CN108047835B - Electrostatic shielding graphene anticorrosive paint and preparation method thereof - Google Patents
Electrostatic shielding graphene anticorrosive paint and preparation method thereof Download PDFInfo
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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
- C09D127/00—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 a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
- C09D127/16—Homopolymers or copolymers of vinylidene fluoride
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- C09D171/00—Coating compositions based on polyethers obtained by reactions forming an ether link in the main chain; Coating compositions based on derivatives of such polymers
- C09D171/02—Polyalkylene oxides
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- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- 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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- C08L2201/04—Antistatic
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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Abstract
The invention relates to the field of coatings, in particular to an electrostatic shielding graphene anticorrosive coating and a preparation method thereof, wherein the electrostatic shielding graphene anticorrosive coating comprises the following substances in parts by weight: 60-80 parts of organic polymer emulsion, 10-25 parts of electrostatic shielding agent, 5-20 parts of conductive filler, 5-8 parts of dispersing agent, 3-8 parts of coupling agent, 1-5 parts of defoaming agent and 3-9 parts of flatting agent; the electrostatic shielding agent sequentially comprises porous microspheres, a graphene film and a polyacetylene film from inside to outside, and graphite can be uniformly distributed on the surfaces of the porous microspheres and then sealed by the polyacetylene film to prevent the agglomeration of the graphene film. The electrostatic shielding agent is added into the coating, so that the electrostatic shielding effect and stability of the coating can be obviously improved, the agglomeration of graphene in the coating can be prevented, the stability of the graphene is improved, and the stability of the coating is improved.
Description
Technical Field
The invention relates to the field of coatings, in particular to an electrostatic shielding graphene anticorrosive coating and a preparation method thereof.
Background
Electrostatic discharge is a phenomenon which is common in daily life, and in a dry environment, a human body sometimes feels electricity when contacting a metal object and occasionally sees electric sparks, namely the electrostatic discharge phenomenon, namely the ESD phenomenon. Due to mutual friction between objects, static electricity is easy to accumulate, static electricity harm occurs, normal work of electronic computers and precision instruments is disturbed, and explosion and fire disasters can be caused in serious cases. Electrostatic discharge produces a brief discharge current and a strong magnetic discharge field. The malfunction of the running electronic equipment can be caused, and even the internal components are damaged, so that the equipment loses functions.
The polymer material is a material composed of a compound having a relatively high molecular mass, and includes rubber, plastic, fiber, paint, adhesive, polymer-based composite material, and the like. Most of polymer materials based on polymer compounds are insulators, but are also charged by static electricity. Static electricity accumulated on the surfaces of non-metal parts such as high polymer materials can be discharged to a certain degree, so that various precision instruments and precision electronic components are broken down and scrapped, and even inflammable and explosive substances are ignited or exploded, and huge life and property losses are caused. In addition, static electricity accumulated on the surface of the plastic product is difficult to be purified due to serious dust absorption, thereby affecting the appearance of the plastic product and the application in ultra-clean environments (such as operating rooms, computer rooms, precision instruments and the like). In order to prevent static electricity from adhering to the surface of the polymer material, there are two methods for treating the polymer material: one is external coating type, and the other is internal addition type. The external coating type is to form a coating film on the surface of plastic by using an antistatic coating to prevent generation or accumulation of static electricity. Chen Zhanli et al use acrylic resin as a base material, and add some conductive materials such as graphite to make the surface resistivity of the coating be 106-9 ohm/cm. However, most of the paints obtained by the method of adding the conductive material have poor adhesion and oil resistance, and the cost is relatively high. Because some conductive coatings can be used for static prevention, the conductive coatings can also be directly coated on the surface of the plastic to form an antistatic layer to play a role in static prevention, for example, the conductive polyaniline composite nano-coating can be directly sprayed or brushed on the plastic substrate. However, these materials are not easy to handle and are difficult to process.
Chinese patent with application number CN201410396314.8 discloses a highly hydrophobic antistatic composite coating and a preparation method thereof, wherein graphite powder and sodium nitrate are added into concentrated sulfuric acid, potassium permanganate is added after ice bath stirring, distilled water is slowly dripped, excessive potassium permanganate is removed, sulfate ions are filtered to obtain graphite oxide, the graphite oxide is added into an organic solvent, and graphene oxide solution is prepared through ultrasonic treatment; adding isocyanic acid, a long-chain modifier and a reducing agent into the graphene oxide solution in sequence to chemically modify the graphene oxide, washing and drying to obtain modified graphene; resin is used as a matrix, and the resin and the modified graphene are uniformly dispersed through ultrasonic blending or rapid stirring to obtain the highly hydrophobic anti-static composite coating. The composite coating provided by the invention has both hydrophobicity and antistatic performance, does not contain any fluorine-containing substance, is environment-friendly and has excellent durability, but because graphene can generate self-aggregation to destroy the uniformity and compactness of dispersion, the graphene is aggregated when being applied to the coating, and stress concentration is generated inside a coating film to reduce the mechanical performance and the anticorrosive performance. At present, graphene is applied in an anticorrosive coating and has the defects of difficult dispersion and easy overlapping and aggregation of graphene layers.
Disclosure of Invention
Aiming at the defect that graphene is easy to be overlapped and aggregated in the coating in the prior art, the invention aims to provide the preparation method of the electrostatic shielding graphene anticorrosive coating, which has excellent electrostatic shielding effect and anticorrosive performance and uniform distribution of graphene.
In order to solve the problems, the invention adopts the following technical scheme:
an electrostatic shielding graphene anticorrosive paint comprises the following substances in parts by weight: 60-80 parts of organic polymer emulsion, 10-25 parts of electrostatic shielding agent, 5-20 parts of conductive filler, 5-8 parts of dispersing agent, 3-8 parts of coupling agent, 1-5 parts of defoaming agent and 3-9 parts of flatting agent; wherein the electrostatic shielding agent is spherical particles and sequentially comprises porous microspheres, a graphene film and a polyacetylene film from inside to outside
The electrostatic shielding agent comprises porous microspheres, a graphene film and a polyacetylene film from inside to outside in sequence, wherein the graphene film is uniformly distributed on the surfaces of the porous microspheres and then is sealed by the polyacetylene film to prevent the graphene film from agglomerating.
According to the invention, in order to optimize the electrostatic shielding effect of the graphene anticorrosive paint and improve the dispersibility of graphene, under the preferable conditions, the electrostatic shielding graphene anticorrosive paint comprises the following substances in parts by weight: 65-75 parts of organic polymer emulsion, 15-20 parts of electrostatic shielding agent, 10-15 parts of conductive filler, 5-8 parts of dispersing agent, 3-8 parts of coupling agent, 1-5 parts of defoaming agent and 3-9 parts of flatting agent.
According to the invention, in order to optimize the electrostatic shielding effect of the graphene anticorrosive coating and improve the dispersibility of the graphene film, under the preferable condition, the specific surface area of the porous microspheres is 500-800 m2The particle size is 1-20 microns, and the pore diameter is 10-80 nanometers.
According to the invention, in order to improve the stability of the electrostatic shielding agent, under the preferable condition, the thickness of the graphene film is 20-50 nanometers; the thickness of the polyethylene film is 0.5-5 microns.
According to the present invention, it is preferable that the organic polymer emulsion has a solid content of more than 30% and is at least one selected from the group consisting of polyvinylidene fluoride emulsion, polybutylene terephthalate emulsion, polyarylate emulsion, polyvinyl acetate emulsion, nylon 6 emulsion, polymethyl methacrylate emulsion, polyaniline emulsion, polyethylene oxide emulsion, polyvinylpyrrolidone emulsion, polyacrylonitrile emulsion, polycaprolactone emulsion, polyurethane emulsion, fluorinated polyurethane emulsion, polysulfone emulsion, polyethersulfone emulsion, polyvinylidene fluoride-hexafluoropropylene emulsion, polyvinylidene fluoride-tetrafluoroethylene-perfluoromethyl vinyl ether emulsion, and polyvinylidene fluoride-chlorotrifluoroethylene emulsion.
According to the present invention, preferably, the conductive filler is at least one selected from carbon nanotubes, carbon fibers, metal nanowires, metal nanoparticles, metal oxide particles, and carbon black, and may be at least one selected from gold nanowires, silver nanoparticles, and the like.
According to the invention, the dispersant is preferably at least one selected from water glass, sodium tripolyphosphate, sodium hexametaphosphate, sodium pyrophosphate, triethylhexylphosphoric acid, methylpentanol, cellulose derivatives, polyacrylamide, Guel gum, fatty acid polyglycol ester, polyethylene glycol 200 or 400.
According to the present invention, it is preferable that the coupling agent is at least one selected from the group consisting of aminopropyltriethoxysilane, aminopropyltrimethoxysilane, 2-aminoethylaminopropyltrimethoxysilane, diethylenetriaminopropyltrimethoxysilane, aminoethylaminopropylmethyldimethoxysilane, aminoethylaminopropyltriethoxysilane, ureidopropyltriethoxysilane, and ureidopropyltrimethoxysilane.
According to the present invention, it is preferable that the defoaming agent is at least one selected from the group consisting of silicone emulsion, higher alcohol fatty acid ester complex, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether, and polydimethylsiloxane.
According to the invention, the levelling agent is preferably selected from BYK 331, BYK 346, BYK348, BYK 354 of German Bick chemistry, or at least one of TEGO 440, TEGO 450, TEGO 482 of German digao.
The invention also provides a preparation method of the electrostatic shielding graphene anticorrosive paint, which comprises the following steps:
(1) placing the porous microspheres and a surfactant in a dispersion liquid of graphene oxide, performing ultrasonic dispersion for 10-30 min, then drying, spraying polyacetylene on the surfaces of the porous microspheres by using a spray dryer, and drying to obtain an electrostatic shielding agent;
(2) and uniformly mixing the organic polymer emulsion, the conductive filler, the dispersing agent, the coupling agent, the defoaming agent and the leveling agent, and then adding the electrostatic shielding agent for uniform ultrasonic dispersion to obtain the electrostatic shielding graphene anticorrosive paint.
Compared with the prior art, the preparation method of the electrostatic shielding graphene anticorrosive paint has the outstanding characteristics and excellent effects that:
the electrostatic shielding agent comprises porous microspheres, a graphene film and a polyacetylene film from inside to outside in sequence, and graphite can be uniformly distributed on the surfaces of the porous microspheres and then sealed by the polyacetylene film to prevent the agglomeration of the graphene film. The electrostatic shielding agent is added into the coating, so that the electrostatic shielding effect and stability of the coating can be obviously improved, the agglomeration of graphene in the coating can be prevented, the stability of the graphene is improved, and the stability of the coating is improved.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but it should not be construed that the scope of the present invention is limited to the following examples. Various substitutions and alterations can be made by those skilled in the art and by conventional means without departing from the spirit of the method of the invention described above.
Example 1
An electrostatic shielding graphene anticorrosive paint comprises the following substances in parts by weight: 65 parts of polyvinylidene fluoride-tetrafluoroethylene-perfluoromethyl vinyl ether emulsion, 15 parts of electrostatic shielding agent, 15 parts of gold nanowire, 5 parts of sodium tripolyphosphate, 8 parts of aminopropyltriethoxysilane, 2 parts of polyoxypropylene glycerol ether and 3543 parts of BYK.
The preparation method of the electrostatic shielding graphene anticorrosive paint comprises the following steps:
placing porous carbon microspheres and surfactant stearic acid in dispersion liquid of graphene oxide, performing ultrasonic dispersion for 10-30 min, drying, spraying polyacetylene on the surfaces of the porous microspheres by using a spray dryer, and drying to obtain an electrostatic shielding agent;
uniformly mixing polyvinylidene fluoride-tetrafluoroethylene-perfluoromethyl vinyl ether emulsion, gold nanowires, sodium tripolyphosphate, aminopropyltriethoxysilane, polyoxypropylene glycerol ether and BYK 354, adding an electrostatic shielding agent, and uniformly dispersing by ultrasound to obtain the electrostatic shielding graphene anticorrosive paint.
In this embodiment, the specific surface area of the porous carbon microsphere is 750m2(ii)/g, particle size 15 microns, pore size 50 nanometers;
the thickness of the graphene film is 30 nanometers; the thickness of the polyacetylene thin film is 3 micrometers.
Example 2
An electrostatic shielding graphene anticorrosive paint comprises the following substances in parts by weight: 75 parts of polyvinylidene fluoride emulsion, 20 parts of electrostatic shielding agent, 10 parts of carbon black, 8 parts of sodium tripolyphosphate, 3 parts of diethylenetriaminopropyltrimethoxysilane, 3 parts of polyoxypropylene glycerol ether and 9 parts of BYK 348.
The preparation method of the electrostatic shielding graphene anticorrosive paint comprises the following steps:
placing porous polystyrene microspheres and surfactant sodium fatty alcohol sulfate in dispersion liquid of graphene oxide, performing ultrasonic dispersion for 10-30 min, drying, spraying polyacetylene on the surfaces of the porous microspheres by using a spray dryer, and drying to obtain an electrostatic shielding agent; the using amount of the fatty alcohol sodium sulfate is 5 percent of the mass of the porous polystyrene microsphere;
uniformly mixing polyvinylidene fluoride emulsion, carbon black, sodium tripolyphosphate, diethylenetriaminopropyltrimethoxysilane, polyoxypropylene glycerol ether and BYK348, adding an electrostatic shielding agent, and uniformly dispersing by ultrasound to obtain the electrostatic shielding graphene anticorrosive paint.
In this embodiment, the specific surface area of the porous microspheres is 680m2(ii)/g, particle size of 10 microns, pore size of 20 nanometers;
the thickness of the graphene film is 35 nanometers; the thickness of the polyacetylene thin film is 4 micrometers.
Example 3
An electrostatic shielding graphene anticorrosive paint comprises the following substances in parts by weight: 80 parts of polyurethane emulsion, 25 parts of electrostatic shielding agent, 5 parts of silver nanoparticles, 8 parts of polyacrylamide, 3 parts of aminopropyltriethoxysilane, 5 parts of polyoxyethylene polyoxypropylene amine ether and 3463 parts of BYK;
the preparation method of the electrostatic shielding graphene anticorrosive paint comprises the following steps:
placing porous ceramic microspheres and a fluorocarbon surfactant in dispersion liquid of graphene oxide, performing ultrasonic dispersion for 10-30 min, drying, spraying polyacetylene on the surfaces of the porous microspheres by using a spray dryer, and drying to obtain an electrostatic shielding agent;
uniformly mixing the polyurethane emulsion, the silver nanoparticles, the polyacrylamide, the aminopropyltriethoxysilane, the polyoxyethylene polyoxypropylene amine ether and the BYK 346, adding an electrostatic shielding agent, and uniformly dispersing by ultrasonic to obtain the electrostatic shielding graphene anticorrosive paint.
In this embodiment, the specific surface area of the porous ceramic microspheres is 800m2(ii)/g, particle size of 1 micron, pore size of 10 nanometers;
the thickness of the graphene film is 20 nanometers; the thickness of the polyacetylene film is 0.5 micrometer.
Example 4
An electrostatic shielding graphene anticorrosive paint comprises the following substances in parts by weight: 60 parts of fatty acid polyethylene glycol ester, 10 parts of electrostatic shielding agent, 20 parts of carbon nano tube, 5 parts of polyacrylamide, 8 parts of diethylenetriaminopropyltrimethoxysilane, 1 part of polyoxyethylene polyoxypropylene amine ether and 4409 parts of TEGO 4409;
the preparation method of the electrostatic shielding graphene anticorrosive paint comprises the following steps:
placing porous glass microspheres and aeo-9 surfactant in dispersion liquid of graphene oxide, performing ultrasonic dispersion for 10-30 min, drying, spraying polyacetylene on the surfaces of the porous microspheres by using a spray dryer, and drying to obtain an electrostatic shielding agent;
uniformly mixing fatty acid polyethylene glycol ester, a carbon nano tube, polyacrylamide, diethylenetriaminopropyltrimethoxysilane, polyoxyethylene polyoxypropylene ether and TEGO 440, adding an electrostatic shielding agent, and uniformly dispersing by ultrasound to obtain the electrostatic shielding graphene anticorrosive coating.
In this example, the specific surface area of the porous glass microspheres was 500m2(ii)/g, particle size of 20 microns, pore size of 80 nanometers;
the thickness of the graphene film is 50 nanometers; the thickness of the polyacetylene thin film is 5 micrometers.
Comparative example:
an electrostatic shielding graphene anticorrosive paint comprises the following substances in parts by weight: 65 parts of polyvinylidene fluoride-tetrafluoroethylene-perfluoromethyl vinyl ether emulsion, 5 parts of graphene, 15 parts of gold nanowires, 5 parts of sodium tripolyphosphate, 8 parts of aminopropyltriethoxysilane, 2 parts of polyoxypropylene glycerol ether and 3543 parts of BYK.
Experimental analysis:
the anticorrosive coatings in examples 1-4 and comparative examples are coated on a substrate, and dried to obtain anticorrosive coatings, and the conductivity of each coating is detected, wherein the experimental results are shown in table 1.
| Sample (I) | Resistivity (omega/cm)2） |
| Example 1 | 3×103 |
| Example 2 | 4×102 |
| Example 3 | 8×102 |
| Example 4 | 1×103 |
| Comparative example | 9×108 |
Claims (5)
1. The electrostatic shielding graphene anticorrosive paint is characterized by comprising the following substances in parts by weight: 60-80 parts of organic polymer emulsion, 10-25 parts of electrostatic shielding agent, 5-20 parts of conductive filler, 5-8 parts of dispersing agent, 3-8 parts of coupling agent, 1-5 parts of defoaming agent and 3-9 parts of flatting agent; the electrostatic shielding agent is spherical particles and sequentially comprises porous microspheres, a graphene film and a polyacetylene film from inside to outside, and the specific surface area of the porous microspheres is 500-800 m2The graphene film has the advantages that the particle size is 1-20 micrometers, the pore diameter is 10-80 nanometers, and the thickness of the graphene film is 20-50 nanometers; the thickness of the polyethylene film is 0.5-5 microns;
the graphene anticorrosive paint is prepared by the following method:
(1) placing the porous microspheres and a surfactant in a dispersion liquid of graphene oxide, performing ultrasonic dispersion for 10-30 min, then drying, spraying polyacetylene on the surfaces of the porous microspheres by using a spray dryer, and drying to obtain an electrostatic shielding agent;
(2) and uniformly mixing the organic polymer emulsion, the conductive filler, the dispersing agent, the coupling agent, the defoaming agent and the leveling agent, and then adding the electrostatic shielding agent for uniform ultrasonic dispersion to obtain the electrostatic shielding graphene anticorrosive paint.
2. The electrostatic shielding graphene anticorrosive paint according to claim 1, which is characterized by comprising the following substances in parts by weight: 65-75 parts of organic polymer emulsion, 15-20 parts of electrostatic shielding agent, 10-15 parts of conductive filler, 5-8 parts of dispersing agent, 3-8 parts of coupling agent, 1-5 parts of defoaming agent and 3-9 parts of flatting agent.
3. The electrostatic shielding graphene anticorrosive coating according to claim 1, wherein the organic polymer emulsion has a solid content of more than 30% and is at least one selected from polyvinylidene fluoride emulsion, polybutylene terephthalate emulsion, polyarylate emulsion, polyvinyl acetate emulsion, nylon 6 emulsion, polymethyl methacrylate emulsion, polyaniline emulsion, polyethylene oxide emulsion, polyvinylpyrrolidone emulsion, polyacrylonitrile emulsion, polycaprolactone emulsion, polyurethane emulsion, fluorinated polyurethane emulsion, polysulfone emulsion, polyethersulfone emulsion, polyvinylidene fluoride-hexafluoropropylene emulsion, polyvinylidene fluoride-tetrafluoroethylene-perfluoromethylvinylether emulsion, and polyvinylidene fluoride-chlorotrifluoroethylene emulsion.
4. The electrostatic shielding graphene anticorrosive paint according to claim 1, wherein the conductive filler is at least one selected from carbon nanotubes, carbon fibers, metal nanowires, metal nanoparticles, metal oxide particles, or carbon black.
5. The electrostatic shielding graphene anticorrosive paint according to claim 1, wherein the coupling agent is at least one selected from aminopropyltriethoxysilane, aminopropyltrimethoxysilane, 2-aminoethylaminopropyltrimethoxysilane, diethylenetriaminopropyltrimethoxysilane, aminoethylaminopropylmethyldimethoxysilane, aminoethylaminopropyltriethoxysilane, ureidopropyltriethoxysilane, and ureidopropyltrimethoxysilane.
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| CN111718650B (en) * | 2020-07-07 | 2021-04-20 | 吉林大学 | Polyether sulfone/polyaniline base coating and polyether sulfone/polytetrafluoroethylene surface coating double-layer coating composition and preparation method of double-layer coating |
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