CN109666350B - Water-based conductive coating containing high-conductivity graphene and preparation method thereof - Google Patents
Water-based conductive coating containing high-conductivity graphene and preparation method thereof Download PDFInfo
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- CN109666350B CN109666350B CN201710958202.0A CN201710958202A CN109666350B CN 109666350 B CN109666350 B CN 109666350B CN 201710958202 A CN201710958202 A CN 201710958202A CN 109666350 B CN109666350 B CN 109666350B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
Abstract
The invention provides a water-based conductive coating, which comprises water-based resin, high-conductivity graphene slurry and an auxiliary agent. According to the invention, the graphene raw material is selected, the high-conductivity graphene is added, a specific type is selected as a slurry mixing auxiliary agent in the auxiliary agent of the water-based paint to form slurry with the high-conductivity graphene, and the slurry is mixed with other components as a whole, so that the graphene can be uniformly dispersed in the paint, and thus the special conductive water-based paint with excellent performances in all aspects is obtained, and the special conductive water-based paint has the characteristics of high conductivity and electromagnetic shielding performance, high hardness, good adhesive force, good corrosion resistance, no pollution and the like, and can meet various market demands. Meanwhile, the preparation method has the advantages of simple process, mild conditions, safety and environmental protection, and is more suitable for industrialized mass production.
Description
Technical Field
The invention belongs to the technical field of water-based paint, relates to water-based conductive paint and a preparation method thereof, and particularly relates to water-based conductive paint containing high-conductivity graphene and a preparation method thereof.
Background
Graphene (Graphene) is a new material with a single-layer sheet structure and composed of carbon atoms, is a two-dimensional crystal which is composed of carbon atoms and has only one layer of atomic thickness, is the thinnest material and the toughest material which enter the application field at present, has the fracture strength 200 times higher than that of steel, has good elasticity, and has the stretching amplitude which can reach 20 percent of the self size; meanwhile, the graphene also has excellent conductivity, so that the internal resistance can be reduced, and the circulation stability of the supercapacitor is improved; in addition, graphene is almost completely transparent, absorbs only 2.3% of light, and is very dense and impenetrable by even the smallest gas atoms (helium atoms). Due to the characteristics, the graphene is very suitable for various subjects and fields, is widely applied to the aspects of energy storage materials, environmental engineering and sensitive sensing due to the excellent physicochemical properties of the graphene, is called as 'black gold' or 'king of new materials', has wide potential application prospects, becomes a focus and a research hotspot in the world at present, and is industrialized from the research stage, so that the graphene and other derivatives are widely participated in various industries.
With the continuous development of electronic information technology, electronic products are widely applied to various fields in life, and the work of the electronic products brings great convenience to people and releases a large amount of electromagnetic radiation to harm the health of people. The housings of audio and video equipment, precision medical equipment, computers, mobile phones and other equipment are mostly plastic housings, and the plastic housings are easy to generate static electricity. Therefore, to ensure the normal operation of electrical and electronic equipment, to protect human health, ecological natural activities, etc., shielding of such equipment and devices is required to reduce electromagnetic radiation and interference. A commonly used method for preventing electromagnetic radiation is to form a conductive layer on the surface of the substrate, so that the substrate has the capability of conducting current and eliminating accumulated static charges, thereby preventing electromagnetic radiation interference. The conductive coating has excellent antistatic and electromagnetic shielding performance, and can be conveniently sprayed or brushed on the surfaces of materials in various shapes to form an electromagnetic shielding conductive layer, so that the material can achieve the purpose of shielding electromagnetic waves. At present, most of conductive coatings on plastic surfaces adopt solvent-type conductive coatings, which have serious influence on the environment and the health of people. Therefore, the waterborne conductive coating comes along, but the existing waterborne conductive coating has some defects: the water-based coating has low adhesive force and is easy to fall off; the silver conductive paint has good conductivity, but is easy to have silver migration phenomenon; copper-based conductive paint is easily oxidized.
In recent years, due to the respective excellent characteristics of graphene, there have been reports on the use of graphene in aqueous conductive coatings, as disclosed in CN106590400A, but in practical applications, graphene has many problems and constraints, such as easy agglomeration of graphene. Due to the fact that the graphene and the graphene derivative have large specific surface areas and strong van der Waals acting forces exist among the graphene and the graphene derivative, agglomeration and winding phenomena are obvious, the graphene and the graphene derivative cannot be stably dispersed, and the graphene derivative are easy to agglomerate together again after dispersion and are difficult to open. Therefore, the effect is not ideal when graphene is added into the water-based paint as a filler, and although a large amount of research is carried out to improve the dispersion effect of graphene by adding different types of dispersants or modification, the effect is still poor in practical application, and other impurities are additionally introduced to cause negative effects on subsequent research.
Therefore, how to obtain a water-based conductive coating, which can further improve the performance of the water-based conductive coating, has become a problem to be solved by many application manufacturers and a front-line research and development staff.
The graphene can be better distributed in a coating system, and is a key factor influencing the performance of the coating.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an aqueous conductive coating and a preparation method thereof, and particularly to an aqueous conductive coating containing highly conductive graphene.
The invention provides a water-based conductive coating, which comprises water-based resin, high-conductivity graphene slurry and an auxiliary agent.
Preferably, the carbon content of the high-conductivity graphene is greater than or equal to 98%;
the conductivity of the high-conductivity graphene is greater than or equal to 40000S/m.
Preferably, the high-conductivity graphene slurry comprises high-conductivity graphene, a slurry mixing auxiliary agent and water;
the slurry mixing auxiliary agent comprises one or more of a defoaming agent, a leveling modifier and a wetting agent;
the water-based resin comprises one or more of water-based acrylic acid, water-based alkyd resin, water-based epoxy resin, water-based polyaniline resin, water-based fluorocarbon resin and water-based perchloroethylene resin;
the auxiliary agent comprises an anti-flash rust agent and/or a film forming auxiliary agent.
Preferably, the coating composition is a mixture of, based on the whole of the aqueous conductive coating material,
20-80 parts by weight of the water-based resin;
1-30 parts by weight of high-conductivity graphene;
0.5-8 parts by weight of a slurry mixing auxiliary agent;
10-30 parts by weight of water;
and 0.5-4 parts by weight of an auxiliary agent.
Preferably, the coating composition is a mixture of, based on the whole of the aqueous conductive coating material,
0.1-2 parts by weight of a defoaming agent;
0.1-2.5 parts by weight of the leveling agent;
0.1-2.5 parts by weight of the rheology modifier;
0.1-2 parts by weight of a wetting agent;
the flash rust inhibitor is 0.5-3.5 parts by weight;
the film forming auxiliary agent is 0.2-2 parts by weight.
Preferably, the antifoaming agent comprises one or more of tego902w, tego901, BYK-24, tego1488, and KOOLY-3150;
the leveling agent comprises one or more of silok8244, silok315, silok23, silok8066 and silok 333;
the rheology modifier comprises one or more of RM-8W, RM-2020n and RM-12 w;
the wetting agent comprises one or more of tego twin 4100, Surfynol 104A, silok8030 and silok 8008;
the antiscratch agent comprises one or more of sodium nitrite aqueous solution, NALZIN FA 179, CH07A and R-760F;
the coalescent includes one or more of texanol, DPnB, DPnP, TPnB, and DPM.
The invention also provides a preparation method of the water-based conductive coating, which comprises the following steps:
1) the method comprises the following steps of mixing high-conductivity graphene, a slurry mixing auxiliary agent and water for the first time, and then grinding to obtain high-conductivity graphene slurry;
2) and mixing the high-conductivity graphene slurry obtained in the step, the water-based resin and the auxiliary agent again, and standing to obtain the water-based conductive coating.
Preferably, the high-conductivity graphene is prepared by the following method:
A) reacting graphite with a small molecular intercalation agent to obtain intercalated graphite;
B) performing high-temperature expansion on the intercalated graphite obtained in the step to obtain expanded graphite;
C) and stripping the expanded graphite obtained in the step in a stripping medium to obtain the graphene.
Preferably, the mass ratio of the graphite to the small molecule intercalation agent is 1: (1-5);
the mass ratio of the graphite to the stripping medium is 1: (50-300);
the reaction time is 10-30 hours; the reaction temperature is 0-40 ℃;
the peeling means includes one or more of ultrasonic peeling, sand grinding peeling, ball milling peeling and shearing peeling.
Preferably, the step 2) is specifically:
21) mixing the water-based resin and the auxiliary agent to obtain a mixture;
22) adding the mixture obtained in the step into the high-conductivity graphene slurry, mixing again, and standing to obtain the water-based conductive coating;
the remixing time is 15-60 min; the re-mixing rotating speed is 300-700 r/min;
the standing time is 15-45 min.
The invention provides a water-based conductive coating, which comprises water-based resin, high-conductivity graphene slurry and an auxiliary agent. Compared with the prior art, the invention aims at the problems of low adhesion of the water-based coating and easy falling off existing in the conductive performance of the existing water-based paint; the silver conductive paint has good conductivity, but is easy to have silver migration phenomenon; the copper-based conductive coating has the defects of easy oxidation and the like, and adopts graphene as a modified material of the water-based conductive coating; the method aims at the problems that the existing graphene is added into the water-based paint as a filler, the agglomeration is easy, the effect is not ideal, and other impurities are additionally introduced by adding different types of dispersing agents or modification modes.
According to the invention, the graphene raw material is creatively selected, the high-conductivity graphene is added, and in the auxiliary agent of the water-based paint, a specific kind is selected as a slurry mixing auxiliary agent to form slurry with the high-conductivity graphene, and then the slurry is mixed with other components as a whole, so that the graphene can be uniformly dispersed in the paint, and the special conductive water-based paint with excellent performances in all aspects is obtained, and has the characteristics of high conductivity and electromagnetic shielding performance, high hardness, good adhesive force, good corrosion resistance, no pollution and the like, and can meet various market requirements. Meanwhile, the preparation method has the advantages of simple process, mild conditions, safety and environmental protection, and is more suitable for industrialized mass production.
The preparation method provided by the invention is low in cost, can solve the problem that graphene is not uniformly mixed in a water-based paint system and is easy to agglomerate, can ensure uniform dispersion of graphene materials, and has a good flat laying state and fewer wrinkles; and the prepared coating has high conductivity and electromagnetic shielding performance, and also has the characteristics of high hardness, good adhesion, good corrosion resistance, environmental friendliness and the like.
Experimental results show that the resistivity of the water-based conductive coating containing the high-conductivity graphene is at least 1 omega-m, the hardness of a paint film is 2H, the adhesive force is grade 1, and the neutral salt spray time is over 600H.
Drawings
Fig. 1 is an atomic force microscope photograph of highly conductive graphene prepared in example 1 of the present invention;
fig. 2 is a thickness data curve of the highly conductive graphene prepared in example 1 according to the present invention measured by an atomic force microscope;
FIG. 3 is a schematic diagram of a process flow for preparing the composite waterborne acrylic conductive coating according to the present invention;
FIG. 4 is a scanning electron microscope image of the composite waterborne acrylic conductive coating prepared in example 2 of the present invention;
FIG. 5 is a paint film adhesion test chart of the composite waterborne acrylic conductive paint prepared in example 2 of the present invention;
FIG. 6 is a paint film impact resistance test chart of the composite waterborne acrylic conductive paint prepared in example 2 of the present invention.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in their purity, and the present invention preferably employs the conventional purity used in the field of analytical purity or aqueous coating composite materials.
All the raw materials, the marks and the acronyms thereof belong to the conventional marks and acronyms in the field, each mark and acronym is clear and definite in the field of related application, and the raw materials can be purchased from the market or prepared by a conventional method by the technical staff in the field according to the marks, the acronyms and the corresponding application.
The invention provides a water-based conductive coating, which comprises water-based resin, high-conductivity graphene slurry and an auxiliary agent.
The waterborne resin is not particularly limited in the present invention, and the type and type of the waterborne resin are well known to those skilled in the art, and those skilled in the art can select and adjust the waterborne resin according to the actual application, product requirements and quality requirements, and the waterborne resin of the present invention preferably includes one or more of waterborne acrylic acid, waterborne alkyd resin, waterborne epoxy resin, waterborne polyaniline resin, waterborne fluorocarbon resin and waterborne perchloroethylene resin, more preferably waterborne acrylic acid, waterborne alkyd resin, waterborne epoxy resin, waterborne polyaniline resin, waterborne fluorocarbon resin or waterborne perchloroethylene resin, and most preferably waterborne acrylic acid and/or waterborne alkyd resin.
The other parameters of the aqueous resin are not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to the practical application, product requirements and quality requirements.
The adding amount of the aqueous resin is not particularly limited, and the proportion of the conventional aqueous resin of the aqueous conductive coating material known to those skilled in the art can be selected and adjusted by those skilled in the art according to the actual application situation, the product requirement and the quality requirement, and the adding amount of the aqueous resin is preferably 20 to 80 parts by weight, more preferably 30 to 70 parts by weight, and more preferably 40 to 60 parts by weight.
In order to improve the practicability of the water-based conductive coating and widen the application field, the water-based conductive coating also comprises an auxiliary agent.
The addition amount of the auxiliary agent is not particularly limited, and the conventional auxiliary agent of the water-based paint is well known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to the actual application situation, the product requirement and the quality requirement, and the addition amount of the auxiliary agent is preferably 0.5 to 4 parts by weight, more preferably 1 to 3.5 parts by weight, more preferably 1.5 to 3.0 parts by weight, and more preferably 2.0 to 2.5 parts by weight.
The kind of the assistant is not particularly limited in the present invention, and may be a water-based paint assistant well known to those skilled in the art, and those skilled in the art can select and adjust the assistant according to the actual application, product requirements and quality requirements, and the assistant of the present invention preferably includes a flash rust inhibitor and/or a film-forming assistant, and more preferably includes a flash rust inhibitor and a film-forming assistant.
The addition amount of the flash rust inhibitor is not particularly limited, and the conventional flash rust inhibitor for the water-based paint can be prepared according to the mixing ratio well known to a person skilled in the art, and can be selected and adjusted by the person skilled in the art according to the actual application situation, the product requirement and the quality requirement, and the addition amount of the flash rust inhibitor is preferably 0.5-3.5 parts by weight, more preferably 1-3 parts by weight, and more preferably 1.5-2.5 parts by weight.
The anti-flash rust agent is not particularly limited, and can be selected and adjusted by the skilled person according to the actual application situation, the product requirement and the quality requirement, and the anti-flash rust agent preferably comprises one or more of sodium nitrite aqueous solution, NALZIN FA 179, CH07A and R-760F, and more preferably comprises sodium nitrite aqueous solution, NALZIN FA 179, CH07A or R-760F.
The addition amount of the film-forming aid is not particularly limited, and the conventional film-forming aid for the water-based paint can be prepared according to the proportion well known by the technicians in the field, and the technicians in the field can select and adjust the film-forming aid according to the actual application condition, the product requirement and the quality requirement, wherein the addition amount of the film-forming aid is preferably 0.2-2 parts by weight, more preferably 0.5-1.7 parts by weight, and more preferably 0.8-1.4 parts by weight.
The specific choice of the film-forming aid is not particularly limited by the present invention, and may be selected and adjusted by those skilled in the art according to the actual application, product requirements and quality requirements, and the film-forming aid for aqueous coating materials preferably includes one or more of texanol, DPnB, DPnP, TPnB and DPM, and more preferably texanol, DPnB, DPnP, TPnB or DPM.
The definition of graphene in the highly conductive graphene slurry is not particularly limited, and may be defined by graphene known to those skilled in the art, and those skilled in the art can select and adjust the graphene slurry according to practical application, product requirements and quality requirements, and the graphene in the present invention is preferably graphene in a broad sense, i.e. a graphene-based material, preferably includes one or more of graphene, graphene oxide, reduced graphene oxide and modified graphene, more preferably graphene, graphene oxide, reduced graphene oxide or modified graphene, and most preferably graphene.
The definition and parameters of the high-conductivity graphene in the high-conductivity graphene slurry are not particularly limited, and the definition and parameters of the high-conductivity graphene well known to those skilled in the art can be used, and those skilled in the art can select and adjust the definition and parameters according to the actual application situation, the product requirement and the quality requirement, in order to further improve the performance of the aqueous conductive coating, the carbon content of the high-conductivity graphene is preferably greater than or equal to 98%, more preferably greater than or equal to 98.5%, and more preferably greater than or equal to 99%. The conductivity of the highly conductive graphene is preferably 40000S/m or more, more preferably 45000S/m or more, still more preferably 55000S/m or more, and still more preferably 60000S/m or more.
The structure of the highly conductive graphene is not particularly limited in the present invention, and may be a structure of graphene known to those skilled in the art, and those skilled in the art can select and adjust the structure according to the actual application, product requirements, and quality requirements, and the highly conductive graphene of the present invention is in a flake shape, and the thickness of the highly conductive graphene is preferably not more than 100nm, more preferably not more than 50nm, and especially preferably not more than 30 nm.
The specific composition of the high-conductivity graphene slurry is not particularly limited, and a person skilled in the art can select and adjust the slurry according to the actual application condition, the product requirement and the quality requirement.
The addition amount of the highly conductive graphene is not particularly limited, and can be selected and adjusted by the skilled in the art according to the actual application situation, the product requirement and the quality requirement, and is preferably 1 to 30 parts by weight, more preferably 5 to 25 parts by weight, and more preferably 10 to 20 parts by weight.
The addition amount of the mixing aid is not particularly limited, and can be selected and adjusted by the person skilled in the art according to the actual application situation, the product requirements and the quality requirements, and the addition amount of the mixing aid is preferably 0.5 to 8 parts by weight, more preferably 1.5 to 7 parts by weight, more preferably 2.5 to 6 parts by weight, and more preferably 3.5 to 5 parts by weight.
The adding amount of the water is not particularly limited, and the proportion of the conventional solvent in the water-based paint is known by the skilled in the art, and the skilled in the art can select and adjust the water according to the actual application situation, the product requirement and the quality requirement, and the adding amount of the water is preferably 10-30 parts by weight, more preferably 12-28 parts by weight, more preferably 15-25 parts by weight, and more preferably 18-22 parts by weight.
The invention has no particular limitation on the type of the slurry mixing auxiliary agent, and the slurry mixing auxiliary agent can be an aqueous coating auxiliary agent well known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to the actual application situation, the product requirements and the quality requirements.
The invention creatively selects the assistant of the water-based conductive coating and mixes the assistant with the high-conductivity graphene, thereby effectively improving the dispersibility of the graphene in the coating and greatly improving the performance of the water-based coating.
The addition amount of the defoaming agent is not particularly limited, and the conventional defoaming agent for the water-based coating is well known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to the actual application, product requirements and quality requirements, and the addition amount of the defoaming agent is preferably 0.1 to 2 parts by weight, more preferably 0.3 to 1.8 parts by weight, more preferably 0.5 to 1.5 parts by weight, and more preferably 0.8 to 1.2 parts by weight.
The concrete selection of the defoaming agent is not particularly limited by the invention, and the defoaming agent for the water-based paint is well known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to the actual application situation, the product requirement and the quality requirement, and the defoaming agent of the invention preferably comprises one or more of tego902w, tego901, BYK-24, tego1488 and KOOLY-3150, and more preferably tego902w, tego901, BYK-24, tego1488 or KOOLY-3150.
The addition amount of the leveling agent is not particularly limited, and the proportion of the conventional leveling agent of the water-based paint known to those skilled in the art can be selected and adjusted by those skilled in the art according to the actual application situation, the product requirements and the quality requirements, and the addition amount of the leveling agent is preferably 0.1 to 2.5 parts by weight, more preferably 0.5 to 2.0 parts by weight, and more preferably 1 to 1.5 parts by weight.
The specific choice of the leveling agent is not particularly limited by the present invention, and the leveling agent can be selected and adjusted by the skilled person according to the practical application, product requirements and quality requirements, and the leveling agent of the present invention preferably comprises one or more of silok8244, silok315, silok23, silok8066 and silok333, more preferably silok8244, silok315, silok23, silok8066 or silok 333.
The addition amount of the leveling modifier is not particularly limited, and the proportion of the conventional leveling modifier of the water-based paint known to a person skilled in the art can be selected and adjusted by the person skilled in the art according to the actual application situation, the product requirement and the quality requirement, and the addition amount of the leveling modifier is preferably 0.1-2.5 parts by weight, more preferably 0.5-2.0 parts by weight, and more preferably 1-1.5 parts by weight.
The concrete choice of the leveling modifier is not particularly limited by the invention, and the leveling modifier for the waterborne coating is well known to the skilled person, and can be selected and adjusted by the skilled person according to the actual application situation, the product requirement and the quality requirement, and the leveling modifier of the invention preferably comprises one or more of RM-8W, RM-2020n and RM-12w, and more preferably RM-8W, RM-2020n or RM-12 w.
The addition amount of the wetting agent is not particularly limited, and the conventional wetting agent proportion of the water-based paint known to those skilled in the art can be used, and those skilled in the art can select and adjust the wetting agent according to the actual application situation, the product requirement and the quality requirement, and the addition amount of the wetting agent is preferably 0.1 to 2 parts by weight, more preferably 0.3 to 1.8 parts by weight, more preferably 0.5 to 1.5 parts by weight, and more preferably 0.8 to 1.2 parts by weight.
The specific choice of the wetting agent is not particularly limited by the present invention, and may be any wetting agent for aqueous coating materials known to those skilled in the art, and those skilled in the art can select and adjust the wetting agent according to the actual application, product requirements and quality requirements, and the wetting agent of the present invention preferably includes one or more of tego twin 4100, Surfynol 104A, silok8030 and silok8008, and more preferably tego twin 4100, Surfynol 104A, silok8030 or silok 8008.
The source of the high-conductivity graphene is not particularly limited, and the high-conductivity graphene can be obtained from conventional sources well known to those skilled in the art, can be purchased in the market, and can also be prepared by themselves, and those skilled in the art can select and adjust the high-conductivity graphene according to the actual application situation, the product requirements and the quality requirements, so that the performance of the water-based conductive coating is further improved, the dispersibility of the high-conductivity graphene in the water-based coating is improved, and the high-conductivity graphene is preferably prepared by the following method:
A) reacting graphite with a small molecular intercalation agent to obtain intercalated graphite;
B) performing high-temperature expansion on the intercalated graphite obtained in the step to obtain expanded graphite;
C) and stripping the expanded graphite obtained in the step in a stripping medium to obtain the graphene.
The invention firstly reacts graphite with a micromolecular intercalation agent to obtain the intercalation graphite.
The selection of the graphite is not particularly limited by the present invention, and the graphite material known to those skilled in the art can be selected and adjusted by those skilled in the art according to actual production conditions, product requirements and quality requirements, and the graphite of the present invention preferably includes one or more of graphite powder, flake graphite, artificial graphite, expandable graphite and expanded graphite, and more preferably includes graphite powder, flake graphite, artificial graphite, expandable graphite or expanded graphite.
The particle size of the graphite powder is not particularly limited, the particle size of the graphite powder known to those skilled in the art can be selected and adjusted by those skilled in the art according to actual production conditions, product requirements and quality requirements, and the particle size of the graphite powder is preferably 50-10000 meshes, more preferably 100-5000 meshes, more preferably 500-3000 meshes, and most preferably 1000-2000 meshes.
The carbon content of the graphite of the present invention is not particularly limited, and may be the carbon content of graphite powder known to those skilled in the art, and those skilled in the art can select and adjust the carbon content according to the actual production situation, the product requirement and the quality requirement, and the carbon content of the graphite of the present invention is preferably equal to or greater than 70%, more preferably equal to or greater than 80%, most preferably equal to or greater than 90%, specifically 70% to 95%, and may also be 75% to 90%, or 78% to 93%.
The small molecule intercalator is selected without any particular limitation, and can be selected and adjusted by those skilled in the art according to actual production conditions, product requirements and quality requirements, and is preferably a small molecule high temperature decomposable compound, more preferably one or more of sulfuric acid, nitric acid, urea, sodium bicarbonate, sodium dihydrogen carbonate, disodium hydrogen carbonate, oxalic acid, phosphoric acid, perchloric acid, periodic acid and trifluoromethanesulfonic acid, and more preferably sulfuric acid, nitric acid, urea, sodium hydrogen carbonate, sodium dihydrogen carbonate, disodium hydrogen carbonate, oxalic acid, phosphoric acid, perchloric acid, periodic acid or trifluoromethanesulfonic acid, in order to improve the performance of the final product. More preferably sulfuric acid, nitric acid, urea, sodium bicarbonate, sodium dihydrogen carbonate, disodium hydrogen carbonate, oxalic acid or phosphoric acid.
The invention has no special limitation on the dosage of the small molecule intercalation agent, and a person skilled in the art can select and adjust the dosage according to the actual production condition, the product requirement and the quality requirement, and in order to improve the performance of the final product, the mass ratio of the graphite to the small molecule intercalation agent is preferably 1: (1-5), more preferably 1: (1.5 to 4.5), more preferably 1: (2-4), most preferably 1: (2.5-3.5).
The reaction temperature is not particularly limited, and can be selected and adjusted by a person skilled in the art according to actual production conditions, product requirements and quality requirements, and in order to improve the performance of a final product and the advantages of a liquid phase separation method, the reaction temperature is particularly maintained at room temperature, namely the reaction temperature is preferably 0-40 ℃, more preferably 5-35 ℃, more preferably 10-30 ℃, and more preferably 15-25 ℃.
The reaction time is not particularly limited in the present invention, and the conventional intercalation reaction time of a liquid phase separation method known to those skilled in the art may be used, and those skilled in the art may select and adjust the reaction time according to the actual production situation, product requirements and quality requirements, and the reaction time in the present invention is preferably 10 to 30 hours, more preferably 12 to 28 hours, more preferably 15 to 25 hours, more preferably 17 to 24 hours, and specifically may be 10 hours, 15 hours, 20 hours or 30 hours.
According to the invention, the graphite is intercalated by adopting the micromolecular high-temperature decomposable intercalation agent, and micromolecular high-temperature decomposable compounds can realize that micromolecules enter the interlayer, so that the graphite reaction is reduced, and the complete structure of a graphite sheet layer is maintained; and the reaction condition of high temperature and high pressure is avoided, the temperature of intercalation reaction is further reduced, effective intercalation of graphite can be realized under the moderate conditions of lower temperature and common room temperature, a graphite intercalation compound is obtained, the loss and energy consumption in the preparation process are reduced, and the preparation method is green and environment-friendly.
In order to improve the practicability of the preparation method and complete the process route, the method preferably further comprises a post-treatment step after the reaction. The present invention does not specifically limit the specific steps of the post-treatment, and the post-treatment steps known to those skilled in the art can be selected and adjusted according to the actual production situation, the product requirements and the quality requirements, and the post-treatment of the present invention preferably includes water washing and separation, more preferably water washing to neutrality and centrifugal separation.
The invention then expands the intercalated graphite obtained in the above steps at high temperature to obtain expanded graphite.
The temperature of the high-temperature expansion is not particularly limited, the temperature of the high-temperature expansion is selected and adjusted by the temperature of the expansion known by the technical personnel in the field, and the technical personnel in the field can select and adjust the temperature according to the actual production condition, the product requirement and the quality requirement, and in order to improve the performance of the final product and the advantages of a liquid phase separation method, the temperature of the high-temperature expansion is preferably 500-1200 ℃, more preferably 600-1100 ℃, more preferably 700-1000 ℃, and more preferably 800-900 ℃.
The time of the high-temperature expansion is not particularly limited, and the time of the high-temperature expansion known to those skilled in the art can be selected and adjusted by those skilled in the art according to actual production conditions, product requirements and quality requirements, and the time of the high-temperature expansion is preferably 5 to 60 seconds, more preferably 10 to 55 seconds, more preferably 15 to 50 seconds, more preferably 25 to 40 seconds, and particularly may be 5 seconds, 10 seconds, 30 seconds or 60 seconds.
Finally, the expanded graphite obtained in the step is peeled in a peeling medium to obtain the graphene.
The exfoliated media of the present invention may also be understood as a dispersed phase, i.e., exfoliated after the expanded graphite has been diluted with a dispersant.
The selection of the stripping medium is not particularly limited by the present invention, and may be selected and adjusted by those skilled in the art according to the actual production situation, the product requirements and the quality requirements, and the stripping medium preferably includes one or more of water, urea aqueous solution, sodium dodecylbenzene sulfonate aqueous solution, ethanol aqueous solution, N-methylpyrrolidone, N-dimethylimide, tetrabutylammonium hydroxide, sodium dodecylsulfonate aqueous solution, sodium dodecylsulfate aqueous solution, tween 80, cetyltrimethylammonium bromide, nonylphenol polyether, P-123 and Dev2043, more preferably water, urea aqueous solution, sodium dodecylbenzene sulfonate aqueous solution, ethanol aqueous solution, N-methylpyrrolidone, N, n-dimethyl imide, tetrabutylammonium hydroxide, sodium dodecyl sulfate aqueous solution, Tween 80, hexadecyl trimethyl ammonium bromide, nonylphenol polyether, P-123 or Dev2043, specifically urea aqueous solution, sodium dodecyl benzene sulfonate aqueous solution, ethanol aqueous solution, N-methyl pyrrolidone or N, N-dimethyl imide, or water or organic matter aqueous solution.
The amount of the stripping medium used is not particularly limited, and can be selected and adjusted by those skilled in the art according to actual production conditions, product requirements and quality requirements, and in order to improve the performance of the final product, the mass ratio of the graphite to the stripping medium is preferably 1: (50-300), more preferably 1: (100 to 250), more preferably 1: (150-200).
The stripping temperature is not particularly limited, and the stripping temperature known to those skilled in the art can be selected and adjusted according to actual production conditions, product requirements and quality requirements, and is preferably room temperature, i.e., preferably 0 to 40 ℃, more preferably 5 to 35 ℃, more preferably 10 to 30 ℃, and more preferably 15 to 25 ℃ in order to improve the performance of the final product and the advantages of a liquid phase separation method.
The stripping time is not particularly limited in the present invention, and the stripping time known to those skilled in the art may be selected and adjusted by those skilled in the art according to actual production conditions, product requirements and quality requirements, and the stripping time in the present invention is preferably 3 to 24 hours, more preferably 6 to 20 hours, more preferably 10 to 16 hours, and specifically may be 3 hours, 6 hours, 9 hours or 24 hours.
The stripping manner is not particularly limited by the present invention, and may be selected and adjusted by those skilled in the art according to the actual production situation, product requirements and quality requirements, and for improving the performance of the final product, the stripping manner preferably includes one or more of ultrasonic stripping, sand grinding stripping, ball milling stripping and shearing stripping, more preferably ultrasonic stripping, sand grinding stripping, ball milling stripping or shearing stripping, and most preferably ball milling and ultrasonic stripping.
In order to improve the practicability of the preparation method and complete the process route, the method preferably further comprises a post-treatment step after stripping. The present invention does not specifically limit the specific steps of the post-treatment, which may be selected and adjusted by those skilled in the art according to the actual production situation, the product requirements and the quality requirements, and the post-treatment of the present invention preferably includes washing and/or drying.
The washing method of the present invention is not particularly limited, and may be selected and adjusted according to actual production conditions, product requirements and quality requirements by those skilled in the art, and the washing method of the present invention is preferably water washing. The standard of the washing is preferably to the pH value of 6-7.5, namely the pH value of the water after washing is preferably 6-7.5, and more preferably 6.5-7.
The present invention is not particularly limited to the specific steps and conditions for drying, and the specific steps and conditions for drying are well known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to the actual production situation, the product requirement and the quality requirement, and the drying manner of the present invention is preferably vacuum drying. The drying temperature is preferably 60-100 ℃, more preferably 70-90 ℃, and more preferably 75-85 ℃. The drying time is preferably 6-24 hours, more preferably 10-20 hours, and more preferably 12-18 hours.
The invention particularly adopts the combination of the process routes of micromolecule intercalation-high temperature expansion-ultrasonic ball milling stripping, and can quickly prepare the graphene under mild conditions at low cost. The graphene prepared by the invention has a complete lamellar structure, does not carry out surface modification, keeps the intrinsic characteristics of a two-dimensional lamellar,
according to the invention, the graphene raw material is creatively selected, the high-conductivity graphene with specific steps or parameters is further preferably added, specific types are selected from the additives of the water-based paint as a slurry mixing additive to form slurry with the high-conductivity graphene, the slurry is then mixed with other components as a whole, and finally, specific additives and the proportion combination of the components are combined, so that the graphene can be uniformly dispersed in the paint, and the special conductive water-based paint with excellent performances in all aspects is obtained, and has the characteristics of high conductivity and electromagnetic shielding performance, high hardness, good adhesion, good corrosion resistance, no pollution and the like, and can meet various market requirements.
The invention also provides a preparation method of the water-based conductive coating, which comprises the following steps:
1) the method comprises the following steps of mixing high-conductivity graphene, a slurry mixing auxiliary agent and water for the first time, and then grinding to obtain high-conductivity graphene slurry;
2) and mixing the high-conductivity graphene slurry obtained in the step, the water-based resin and the auxiliary agent again, and standing to obtain the water-based conductive coating.
The selection and composition of the raw materials required in the preparation process and the corresponding preferred principle can be corresponding to the selection and composition of the raw materials corresponding to the waterborne conductive coating and the corresponding preferred principle, and are not described in detail herein.
According to the invention, firstly, high-conductivity graphene, a slurry mixing auxiliary agent and water are primarily mixed and then ground to obtain high-conductivity graphene slurry.
The specific parameters of the highly conductive graphene are not particularly limited, and may be selected and adjusted by those skilled in the art according to the practical application, product requirements, and quality requirements, and the proportion of the graphene with 5 or less layers in the highly conductive graphene according to the present invention is preferably 80% or more, more preferably 85% or more, and more preferably 90% or more.
The way of the primary mixing is not particularly limited in the present invention, and the mixing way known to those skilled in the art can be selected and adjusted by those skilled in the art according to the actual production situation, the product requirement and the quality requirement, and the primary mixing of the present invention preferably includes stirring mixing.
The time for the primary mixing is not particularly limited, and the mixing time known to those skilled in the art can be selected and adjusted by those skilled in the art according to the actual production situation, the product requirement and the quality requirement, and the time for the primary mixing is preferably 15-60 min, more preferably 25-50 min, and more preferably 35-50 min.
The rotation speed of the primary mixing is not particularly limited in the invention, and can be selected and adjusted by the person skilled in the art according to the actual production condition, the product requirement and the quality requirement, and the rotation speed of the primary mixing is preferably 300-700 r/min, more preferably 350-650 r/min, more preferably 400-600 r/min, more preferably 450-550 r/min.
The grinding mode is not particularly limited by the invention, and can be selected and adjusted by the person skilled in the art according to the actual production situation, the product requirements and the quality requirements, and the grinding mode of the invention preferably comprises wet grinding, and more preferably wet ball milling.
The grinding time is not particularly limited in the invention, and the grinding time known by the skilled in the art can be selected and adjusted by the skilled in the art according to the actual production condition, the product requirement and the quality requirement, and the grinding time in the invention is preferably 20-80 min, more preferably 30-70 min, and more preferably 40-60 min.
The grinding rotating speed is not particularly limited, and can be selected and adjusted by a person skilled in the art according to the actual production condition, the product requirement and the quality requirement, and the grinding rotating speed is preferably 200-800 r/min, more preferably 300-700 r/min, and more preferably 400-600 r/min.
According to the invention, the high-conductivity graphene slurry obtained in the above step, the water-based resin and the auxiliary agent are mixed again and then are kept stand to obtain the water-based conductive coating.
The invention further improves the performance of the water-based conductive coating, improves the dispersibility of the high-conductivity graphene in the water-based coating, optimizes and completes the process route, and the step 2) is preferably as follows:
21) mixing the water-based resin and the auxiliary agent to obtain a mixture;
22) adding the mixture obtained in the step into the high-conductivity graphene slurry, mixing again, and standing to obtain the water-based conductive coating;
according to the invention, firstly, the aqueous resin and the auxiliary agent are mixed to obtain a mixture.
The mixing method and parameters are not particularly limited in the present invention, and can be selected and adjusted by those skilled in the art according to the actual production situation, the product requirement and the quality requirement, and the mixing method of the present invention preferably includes stirring mixing.
The mixture obtained in the step is added into the high-conductivity graphene slurry to be mixed again, and then the mixture is placed still to obtain the water-based conductive coating.
The mode of the remixing in the present invention is not particularly limited, and may be a mixing mode known to those skilled in the art, and may be selected and adjusted by those skilled in the art according to the actual production situation, the product requirement and the quality requirement, and the remixing in the present invention preferably includes stirring mixing and/or ultrasonic dispersion, and more preferably stirring mixing while ultrasonic.
The time for the remixing is not particularly limited in the present invention, and the mixing time known to those skilled in the art may be used, and those skilled in the art may select and adjust the remixing time according to the actual production situation, the product requirement and the quality requirement, and the remixing time in the present invention is preferably 15 to 60min, more preferably 25 to 50min, and more preferably 35 to 50 min.
The rotation speed of the remixing in the invention is not particularly limited, and the rotation speed of the remixing in the invention is selected and adjusted according to the actual production condition, the product requirement and the quality requirement, and the rotation speed of the remixing in the invention is preferably 300-700 r/min, more preferably 350-650 r/min, more preferably 400-600 r/min, more preferably 450-550 r/min.
The standing time is not particularly limited, and can be selected and adjusted by a person skilled in the art according to the actual production condition, the product requirement and the quality requirement, and the standing time is preferably 15-45 min, more preferably 20-40 min, and more preferably 25-35 min.
The steps of the invention provide a water-based conductive coating containing high-conductivity graphene, the invention creatively selects the graphene raw material, selects the high-conductivity graphene with specific steps or parameters, and can quickly prepare the graphene with low cost under mild conditions by adopting the combination of the process routes of small molecule intercalation, high temperature expansion and ultrasonic ball milling stripping; and the prepared graphene has a complete lamellar structure, is not subjected to surface modification, and keeps the intrinsic characteristics of a two-dimensional lamellar. The invention further selects a specific kind as a slurry mixing auxiliary agent from the auxiliary agents of the water-based paint to form slurry with the high-conductivity graphene, then mixes the slurry with other components as a whole, and finally combines the specific auxiliary agent and the proportion combination of the components to ensure that the graphene can be uniformly dispersed in the paint, thereby obtaining the special conductive water-based paint with excellent performances in all aspects, showing higher conductivity and electromagnetic shielding performance, having other characteristics of high hardness, good adhesive force, good corrosion resistance, no pollution and the like, and being capable of adapting to various marketization requirements.
The preparation method provided by the invention is low in cost, can solve the problem that graphene is not uniformly mixed in a water-based paint system and is easy to agglomerate, can ensure uniform dispersion of graphene materials, and has a good flat laying state and fewer wrinkles; and the prepared coating has high conductivity and electromagnetic shielding performance, and also has the characteristics of high hardness, good adhesion, good corrosion resistance, environmental friendliness and the like.
Experimental results show that the resistivity of the water-based conductive coating containing the high-conductivity graphene is at least 1 omega-m, the hardness of a paint film is 2H, the adhesive force is grade 1, and the neutral salt spray time is over 600H.
For further illustration of the present invention, the following will describe in detail a method for preparing an aqueous conductive coating according to the present invention with reference to the following examples, but it should be understood that these examples are carried out on the premise of the technical solution of the present invention, and the detailed embodiments and specific procedures are given, only for further illustration of the features and advantages of the present invention, not for limitation of the claims of the present invention, and the scope of the present invention is not limited to the following examples.
Example 1
High-conductivity graphene
The raw material is 1000 mesh natural graphite (Qingdao Dongkai graphite Co., Ltd.). Mixing 10g of graphite and 50g of sodium bicarbonate, dispersing the mixture in 100g of water, mechanically stirring the mixed solution, reacting for 20 hours at room temperature, adding 400g of water for dilution, and centrifuging to obtain the intercalated graphite. The intercalated graphite was placed in a muffle furnace at 1000 ℃ and expanded for 30 s. Dispersing 5g of expanded graphite in 5 LN-methyl pyrrolidone, ultrasonically stripping at 800W for 8h, ball-milling at 300rmp for 2h, centrifuging, washing with water, and drying to obtain the high-conductivity graphene.
The highly conductive graphene prepared in example 1 of the present invention was characterized.
Referring to fig. 1, fig. 1 is an atomic force microscope photograph of highly conductive graphene prepared in example 1 of the present invention.
The atomic force microscope photo in fig. 1 shows that the graphene sheet layer has a flat sheet structure, the plane size is about 6 μm, surface modification is not performed, and the intrinsic characteristics of a two-dimensional sheet layer are maintained, so that the graphene sheet layer has good conductivity.
The thickness of the highly conductive graphene prepared in embodiment 1 of the present invention is detected.
The test method comprises the following steps: the graphene sample thickness was measured by a PARK NX-10 atomic force microscope.
Referring to fig. 2, fig. 2 is a thickness data curve of the highly conductive graphene prepared in example 1 of the present invention measured by an atomic force microscope.
From the data analysis in fig. 2, it can be seen that the graphene thickness is 3nm or less and the number of layers is 10 or less.
The high-conductivity graphene prepared by the embodiment of the invention is subjected to element analysis.
The test method comprises the following steps: the element analysis of the graphene sample is obtained by testing an ELEMENTAR element analyzer.
Referring to table 1, table 1 is elemental analysis data of the highly conductive graphene prepared according to the embodiment of the present invention.
TABLE 1
As can be seen from table 1, the carbon content of the highly conductive graphene prepared in example 1 of the present invention reaches 99.414%.
The high-conductivity graphene prepared by the embodiment of the invention is measured for conductivity by a four-probe conductivity test method.
The test method comprises the following steps: the conductivity of the graphene samples was measured by pressing the samples into wafers of 10mm diameter, using a suzhou lattice four-probe conductivity tester.
The conductivity of the high-conductivity graphene prepared in the embodiment 1 of the invention reaches 51000S/m.
Example 2
Weighing 1.0g of the high-conductivity graphene dry powder prepared in the example 1, 10g of deionized water, 0.1g of a defoaming agent, 0.1g of a leveling agent, 0.1g of a wetting agent and 0.5g of a rheology modifier, and primarily mixing uniformly in a specified container; and (3) adding the preliminarily mixed materials into a ball mill for grinding for about 1h to fully grind the materials. 50g of water-based acrylic resin is weighed, 0.2g of flash rust inhibitor and 0.5g of film-forming assistant are added, and the mixture is fully stirred to be uniformly mixed. Mixing the ground slurry and the waterborne acrylic resin added with the specified auxiliary agent, adding the mixture into a specified container, and compounding for about 1.5 hours under the condition of ultrasonic 20kHz mechanical stirring for 200 r/min; and standing the compounded water-based paint at room temperature for about 30min to obtain the compound water-based acrylic conductive paint.
Referring to fig. 3, fig. 3 is a process flow diagram for preparing the composite waterborne acrylic conductive coating.
The paint film of the composite waterborne acrylic conductive paint prepared in the embodiment 2 of the invention is characterized.
Referring to fig. 4, fig. 4 is a scanning electron microscope image of the composite waterborne acrylic conductive coating prepared in example 2 of the present invention.
As can be seen from fig. 4, the graphene is uniformly mixed in the water-based paint system, does not agglomerate, is uniformly dispersed, and has a better flat state and less wrinkles.
The paint film of the composite waterborne acrylic conductive paint prepared in the embodiment 2 of the invention is subjected to adhesion detection by a circling method.
Referring to fig. 5, fig. 5 is a paint film adhesion test chart of the composite waterborne acrylic conductive paint prepared in example 2 of the present invention.
As can be seen from FIG. 5, the paint film adhesion of the composite waterborne acrylic conductive paint prepared by the invention is grade 1.
The paint film of the composite waterborne acrylic conductive paint prepared in the embodiment 2 of the invention is subjected to impact resistance detection.
Referring to fig. 6, fig. 6 is a paint film impact resistance test chart of the composite waterborne acrylic conductive paint prepared in example 2 of the present invention.
As can be seen from FIG. 6, the impact resistance of the paint film of the composite waterborne acrylic conductive paint prepared by the invention is more than 70.
The specific detection method and standard refer to corresponding methods and standards in national standards.
Referring to table 2, table 2 shows paint film property data of the composite waterborne conductive paint prepared by the embodiment of the invention.
TABLE 2
| Test items | Example 1 | Example 2 | Example 3 | |
| Paint film appearance | Is flat and smooth | Is flat and smooth | Is flat and smooth | |
| Water resistance | Normal paint film | Normal paint film | Normal paint film | |
| | Level | 1 | |
|
| |
70 | 70 | 50 | |
| Hardness of | H | H | | |
| Flexibility mm | ||||
| 1 | 1 | 1 | ||
| Salt spray resistance for 120h | Normal paint film | Normal paint film | Normal paint film | |
| Resistivity of | 200Ω/m | 5Ω/m | 20Ω/m |
Example 3
Weighing 10.0g of the high-conductivity graphene dry powder prepared in the example 1, 100g of deionized water, 0.8g of a defoaming agent, 0.8g of a leveling agent, 1.2g of a wetting agent and 3.5g of a rheology modifier, and primarily mixing uniformly in a specified container; and (3) adding the preliminarily mixed materials into a ball mill for grinding for about 1h to fully grind the materials. 50g of water-based acrylic resin is weighed, 0.8g of anti-flash rust agent and 2.5g of film-forming auxiliary agent are added, and the mixture is fully stirred to be uniformly mixed. Mixing the ground slurry and the waterborne acrylic resin added with the specified auxiliary agent, adding the mixture into a specified container, and compounding for about 2.0 hours under the condition of ultrasonic 20kHz mechanical stirring for 200 r/min; and standing the compounded water-based paint at room temperature for about 30min to obtain the compound water-based acrylic conductive paint.
The paint film of the composite waterborne acrylic conductive paint prepared in the embodiment 3 of the invention is detected.
The specific detection standard refers to corresponding standard in national standard.
Referring to table 2, table 2 shows paint film property data of the composite waterborne conductive paint prepared by the embodiment of the invention.
Example 4
Weighing 3.0g of commercially available high-conductivity graphene dry powder with the carbon content of more than or equal to 98% and the conductivity of more than or equal to 45000S/m, 25g of deionized water, 0.2g of defoaming agent, 0.3g of flatting agent, 0.2g of wetting agent and 1.2g of rheology modifier, and primarily mixing uniformly in a specified container; and (3) adding the preliminarily mixed materials into a ball mill for grinding for about 1h to fully grind the materials. 50g of water-based alkyd resin is weighed, 0.4g of anti-flash rust agent and 1.0g of film-forming auxiliary agent are added, and the mixture is fully stirred to be uniformly mixed. Mixing the ground slurry and the waterborne acrylic resin added with the specified auxiliary agent, adding the mixture into a specified container, and compounding for about 1.5 hours under the condition of ultrasonic 20kHz mechanical stirring for 200 r/min; and standing the compounded water-based paint at room temperature for about 30min to obtain the compound water-based acrylic conductive paint.
The paint film of the composite waterborne acrylic conductive paint prepared in the embodiment 4 of the invention is detected.
The specific detection standard refers to corresponding standard in national standard.
Referring to table 2, table 2 shows paint film property data of the composite waterborne conductive paint prepared by the embodiment of the invention.
The above detailed description of the present invention provides a highly conductive graphene-containing aqueous conductive coating and a method for preparing the same, and the principles and embodiments of the present invention are described herein with reference to specific examples, which are provided to facilitate understanding of the methods and their core concepts, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any combination of the methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (8)
1. The water-based conductive coating is characterized by comprising water-based resin, high-conductivity graphene slurry and an auxiliary agent;
based on the whole of the waterborne conductive coating,
20-80 parts by weight of the water-based resin;
1-30 parts by weight of high-conductivity graphene;
0.5-4 parts by weight of an auxiliary agent;
the high-conductivity graphene slurry comprises high-conductivity graphene, a slurry mixing auxiliary agent and water;
0.5-8 parts by weight of a slurry mixing auxiliary agent;
10-30 parts by weight of water;
the carbon content of the high-conductivity graphene is more than or equal to 98 percent;
the conductivity of the high-conductivity graphene is greater than or equal to 40000S/m;
the slurry mixing auxiliary agent comprises one or more of a defoaming agent, a leveling agent, a rheology modifier and a wetting agent.
2. The aqueous conductive coating of claim 1, wherein the aqueous resin comprises one or more of an aqueous acrylic acid, an aqueous alkyd resin, an aqueous epoxy resin, an aqueous polyaniline resin, an aqueous fluorocarbon resin, and an aqueous perchloroethylene resin;
the auxiliary agent comprises an anti-flash rust agent and/or a film forming auxiliary agent.
3. The aqueous conductive coating material according to claim 2, wherein the aqueous conductive coating material is, as a whole,
0.1-2 parts by weight of a defoaming agent;
0.1-2.5 parts by weight of the leveling agent;
0.1-2.5 parts by weight of the rheology modifier;
0.1-2 parts by weight of a wetting agent;
the flash rust inhibitor is 0.5-3.5 parts by weight;
the film forming auxiliary agent is 0.2-2 parts by weight.
4. The aqueous conductive coating of claim 2, wherein the defoamer comprises one or more of tego902w, tego901, BYK-24, tego1488, and KOOLY-3150;
the leveling agent comprises one or more of silok8244, silok315, silok23, silok8066 and silok 333;
the rheology modifier comprises one or more of RM-8W, RM-2020n and RM-12 w;
the wetting agent comprises one or more of tego twin 4100, Surfynol 104A, silok8030 and silok 8008;
the antiscratch agent comprises one or more of sodium nitrite aqueous solution, NALZIN FA 179, CH07A and R-760F;
the coalescent includes one or more of texanol, DPnB, DPnP, TPnB, and DPM.
5. The preparation method of the water-based conductive coating as claimed in any one of claims 1 to 4, characterized by comprising the following steps:
1) the method comprises the following steps of mixing high-conductivity graphene, a slurry mixing auxiliary agent and water for the first time, and then grinding to obtain high-conductivity graphene slurry;
2) and mixing the high-conductivity graphene slurry obtained in the step, the water-based resin and the auxiliary agent again, and standing to obtain the water-based conductive coating.
6. The preparation method according to claim 5, wherein the high-conductivity graphene is prepared by the following method:
A) reacting graphite with a small molecular intercalation agent to obtain intercalated graphite;
B) performing high-temperature expansion on the intercalated graphite obtained in the step to obtain expanded graphite;
C) and stripping the expanded graphite obtained in the step in a stripping medium to obtain the graphene.
7. The preparation method according to claim 6, wherein the mass ratio of the graphite to the small molecule intercalation agent is 1: (1-5);
the mass ratio of the graphite to the stripping medium is 1: (50-300);
the reaction time is 10-30 hours; the reaction temperature is 0-40 ℃;
the peeling means includes one or more of ultrasonic peeling, sand grinding peeling, ball milling peeling and shearing peeling.
8. The preparation method according to claim 5, wherein the step 2) is specifically:
21) mixing the water-based resin and the auxiliary agent to obtain a mixture;
22) adding the mixture obtained in the step into the high-conductivity graphene slurry, mixing again, and standing to obtain the water-based conductive coating;
the remixing time is 15-60 min; the re-mixing rotating speed is 300-700 r/min;
the standing time is 15-45 min.
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| CN110564233B (en) * | 2019-06-17 | 2021-06-29 | 山东欧铂新材料有限公司 | Water-based graphene conductive coating and preparation method thereof |
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