CN110436443B - Carbon nano tube dispersing agent and preparation method and application thereof - Google Patents
Carbon nano tube dispersing agent and preparation method and application thereof Download PDFInfo
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- C01B32/00—Carbon; Compounds thereof
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- C01B32/15—Nano-sized carbon materials
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- C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
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- C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
- C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
- C08F299/026—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight
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- C01B2202/06—Multi-walled nanotubes
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- C01B2202/20—Nanotubes characterized by their properties
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Abstract
The invention discloses a carbon nano tube dispersing agent, a preparation method and application thereof, wherein the carbon nano tube dispersing agent contains a copolymer of poly (ethylene glycol) phenyl ether acrylic acid and poly (ethylene glycol) methyl ether acrylic ester. The carbon nano tube dispersing agent has remarkable dispersing effect on the carbon nano tube in water and organic solvents, and the minimum use amount of the dispersing agent can be reduced to 10% of the total mass of the carbon nano tube.
Description
Technical Field
The invention belongs to the technical field of carbon nanotubes, and particularly relates to a carbon nanotube dispersing agent, a preparation method and application thereof.
Background
Carbon Nanotubes (CNTs) were found in 1991 and have been known for 30 years. The carbon nano tube has excellent performances such as extremely high modulus, tensile strength, ultra-high toughness and the like, and becomes a preferred additive of the high-performance composite material. However, since the carbon nanotubes are nano-materials, they are extremely easy to aggregate, and if they cannot be dispersed in the material effectively, their reinforcing effect on the material will be greatly reduced. An important issue in the current carbon nanotube research is to solve the dispersion of carbon nanotubes in various media such as solvents, polymers, cements, ceramics, etc., and the compatibility between interfaces.
The dispersion technology of CNTs can be classified into physical dispersion and chemical dispersion from the current literature. The physical dispersion method mainly comprises high-energy ball milling, ultrasonic oscillation, electric field induction, high-speed shearing, centrifugal stirring and the like. The chemical dispersion method mainly comprises a mixed acid oxidation method, a surfactant method and the like. Research shows that the agglomeration phenomenon of CNTs can not be overcome basically by using a physical dispersion method, and the length-diameter ratio of CNTs is easy to reduce, so that the CNTs can be shortened when being treated by using a physical method. [ Wu Xiwang, xiaoFeng, etc. ] -method and mechanism for dispersing nanotubes. Material guidance: summary, 2011, 25:16]
The mixed acid oxidation method can oxidize the surfaces of CNTs, and the surfaces of CNTs are provided with hydrophilic groups such as hydroxyl groups, carboxyl groups and the like, so that the dispersion of CNTs in an aqueous system is promoted. However, this approach also tends to disrupt the microstructure of CNTs and thus affect their properties, particularly electrical properties. The surfactant forms micelle layer or adsorption layer on the surface of CNTs through non-covalent bond, and promotes the dispersion of CNTs through steric hindrance rejection. The method can also improve the compatibility of CNTs and other substances, has no damage to the structure of CNTs, and has limited capability of overcoming agglomeration. At present, scholars at home and abroad comprehensively and cooperatively use a plurality of dispersing methods for the dispersing process of CNTs, and obtain good effects. [ Cui Hongzhi, yang Jiaming, lin, development of carbon nanotube dispersing technology and carbon nanotube and cement-based composite materials, material guide A: review, 2016,30:91]
It is considered that both physical and chemical dispersion of carbon nanotubes may deteriorate the properties of carbon nanotubes, such as aspect ratio and conductivity. Accordingly, the current dispersion technology of carbon nanotubes is still further improved.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, an object of the present invention is to provide a carbon nanotube dispersing agent, a preparation method and an application thereof, wherein the carbon nanotube dispersing agent has a remarkable dispersing effect on carbon nanotubes in both aqueous and organic solvents, and the minimum use amount of the carbon nanotube dispersing agent can be reduced to 10% of the total mass of the carbon nanotubes.
According to one aspect of the present invention, a carbon nanotube dispersant is provided, which according to an embodiment of the present invention contains a copolymer of poly (ethylene glycol) phenyl ether acrylic acid and poly (ethylene glycol) methyl ether acrylate.
The present inventors completed based on the following findings:
the inventor finds that the copolymer obtained by copolymerizing poly (ethylene glycol) phenyl ether acrylic acid and poly (ethylene glycol) methyl ether acrylic acid ester contains a nonionic hydrophilic monomer and a monomer containing a benzene ring structure, wherein the nonionic unit can provide steric hindrance and the dissolving capability in aqueous and oily solvents, and the benzene ring structural unit can generate an electronic attraction effect similar to pi-pi superposition due to the similarity of a five-membered ring or a six-membered ring structure on a carbon nano tube, and can further form good affinity with the carbon nano tube so as to be adsorbed on the surface of the carbon nano tube. Accordingly, the inventors have found that the copolymer is used as a carbon nanotube dispersing agent, and that the dispersing effect is very excellent and that the copolymer has a good dispersing effect on carbon nanotubes in both an aqueous medium and an organic solvent medium.
According to a second aspect of the present invention, there is provided a method of preparing a carbon nanotube dispersant, according to an embodiment of the present invention, the method comprising: and (3) carrying out copolymerization reaction on poly (ethylene glycol) phenyl ether acrylic acid and poly (ethylene glycol) methyl ether acrylic ester so as to obtain the carbon nano tube dispersing agent. Therefore, the method for preparing the carbon nanotube dispersing agent has the advantages of low cost of raw materials, simple synthesis method, only one-step copolymerization reaction, and easiness in carrying out the copolymerization reaction.
In addition, the method for preparing a carbon nanotube dispersing agent according to the above embodiment of the present invention may have the following additional technical features:
in some embodiments of the invention, the copolymerization is carried out in an organic solvent, which is an alcoholic solvent, an ester solvent, a ketone solvent, an aromatic solvent, N-methylpyrrolidone, or N, N-dimethylformamide.
In some embodiments of the invention, the copolymerization is performed in an inorganic solvent, which is water or brine.
In some embodiments of the invention, the mass ratio of the poly (ethylene glycol) methyl ether acrylate to the poly (ethylene glycol) phenyl ether acrylic acid is (2-4): 1. thereby, the qualified copolymer can be effectively prepared.
In some embodiments of the present invention, the method for preparing a carbon nanotube dispersing agent of the above embodiments includes:
(1) The mass ratio of N, N-dimethylformamide, poly (ethylene glycol) methyl ether acrylate to poly (ethylene glycol) phenyl ether acrylic acid is 40:4: (1-2) mixing, and introducing nitrogen to deoxidize for 20 minutes;
(2) Adding a proper amount of azodiisobutyronitrile as an initiator, and carrying out copolymerization reaction on the poly (ethylene glycol) methyl ether acrylate and the poly (ethylene glycol) phenyl ether acrylic acid for 5-8 hours at the temperature of 60-100 ℃;
(3) The solvent was removed by rotary evaporation to obtain the carbon nanotube dispersant.
According to a third aspect of the present invention, the present invention also provides a method for preparing a carbon nanotube dispersion slurry, which uses the carbon nanotube dispersing agent described in the previous embodiments according to the embodiment of the present invention.
In addition, the method for preparing a carbon nanotube dispersion slurry according to the above embodiment of the present invention may have the following additional technical features:
in some embodiments of the present invention, the method for preparing a carbon nanotube dispersion slurry includes: and dissolving the carbon nanotube dispersing agent into a solvent in advance, and then adding the carbon nanotubes for dispersing so as to obtain the carbon nanotube dispersing slurry.
In some embodiments of the invention, the mass ratio of the carbon nanotubes to the carbon nanotube dispersant is (10-1): (1-10), preferably (3-1): (1-3).
In some embodiments of the invention, the carbon nanotube dispersion slurry comprises: 0.1 to 10 weight parts of carbon nano tube, 0.01 to 10 weight parts of carbon nano tube dispersing agent and 80 to 99.9 weight parts of solvent.
In some embodiments of the invention, the carbon nanotubes are single-walled carbon nanotubes or multi-walled carbon nanotubes and the solvent is water or an organic solvent. Therefore, the carbon nanotube dispersing agent of the embodiment of the invention has wide applicability, has good dispersing effect on single-wall carbon nanotubes and multi-wall carbon nanotubes, and also has good dispersing effect on carbon nanotubes in water and organic solvent media.
Drawings
FIG. 1 is a dispersion state of a carbon nanotube dispersion slurry prepared in example 4 of the present invention.
FIG. 2 is a dispersion state of a carbon nanotube dispersion slurry prepared in example 5 of the present invention.
FIG. 3 is a dispersion state of the carbon nanotube dispersion slurry prepared in comparative example 1 of the present invention.
Fig. 4 is a dispersion state of the carbon nanotube dispersion slurry prepared in comparative example 2 of the present invention.
Detailed Description
The following detailed description of embodiments of the invention is exemplary and intended to be illustrative of the invention and not to be construed as limiting the invention.
According to one aspect of the present invention, a carbon nanotube dispersant is provided. According to an embodiment of the present invention, the carbon nanotube dispersant contains a copolymer of poly (ethylene glycol) phenyl ether acrylic acid and poly (ethylene glycol) methyl ether acrylate.
Thus, the carbon nanotube dispersing agent of the embodiment of the invention is obtained by a random copolymerization method of at least two different functional monomers, namely, a copolymer containing at least one nonionic hydrophilic monomer and at least one monomer containing at least one benzene ring structure. The inventor finds that the poly (ethylene glycol) phenyl ether acrylic acid has a benzene ring structure, and the benzene ring structure is similar to a five-membered ring or a six-membered ring structure on the carbon nano tube, so that a pi-pi superposition-like effect can be generated with the carbon nano tube, and the copolymer is easy to adsorb on the surface of the carbon nano tube; and the side chain of the copolymer, namely poly (ethylene glycol) methyl ether acrylate, can provide steric hindrance, so that the aggregation of the carbon nano tubes is effectively prevented, the dispersing effect is outstanding, and meanwhile, the dispersibility of the carbon nano tubes in other resins is enhanced.
In addition, experiments prove that after the carbon nanotube dispersing agent provided by the embodiment of the invention is added, the dispersibility of the carbon nanotubes is obviously improved in water or an organic solvent, so that the carbon nanotube dispersing agent provided by the embodiment of the invention is a universal dispersing agent. And the dispersing effect is outstanding, the using amount is very small, and the minimum using amount is only 10% of the total mass of the carbon nano tube, so that the cost can be reduced, and the influence of the dispersing agent on the performance of the resin composite material, such as processability, mechanical property, durability and the like, can be obviously reduced.
According to a second aspect of the present invention, there is provided a method of preparing a carbon nanotube dispersant, according to an embodiment of the present invention, the method comprising: poly (ethylene glycol) phenyl ether acrylic acid and poly (ethylene glycol) methyl ether acrylate are subjected to copolymerization reaction. Therefore, the method for preparing the carbon nanotube dispersing agent has the advantages of low cost of raw materials, simple synthesis method, only one-step copolymerization reaction, and easiness in carrying out the copolymerization reaction.
According to an embodiment of the present invention, the copolymerization of poly (ethylene glycol) phenyl ether acrylic acid and poly (ethylene glycol) methyl ether acrylate may be performed in an organic solvent, for example, in an alcohol solvent, an ester solvent, a ketone solvent, an aromatic hydrocarbon solvent, N-methylpyrrolidone, or N, N-dimethylformamide. Therefore, the copolymerization reaction is easy to carry out, and the reaction conditions are warm. After the copolymerization reaction is completed, the solvent may be recovered by evaporation.
According to an embodiment of the present invention, the above-mentioned copolymerization is preferably performed in N, N-dimethylformamide, whereby the effect of the copolymerization can be further improved.
The copolymerization reaction described above may also be carried out in an inorganic solvent, for example, in water or brine, according to an embodiment of the present invention. Therefore, the method for preparing the carbon nano tube has the advantages of mild conditions, low cost, no pollution and no special environmental requirement.
According to the specific embodiment of the invention, in the method for preparing the carbon nanotube dispersing agent, the mass ratio of the poly (ethylene glycol) methyl ether acrylate to the poly (ethylene glycol) phenyl ether acrylic acid serving as a copolymerization reaction raw material is (2-4): 1. the inventors have found that, in the above mass ratio, it is possible to ensure that there are both sufficient benzene ring groups to cause the dispersant to adsorb onto the carbon nanotubes and sufficient poly (ethylene glycol) methyl ether groups to provide steric hindrance to cause the carbon nanotubes to disperse. In addition, the mass ratio can be adopted to effectively prepare qualified copolymer, preferably the molecular weight of the copolymer is 5000-200000, if the mass ratio is too large or too small, the molecular weight of the copolymer finally prepared can be influenced, and if the molecular weight is too small, the volume steric hindrance provided by the dispersing agent is not large enough, and the dispersing effect is poor; if the molecular weight is too large, the dispersant molecules may be simultaneously connected to a plurality of carbon nanotubes, so that the nanotubes are more unevenly dispersed.
According to a specific embodiment of the present invention, the method for preparing a carbon nanotube dispersing agent according to the above embodiment specifically includes: (1) The mass ratio of N, N-dimethylformamide, poly (ethylene glycol) methyl ether acrylate to poly (ethylene glycol) phenyl ether acrylic acid is 40:4: (1-2) mixing, and introducing nitrogen to deoxidize for 20 minutes; (2) Adding a proper amount of azodiisobutyronitrile as an initiator, and carrying out copolymerization reaction on the poly (ethylene glycol) methyl ether acrylate and the poly (ethylene glycol) phenyl ether acrylic acid for 5-8 hours at the temperature of 60-100 ℃; (3) The solvent was removed by rotary evaporation to obtain the carbon nanotube dispersant.
Therefore, the copolymer of poly (ethylene glycol) phenyl ether acrylic acid and poly (ethylene glycol) methyl ether acrylic ester can be effectively prepared by adopting the method. Particularly, by adopting the reaction conditions, the copolymer with proper molecular weight can be prepared, and further the dispersion effect of the carbon nano tube can be obviously improved.
According to a third aspect of the present invention, the present invention also provides a method for preparing a carbon nanotube dispersion slurry, which uses the carbon nanotube dispersing agent described in the previous embodiments according to the embodiment of the present invention.
Thus, in the carbon nanotube dispersing slurry prepared by using the carbon nanotube dispersing agent in the previous embodiment, the carbon nanotubes have good dispersing effect and almost no agglomeration phenomenon. Therefore, the carbon nano tube dispersion slurry is adopted to prepare the composite material, so that the carbon nano tube can be uniformly dispersed in various materials, the performances of high modulus, high stretching, ultrahigh toughness and the like of the carbon nano tube can be furthest exerted, and the reinforcing effect of the composite material can be remarkably improved. Meanwhile, as the dispersibility of the carbon nano tube is good, the maximum enhancement effect can be achieved by using the minimum dosage, so that the dosage can be reduced, and the cost for preparing the composite material is reduced.
According to an embodiment of the present invention, the method for preparing the carbon nanotube dispersion slurry specifically includes: and dissolving the carbon nanotube dispersing agent into a solvent in advance, and then adding the carbon nanotubes for dispersing so as to obtain the carbon nanotube dispersing slurry. Thus, the dispersion effect of the carbon nanotubes can be further improved by adopting the above-mentioned mixing effect.
According to the specific embodiment of the invention, after the carbon nanotubes are added, the carbon nanotubes can be uniformly dispersed by grinding, ultrasonic, high-speed dispersion and the like.
According to the embodiment of the invention, in the method for preparing the carbon nano tube dispersion slurry, the mass ratio of the carbon nano tube to the carbon nano tube dispersing agent is (10-1): 1-10, namely that the minimum using amount of the carbon nano tube dispersing agent can be 10% of the carbon nano tube. Therefore, the carbon nano tube dispersing agent provided by the embodiment of the invention has good dispersing effect, so that the dosage is less and the cost is lower.
According to a specific embodiment of the present invention, the mass ratio of the carbon nanotubes to the carbon nanotube dispersing agent is preferably (3-1):
(1-3). The dispersing effect of the carbon nano tube dispersing agent is optimal in the dosage range.
According to an embodiment of the present invention, the carbon nanotube dispersion slurry prepared by the above method comprises: 0.1 to 10 weight parts of carbon nano tube, 0.01 to 10 weight parts of carbon nano tube dispersing agent and 80 to 99.9 weight parts of solvent. Therefore, the carbon nanotube dispersing agent can disperse carbon nanotubes with the concentration of 0.1-10% by weight, so that a good dispersing effect can be achieved on the carbon nanotubes with high concentration.
According to an embodiment of the present invention, the carbon nanotubes in the carbon nanotube dispersion slurry prepared above may be single-walled carbon nanotubes or multi-walled carbon nanotubes. Therefore, the carbon nanotube dispersing agent provided by the embodiment of the invention has good dispersing effect on single-wall carbon nanotubes and multi-wall carbon nanotubes, and the application range of the carbon nanotube dispersing agent is obviously improved.
According to an embodiment of the present invention, the solvent in the carbon nanotube dispersion slurry prepared as described above may be water or an organic solvent. The copolymer of the carbon nanotube dispersing agent provided by the embodiment of the invention has nonionic units, and further has dissolving capacity in both aqueous and organic solvents, so that the carbon nanotube dispersing agent can be used for dispersing carbon nanotubes in water and carbon nanotubes in organic solvents.
Example 1
Preparation of carbon nanotube dispersant
On a magnetically stirred controlled heater equipped (oil bath heating), a 500mL round bottom reaction flask was fitted, placed in a magnetic stirrer, 200 g of N, N-dimethylformamide, 20 g of poly (ethylene glycol) methyl ether acrylate (mn=950, from SIGMA-ALDRICH, purified with neutral aluminum trioxide before use) and 5g of poly (ethylene glycol) phenyl ether acrylic acid (mn=324, from SIGMA-ALDRICH, purified with neutral aluminum trioxide before use) were added, then magnetic stirring was turned on, and deoxygenated with nitrogen for 20 minutes, then 0.1 g of Azobisisobutyronitrile (AIBN) was added as initiator. The reaction is carried out at 80 ℃, heating is stopped after 5 hours, the round bottom flask is taken out, the round bottom flask is naturally cooled to room temperature, and then the solvent is removed by a rotary evaporation method (the solvent can be recycled) to obtain the solid carbon nano tube dispersing agent.
The resulting copolymer had a molecular weight Mn of 22569 g/mol and a molecular weight distribution Mw/mn=1.95. Molecular weight was determined by Gel Permeation Chromatography (GPC) with a parallax refractive detector, calibrated with polystyrene PS, tetrahydrofuran as the mobile phase.
Example 2
Preparation of carbon nanotube dispersant
On a magnetically stirred controlled heater equipped (oil bath heating), a 500mL round bottom reaction flask was fitted, placed in a magnetic stirrer, 200 g of N, N-dimethylformamide, 20 g of poly (ethylene glycol) methyl ether acrylate (mn=500, from SIGMA-ALDRICH, purified with neutral aluminum trioxide before use) and 5g of poly (ethylene glycol) phenyl ether acrylic acid (mn=324, from SIGMA-ALDRICH, purified with neutral aluminum trioxide before use) were added, then magnetic stirring was turned on, and deoxygenated with nitrogen for 20 minutes, then 0.05 g of Azobisisobutyronitrile (AIBN) was added as initiator. The reaction is carried out at 80 ℃, heating is stopped after 8 hours, the round bottom flask is taken out, the round bottom flask is naturally cooled to room temperature, and then the solvent is removed by a rotary evaporation method (the solvent can be recycled) to obtain the solid carbon nano tube dispersing agent.
The resulting copolymer had a molecular weight Mn of 113333 g/mol and a molecular weight distribution Mw/mn=3.23. Molecular weight was determined by Gel Permeation Chromatography (GPC) with a parallax refractive detector, calibrated with polystyrene PS, tetrahydrofuran as the mobile phase.
Example 3
Preparation of carbon nanotube dispersant
On a magnetically stirred controlled heater equipped (oil bath heating), a 500mL round bottom reaction flask was fitted, placed in a magnetic stirrer, 200 g of N, N-dimethylformamide, 20 g of poly (ethylene glycol) methyl ether acrylate (mn=500, from SIGMA-ALDRICH, purified with neutral aluminum trioxide before use) and 10g of poly (ethylene glycol) phenyl ether acrylic acid (mn=324, from SIGMA-ALDRICH, purified with neutral aluminum trioxide before use) were added, then magnetic stirring was turned on, and deoxygenated with nitrogen for 20 minutes, then 0.1 g of Azobisisobutyronitrile (AIBN) was added as initiator. The reaction is carried out at 80 ℃, heating is stopped after 8 hours, the round bottom flask is taken out, the round bottom flask is naturally cooled to room temperature, and then the solvent is removed by a rotary evaporation method (the solvent can be recycled) to obtain the solid carbon nano tube dispersing agent.
The resulting copolymer had a molecular weight Mn of 42563 g/mol and a molecular weight distribution Mw/mn=2.56. Molecular weight was determined by Gel Permeation Chromatography (GPC) with a parallax refractive detector, calibrated with polystyrene PS, tetrahydrofuran as the mobile phase.
Example 4
Preparation of carbon nanotube Dispersion slurry (carbon nanotube dispersing agent prepared by Using example 1)
10g of the carbon nanotube dispersing agent prepared in example 1 was added to 1000g of deionized water, mixed uniformly, and put into a cylindrical metal container together with 10g of commercially available multiwall carbon nanotubes, and immersed for 30 minutes. Then, the mixture was subjected to ultrasonic dispersion treatment with an ultrasonic probe for 10 minutes (50% power, ultrasonic cell tissue pulverizer (20 KHz,1500W, sony ultrasonic Co., ltd.) using a high-speed shearing and dispersing machine (2000 rpm, WRL type high-shearing homogenizing emulsifying machine type I, winz lozenges mechanical technologies Co., ltd.) in order, and high-speed shearing and dispersing for 10 minutes (2000 rpm). Finally, the carbon nano tube dispersion slurry with uniform dispersion is obtained.
In the obtained carbon nanotube dispersion slurry, the concentration of the carbon nanotubes is 1 weight percent, and the mass ratio of the carbon nanotube dispersing agent to the carbon nanotubes is 1:1.
example 5
Preparation of carbon nanotube Dispersion slurry (carbon nanotube dispersing agent prepared Using example 2)
5g of the carbon nanotube dispersing agent prepared in example 2 was added to 500g N-methylpyrrolidone (NMP), mixed uniformly, and put into a cylindrical metal vessel together with 5g of commercially available multi-walled carbon nanotubes, and immersed for 30 minutes. Then, the mixture was subjected to ultrasonic dispersion treatment with an ultrasonic probe for 10 minutes (50% power, ultrasonic cell tissue pulverizer (20 KHz,1500W, sony ultrasonic Co., ltd.) using a high-speed shearing and dispersing machine (2000 rpm, WRL type high-shearing homogenizing emulsifying machine type I, winz lozenges mechanical technologies Co., ltd.) in order, and high-speed shearing and dispersing for 10 minutes (2000 rpm). Finally, the carbon nano tube dispersion slurry with uniform dispersion is obtained.
In the obtained carbon nanotube dispersion slurry, the concentration of the carbon nanotubes is 1 weight percent, and the mass ratio of the carbon nanotube dispersing agent to the carbon nanotubes is 1:1.
example 6
Preparation of carbon nanotube Dispersion slurry (carbon nanotube dispersing agent prepared Using example 3)
10g of the carbon nanotube dispersing agent prepared in example 3 was added to 500g of dimethyl sulfoxide (DMSO), mixed well, and put into a cylindrical metal container together with 10g of commercially available multi-wall carbon nanotubes, and immersed for 30 minutes. Then, the mixture was subjected to ultrasonic dispersion treatment with an ultrasonic probe for 10 minutes (50% power, ultrasonic cell tissue pulverizer (20 KHz,1500W, sony ultrasonic Co., ltd.) using a high-speed shearing and dispersing machine (2000 rpm, WRL type high-shearing homogenizing emulsifying machine type I, winz lozenges mechanical technologies Co., ltd.) in order, and high-speed shearing and dispersing for 10 minutes (2000 rpm). Finally, the carbon nano tube dispersion slurry with uniform dispersion is obtained.
In the obtained carbon nanotube dispersion slurry, the concentration of the carbon nanotubes is 2 weight percent, and the mass ratio of the carbon nanotube dispersing agent to the carbon nanotubes is 1:1.
comparative example 1
Preparation of carbon nanotube Dispersion slurry (without dispersant)
1000g deionized water was placed in a cylindrical metal container along with 10g of commercially available multi-walled carbon nanotubes and immersed for 30 minutes. Then, the mixture was subjected to ultrasonic dispersion treatment with an ultrasonic probe for 10 minutes (50% power, ultrasonic cell tissue pulverizer (20 KHz,1500W, sony ultrasonic Co., ltd.) using a high-speed shearing and dispersing machine (2000 rpm, WRL type high-shearing homogenizing emulsifying machine type I, winz lozenges mechanical technologies Co., ltd.) in order, and high-speed shearing and dispersing for 10 minutes (2000 rpm). Finally, the carbon nano tube dispersion slurry with uniform dispersion is obtained.
The concentration of carbon nanotubes in the obtained carbon nanotube dispersion slurry was 1 wt%.
Comparative example 2
Preparation of carbon nanotube Dispersion slurry (without dispersant)
500g N-methylpyrrolidone (NMP) was placed in a cylindrical metal vessel together with 10g of commercially available multi-walled carbon nanotubes and immersed for 30 minutes. Then, the mixture was subjected to ultrasonic dispersion treatment with an ultrasonic probe for 10 minutes (50% power, ultrasonic cell tissue pulverizer (20 KHz,1500W, sony ultrasonic Co., ltd.) using a high-speed shearing and dispersing machine (2000 rpm, WRL type high-shearing homogenizing emulsifying machine type I, winz lozenges mechanical technologies Co., ltd.) in order, and high-speed shearing and dispersing for 10 minutes (2000 rpm). Finally, the carbon nano tube dispersion slurry with uniform dispersion is obtained.
The concentration of carbon nanotubes in the resulting carbon nanotube dispersion slurry was 2 wt%.
Representation of the state of dispersion
Sample preparation:
the carbon nanotube dispersion slurries prepared in example 4, example 5, comparative example 1 and comparative example 2 were each dispersed in 0.1 g of deionized water, respectively, and were slightly stirred and uniformly dispersed to obtain samples to be measured.
Sample detection:
and respectively taking 1 drop of a sample to be measured on the copper mesh covered with the carbon film, and naturally airing. The dispersion state was checked by transmission electron microscopy. The results are shown in FIGS. 1-4, respectively.
Conclusion:
as can be seen from fig. 1 to 2, the carbon nanotubes in the carbon nanotube dispersion slurries prepared in example 4 and example 5 were dispersed with little large-area agglomeration, and the distribution was uniform although there was less entanglement; as can be seen from fig. 3 to 4, the carbon nanotubes in the carbon nanotube dispersion slurry prepared in comparative example 1 and comparative example 2, to which the dispersant was not added, were severely entangled with each other and distributed in a cluster. It can be confirmed that the carbon nanotube dispersing agent prepared by using examples 1 and 2 of the present invention and the method of using the same have a very good dispersing effect on carbon nanotubes.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (2)
1. A method of preparing a carbon nanotube dispersion slurry comprising: dissolving a carbon nanotube dispersing agent into a solvent in advance, adding carbon nanotubes, adsorbing the carbon nanotube dispersing agent on the surface of the carbon nanotubes to disperse the carbon nanotubes so as to obtain carbon nanotube dispersing slurry,
the preparation method of the carbon nano tube dispersing agent comprises the following steps:
(1) The mass ratio of N, N-dimethylformamide, poly (ethylene glycol) methyl ether acrylate to poly (ethylene glycol) phenyl ether acrylic acid is 40:4: (1-2) mixing, and introducing nitrogen to deoxidize for 20 minutes;
(2) Adding a proper amount of azodiisobutyronitrile as an initiator, and carrying out copolymerization reaction on the poly (ethylene glycol) methyl ether acrylate and the poly (ethylene glycol) phenyl ether acrylic acid for 5-8 hours at the temperature of 80 ℃;
(3) Removing the solvent by rotary evaporation so as to obtain the carbon nanotube dispersing agent;
the carbon nanotube dispersion slurry comprises: 0.1 to 10 weight parts of carbon nano tube, 0.01 to 10 weight parts of carbon nano tube dispersing agent and 80 to 99.9 weight parts of solvent.
2. The method of claim 1, wherein the carbon nanotubes are single-walled carbon nanotubes or multi-walled carbon nanotubes.
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