KR102017278B1 - Method for coating carbon fiber with carbon nanotube-polymer composite - Google Patents

Method for coating carbon fiber with carbon nanotube-polymer composite Download PDF

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KR102017278B1
KR102017278B1 KR1020150138834A KR20150138834A KR102017278B1 KR 102017278 B1 KR102017278 B1 KR 102017278B1 KR 1020150138834 A KR1020150138834 A KR 1020150138834A KR 20150138834 A KR20150138834 A KR 20150138834A KR 102017278 B1 KR102017278 B1 KR 102017278B1
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carbon fiber
carbon
solution
interfacial polymerization
coated
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KR20170039828A (en
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장형식
박영빈
조범곤
황상하
조동현
강경연
이승용
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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • 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
    • 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
    • D06B3/00—Passing of textile materials through liquids, gases or vapours to effect treatment, e.g. washing, dyeing, bleaching, sizing, impregnating
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
    • D06C3/00—Stretching, tentering or spreading textile fabrics; Producing elasticity in textile fabrics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
    • D06C7/00—Heating or cooling textile fabrics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon

Abstract

The present invention relates to a surface coating method of carbon fiber for coating an interfacial polymerized carbon nanotube polymer composite on a carbon fiber, wherein the carbon nanotube polymer composite interfacially polymerized in the process of dipping and collecting the carbon fiber in an interfacial polymerization solution As a method of coating on the surface of the carbon fiber, not only the carbon nanotubes can be more uniformly distributed on the carbon fiber, but also the polymer composite is formed by interfacial polymerization and the coating can be carried out immediately, which is faster than the conventional coating method. It can be made, continuous process is possible.

Description

Carbon fiber coating method using carbon nanotube polymer composite {METHOD FOR COATING CARBON FIBER WITH CARBON NANOTUBE-POLYMER COMPOSITE}

The present invention relates to a surface coating method of carbon fiber, and more particularly, to a method of modifying the surface of the carbon fiber using interfacial polymerization.

In general, the interface between the fiber and the matrix in the fiber-reinforced composite material greatly affects the final physical properties of the composite material, it is very important to examine the interfacial properties between these materials when compounding. In fact, the interfacial properties extend to the mechanical properties of the composite material, so it is necessary to properly control it according to the performance of the material required for design. The interfacial strength between the fibers and the resin can be controlled mainly by the surface treatment of the fibers, the selection of the fibers or the matrix resin, and the like. Therefore, studies are being actively conducted to improve the physical and chemical properties of the composite by wet or dry the surface of the fiber or by adding organic / inorganic fillers.

In particular, many researches have been conducted to increase the surface area of fibers by growing carbon nanotubes having excellent physical properties on the surface of carbon fibers (WO87 / 07559). However, in order to grow carbon nanotubes are carried out at a high temperature of about 600 ~ 1100 ℃ This environment can damage the carbon fiber itself. In addition, Thostenson et al. Extracted the polymer in which the carbon nanotubes are dispersed by melt spinning (US Patent No. 7285591). However, this method has a disadvantage in that it is difficult to use commercially because the process cost is expensive and precise control of the process conditions is difficult.

The problem to be solved by the present invention is to provide a method for coating the carbon nanotubes on the surface of the carbon fiber in a simpler and continuous process.

Another object of the present invention is to provide a method for producing a surface-coated carbon fiber.

Another object of the present invention is to provide an apparatus for coating the surface of the carbon fiber.

The present invention to solve the above technical problem,

Preparing an interfacial polymerization solution in which carbon nanotubes are dispersed and capable of producing a polymer;

Preparing carbon fibers to be coated; And

It provides a carbon fiber surface coating method comprising the step of coating the carbon nanotube polymer composite on the surface of the carbon fiber by passing the carbon fiber while forming a carbon nanotube polymer composite layer on the interface of the interfacial polymerization solution.

In addition, the interfacial polymerization solution in which the carbon nanotubes are dispersed,

Preparing a first solution in which a first monomer and carbon nanotubes are dispersed in a first solvent;

Preparing a second solution by dispersing a second monomer in a second solvent which is not mixed with the first solution; And

Combining the second solution with the first solution to form an interfacial polymerization solution;

It may be prepared by.

In addition, the method of dispersing the carbon nanotubes in the first solution may be selected from a method of directly dispersing in the first solvent or a method of preparing and dispersing a dispersion solution in which the carbon nanotubes are dispersed.

In addition, the carbon nanotube polymer composite layer may be formed by the polymerization proceeds at the interface between the first solution and the second solution.

In addition, the method may further comprise the step of winding the coated carbon fiber to dry in the form of a roll to collect.

In addition, the steps may be to proceed in a continuous process.

In addition, the polymer produced by the interfacial polymerization may be a polycarbonate-based, polyamide-based, polyurea-based, or polyurethane-based resin.

In addition, the first solution mixed with the carbon nanotube dispersion solution may be an organic phase.

In addition, the method, the carbon fiber supplied to the interfacial polymerization solution may be to pass through the carbon nanotube polymer composite layer through a first solution in which carbon nanotubes are dispersed.

In addition, the concentration of carbon nanotubes included in the interfacial polymerization solution may be 0.1 to 1% by weight based on the total weight of the first solution.

In addition, the carbon nanotubes coated on the surface of the carbon fiber by the above method may not exhibit orientation.

The present invention also provides a carbon nanotube composite polymer coated carbon fiber prepared by the above method.

The maximum value (τ cnt / τ 0 ) of the interfacial shear strength of the carbon fiber may be 1.5 or more.

In addition, the interfacial shear strength of the carbon fiber may be improved by at least 50% compared to before coating.

The present invention also provides a carbon fiber supply means for unwinding and supplying a roll-shaped carbon fiber;

An interfacial polymerization reaction vessel for storing and interfacial polymerization the interfacial polymerization solution in which carbon nanotubes are dispersed;

A carbon fiber supply unit positioned under the interfacial polymerization reactor and introducing carbon fiber supplied from the carbon fiber supply unit into the interfacial polymerization reactor;

Carbon fiber moving means for moving the carbon fiber supplied from the carbon fiber supply part upward in the reaction vessel; And

It provides a surface coating apparatus of the carbon fiber having a collecting means for winding the coated carbon fiber in the form of a roll.

The moving means may be to allow the carbon fiber to move with a certain elasticity.

The apparatus may also be further provided with means for drying the coated carbon fibers.

The surface-modified carbon fiber of the present invention can be coated such that carbon nanotubes do not exhibit orientation by coating a polymer containing carbon nanotubes on the surface thereof, and interfacially polymerized in an interfacial polymerization solution in which carbon nanotubes are mixed. By coating the polymer composite on the surface of the carbon fiber, not only the coating can be more homogeneous, but also the polymerization of the polymer composite at the same time as the carbon fiber collection process due to the nature of the interfacial polymerization, a faster process than the conventional coating method, and continuous Provided is a method of coating carbon fibers that can be processed.

1 is a process diagram schematically showing the surface coating method of the present invention.
Figure 2a is a SEM image of the surface of the carbon fiber coated CNT / polymer composite containing 0.5wt% CNT.
Figure 2b is a SEM image of the surface of the carbon fiber coated with CNT / polymer composite containing CNT 1.0wt%.
3 is a graph showing a load-strain curve of carbon fibers according to Examples and Comparative Examples.
4 is a graph showing interfacial shear strength of carbon fibers according to Examples and Comparative Examples.

As the invention allows for various changes and numerous embodiments, particular embodiments will be illustrated in the drawings and described in detail in the written description. However, this is not intended to limit the present invention to specific embodiments, it should be understood to include all transformations, equivalents, and substitutes included in the spirit and scope of the present invention. In the following description of the present invention, if it is determined that the detailed description of the related known technology may obscure the gist of the present invention, the detailed description thereof will be omitted.

The present invention comprises the steps of preparing an interfacial polymerization solution in which carbon nanotubes are dispersed and capable of producing a polymer;

Preparing carbon fibers to be coated; And

It provides a carbon fiber surface coating method comprising the step of coating the carbon nanotube polymer composite on the surface of the carbon fiber by passing the carbon fiber while forming a carbon nanotube polymer composite layer on the interface of the interfacial polymerization solution.

In addition, the present invention provides a carbon fiber surface is modified by coating the surface with the coating method described above.

In addition, the present invention provides a coating apparatus used in the coating process.

The present invention is a method of coating or bonding growth of carbon nanotubes on the surface of carbon fibers by conventional CVD (chemical vapor deposition) and EPD (electrophoresis) in which carbon nanotubes are introduced into carbon fibers. Due to the orientation in the phase, there is a problem in that the reinforcing effect in the vertical direction of the fiber is lowered, from which mechanical properties such as tensile strength of the carbon fiber is lowered. Therefore, the present invention is to coat the carbon nanotube polymer composite polymerized by the interfacial polymerization method on the carbon fiber, to coat a larger amount of carbon fiber on the carbon fiber to improve the interfacial properties between the carbon fiber and the polymer, By reducing the orientation of the coated carbon nanotubes, it is possible to improve the mechanical property deterioration effect of the conventional direct growth method.

In addition, the interfacial polymerization solution in which the carbon nanotubes are dispersed,

Preparing a first solution in which a first monomer and carbon nanotubes are dispersed in a first solvent;

Preparing a second solution by dispersing a second monomer in a second solvent which is not mixed with the first solution; And

Combining the second solution with the first solution to form an interfacial polymerization solution;

It can be prepared by.

In addition, the carbon nanotube polymer composite layer may be formed by the polymerization proceeds at the interface between the first solution and the second solution.

The polymer may be applied to any kind of polymer synthesized by interfacial polymerization, for example, may be selected from polycarbonate-based, polyamide-based, polyurea-based, or polyurethane-based resins, and the monomer may be a kind of the polymer. It can be selected differently according to.

According to one embodiment, the polymer used in the carbon nanotube polymer composite of the present invention may be a polyamide resin, the polyamide resin may be formed by the interfacial reaction of the polyfunctional amine and acyl halide monomers, The carbon nanotubes may be polymerized by a method widely used in the art except that the carbon nanotubes are mixed in a solvent.

For example, the polyfunctional amine is 1,4-phenylenediamine, 1,3-phenylenediamine, 2,5-diaminotoluene, N, N'-diphenylethylene diamine, 4-methoxyphenylenediamine One kind selected from the group consisting of hexamethylene diamine, hexamethylene diamine, para-phenylene diamine, meta-phenylene diamine, and mixtures thereof may be used.

In addition, the amine-reactive compound may be acyl halide, polyfunctional sulfonyl halide or polyfunctional isocyanate, for example, trimezoyl chloride, terephthaloyl chloride, isophthaloyl chloride, sebacoyl chloride and mixtures thereof One polyfunctional acyl halide selected from the group consisting of can be used.

According to one embodiment, the polyfunctional amine in the monomer may be used in the polymerization reaction in an aqueous solution state using distilled water as a solvent, the amine reactive compound is insoluble in water and inert to the polymerization reaction, is produced by the polymerization reaction Organic compounds capable of dissolving the polymer can be used, for example, chlorinated aliphatic hydrocarbons such as methylene chloride, tetrachloroethane, chloroform, 1,2-dichloroethylene, carbon tetrachloride, trichloroethane, dichloroethane and the like; Chlorinated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, chlorotoluene and the like; Organic compounds selected from acetophenone, cyclohexane, anisole and mixtures thereof may be used, but are not limited thereto.

In addition, the aqueous solution may include one or more compounds selected from the group consisting of alkali metal or alkaline earth metal compounds, and the alkali metal compound may be sodium hydroxide (NaOH) or potassium hydroxide (KOH).

In addition, when the polycarbonate is applied as a polymer, it may be prepared by interfacial polymerization with a diphenol compound and a carbonate precursor as a monomer.

Diphenols that can be used for the polycarbonate interfacial polymerization are bisphenols, for example 1,1-bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 4,4- Bis (4-hydroxyphenyl) heptane and the like; Dihydric phenol ethers such as bis (4-hydroxyphenyl) ether, bis (3,5-dichloro-4-hydroxyphenyl) ether and the like; Dihydroxy diphenyls such as p, p'-dihydroxydiphenyl, 3,3'-dichloro-4,4'-dihydroxy-diphenyl and the like; Dihydroxyaryl sulfones such as bis (4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (3-methyl-5-ethyl-4-hydroxyphenyl ) Sulfone and the like; Dihydroxy benzene, resorcinol, hydroquinone; Halo- and alkyl-substituted dihydroxy benzenes such as 1,4-dihydroxy-2-chlorobenzene, 1,4-dihydroxy-2,3-dichlorobenzene, 1,4-dihydroxy 2-methylbenzene and the like; And dihydroxy diphenyl sulfoxides such as bis (4-hydroxyphenyl) sulfoxide, bis (3,5-dibromo-4-hydroxyphenyl) sulfoxide and the like can be used.

The carbonate precursor may be carbonyl halide or haloformate. For example, the carbonyl halide may be carbonyl bromide, carbonyl chloride, carbonyl fluoride, or the like; Or mixtures thereof, haloformates include bishaloformates of dihydric phenols (bischloroformates such as hydroquinone) or glycols bishaloformates (ethylene glycol, neopentyl glycol, polyethylene glycol, etc.). Formate), and carbonyl chloride also known as commonly used phosgene can be used.

The solution used for the polycarbonate interfacial polymerization may be the same as the solution used in the polyamide, the diphenol compound is mixed in an aqueous solution mixed with a basic compound, the carbonate precursor is dissolved in an organic solvent to interfacial polymerization It may be.

When polyurethane is used as the interfacial polymerization polymer, any monomer may be used as long as it is a conventionally used monomer, for example, polyisocyanate and polyol may be performed by reacting.

As said polyisocyanate, For example, polymeric methylene diphenyl diisocyanate, m-phenylene isocyanate, p-phenylene isocyanate, naphthalene-1, 4- diisocyanate, diphenyl methane-4,4'- diisocyanate, At least one selected from polyisocyanates such as 3,3 'dimethyl diphenyl methane-4,4'-diisocyanate, xylene-1,4-diisocyanate and the like.

The polyol may be, for example, one or more selected from ethylene glycol, glycerin, or a mixture thereof.

In addition, when polyurea is used as the polymer resin, as the monomer, polyisocyanate and polyamine may be one that is interfacially polymerized.

The polyisocyanate can be used without limitation as long as it is generally used, for example, polymeric methylene diphenyl diisocyanate, m-phenylene isocyanate, p-phenylene isocyanate, naphthalene-1,4-diisocyanate, diphenyl methane At least one selected from polyisocyanates such as -4,4'-diisocyanate, 3,3 'dimethyl diphenyl methane-4,4'-diisocyanate, xylene-1,4-diisocyanate and the like.

The polyamine may be selected from, for example, ethylenediamine, hexamethylenediamine, diethylene triamine, xylene diamine, triethylene tetramine, and phenylene diamine, but is not limited thereto.

The solution used for interfacial polymerization of the polyurethane and polyurea may be the same as the solution used for interfacial polymerization of the polyamide. According to a preferred embodiment, the polyisocyanate compound is dissolved in an organic solvent, and a polyol or The polyamine compound may be used for the interfacial polymerization in an aqueous solution.

According to one embodiment, the carbon nanotubes are used by directly dispersing in the first solution, or by dispersing the carbon nanotubes in any one of solvents used for distilled water or interfacial polymerization in advance to prepare a dispersion solution and the monomer containing It may be used mixed with one solution or a second solution.

According to one embodiment, the method may further include the step of ultrasonication to improve the dispersibility of the carbon nanotubes contained in the solvent. Preferably, it may be a solution in which the carbon nanotubes are dispersed in an organic solvent located at the lower portion of the interfacial reaction.

In addition, the dispersion solution may further include a surfactant for dispersing the carbon nanotubes, for example, may be used at least one selected from nonionic surfactants such as NP40, Triton X-100, Tween20. However, the present invention is not limited thereto, and the surfactant may be used when the carbon nanotubes are mixed and reacted with an aqueous solution.

According to one embodiment, the carbon nanotubes may be included in 0.1 to 1% by weight based on the total weight of the dispersion solution (first solution), the first monomer and the second monomer is adsorbed to the polymer structure during the interfacial polymerization surface It may be to be coated on.

In the present invention, the carbon fiber having a diameter of about micrometers can be used without limitation in raw materials and production methods, and the diameter is preferably 0.5 micrometer or more. If it is less than 0.5 micrometer, it is not preferable because there is no mass productivity.

In addition, the carbon fiber used in the present invention can be applied to products requiring high tensile strength, the shape may be composed of 3000 filaments per strand in the form of strands. The diameter of the filament is 7 micrometers, the surface of the carbon fiber may be epoxy sizing treatment, according to one embodiment of the present invention, the desizing treatment to improve the interfacial properties between the polymer and the fiber when coating the polymer Can be used.

1 is a process chart showing a carbon fiber coating process of a carbon nanotube polymer composite using interfacial polymerization according to an embodiment of the present invention.

Referring to Figure 1, the carbon fiber yarn is supplied to the reaction vessel in which the interfacial polymerization occurs from the roll-shaped carbon fiber supply means for supplying the carbon fiber, at the same time the first solution and the first carbon and carbon nanotubes and the first monomer At the interface of the second solution containing the second monomer and the second solvent, the first monomer and the second monomer react to form a polymer resin to form a carbon nanotube polymer composite layer, and as the carbon fibers are collected through the interface, the interface As the polymerization is continuously performed, the coating process may proceed as the carbon nanotube polymer composite is adsorbed onto the surface of the carbon fiber. If the polymer is continuously collected from the interface as in the case of general interfacial polymerization, the polymerization is continuously performed. Therefore, the composite is continuously polymerized at the interface in the process of collecting carbon fibers through the supply means and through the interface. Can be coated.

In addition, the coated carbon fiber may further comprise the step of drying the carbon fiber before or after being wound by the collecting means.

The carbon fiber coating device is basically

Carbon fiber supply means for unwinding and supplying carbon fiber in a roll form;

An interfacial polymerization reaction vessel for storing and interfacial polymerization the interfacial polymerization solution in which carbon nanotubes are dispersed;

A carbon fiber supply unit positioned under the interfacial polymerization reactor and introducing carbon fiber supplied from the carbon fiber supply unit into the interfacial polymerization reactor;

Carbon fiber moving means for moving the carbon fiber supplied from the carbon fiber supply part upward in the reaction vessel; And

It is provided with a collecting means for collecting the coated carbon fiber in the form of a roll.

The moving means may be installed in the reaction vessel and serve to maintain the surface of the carbon fiber evenly while the carbon fiber has a certain elasticity, thereby, the surface-polymerized carbon nanotube polymer composite to be evenly coated on the surface Can be. An example of the moving means may be illustrated as a rotary roll as shown in FIG. 1, but is not limited thereto.

The device may further comprise means for drying the coated carbon fibers.

In this case, the carbon nanotubes may be dispersed in either an organic solvent located in the lower layer of the interface or a water-soluble solvent located in the upper layer, but it is preferable to prevent the carbon nanotubes from being adsorbed further in the process of collecting the carbon fibers. It is preferable to be dispersed in an organic solvent located in the lower layer in terms of the uniformity and coating uniformity, and when dispersed in an aqueous solution may further include a surfactant for effective dispersibility.

The present invention provides a method for enabling the coating of carbon fibers at the same time as the synthesis of the composite by contacting the carbon fibers to the carbon nanotube / polymer composite formed using interfacial polymerization. Carbon nanotube polymer composite coating method on the carbon fiber using the interfacial polymerization has the advantages of the process that the polymer polymerization and the coating of the carbon fiber can be carried out continuously and carbon nanotubes in advance on the surface of the carbon fiber like the conventional CVD, EPD method More carbon nanotubes can be added to the carbon fiber surface coating than the method of joint growth of the tube.

Carbon nanotubes used in the present invention are single-wall carbon nanotubes (SWNT), double-wall carbon nanotubes (DWNT), multi-wall carbon nanotubes (Multi-Wall Carbon Nanotube, MWNT) can be used without limitation of any kind of carbon nanotubes selected, and may be subjected to the step of purifying the carbon nanotubes by removing impurities for more efficient manufacturing, for example, by treating with hydrochloric acid or nitric acid It can be used to purify the purity of the carbon nanotubes by more than 99%.

 In addition, the method of joint growth of carbon nanotubes by CVD and EPD method is a problem that the reinforcing effect of the carbon fiber in the vertical direction is lowered due to the orientation of the carbon nanotubes, and the separation and orientation of the carbon nanotubes are disturbed during processing. There is a problem, and the method of impregnating the carbon nanotubes by dispersing them in a polymer in advance or solution melts the carbon nanotubes are oriented in the processing direction during the processing process has a disadvantage of low physical properties compared to the amount used, the present invention composite The method of forming the carbon nanotubes exhibits intermediate characteristics of the two conventional methods, thereby reducing the effect of lowering the carbon fiber properties due to the orientation of the carbon nanotubes compared to the conventional methods. Can be. In particular, the introduction of carbon nanotubes improves the interfacial properties between the carbon fibers and the polymer, thereby effectively transferring loads, and thus, may significantly increase the interfacial shear strength and tensile strength.

Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, the scope of the present invention should not be construed as limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

< Example  1> 0.5wt% Carbon Nanotubes- PA610 ( Polyamid610 , Nylon610 A) composite coating

In a 500 mL beaker, 350 mL of dichloromethane, 1.5 g (0.5 wt%) of carbon nanotubes, and 7 ml of sebacoyl chloride were prepared. The first solution was an organic phase. A second solution, which is an aqueous solution in which 9.2 g of hexamethylene diamine (HMDA) and 1.6 g of sodium hydroxide (NaOH), was added to the prepared first solution. The dispersion solution of the organic phase and the multi-walled carbon nanotubes formed a separate phase as shown in FIG. 1. The first solution, which is an organic phase in which carbon nanotubes are dispersed, is located below, and the second solution, which is an aqueous solution, is present therein. Carbon fiber yarn is supplied to the lower part of the container in which the first solution is located and passes through the center of the interface between the first solution and the second solution, and the polymerization of the PA 610 and the carbon nanotube composite occurs continuously. Is coated on. The coated carbon fiber was wound up and collected, washed sufficiently with distilled water, and dried in a vacuum dryer at 80 to 100 ° C. to completely remove moisture after natural drying.

Surface SEM image of the prepared carbon fiber is shown in Figure 2a.

< Example  2> 1.0 wt% carbon nanotubes- PA610 ( Polyamid610 , Nylon610 A) composite coating

In a 500 mL beaker, 350 mL of dichloromethane (carbon tetrachloride), 3 g (1.0 wt%) of carbon nanotubes, and 7 ml of sebacoyl chloride were prepared. A second solution of 9.2 g of hexamethylene diamine (HMDA) and 1.6 g of sodium hydroxide (NaOH) in 200 mL of distilled water (DI water) was added to the prepared first solution. The dispersion solution of organic phase and multi-walled carbon nanotubes formed a separate phase as shown in FIG. 1. The first solution, which is an organic phase in which carbon nanotubes are dispersed, is located below, and the second solution, which is an aqueous solution, is present therein. Carbon fiber yarn is supplied to the lower part of the container in which the first solution is located and passes through the center of the interface between the first solution and the second solution, and the polymerization of the PA 610 and the carbon nanotube composite occurs continuously. Is coated on. The coated carbon fiber was wound up and collected, washed sufficiently with distilled water, and dried in a vacuum dryer at 80 to 100 ° C. to completely remove moisture after natural drying.

Surface SEM image of the prepared carbon fiber is shown in Figure 2b.

< Comparative example  1> Sizing  Processed Carbon fiber

120.0 g of an epoxy compound was added to a flask, and 30 g of polyethylene glycol (20%) was mixed with respect to the weight of the epoxy compound. The mixture was heated at 60 ° C. at a constant stirring rate for about 30 minutes, and after adding 2 g of a catalyst, the temperature was heated to 100 ° C. and maintained for about 6 hours. Heating is complete and the temperature is cooled to room temperature. Thus prepared carbon fiber sizing aqueous dispersion was diluted by stirring at distilled water at a concentration of 3 to 10% by weight at a speed of 14,000rpm / min, and the carbon fibers were sized after the surface treatment.

< Comparative example  2> PA610 ( Polyamid610 , Nylon610 A) coated Carbon fiber

An organic phase was prepared by mixing 350 mL of dichloromethane and 7 mL of sebacoyl chloride in a 500 mL beaker. An aqueous solution of 9.2 g of hexamethylene diamine (HMDA) and 1.6 g of sodium hydroxide (NaOH) was dissolved in 200 mL of distilled water (DI water). The organic phase and the aqueous solution formed separate phases as shown in FIG. 1. At the bottom is the organic phase and above it the aqueous solution. The yarn of carbon fiber is supplied to the lower part of the container in which the organic phase is located, and the nylon 610 polymerization is continuously coated while the yarn of carbon fiber passes through the center of the interface between the organic phase and the aqueous solution, and coated on the carbon fiber. The coated carbon fibers were wound up and collected, washed sufficiently with distilled water, dried in a vacuum dryer at 80 to 100 ° C. in order to completely remove moisture after natural drying.

Experimental Example

Tensile strain and Interfacial Shear Strength  Measure

In Example 2 and Comparative Examples 1 and 2, the tensile strain and the interfacial shear strength of the surface-modified carbon fibers were measured using a single fiber pullout test.

The PA6 (Polymide6, Nylon6) film, thermally fused to the fiber ends, was fixed to the support and loaded in the direction of the fiber axis to generate shear load at the fiber-matrix interface to measure the strength when the fiber pulled out. . Tensile velocity was performed at 10 mm / min.

The load-displacement curves for the results are shown in FIG. 3 and the interfacial shear strength is shown in FIG. 4.

It can be seen from the measurement results that the physical properties such as tensile strength and interfacial shear strength of the surface-modified carbon fiber by the coating method of the present invention are significantly increased.

The specific parts of the present invention have been described in detail above, and it is apparent to those skilled in the art that such specific descriptions are merely preferred embodiments, and thus the scope of the present invention is not limited thereto. something to do. Thus, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims (18)

Preparing an interfacial polymerization solution in which carbon nanotubes are dispersed and capable of producing a polymer;
Preparing carbon fibers to be coated; And
Coating the carbon nanotube polymer composite on the surface of the carbon fiber by passing the carbon fiber while forming a carbon nanotube polymer composite layer at an interface of the interfacial polymerization solution,
The interfacial shear strength of the carbon fiber after coating is improved by at least 50% compared to before coating the carbon fiber surface coating method. The method of claim 1,
The interfacial polymerization solution in which the carbon nanotubes are dispersed,
Preparing a first solution in which a first monomer and carbon nanotubes are dispersed in a first solvent;
Preparing a second solution by dispersing a second monomer in a second solvent which is not mixed with the first solution; And
Combining the second solution with the first solution to form an interfacial polymerization solution;
Carbon fiber surface coating method that is prepared by. The method of claim 2,
The method of dispersing the carbon nanotubes in the first solution is selected from the method of directly dispersing in the first solvent or a method of preparing and dispersing a dispersion solution in which the carbon nanotubes are dispersed. The method of claim 2,
The carbon nanotube polymer composite layer is a carbon fiber surface coating method is formed by the polymerization proceeds at the interface of the first solution and the second solution. The method of claim 1,
Carbon fiber surface coating method further comprising the step of winding the coated carbon fiber in the form of a roll after drying. The method of claim 1,
Wherein the steps are carried out in a continuous process carbon fiber surface coating method. The method of claim 1,
Carbon fiber surface coating method wherein the polymer produced by the interfacial polymerization is a polycarbonate-based, polyamide-based, polyurea-based or polyurethane-based resin. The method of claim 2,
A carbon fiber surface coating method in which a first solution mixed with a carbon nanotube dispersion solution is an organic phase. The method of claim 2,
The carbon fiber supplied to the interfacial polymerization solution is a carbon fiber surface coating method that passes through the carbon nanotube polymer composite layer through a first solution in which carbon nanotubes are dispersed. The method of claim 2,
The concentration of carbon nanotubes contained in the interfacial polymerization solution is 0.1 to 1% by weight based on the total weight of the first solution of the surface coating method of the carbon fiber. The method of claim 1,
Carbon fiber surface coating method characterized in that the carbon nanotubes coated on the surface of the carbon fiber does not exhibit orientation. Carbon nanotube composite polymer coated carbon fiber prepared by the method of any one of claims 1 to 11. The method of claim 12,
Carbon nanotube composite polymer coated carbon fiber, characterized in that the maximum value (τ cnt / τ 0 ) of the interfacial shear strength of the carbon fiber is 1.5 or more. delete The method of claim 12,
Carbon nanotube composite polymer coated carbon fiber, characterized in that the coated carbon nanotubes do not exhibit orientation. Carbon fiber supply means for unwinding and supplying carbon fiber in a roll form;
An interfacial polymerization reaction vessel for storing and interfacial polymerization the interfacial polymerization solution in which carbon nanotubes are dispersed;
A carbon fiber supply unit positioned under the interfacial polymerization reactor and introducing carbon fiber supplied from the carbon fiber supply unit into the interfacial polymerization reactor;
Carbon fiber moving means for moving the carbon fiber supplied from the carbon fiber supply part upward in the reaction vessel; And
Collecting means for winding the coated carbon fiber in the form of a roll,
The interfacial shear strength of the carbon fiber after coating is improved by more than 50% compared to before coating the surface of the carbon fiber. The method of claim 16,
The moving means is a surface coating apparatus of the carbon fiber to allow the carbon fiber to move with a certain elasticity. The method of claim 16,
Surface coating apparatus of the carbon fiber which further comprises a means for drying the coated carbon fiber.
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