TWI403460B - Carbon nanotube compound and method for producing the same - Google Patents

Abstract

The invention provides a carbon nanotube compound and method for producing the same. The method of the invention comprises the following steps. Firstly, Aniline-trimer and DMAc(dimethyl acetamide) solution are mixed to form a first solution. Secondly, Dianhydride and DMAc solution are mixed to form a second solution. The first solution and the second are mixed to form a third solution. Additionally, carboxyl-multi wall carbon nanotube (c-MWNT), Diaminodiphenylether and DMAc solution are mixed to form a fourth solution. The third solution and the fourth are mixed to form a poly amic acid/c-MWNT solution. Some poly amic acid/c-MWNT solution is spread on a substrate and processed with a thermal treatment, and a carbon nanotube compound is eventually produced.

Description

Nano carbon tube composite and preparation method thereof

This invention relates to a carbon nanotube composite and, in particular, to a composite of a carboxylated multi-layered carbon nanotube.

Due to the development of high-tech industries, the influence of electromagnetic waves on instruments and equipment and the human body has received much attention and attention.

Most of the current electronic devices are made of plastics that are light in weight, low in cost, easy to design, and have insulating properties. Therefore, they are likely to cause static electricity accumulation during use and cannot eliminate the interference of electronic noise. These problems are common to equipment, environment, and individuals. Has a considerable impact. Electromagnetic compatibility (EMC) standards have been published in many countries, and equipment that cannot meet electromagnetic compatibility standards is not allowed to be sold in new countries. Therefore, the development of electromagnetic compatibility technology and shielding materials has become one of the key technologies that must be understood and mastered in electronic product design. Due to its superior electrical and dielectric properties, conductive polymers are attracting attention in electromagnetic shielding materials.

Therefore, the present invention provides a method for manufacturing a carbon nanotube composite, which can produce a carbon nanotube composite having electromagnetic radiation resistance, thereby providing various electronic products on the market as a shielding material and further improving The original application area or the new application category.

One aspect of the present invention is to provide a method for making a carbon nanotube composite.

According to a specific embodiment, the method of the invention comprises the following steps. First, a monoaniline trimer and a monodimethylethylamine solution are mixed to form a first solution. Next, the mixed bis-anhydride and the dimethylethylamine solution are dissolved to form a second solution. The second solution and the first solution are further mixed to form a third solution. Thereafter, a monocarboxylated multilayer carbon nanotube, a diaminodiphenyl ether, and a monodimethylethylamine solution were mixed to form a fourth solution.

Further, the fourth solution and the third solution are mixed to obtain a polyglycolic acid/carbon nanotube solution. Finally, a portion of the polyphosphonic acid/nanocarbon tube solution is coated on a carrier and the carrier and a portion of the polyaminic acid/carbon nanotube solution coated on the carrier are subjected to a solution. A heat treatment procedure is performed to form the carbon nanotube composite on the carrier.

Another aspect of the invention is to provide a carbon nanotube composite. It may be a poly-proline polymer/nanocarbon tube composite.

According to another embodiment of the present invention, the carbon nanotube composite comprises a poly-proline polymer and a plurality of carboxylated multilayer carbon nanotubes, which are evenly distributed in the poly-proline polymer.

Since the carbon nanotubes themselves have a weak van der Waals force, they tend to get together, and there is no force between them and the polymer material, so they cannot be uniformly combined with the polymer material. Compared with the prior art, the invention has the advantages of performing a carboxylation process on the surface of the carbon nanotubes to produce a carboxylic acid group (-COOH) on the surface thereof, and imparting the solubility properties of the carbon nanotubes to be evenly distributed in the polymer. .

The advantages and spirit of the present invention will be further understood from the following detailed description of the invention.

The present invention provides a method of making a carbon nanotube composite. The carbon nanotube composite may be a poly-proline polymer/nanocarbon tube composite. The carbon nanotube is a carboxylated multilayer carbon nanotube and is evenly distributed in the polyamic acid polymer. Specific embodiments in accordance with the present invention are disclosed below.

Referring to FIG. 1, FIG. 1 is a flow chart of a method according to an embodiment of the present invention.

As shown in FIG. 1, in the specific embodiment, the method comprises the following steps. First, in step S110, a monoaniline trimer and a dimethylethylamine solution are mixed to form a first solution. Subsequently, in step S112, the mixed bis-anhydride and the dimethylethylamine solution are dissolved to form a second solution according to the method. Next, in step S114, the second solution and the first solution are mixed to form a third solution according to the method. Then, according to the method, in step S116, the monocarboxylated multilayer carbon nanotube, the diaminodiphenyl ether and the monodimethylethylamine solution are mixed to form a fourth solution. In practice, the proportion of each component of the fourth solution may be adjusted as appropriate.

Further, in step S118, the fourth solution and the third solution are mixed according to the method to obtain a poly-proline/nanocarbon tube solution. Finally, according to the method, in step S120, a portion of the poly-proline/nanocarbon tube solution is coated on a carrier and the carrier and a portion coated on the carrier are coated with the poly-proline The carbon nanotube solution is subjected to a heat treatment process to form the carbon nanotube composite on the carrier.

The implementation environment of the method of the present invention will be specifically described below. It is to be noted that the following processes, materials, experimental parameters, and various data are merely illustrative of the invention and are not intended to limit the scope of the invention.

First, 0.1363 g (0.47 mmol) of the aniline trimer was weighed and dissolved in 6 g of dimethylethylamine, and stirred at room temperature for 24 hours to form a first solution. Subsequently, 0.5205 g (1 mmol) of bis-anhydride was weighed and dissolved in 1.5 g of dimethylethylamine, and stirred at room temperature for 30 minutes to form a second solution. Next, the second solution and the first solution were mixed and stirred at room temperature for 24 hours to form a third solution. Then, about 0.5 to 3% by weight of the fourth solution of the carboxylated multilayer carbon nanotubes and 0.2002 g (1 mmol) of diaminodiphenyl ether are dissolved in 2.5 g of dimethylethylamine, and Stir at room temperature for 24 hours to form a fourth solution.

Further, the fourth solution and the third solution were mixed and stirred at room temperature for 24 hours to obtain a polyglycolic acid/nanocarbon tube solution. Finally, an appropriate amount of the polyaminic acid/nanocarbon tube solution is coated on a glass plate and the glass plate and a portion of the polyaminic acid/carbon nanotube solution coated on the glass plate are subjected to a solution. A heat treatment procedure is performed to form the carbon nanotube composite on the carrier.

The temperature of the heat treatment procedure is gradually increased from room temperature to about 300 ° C, and then gradually lowered from 300 ° C to room temperature. The details of the heat treatment procedure for the formation of the carbon nanotube composite are shown in Table 1.

In this embodiment, the carbon nanotube composite is a poly-proline polymer/nanocarbon tube composite. The carbon nanotube is a carboxylated multilayer carbon nanotube and is evenly distributed in the polyamic acid polymer. Further, in practical applications, the molar ratio of the aforementioned aniline trimer: dianhydride:diaminodiphenyl ether may be, but is not limited to, 0.47:1:1. In addition, in practical applications, the ratio of the different proportions of the carboxylated multi-layered carbon nanotubes is about 0.5 to 3% by weight of the fourth solution.

In practical applications, the above-mentioned carboxylated multi-layered carbon nanotubes are further prepared by mixing a multi-layered carbon nanotube and a sulfuric acid/nitric acid mixed solution in a supersonic oscillation environment for a surface functionalization process. The carboxylated multilayer carbon nanotube is obtained. Wherein, the multi-layered carbon nanotube is added to the sulfuric acid/nitric acid mixed solution to generate a carboxylation reaction to cause a monocarboxylic acid group on the surface of the multi-layered carbon nanotube. Moreover, the ratio of sulfuric acid to nitric acid in the sulfuric acid/nitric acid mixed solution may be 3:1; and the purity of the sulfuric acid may be 90%; the purity of the nitric acid may be 70%. Please note that in practice, the ratio of sulfuric acid to nitric acid in the sulfuric acid/nitric acid mixed solution, the sulfuric acid and the purity of the nitric acid may be adjusted as appropriate.

The implementation environment of the method for producing the carboxylated multilayer carbon nanotube will be specifically described below. It is to be noted that the following processes, materials, experimental parameters, and various data are merely illustrative of the invention and are not intended to limit the scope of the invention.

First, a multi-layered carbon nanotube was added to a sulfuric acid/nitric acid mixed solution, and ultrasonically oscillated for 23 hours at 20 ± 5 °C. Wherein the ratio of sulfuric acid to nitric acid in the sulfuric acid/nitric acid mixed solution is 3:1; and the purity of the sulfuric acid is 90%; the purity of the nitric acid is 70%. Subsequently, the above product was suction filtered and rinsed four times with deionized water and methanol. The filtered carboxylated multi-layered carbon nanotubes were placed in an oven at a temperature of 60 ° C and a drying time of 24 hours to remove excess water, and finally the carboxylated multilayer carbon nanotubes were obtained.

Please refer to Figure 2. Figure 2 is a flow chart showing the preparation method of the aniline trimer in Figure 1. First, in step S510, p-phenylenediamine, an aqueous solution of hydrochloric acid, and a solution of ethanol are mixed to form a first mixed solution. Next, according to the method, in step S512, ammonium persulfate and the first mixed solution are mixed to form a second mixed solution, and the reaction is continuously stirred. Next, in step S514, according to the method, an aniline monomer is added to form a third mixed solution, and stirring is continued. Subsequently, according to the method, in step S516, the third mixed solution is filtered under a reduced pressure environment to obtain a first product. Then, according to the method, in step S518, the first product and an ammonium hydroxide solution are mixed to form a fourth mixed solution, and stirring is continued. Further, according to the method, in step S520, the fourth mixed solution is filtered under a reduced pressure environment to obtain a second product. Finally, in step S522, the second product is subjected to column chromatography purification to obtain the aniline trimer.

The implementation environment of the method for producing the aniline trimer will be specifically described below. It is to be noted that the following processes, materials, experimental parameters, and various data are merely illustrative of the invention and are not intended to limit the scope of the invention.

First, 0.86 g (8 mmol) of p-phenylenediamine was dissolved in 100 ml of a 1 M hydrogen chloride solution and 40 ml of ethanol, and the reaction was carried out in an ice bath at -5 ° C to form a first mixed solution. Next, 1.8 g (8 mmol) of ammonium persulfate was weighed into the above first mixed solution to form a second mixed solution, and the reaction was continuously stirred. After about 5 minutes of reaction, when the product turned brown, 1.5 ml (16 mmol) of the aniline monomer was quickly added to form a third mixed solution, and stirring was continued. After a few minutes, the product turned blue and the reaction was stirred for 30 minutes.

Subsequently, the product was suction-filtered, and the product was washed with 30 ml of 1 M hydrogen chloride and 80 ml of a distilled aqueous solution to obtain a first product. The first product was added to 40 ml of a 1 M ammonium hydroxide solution to form a fourth mixed solution, and the reaction was continuously stirred at room temperature for 1 to 2 hours. The fourth mixed solution was further suction filtered and the product was rinsed with distilled water and rinsed until the pH was near neutral to obtain a second product which was blue-brown. Finally, the second product is subjected to column chromatography purification to obtain the aniline trimer.

Since the carbon nanotubes themselves have a weak van der Waals force, they tend to get together, and there is no force between them and the polymer material, so they cannot be uniformly combined with the polymer material. Compared with the prior art, the invention has the advantages of performing a carboxylation process on the surface of the carbon nanotubes to produce a carboxylic acid group (-COOH) on the surface thereof, and imparting the solubility properties of the carbon nanotubes to be evenly distributed in the polymer. .

The features and spirit of the present invention will be more apparent from the detailed description of the preferred embodiments. On the contrary, the intention is to cover various modifications and equivalents within the scope of the invention as claimed. Therefore, the scope of the patented scope of the invention should be construed as broadly construed in the

S110~S120. . . Process step

S510~S522. . . Process step

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow chart showing a method of making a carbon nanotube composite in accordance with an embodiment of the present invention.

Figure 2 is a flow chart showing the preparation method of the aniline trimer in Figure 1.

S110~S120. . . Process step

Claims (10)

A method for preparing a carbon nanotube composite comprising the steps of: mixing a monoaniline trimer and a dimethylethylamine solution to form a first solution; mixing a bis-anhydride and a dimethylethylamine solution Forming a second solution; mixing the second solution and the first solution to form a third solution; mixing the carboxylated multi-layered carbon nanotubes, diaminodiphenyl ether, and monodimethylethylamine solution to form a a fourth solution; mixing the fourth solution and the third solution to obtain a poly-proline/nanocarbon tube solution; and coating a portion of the poly-proline/nanocarbon tube solution on a carrier and The carrier and a portion of the polyaminic acid/carbon nanotube solution coated on the carrier are subjected to a heat treatment process to form the carbon nanotube composite on the carrier. The method of claim 1, wherein the aniline trimer: dianhydride: diaminodiphenyl ether has a Mohr number ratio of about 0.47:1:1. The method of claim 1, wherein the ratio of the different proportions of the carboxylated multi-layered carbon nanotubes is about 0.5 to 3% by weight of the fourth solution. The method of claim 1, wherein the temperature of the heat treatment procedure is increased stepwise from room temperature to about 300 °C. The method of claim 1, further comprising the steps of: mixing a multi-layered carbon nanotube and a sulfuric acid/nitric acid mixed solution to perform a surface functionalization process, thereby causing a surface of the multilayered carbon nanotube to be produced. A carboxylic acid group to obtain the carboxylated multilayer carbon nanotube. The method of claim 5, wherein the ratio of sulfuric acid to nitric acid in the sulfuric acid/nitric acid mixed solution is 3:1; and the purity of the sulfuric acid is 90%; The acid purity is 70%. The method of claim 5, wherein the surface functionalization process is carried out in an ultrasonically oscillating environment. The method of claim 1, further comprising the steps of: mixing p-phenylenediamine, a hydrogen chloride solution, and a monoethanol solution to form a first mixed solution; mixing ammonium persulfate and the first mixed solution to form a second mixed solution, and continuously stirring the reaction; adding an aniline monomer to form a third mixed solution, and continuously stirring; filtering the third mixed solution under a reduced pressure to obtain a first product; mixing the first product And an ammonium hydroxide solution to form a fourth mixed solution, and continuously stirring; filtering the fourth mixed solution under a reduced pressure environment to obtain a second product; and subjecting the second product to column chromatography purification, The aniline trimer is obtained. The method of claim 7, wherein the molar ratio of p-phenylenediamine: ammonium persulfate: aniline monomer is about 1:1:2. A carbon nanotube composite produced by the method of any one of claims 1 to 9.