KR102006719B1 - Carbon nanotube fiber composite and the producing method thereof - Google Patents

Carbon nanotube fiber composite and the producing method thereof Download PDF

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KR102006719B1
KR102006719B1 KR1020150174115A KR20150174115A KR102006719B1 KR 102006719 B1 KR102006719 B1 KR 102006719B1 KR 1020150174115 A KR1020150174115 A KR 1020150174115A KR 20150174115 A KR20150174115 A KR 20150174115A KR 102006719 B1 KR102006719 B1 KR 102006719B1
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carbon nanotube
fiber composite
nanotube fiber
polyaniline
coating layer
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KR20170067437A (en
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남현
오유진
이영호
공명진
송동수
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주식회사 엘지화학
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
    • D06B1/00—Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating
    • D06B1/02—Applying liquids, gases or vapours onto textile materials to effect treatment, e.g. washing, dyeing, bleaching, sizing or impregnating by spraying or projecting
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    • D06B—TREATING TEXTILE MATERIALS USING LIQUIDS, GASES OR VAPOURS
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    • D06B3/00—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating
    • D06B3/04—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating of yarns, threads or filaments
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    • D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
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    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
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    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
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Abstract

The present invention relates to a carbon nanotube fiber composite and a method for manufacturing the same, and more particularly, to produce a high-density carbon nanotube fiber without using a strong acid and an oxidizing agent, to form a coating layer on the carbon nanotube fiber and to the coating layer The present invention relates to a carbon nanotube fiber composite material and a method of manufacturing the same, which may form a crosslinking between carbon nanotube fibers from a thiol-based crosslinking agent to achieve high density and high strength of the carbon nanotube fibers.

Description

Carbon nanotube fiber composite and the producing method

The present invention relates to a carbon nanotube fiber composite material and a method for manufacturing the same, which include a coating layer formed on the surface of a carbon nanotube fiber and a crosslinking agent which is bonded thereto to form crosslinking between fibers, thereby achieving high density and high strength of the fiber.

Carbon nanotubes are tiny molecules that are 1 nm in diameter, with long, long carbons connected by hexagonal rings. Specifically, a honeycomb carbon plane in which three carbon atoms are bonded to each other is rolled to form a tube-shaped carbon crystal having a diameter of 0.5 to 10 nm, and has high tensile strength and electrical conductivity, and is drawing attention as a next-generation advanced material.

Carbon nanotubes can be utilized in various types of materials. Particularly, when agglomerated carbon nanotubes are processed into a fiber form, super-strength fibers that are not broken, highly durable fibers that resist heat and friction, and nanofibers having excellent electrical conductivity and thermal conductivity can be manufactured. It is thought to be endless. Even today, carbon nanotube fibers are used in high-tech precision industries, including semiconductors and displays, in the form of antistatic fibers and low-hardness high-capacitance fibers, which significantly increase their productivity.

These carbon nanotube fibers are subjected to further processing to have appropriate strength and physical properties before commercialization. In particular, in the case of using the direct spinning (direct spinning method), which is one of the conventional manufacturing methods in the production of carbon nanotube fibers, there is an advantage that a large amount of carbon nanotube fibers can be produced compared to other methods, but long and stable There is a disadvantage in that it is difficult to produce a fiber in the form, it is common to use a modified after manufacture, such as forming a coating layer.

There have been steady studies and attempts on the production of modified carbon nanotube fibers, and one of the conventionally used methods is to introduce a functional group on the surface of carbon nanotube fibers using a strong acid, and then Try chemical bonds. However, the above method can improve the strength of the carbon nanotube fibers, but by using a strong acid or oxidizing agent to form defects on the surface of the fiber during the treatment process from which the characteristics of the carbon nanotube fibers inherent There is a disadvantage to reduce. In addition, the reaction time is long, and high temperature conditions for reflux of the strong acid are indispensable, and after the reaction, there is an inconvenience such as having a problem of treating the used strong acid.

Therefore, there is a need for an improved proposal for a manufacturing method capable of imparting excellent strength to carbon nanotube fibers without the use of strong acids and oxidants.

Carbon nanotube fiber post-treatment method for improving mechanical strength (Korea Patent No. 10-1415255)

The inventors of the present invention have conducted various studies in order to solve the above-mentioned problems. As a result, a crosslinking agent between carbon nanotube fibers is treated by treating a thiol-based crosslinking agent coating a polyaniline layer on the surface of the carbon nanotube fibers and binding thereto. The carbon nanotube fiber composite to be formed was prepared, and from this, it was confirmed that the production of carbon nanotube fibers of high density and high strength without using a strong acid and an oxidizing agent was completed.

It is therefore an object of the present invention to provide a stable, high density and high strength carbon nanotube fiber composite.

It is still another object of the present invention to provide a method for producing a carbon nanotube fiber composite having improved process efficiency and convenience without using strong acid and oxidizing agent.

The present invention to achieve the above object,

A plurality of carbon nanotube fibers; And

A polyaniline coating layer formed on the fibers; Including,

The plurality of carbon nanotube fibers provide a carbon nanotube fiber composite that forms cross-fiber crosslinking with a thiol-based crosslinking agent that binds on the polyaniline coating layer.

In addition, the present invention,

(a) forming a polyaniline coating layer on the plurality of carbon nanotube fiber surfaces;

(b) coating a thiol-based crosslinker solution on the coating layer; And

(c) performing a crosslinking reaction;

It provides a method for producing the carbon nanotube fiber composite.

Through the above problem solving means, the carbon nanotube fiber composite of the present invention is integrated at a high density to have a stable and high strength.

In addition, according to the manufacturing method of the carbon nanotube fiber composite of the present invention, it is possible to modify without using a strong acid and an oxidizing agent without causing defects on the surface of the carbon nanotube fiber, high temperature for reflux during the process No conditions are required, the reaction time is also significantly reduced, and the hassle of the used strong acid treatment is not followed, thereby improving the efficiency and convenience of the overall process.

1 is a longitudinal cross-sectional view of the carbon nanotube fiber composite of the present invention.
FIG. 2 is a scanning electron microscope photograph of a bundle surface of carbon nanotube fibers having no coating layer and no crosslinking.
3 is a scanning electron microscope photograph of the bundle surface of the carbon nanotube fibers having a coating layer and crosslinking according to the present invention.
Figure 4 is an IR data analysis result image for the carbon nanotube fiber composite according to the present invention.

The present invention proposes a carbon nanotube fiber composite having excellent strength and a manufacturing method capable of producing the same without using a strong acid and an oxidizing agent. Specifically, the carbon nanotube fiber composite of the present invention is formed with a polymer layer on the surface of individual strands of carbon nanotube fibers densely packed in bundles, and crosslinked from a thiol-based crosslinking agent bound to each of the polymer layers. Fiber bundles made of carbon nanotube fibers cross-linked from each other to achieve high density and high strength.

As used herein, the term 'carbon nanotube fiber composite' refers to a fiber unit composed of two or more carbon nanotube fiber strands capable of forming crosslinks. In general, carbon nanotube fibers are used to bundle a plurality of fibers in bundle form for commercial use, and thus the 'carbon nanotube fiber composite' may be a bundle of fibers or a component part of the same. Can be.

Meanwhile, the 'thiol-based crosslinking agent' refers to a double bond (N = ph) moiety in a polyaniline while having at least two, preferably two to six, thiol groups (SH-) for crosslinking in a molecular structure. It refers to a material capable of reacting with and forming crosslinks between carbon nanotube fibers.

Hereinafter, the content of the present invention will be described in more detail. However, the following contents are described only for the most representative embodiments in order to help the understanding of the present invention, and the scope of the present invention is not limited thereto, and the present invention should be understood to cover all ranges equivalent to the following contents.

Carbon Nanotube Fiber Composites

The carbon nanotube fiber composite of the present invention will be described in detail with reference to FIG. 1.

Figure 1 is a cross-sectional view in the longitudinal direction showing the structure of the carbon nanotube fiber composite according to the present invention, the thiol-based compound is shown in the form of an alkanedithiol (n = 1 ~ 10) as an example but not necessarily limited thereto It is not.

Referring to Figure 1, the carbon nanotube fiber composite 100 of the present invention is a carbon nanotube fiber 100, a polyaniline coating layer 20 formed on the surface of the fiber and the thiol-based crosslinking agent (20) bonded to the polyaniline coating layer ( 30), and the thiol-based crosslinking agent bonded to the polyaniline coating layer forms crosslinking between the carbon nanotube fibers.

Referring to the configuration of the carbon nanotube fiber composite material 100 of the present invention in more detail as follows.

The carbon nanotube fiber 10 is not particularly limited in the present invention, and may have various diameters and lengths according to its use. For example, the diameter can be 1 ~ 100um, the specific diameter and length can be adjusted as much as the device used in the fabrication process.

The polyaniline constituting the polyaniline coating layer 10 has a quinoid diamine (-N = Ph = N-, (a)) and a benzenoid diamine in its molecular structure, as shown in Formula 1 below. It is composed of two parts, (benzenoid diamine, -NH-Ph-NH-, (b)).

Figure 112015120106314-pat00001

The fully oxidized polyaniline is called pernigraniline, the fully reduced polyaniline is called leucoemeraldine and the half-oxidized polyaniline (also called half reduced) is called emeraldine. In Formula 1, x = 1, y = 0, furinigralyn, x = 0, y = 1, leucomeraldine, and x = y = 0.5, emeraldine (Macromolecules, 1994, 27, 518-525). . In other words, the funniranine corresponds to a structure having only quinoid diamines, rucoemeraldines only benzenoid diamines, and emeraldines half and half of quinoid diamines and benzenoid diamines.

The polyaniline constituting the polyaniline coating layer 10 of the present invention must have a structure including a quinoid diamine (-N = Ph = N-) in order to react with a crosslinking agent to form a bond, such as furnigraline or emeraldine Polyaniline in a state, or a mixture thereof. The greater the degree of oxidization, the greater the amount of quinoid diamine moieties, thereby providing more cross-linking sites.

The polyaniline coating layer 10 is preferably 0.1 to 0.2 times the diameter of the carbon nanotube fiber diameter. If the thickness is less than the above range, the amount of polyaniline to be coated is too small to provide a base material for crosslinking formation. If the thickness is greater than the above range, problems such as reducing the physical properties of carbon nanotube fibers may occur due to the excessively thick coating layer. Because it can.

As the thiol-based crosslinking agent 30, alkanedithiol (n = 1 to 10) is shown as an example in FIG. 1, but if the structure can be located between the carbon nanotube fibers 10, the compound must be alkane as a matrix. The present invention is not limited thereto and is not necessarily limited to dithiols. Specifically, a thiol compound including two to six thiol groups (-SH) in a molecular structure is possible, and when having at least two or more thiol groups, both carbon nanotube fibers 10 may be bonded to form crosslinks. This is because, when the number of thiols in the molecular structure increases to six or more, the size of the molecule itself becomes large and it is difficult to be located between the carbon nanotube fibers 10.

As the thiol crosslinking agent 30 of the present invention, dithiols, trithiols, tetrathiols and the like are preferably used. More preferably, 1,2-ethanedithiol and 1,1-propanedithio are used. Ol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 2,5-hexanedithiol, 1,6-hexanedithiol, 2,9 One kind selected from the group consisting of -decanedithiol, 1,2,3-propanetrithiol, 1,8-octanedithiol, 1,4-dithiophenol and combinations thereof can be used. .

The polyaniline coating layer 20 described above and the thiol-based crosslinking agent 30 bonded thereto form a crosslink between the carbon nanotube fibers 10.

Specifically, the crosslink is formed by reaction of the thiol group in the thiol-based crosslinker molecular structure with respect to the quinoid moiety in the polyaniline molecular structure.

For the sake of understanding, as an example of the crosslinked structure of the carbon nanotube fiber 100 of the present invention, a polyaniline coating layer crosslinked with 1,3-propanedithiol is represented by the following Chemical Formula 2 (showing a crosslinking site) .

Figure 112015120106314-pat00002

The carbon nanotube fiber composite material 100 of the present invention, which forms a crosslink on the polyaniline coating layers of different carbon nanotube fibers as shown in Formula 2, has a structural feature that effectively reduces gaps between fiber strands in the fiber bundle. Enables high density. Accordingly, when the spacing between the individual fiber strands is narrowed, the mutual attraction, for example, the pie-pie bonding force present between the carbon nanotube fibers is increased, and the bonding strength provided by the crosslinking itself is added to improve the strength of the entire fiber bundle.

<Method for producing carbon nanotube fiber composite material>

Meanwhile, the carbon nanotube composite described above

(a) forming a polyaniline coating layer on the plurality of carbon nanotube fiber surfaces;

(b) coating a thiol-based crosslinker solution on the coating layer; And

(c) performing a crosslinking reaction;

It can be prepared through a method for producing a carbon nanotube fiber composite.

At this time, as the carbon nanotube fiber of the step (a) of the manufacturing method of the present invention, it is most preferable to use the one prepared by direct spinning (direct spinning, direct spinning method). Direct spinning is one of the dry methods for producing carbon nanotube fibers, in which carbon nanotubes are synthesized in a heating furnace by injecting a liquid carbon source and a catalyst together with a carrier gas into the upper inlet of a vertical heating furnace. And it refers to a method that can be obtained by winding the carbon nanotube aggregate that is lowered to the bottom of the furnace with a carrier gas (wind-up) inside or outside the furnace.

Hereinafter, the above production method will be described in more detail.

In the step (a), the polyaniline is evenly coated on the surfaces of the plurality of carbon nanotube fibers 10 to form the polyaniline coating layer 20. Specifically, the polyaniline coating layer 20 may be formed by providing a coating solution containing polyaniline on the surface of the carbon nanotube fibers 10 and then performing heat treatment.

The solvent for dissolving the polyaniline is preferably N-methyl-2-pyrrolidone (N-Methyl-2-pyrrolidone, NMP), dimethyl sulfoxide (DMSO), N, N- dimethylformamide ( N, N-dimethylformamide (DMF), N, N-dimethylacetamide (N, N-dimethylacetamide, DMAC) may be used one or more selected from the group consisting of.

The method of coating the polyaniline solution may be both spraying or dipping, but preferably by dipping. Since the impregnation time may vary depending on the specific process conditions when the immersion process is performed, the impregnation time is not necessarily limited to any specific range, but may be preferably 30 minutes to 12 hours. This is because a sufficient impregnation effect is less likely to be seen below the time range, and a difference in impregnation effects is not so large that it is uneconomical. Given both the efficiency of the process and the impregnation rate, the impregnation can usually be carried out most preferably within two hours.

After sufficiently impregnating the carbon nanotube fibers 10 with the polyaniline solution, it is taken out to remove excess solvent and heated so that the polyaniline penetrates evenly to the inside of the plurality of bundled carbon nanotube fibers. Make sure that it is firmly attached to its surface. Further excess solvent may be further removed during the heating process, and a vacuum oven may be used as necessary.

The heating temperature of the present step may be preferably 50 to 150 ° C. It is because even below the above-mentioned temperature range, the evenly impregnated effect of polyaniline on carbon nanotube fibers is not sufficiently exhibited, and if it is exceeded, problems such as thermal decomposition, vaporization or other side reactions of polyaniline may occur. Most preferably, heating temperature can be about 100 degreeC.

The heating time is not particularly limited since the heating time may be changed according to specific process conditions. However, when the heating time is too short, the polyaniline penetration into the carbon nanotube fiber bundle and the even adsorption effect on the surface may be reduced, and the length is too long. In some cases, meaningless processes can continue and be uneconomical. Therefore, in order to exhibit sufficient effects of the present invention and to carry out an efficient process, heating is preferably performed for 30 minutes to 12 hours, more preferably within 1 hour.

Next, the step (b) is to coat the thiol-based crosslinking agent 30 solution on the polyaniline coating layer 20 coated on the carbon nanotube fibers 10. However, the crosslinking agent coating in the step (b) is to be clearly distinguished from the polyaniline coating in the step (a) described above in a specific sense. That is, the coating of this step has a meaning as a material treatment for forming crosslinking between carbon nanotube fibers, not for forming an independent coating layer on each carbon nanotube fiber.

The method of providing the coating solution may be both spraying or dipping, but preferably by dipping.

In the immersion step, the impregnation time may vary depending on the specific process conditions, but is not necessarily limited to any specific range, but preferably 30 minutes to 12 hours. This is because a sufficient impregnation effect is less likely to be seen below the time range, and a difference in impregnation effects is not so large that it is uneconomical. Considering both the efficiency of the process and the impregnation rate, the impregnation can be performed preferably within 2 hours.

The total content of the thiol-based crosslinking agent includes carbon nanotube fibers in a weight ratio of 1: 0.1 to 1: 1.

This is because when the content of the crosslinking agent is less than the above range, the crosslinking effect is reduced, and when the content of the crosslinking agent is above the above range, side reactions may occur, thereby deteriorating the physical properties of the carbon nanotube fibers.

Next, step (c) is a step of forming crosslinking between the carbon nanotube fibers through the reaction of the polyaniline and the thiol crosslinking agent.

The crosslinking reaction may be performed by heat treatment at 150 to 250 ° C. or by irradiation with ultraviolet rays. The crosslinking mode may vary depending on the type of specific crosslinking material.

In the case of the heat treatment, if the coating was impregnated with the carbon nanotube fibers 10 in the crosslinking agent coating solution in step (b), the carbon nanotube fibers 10 were removed from the coating solution to remove excess solvent and then heated. It is preferred that the excess solvent may be further removed during the heating process. At this time, a vacuum oven or the like may be used as necessary.

The heating temperature for the heat treatment of this step is preferably set to 150 ~ 250 ℃. It is because the crosslinking reaction is less likely to appear sufficiently below the temperature range, and problems such as thermal decomposition, vaporization, and side reaction of the polyaniline and / or thiol crosslinking agent may occur above. Most preferably, this step can be carried out at a temperature of about 200 ℃.

The heating time may vary depending on the specific process conditions, but is not limited to any specific range. However, if the heating time is too short, the crosslinking reaction efficiency may be lowered. If the heating time is too long, the nonsense process may be continued and uneconomical. In order to exhibit sufficient effects of the invention and to carry out an efficient process, the heating may be preferably performed for 30 minutes to 12 hours, more preferably for about 2 hours.

The method for producing the carbon nanotube fiber composite 100 of the present invention described above is characterized by not using a strong acid and an oxidizing agent. Therefore, no defects are formed on the surface of the carbon nanotube fibers during the manufacturing process or other excellent physical properties of the carbon nanotube fibers are not deteriorated, and lower temperature conditions and shorter process times can be ensured compared to the prior art, thereby making the process convenient and efficient. This is improved.

The carbon nanotube fiber composite prepared as described above may have high density and high strength, and may be applied to various fields of clothing, semiconductors, displays, and sensors in the form of super strong fibers, high durability fibers, conductive fibers, and the like.

Hereinafter, the preparation examples, examples and experimental examples are presented to help the understanding of the present invention. However, the following contents are only examples of configurations and effects of the present invention, and the scope and effects of the present invention are not limited thereto.

< Production Example >- direct Spinning  Preparation of Carbon Nanotube Fibers Using

A spinning solution in which 4.0% by weight of thiophene was mixed with 96.0% by weight of acetone and hydrogen as a carrier gas were prepared. 10 ml / hr of the spinning solution, 2 L / min of carrier gas, and ferrocene, a catalyst precursor, were sublimed at 80 ° C. and heated together with a carrier gas to a temperature of 1,200 ° C. at a rate of 0.015 L / min. Flowed to the top. Thereafter, the carbon nanotube fibers discharged to the outlet of the reactor bottom were recovered by winding with a winding means composed of bobbins.

 < Example >-Coating layer introduction and crosslinking reaction

1.Polyaniline impregnation

0.50 g of polyaniline (emeraldine state, molecular weight> 15,000) was stirred at 20.0 g of N-methyl-2-pyrrolidone for 1 hour. The polyaniline solution dissolved in NMP became dark green, and the solution was impregnated with carbon nanotube fibers produced by the preparation process of the preparation for 2 hours. In this process, the polyaniline solution penetrated into the carbon nanotube fibers, and after sufficient impregnation, the carbon nanotube fibers were taken out of the solution to remove the excess polyaniline solution and heated at 100 ° C. for 1 hour.

2. Impregnation and crosslinking reaction of thiol crosslinking agent

Carbon nanotube fibers subjected to the polyaniline impregnation process were impregnated with 1,3-propanedithiol (1,3-propanedithiol) for 2 hours and then heated at 200 ° C. for 2 hours to carry out a crosslinking reaction.

< Experimental Example  1>-Surface Observation of Carbon Nanotube Fiber Bundles

The surface of the carbon nanotube fiber bundles prepared according to Preparation Example and Example 1 was compared by using a scanning electron microscope (20 μm).

The bundle surface observation results of the carbon nanotube fibers prepared according to the preparation example are shown in FIG. 2, and the bundle surface observation results of the carbon nanotube fiber composites prepared according to the example are shown in FIG. 3.

As a result of the observation, as shown in FIG. 2, the bundle of carbon nanotube fibers having no coating layer and no crosslinking has a large and distinct gap between fiber strands in the bundle, and as shown in FIG. 3, according to the present invention. The bundle consisting of carbon nanotube fiber composites having a crosslinking with the coating layer was confirmed that the gap between the fibers in the bundle is hardly observed and composed of high density.

< Experimental Example  2>-IR data analysis for carbon nanotube fiber composites

In Experimental Example 2, the final structure was confirmed by performing IR analysis on the carbon nanotube fiber composite according to the present invention. IR data is shown in FIG. 4.

Referring to the IR data of Figure 4, it can be seen that the polyaniline coating layer and the thiol-based crosslinking agent crosslinking on the carbon nanotube fiber composite of the present invention.

< Experimental Example 3>-carbon  Measurement of Breaking Strength of Nanotube Fiber Composites

In Experimental Example 3, the Favimat + Fiber Test device manufactured by Textechno was used to measure the breaking strength of the carbon nanotube fiber composite according to the present invention. The grip distance of the specimen was 20 mm and the grip was held at a speed of 2 mm / min in the tensile direction. The breaking strength was measured until the fracture occurred.

The measurement results of the breaking strength are shown in Table 1 below.

Sample Processing method Breaking strength ( cN ) Example Crosslink 3.15 Production Example Pristine 2.17

Referring to Table 1, the carbon nanotube fiber composite having a coating layer and crosslinking of the present invention prepared according to the embodiment can be confirmed that the break strength is improved by about 1.5 times compared to the case of the preparation example without a coating layer.

100: carbon nanotube fiber composite
10: carbon nanotube fiber
20: polyaniline coating layer
30: thiol crosslinking agent

Claims (11)

A plurality of carbon nanotube fibers; And
And a polyaniline coating layer formed on the fibers.
The plurality of carbon nanotube fibers to form cross-fiber crosslinking by a thiol-based crosslinking agent bound on the polyaniline coating layer,
The thiol-based crosslinking agent is a carbon nanotube fiber composite, characterized in that it comprises two to six thiol groups (SH-) in the molecular structure.
The method of claim 1,
The carbon nanotube fiber composite is characterized in that the diameter of 1 ~ 100um.
The method of claim 1,
The polyaniline coating layer is carbon nanotube fiber composite, characterized in that it comprises polyaniline in the emeraldine (emeraldine) or furnigranaline (pernigranaline) state.
The method of claim 1,
The polyaniline coating layer is carbon nanotube fiber composite, characterized in that the thickness is 0.1 to 0.2 times the diameter of the carbon nanotube fiber.
delete The method of claim 1,
The thiol crosslinking agent is 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 2,5-hexanedithiol, 1,6-hexanedithiol, 2,9-decanedithiol, 1,2,3-propanetrithiol, 1,8-octanedithiol, 1,4 Carbon nanotube fiber composite material, characterized in that it is one kind selected from the group consisting of dithiophenol and combinations thereof.
(a) forming a polyaniline coating layer on the plurality of carbon nanotube fiber surfaces;
(b) coating a thiol-based crosslinking agent solution containing 2 to 6 thiol groups (SH-) in a molecular structure on the coating layer; And
(c) performing a crosslinking reaction;
A method for producing the carbon nanotube fiber composite of claim 1.
The method of claim 7, wherein
The polyaniline coating layer forming step is a method for producing a carbon nanotube fiber composite, characterized in that the carbon nanotube fibers are coated with a polyaniline coating solution and then heat treated.
The method according to claim 7 or 8,
The coating is a method of producing a carbon nanotube fiber composite, characterized in that carried out by a spraying or dipping process.
The method of claim 8,
The heat treatment is a method for producing a carbon nanotube fiber composite, characterized in that carried out at 50 ~ 150 ℃.
The method of claim 7, wherein
The crosslinking reaction is a method of producing a carbon nanotube fiber composite, characterized in that carried out by heat treatment at 150 ~ 250 ℃ or irradiated with ultraviolet light.
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