CN110964366A - Carbon-series conductive filler in water-based conductive electrostatic coating and preparation method thereof - Google Patents
Carbon-series conductive filler in water-based conductive electrostatic coating and preparation method thereof Download PDFInfo
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Abstract
A carbon-series conductive filler in a water-based conductive electrostatic coating and a preparation method thereof relate to the technical field of water-based coatings, and particularly design a conductive filler in a water-based conductive electrostatic coating and a preparation method thereof. The invention aims to improve the agglomeration phenomenon of the carbon-based conductive filler in the existing water-based conductive electrostatic coating. Preparing a carbon-based conductive filler in the water-based conductive electrostatic coating: firstly, calcining a carbon oxide conductive filler raw material at a high temperature; secondly, primary modification; and thirdly, grafting functional groups. The invention improves the dispersibility, conductivity, thermal stability, corrosion resistance and the like of the filler in the aqueous resin matrix.
Description
Technical Field
The invention relates to the technical field of water-based paint, in particular to a conductive filler in water-based conductive electrostatic paint and a preparation method thereof.
Background
The oil storage tank is an important device of an oil field, an oil refinery, an oil depot and a gas station, and the safe and long-term operation of the oil storage tank is always valued by the nation. Static electricity is generated due to friction in the processes of transportation, storage and filling of oil products, if the accumulated static electricity is not led out in time, when the discharge energy reaches the explosion limit of a mixture of combustible oil product steam and air, static electricity can be ignited or even exploded at any time, and great threats are brought to national property, ecological environment and personal safety.
The static conductive coating is a functional coating capable of conducting current, and can lead accumulated static out in time to avoid disaster accidents. The static conductive anticorrosive paint can reduce the corrosion rate and improve the static prevention effect of the storage tank. The water-based conductive coating has the advantages of low content, low pollution and the like, greatly saves energy and resources, and has good development prospect. The main research direction of foreign conductive anticorrosive coatings is to develop a conductive anticorrosive coating with high conductivity, low cost and environmental protection. The research of researchers in China focuses on developing multifunctional environment-friendly coatings with excellent static conductivity and corrosion resistance.
The electrostatic conductive coating is classified into an additive type (also called a doped type) and an intrinsic type. The film forming substance of the intrinsic conductive coating is a high molecular polymer with conductivity, the production cost is high, the preparation process is complex, and the large-scale industrial application is not much at present; the base resin of the additive type conductive coating is not conductive, conductive fillers (such as polypyrrole, graphite, conductive carbon black, carbon fibers, conductive metal powder and the like) with certain mass are required to be added to improve the static conductive performance of the resin, the preparation process is relatively simple, the types of the conductive fillers are various, the cost is low, the conductive fillers have good corrosion resistance, and the conductive fillers are widely applied to corrosion resistance and static conduction of the inner wall of an oil tank.
The dispersibility of the carbon-based conductive filler in an aqueous resin matrix solution is a problem. Carbon-based conductive fillers such as carbon black and graphite have a large specific surface area, are very likely to form a space conductive network, and can provide a composite system with good conductivity, but have strong structural properties, small particles and large surface energy, and the carbon-based conductive filler particles dispersed in an aqueous resin matrix solution are aggregated and aggregated nearby along with resin shrinkage during drying and curing, and finally form large aggregated groups, which affects the conductivity of a coating.
Disclosure of Invention
The invention aims to improve the agglomeration phenomenon of the carbon-based conductive filler in the existing water-based conductive electrostatic coating and improve the dispersibility, conductivity, thermal stability, corrosion resistance and the like of the filler in a water-based resin matrix.
The carbon series conductive filler in the water-based conductive electrostatic coating is prepared by the following steps:
firstly, calcining a carbon oxide conductive filler raw material at a high temperature;
secondly, primary modification: adding a modifying solvent into the carbon conductive filler calcined and oxidized at high temperature, adjusting the pH value to 3-5 by using organic acid, dropwise adding a primary modifier under the conditions of constant temperature and negative pressure, stirring and refluxing, cooling, filtering and drying to obtain a primary modified conductive filler;
thirdly, grafting functional groups: adding the primary modified conductive filler into a grafting solvent under the nitrogen atmosphere, then adding a modifying reagent, carrying out ultrasonic treatment, stirring, heating to 40-90 ℃, reacting for 30-150 min, and repeating the ultrasonic and heating stirring processes for N times; filtering, and repeatedly cleaning with acetone; and then drying and cooling to obtain the carbon-based conductive filler in the water-based conductive electrostatic coating.
The invention is calcined and oxidized at high temperature in order to realize the oxidation and modification of the microscopic surface of the carbon-based conductive filler raw material; the primary modification is to modify functional modifiers for transition on the microscopic surface, fault side and defect positions of the carbon-based conductive filler subjected to high-temperature calcination and oxidation, and to graft functional groups in the next step, so that the carbon-based conductive filler plays a role of a transition layer for realizing the characteristics of high dispersion, corrosion resistance and the like. The functional group grafting can further improve the dispersibility of the primary modified conductive filler in the water-based paint/emulsion, the functional group can promote the compatibility with the water-based paint/emulsion, can avoid the self-polymerization of the carbon conductive filler, and can provide better characteristics of corrosion resistance, thermal stability and the like for the water-based electrostatic conductive paint.
Drawings
Fig. 1 and 2 are microscopic views of the carbon-based conductive filler raw material in example 1 before high-temperature calcination and oxidation.
Fig. 3 and 4 are micrographs of the carbon-based conductive filler after high-temperature calcination and oxidation in example 1.
Fig. 5 is an XRD pattern of the carbon-based conductive filler after the high-temperature calcination and oxidation for different constant temperature periods in example 1.
FIG. 6 is a microscopic view of the carbon-based conductive filler material of example 2 before high-temperature calcination and oxidation.
Fig. 7 is a microscopic view of the carbon-based conductive filler after high-temperature calcination and oxidation in example 2.
Fig. 8 is an XRD pattern of the carbon-based conductive filler after the high-temperature calcination and oxidation for different constant temperature periods in example 2.
Fig. 9 is a microscopic view of the primarily modified conductive filler after the primary modification of example 3.
Fig. 10 is an infrared spectrum of the primary modified conductive filler after the primary modification of example 3.
Fig. 11 is a microscopic view of the primarily modified conductive filler after the primary modification of example 4.
Fig. 12 is an infrared spectrum of the primary modified conductive filler after the primary modification of example 4.
FIG. 13 is a microscopic view of a carbon-based conductive filler in the waterborne conductive coating of example 5.
FIG. 14 is an infrared spectrum of a carbon-based conductive filler in an aqueous conductive electrostatic coating of example 5.
FIG. 15 is a microscopic view of a carbon-based conductive filler in the aqueous conductive electrostatic coating of example 6.
FIG. 16 is an infrared spectrum of a carbon-based conductive filler in an aqueous conductive electrostatic coating of example 6.
FIG. 17 is a macroscopic photograph of the uniformity of dry cure of an electrostatic conductive coating prepared using the carbon-based conductive filler in the aqueous electrostatic conductive coating obtained in example 6.
FIG. 18 is a microscopic electron microscope picture of a dried and cured static conductive coating prepared using the carbon-based conductive filler in the aqueous static conductive coating obtained in example 6.
Fig. 19 is a graph showing the results of a conductivity test after drying and curing of an electrostatic conductive coating prepared using the carbon-based conductive filler in the aqueous electrostatic conductive coating obtained in example 6.
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The first embodiment is as follows: the carbon-based conductive filler in the water-based conductive electrostatic coating is prepared by the following steps:
firstly, calcining a carbon oxide conductive filler raw material at a high temperature;
secondly, primary modification: adding a modifying solvent into the carbon conductive filler calcined and oxidized at high temperature, adjusting the pH value to 3-5 by using organic acid, dropwise adding a primary modifier under the conditions of constant temperature and negative pressure, stirring and refluxing, cooling, filtering and drying to obtain a primary modified conductive filler;
thirdly, grafting functional groups: adding the primary modified conductive filler into a grafting solvent under the nitrogen atmosphere, then adding a modifying reagent, carrying out ultrasonic treatment, stirring, heating to 40-90 ℃, reacting for 30-150 min, and repeating the ultrasonic and heating stirring processes for N times; filtering, and repeatedly cleaning with acetone; and then drying and cooling to obtain the carbon-based conductive filler in the water-based conductive electrostatic coating.
And (3) dropwise adding the primary modifier under the conditions of constant temperature and negative pressure, so that the primary modifier is completely dissolved in the acidic mixed solution, and the stability of the acidic mixed solution is maintained, so that the phenomena of sedimentation, agglomeration and the like do not occur.
The second embodiment is as follows: the present embodiment differs from the first embodiment in that: stirring and mixing the carbon-series conductive filler raw materials uniformly, standing for 1-5h, adding an oxidation-assisted functional monomer, keeping the temperature of 30-80 ℃, stirring until the mixture is uniform, and then calcining at high temperature in a mixed atmosphere; wherein the heating rate of the high-temperature calcination is 4 ℃/min to 20 ℃/min, and the temperature is kept constant for 1h to 10h when the temperature is raised to 300 ℃ to 500 ℃. Other steps and parameters are the same as those in the first embodiment.
The control of the oxidation speed and the modification speed of the microscopic surface of the carbon-based conductive filler is realized by controlling the heating rate of the high-temperature calcination. The oxidation degree is accelerated due to the overhigh temperature rise rate, and the completeness of the carbon-series material is reduced due to excessive theoretical visual defects; and the energy consumption is increased when the temperature rise rate is too low, the production period is prolonged, and the auxiliary oxidant is separated from the surface of the conductive material due to the slow calcination speed.
The temperature-constant time of the embodiment can control the depth of the oxidation and modification of the microscopic surface of the carbon-based conductive filler.
The third concrete implementation mode: the present embodiment is different from the first or second embodiment in that: the carbon-based conductive filler is prepared from one or more of single-layer graphene oxide, single-layer reduced graphene, multi-layer graphene oxide, multi-layer reduced graphene, single-arm carbon nanotubes, multi-wall carbon nanotubes, graphite and carbon black. The other is the same as in the first or second embodiment.
The fourth concrete implementation mode: the present embodiment is different from one of the first to third embodiments in that: the oxidation-assisted functional monomer is one or more of isooctyl polyoxyethylene ether, octadecanol polyoxyethylene ether, phenethyl diphenol polyoxyethylene ether, fatty amide polyoxyethylene ether, rosin acid polyoxyethylene ester, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene glycol monomethyl ether acrylate, 2-hydroxyethyl acrylate, trimethylolpropane triacrylate and glycerol polyoxyethylene ether polyoxypropylene ether fatty acid ester. The others are the same as in one of the first to third embodiments.
The fifth concrete implementation mode: the present embodiment is different from one of the first to fourth embodiments in that: the primary modifier is one or more of 3-carboxypropyltrimethoxysilane, N- (2-aminoethyl) -3-aminobutyltrimethoxysilane, 3-carboxypropylethyldimethoxysilane, 3-carboxypropylethyldiethoxysilane, 3-hydroxypropyl triethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3-methacryloxyethyltrimethoxysilane. The other is the same as one of the first to fourth embodiments.
The sixth specific implementation mode: the present embodiment is different from one of the first to fifth embodiments in that: the modifying reagent is 1, 6-hexanediamine, N-ethylethylenediamine, N-N-propylethylenediamine, N-isopropylethylenediamine, N-dimethylethylenediamine, triethylenediamine, NN' -diethylethylenediamine, N-dimethylphenylenediamine, 2-nitro-1, 4-phenylenediamine, 2-dimethyl-1, 3-propanediamine, 1, 8-diaminonaphthalene, 2, 3-diaminonaphthalene, 1, 5-diaminonaphthalene, triethylenetetramine, N-chlorosuccinimide, N-diethylchloroacetamide, chlorooximinoacetic acid ethyl ester, chlorohexadecylpyridine, 4-chlorothiobenzamide, 2-amino-4-chlorobenzothiazole, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, methylpropyldiethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, hexadecyltrimethoxysilane, propyltrimethoxysilane, octyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane and/or 3-acetoxypropyltrimethoxysilane. The other is the same as one of the first to fifth embodiments.
The seventh embodiment: the present embodiment is different from one of the first to sixth embodiments in that: the grafting solvent is one or more of toluene, xylene, ethylbenzene, diethylbenzene, propylbenzene, isopropylbenzene, ethylene glycol monophenyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, phenol, cresol, methyl ether, diethyl ether, propyl ether, isopropyl ether, methyl n-butyl ether, acetone, methyl acetone, butanone and pentanone. The other is the same as one of the first to sixth embodiments.
The specific implementation mode is eight: the present embodiment is different from the first to seventh embodiments in that: the modifying solvent is toluene, xylene, isopropanol, n-butanol, ethanol or n-hexane. The other is the same as one of the first to seventh embodiments.
The specific implementation method nine: the present embodiment is different from the first to eighth embodiments in that: the mass ratio of the carbon-based conductive filler raw material to the pro-oxidative functional monomer is (5-10) to (2-5). The rest is the same as the first to eighth embodiments.
The detailed implementation mode is ten: the present embodiment is different from one of the first to ninth embodiments in that: the mixed atmosphere consists of inert gas and oxygen; the volume ratio of the inert gas to the oxygen is (1:10) - (1: 2). The other is the same as one of the first to ninth embodiments.
The composition and proportion of the mixed atmosphere in the high-temperature calcination oxidation process and the selection of the high-temperature calcination oxygen temperature gradient have important influence on increasing the activity of the microscopic active sites and components of the carbon-based conductive filler raw material.
The concrete implementation mode eleven: the present embodiment is different from the first to tenth embodiments in that: the mass ratio of the carbon-based conductive filler subjected to high-temperature calcination and oxidation to the primary modifier in the second step is (10-50): 2-10. The rest is the same as one of the first to tenth embodiments.
The specific implementation mode twelve: this embodiment is different from the first to eleventh embodiments in that: the mass ratio of the primary modified conductive filler to the grafting solvent is 1: 5-1: 50. The rest is the same as in one of the first to eleventh embodiments.
The specific implementation mode is thirteen: the present embodiment is different from the first to twelfth embodiments in that: the mass ratio of the primary modified conductive filler to the modifying reagent is 1: 1-10: 1. The rest is the same as the first to twelfth embodiments.
The specific implementation mode is fourteen: the present embodiment is different from one of the first to thirteenth embodiments in that: the organic acid is p-toluenesulfonic acid, sorbic acid, cinnamic acid, caffeic acid, maleic acid or maleic anhydride aqueous solution. The rest is the same as one of the first to the thirteenth embodiments.
The concrete implementation mode is fifteen: the present embodiment is different from the first to fourteenth embodiments in that: in the second step, the constant temperature is 60-90 ℃. The rest is the same as the first to the fourteenth embodiments.
The specific implementation mode is sixteen: the present embodiment is different from the first to fifteenth embodiments in that: in the second step, the negative pressure is-0.02 MPa to-0.06 MPa. The rest is the same as one of the first to fifteenth embodiments.
Seventeenth embodiment: the present embodiment is different from the first to sixteenth embodiments in that: filtering in the third step under the condition that the temperature of the reaction system is not lower than 40 ℃. The rest is the same as in one to sixteen embodiments.
The specific implementation mode is eighteen: the present embodiment is different from the first to seventeenth embodiments in that: the ultrasonic treatment time is 1 min-30 min. The rest is the same as one of the first to seventeenth embodiments.
The ultrasonic treatment can improve the probability of the modifying agent entering the micropores of the primary modified conductive filler.
The detailed embodiment is nineteen: the present embodiment is different from the first to eighteen embodiments in that: in the third step, N is 3-5. The rest is the same as in one of the first to eighteen embodiments.
The specific implementation mode twenty: the present embodiment is different from the first to nineteenth embodiments in that: and in the third step, repeatedly cleaning the glass substrate with acetone for 1-5 times. The others are the same as in one of the first to nineteenth embodiments.
The specific implementation mode is twenty one: the present embodiment is different from the first to the twentieth embodiments in that: the drying temperature in the third step is 80-120 ℃, and the vacuum drying time is 3-12 h. The rest is the same as in one of the first to twenty embodiments.
Example 1
High-temperature calcination and oxidation:
taking 10g of a carbon-series conductive filler raw material (consisting of 5 g of graphene and 5 g of graphite), stirring and mixing uniformly, and standing for 2 h; then 5 g of a functional monomer of the pro-oxidative type (3 g) was addedRosin acidPolyoxyethylene ester and 2 gPentaerythritol triacrylateComposition) and keeping the temperature at 60 ℃ to stir until the mixture is uniform and then standing for later use. Putting the mixed mixture for later use into a ceramic crucible and then placing the ceramic crucible into a muffle furnace, and introducing mixed gas of oxygen and inert atmosphere (argon) into the muffle furnace, wherein the volume ratio of the argon to the oxygen is 1: 5; heating to 450 ℃ according to the heating rate of 10 ℃/min, and keeping the temperature at 450 ℃ for 3h and 4.5 h.
Example 2
High-temperature calcination and oxidation:
taking 10g of a carbon-series conductive filler raw material (consisting of 5 g of multi-wall carbon nano tubes and 5 g of single-arm carbon nano tubes), stirring and mixing uniformly, and standing for 5 hours; then 8 g of oxidation-assisted functional monomer (consisting of 4 g of isooctyl polyoxyethylene ether and 4 g of octadecanol-based polyoxyethylene ether) is added, the mixture is kept at 60 ℃, stirred until the mixture is uniform and then kept stand for standby application. Putting the mixed mixture for later use into a ceramic crucible and then placing the ceramic crucible into a muffle furnace, and introducing mixed gas of oxygen and inert atmosphere (argon) into the muffle furnace, wherein the volume ratio of the argon to the oxygen is 1: 8; heating to 450 ℃ according to the heating rate of 10 ℃/min, and keeping the temperature at 450 ℃ for 3h and 4.5 h.
Example 3
Preliminary modification
10g of the carbon-based conductive filler calcined and oxidized at a high temperature in example 1 was added with a modifying solvent (xylene), and then with an organic acid (xylene)Sorbic acid) Adjusting the pH value to 4, and then carrying out water bath reaction on a magnetic heating stirrer; a vacuum pump is used for maintaining the negative pressure state of the reaction system, and the reactor is kept at-0.05 MPa; the method is characterized in that 10g of primary modifier (3-methacryloyloxyethyl trimethoxy silane) is dropwise added in a constant pressure manner, so that the primary modifier is completely dissolved in the acidic mixed solution, and the stability of the acidic mixed solution is maintained, so that the phenomena of sedimentation or agglomeration and the like are avoided. And (3) keeping the constant temperature of the primary modified water bath at 80 ℃, stirring and refluxing in the dripping process, stopping the reaction 4 hours after the dripping is finished, cooling the modified product, filtering and drying in vacuum.
Example 4
Preliminary modification
10g of the carbon conductive filler oxidized in the high-temperature calcination of example 2 was added with a modifying solvent (xylene), and then with an organic acid (xylene)Sorbic acid) Adjusting the pH value to 4, and then carrying out water bath reaction on a magnetic heating stirrer; a vacuum pump is used for maintaining the negative pressure state of the reaction system, and the reactor is kept at-0.05 MPa; the method is characterized in that 10g of primary modifier (3-methacryloyloxyethyl trimethoxy silane) is dropwise added in a constant pressure manner, so that the primary modifier is completely dissolved in the acidic mixed solution, and the stability of the acidic mixed solution is maintained, so that the phenomena of sedimentation or agglomeration and the like are avoided. And (3) keeping the constant temperature of the primary modified water bath at 80 ℃, stirring and refluxing in the dripping process, stopping the reaction 4 hours after the dripping is finished, cooling the modified product, filtering and drying in vacuum.
Example 5
Grafting of functional groups
Adding the primary modified conductive filler prepared in the embodiment 3 into a grafting solvent (methyl ether) in a nitrogen atmosphere, wherein the mass ratio of the primary modified conductive filler to the methyl ether is 1: 5; then the modifying reagent (3-methacryloxypropylmethyldiethoxysilane and4-chlorothiobenzamide3-methacryloxypropylmethyldiethoxysilaneAnd4-chlorothiobenzene CarboxamidesThe volume ratio of the modified reagent to the primary modified conductive filler is 1:1), the modified reagent and the primary modified conductive filler are subjected to ultrasonic treatment for 10 minutes, then are stirred and heated to 60 ℃ for reaction for 100 minutes, and the ultrasonic and heating stirring processes are repeated for 5 times; filtering the reaction system at the temperature of not lower than 40 ℃, and repeatedly cleaning the reaction system for 5 times by using acetone; and then, carrying out vacuum drying and standing for 12h at 100 ℃, and cooling to obtain the carbon-based conductive filler in the water-based conductive electrostatic coating.
Example 6
Grafting of functional groups
Adding the primary modified conductive filler prepared in the example 4 into a grafting solvent (isopropanol) in a nitrogen atmosphere, wherein the mass ratio of the primary modified conductive filler to the isopropanol is 2: 5; then adding modifying reagents (2, 2-dimethyl-1, 3-propane diamine and 3-methacryloxypropyl trimethoxy silane,2, 2-dimethyl-1, 3-propanediamineThe volume ratio of the modified conductive filler to 3-methacryloxypropyltrimethoxysilane is 1:1), the mass ratio of the modified reagent to the primary modified conductive filler is 1:5, the ultrasonic treatment is carried out for 10 minutes, the mixture is stirred and heated to 60 ℃ for reaction for 100min, and the ultrasonic and heating stirring processes are repeated for 5 times; filtering the reaction system at the temperature of not lower than 40 ℃, and repeatedly cleaning the reaction system for 5 times by using acetone; and then, carrying out vacuum drying and standing for 12h at 100 ℃, and cooling to obtain the carbon-based conductive filler in the water-based conductive electrostatic coating.
The static conductive coating prepared by using the carbon-based conductive filler in the water-based static conductive coating obtained in the embodiment, wherein the water-based resin matrix solution is a polyurethane water-based emulsion; the adding amount of the carbon-series conductive filler is 5 to 20 percent of the mass of the aqueous resin matrix solution. A macroscopic photograph of the uniformity of the waterborne electrostatic conductive coating added with 10% of the carbon-based conductive filler after drying and curing is shown in fig. 17; a microscopic electron microscope picture of the static conductive coating after drying and curing is shown in fig. 18; FIG. 19 shows the results of the conductivity test after the electrostatic conductive coating is dried and cured, with a surface resistance of 2.3 x 107Ω。
Although the invention has been described above by way of general illustration and specific embodiments, it is within the scope of the invention as claimed that modifications and improvements may be made thereto without departing from the spirit of the invention.
Claims (10)
1. The preparation method of the carbon-based conductive filler in the water-based conductive electrostatic coating is characterized in that the carbon-based conductive filler in the water-based conductive electrostatic coating is prepared according to the following steps:
firstly, calcining a carbon oxide conductive filler raw material at a high temperature;
secondly, primary modification: adding a modifying solvent into the carbon conductive filler calcined and oxidized at high temperature, adjusting the pH value to 3-5 by using organic acid, dropwise adding a primary modifier under the conditions of constant temperature and negative pressure, stirring and refluxing, cooling, filtering and drying to obtain a primary modified conductive filler;
thirdly, grafting functional groups: adding the primary modified conductive filler into a grafting solvent under the nitrogen atmosphere, then adding a modifying reagent, carrying out ultrasonic treatment, stirring, heating to 40-90 ℃, reacting for 30-150 min, and repeating the ultrasonic and heating stirring processes for N times; filtering, and repeatedly cleaning with acetone; and then drying and cooling to obtain the carbon-based conductive filler in the water-based conductive electrostatic coating.
2. The preparation method of the carbon-based conductive filler in the water-based conductive electrostatic paint according to claim 1, characterized in that the raw materials of the carbon-based conductive filler are uniformly stirred and mixed, then the oxidation-assisted functional monomer is added and stirred at 30-80 ℃ until the mixture is uniform, and then the mixture is calcined at high temperature in a mixed atmosphere; wherein the heating rate of the high-temperature calcination is 4 ℃/min to 20 ℃/min, and the temperature is kept constant for 1h to 10h when the temperature is raised to 300 ℃ to 500 ℃.
3. The method for preparing the carbon-based conductive filler in the aqueous conductive electrostatic coating according to claim 2, wherein the raw material of the carbon-based conductive filler is one or more of single-layer graphene oxide, single-layer reduced graphene, multi-layer graphene oxide, multi-layer reduced graphene, single-arm carbon nanotubes, multi-wall carbon nanotubes, graphite and carbon black; the oxidation-assisted functional monomer is one or more of isooctyl polyoxyethylene ether, octadecanol polyoxyethylene ether, phenethyl diphenol polyoxyethylene ether, fatty amide polyoxyethylene ether, rosin acid polyoxyethylene ester, pentaerythritol triacrylate, pentaerythritol tetraacrylate, ethylene glycol monomethyl ether acrylate, 2-hydroxyethyl acrylate, trimethylolpropane triacrylate and glycerol polyoxyethylene ether polyoxypropylene ether fatty acid ester.
4. The method for preparing the carbon-based conductive filler in the aqueous conductive static coating according to claim 1, wherein the primary modifier is one or more of 3-carboxypropyltrimethoxysilane, N- (2-aminoethyl) -3-aminobutyltrimethoxysilane, 3-carboxypropylethyldimethoxysilane, 3-carboxypropylethyldiethoxysilane, 3-hydroxypropyltriethoxysilane, 3-methacryloxypropyltrimethoxysilane and 3-methacryloxyethyltrimethoxysilane.
5. The method for preparing the carbon-based conductive filler in the aqueous electrostatic conductive coating according to claim 1, wherein the modifying agent is 1, 6-hexanediamine, N-ethylethylenediamine, N-N-propylethylenediamine, N-isopropylethylenediamine, N-dimethylethylenediamine, triethylenediamine, NN' -diethylethylenediamine, N-dimethylphenylenediamine, 2-nitro-1, 4-phenylenediamine, 2-dimethyl-1, 3-propanediamine, 1, 8-diaminonaphthalene, 2, 3-diaminonaphthalene, 1, 5-diaminonaphthalene, triethylenediamine, N-chlorosuccinimide, N-diethylchloroacetamide chloride, ethylhydroxamoacetate, cetylpyridinium chloride, 4-chlorothiobenzamide, N-dimethylnaphthalenes, 2-amino-4-chlorobenzothiazole, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldiethoxysilane, methylpropyldiethoxysilane, octyltriethoxysilane, dodecyltrimethoxysilane, hexadecyl trimethoxy silane, propyl trimethoxy silane, octyl trimethoxy silane, 3-methacryloxypropyl triethoxy silane, 3-methacryloxypropyl methyl dimethoxy silane, 3-methacryloxypropyl methyl diethoxy silane and one or more of 3-acetoxypropyl trimethoxy silane.
6. The method for preparing the carbon-based conductive filler in the water-based conductive electrostatic paint as claimed in claim 1, wherein the grafting solvent is one or more of toluene, xylene, ethylbenzene, diethylbenzene, propylbenzene, isopropylbenzene, ethylene glycol monophenyl ether, ethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, phenol, cresol, methyl ether, diethyl ether, propyl ether, isopropyl ether, methyl n-butyl ether, acetone, methyl acetone, butanone and pentanone.
7. The method for preparing the carbon-based conductive filler in the aqueous conductive electrostatic paint according to claim 1, wherein the modifying solvent is toluene, xylene, isopropanol, n-butanol, ethanol or n-hexane.
8. The method for preparing the carbon-based conductive filler in the water-based conductive electrostatic coating as claimed in claim 2, wherein the mass ratio of the raw material of the carbon-based conductive filler to the pro-oxidative functional monomer is (5-10): 2-5); the mixed atmosphere consists of inert gas and oxygen; the volume ratio of the inert gas to the oxygen is (1:10) - (1: 2).
9. The method for preparing the carbon-based conductive filler in the water-based conductive electrostatic coating according to claim 1, wherein the mass ratio of the carbon-based conductive filler subjected to high-temperature calcination and oxidation to the primary modifier in the second step is (10-50): (2-10); the mass ratio of the primary modified conductive filler to the grafting solvent in the third step is (1:5) - (1: 50); the mass ratio of the primary modified conductive filler to the modifying reagent in the third step is (1:1) - (10: 1).
10. A carbon-based conductive filler in an aqueous conductive electrostatic paint, characterized in that the carbon-based conductive filler in the aqueous conductive electrostatic paint is the carbon-based conductive filler prepared by the method of claim 1.
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