CN109762305B - Graphene master batch and preparation method thereof - Google Patents
Graphene master batch and preparation method thereof Download PDFInfo
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- CN109762305B CN109762305B CN201910061162.9A CN201910061162A CN109762305B CN 109762305 B CN109762305 B CN 109762305B CN 201910061162 A CN201910061162 A CN 201910061162A CN 109762305 B CN109762305 B CN 109762305B
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Abstract
The application relates to the field of graphene materials, in particular to a graphene master batch and a preparation method thereof. A preparation method of graphene master batches mainly comprises the following steps: carrying out surface treatment on the fiber carrier by using graphene slurry to obtain a fiber carrier with the surface coated with graphene, namely an intermediate product; performing surface treatment on the intermediate product by using the polymer slurry to obtain an intermediate product with a polymer coated on the surface, namely a coating material; and (4) granulating the coating material. The preparation method of the graphene master batch is simple in process, low in cost and easy to obtain raw materials, environment-friendly, free of introduction of organic solvents, free of complicated and expensive equipment, and easy to realize industrial production.
Description
Technical Field
The application relates to the field of graphene materials, in particular to a graphene master batch and a preparation method thereof.
Background
Graphene as a novel two-dimensional carbon nano material has excellent properties such as high electrical conductivity, thermal conductivity, high specific surface area and Young modulus. Theoretical studies have shown that the room temperature thermal conductivity of single layer graphene is the material with the highest thermal conductivity known to date.
The polymer nano composite material is prepared by dispersing the nano additive in the polymer matrix, and researches show that when the graphene is used as the additive and the addition amount is low, the performance of the polymer can be greatly enhanced. However, since graphene has a large specific surface area and intrinsic van der waals forces exist between graphene sheets, the graphene sheets are very easily agglomerated.
Disclosure of Invention
An object of the embodiment of the application is to provide a graphene master batch and a preparation method thereof, which aim to solve the problem that an existing graphene composite material is easy to agglomerate.
The first aspect of the present application provides a preparation method of a graphene master batch, which mainly includes the following steps:
carrying out surface treatment on the fiber carrier by using graphene slurry to obtain a fiber carrier with the surface coated with graphene, namely an intermediate product;
performing surface treatment on the intermediate product by using the polymer slurry to obtain an intermediate product with a polymer coated on the surface, namely a coating material;
and (4) granulating the coating material.
In the prior art, only a small amount of graphene can be added when powder graphene and polymer are granulated, and the particles of polymer powder are large, so that the graphene is coated on the surfaces of polymer particles in the premixing process, but the coating amount is limited, and only a small amount of graphene can be coated on the surfaces of the polymer particles, so that when the addition amount of the graphene is increased, most of the graphene cannot be coated on the surfaces of the polymer particles, and thus agglomeration can be caused during melting.
This application adopts graphite alkene thick liquids to carry out surface treatment to the fibre carrier, with graphite alkene thick liquids cladding outside the fibre carrier, the fibre is as the carrier, and graphite alkene is as carrying the thing, can load a large amount of graphite alkene in the fibre surface, and is difficult for agglomerating, has solved above-mentioned problem.
The surface of the graphene is coated with a layer of polymer film, the fiber carrier, the graphene and the polymer film form a sandwich structure, and the graphene can be prevented from falling off in the subsequent process. In addition, in the subsequent preparation process of the graphene master batch, the two surfaces of the graphene sheet layer are respectively wrapped by the fiber and the polymer, so that agglomeration can be avoided, and better dispersion can be obtained.
The method provided by the application can adopt graphene slurry, but is not limited to graphene slurry, and can be suitable for graphene in various forms. In addition, the graphene master batch containing high-content graphene can be prepared, the surfaces of the graphene sheets in microscale can be fully contacted with the polymer, the problem of agglomeration among graphene sheet layers can be effectively solved, and the graphene is uniformly dispersed in the master batch and mutually overlapped to form a comprehensive three-dimensional graphene network.
In some embodiments of the first aspect of the present application, the surface treatment of the fiber carrier with the graphene slurry specifically includes placing the fiber carrier in the graphene slurry to perform impregnation or padding, and then drying;
the surface treatment of the intermediate product with the polymer syrup specifically includes placing the intermediate product in the polymer syrup to be impregnated or padded, and then drying.
The graphene can be uniformly and continuously coated on the surface of the fiber carrier in a dipping or padding mode, and has certain adhesive force. Through multiple times of dipping or padding treatment, graphene can be covered on the surface of the fiber carrier as much as possible, and the content of the graphene in the final master batch is increased.
A layer of polymer is wrapped on the surface of the intermediate product in a dipping or padding mode, so that a layer of film is formed on the surface of the intermediate product, the dipping or padding mode is favorable for the comprehensive contact of graphene and the polymer, on one hand, the graphene can form a mutually overlapped three-dimensional net structure in the master batch preparation process, on the other hand, the graphene is coated with a polymer fiber carrier in the interior, and the problem of graphene agglomeration in the master batch preparation process can be effectively solved by a sandwich structure formed by coating the outside with the polymer.
In some embodiments of the first aspect of the present application, in the step of immersing or padding the fiber support in the graphene slurry, multiple immersing or multiple padding is adopted, and each immersing or each padding is followed by drying and then immersing or padding.
In some embodiments of the first aspect of the present application, the graphene paste is composed of graphene, a conductive additive, a polymer, and a solvent.
The conductive additive is at least one of one or a combination of more than two of conductive carbon black, graphite, carbon nano tube and carbon fiber.
The polymer is any one of polyester, polyurethane, water-based epoxy resin, phenolic aldehyde, polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, polymaleic anhydride, polyquaternary ammonium salt, polyacrylamide, hydrolyzed polyacrylamide or polyacrylic water-based resin.
The solvent of the graphene slurry comprises 10-85% of ethanol aqueous solution by volume fraction.
The mixed solution of water and ethanol is used as the solvent of the graphene slurry, so that the dispersibility of graphene in the slurry can be improved, and other substances can be prevented from being introduced into the graphene master batch, and the pollution is reduced. The conductive additive can increase the conductivity of the graphene, the use of the conductive additive can reduce the using amount of the graphene, promote the effective dispersion of the graphene, and can play a role in perfecting and reinforcing a three-dimensional network formed by the graphene in the master batch. The polymer is beneficial to the graphene to spread on the surface of the fiber carrier to form a film and to coat on two sides of the graphene, so that the agglomeration of the graphene is reduced.
In some embodiments of the first aspect of the present application, the graphene and the conductive additive have a total solid content of 1% to 8%; the mass ratio of the graphene to the conductive additive is 1: 0.1 to 1; the mass ratio of the sum of the mass of the graphene and the conductive additive to the mass of the polymer is 1: 0.1-10.
The solid contents of the graphene and the conductive additive are 1% -8%, so that the graphene in the slurry can be efficiently covered on the surface of the fiber carrier to form a continuous graphene lamellar structure.
In some embodiments of the first aspect of the present application, the solvent of the polymer syrup is water and the solids content of the polymer is 1% to 20%.
So that the polymer can be continuously attached to the graphene surface.
In some embodiments of the first aspect of the present application, the above-mentioned fibrous support has a diameter of less than 30um, preferably a fibrous support diameter of less than 5 um.
The fiber carrier with the diameter smaller than 5um has a large specific surface area, an infinite space is provided for the attachment of graphene, the fiber diameter is micro-nano-scale, and the graphene is coated on the surface of the fiber to realize the compounding of graphene and polymer with the same scale.
In some embodiments of the first aspect of the present application, the material of the fiber carrier comprises any one of polyester, polyamide, polypropylene, spandex or polyvinyl alcohol fibers.
The polymer slurry comprises any one of polyester, polyurethane, epoxy, phenolic aldehyde, polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, polymaleic anhydride, polyquaternary ammonium salt, polyacrylamide, hydrolyzed polyacrylamide or polyacrylic resin.
In some embodiments of the first aspect of the present application, the granulating of the coating further comprises subjecting the coating to at least one surface treatment of surface-coating graphene and at least one surface treatment of surface-coating polymer; the fibrous support is space-coated with multiple layers of graphene and multiple layers of polymer.
The fiber carrier can be coated with multiple layers of graphene and multiple layers of polymers at intervals according to final requirements.
In some embodiments of the first aspect of the present application, the graphene has a sheet size of 0.1 μm to 25 μm. The microscopic graphene lamellar structure can be formed on the surface of the fiber carrier.
The graphene master batch is prepared by the preparation method of the graphene master batch provided by the first aspect of the application.
The graphene master batch provided by the embodiment of the application can be used for adding high-content graphene, the graphene and the polymer are coated at intervals in multiple ways, the polymer can be effectively contacted with two surfaces of the graphene in a melting process, graphene sheets coated with the polymer on the surfaces are formed, and the graphene is prevented from being agglomerated again, so that good dispersion is obtained. The surface of the fiber carrier is coated with the graphene, so that the graphene master batch has a mutually-lapped three-dimensional graphene network, and the master batch has remarkable performances of electric conduction, heat conduction, far infrared, antibiosis and the like.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained from the drawings without inventive effort.
Fig. 1 shows a schematic view of an internal structure of a graphene master batch provided in an embodiment of the present application.
Fig. 2 shows a scanning electron microscope image of the graphene master batch provided in comparative example 1;
fig. 3 shows a scanning electron microscope image of the graphene master batch provided in comparative example 2;
fig. 4 shows a scanning electron microscope image of the graphene master batch provided in example 5.
Icon: 101-a fibrous support; 102-a first graphene layer; 103-a first polymer layer; 104-a second graphene layer; 105-a second polymer layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The graphene masterbatch and the preparation method thereof according to the embodiment of the present application are specifically described below.
The application provides a preparation method of graphene master batches, which mainly comprises the following steps:
and carrying out surface treatment on the fiber carrier by using the graphene slurry to obtain the fiber carrier with the surface coated with graphene, namely an intermediate product.
And (3) carrying out surface treatment on the intermediate product by adopting the polymer slurry to obtain the intermediate product with the surface coated with the polymer, namely the coating material.
And (4) granulating the coating material.
The graphene slurry is adopted to carry out surface treatment on the fiber carrier, the graphene slurry is coated outside the fiber carrier, the fiber is used as the carrier, the graphene is used as a carrying object, a large amount of graphene can be loaded on the surface of the fiber, and the problem that only a small amount of graphene can be loaded is solved.
In addition, compared with graphene powder, the graphene slurry can enable graphene to be spread in a slurry solvent as much as possible, the graphene is favorably spread on the surface of a fiber after surface treatment, and in the subsequent melting and granulating process, the two sides of the spread graphene are coated with polymers, so that the curling and wrinkling of the graphene in master batches can be reduced, the agglomeration is reduced to a greater extent, and the performance of the graphene can be exerted to the greatest extent in the later use.
Further, in some embodiments of the present application, the fibrous support is placed in the graphene slurry for impregnation or padding, and then dried.
The graphene can be uniformly and continuously coated on the surface of the fiber carrier in a dipping or padding mode, and has certain adhesive force. Through multiple times of dipping or padding treatment, graphene can be covered on the surface of the fiber carrier as much as possible, and the content of the graphene in the final master batch is increased.
It is understood that in other embodiments of the present application, the fiber carrier coated with graphene may also be implemented in other manners, for example, by spraying.
Further, in some embodiments of the present application, the graphene paste is composed of graphene, a conductive additive, a polymer, and a solvent.
The conductive additive is at least one of conductive carbon black, graphite, carbon nanotubes and carbon fibers.
The polymer is any one of polyester, polyurethane, water-based epoxy resin, phenolic aldehyde, polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, polymaleic anhydride, polyquaternary ammonium salt, polyacrylamide, hydrolyzed polyacrylamide or polyacrylic acid;
the solvent of the graphene slurry comprises 10-85% of ethanol aqueous solution by volume fraction.
Further, the total solid content of the graphene and the conductive additive is 1-8%; the mass ratio of the graphene to the conductive additive is 1: 0.1 to 1; the mass ratio of the sum of the mass of the graphene and the conductive additive to the mass of the polymer is 1: 0.1-10.
The mixed solution of water and ethanol as the solvent of the graphene slurry can increase the dispersibility of graphene in the slurry, is beneficial to spreading of graphene in a fiber carrier and even in the graphene master batch, and can avoid introducing other substances into the graphene master batch and reduce pollution. The conductive additive can increase the conductivity of the graphene, the use of the conductive additive can reduce the using amount of the graphene, promote the effective dispersion of the graphene, and can play a role in perfecting and reinforcing a three-dimensional network formed by the graphene in the master batch. The polymer in the graphene slurry is beneficial to the graphene spreading on the surface of the fiber carrier to form a film, and two surfaces of the graphene can be coated with a small amount of polymer in the slurry, so that the agglomeration between graphene sheets is further reduced. The solid contents of the graphene and the conductive additive are 1% -8%, so that the graphene in the slurry can be efficiently covered on the surface of the fiber carrier to form a continuous graphene lamellar structure.
It is understood that in other embodiments of the present application, the solution in the graphene paste may be other, such as acetone, water, etc.
The solvent of the graphene slurry is an ethanol aqueous solution with a volume fraction of 10% to 85%. Compared with the graphene slurry with water as the solvent, the dispersibility of the graphene in the slurry is greatly increased. Further, the solvent of the graphene slurry is an ethanol aqueous solution with the volume fraction of 30% -75%. In some embodiments of the present application, the above-mentioned fiber carrier has a diameter of less than 30um, and further preferably, the fiber diameter is less than 5 um.
The fiber carrier with the diameter smaller than 5um has a large specific surface area, an infinite space is provided for the attachment of graphene, the fiber diameter is micro-nano-scale, and the graphene is coated on the surface of the fiber to realize the compounding of graphene and polymer with the same scale.
In some embodiments of the present application, the material of the fibrous carrier comprises any one of polyester, nylon, polypropylene, spandex, or polyvinyl alcohol fibers.
Furthermore, the fiber carrier can be short fibers, fiber bundles, woven fabrics, knitted fabrics or non-woven fabrics, wherein the double or multiple coating of graphene and polymers by adopting the fabrics can obviously improve the production efficiency, and the preparation of the graphene master batch is to crush the carrier fabrics coated with the graphene and the polymers, fully dry the powder and then melt and extrude the powder in a screw extruder for granulation.
Further, in some embodiments of the present application, a fiber support having a profiled cross section, such as a Y-shape, a cross shape, a triangle shape, etc., is used, which can further increase the specific surface area of the fiber; when the loading capacity of graphite alkene is increased, irregular surface can increase the impetus of graphite alkene, increases the adhesive force, avoids droing.
In some embodiments of the present application, the graphene has a sheet size of 0.1 μm to 25 μm.
The sheet size of the graphene is 0.1-25 μm, and a microscopic graphene sheet structure can be formed on the surface of the fiber carrier.
And coating graphene on the surface of the fiber carrier to obtain an intermediate product, and then carrying out surface treatment on the intermediate product by adopting the polymer slurry to obtain the intermediate product coated with the polymer on the surface, namely the coating material.
The graphene master batch is characterized in that the surface of graphene is coated with a layer of polymer film, the fiber carrier, the graphene and the polymer film form a sandwich structure, the graphene can be uniformly and continuously loaded on the surface of the fiber carrier, and the polymer can be uniformly and continuously loaded on the surface of the graphene, so that the two surfaces of the graphene can be comprehensively and efficiently contacted with the polymer, in the subsequent preparation process of the graphene master batch, the two surfaces of the graphene sheet layer are respectively coated with the polymer fiber and the polymer, the agglomeration can be avoided, and better dispersion can be obtained.
In some embodiments of the present application, the intermediate product is placed in a polymer slurry for impregnation or padding, and then dried to obtain a coating.
A layer of polymer is wrapped on the surface of the intermediate product in a dipping or padding mode, so that a layer of film is formed on the surface of the intermediate product, and the dipping or padding mode is beneficial to increasing the combination of graphene and the polymer to form a mutually overlapped three-dimensional porous net-shaped structure.
It should be noted that, in other embodiments of the present application, other means, such as spraying, coating, etc., may be used to coat the intermediate product with a layer of polymer.
In some embodiments herein, the solvent of the polymer slurry is water and the solids content of the polymer is 1% to 20%.
The water is used as a solvent of the polymer slurry, so that the environment is protected, the cost is low, and in addition, other impurities cannot be introduced into the final graphene master batch.
The solid content of the polymer of 1-20% can enable the polymer to continuously attach to the graphene surface.
In some embodiments of the present application, the polymer comprises any one of polyester, polyurethane, epoxy, phenolic, polyvinyl alcohol, polyvinyl pyrrolidone, polymaleic anhydride, polyquaternary ammonium salts, polyethylene glycol, polyacrylamide, hydrolyzed polyacrylamide, or polyacrylic resins.
And (4) granulating the coating material. And carrying out melt blending, dispersing, extruding, solidifying and granulating on the coating material.
The method provided by the application has the advantages of simple preparation process of the graphene master batch, low cost and easy obtainment of raw materials, environmental protection, no introduction of organic solvent, no need of complex and expensive equipment, and easy realization of industrial production.
The method is suitable for the graphene in various forms, is not limited to graphene slurry, and can be used for preparing the master batch containing the graphene with high content, the surfaces of the graphene sheets in the microscale can be fully contacted with the polymer, so that the problem of agglomeration among the graphene sheet layers can be effectively solved, the graphene is uniformly dispersed in the master batch, and the graphene sheets are mutually overlapped to form a comprehensive three-dimensional graphene network.
In some embodiments of the present application, the granulating of the coating material further comprises performing at least one surface treatment of surface-coating graphene and at least one surface treatment of surface-coating polymer on the coating material; the fibrous support is space-coated with multiple layers of graphene and multiple layers of polymer.
In other words, the surface of the fiber carrier can be coated with multiple layers of graphene and multiple layers of polymers as required; the method comprises the steps of preparing a layer of graphene, a layer of polymer, a layer of graphene and a layer of polymer.
The application provides a graphene master batch, and the graphene master batch is prepared by the preparation method of the graphene master batch provided by the application.
Fig. 1 shows a schematic diagram of an internal structure of a graphene master batch provided in an embodiment of the present application, please refer to fig. 1.
The graphene master batch comprises a fiber carrier 101, a first graphene layer 102, a first polymer layer 103, a second graphene layer 104 and a second polymer layer 105.
The fiber carrier 101 and the first graphene layer 102 have parts which are mutually inserted at the boundary, and the first polymer layer 103 and the second graphene layer 104 have parts which are mutually inserted at the boundary.
It should be noted that in other embodiments of the present application, a layer of graphene and a layer of polymer may be disposed outside the fiber carrier 101. The present embodiment does not limit it.
The graphene master batch provided by the embodiment of the application can avoid the falling-off of graphene in the subsequent process, is beneficial to the fact that the two sides of the graphene can effectively contact with a polymer in the melting process, forms a graphene sheet with the polymer coated on the surface, and avoids the re-agglomeration of the graphene, so that good dispersion is obtained. The graphene master batch has mutually overlapped three-dimensional graphene networks, and the master batch has remarkable performances of electric conduction, heat conduction, far infrared, antibiosis and the like.
The features and properties of the present application are described in further detail below with reference to examples.
Example 1
The embodiment provides a graphene master batch, which is mainly prepared through the following steps:
taking a polyester fiber carrier with the diameter of 30 um; placing the fiber carrier into graphene slurry for dipping, and then drying to obtain an intermediate product; the graphene slurry consists of graphene, carbon nanotubes and a solvent, wherein the solid content of the graphene and the carbon nanotubes in the slurry is 1%, and the mass ratio of the graphene to the carbon nanotubes is 5: 2; the sheet size of the graphene is 9 μm, and the solvent of the graphene slurry is an ethanol aqueous solution with a volume fraction of 10%.
Placing the intermediate product into polymer slurry for dipping and then drying to obtain a coating material; the polymer is water-based polyester; the solvent of the polymer slurry was water, and the solid content of the polymer was 1%.
Repeating the steps for 3 times to obtain the coating with the surface coated with the multilayer graphene and the polymer at intervals.
And (4) granulating the coating material by adopting a double-screw extruder.
Example 2
The embodiment provides a graphene master batch, which is mainly prepared through the following steps:
taking a polyvinyl alcohol fiber carrier with the diameter of 20 um; placing the fiber carrier in graphene slurry for padding, and then drying to obtain an intermediate product; the graphene slurry is composed of graphene, graphite, polyvinyl alcohol and a solvent, wherein the solid content of the graphene and the graphite in the slurry is 3%, and the mass ratio of the graphene to the graphite is 8: 2, the sheet size of the graphene is 7 μm, and the solvent of the graphene slurry is an ethanol aqueous solution with a volume fraction of 85%.
Placing the intermediate product into polymer slurry for padding, and then drying to obtain a coating material; the polymer is water-based polyvinyl alcohol; the solvent of the polymer slurry was water, and the solid content of the polymer was 3%.
Repeating the steps for 2 times to obtain the coating with the surface coated with the multilayer graphene and the polymer at intervals.
And (4) granulating the coating material by adopting a double-screw extruder.
Example 3
The embodiment provides a graphene master batch, which is mainly prepared through the following steps:
taking a polypropylene fiber carrier with the diameter of 10 um; placing the fiber carrier in graphene slurry for padding, and then drying to obtain an intermediate product; the graphene slurry consists of graphene, conductive carbon black, carbon nanotubes, polyacrylic acid and a solvent; the solid contents of the graphene, the conductive carbon black and the carbon nano tube in the slurry are 3.5%, and the mass ratio of the graphene to the conductive carbon black to the carbon nano tube is 6: 3: 1, the solid content of polyacrylic acid in the slurry is 2 percent; the sheet size of the graphene is 5 μm, and the solvent of the graphene slurry is an ethanol aqueous solution with a volume fraction of 30%.
Placing the intermediate product into polymer slurry for padding, and then drying to obtain a coating material; the polymer is water-based polyacrylic acid, the solvent of the polymer slurry is water, and the solid content of the polymer is 1%.
Repeating the steps for 3 times to obtain the coating with the surface coated with the multilayer graphene and the polymer at intervals. And (4) granulating the coating material by adopting a double-screw extruder.
Example 4
The embodiment provides a graphene master batch, which is mainly prepared through the following steps:
taking a polyester fiber carrier with the diameter of 5 um;
placing the fiber carrier into graphene slurry for dipping or padding, and then drying to obtain an intermediate product; the graphene slurry is composed of graphene, conductive carbon black, water-based polyester and a solvent, wherein the solid contents of the graphene and the conductive carbon black in the slurry are 2.5%, and the mass ratio of the graphene to the conductive carbon black is 9: 1, the solid content of the water-based polyester in the slurry is 2%, the sheet size of the graphene is 7 microns, and the solvent of the graphene slurry is an ethanol aqueous solution with the volume fraction of 15%.
Placing the intermediate product into polymer slurry for dipping or padding, and then drying to obtain a coating material; the polymer is water-based polyester; the solvent of the polymer slurry was water, and the solid content of the polymer was 1%.
Repeating the steps for 4 times to obtain the coating with the surface coated with the multilayer graphene and the polymer at intervals.
And (4) granulating the coating material by adopting a double-screw extruder.
Example 5
The embodiment provides a graphene master batch, which is mainly prepared through the following steps:
taking a polyester fiber carrier with the diameter of 14 um; placing the fiber carrier in graphene slurry for padding, and then drying to obtain an intermediate product; the graphene slurry consists of 3% of graphene, 7 μm of graphene sheet size, 1.5% of waterborne polyurethane and a solvent, wherein the solvent of the graphene slurry is an ethanol aqueous solution with a volume fraction of 50%.
Placing the intermediate product into polymer slurry for dipping or padding, and then drying to obtain a coating material; the polymer is waterborne polyurethane; the solvent of the polymer slurry was water, and the solid content of the polymer was 1.5%.
Repeating the steps for 2 times to obtain the coating with the surface coated with the multilayer graphene and the polymer at intervals.
And (4) granulating the coating material by adopting a double-screw extruder.
Comparative example 1
PET particles and graphene powder are mixed to prepare master batches with the mass fraction of graphene being 1%.
Comparative example 2
PET powder and graphene powder are mixed to prepare master batch with 5% of graphene mass fraction.
Test example 1
The surface resistance test was performed on the graphene mother particles provided in examples 1 to 5, and the results are shown in table 1.
Table 1 performance test results of graphene masterbatches provided in examples 1-5 of example 1
| Group of | Surface resistance (omega) |
| Example 1 | 107 |
| Example 2 | 105 |
| Example 3 | 104 |
| Example 4 | 103 |
| Example 5 | 104 |
As can be seen from table 1, the conductivities provided in examples 1 to 5 are all better, and the surface resistance of example 4 is lower, which is better than the graphene mother particles provided in examples 1 to 3 and example 5.
Test example 2
Scanning electron microscopy is adopted to shoot pictures of the graphene master batches provided in comparative examples 1-2 and example 5. Fig. 2 shows a scanning electron microscope image of the graphene master batch provided in comparative example 1; fig. 3 shows a scanning electron microscope image of the graphene master batch provided in comparative example 2; fig. 4 shows a scanning electron microscope image of the graphene master batch provided in example 5.
As can be seen from fig. 2 to 3, the agglomeration of the graphene of comparative examples 1 to 2 is more evident; the graphene of the graphene masterbatch provided in example 5 is uniformly dispersed, and the graphene is in a spread state.
The graphene master batch provided by the embodiment of the application has the advantages of high graphene content and good graphene dispersibility.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.
Claims (10)
1. The preparation method of the graphene master batch is characterized by mainly comprising the following steps:
carrying out surface treatment on the fiber carrier by using graphene slurry to obtain a fiber carrier with the surface coated with graphene, namely an intermediate product;
performing surface treatment on the intermediate product by using polymer slurry to obtain an intermediate product with a polymer coated on the surface, namely a coating material;
granulating the coating material;
the graphene paste comprises graphene, a conductive additive, a polymer and a solvent;
the conductive additive comprises at least one of conductive carbon black, graphite, carbon nanotubes and carbon fibers;
the total solid content of the graphene and the conductive additive is 1-8%; the mass ratio of the graphene to the conductive additive is 1: 0.1 to 1; the mass sum of the graphene and the conductive additive and the mass ratio of the graphene to the polymer in the graphene slurry is 1: 0.1 to 10;
the fiber carrier is made of any one of terylene, chinlon, polypropylene fiber, spandex and polyvinyl alcohol fiber;
the surface treatment of the intermediate product by using the polymer slurry specifically comprises the steps of placing the intermediate product in the polymer slurry for dipping or padding, and then drying.
2. The preparation method of the graphene masterbatch according to claim 1, wherein the surface treatment of the fiber carrier by using the graphene slurry specifically comprises placing the fiber carrier in the graphene slurry to perform impregnation or padding, and then drying.
3. The preparation method of the graphene master batch according to claim 2, wherein in the step of placing the fiber carrier in the graphene slurry for dipping or padding, a multi-dipping or multi-padding mode is adopted, and each dipping or each padding is followed by drying and then dipping or padding.
4. The method for preparing the graphene masterbatch according to claim 1, wherein the polymer in the graphene slurry is any one of aqueous polyester, aqueous polyurethane, aqueous epoxy resin, polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, polymaleic anhydride, polyquaternary ammonium salt, polyacrylamide and polyacrylic aqueous resin;
the solvent of the graphene slurry comprises 10-85% of ethanol aqueous solution by volume fraction.
5. The preparation method of the graphene master batch according to claim 1, wherein the solvent of the polymer slurry is water, and the solid content of the polymer is 1% -20%.
6. The method for preparing the graphene masterbatch according to claim 1, wherein the diameter of the fiber carrier is less than 30 μm.
7. The method for preparing the graphene masterbatch according to claim 6, wherein the diameter of the fiber carrier is less than 5 μm.
8. The method of claim 1, wherein the polymer in the polymer slurry comprises any one of water-based polyester, water-based polyurethane, water-based epoxy resin, polyvinyl alcohol, polyethylene glycol, polyvinylpyrrolidone, polymaleic anhydride, polyquaternary ammonium salt, polyacrylamide, and polyacrylic acid.
9. The preparation method of the graphene master batch according to claim 1, wherein before granulating the coating material, the coating material is subjected to at least one surface treatment of surface coating graphene and at least one surface treatment of surface coating polymer; and (3) enabling the fiber carrier to be coated with multiple layers of graphene and multiple layers of polymers at intervals.
10. The graphene master batch is characterized in that the graphene master batch is prepared by the preparation method of the graphene master batch according to any one of claims 1 to 9.
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