CN110615427B - Preparation method of high-flexibility self-crosslinking carbon nanotube film - Google Patents
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Abstract
The invention discloses a preparation method of a high-flexibility self-crosslinking carbon nanotube film, and belongs to the field of nano materials. The technical scheme is as follows: (1) adding a carboxylated carbon nanotube into a solvent dissolved with a surfactant to obtain a system A; (2) adding a hydroxylated carbon nano tube or an aminated carbon nano tube into a solvent dissolved with a surfactant to obtain a system B; (3) mixing the system A and the system B, and uniformly dispersing; (4) performing suction filtration to obtain a carbon nanotube film; (5) heating to perform self-crosslinking reaction, and drying after the reaction is finished to obtain the high-flexibility self-crosslinking carbon nanotube film; the stress and the strain of the obtained film can respectively reach 59.22MPa and 12.15%, and compared with a pure carbon nanotube film, the stress and the strain are respectively improved by 3.32 times and 14.82 times. The method provided by the invention improves the mechanical property of the carbon nano tube film.
Description
Technical Field
The invention belongs to the field of nano materials, and particularly relates to a method for preparing a self-crosslinking carbon nano tube film with high flexibility and high mechanical strength by using a convenient method of vacuum filtration of a uniform solution of carbon nano tubes by taking functionalized carbon nano tubes (hydroxyl, carboxyl, amino and the like) as raw materials.
Background
The carbon nano tube has potential application in various fields by virtue of excellent mechanical, electrical and thermal properties. However, the excellent performance of the carbon nanotube is only for a single nanotube, and if the carbon nanotube is applied to a large scale, the carbon nanotube is likely to be prepared into a material with a macroscopic scale, so that the application value of the carbon nanotube can be exerted. Carbon nanotube films have attracted considerable attention as macroscopic materials for carbon nanotubes in the fields of research and application, such as heat dissipation, electromagnetic interference shielding, lightning protection, sensors, and electric drives, due to their excellent functional properties. The existing methods for preparing the carbon nanotube film comprise a vacuum filtration method, a nanotube array forward pressure method, an external magnetic field vacuum filtration method and the like, but the mechanical property change range of the nanotube film prepared by different methods is also large. The most commonly used method for preparing carbon nanotube films at present is a vacuum filtration method, which is considered to be a simple and promising method for mass production. For example, Zhang et al prepared CARBON nanotube films [ CARBON,94,2015, 101-113 ] by vacuum filtration, however, the CARBON nanotube films obtained by the method actually have poor mechanical properties. In practical application, a carbon nanotube film with large size and good mechanical properties is usually required.
Disclosure of Invention
In order to solve the problems of complex process, poor product flexibility (poor mechanical property) and the like in the common method for preparing the carbon nanotube film, the invention provides a method for preparing the high-flexibility self-crosslinking carbon nanotube film.
The invention is realized by the following technical scheme:
(1) adding a carboxylated carbon nanotube into a solvent dissolved with a surfactant to obtain a system A; (2) adding a hydroxylated carbon nano tube or an aminated carbon nano tube into a solvent dissolved with a surfactant to obtain a system B; (3) mixing the system A and the system B, and uniformly dispersing; (4) carrying out suction filtration through a nylon filter membrane to obtain a carbon nano tube film; (5) placing the carbon nano tube film in water, heating to perform a self-crosslinking reaction, and drying after the reaction is finished to obtain a high-flexibility self-crosslinking carbon nano tube film; the above steps are performed in the order of (1), (2), (3) and (4) or in the order of (2), (1), (3) and (4).
The surfactant in the step (1) or the step (2) is one or two or three of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and triton.
The solvent in the step (1) or the step (2) is one or two or three of deionized water, N-N dimethylformamide or N-methylpyrrolidone.
The concentration of the surfactant in the solvent in the step (1) or the step (2) is 50-1000 mg/L.
The mass ratio of the carboxylated carbon nanotubes, the hydroxylated carbon nanotubes or the aminated carbon nanotubes to the surfactant in the step (1) or the step (2) is 1 (1-15).
And (3) respectively carrying out ultrasonic dispersion on the system A and the system B in the step (1) or the step (2) for 10-12 hours to uniformly disperse the carbon nano tubes.
The concentration of the carboxylated carbon nanotubes in the system A in the step (1) or the step (2) is the same as the mass volume concentration (mg/L) of the hydroxylated carbon nanotubes or the aminated carbon nanotubes in the system B.
The mixing volume ratio of the system A to the system B in the step (3) is 1 (0.5-1.5); the dispersion method is ultrasonic dispersion, and the dispersion time is 4-5 hours.
And (4) the nylon filter membrane is a circular filter membrane with the diameter of 0.45 um.
The reaction temperature in the step (5) is 40-240 ℃, and the reaction time is 1-24 hours.
And (5) drying at 90 ℃ for 10 hours.
The technical effects are as follows:
for example, as shown in fig. 2, the mechanical properties of the self-crosslinking carbon nanotube film prepared by the invention are superior to those of a carboxyl, amino and hydroxyl functionalized carbon nanotube film of a control group, and the mechanical properties of the self-crosslinking carbon nanotube film of esterification reaction or the acylated self-crosslinking carbon nanotube film are also superior to those of the carbon nanotube film of the control group. The acylation self-crosslinking carbon nano tube film prepared in a water system has the best comprehensive mechanical property, the stress and the strain are 59.22MPa and 12.15 percent respectively, and compared with a pure carbon nano tube film, the stress and the strain are improved by 3.32 times and 14.82 times respectively. In conclusion, the method provided by the invention improves the mechanical property of the carbon nanotube film, so that the preparation method of the self-crosslinking carbon nanotube film is an effective means for improving the mechanical property of the carbon nanotube film, and the acylation self-crosslinking reaction is most beneficial to improving the mechanical property of the carbon nanotube film in a water system.
Brief description of the drawings
FIG. 1 is a digital photograph of different types of self-crosslinking carbon nanotube films; FIG. 1.a) is an esterified self-crosslinked carbon nanotube film prepared by hydroxylated carbon nanotubes and carboxylated carbon nanotubes in a deionized water solution system. FIG. 1.b) is an esterified self-crosslinking carbon nanotube film prepared from hydroxylated carbon nanotubes and carboxylated carbon nanotubes in an N-N dimethylformamide solution system. FIG. 1.c) is the acylated self-crosslinked carbon nanotube film prepared by aminated carbon nanotube and carboxylated carbon nanotube in deionized water solution system. FIG. 1.d) is the acylation self-crosslinking carbon nanotube film prepared by amination carbon nanotube and carboxylation carbon nanotube in N-N dimethyl formamide solution system.
FIG. 2 is a comparison of the microscopic morphologies of different types of self-crosslinked carbon nanotube films, in which a pure carbon nanotube film, a carboxylated carbon nanotube film, a hydroxylated carbon nanotube film, an aminated carbon nanotube film, a carboxyl and hydroxyl esterified self-crosslinked carbon nanotube film prepared in a water system, a carboxyl and hydroxyl esterified self-crosslinked carbon nanotube film prepared in an N-N Dimethylformamide (DMF) system, a carboxyl and aminoacylated self-crosslinked carbon nanotube film prepared in a water system, and a carboxyl and aminoacylated self-crosslinked carbon nanotube film prepared in an N-N Dimethylformamide (DMF) system are represented by a), b), c), d), e), f), g), and h), respectively.
FIG. 3 is a comparison of mechanical properties of different types of self-crosslinking carbon nanotube films, wherein the pure carbon nanotube film, the carboxylated carbon nanotube film, the hydroxylated carbon nanotube film, the aminated carbon nanotube film, the carboxyl and hydroxyl esterified self-crosslinking carbon nanotube film prepared in a water system, the carboxyl and hydroxyl esterified self-crosslinking carbon nanotube film prepared in an N-N Dimethylformamide (DMF) system, the carboxyl and amino acylated self-crosslinking carbon nanotube film prepared in a water system, and the carboxyl and amino acylated self-crosslinking carbon nanotube film prepared in an N-N Dimethylformamide (DMF) system are represented by A, B, C, D, E, F, G and H, respectively.
FIG. 4 is a comparison of electrical properties of different types of self-crosslinked carbon nanotube films, wherein a pure carbon nanotube film, a carboxylated carbon nanotube film, a hydroxylated carbon nanotube film, an aminated carbon nanotube film, a carboxyl and hydroxyl esterified self-crosslinked carbon nanotube film prepared in a water system, a carboxyl and hydroxyl esterified self-crosslinked carbon nanotube film prepared in an N-N Dimethylformamide (DMF) system, a carboxyl and aminoacylated self-crosslinked carbon nanotube film prepared in a water system, and a carboxyl and aminoacylated self-crosslinked carbon nanotube film prepared in an N-N Dimethylformamide (DMF) system are represented by A, B, C, D, E, F, G and H films, respectively.
Detailed Description
The dispersing agents such as sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, triton and the like selected by the invention are all commercially available analytical pure reagents, and solvents such as deionized water, N-N dimethylformamide, N-methylpyrrolidone and the like; the used glass instruments, water baths, stirrers and the like are instruments and equipment commonly used in laboratories.
EXAMPLE 1 preparation of carboxyl and hydroxyl esterified self-crosslinking carbon nanotube film in Water System
(1) Adding a carboxylated carbon nanotube into a solvent dissolved with a surfactant to obtain a system A; (2) adding the hydroxylated carbon nano tube into a solvent dissolved with a surfactant to obtain a system B; (3) mixing the system A and the system B, and uniformly dispersing; (4) carrying out suction filtration through a nylon filter membrane to obtain a carbon nano tube film; (5) placing the carbon nano tube film in water, heating to perform a self-crosslinking reaction, and drying after the reaction is finished to obtain a high-flexibility self-crosslinking carbon nano tube film; the above steps are performed in the order of (1), (2), (3) and (4) or in the order of (2), (1), (3) and (4).
And (3) the surfactant in the step (1) or the step (2) is sodium dodecyl sulfate.
The solvent in the step (1) or the step (2) is deionized water.
The concentration of the surfactant in the solvent in the step (1) or the step (2) is 50 mg/L.
The mass ratio of the carboxylated carbon nanotubes to the hydroxylated carbon nanotubes to the surfactant in the step (1) or the step (2) is 1:1.
And (3) respectively carrying out ultrasonic dispersion on the system A and the system B in the step (1) or the step (2) for 10 hours to uniformly disperse the carbon nanotubes.
And (3) the concentration of the carboxylated carbon nanotubes in the system A in the step (1) or the step (2) is the same as the mass volume concentration (mg/L) of the hydroxylated carbon nanotubes in the system B.
The mixing volume ratio of the system A to the system B in the step (3) is 1: 0.5; the dispersion method is ultrasonic dispersion, and the dispersion time is 4 hours.
And (4) the nylon filter membrane is a circular filter membrane with the diameter of 0.45 um.
The reaction temperature in the step (5) is 40 ℃, and the reaction time is 1 hour.
And (5) drying at 90 ℃ for 10 hours.
EXAMPLE 2 preparation of carboxyl and hydroxyl esterified self-crosslinking carbon nanotube film in Water System
(1) Adding a carboxylated carbon nanotube into a solvent dissolved with a surfactant to obtain a system A; (2) adding the hydroxylated carbon nano tube into a solvent dissolved with a surfactant to obtain a system B; (3) mixing the system A and the system B, and uniformly dispersing; (4) carrying out suction filtration through a nylon filter membrane to obtain a carbon nano tube film; (5) placing the carbon nano tube film in water, heating to perform a self-crosslinking reaction, and drying after the reaction is finished to obtain a high-flexibility self-crosslinking carbon nano tube film; the above steps are performed in the order of (1), (2), (3) and (4) or in the order of (2), (1), (3) and (4).
And (3) the surfactant in the step (1) or the step (2) is sodium dodecyl benzene sulfonate.
The solvent in the step (1) or the step (2) is deionized water.
The concentration of the surfactant in the solvent in the step (1) or the step (2) is 1000 mg/L.
The mass ratio of the carboxylated carbon nanotubes to the hydroxylated carbon nanotubes to the surfactant in the step (1) or the step (2) is 1: 15.
And (3) respectively carrying out ultrasonic dispersion on the system A and the system B in the step (1) or the step (2) for 12 hours to uniformly disperse the carbon nanotubes.
And (3) the concentration of the carboxylated carbon nanotubes in the system A in the step (1) or the step (2) is the same as the mass volume concentration (mg/L) of the hydroxylated carbon nanotubes in the system B.
The mixing volume ratio of the system A to the system B in the step (3) is 1: 1.5; the dispersion method is ultrasonic dispersion, and the dispersion time is 5 hours.
And (4) the nylon filter membrane is a circular filter membrane with the diameter of 0.45 um.
The reaction temperature in the step (5) is 240 ℃, and the reaction time is 24 hours.
And (5) drying at 90 ℃ for 10 hours.
Example 3 preparation of carboxyl and hydroxyl esterified self-crosslinking carbon nanotube film in Water System
(1) Adding a carboxylated carbon nanotube into a solvent dissolved with a surfactant to obtain a system A; (2) adding the hydroxylated carbon nano tube into a solvent dissolved with a surfactant to obtain a system B; (3) mixing the system A and the system B, and uniformly dispersing; (4) carrying out suction filtration through a nylon filter membrane to obtain a carbon nano tube film; (5) placing the carbon nano tube film in water, heating to perform a self-crosslinking reaction, and drying after the reaction is finished to obtain a high-flexibility self-crosslinking carbon nano tube film; the above steps are performed in the order of (1), (2), (3) and (4) or in the order of (2), (1), (3) and (4).
The surfactant in the step (1) or the step (2) is triton.
The solvent in the step (1) or the step (2) is deionized water.
The concentration of the surfactant in the solvent in the step (1) or the step (2) is 500 mg/L.
The mass ratio of the carboxylated carbon nanotubes to the hydroxylated carbon nanotubes to the surfactant in the step (1) or the step (2) is 1: 8.
And (3) respectively carrying out ultrasonic dispersion on the system A and the system B in the step (1) or the step (2) for 11 hours to uniformly disperse the carbon nanotubes.
And (3) the concentration of the carboxylated carbon nanotubes in the system A in the step (1) or the step (2) is the same as the mass volume concentration (mg/L) of the hydroxylated carbon nanotubes in the system B.
The mixing volume ratio of the system A to the system B in the step (3) is 1: 1.0; the dispersion method is ultrasonic dispersion, and the dispersion time is 4.5 hours.
And (4) the nylon filter membrane is a circular filter membrane with the diameter of 0.45 um.
The reaction temperature in the step (5) is 170 ℃, and the reaction time is 12 hours.
And (5) drying at 90 ℃ for 10 hours.
EXAMPLE 4 preparation of carboxyl and hydroxyl esterified self-crosslinking carbon nanotube film in N-N Dimethylformamide (DMF) System
The difference from example 1 is that: the solvent in the step (1) or the step (2) is N-N Dimethylformamide (DMF).
EXAMPLE 5 preparation of carboxyl and hydroxyl esterified self-crosslinking carbon nanotube film in N-N Dimethylformamide (DMF) System
The difference from example 2 is that: the solvent in the step (1) or the step (2) is N-N Dimethylformamide (DMF).
EXAMPLE 6 preparation of carboxyl and hydroxyl esterified self-crosslinking carbon nanotube film in N-N Dimethylformamide (DMF) System
The difference from example 3 is that: the solvent in the step (1) or the step (2) is N-N Dimethylformamide (DMF).
EXAMPLE 7 preparation of carboxyl and aminoacylation self-crosslinking carbon nanotube film in Water System
The difference from example 1 is that: all the hydroxylated carbon nanotubes in example 1 were replaced with aminated carbon nanotubes.
EXAMPLE 8 preparation of carboxyl and aminoacylation self-crosslinking carbon nanotube film in Water System
The difference from example 2 is that: all the hydroxylated carbon nanotubes in example 1 were replaced with aminated carbon nanotubes.
EXAMPLE 9 preparation of carboxyl and aminoacylation self-crosslinking carbon nanotube film in Water System
The difference from example 3 is that: all the hydroxylated carbon nanotubes in example 1 were replaced with aminated carbon nanotubes.
EXAMPLE 10 preparation of carboxyl and aminoacylation self-crosslinking carbon nanotube film in N-N Dimethylformamide (DMF) System
The difference from example 7 is that: the solvent in the step (1) or the step (2) is N-N Dimethylformamide (DMF).
EXAMPLE 11 preparation of carboxyl and aminoacylation self-crosslinking carbon nanotube film in N-N Dimethylformamide (DMF) System
The difference from example 8 is that: the solvent in the step (1) or the step (2) is N-N Dimethylformamide (DMF).
EXAMPLE 12 preparation of carboxyl and aminoacylation self-crosslinking carbon nanotube film in N-N Dimethylformamide (DMF) System
The difference from example 9 is that: the solvent in the step (1) or the step (2) is N-N Dimethylformamide (DMF).
Comparative example
Preparation process of pure carbon nanotube film, carboxylated carbon nanotube film, hydroxylated carbon nanotube film and aminated carbon nanotube film
Preparing a pure carbon nanotube film:
adding 1g of triton into 1L of distilled water, mechanically stirring for 1 hour to completely dissolve the triton to obtain a dispersant aqueous solution, adding 0.2g of pure single-walled carbon nanotubes into the dispersant aqueous solution, mechanically stirring for 2 hours, then performing ultrasonic dispersion for 2 hours to form a uniformly and stably dispersed carbon nanotube dispersion solution, performing vacuum suction filtration by using a nylon filter membrane through a vacuum suction filtration device to form a carbon nanotube membrane on the filter membrane, respectively filtering and washing for 3 times by using ethanol and distilled water, then putting the carbon nanotube membrane and the filter membrane after suction filtration into a blast oven, heating for 3 hours at 95 ℃, taking out after the temperature is reduced to room temperature, and directly peeling off the nylon filter membrane to obtain the carbon nanopaper.
Preparing a carboxylated carbon nanotube film:
adding 1g of triton into 1L of distilled water, mechanically stirring for 1 hour to completely dissolve the triton to obtain a dispersant aqueous solution, adding 0.2g of carboxylated single-walled carbon nanotubes into the dispersant aqueous solution, mechanically stirring for 2 hours, then performing ultrasonic dispersion for 2 hours to form a uniformly and stably dispersed carbon nanotube dispersion solution, performing vacuum suction filtration by using a nylon filter membrane through a vacuum suction filtration device to form a carbon nanotube membrane on the filter membrane, then respectively filtering and washing for 3 times by using ethanol and distilled water, then putting the carbon nanotube membrane and the filter membrane after suction filtration into a blast oven, heating for 3 hours at 95 ℃, taking out after the temperature is reduced to room temperature, and directly peeling off the nylon filter membrane to obtain the carboxylated carbon nanopaper.
The difference from the preparation of the pure carbon nanotube film is that: the carbon nanotube is a carboxylated carbon nanotube.
Preparing a hydroxylated carbon nanotube film:
adding 1g of triton into 1L of distilled water, mechanically stirring for 1 hour to completely dissolve the triton to obtain a dispersant aqueous solution, adding 0.2g of hydroxylated single-walled carbon nanotubes into the dispersant aqueous solution, mechanically stirring for 2 hours, then performing ultrasonic dispersion for 2 hours to form a uniformly and stably dispersed carbon nanotube dispersion solution, performing vacuum suction filtration by using a nylon filter membrane through a vacuum suction filtration device to form a carbon nanotube membrane on the filter membrane, then respectively filtering and washing for 3 times by using ethanol and distilled water, then putting the carbon nanotube membrane and the filter membrane after suction filtration into a blast oven, heating for 3 hours at 95 ℃, taking out after the temperature is reduced to room temperature, and directly peeling off the nylon filter membrane to obtain the hydroxylated carbon nanopaper.
The difference from the preparation of the pure carbon nanotube film is that: the carbon nanotube is a carboxylated carbon nanotube.
Preparing an aminated carbon nanotube film:
adding 1g of triton into 1L of distilled water, mechanically stirring for 1 hour to completely dissolve the triton to obtain a dispersant aqueous solution, adding 0.2g of aminated single-walled carbon nanotube into the dispersant aqueous solution, mechanically stirring for 2 hours, then performing ultrasonic dispersion for 2 hours to form a uniformly and stably dispersed carbon nanotube dispersion solution, performing vacuum suction filtration by using a nylon filter membrane through a vacuum suction filtration device to form a carbon nanotube membrane on the filter membrane, respectively filtering and washing for 3 times by using ethanol and distilled water, then putting the carbon nanotube membrane and the filter membrane after suction filtration into a blast oven, heating for 3 hours at 95 ℃, taking out after the temperature is reduced to room temperature, and directly peeling off the nylon filter membrane to obtain the aminated carbon nanopaper.
The difference from the preparation of the pure carbon nanotube film is that: the carbon nanotube is an aminated carbon nanotube.
And (3) characterization:
the product prepared in example 2 was used for the carboxyl and hydroxyl esterified self-crosslinking carbon nanotube film prepared in the water system, the product prepared in example 5 was used for the carboxyl and hydroxyl esterified self-crosslinking carbon nanotube film prepared in the N-N Dimethylformamide (DMF) system, the product prepared in example 8 was used for the carboxyl and aminoacylated self-crosslinking carbon nanotube film prepared in the water system, and the product prepared in example 11 was used for the carboxyl and aminoacylated self-crosslinking carbon nanotube film prepared in the N-N Dimethylformamide (DMF) system, and the above products and the products of the comparative examples were subjected to performance characterization.
The invention utilizes the self-crosslinking acylation and esterification reaction between the carboxylated carbon nano tube and the hydroxylated or aminated carbon nano tube in the prepared carbon nano tube film to form the self-crosslinking high-flexibility carbon nano tube film, and a typical digital photo of the self-crosslinking carbon nano tube film with high flexibility is shown in figure 1. FIG. 1.a shows an esterified self-crosslinked carbon nanotube film prepared by hydroxylated carbon nanotubes and carboxylated carbon nanotubes in a deionized water solution system. FIG. 1.b is an esterified self-crosslinking carbon nanotube film prepared from hydroxylated carbon nanotubes and carboxylated carbon nanotubes in an N-N dimethylformamide solution system. FIG. 1.c shows the acylated self-crosslinked carbon nanotube film prepared by aminated carbon nanotube and carboxylated carbon nanotube in deionized water solution system. FIG. 1.d shows the acylated self-crosslinked carbon nanotube film prepared with aminated carbon nanotube and carboxylated carbon nanotube in N-N dimethyl formamide solution system. As can be seen from the figure, the four carbon nanotube films have flat and smooth surfaces and obvious metallic luster, which is because the carbon nanotubes have certain metallic properties.
FIG. 2 is a comparison of the microscopic morphologies of different types of self-crosslinked carbon nanotube films, in which a pure carbon nanotube film, a carboxylated carbon nanotube film, a hydroxylated carbon nanotube film, an aminated carbon nanotube film, a carboxyl and hydroxyl esterified self-crosslinked carbon nanotube film prepared in a water system, a carboxyl and hydroxyl esterified self-crosslinked carbon nanotube film prepared in an N-N Dimethylformamide (DMF) system, a carboxyl and aminoacylated self-crosslinked carbon nanotube film prepared in a water system, and a carboxyl and aminoacylated self-crosslinked carbon nanotube film prepared in an N-N Dimethylformamide (DMF) system are represented by a), b), c), d), e), f), g), and h), respectively. As can be seen from the figure, the carbon nanotube film is formed by freely distributing and overlapping carbon nanotube bundles, and the carbon nanotube film has a porous structure, so that the disordered carbon nanotube film has isotropy. However, comparing fig. 2a) -h), it can be seen that the carboxyl and hydroxyl esterified self-crosslinking carbon nanotube film prepared in the water system and the carboxyl and aminoacylated self-crosslinking carbon nanotube film prepared in the water system have higher tightness and smaller surface pore size. This is due to the higher strength of the interaction between the carbon nanotubes, and it can be concluded that the carbon nanotube film prepared in the water system has a higher number of chemical bonds. So that the carboxyl and hydroxyl esterified self-crosslinking carbon nano tube film prepared in the water system and the carboxyl and amino acylated self-crosslinking carbon nano tube film prepared in the water system have better mechanical properties.
For example, as shown in fig. 3, the mechanical properties of the self-crosslinking carbon nanotube film prepared by the invention are superior to those of a carboxyl, amino and hydroxyl functionalized carbon nanotube film of a control group, and the mechanical properties of the self-crosslinking carbon nanotube film of esterification reaction or the acylated self-crosslinking carbon nanotube film are also superior to those of the carbon nanotube film of the control group. The acylation self-crosslinking carbon nano tube film prepared in a water system has the best comprehensive mechanical property, the stress and the strain are 59.22MPa and 12.15 percent respectively, and compared with a pure carbon nano tube film, the stress and the strain are improved by 3.32 times and 14.82 times respectively. In conclusion, the method provided by the invention improves the mechanical property of the carbon nanotube film, so that the preparation method of the self-crosslinking carbon nanotube film is an effective means for improving the mechanical property of the carbon nanotube film, and the acylation self-crosslinking reaction is most beneficial to improving the mechanical property of the carbon nanotube film in a water system.
The pair of electrical properties of the self-crosslinked carbon nanotube film prepared by the present invention is shown in table 1. The measurement of the slice resistivity of the carbon nanotube film of the different kinds of control group and the self-crosslinked carbon nanotube film was measured by a four-point probe method, and the slice resistivity of the carbon nanotube film of the different kinds of control group and the self-crosslinked carbon nanotube film was as shown in table 1. In the contrast group, the resistivity arrangement sequence of the carbon nano tube film is that a pure carbon nano tube film is larger than a carboxylated carbon nano tube film is larger than an aminated carbon nano tube film is larger than a hydroxylated carbon nano tube film, the average slice resistivity of the self-crosslinked carbon nano tube film is vertically floated on the average value of the sum of the slice resistivities of the films made of two carbon nano tubes forming the self-crosslinked carbon nano tube film, the slice resistivity of the single-component functionalized carbon nano tube film is not greatly different from that of the contrast group, the slice resistivity of the self-crosslinked carbon nano tube film prepared in a DMF system is higher than that of the self-crosslinked carbon nano tube film prepared in a water system, the slice resistivity of the esterified self-crosslinked carbon nano tube film is lower than that of the acylated self-crosslinked carbon nano tube film, and the slice resistivity arrangement sequence of the self-crosslinked carbon nano tube film is that the acylated self-crosslinked carbon nano tube film (DMF system) is larger than that of the esterified self-crosslinked carbon nano tube film System) > esterification self-crosslinking carbon nanotube film (water system).
Claims (10)
1.A preparation method of a high-flexibility self-crosslinking carbon nanotube film is characterized by comprising the following steps: the method comprises the following steps:
(1) adding a carboxylated carbon nanotube into a solvent dissolved with a surfactant to obtain a system A;
(2) adding a hydroxylated carbon nano tube or an aminated carbon nano tube into a solvent dissolved with a surfactant to obtain a system B;
(3) mixing the system A and the system B, and uniformly dispersing;
(4) carrying out suction filtration through a nylon filter membrane to obtain a carbon nano tube film;
(5) placing the carbon nano tube film in water, heating to perform a self-crosslinking reaction, and drying after the reaction is finished to obtain a high-flexibility self-crosslinking carbon nano tube film;
the above steps are performed in the order of (1), (2), (3) and (4) or in the order of (2), (1), (3) and (4).
2. The method of claim 1, wherein: the surfactant in the step (1) or the step (2) is one or two or three of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate and triton.
3. The method of claim 1, wherein: the solvent in the step (1) or the step (2) is one or two or three of deionized water, N-N dimethylformamide or N-methylpyrrolidone.
4. The method of claim 1, wherein: the concentration of the surfactant in the solvent in the step (1) or the step (2) is 50-1000 mg/L.
5. The method of claim 1, wherein: the mass ratio of the carboxylated carbon nanotubes, the hydroxylated carbon nanotubes or the aminated carbon nanotubes to the surfactant in the step (1) or the step (2) is 1 (1-15).
6. The method of claim 1, wherein: and (3) respectively carrying out ultrasonic dispersion on the system A and the system B for 10-12 hours in the step (1) or the step (2).
7. The method of claim 1, wherein: the concentration of the carboxylated carbon nanotubes in the system A in the step (1) or the step (2) is the same as that of the hydroxylated carbon nanotubes or the aminated carbon nanotubes in the system B, and the concentration is mass volume concentration, and the unit is mg/L.
8. The method of claim 7, wherein: the mixing volume ratio of the system A to the system B in the step (3) is 1 (0.5-1.5); the dispersion method is ultrasonic dispersion, and the dispersion time is 4-5 hours.
9. The method of claim 1, wherein: the reaction temperature in the step (5) is 40-240 ℃, and the reaction time is 1-24 hours.
10. The method of claim 1, wherein: and (5) drying at 90 ℃ for 10 hours.
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| JP2008127675A (en) * | 2006-11-24 | 2008-06-05 | Univ Nihon | Hydrophilic polymeric modified carbon nanotube film |
| CN101249957A (en) * | 2008-02-28 | 2008-08-27 | 上海应用技术学院 | Carbon nano-tube having quaternary amines group on surface and preparation thereof |
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| CN1844209A (en) * | 2006-03-14 | 2006-10-11 | 同济大学 | Process for preparing multifunctional carbon nanotube for epoxy resin nano composites |
| JP2008127675A (en) * | 2006-11-24 | 2008-06-05 | Univ Nihon | Hydrophilic polymeric modified carbon nanotube film |
| CN101249957A (en) * | 2008-02-28 | 2008-08-27 | 上海应用技术学院 | Carbon nano-tube having quaternary amines group on surface and preparation thereof |
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