CN108047564B - Conductive plastic and preparation method thereof - Google Patents
Conductive plastic and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a conductive plastic and a preparation method thereof, wherein the method comprises the following steps: (1) premixing graphene powder and polymer particles to obtain a premix; (2) mixing the premix with the carbon nano tube powder to obtain a mixture; (3) and carrying out extrusion granulation or injection molding on the mixture to obtain the conductive plastic. Therefore, the graphene powder and the polymer particles are premixed, so that the surface of the polymer particles is completely covered or partially covered with a layer of graphene powder, the polymer particles and the graphene powder are in surface-to-surface contact, and the contact resistance is small; then mixing the obtained premix with carbon nanotube powder, wherein the carbon nanotube can form a conductive network, the graphene powder can play a role in linking and bridging and is contacted with the carbon nanotube to form a linking point, and then the mixture is extruded for granulation or injection molding or compression molding to form conductive plastic with strong conductive capability and high stability.
Description
Technical Field
The invention belongs to the field of plastics, and particularly relates to conductive plastic and a preparation method thereof.
Background
Most of the fillers for the current conductive plastics are conductive carbon black, metal fibers, carbon nanotubes and the like, and a small part of documents use graphene as the conductive filler. The effect is better by two nano fillers, namely lamellar graphene and carbon nano tube. However, the problem that the graphene is difficult to disperse and the stability of the conductive network is slightly poor when the graphene filler is simply added exists. And the simple addition of CNT as filler results in high contact resistance between polymer particles and carbon nanotubes, and poor stability of the conductive network.
Therefore, the existing conductive plastics are in need of further improvement.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, it is an object of the present invention to provide an electrically conductive plastic and a method for producing the same. According to the preparation method, the graphene powder and the polymer particles are premixed, then the obtained premix is mixed with the carbon nano tube, and the obtained mixture is subjected to extrusion granulation or injection molding or compression molding, so that the conductive plastic with high conductivity and stability can be obtained.
In one aspect of the invention, the invention provides a method of preparing a conductive plastic, the method comprising, according to an embodiment of the invention:
(1) premixing graphene powder and polymer particles to obtain a premix;
(2) mixing the premix with carbon nanotube powder to obtain a mixture;
(3) and carrying out extrusion granulation, injection molding or compression molding on the mixture so as to obtain the conductive plastic.
According to the method for preparing the conductive plastic, the graphene powder and the polymer particles are premixed, so that the surface of the polymer particles is completely covered or partially covered with a layer of graphene powder, the polymer particles and the graphene powder are in surface-to-surface contact, and the contact resistance is small; then mixing the obtained premix with carbon nanotube powder, wherein the carbon nanotube can form a conductive network, the graphene powder can play a role in linking and bridging and is contacted with the carbon nanotube to form a linking point, and then the mixture is extruded for granulation or injection molding or compression molding to form conductive plastic with strong conductive capability and high stability.
In addition, the method for preparing the conductive plastic according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, in step (1), the graphene is at least one selected from the group consisting of single-layer graphene, multi-layer graphene, hydroxylated-modified single-layer graphene, carboxylated-modified single-layer graphene, aminated-modified single-layer graphene, hydroxylated-modified multi-layer graphene, carboxylated-modified multi-layer graphene, aminated-modified multi-layer graphene, nitrogen-doped single-layer graphene, sulfur-doped single-layer graphene, boron-doped single-layer graphene, nitrogen-doped multi-layer graphene, sulfur-doped multi-layer graphene, and boron-doped multi-layer graphene. Therefore, the conductive plastic is beneficial to improving the conductive capability and stability of the conductive plastic.
In some embodiments of the present invention, in step (1), the polymer microparticles are at least one selected from the group consisting of polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyamide, polyethylene terephthalate, polybutylene terephthalate, acrylonitrile-butadiene-styrene copolymer, polymethyl methacrylate, epoxy resin, styrene-based TPE thermoplastic elastomer, TPE olefinic thermoplastic elastomer and polyurethane-based TPE thermoplastic elastomer. Therefore, the conductive capability and stability of the conductive plastic can be further improved.
In some embodiments of the invention, in step (1), the pre-mixing is ball milling, mechanical stirring, mechanical shearing, or solution mixing. Therefore, the conductive capability and stability of the conductive plastic can be further improved.
In some embodiments of the present invention, in step (1), the mass ratio of the graphene powder to the polymer microparticles is 1: (1 to 1000), preferably 1: (4-499). Therefore, the conductive capability and stability of the conductive plastic can be further improved.
In some embodiments of the invention, in step (2), the carbon nanotube is at least one selected from the group consisting of a single-walled carbon nanotube, a multi-walled carbon nanotube, a hydroxylated modified single-walled carbon nanotube, a carboxylated modified single-walled carbon nanotube, an aminated modified single-walled carbon nanotube, a hydroxylated multi-walled carbon nanotube, a carboxylated multi-walled carbon nanotube, an aminated modified multi-walled carbon nanotube, a nitrogen-doped single-walled carbon nanotube, a sulfur-doped single-walled carbon nanotube, a boron-doped single-walled carbon nanotube, a nitrogen-doped multi-walled carbon nanotube, a sulfur-doped multi-walled carbon nanotube, and a boron-doped multi-walled carbon nanotube. Therefore, the conductive capability and stability of the conductive plastic can be further improved.
In some embodiments of the present invention, in the step (2), the mass ratio of the carbon nanotubes to the premix is 1: (1 to 1000), preferably 1: (4-499). Therefore, the conductive capability and stability of the conductive plastic can be further improved.
In some embodiments of the invention, in step (2), the mixing is ball milling, mechanical stirring, or mechanical shearing. Therefore, the conductive capability and stability of the conductive plastic can be further improved.
In yet another aspect of the present invention, a conductive plastic is provided. According to the embodiment of the invention, the conductive plastic is prepared by adopting the method. Thus, the conductive plastic has excellent conductivity and stability.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a schematic flow diagram of a method of making a conductive plastic according to one embodiment of the present invention;
FIG. 2 is a schematic view of the microstructure of the compound obtained in example 4 according to the invention;
FIG. 3 is a schematic view of the microstructure of the conductive plastic obtained according to example 4;
FIG. 4 is a schematic view of the microstructure of the compound obtained according to comparative example 1;
FIG. 5 is a schematic view of the microstructure of the conductive plastic obtained according to comparative example 1;
FIG. 6 is a schematic view of the microstructure of the compound obtained according to comparative example 2;
fig. 7 is a schematic view of the microstructure of the conductive plastic obtained according to comparative example 2.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In one aspect of the present invention, the present invention provides a method of preparing a conductive plastic, according to an embodiment of the present invention, with reference to fig. 1, the method comprising:
s100: premixing graphene powder and polymer particles
In the step, the graphene powder and the polymer particles are premixed so as to obtain a premix. The inventors found that by premixing the graphene powder and the polymer fine particles, the surface of the polymer fine particles can be completely covered or partially covered with a layer of graphene powder, and the polymer fine particles and the graphene powder are in surface-to-surface contact, so that the contact resistance is low.
According to an embodiment of the present invention, the specific type of the graphene is not particularly limited, and may be selected by a person skilled in the art according to actual needs, and according to an embodiment of the present invention, the graphene may be at least one selected from the group consisting of single-layer graphene, multi-layer graphene, hydroxylated single-layer graphene, carboxylated single-layer graphene, aminated single-layer graphene, hydroxylated multi-layer graphene, carboxylated multi-layer graphene, aminated multi-layer graphene, nitrogen-doped single-layer graphene, sulfur-doped single-layer graphene, boron-doped single-layer graphene, nitrogen-doped multi-layer graphene, sulfur-doped multi-layer graphene, and boron-doped multi-layer graphene.
According to a further embodiment of the present invention, the specific type of the polymer is not particularly limited, and may be selected by those skilled in the art according to actual needs, and according to a specific embodiment of the present invention, the polymer particles are at least one selected from the group consisting of polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyamide, polyethylene terephthalate, polybutylene terephthalate, acrylonitrile-butadiene-styrene copolymer, polymethyl methacrylate, epoxy resin, styrene type TPE thermoplastic elastomer, olefin type TPE thermoplastic elastomer, and polyurethane type TPE thermoplastic elastomer.
According to another embodiment of the present invention, the premixing is not particularly limited, and may be selected by those skilled in the art according to actual needs, and according to a specific embodiment of the present invention, the premixing may be ball milling, mechanical stirring, mechanical shearing, or solution mixing. The inventors have found that by premixing graphene powder and polymer fine particles according to the above method, the surface of the polymer fine particles can be completely or partially covered with a layer of graphene powder, and the polymer fine particles and the graphene powder are in surface-to-surface contact, and thus the contact resistance is low. Specifically, the ball milling process may be: weighing graphene powder and polymer particles in a certain proportion, putting the graphene powder and the polymer particles into a ball milling tank, and carrying out ball milling for 10-360 min to obtain a premix; the mechanical stirring process may be: putting the graphene powder and the polymer particles in a certain proportion into a mechanical stirrer, and stirring at a high speed for 1-30 min to obtain a premix; the mechanical shearing process may be: putting the graphene powder and the polymer particles in a certain proportion into a high-speed shearing machine, and shearing at a high speed for 1-30 min to obtain a premix; the solution mixing may be: putting a certain proportion of graphene powder and polymer particles into a reaction container, adding solvents such as water or ethanol and the like, emulsifying and shearing at a high speed for 1-30 min, and then filtering and drying to obtain the premix.
According to another embodiment of the present invention, the mass ratio of the graphene powder to the polymer microparticles is not particularly limited, and may be selected by a person skilled in the art according to actual needs, and according to one embodiment of the present invention, the mass ratio of the graphene powder to the polymer microparticles may be 1: (1 to 1000), preferably 1: (4-499).
S200: mixing the premix with the carbon nanotube powder
In the step, the premix is mixed with the carbon nanotube powder to obtain a mixture. The inventor finds that the carbon nano tubes can form a conductive network by mixing the premix completely or partially covering the surface of the obtained polymer particles with a layer of graphene powder, and the graphene powder in the premix can play the roles of linking and bridging and is contacted with the carbon nano tubes to form linking points so as to form a composite conductive network.
According to an embodiment of the present invention, the specific type of the carbon nanotube is not particularly limited, and may be selected by a person skilled in the art according to actual needs, and according to an embodiment of the present invention, the carbon nanotube may be at least one selected from the group consisting of a single-walled carbon nanotube, a multi-walled carbon nanotube, a hydroxylated modified single-walled carbon nanotube, a carboxylated modified single-walled carbon nanotube, an aminated modified single-walled carbon nanotube, a hydroxylated multi-walled carbon nanotube, a carboxylated multi-walled carbon nanotube, an aminated modified multi-walled carbon nanotube, a nitrogen-doped single-walled carbon nanotube, a sulfur-doped single-walled carbon nanotube, a boron-doped single-walled carbon nanotube, a nitrogen-doped multi-walled carbon nanotube, a sulfur-doped multi-walled carbon nanotube, and a boron-doped multi-walled carbon nanotube.
According to still another embodiment of the present invention, the mass ratio of the carbon nanotubes to the premix is not particularly limited and may be selected by those skilled in the art according to actual needs, and according to a specific embodiment of the present invention, the mass ratio of the carbon nanotubes to the premix may be 1: (1 to 1000), preferably 1: (4-499).
According to another embodiment of the present invention, the specific operation type of mixing is not particularly limited, and may be selected by those skilled in the art according to actual needs, and according to one embodiment of the present invention, the mixing may be ball milling, mechanical stirring or mechanical shearing. The inventor finds that by mixing the obtained premix and the carbon nano tubes in the mixing mode, the graphene powder in the premix can play the roles of linking and bridging, and contacts with the carbon nano tubes to form linking points, so that a composite conductive network is formed. Specifically, the ball milling process may be: weighing a certain proportion of premix and carbon nanotube powder, putting into a ball milling tank, and carrying out ball milling for 5-60 min to obtain a mixture; the mechanical stirring process may be: putting the premix and the carbon nano tube powder in a certain proportion into a mechanical stirrer, and stirring at a high speed for 1-10 min to obtain a mixture; the mechanical shearing process may be: and putting the premix and the carbon nano tube powder in a certain proportion into a high-speed shearing machine, and shearing at a high speed for 1-10 min to obtain a mixture.
S300: extruding and granulating or injection molding or compression molding the mixture
In the step, the mixture is subjected to extrusion granulation, injection molding or compression molding so as to obtain the conductive plastic. Specifically, the extrusion granulation process can adopt twin-screw extrusion granulation. It should be noted that the conditions of the extrusion granulation, injection molding and compression molding process can be selected by those skilled in the art according to actual needs.
According to the method for preparing the conductive plastic, the graphene powder and the polymer particles are premixed, so that the surface of the polymer particles is completely covered or partially covered with a layer of graphene powder, the polymer particles and the graphene powder are in surface-to-surface contact, and the contact resistance is small; then mixing the obtained premix with carbon nanotube powder, wherein the carbon nanotube can form a conductive network, the graphene powder can play a role in linking and bridging and is contacted with the carbon nanotube to form a linking point, and then the mixture is extruded for granulation or injection molding or compression molding to form conductive plastic with strong conductive capability and high stability.
In yet another aspect of the present invention, a conductive plastic is provided. According to the embodiment of the invention, the conductive plastic is prepared by adopting the method. Thus, the conductive plastic has excellent conductivity and stability. It should be noted that the advantages of the features described above with respect to the method for preparing the conductive plastic apply equally to the conductive plastic and are not described in detail here.
The invention will now be described with reference to specific examples, which are intended to be illustrative only and not to be limiting in any way.
Example 1
Mixing graphene powder (with a lamella thickness of 1-10 layers and a lamella size of 3-10 microns) and polypropylene particles according to a mixing mass ratio of 3: 96.5, weighing, putting into a mechanical stirrer, and stirring for 1-30 min to obtain a premix; and then mixing the premix and single-walled carbon nanotube powder (with the pipe diameter of 2-5 nm and the length of 2-5 microns) according to a mixing mass ratio of 99.5: weighing 0.5, putting into a mechanical stirrer, and stirring at a high speed for 1-10 min to obtain a mixture; and finally, extruding and granulating the mixture to obtain the conductive plastic master batch.
Example 2
Mixing graphene powder (with a lamella thickness of 1-10 layers and a lamella size of 3-10 mu m) and polystyrene particles according to a mixing mass ratio of 0.5: 99.4, weighing, putting into a ball milling tank, and carrying out ball milling for 30-360 min to obtain a premix; and then mixing the premix with multi-walled carbon nanotube powder (with the pipe diameter of 5-10 nm and the length of 5-10 microns) according to a mixing mass ratio of 99.9: weighing 0.1, putting into a ball milling tank, and carrying out ball milling for 5-60 min to obtain a mixture; and finally, carrying out compression molding on the mixture to obtain the conductive plastic product.
Example 3
Mixing hydroxylated graphene powder (with a lamella thickness of 1-10 layers and a lamella size of 3-10 microns) and high-density polyethylene particles according to a mixing mass ratio of 3: 96, weighing, putting into a high-speed shearing machine, and shearing at a high speed for 1-30 min to obtain a premix; and then mixing the premix with hydroxylated single-walled carbon nanotube powder (the pipe diameter is 2-5 nm, the length is 2-5 mu m) according to a mixing mass ratio of 99:1, putting the mixture into a ball milling tank, and carrying out ball milling for 5-60 min to obtain a mixture. And finally, extruding and granulating the mixture to obtain the conductive plastic master batch.
Example 4
Mixing graphene powder (with a lamella thickness of 1-10 layers and a lamella size of 3-10 microns) and polypropylene particles according to a mixing mass ratio of 3: 96 weighing, putting into a reaction container, adding solvents such as water or ethanol, emulsifying and shearing at a high speed for 1-30 min, and filtering and drying to obtain the premix. And weighing the premix and the multi-walled carbon nanotube powder (with the pipe diameter of 5-10 nm and the length of 5-10 microns) according to the mixing mass ratio of 99:1, putting the mixture into a high-speed shearing machine, and shearing the mixture at a high speed for 1-10 min to obtain a mixture. And finally, extruding and granulating the mixture to obtain the conductive plastic master batch. The microstructure of the obtained mixture is schematically shown in fig. 2, and the microstructure of the obtained conductive plastic is schematically shown in fig. 3. As can be seen from fig. 2, in the obtained mixture, the polymer powder particles and the graphene are in surface-to-surface contact, the contact resistance is small, the conductive network is a composite network formed by the carbon nanotubes and the graphene, the capability of forming the conductive network is strong, and the stability of the conductive network is high; as can be seen from fig. 3, the conductive plastic graphene/carbon nanotubes obtained by compression molding form a conductive network distributed in a continuous polymer phase, and the graphene can play a role in linking and bridging in the conductive network, so that the conductive network has high capacity and high stability.
Comparative example 1
Mixing polypropylene particles and single-walled carbon nanotube powder (with the pipe diameter of 2-5 nm and the length of 2-5 mu m) according to the mixing mass ratio of 96.5: 3.5, weighing, putting into a mechanical stirrer, and stirring at a high speed for 1-10 min to obtain a mixture; and finally, extruding and granulating the mixture to obtain the conductive plastic master batch. The microstructure of the obtained mixture is schematically shown in fig. 4, and the microstructure of the obtained conductive plastic is schematically shown in fig. 5. As shown in fig. 4, the polymer powder particles and the carbon nanotubes are in point-to-surface contact, the conductive network is in line-to-line contact formed by the carbon nanotubes, and the contact resistance between the polymer powder and the carbon nanotubes is relatively large; as can be seen from fig. 5, the carbon nanotubes in the conductive plastic obtained by extrusion and granulation form a conductive network and are discontinuously distributed in the polymer phase.
Comparative example 2
Mixing polypropylene particles and graphene powder (with the thickness of a lamella layer being 1-10 layers and the size of the lamella layer being 3-10 mu m) according to a mixing mass ratio of 96.5: 3.5, weighing, putting into a mechanical stirrer, and stirring at a high speed for 1-10 min to obtain a mixture; and finally, extruding and granulating the mixture to obtain the conductive plastic master batch. The microstructure of the resulting mixture is schematically shown in fig. 6, and the microstructure of the resulting conductive plastic is schematically shown in fig. 7. As can be seen from fig. 6, the polymer powder particles and the graphene are in surface-to-surface contact, and the conductive network is a discontinuous graphene sheet layer; as can be seen from fig. 7, the graphene sheet layer in the conductive plastic obtained by extrusion granulation forms a conductive network discontinuously distributed in the polymer phase.
Comparative example 3
Mixing graphene powder (with a lamella thickness of 1-10 layers and a lamella size of 3-10 mu m) and polystyrene particles according to a mixing mass ratio of 0.6: 99.4, weighing, putting into a ball milling tank, and carrying out ball milling for 30-360 min to obtain a mixture; and finally, carrying out compression molding on the mixture to obtain the conductive plastic product.
Comparative example 4
Mixing multi-wall carbon nano tube powder (with the tube diameter of 5-10 nm and the length of 5-10 mu m) and polystyrene particles according to the mixing mass ratio of 0.6: 99.4, weighing, putting into a ball milling tank, and carrying out ball milling for 30-360 min to obtain a mixture; and finally, carrying out compression molding on the mixture to obtain the conductive plastic product.
Comparative example 5
Mixing polypropylene particles and graphene powder (with the thickness of a lamella ranging from 1 to 10, and the size of the lamella ranging from 3 to 10 microns) according to a mixing mass ratio of 4: 96 weighing, putting into a reaction container, adding solvents such as water or ethanol, emulsifying and shearing at a high speed for 1-30 min, filtering, drying, extruding and granulating to obtain the conductive plastic master batch.
Comparative example 6
Mixing polypropylene particles and multi-walled carbon nanotube powder (with the pipe diameter of 5-10 nm and the length of 5-10 mu m) according to a mixing mass ratio of 4: 96 weighing, putting into a reaction container, adding solvents such as water or ethanol, emulsifying and shearing at a high speed for 1-30 min, filtering, drying, extruding and granulating to obtain the conductive plastic master batch.
Evaluation:
1. the conductivity and stability of the conductive plastics obtained in examples 1 to 4 and comparative examples 1 to 6 were evaluated, respectively.
2. Evaluation index and test method:
testing of conductivity: reference GB/T1410-: 1980 solid insulation volume resistivity and surface resistivity test methods;
preparation of a test sample: weighing a certain amount of conductive master batch, and forming into sheets with the size of 80 multiplied by 2mm on a hot press. The volume resistivity of the material was then tested using a high digital resistivity meter, PC68, a sixth electric power plant, shanghai.
Evaluation of stability: and preparing three test samples at the same time, testing the volume resistivity, and judging the stability of the material according to the variation range of the volume resistivity.
TABLE 1 Properties of conductive plastics obtained in examples 1 to 4 and comparative examples 1 to 6
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean 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 invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer 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, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (11)
1. A method of making a conductive plastic, comprising:
(1) premixing graphene powder and polymer particles to obtain a premix;
(2) mixing the premix with carbon nanotube powder to obtain a mixture;
(3) and carrying out extrusion granulation, injection molding or compression molding on the mixture so as to obtain the conductive plastic.
2. The method of claim 1, wherein in step (1), the graphene is at least one selected from the group consisting of single-layer graphene, multi-layer graphene, hydroxylated modified single-layer graphene, carboxylated modified single-layer graphene, aminated modified single-layer graphene, hydroxylated modified multi-layer graphene, carboxylated modified multi-layer graphene, aminated modified multi-layer graphene, nitrogen-doped single-layer graphene, sulfur-doped single-layer graphene, boron-doped single-layer graphene, nitrogen-doped multi-layer graphene, sulfur-doped multi-layer graphene, and boron-doped multi-layer graphene.
3. The method according to claim 1, wherein in step (1), the polymer microparticles are at least one selected from the group consisting of polyethylene, polypropylene, polyvinyl chloride, polystyrene, polyamide, polyethylene terephthalate, polybutylene terephthalate, acrylonitrile-butadiene-styrene copolymer, polymethyl methacrylate, epoxy resin, styrene-type TPE thermoplastic elastomer, olefin-type TPE thermoplastic elastomer, and polyurethane-type TPE thermoplastic elastomer.
4. The method of claim 1, wherein in step (1), the premixing is ball milling, mechanical stirring, mechanical shearing or solution mixing.
5. The method according to claim 1, wherein in the step (1), the mass ratio of the graphene powder to the polymer microparticles is 1: (1-1000).
6. The method according to claim 1 or 5, wherein in the step (1), the mass ratio of the graphene powder to the polymer microparticles is 1: (4-499).
7. The method according to claim 1, wherein in step (2), the carbon nanotube is at least one selected from the group consisting of a single-walled carbon nanotube, a multi-walled carbon nanotube, a hydroxylated modified single-walled carbon nanotube, a carboxylated modified single-walled carbon nanotube, an aminated modified single-walled carbon nanotube, a hydroxylated multi-walled carbon nanotube, a carboxylated multi-walled carbon nanotube, an aminated modified multi-walled carbon nanotube, a nitrogen-doped single-walled carbon nanotube, a sulfur-doped single-walled carbon nanotube, a boron-doped single-walled carbon nanotube, a nitrogen-doped multi-walled carbon nanotube, a sulfur-doped multi-walled carbon nanotube, and a boron-doped multi-walled carbon nanotube.
8. The method according to claim 7, wherein in the step (2), the mass ratio of the carbon nanotubes to the premix is 1: (1-1000).
9. The method according to claim 1 or 8, wherein in the step (2), the mass ratio of the carbon nanotubes to the premix is 1: (4-499).
10. The method of claim 9, wherein in step (2), the mixing is ball milling, mechanical stirring, or mechanical shearing.
11. An electrically conductive plastic, characterized in that it is produced by the process according to any one of claims 1 to 10.
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