KR101740887B1

KR101740887B1 - Novel Pyrene Compounds, Carbon Nanomaterials modified with the Compounds, and Carbon Nanomaterial/Polyamide Composite

Info

Publication number: KR101740887B1
Application number: KR1020150125710A
Authority: KR
Inventors: 한미정; 임현화
Original assignee: 한국화학연구원
Priority date: 2015-09-04
Filing date: 2015-09-04
Publication date: 2017-05-29
Also published as: KR20170028725A

Abstract

The present invention relates to a novel pyrene compound, a carbon nanomaterial modified by the compound, and a carbon nanomaterial / polyamide composite.
Since the modified carbon nanomaterial provided by the present invention can be uniformly dispersed in a polymer material such as polyamide, the composite material mixed with the polymer matrix has an effect of greatly improving the mechanical and electrical properties.

Description

[0001] The present invention relates to novel pyrene compounds, carbon nanomaterials modified by the compounds, and carbon nanomaterials / polyamide composites (Novel Pyrene Compounds, Carbon Nanomaterials modified with the Compounds, and Carbon Nanomaterials / Polyamide Composites)

The present invention relates to a novel pyrene compound, a carbon nanomaterial modified by the compound, and a carbon nanomaterial / polyamide composite.

Carbon nanomaterials have attracted attention in academia and industry because of their excellent physical properties. In particular, carbon nanomaterials having excellent mechanical properties and electrical conductivity are useful for the development of multifunctional polymer composites.

However, there are some problems to be solved in order to develop a composite material having excellent mechanical and electrical properties by introducing a carbon nanomaterial into a polymer material. The first priority is that carbon nanomaterials do not dissolve in water or organic solvents and are therefore difficult to uniformly disperse into polymer matrix. The second problem is that the carbon nanotubes do not have a functional group on the outer wall, and thus the external force generated in the matrix is not effectively transferred to the carbon nanotubes because the interfacial adhesion with the polymer matrix is very low. Therefore, it is required to develop a composite material capable of maximizing the interfacial adhesion between the carbon nanomaterial and the polymer matrix while uniformly dispersing the carbon nanomaterial in the polymer matrix in order to produce the high-performance carbon nanomaterial / polymer composite.

As a technique for combining a carbon nanomaterial and a polymer matrix, there has been reported a technique of uniformly dispersing a carbon nanomaterial in a polymer matrix by using an additive such as a dispersant or a compatibilizer (see Patent Documents 1 to 3). A technology for introducing a functional group capable of forming multiple hydrogen bonds through modification of a carbon nanomaterial to form a supramolecular structure between materials without using additives such as a dispersant or a compatibilizer [Patent Document 4 and Patent Document 4] 5] have been reported.

In Patent Documents 4 and 5, carbon nanomaterials in which functional groups capable of forming three or more multiple hydrogen bonds are introduced by mixing a polyisocyanate compound and a pyrimidine compound in a carbon nanomaterial are reacted. However, since the polyisocyanate compound and the pyrimidine compound used as modifiers of the carbon nanomaterial are randomly and randomly bonded to the carbon nanomaterial, it is not easy to control the amount of modification. Also, prior to the modification of the carbon nanomaterial, pretreatment is performed with an acid such as sulfuric acid or nitric acid to convert the terminal of the carbon nanomaterial into a carboxyl group (COOH), and then a polyisocyanate compound and / or a pyrimidine compound There is a possibility of deteriorating the inherent structure of the carbon nanotubes, which may deteriorate the excellent properties of the carbon nanotubes.

Therefore, it is necessary to develop a novel modifier that can quantitatively control the degree of modification without deteriorating the inherent properties of carbon nanomaterials in the technical field of manufacturing multifunctional polymer composites by reforming carbon nanomaterials.

Korean Patent Registration No. 10-1017019 Korean Patent Registration No. 10-1051969 Korean Patent Registration No. 10-1293920 Korean Patent Registration No. 10-1454407 Korean Patent Registration No. 10-1454454

An object of the present invention is to provide a novel pyrene compound useful as a modifier for carbon nanomaterials.

Another object of the present invention is to provide a carbon nanomaterial modified by the non-covalent bonding of the pyrene compound to the surface.

Another object of the present invention is to provide a carbon nanomaterial / polyamide composite material in which the modified carbon nanomaterial is uniformly dispersed in a matrix of a polyamide resin.

In order to solve the above problems, the present invention can be characterized by a pyrene compound represented by the following formula (1).

[Chemical Formula 1]

Wherein m and n are each an integer of 0, 1, 2 or 3, X is a C ₁ to C ₁₀ alkane, a C _{4 to} C ₇ cycloalkane, or a C _{6 to} C ₁₂ aromatic ring It represents a divalent group derived from the group consisting of the alkanes, cyclo alkanes, or an aromatic ring may be unsubstituted or substituted with one to three substituents selected from the group of C ₁ ~C _6, respectively)

Another aspect of the present invention relates to a modified carbon nanomaterial, which is characterized in that a modified carbon nanomaterial in which a pyrene compound represented by the general formula (1) is non-covalently bonded to the end of a carbon nanomaterial.

Another aspect of the present invention relates to a carbon nanomaterial / polyamide composite material, wherein the carbon nanomaterial / polyamide composite material includes the modified carbon nanomaterial in a polyamide resin matrix.

The pyrene compound of the present invention has a pyrene functional group, and the surface of the carbon nanotube is adsorbed to the surface of the carbon nanotube by interaction of the carbon nanotube and pyrene with the π-π interaction.

Also, since the modified carbon nanomaterial of the present invention has a ureidopyrimidinone functional group capable of forming three or more multiple hydrogen bonds, the network of carbon nanotubes And prevents the agglomeration of carbon nanotubes, so that it can be dispersed evenly in a polymer material such as polyamide.

Therefore, the carbon nanomaterial / polyamide composite material of the present invention is useful as an electronic material because of its excellent mechanical and electrical properties.

1 is a TEM photograph of a modified MWCNT / polyamide composite material,
(A) is a TEM photograph of a composite material of a non-covalently modified MWCNT (Example 1) and a polyamide (PA6)
(B) is a TEM photograph of a composite material of a covalently modified MWCNT (Comparative Example 1) and a polyamide (PA6)
(C) is a TEM photograph of a composite of unmodified pristine MWCNT (control) and polyamide (PA6).

The present invention relates to a novel pyrene compound, a carbon nanomaterial modified with the pyrene compound, and a carbon nanomaterial / polyamide composite.

Hereinafter, the present invention will be described in more detail.

The pyrene compound according to the present invention can be represented by the following formula (1).

[Chemical Formula 1]

In the pyrene compound represented by the above-mentioned general formula (1), it is preferable that X is an alicyclic hydrocarbon group composed of ethane, n-butane, n-hexane, cyclobutane, cyclohexane, isophorone, benzene, biphenyl, toluene, Lt; / RTI >

Specific examples of the pyrene compound represented by the formula (1) may be represented by the following formula (1a), (1b) or (1c)

[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

The present invention is also characterized by a process for producing a pyrene compound represented by the above formula (1).

According to the following Reaction Scheme 1, a process for producing a pyrene compound according to the present invention comprises:

I) reacting a 2-amino-4 ( 1H ) -oxo-6-methylpyrimidine represented by the following formula 2 with a diisocyanate compound represented by the following formula 3 to obtain a ureido isocyanate compound represented by the following formula Manufacturing process; And

Ii) reacting a ureido isocyanate compound represented by the following formula (4) with 1-pyrene methanol represented by the following formula (5) to prepare a pyrene derivative represented by the following formula (1); .

[Reaction Scheme 1]

(Wherein X, n and m are each as defined above)

In the above Reaction Scheme 1, i) reaction is carried out by heating an amine compound and a diisocyanate compound as a urea synthesis reaction under a nitrogen atmosphere at a temperature in the range of 50 ° C to 150 ° C.

In the above Reaction Scheme 1, ii) the reaction is carried out by dissolving 1-pyrene methanol in a conventional organic solvent as a carbamate synthesis reaction, and then heating and refluxing the ureido isocyanate compound prepared in the above reaction i). As the catalyst, a tin (Sn) -based compound can be used, and specifically, dibutyltin dilaurate can be used. The organic solvent used in the reaction may be a conventional solvent such as methylene chloride, chloroform, ethyl acetate, benzene, toluene, tetrahydrofuran, dioxane and the like. The reaction temperature may be a reflux temperature of the solvent used and may be maintained within a temperature range of about 40 ° C to 120 ° C.

When the reaction is terminated, the temperature of the reaction mixture is lowered to room temperature, and the target pyrene compound represented by the formula (1) can be obtained through a conventional purification method such as column chromatography or the like.

Further, the present invention is characterized by a carbon nanomaterial modified by a pyrene compound represented by the above formula (1).

The carbon nanomaterials are commonly used in the field, and include single wall carbon nanotubes (SWCNTs), double wall carbon nanotubes (DWCNTs), multiwall carbon nanotubes (MWCNTs), single layer grains, Carbon black, and carbon fiber. Further, the present invention does not limit the selection of carbon nanomaterials.

In the modified carbon nanomaterial of the present invention, the pyrene compound represented by Formula 1 is bonded to the surface of the carbon nanomaterial through noncovalent bonding.

In the case of Patent Document 4 and Patent Document 5, a pretreatment process of introducing a carboxyl group (COOH) by heating a carbon nanomaterial to a mixed solution of sulfuric acid and nitric acid in advance at about 80 ° C. was carried out in order to modify the carbon nanomaterial. That is, as exemplified in Patent Documents 4 and 5, a carbon nanomaterial into which a carboxyl group (COOH) has been introduced can firmly chemically bond the modifier to the carbon nanotube through a 'covalent bond' with the modifier, It has been pointed out that there is a disadvantage that the sheet resistance of the tube is damaged and the sheet resistance value of the modified carbon nanomaterial is kept high.

However, in the present invention, the pyrene compound represented by Formula 1 is adsorbed on the surface of the carbon nanomaterial by 'non-covalent bond' using the ultrasonic dispersion method without the pretreatment of the carbon nanomaterial with an acid, Lt; / RTI > As a result, the modified carbon nanomaterial of the present invention can improve the dispersibility of the carbon nanomaterials without deforming the inherent internal structure of the carbon nanomaterial. As a result, the modified carbon nanomaterial of the present invention maintains a low sheet resistance value of about 1.64 to 2.38? /?, And thus can be effectively used as an electrically conductive material.

Further, the modified carbon nanomaterial of the present invention can easily control the degree of modification by controlling the amount of the modifier. Considering various physical properties of the modified carbon nanomaterial, the pyrene compound represented by Formula 1 may be used in a weight ratio of 1: 0.2 to 3 by weight of the carbon nanomaterial, preferably 1: 0.5 to 2: , And more preferably in the range of 1: 0.5 to 1 by weight.

The present invention also features a carbon nanomaterial / polyamide composite comprising a modified carbon nanomaterial and a polyamide resin.

The modified carbon nanomaterial of the present invention has excellent dispersibility because the pyrene compound is adsorbed on the surface of the carbon nanotube by the non-covalent bond and the surface thereof is modified. Therefore, it is preferable to add the dispersant or compatibilizer to the polymer matrix It is possible to distribute evenly. When the carbon nanomaterial / polyamide composite material is produced, the carbon nanomaterial modified based on 100 parts by weight of the polyamide resin may be included in the range of 0.1 to 20 parts by weight, preferably in the range of 0.5 to 10 parts by weight .

The present invention as described above will be described in more detail with reference to the following Synthesis Examples, Examples and Application Examples, but the present invention is by no means limited thereto.

[Synthesis Example] Synthesis of pyrene compound

SYNTHESIS EXAMPLE 1 Synthesis of Pyrene Compound of Formula 1a

1) Synthesis of ureido isocyanate compound of formula (4a)

2-Amino-4 ( 1H ) -oxo-6-methylpyrimidine (5 g) was added to hexamethylene diisocyanate (100 mL) under nitrogen atmosphere and the reaction was allowed to proceed at 90 ° C for 18 hours. When the reaction was completed, the temperature of the reaction mixture was lowered to room temperature, excess hexane was added thereto, filtration was performed, and the mixture was sufficiently washed with hexane. The filtered solid was dried in an oven to give the compound of formula (4a).

¹ H NMR (CDCl ₃ )? 1.39-1.41 (m, 4H), 1.60-1.62 (m, 4H), 2.23 (s, 3H), 3.22-3.31 (s, 1 H), 11.86 (s, 1 H), 13.11 (s, 1 H)

2) Synthesis of Compound (I)

1-Pyrene methanol (1 g, 4.3 mmol) and chloroform (150 mL) were added under nitrogen atmosphere, and the mixture was stirred for 10 minutes. The compound of Formula 4a (1.9 g, 6.5 mmol) was added to the reaction mixture, stirred for 30 minutes, and refluxed for 24 hours. When the reaction was completed, the temperature of the reaction mixture was lowered to room temperature, and then the product was isolated by column chromatography to obtain the compound of formula (Ia).

^{_{1 H NMR (CDCl 3) δ}} 1.25-1.59 (m, 10 H), 1.91 (m, 2H), 3.23 (s, 3H), 5.41 (s, 1H), 5.66 (s, 1H), 5.79 (s, 2H), 7.93-8.30 (m, 9H), 9.98 (s, 1H), 11.48 (s,

Synthesis Example 2. Synthesis of pyrene compound of formula 1b

1) Synthesis of ureido isocyanate compound of formula (4b)

2-Amino-4 (1 H ) -oxo-6-methylpyrimidine (5 g) was added to isophorone diisocyanate (100 mL) under nitrogen atmosphere and the reaction was allowed to proceed at 90 ° C for 18 hours. When the reaction was completed, the temperature of the reaction mixture was lowered to room temperature, and then the product was separated by column chromatography to obtain the compound of Formula 4b.

^{_{1 H NMR (CDCl 3) δ}} 0.95-1.15 (m, 11H), 1.68-1.81 (m, 3H), 2.21 (s, 3H), 3.05 (s, 2H), 5.82 (s, 1H), 10.03 (s , &Lt; / RTI > 1H), 11.90 (s, 1H), 13.08

2) Synthesis of Compound (1b)

1-pyrene methanol (1 g, 4.3 mmol) and chloroform (150 mL) were added to the solution under nitrogen atmosphere, and the mixture was stirred for 10 minutes. Then, the compound of Formula 4b (2.3 g, 6.5 mmol) was added thereto and stirred for 30 minutes. To the reaction mixture was added dibutyltin dilaurate (1.3 g, 2.1 mmol) as a catalyst and subjected to a reflux reaction for 24 hours. When the reaction was completed, the temperature of the reaction mixture was lowered to room temperature, the solvent was removed under reduced pressure, and the resultant product was separated by column chromatography to obtain a compound of formula (Ib).

^{_{1 H NMR (CDCl 3) δ}} 0.85-1.2 (m, 11H), 1.67-2.14 (m, 7H), 2.86-3.00 (m, 2H), 3.62-3.82 (m, 1H), 5.72-5.81 (m, 4H), 7.95-8.26 (m9H), 9.90 (s, IH), 11.61

SYNTHESIS EXAMPLE 3 Synthesis of Pyrene Compound of Formula 1c

1) Synthesis of ureido isocyanate compound of formula (4c)

2-Amino-4 (1 H ) -oxo-6-methylpyrimidine (5 g) was added to m-xylene diisocyanate (100 mL) under a nitrogen atmosphere, and the mixture was reacted at 90 ° C for 18 hours. When the reaction was completed, the temperature of the reaction mixture was lowered to room temperature, and a small amount of dichloromethane and excess amount of hexane were poured. The solid was filtered, extracted with soxhlet with ethyl acetate and then dried in an oven to obtain the compound of formula (4c).

¹ H NMR (CDCl ₃ )? 2.21 (s, 3H), 4.44-4.48 (m, 4H), 5.82 (s, IH), 7.18-7.22 (s, 1 H), 12.04 (s, 1 H), 12.96 (s, 1 H)

2) Synthesis of Compound (1c)

1-pyrene methanol (1 g, 4.3 mmol) and chloroform (200 mL) were added under nitrogen atmosphere, and the mixture was stirred for 10 minutes. Then, the compound of Formula 4c (2.0 g, 6.5 mmol) was added thereto and stirred for 30 minutes. To the reaction mixture was added dibutyltin dilaurate (1.3 g, 2.1 mmol) as a catalyst and subjected to a reflux reaction for 24 hours. When the reaction was completed, the temperature of the reaction mixture was lowered to room temperature, the solvent was removed under reduced pressure, and the resultant product was separated by column chromatography to obtain a compound of formula (1c).

^{_{1 H NMR (CDCl 3) δ}} 2.21 (s, 3H), 4.22 (s, 2H), 4.42 (s, 2H), 5.78 (s, 2H), 5.40 (s, 1H), 5.62 (s, 1H), 1H), 7.18-7.22 (m, 1 H), 7.31-7.36 (m, 3H), 7.75-8.12 (m 9H), 9.90

EXAMPLES Preparation of Modified MWCNTs

Example 1. Preparation of MWCNT modified by noncovalent multiple hydrogen bonds

(0.1 g) synthesized in Synthesis Example 1 was dissolved in tetrahydrofuran (200 mL), and then multi-walled carbon nanotubes (MWCNT; 0.2 g) were added, ultrasonically vibrated for 30 minutes, and filtered. Washed with tetrahydrofuran and chloroform, and then dried in an oven to prepare a surface modified MWCNT by the noncovalent method.

Examples 2 to 7. Preparation of MWCNT modified by noncovalent multiple hydrogen bonding

The surface-modified MWCNT was prepared by the non-covalent method in Example 1, and the type of modifier and the weight ratio of modifier to MWCNT were varied as shown in Table 1 below.

Comparative Example 1. Preparation of MWCNTs Modified by Covalent Multiple Hydrogen Bonds

Pristine MWCNT was added to the mixed acid (sulfuric acid / nitric acid = 3/1 volume ratio) and reacted at 50 ° C for 24 hours. When the reaction was completed, the temperature was lowered to room temperature and then washed with water and methanol until the pH reached 7. The thus prepared MWCNT-COOH was put into a vacuum dryer and dried at 80 ° C.

MWCNT-COOH (0.2 g) and the compound of formula (4a) (0.1 g) were added in a nitrogen atmosphere, and then N, N-dimethylformamide (200 mL) was added. After ultrasonic treatment for 1 hour, reaction was carried out at 100 ° C for 18 hours. After the reaction was completed, the temperature was lowered to room temperature, filtered, sufficiently washed with N, N-dimethylformamide and chloroform, and then dried in an oven to prepare a surface modified MWCNT by a sharing method.

Comparative Examples 1 to 5. Preparation of MWCNTs Modified by Covalent Multiple Hydrogen Bonds

The surface modified MWCNT was prepared in the same manner as in Comparative Example 1 except that the kind of the modifier and the weight ratio of the modifier to the MWCNT-COOH were changed as shown in Table 1 below.

A pellet-type specimen was prepared from the modified MWCNTs prepared in Examples 1 to 7 and Comparative Examples 1 to 5 and 0.01 g of pristine MWCNT as a control group, respectively. The sheet resistance of the prepared pellet specimens was measured by a 4-point probe method. The results are shown in Table 1 below.

Properties of Modified MWCNTs division Modification method Modified MWCNT pellet sheet resistance
(Ω / □) Modifier MWCNT: weight ratio of modifier Example 1 Non-shared Compound 1a 1: 0.5 1.64 Example 2 Non-shared Compound 1a 1: 1 1.67 Example 3 Non-shared Compound 1a 1: 2 1.71 Example 4 Non-shared Compound 1b 1: 0.5 2.01 Example 5 Non-shared Compound 1b 1: 1 2.38 Example 6 Non-shared Compound 1c 1: 0.5 1.89 Example 7 Non-shared Compound 1c 1: 1 1.92 Comparative Example 1 share Compound 4a 1: 0.5 4.22 Comparative Example 2 share Compound 4a 1: 1 6.03 Comparative Example 3 share Compound 4a 1: 2 12.76 Comparative Example 4 share Compound 4b 1: 1 4.35 Comparative Example 5 share Compound 4c 1: 1 4.38 Control group pristine MWCNT - 1.52

Table 1 shows the results of confirming the electrical properties of the modified pellets of MWCNT by measuring the sheet resistance. According to the above Table 1, it can be seen that the modified MWCNTs have different electrical properties of the modified MWCNTs due to the modification method of the carbon nanomaterials and the modifier, and the modifier content. Particularly, the modification method has a great influence on the electrical properties of the MWCNT itself .

[Application example] Manufacture of carbon nanomaterial / polyamide composite

The modified MWCNTs prepared in Examples 1 to 7 and Comparative Examples 1 to 5 were prepared by nano-composite films of polyamide 6 (PA6), and their mechanical and electrical properties were measured.

That is, 0.2 g of PA6 was dissolved in 1,1,1,3,3,3-hexafluoro-2-propanol (5 mL) to prepare a PA6 solution. 0.01 g (5 phr) of modified MWCNT was added to the PA6 solution, and the solution was ultrasonicated for 40 minutes and stirred for 30 minutes to prepare a composite solution. The film specimens were prepared by using the prepared composite solution. The film resistances were measured by the 4-point probe method and the tensile strength and Young's Modulus were measured using Instron 4482 The results are shown in Table 2 below.

division Composition of composites Properties of composites Polyamide Modified MWCNT PA6: weight ratio of modified MWCNT Film sheet resistance
(Ω / □) The tensile strength
(MPa) Young's modulus
(MPa) Application example 1 PA6 Example 1 100: 5 52.77 37.33 872.99 Application example 2 PA6 Example 2 100: 5 59.35 37.99 874.78 Application Example 3 PA6 Example 3 100: 5 60.69 38.66 887.69 Application example 4 PA6 Example 4 100: 5 67.06 36.45 848.84 Application Example 5 PA6 Example 5 100: 5 79.84 36.29 846.25 Application Example 6 PA6 Example 6 100: 5 61.53 36.52 869.14 Application Example 7 PA6 Example 7 100: 5 65.55 36.98 865.43 Comparative Application Example 1 PA6 Comparative Example 1 100: 5 140.10 35.52 810.28 Comparative Application Example 2 PA6 Comparative Example 2 100: 5 269.08 35.27 814.22 Comparative Application Example 3 PA6 Comparative Example 3 100: 5 262.96 34.62 776.60 Comparative Application Example 4 PA6 Comparative Example 4 100: 5 131.28 34.73 700.45 Comparative Application Example 5 PA6 Comparative Example 5 100: 5 285.83 35.97 739.33 Control Example PA6 pristine MWCNT 100: 5 152.42 31.21 699.94

According to the results shown in the above Table 2, the modified MWCNT / PA6 composites of Application Examples 1 to 7 were prepared using modified MWCNTs (Examples 1 to 7) through non-covalent bonding and confirmed that both mechanical and electrical properties were excellent .

1 also shows a transmission electron microscope (TEM) of the modified MWCNT / PA6 composite prepared in (A) Application Example 1, (B) Comparative Application Example 1, and (C) Control Example. FIG. 1 (A) is a TEM photograph of a MWCNT / PA6 composite modified through non-covalent bonding. It can be seen that MWCNTs are uniformly dispersed in the polymer matrix in comparison with (B) and (C).

Claims

A pyrene compound represented by the following formula (1).
[Chemical Formula 1]

The method according to claim 1,
Wherein X is a divalent radical derived from the group consisting of ethane, n-butane, n-hexane, cyclobutane, cyclohexane, isophorone, benzene, biphenyl, toluene, xylene or naphthalene .

The method according to claim 1,
A pyrene compound represented by the following formula (1a), (1b) or (1c).
[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

A modified carbon nanomaterial in which a pyrene compound represented by the following formula (1) is noncovalently bonded to the end of a carbon nanomaterial.
[Chemical Formula 1]

5. The method of claim 4,
Wherein X is a divalent radical derived from the group consisting of ethane, n-butane, n-hexane, cyclobutane, cyclohexane, isophorone, benzene, biphenyl, toluene, xylene or naphthalene Modified carbon nanomaterial.

5. The method of claim 4,
Wherein the pyrene compound is a compound represented by the following formula (1a), (1b) or (1c).
[Formula 1a]

[Chemical Formula 1b]

[Chemical Formula 1c]

5. The method of claim 4,
The carbon nanomaterial may be selected from the group consisting of single wall carbon nanotubes (SWCNTs), double wall carbon nanotubes (DWCNTs), multiwall carbon nanotubes (MWCNTs), single layer graphens, multilayer graphens, carbon black, Lt; RTI ID = 0.0 > carbon nanomaterial. &Lt; / RTI >

5. The method of claim 4,
Wherein the pyrene compound is bound in a weight ratio of 1: 0.2 to 3 based on the weight of the carbon nanomaterial.

Polyamide resin: and
A modified carbon nanomaterial according to any one of claims 4 to 8;
Carbon nanomaterial / polyamide composite.

10. The method of claim 9,
And 0.1 to 20 parts by weight of the modified carbon nanomaterial based on 100 parts by weight of the polyamide resin.