CN110330865A - Modified anti-corrosion primer of a kind of graphene and preparation method thereof - Google Patents
Modified anti-corrosion primer of a kind of graphene and preparation method thereof Download PDFInfo
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- CN110330865A CN110330865A CN201910681031.0A CN201910681031A CN110330865A CN 110330865 A CN110330865 A CN 110330865A CN 201910681031 A CN201910681031 A CN 201910681031A CN 110330865 A CN110330865 A CN 110330865A
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- graphene
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Classifications
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/106—Anti-corrosive paints containing metal dust containing Zn
-
- 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
- C08K3/08—Metals
- C08K2003/0893—Zinc
Abstract
The invention discloses modified anti-corrosion primers of a kind of graphene and preparation method thereof, it is related to anticorrosive paint technology field, the modified anti-corrosion primer of the graphene is mixed by component A and the component B ratio of 3-5:1 in mass ratio, the component A is calculated in mass percent, it include 25%~35% epoxy resin, 35%~45% zinc powder, 0.5%~1% graphene, 10%~25% solvent and 1%~5% filler, the component B is calculated in mass percent, it include 15%~20% n-butanol, 45%~60% dimethylbenzene and 15%~20% curing agent, 1%~5% auxiliary agent, mainly pass through the close ordered stacks of stratiform and various excellent physics and chemical property of graphene, resin and zinc powder ordered arrangement is set to form fine and close protection Film improves the antiseptic property of anticorrosive paint to realize on the basis of reducing zinc powder dosage.
Description
Technical field
The present invention relates to anticorrosive paint technology fields, and in particular to a kind of modified anti-corrosion primer of graphene and its preparation side
Method.
Background technique
Anticorrosive paint is widely applied in the industrial production, and along with the quickening of globalization process, marine trade is obtained vigorously
Development.In this high humidity environment with high salt in ocean, metal base is faced with seawater immersion, salt fog erosion, alternation of wetting and drying, pressure friendship
For etc. numerous environmental tests, easily cause to corrode, destroy original metal structure.Caused by China's industrial corrosions in 2014
Loss reaches 1.5 trillion yuans, wherein loses caused by marine corrosion and has just reached 200,000,000,000.By preventing oceanographic equipment coating again
Rotten coating can effectively improve resistance to corrosion, and the most widely used anti-corrosion means at present.Existing zinc-rich etc. is prevented again
The problems such as rotten coating is low, seriously polluted, workability is bad there are filler utilization rate, it would be highly desirable to solve.
Graphene is to be made of carbon atom in strict accordance with hexagon arrangement, is a kind of sp2The two-dimensional hexagonal honeycomb of hydridization
Lattice carbon nanomaterial.The long carbon-carbon bond of graphene is about 0.142nm, and each lattice is interior, and there are three keys, form stable six
Side shape, structure are highly stable.The special crystal structure of graphene makes it have excellent physical and chemical performance, is the crystalline substance being currently known
Intensity and the highest crystalline material of hardness in body material.Its Young's modulus is up to 1100GPa, strength degree 42N/m2, fracture
Intensity is up to 130GPa, and electron mobility is up to 2 × 105cm2/ (Vs), thermal conductivity at room temperature are about 5000W/ (mK),
Visible light transmittance reaches 97.7%, excellent hydrophobic, oleophobic performance, up to 2630m2The theoretical specific surface area etc. of/g.Graphite
The unique performance of alkene, makes it have a wide range of applications in anticorrosive paint field.
Graphene possesses great specific surface area, the interaction of piece interlayer strong pi-pi bond and Van der Waals force, so that base
Agglomeration easily occurs for the graphene in body, so that the coating being prepared easily is formed hole, causes defect.This does not have not only
Improve performance, enters the substrate offer that coating penetrates into metal to corrosion factors such as hydrone, oxygen, chloride ions instead
Channel, accelerates corrosion of metal, therefore be difficult that directly graphene is applied in coating.
Summary of the invention
It is an object of the invention to: modified anti-corrosion primer of a kind of graphene and preparation method thereof is provided, existing richness is solved
That there are filler utilization rates is low, seriously polluted for the anticorrosive paints such as zinc, workability is bad, and graphene easily occur to reunite it is existing
As making the coating being prepared easily form hole, entering coating to corrosion factors such as hydrone, oxygen, chloride ions and penetrate into
The substrate of metal provides channel, accelerates corrosion of metal, is difficult that graphene is directly applied to the problems in coating.
The technical solution adopted by the invention is as follows:
A kind of modified anti-corrosion primer of graphene, the modified anti-corrosion primer of the graphene is by component A and component B 3- in mass ratio
The ratio of 5:1 mixes, and the component A is calculated in mass percent, and includes 25%~35% epoxy resin, 35%~
45% zinc powder, 0.5%~1% graphene, 10%~25% solvent and 1%~5% filler, the component B is with matter
Measure percentage meter, include 15%~20% n-butanol, 45%~60% dimethylbenzene and 15%~20% curing agent,
1%~5% auxiliary agent.
A kind of preparation method of the modified anti-corrosion primer of graphene, comprising the following steps:
(1) appropriate epoxy resin is added in stirring container and is stirred evenly；
(2) weighed zinc powder, solvent, graphene and filler in proportion is added in the stirring container described in step (1), after
Continue and is stirred evenly in stirring container；
(3) resulting material in step (2) is put into grinder and is ground, component A is made；
(4) suitable dimethylbenzene and n-butanol are mixed, and curing agent is added, added auxiliary agent, stirred in stirring container
It mixes
Even obtained component B；
(5) component B made from component A made from step (3) and step (4) is mixed according to the mass ratio of 3-5:1, system
Obtain the modified anti-corrosion primer of the graphene.
Further, in the step (1), the revolving speed of stirring container is 1000~1500r/min.
Further, in the step (2), the revolving speed of stirring container is 2000~3000r/min.
Further, in the step (4), the revolving speed of stirring container is 700~1500r/min.
Further, the zinc powder in the step (2) be spherical or sheet, size be 500 mesh, 800 mesh, 1000 mesh or
1250 mesh.
Further, the filler in the step (2) is Nano-meter SiO_22, micaceous iron oxide gray, mica powder, talcum powder, phosphorus
At least one of iron powder or blanc fixe.
Further, the solvent in the step (2) is cyclohexanone, isophorone, methyl iso-butyl ketone (MIBK), ethylene glycol only son
At least one of ether, propylene glycol methyl ether acetate or benzyl alcohol.
Further, the curing agent in the step (4) is poly- glutamine, aliphatic cyclic amine fat polyamine divinyl three is pacified,
At least one of triethylene tetramine or aromatic amine.
Further, the auxiliary agent in the step (4) is polyvinylpyrrolidone, silane coupling agent, dodecyl sulphate
At least one of sodium or polyvinyl alcohol.
In conclusion by adopting the above-described technical solution, the beneficial effects of the present invention are:
1. the unique structural features that the graphene itself that the present invention selects has, make it in physical preservation and electrochemical anti-corrosive
Aspect all shows certain advantage.The lamellar structure of graphene is layering, is staggered, and can form " labyrinth in the coating
Formula " shielding construction can effectively inhibit the infiltration, infiltration and diffusion of corrosive medium, improve the physical barrier of coating.Meanwhile
Due to its small-size effect, graphene can be filled into the defect of coating, reduce coating porosity, and enhancing coating is fine and close
Property, further delay or corrosion factor is prevented to be immersed in matrix surface.Graphene has good lubricating action, stone between layers
Coating can be divided into many minizones by the lamellar structure of black alkene, can be effectively reduced coat inside stress, consumption fracture
Energy, and then improve flexibility, impact resistance and the wearability of coating.In addition, the conjugated structure of graphene make it have it is very high
Electron mobility, show good electric conductivity, meanwhile, lamellar structure can also guarantee apply interlayer have preferable electrochemistry
Contact forms conductive network, provides more preferably electrochemical protection.
2. the present invention is tested by the performance to graphene modified anti-corrosive coating, by test result it is found that modified
Anticorrosive paint when less than 50% zinc content, the salt-fog resistant time of graphene modified anti-corrosive coating is 3000h, both reduces
The dosage of zinc powder, and significant the antiseptic property for improving preservative, illustrate the modified anti-corrosive properties to anticorrosive paint of graphene
Can be promoted has larger facilitation effect.
3. the present invention can improve the mechanical property of cold coating by the graphene of addition 0.5%~1%, because of graphite
Alkene and resin have good compatibility, if graphene additional amount is very few, since the compatibility of graphene and resin is not strong, coating
Hardness and impact resistance improve unobvious；If graphene additional amount is excessive, graphene be easy to cause reunion in resin system, makes
Hardness and impact resistance reduce.
4. the modified anti-corrosion primer proportion of graphene provided by the invention is rationally, the table of the mixed solution of n-butanol and dimethylbenzene
Face can be closer to graphene, can remove graphite well, and stable dispersion graphene graphene disperses in coating
Effect is preferable, and agglomeration is lighter.
5. instant component is easy to get, preparation method is simple, can replace most zinc by the way that a small amount of graphene is added
Powder dosage, dust pollution caused by not only greatly reducing in work progress, while coating density is also effectively reduced, meet current
The light-weighted growth requirement of coating material.
Specific embodiment
Below technical solution in the embodiment of the present invention describe clear and completely, it is clear that described implementation
Example is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, this field is common
Technical staff's every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.
Embodiment 1
A kind of modified anti-corrosion primer of graphene, the modified anti-corrosion primer of the graphene is by component A and component B in mass ratio 4:
1 ratio mixes, and the component A is calculated in mass percent, and includes 30% epoxy resin, 40% zinc powder, and 0.8%
Graphene, 18% cyclohexanone and 3% micaceous iron oxide gray, it includes 17% that the component B, which is calculated in mass percent,
N-butanol, 53% dimethylbenzene and 18% poly- glutamine, 3% polyvinylpyrrolidone.
The preparation method of the modified anti-corrosion primer of above-mentioned graphene, comprising the following steps:
(1) appropriate epoxy resin is added in stirring container and is stirred evenly with the revolving speed of 1200r/min；
(2) weighed zinc powder, cyclohexanone, graphene and mica in proportion is added in the stirring container described in step (1)
Iron oxide ash, continuation are stirred evenly in stirring container with the revolving speed of 2500r/min；
(3) resulting material in step (2) is put into grinder and is ground to fineness < 50 μm, component A is made；
(4) suitable dimethylbenzene and n-butanol are mixed, and poly- glutamine is added, add polyvinylpyrrolidone,
Revolving speed in stirring container with 1000r/min stirs evenly obtained component B；
(5) component B made from component A made from step (3) and step (4) is mixed according to the mass ratio of 4:1, institute is made
State the modified anti-corrosion primer of graphene.
Embodiment 2
A kind of modified anti-corrosion primer of graphene, the modified anti-corrosion primer of the graphene is by component A and component B in mass ratio 4:
1 ratio mixes, and the component A is calculated in mass percent, and includes 35% epoxy resin, 45% zinc powder, and 0.6%
Graphene, 16% isophorone and 2% talcum powder, it includes 20% positive fourth that the component B, which is calculated in mass percent,
Alcohol, 50% dimethylbenzene and 20% aromatic amine, 5% silane coupling agent.
The preparation method of the modified anti-corrosion primer of above-mentioned graphene, comprising the following steps:
(1) appropriate epoxy resin is added in stirring container and is stirred evenly with the revolving speed of 1250r/min；
(2) weighed zinc powder, isophorone, graphene and cunning in proportion is added in the stirring container described in step (1)
Mountain flour, continuation are stirred evenly in stirring container with the revolving speed of 2800r/min；
(3) resulting material in step (2) is put into grinder and is ground to fineness < 50 μm, component A is made；
(4) suitable dimethylbenzene and n-butanol are mixed, and aromatic amine is added, add silane coupling agent, held in stirring
Revolving speed in device with 1100r/min stirs evenly obtained component B；
(5) component B made from component A made from step (3) and step (4) is mixed according to the mass ratio of 3:1, institute is made
State the modified anti-corrosion primer of graphene.
Embodiment 3
A kind of performance of the modified anti-corrosion primer of graphene obtained in embodiment 1 is tested, the graphene is modified anti-
The salt-fog resistant time of rotten priming paint is 3000h, has not only reduced the dosage of zinc powder, but also significant the anti-corrosive properties for improving preservative
Can, illustrate that the modified antiseptic property promotion to anticorrosive paint of graphene has larger facilitation effect.
It is observed and is analyzed using microscopic appearance of the scanning electron microscope to graphene modified anti-corrosive coating, specific analysis knot
Fruit is as follows:
The fitting between layers that addition graphene carries out compound epoxy resin section is close, with higher orderly
Degree；And common epoxy resin section is more unordered.Specific reason may be as follows: stone is added in high molecular epoxy resin
After black alkene, since graphene is to high molecular strong suction-operated, so that macromolecule is wrapped in the outside of graphene, thus layer by layer
Accumulation forms orderly layer structure, so that the structure hole of resin after curing is less, it is even closer in conjunction with obtaining.
Be added graphene coating section it is relatively flat, defect and hole are less, close structure and it is orderly；And common painting
Expect in section, the arrangement of zinc powder is more mixed and disorderly, and the wellability of zinc powder and epoxy resin structural is poor, lacks after solidification there are still a large amount of
It falls into.The ordered lamellar structure that possible reason is also due to graphene makes the structure of coating more orderly, to improve painting
The compactness and permeability resistance of material.
Substrate where common anticorrosive paint occurs after the glacial acetic acid accelerated test of 700h experiment in scratch area
Serious corrosion phenomenon, and the substrate of the anticorrosive paint of graphene is added after the test still without apparent corrosion, this also illustrates
The excellent Corrosion Protection of graphene modified anti-corrosive coating.
Although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art,
It is still possible to modify the technical solutions described in the foregoing embodiments, or part of technical characteristic is equal
Replacement, all within the spirits and principles of the present invention, any modification, equivalent replacement, improvement and so on should be included in this hair
Within bright protection scope.
Claims (10)
1. a kind of modified anti-corrosion primer of graphene, which is characterized in that the modified anti-corrosion primer of the graphene is by component A and component B
The ratio of 3-5:1 in mass ratio mixes, and the component A is calculated in mass percent, and includes 25%~35% asphalt mixtures modified by epoxy resin
Rouge, 35%~45% zinc powder, 0.5%~1% graphene, 10%~25% solvent and 1%~5% filler, it is described
Component B is calculated in mass percent, include 15%~20% n-butanol, 45%~60% dimethylbenzene and 15%~20%
Curing agent, 1%~5% auxiliary agent.
2. a kind of preparation method of the modified anti-corrosion primer of graphene, which comprises the following steps:
(1) appropriate epoxy resin is added in stirring container and is stirred evenly；
(2) weighed zinc powder, solvent, graphene and filler in proportion are added in the stirring container described in step (1), continues
It is stirred evenly in stirring container；
(3) resulting material in step (2) is put into grinder and is ground, component A is made；
(4) suitable dimethylbenzene and n-butanol are mixed, and curing agent is added, add auxiliary agent, stirred in stirring container equal
Even obtained component B；
(5) component B made from component A made from step (3) and step (4) is mixed according to the mass ratio of 3-5:1, is made described
Graphene is modified anti-corrosion primer.
3. a kind of preparation method of the modified anti-corrosion primer of graphene according to claim 2, which is characterized in that the step
(1) in, the revolving speed of stirring container is 1000~1500r/min.
4. a kind of preparation method of the modified anti-corrosion primer of graphene according to claim 2, which is characterized in that the step
(2) in, the revolving speed of stirring container is 2000~3000r/min.
5. a kind of preparation method of the modified anti-corrosion primer of graphene according to claim 2, which is characterized in that the step
(4) in, the revolving speed of stirring container is 700~1500r/min.
6. a kind of preparation method of the modified anti-corrosion primer of graphene according to claim 2, which is characterized in that the step
(2) zinc powder in is spherical or sheet, and size is 500 mesh, 800 mesh, 1000 mesh or 1250 mesh.
7. a kind of preparation method of the modified anti-corrosion primer of graphene according to claim 2, which is characterized in that the step
(2) filler in is Nano-meter SiO_22, micaceous iron oxide gray, mica powder, talcum powder, at least one in ferrophosphorus powder or blanc fixe
Kind.
8. a kind of preparation method of the modified anti-corrosion primer of graphene according to claim 2, which is characterized in that the step
(2) solvent in is cyclohexanone, isophorone, methyl iso-butyl ketone (MIBK), ethylene glycol monobutyl ether, propylene glycol methyl ether acetate or benzene first
At least one of alcohol.
9. a kind of preparation method of the modified anti-corrosion primer of graphene according to claim 2, which is characterized in that the step
(4) curing agent in be in poly- glutamine, the peace of aliphatic cyclic amine fat polyamine divinyl three, triethylene tetramine or aromatic amine at least
It is a kind of.
10. a kind of preparation method of the modified anti-corrosion primer of graphene according to claim 2, which is characterized in that the step
Suddenly the auxiliary agent in (4) is at least one in polyvinylpyrrolidone, silane coupling agent, lauryl sodium sulfate or polyvinyl alcohol
Kind.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110791171A (en) * | 2019-11-05 | 2020-02-14 | 立邦工业涂料(上海)有限公司 | Composite nano material reinforced solvent type epoxy primer and preparation method thereof |
| CN111391446A (en) * | 2020-04-13 | 2020-07-10 | 江苏道蓬科技有限公司 | High-toughness corrosion-resistant marine anticorrosive composite coating and preparation method thereof |
| CN113563752A (en) * | 2021-06-29 | 2021-10-29 | 深圳大学 | Marine anticorrosive paint and preparation method thereof |
| CN114410182A (en) * | 2021-12-27 | 2022-04-29 | 中国人民解放军陆军勤务学院 | Preparation process of rapidly-cured conductive anticorrosive composite coating |
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| CN109486359A (en) * | 2018-12-04 | 2019-03-19 | 中国特种飞行器研究所 | A kind of long-acting anticorrosive paint of containing graphene-zinc powder and preparation method thereof |
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| CN109423160A (en) * | 2017-07-13 | 2019-03-05 | 山东欧铂新材料有限公司 | It is a kind of to contain graphene/epoxy resin composite material resin anti-corrosive paint and preparation method thereof |
| CN108997889A (en) * | 2018-08-09 | 2018-12-14 | 湖南省金海科技有限公司 | A kind of ocean naval vessel graphene heavy antisepsis priming paint and preparation method thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110791171A (en) * | 2019-11-05 | 2020-02-14 | 立邦工业涂料(上海)有限公司 | Composite nano material reinforced solvent type epoxy primer and preparation method thereof |
| CN111391446A (en) * | 2020-04-13 | 2020-07-10 | 江苏道蓬科技有限公司 | High-toughness corrosion-resistant marine anticorrosive composite coating and preparation method thereof |
| CN113563752A (en) * | 2021-06-29 | 2021-10-29 | 深圳大学 | Marine anticorrosive paint and preparation method thereof |
| CN114410182A (en) * | 2021-12-27 | 2022-04-29 | 中国人民解放军陆军勤务学院 | Preparation process of rapidly-cured conductive anticorrosive composite coating |
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