KR100689866B1 - Process for synthesizing polymer-grafted carbon nanotubes and its precursor - Google Patents

Abstract

A method for producing carbon nanotubes grafted with a vinyl polymer is provided to minimize degradation of physical properties of carbon nanotubes, including a drop in aspect ratio, to allow uniform dispersion of carbon nanotubes in a polymer matrix without aggregation of carbon nanotubes, and to improve the interfacial adhesion between carbon nanotubes and a polymer. The method for producing carbon nanotubes grafted with a vinyl polymer comprises the steps of: (a) oxidizing carbon nanotubes in the presence of a strong acid to obtain carboxyl- or hydroxyl-functionalized carbon nanotubes; (b) performing an urethane reaction between the carboxyl- or hydroxyl-functionalized carbon nanotubes and a diisocyanate compound to introduce isocyanate groups into both terminals of the carbon nanotubes; (c) reacting the carbon nanotubes having isocyanate groups with an acryl amide or hydroxyacrylate monomer having a vinyl group to obtain vinyl-functionalized carbon nanotubes represented by a formula 1; and (d) polymerizing the vinyl-functionalized carbon nanotubes represented by the formula 1 with vinyl monomers to form vinyl polymers grown on the surfaces of the carbon nanotubes. In formula 1, each of M and M' is a monomer containing a vinyl group double bond, with the proviso that M and M' are the same or different.

Description

Process for producing carbon nanotubes grafted with vinyl polymer and its precursor {Process for Synthesizing Polymer-Grafted Carbon Nanotubes and its Precursor}

1 is a result of nuclear magnetic resonance analysis of the carbon nanotubes in which the vinyl group obtained in the embodiment of the present invention is introduced.

2 is a result of observing a phenomenon in which the carbon nanotubes (b) functionalized with the carboxyl group obtained in the embodiment of the present invention and carbon nanotubes (a), which are raw materials, are dispersed in water with ultrasonic waves and then settled.

Figure 3 is a result of measuring the carbon nanotubes obtained in the embodiment of the present invention by x-ray photoelectron spectroscopy (x-ray photoelectron spectroscopy).

Figure 4 is a result of measuring the carbon nanotubes (CNT) as a raw material and the polystyrene polymer (CNT-PS) grown on the surface of the carbon nanotubes obtained in the embodiment of the present invention by infrared spectroscopy.

5A and 5B are electron scanning microscope (SEM) photographs of carbon nanotubes as raw materials and polystyrene polymers grown on the surface of carbon nanotubes obtained in an embodiment of the present invention, respectively.

6A and 6B are transmission electron microscope images of carbon nanotubes, which are raw materials, and polystyrene polymers grown on the surface of carbon nanotubes obtained in an embodiment of the present invention, respectively.

7 is carbon nanotubes (a, CNT) as raw materials, and carbon nanotubes (b, CNT-COOH) functionalized with carboxyl groups obtained in each step of the embodiment of the present invention, and carbon nanotubes (c, CNT) into which vinyl groups are introduced. -COOH-MAAM) and polystyrene-bonded carbon nanotubes (d, CNT-COOH-MAAM-PS), respectively.

The present invention relates to a method for producing a carbon nanotube grafted with a vinyl polymer and a precursor thereof, in particular, by introducing a vinyl group on the surface of the carbon nanotube and polymerizing it with a vinyl monomer, the vinyl polymer on the surface of the carbon nanotube easily A method of growing and a precursor thereof.

Carbon nanotubes were first invented by Dr. Ijima of the Japan Electric Company (NEC) in 1991, and have attracted considerable attention from the scientific and industrial world as one of the most interesting new materials. In particular, polymer / carbon nanotube nanocomposites have superior mechanical, chemical, thermal, electrical, and optical properties compared to conventional materials, attracting worldwide attention in the development of such ideal materials. Polymer / carbon nanotube nanocomposites are much stronger composites than conventional ones, and have many potential engineering applications, including applications in a variety of advanced IT industries.

Polymer nanocomposites are materials consisting of fillers of 100 nm or less in the polymer matrix. As the first-generation filler used for this purpose, a fibrous form having a high aspect ratio such as carbon fiber and a nanoparticle having a close aspect ratio such as carbon black and silica have been used. In the late 1990s, a plate-like material such as clay was used in the polymer nanocomposite as a second-generation filler. Such polymer nanocomposites have been used in applications for manufacturing polymer products for about 100 years, and their application range is also very wide. In addition, the emergence of polymer / carbon nanotube nanocomposites has attracted worldwide attention as it has the advantage of obtaining various mechanical, thermal, electrical and optical properties that were not possible with conventional materials. Are being announced.

The most important key technologies for producing polymer / carbon nanotube nanocomposites are firstly, uniformly dispersing carbon nanotubes without polymer aggregation in the polymer without impairing the aspect ratio of carbon nanotubes, and secondly, carbon nanotube matrix. Increasing the mutual attraction of the interface between the phosphorus polymer is to always wettability and adhesion. In general, carbon nanotubes have a high van der Waals attractive force, and due to their large surface area and aspect ratio, their own agglomeration occurs, and thus the excellent properties of carbon nanotubes are not uniformly transmitted to the matrix.

The existing domestic and foreign studies to solve these problems are largely divided into first, pretreatment of carbon nanotubes, second, melt mixing, third, in-situ polymerization, fourth, solution treatment method.

The first method, pretreatment of carbon nanotubes, is a method of releasing or surface-treating self-aggregated parts of carbon nanotubes by ultrasonic waves, plasma, or ball-mill. However, this method has a problem that the carbon nanotubes are destroyed during the pretreatment. In addition, as part of the pretreatment method, a method of preparing polymer / carbon nanotube nanocomposites by substituting chemical groups such as -OH, -COCl, and -COOH in order to impart polarity to the inactive carbon nanotube surface has been developed. Angew Chem. Int. Ed., 41, 1853 (2002).

Second, melt mixing method is easy to apply to general processing technology of polymer such as extrusion, injection molding and INTERNAL MIXING, so it is simple in process and does not use environmentally harmful organic solvents. There is an advantage that the rubber material can be used as a matrix. However, in this case, the aggregated form of carbon nanotubes remains as it is, so it is difficult to obtain an ideally dispersed structure. In addition, the cohesion problem of carbon nanotubes can be solved by applying a strong shearing force during the mixing process. However, it is reported that polymers can be decomposed or carbon nanotubes can be destroyed by shearing force before application (Powder Materials: Current Research and Industrial Practices (conference) (2001).

In the third in-situ polymerization method, carbon nanotubes are mixed with a polymer polymer in a liquid state to be used as a matrix and subjected to ultrasonic polymerization, followed by a polymerization process. There is a problem that it is not easy to adjust the viscosity (Materials Science & Engineering, C23,87 (2003)).

The fourth solution is a method developed by Winnie and his team at the University of Pennsylvania (Journal of Polymer Science Part B, Polymer Physics, 41,3333 (2003)). After dissolving the polymer in an organic solvent, carbon nanotubes are dispersed therein. This is a method of uniformly dispersing carbon nanotubes in a polymer by precipitating by mixing the dispersion in a liquid insoluble in a polymer such as water and water. However, this method is far from producing polymer brushes through polymerization on carbon nanotube surfaces.

Recently, more various methods have been tried to manufacture polymer / carbon nanotube nanocomposites. Among them, Professor Isayev of Akron University has applied ultrasonics to extrusion process, which is a polymer processing method. It is known to plan a method for dispersing in a polymer. However, as shown in the previous research of the Isayev group, which used ultrasonic waves for a long time during the extrusion process, this method also pyrolyzes a large amount of polymer exposed to ultrasonic waves due to the high temperature and high pressure caused by the cavitation of ultrasonic waves. The problem is that the physical properties of the polymer itself is lowered.

Chao Gao; Harold W. Kroto; Simon.J.Phys.Chem.B, a cross-linked multi-walled carbon nanotube, jointly studied by a team of researchers from Florida State University, Sussex University, UK and Shanghai Geotong University, China. 2005) was recently introduced. In this case, carbon nanotubes are functionalized by using covalent bonds. This experiment shows that when thionyl chloride (SOCl2) used in the experiment is exposed to moisture, it generates toxic gases to the human body. It can cause laryngitis, swelling, severe lung damage, and even serious skin injuries even when in contact with the skin.

US Patent Publication No. 20040223900A1 and International Patent Publication No. 2005028174A2 also use carbon nanotubes by using covalent bonds. In this case, too, since thionyl chloride (SOCl 2) is used in the course of the experiment, there are such difficulties.

Korean Patent Laid-Open No. 2001-0102598 uses thiourea (CS (NH 2) 2) containing sulfur, but not thionyl chloride, which also has environmental problems.

European Patent 03252762.4 uses non-covalent modifications, such as using van der Waals attraction or enclosing nanotubes in advance with polymers. Such non-covalent modification has the advantage of not deteriorating the inherent physical properties by not damaging the carbon nanotubes, but there is a problem that sufficient stress may not be transmitted due to insufficient adhesion of the interface.

The present invention is to minimize the degradation of physical properties such as reduction of aspect ratio due to damage of carbon nanotubes in the production of polymer / carbon nanotube composite material using a polymer matrix, and effectively in the polymer matrix without agglomeration of carbon nanotubes themselves. The purpose of this invention is to develop a method for uniformly dispersing carbon nanotubes and at the same time improving the adhesion between the carbon nanotubes and the polymer. In particular, in the present invention, in the method for functionalizing carbon nanotubes through direct chemical bonding such as polymers and covalent bonds, an object of the present invention is to provide a new method that is easier and more reproducible, eliminating the use of toxic or environmentally hazardous materials. It is done. To this end, the present inventors attempted a new method, and made a macromonomer that introduced a vinyl group on the surface of the carbon nanotube, and mixed it with a vinyl monomer component to polymerize the polymer, thereby growing a polymer brush from the vinyl group on the surface of the carbon nanotube. It was found that the material can be prepared to complete the present invention.

In the present invention,

(a) oxidizing carbon nanotubes in the presence of a strong acid to obtain carbon nanotubes functionalized with a carboxyl group or a hydroxyl group;

(b) urethane-reacting a carbon nanotube functionalized with a carboxyl group or a hydroxyl group with a diisocyanate compound to introduce isocyanate groups at both ends;

(c) reacting carbon nanotubes having an isocyanate group introduced at both ends thereof with an acrylamide-based or hydroxyacrylate-based monomer having a vinyl group to obtain a carbon nanotube functionalized with a vinyl group represented by Formula 1 below; And

(d) preparing a carbon nanotube grafted with a vinyl polymer comprising the step of polymerizing a carbon nanotube functionalized with a vinyl group of Formula 1 and a vinyl monomer to form a vinyl polymer grown on the surface of the carbon nanotube; A method is provided.

In the present invention,

A carbon nanotube functionalized with a vinyl group represented by the following formula (1) is provided. The carbon nanotubes functionalized with the vinyl group of the formula (1) are macromonomers incorporating vinyl groups on the surface of the carbon nanotubes, and are precursors for preparing carbon nanotubes grafted with polymers.

는 탄소나노튜브이며, M과 M'은 비닐기 이중결합을 포함하는 단량체이며, M=M' 또는 M≠M'이다.)(In the above formula

Is a carbon nanotube, M and M 'is a monomer containing a vinyl group double bond, M = M' or M ≠ M '.)

Other objects and advantages of the present invention will be described below and will be better understood by practice of the present invention.

The manufacturing method of the carbon nanotubes grafted with the vinyl polymer of the present invention comprises the steps of: obtaining a carbon nanotube functionalized with a carboxyl group or a hydroxyl group; Introducing an isocyanate end group; Obtaining carbon nanotubes functionalized with vinyl groups; And polymerizing the vinyl nanofunctionalized carbon nanotube and the vinyl monomer to form a vinyl polymer grown on the carbon nanotube surface. Hereinafter, each step will be described in detail.

Carboxyl groups or With hydroxyl  Obtaining functionalized carbon nanotubes

First, the carbon nanotube surface is oxidized in the presence of a strong acid to obtain a carbon nanotube functionalized with a carboxyl group or a hydroxyl group. As the strong acid, any strong acid capable of oxidizing the carbon nanotube surface to introduce a carboxyl group and a hydroxyl group may be used. As the strong acid, for example, sulfuric acid, nitric acid and the like can be used.

Isocyanate Terminal group  Introduction stage

The carbon nanotubes functionalized by the carboxyl group or hydroxyl group obtained in the above step are urethane reacted with a diisocyanate compound to obtain a precursor having an isocyanate group introduced at both terminals.

As said diisocyanate compound, For example, isophorone diisocyanate; Hexamethylene diisocyanate; Methylenebiscyclohexyl isocyanate; Toluene diisocyanate; Methylene bisphenyl isocyanate etc. can be used individually or in combination of 2 or more types.

The precursor formed by the urethane polymerization has an isocyanate group at both ends, and is combined with an acrylamide-based or hydroxy acrylate-based monomer in the next step to introduce a vinyl group at both ends.

With vinyl  Obtaining functionalized carbon nanotubes

The precursor having isocyanate groups at both ends, obtained in the step, is reacted with an acrylamide or hydroxyacrylate monomer having a vinyl group to obtain a carbon nanotube functionalized with a vinyl group of Formula 1, that is, a precursor having a vinyl group introduced at both ends. .

As said acrylamide- or hydroxy acrylate-type monomer, For example, acrylamide; Methacrylamide; Hydroxymethylacrylamide; Hydroxymethyl acrylate; Hydroxyethyl acrylate; Hydroxyethyl methacrylate; Hydroxymethyl methacrylamide; Hydroxyphenoxypropyl acrylate; Hydroxypropyl acrylate; Hydroxypropyl methacrylate etc. can be used individually or in combination of 2 or more types.

The acrylamide or hydroxy acrylate monomer is preferably used in a 1 to 2 molar ratio with respect to the precursor having an isocyanate group. If the molar ratio is less than 1, unreacted prepolymer may be present, and if the molar ratio is greater than 2, there may be a problem that acrylamide-based or hydroxy acrylate-based monomers may self-polymerize to generate their polymers.

Polymerized to grow on the surface of carbon nanotubes Vinyl  Forming a polymer

The carbon nanotubes functionalized with the vinyl group obtained in the above step are polymerized with a vinyl monomer to form a vinyl polymer grown on the surface of the carbon nanotubes.

There is no particular limitation on the polymerization method, and all of the conventional polymerization methods such as bulk polymerization, solution polymerization, suspension polymerization, dispersion polymerization, emulsion polymerization, precipitation polymerization and the like can be used.

In a preferred embodiment of the present invention, the polymer was grown using solution polymerization. In the case of solution polymerization, the vinyl monomer is preferably used in an amount of 5 to 50 parts by weight, more preferably 10 to 40 parts by weight, based on 100 parts by weight of the dispersion medium. If the amount of the vinyl monomer is less than 5 parts by weight, the economical efficiency is lowered, and if the amount of the vinyl monomer exceeds 50 parts by weight, the stability may decrease and may cause problems in the carbon nanotubes. Carbon nanotubes having a vinyl group according to the present invention (Formula 1) is preferably used in 1 to 50 parts by weight, more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the vinyl monomer. If the amount of the carbon nanotubes having a vinyl group (formula 1) is less than 1 part by weight, a problem may occur that the stability is insufficient during polymerization, and when the amount exceeds 50 parts by weight, a problem may occur that the agglomeration of carbon nanotubes occurs. .

As the vinyl monomer, monomers such as styrene-based, cyan-based vinyl compounds, acrylate-based, and methacrylate-based vinyl compounds, which are conventionally used, may be used. Namely, styrene-based vinyl monomers such as styrene, divinylbenzene, ethylene vinylbenzene, alphamethylstyrene, fluorostyrene, and vinylpyridine; Cyan vinyl compounds such as acrylonitrile and methacrylonitrile; Acrylate compounds such as butyl acrylate, 2-ethylhexylethyl acrylate, glycidyl acrylate, and N, N'-dimethylaminoethyl acrylate; Methacrylate-based compounds such as butyl methacrylate, 2-ethylhexylethyl methacrylate, methyl methacrylate, 2-hydroxyethyl methacrylate and glycidyl methacrylate; Diacrylate-based compounds such as polyethylene glycol diacrylate, 1,3-butylene glycol diacrylate, and 1,6-hexanediacrylate; Dimethacrylate type compounds, such as ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, polyethyleneglycol dimethacrylate, and 1, 3- butylene glycol dimethacrylate Etc. may be used alone or in combination of two or more.

Hereinafter, the present invention will be described in more detail with reference to specific examples and test examples. However, the scope of the present invention is not limited by the following examples, and those skilled in the art to which the present invention pertains should be within the equivalent scope of the technical concept of the present invention and the claims to be described below. Of course, various modifications and variations are possible.

Example

(1) Preparation of Carbon Nanotubes

In this embodiment, MWNTs (multiwalled carbon nanotubes) synthesized by thermal chemical vapor deposition (CVD) were used. First, carbon nanotubes were treated with 3M nitric acid at 60 ° C. for 12 hours and refluxed with 5M hydrochloric acid at 120 ° C. for 6 hours to remove residual metal catalyst before use.

(2) Introduction of carboxyl group

2 g of carbon nanotubes prepared above were added to a 500 ml reactor, and 8 ml of sulfuric acid (68%) and 22 ml of nitric acid (98%) were added and dispersed together in an ultrasonic cleaner for 30 minutes. The carbon nanotubes dispersed in the ultrasonic wave were reacted with stirring at 110 ° C. for 24 hours.

After 24 hours, the temperature of the carbon nanotubes was lowered to room temperature, and the carbon nanotubes were washed with a paper filter and distilled water in a vacuum filter until the pH reached 7 Thereafter, water was completely removed using acetone and dried to obtain a carbon nanotube functionalized with a carboxyl group.

(3) Isocyanate group  Introduction

0.5197 g of carbon nanotubes functionalized with the carboxyl group obtained in the above step and 0.1208 g of hexamethylene diisocyanate were dispersed in a vial for about 1 minute and then reacted while stirring at 75 ° C. for about 6 hours. The combination of hexamethylene diisocyanate (HDI) and a carboxyl group yielded a precursor in which isocyanate groups were introduced at both terminals.

(4) Vinyl  Introduction

0.24 g of methacrylamide was added to the carbon nanotube into which the isocyanate group obtained in the above step was introduced, followed by reacting at room temperature for 24 hours. Grown from carbon nanotubes, vinyl groups were introduced at both ends to obtain functionalized carbon nanotubes capable of polymerizing with vinyl polymers.

(5) Vinyl  Using introduced carbon nanotubes Vinyl  Polymer polymerization

Into a 500 ml reactor, 20 ml of commercially available toluene, 0.1 g of carbon nanotubes and 5 styrene of the vinyl group introduced in (4) were added thereto, dispersed in an ultrasonic cleaner for 5 minutes, and kept at a nitrogen atmosphere at 80 ° C. Solution polymerization was carried out for 24 hours while adding 0.05 g of initiator 2,2-azodiisobutylonitrile (AIBN). The styrene was used after washing the commercial styrene monomer with a caustic soda solution to remove the polymerization inhibitor. As a result of the polymerization, polystyrene grown on carbon nanotubes and polystyrene in which styrene self-polymerized was obtained. After washing several times with tetrahydrofuran (THF), styrene self-reacted to remove the polymerized polystyrene and to obtain polystyrene grown in carbon nanotubes.

Test Example  One

The carbon nanotubes (b) functionalized with the carboxyl group obtained in Example (2) and the carbon nanotubes (a) as raw materials were dispersed in excess water by ultrasonic wave for 5 minutes, and then settled after 48 hours. The results are shown in Figure 2, the carbon nanotubes functionalized with a carboxyl group has a significant increase in dispersion in the liquid, it can be expected that a series of synthetic processes for connecting the double bonds occur uniformly on the surface of all carbon nanotubes as a whole Could.

Test Example  2

Nuclear magnetic resonance ( ¹ H-NMR) analysis of the carbon nanotubes into which the vinyl group obtained in Example (4) was introduced is shown in FIG. 1. It can be seen that the peak showing two vinyl groups between 5 and 6 ppm, as seen in methacrylamide, also appears in the carbon nanotube into which the vinyl group obtained in Example (4) is introduced. Thus, the synthesized material can participate in the polymerization reaction with the polymer due to the presence of a reactive double bond.

Test Example  3

The carbon nanotubes into which the vinyl group obtained in Example (4) was introduced were measured by X-ray photoelectron spectroscopy (XPS). Unlike carbon nanotubes (a) as raw materials, in the carbon nanotubes (b) introduced with vinyl groups through the steps (2), (3) and (4) of the above embodiment, the nitrogen peak generated by the urethane-based and isocyanate bonds 399.7 ( ev) was observed. In the carbon nanotubes (b) introduced with vinyl groups, it was confirmed that the surface of the nanotubes was functionalized.

Test Example  4

The result of measuring the polystyrene polymer (CNT-PS) grown on the surface of the carbon nanotube polymerized in Example (5) by infrared spectroscopy (FR-IR) and the result of measuring carbon nanotube (CNT) as a raw material Shown in The CNT-PS is one of the unique peak of 698cm ^-1 (aromatic ring) and 756cm ^-1 (aromatic ring in combination with carbon-hydrogen) shown polystyrene can be seen it can be seen a noticeable difference.

Test Example  5

Electron scanning micrographs (SEM) of the carbon nanotubes as the raw material and the carbon nanotubes in which the polystyrene obtained in Example (5) is bonded are shown in FIGS. 5A and 5B, respectively. In addition, electron scanning micrographs (SEM) of carbon nanotubes in which carbon nanotubes as raw materials and polystyrene obtained in Example (5) are bonded are shown in FIGS. 6A and 6B, respectively. From these pictures, it can be seen that the polystyrene bonded to the surface of the carbon nanotubes.

Test Example  6

Carbon nanotubes (a, CNT) as raw materials and carbon nanotubes functionalized with carboxyl groups (b, CNT-COOH) obtained in each step of the above embodiment, carbon nanotubes (c, CNT-COOH-MAAM) having vinyl groups introduced therein, In addition, thermogravimetric analysis (TGA) of polystyrene-bonded carbon nanotubes (d, CNT-COOH-MAAM-PS) is shown in FIG. 7. Each sample has a different ratio of weight reduced with increasing temperature, indicating that each step of the embodiment was completely performed.

As described above, in the present invention, the vinyl polymer may be easily grown on the surface of the carbon nanotube by preparing a carbon nanotube having a vinyl group introduced thereon and polymerizing the same with a vinyl monomer. The present invention is superior to the conventional method of grafting polymers to carbon nanotubes, while having excellent stability and economy, and reducing the strong van der Waals attraction of carbon nanotubes without compromising the inherent properties of carbon nanotubes. Since the carbon nanotubes can be uniformly dispersed, it can be widely used as a method for preparing polymer / carbon nanotube nanocomposites having excellent physical properties, and carbon nanotubes grafted with vinyl polymers according to the present invention can be used for electric and electronic It is expected to be used for various purposes in a wide range of applications such as chemicals and chemicals.

Claims (7)

(a) oxidizing carbon nanotubes in the presence of a strong acid to obtain carbon nanotubes functionalized with a carboxyl group or a hydroxyl group; (b) urethane-reacting a carbon nanotube functionalized with a carboxyl group or a hydroxyl group with a diisocyanate compound to introduce isocyanate groups at both ends; (c) reacting carbon nanotubes having an isocyanate group introduced at both ends thereof with an acrylamide-based or hydroxyacrylate-based monomer having a vinyl group to obtain a carbon nanotube functionalized with a vinyl group represented by Formula 1 below; And (d) preparing a carbon nanotube grafted with a vinyl polymer comprising the step of polymerizing a carbon nanotube functionalized with a vinyl group of Formula 1 and a vinyl monomer to form a vinyl polymer grown on the surface of the carbon nanotube; Way. [Formula 1]

(In the above formula

Is a carbon nanotube, M and M 'is a monomer containing a vinyl group double bond, M = M' or M ≠ M '.) The method of claim 1, wherein the diisocyanate compound is isophorone diisocyanate; Hexamethylene diisocyanate; Methylenebiscyclohexyl isocyanate; A method for producing carbon nanotubes grafted with a vinyl polymer, characterized in that one or two or more selected from the group consisting of toluene diisocyanate and methylene bisphenyl isocyanate. The method of claim 1, wherein the acrylamide-based or hydroxy acrylate-based monomer is used in a 1 to 2 molar ratio with respect to the precursor having an isocyanate group. According to claim 3, wherein the acrylamide or hydroxy acrylate monomers, acrylamide; Methacrylamide; Hydroxymethylacrylamide; Hydroxymethyl acrylate; Hydroxyethyl acrylate; Hydroxyethyl methacrylate; Hydroxymethyl methacrylamide; Hydroxyphenoxypropyl acrylate; A method for producing a carbon nanotube grafted vinyl polymer, characterized in that one or two or more selected from the group consisting of hydroxypropyl acrylate and hydroxypropyl methacrylate. The method of claim 1, wherein the vinyl monomer is styrene; Divinylbenzene; Ethylene vinylbenzene; Alphamethylstyrene; Fluorostyrenes; Vinylpyridine; Acrylonitrile; Methacrylonitrile; Butyl acrylate; 2-ethylhexylethyl acrylate; Glycidyl acrylate; N, N'-dimethylaminoethyl acrylate; Butyl methacrylate; 2-ethylhexylethyl methacrylate; Methyl methacrylate; 2-hydroxyethyl methacrylate; Glycidyl methacrylate; Polyethylene glycol diacrylate; 1,3-butylene glycol diacrylate; 1,6-hexanediacrylate; Ethylene glycol dimethacrylate; Diethylene glycol dimethacrylate; Triethylene glycol dimethacrylate; A method for producing a carbon nanotube grafted vinyl polymer, characterized in that one or two or more selected from the group consisting of polyethylene glycol dimethacrylate and 1,3-butylene glycol dimethacrylate. According to claim 5, 100 parts by weight of the dispersion medium in the step (d); 5 to 50 parts by weight of a vinyl monomer; Method for producing a carbon nanotube grafted with a vinyl-based polymer, characterized in that the solution polymerized in the proportion of 1 to 50 parts by weight of carbon nanotubes having a vinyl group of the formula (1). Carbon nanotubes functionalized with a vinyl group represented by the formula (1). [Formula 1]

(In the above formula

Is a carbon nanotube, M and M 'is a monomer containing a vinyl group double bond, M = M' or M ≠ M '.)

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