic functional group formed at the end of the hydrophobic chain;
Preparing a mixed solution by mixing the surface treated reactive nanoparticles and polymer fibers; And
Electrospinning the mixed solution; and
The step of preparing the reactive nanoparticles, to prepare a reactive nanoparticle having an average diameter of 100 nm to 200 nm through an accelerator,
The compound containing a hydrophobic chain and a hydrophilic functional group formed at the end of the hydrophobic chain is oleic acid,
The mixed solution, 40% to 75% by weight of the reactive nanoparticles,
A process for preparing reactive fibers, for fabrics for adsorption and decomposition of chemical agents.
delete The method of claim 7, wherein
The accelerator comprises at least one selected from the group consisting of benzoic acid and acetic acid,
Method of Making Reactive Fibers.
The method of claim 7, wherein
Preparing the surface-treated reactive nanoparticles,
The reaction is performed by mixing the reactive nanoparticles, the compound and the solvent in a weight ratio of 1: 0.8 to 1.2: 5 to 10,
Method of Making Reactive Fibers.
delete delete Woven from a reactive fiber prepared by the method of producing a reactive fiber of claim 1 or a reactive fiber of claim 7,
Fabric for adsorption and decomposition of chemical agents.
The method of claim 13,
It is in the form of a composite fabric further comprising; at least one selected from the group consisting of water and oil repellent cloth and activated carbon fiber (Activated Carbon Fiber),
Fabric for adsorption and decomposition of chemical agents.
delete Made of a fabric for adsorption and decomposition of the chemical agent according to claim 13,
article
The method of claim 16,
It includes at least one selected from the group consisting of protective clothing, gas mask, purifier, battle suit, field tent and camouflage film,
article.

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