CN111500147A - Graphene modified heavy-duty anticorrosive coating, preparation method thereof and graphene modified heavy-duty anticorrosive coating - Google Patents

Graphene modified heavy-duty anticorrosive coating, preparation method thereof and graphene modified heavy-duty anticorrosive coating Download PDF

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CN111500147A
CN111500147A CN202010443153.9A CN202010443153A CN111500147A CN 111500147 A CN111500147 A CN 111500147A CN 202010443153 A CN202010443153 A CN 202010443153A CN 111500147 A CN111500147 A CN 111500147A
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graphene
anticorrosive coating
modified heavy
duty anticorrosive
coating
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史述宾
孙华杰
陈韵吉
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Beijing Graphene Institute BGI
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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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C—CHEMISTRY; METALLURGY
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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
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • 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
    • 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
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20—Diluents or solvents
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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    • C09D7/60—Additives non-macromolecular
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
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    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
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Abstract

The invention provides a graphene modified heavy-duty anticorrosive coating, a preparation method thereof and a graphene modified heavy-duty anticorrosive coating, wherein the graphene modified heavy-duty anticorrosive coating comprises the following components in parts by weight based on the total mass of the graphene modified heavy-duty anticorrosive coating: 20-50% of resin, 20-80% of pigment and filler, 1-20% of graphene dispersion slurry, 2-10% of auxiliary agent and 5-20% of solvent. According to the graphene modified heavy-duty anticorrosive coating, the graphene has good dispersion uniformity and stability in the heavy-duty anticorrosive coating, the obtained coating has good water resistance and salt spray resistance, and the overall anticorrosive efficiency of the coating is improved; due to the addition of the graphene, the content of zinc in the heavy-duty anticorrosive coating is reduced, and the coating cost is greatly reduced. In addition, the graphene modified heavy-duty anticorrosive coating adopts an environment-friendly solvent, so that the emission of organic volatile matters is greatly reduced, and the coating is more environment-friendly.

Description

Graphene modified heavy-duty anticorrosive coating, preparation method thereof and graphene modified heavy-duty anticorrosive coating
Technical Field
The invention relates to the field of coatings, and particularly relates to a graphene modified heavy-duty anticorrosive coating, a preparation method thereof and a graphene modified heavy-duty anticorrosive coating.
Background
Corrosion has always been the biggest challenge in the industries of machinery, chemical engineering, construction, transportation, etc. Compared with the conventional anticorrosive paint, the heavy anticorrosive paint can be applied in a relatively severe corrosive environment, and has a longer protection period than the conventional anticorrosive paint, wherein the epoxy zinc-rich paint is the most common heavy anticorrosive paint and is widely applied to the anticorrosion field. However, a large amount of organic solvent volatilized into the atmosphere in the coating process of the epoxy zinc-rich paint pollutes the atmospheric environment, and meanwhile, the high zinc content of the epoxy zinc-rich paint causes continuous pressure on the cost of the paint. With the increasing requirements on environmental protection, energy conservation and emission reduction, the modification of the epoxy zinc-rich heavy-duty anticorrosive paint is on the way.
Since 2010, graphene has attracted much attention as a novel two-dimensional nanomaterial. The graphene has excellent mechanical property and physical and chemical properties, can play a key role in the coating, remarkably improves the blocking and shielding effects of the coating, and effectively prevents corrosion factors such as environmental atmosphere, substances and the like from permeating the coating to corrode a substrate. The addition of the graphene is also beneficial to reducing the cost of the coating, thinning the coating, obviously improving the mechanical property and salt spray resistance of the coating and the like.
However, graphene is neither hydrophilic nor oleophilic, and how to keep graphene uniformly dispersed and stably stored in the coating is crucial. Meanwhile, the components of the coating are optimally matched, so that the environmental protection and the economical efficiency of the coating are realized, the corrosion resistance of the whole coating is improved, and a high requirement is provided for the heavy-duty anticorrosive coating.
It is noted that the information disclosed in the foregoing background section is only for enhancement of background understanding of the invention and therefore it may contain information that does not constitute prior art that is already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention aims to overcome at least one defect of the prior art, and provides a graphene modified heavy-duty anticorrosive coating, a preparation method thereof and a graphene modified heavy-duty anticorrosive coating, so as to remarkably improve the blocking and shielding effects of the coating and obtain the heavy-duty anticorrosive coating with good anticorrosive performance, environmental protection and economical efficiency.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a graphene modified heavy-duty anticorrosive coating, which takes the total mass of the graphene modified heavy-duty anticorrosive coating as a reference and comprises the following components: 20-50% of resin, 20-80% of pigment and filler, 1-20% of graphene dispersion slurry, 2-10% of auxiliary agent and 5-20% of solvent.
According to an embodiment of the present invention, a graphene dispersion paste includes graphene, a dispersant selected from one or more of polyacrylate copolymer, polyether tertiary amine polymer, polyethylene oxide, urethane-modified acrylic polymer, sodium lignin sulfonate, gallic acid, polycarboxylate, and a dispersion medium, each of the solvent and the dispersion medium is independently selected from one or more of n-butanol, acetone, ethylene glycol butyl ether, propylene glycol methyl ether acetate, and ethanol.
According to one embodiment of the present invention, the graphene accounts for 0.1 to 10% by mass of the graphene dispersion slurry, the dispersant accounts for 0.1 to 10% by mass of the graphene dispersion slurry, and the dispersion medium accounts for 80 to 90% by mass of the graphene dispersion slurry; the mass ratio of the dispersing agent to the graphene is 3: 1-1: 3.
According to one embodiment of the invention, the diameter of the graphene is 5-30 μm, and the thickness of the graphene is less than or equal to 15 nm; the mass ratio of the graphene in the graphene modified heavy-duty anticorrosive coating is 0.01-5%.
According to one embodiment of the invention, the resin is selected from one or more of epoxy resin, acrylic resin, polyurethane resin, organic silicon resin and amino resin, the pigment and filler is selected from one or more of zinc powder, zinc phosphate, aluminum tripolyphosphate, talcum powder, ceramic powder, titanium dioxide and iron oxide powder; the auxiliary agent is selected from one or more of a wetting agent, an antifoaming agent, a leveling agent and an anti-settling agent, wherein the wetting agent is selected from one or more of polyether modified silicone oil, organic modified silicone oil and non-silicon surfactant, the antifoaming agent is selected from one or more of modified polysiloxane, mineral oil compound, ethylene copolymer and non-silicon polymer solution, the leveling agent is selected from one or more of polyether modified silicone oil, modified polysiloxane and acrylic acid copolymer, and the anti-settling agent is selected from one or more of fumed silica, organic bentonite and polyamide wax.
The invention also provides a preparation method of the graphene modified heavy-duty anticorrosive paint, which comprises the following steps: putting the resin into a solvent for primary mixing to obtain resin slurry; placing graphene and a dispersing agent in a dispersion medium for secondary mixing to obtain graphene dispersion slurry; and adding pigment, filler, auxiliary agent and graphene dispersion slurry into the resin slurry, and mixing for three times to obtain the graphene modified heavy-duty anticorrosive coating.
According to one embodiment of the invention, the primary mixing comprises: the resin is placed in a solvent and stirred for 20min to 40min at 800rad/min to 1200rad/min to obtain resin slurry.
According to one embodiment of the invention, the secondary mixing comprises: placing the dispersing agent in a dispersing medium for primary stirring, wherein the primary stirring speed is 800 rad/min-1200 rad/min, and the primary stirring time is 20 min-40 min; adding graphene into the solution after primary stirring, and sequentially carrying out secondary stirring and grinding, wherein the secondary stirring speed is 1000 rad/min-1300 rad/min, and the secondary stirring time is 20 min-40 min; grinding for 40-80 min to obtain graphene dispersion slurry; wherein the grinding is selected from one or more of sand grinding, ball milling and three-roll grinding.
According to one embodiment of the invention, the tertiary mixing comprises: and adding pigment, filler, auxiliary agent and graphene dispersion slurry into the resin slurry, and mixing for three times, wherein the three-time stirring speed is 1200 rad/min-1500 rad/min, and the three-time stirring time is 30 min-60 min, so as to obtain the graphene modified heavy-duty anticorrosive coating.
The invention also provides a graphene modified heavy-duty anticorrosive coating which is prepared from the graphene modified heavy-duty anticorrosive coating, wherein the mass ratio of graphene in the graphene modified heavy-duty anticorrosive coating is 0.01-5%.
According to the technical scheme, the invention has the beneficial effects that:
according to the graphene modified heavy-duty anticorrosive coating provided by the invention, the graphene is subjected to covalent modification by adopting a specific dispersant, so that the dispersion uniformity and stability of the graphene in the heavy-duty anticorrosive coating can be greatly improved; the coating prepared from the graphene modified heavy-duty anticorrosive coating has good water resistance and salt spray resistance, and the overall anticorrosive effect of the coating is improved; due to the addition of the graphene, the content of zinc in the heavy-duty anticorrosive coating is reduced, and the coating cost is greatly reduced. In addition, the graphene modified heavy-duty anticorrosive coating adopts an environment-friendly solvent, so that the emission of organic volatile matters is greatly reduced, and the coating is more environment-friendly.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention.
Fig. 1 is a flow chart of a preparation process of a graphene modified inorganic anticorrosive paint according to an embodiment of the present invention;
fig. 2 is the coating of comparative example 1 without added graphene after 1000 hours of salt spray;
fig. 3 is the heavy duty coating of example 3 without added graphene after 1000 hours of salt spray;
FIG. 4 is an AC impedance spectrum of the coating of comparative example 1 without added graphene after being soaked in a 3.5 wt% sodium chloride solution for 5 days;
FIG. 5 is an AC impedance spectrum of the graphene modified heavy duty coating of example 3 immersed in a 3.5 wt% sodium chloride solution for 5 days;
fig. 6 is a comparison graph of ac impedance spectra of the graphene-modified heavy duty coating of example 3 and the coating of comparative example 1 without added graphene soaked in 3.5 wt% sodium chloride solution for 16 days.
Detailed Description
The following presents various embodiments or examples in order to enable those skilled in the art to practice the invention with reference to the description herein. These are, of course, merely examples and are not intended to limit the invention. The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
The invention provides a graphene modified heavy-duty anticorrosive coating, which takes the total mass of the graphene modified heavy-duty anticorrosive coating as a reference and comprises the following components: 20-50% of resin, 20-80% of pigment and filler, 1-20% of graphene dispersion slurry, 2-10% of auxiliary agent and 5-20% of solvent.
According to the invention, the heavy-duty anticorrosive paint can achieve longer protection period than the conventional anticorrosive paint, but the existing heavy-duty anticorrosive paint usually contains a large amount of organic solvent and pollutes the environment, and the zinc content of epoxy zinc-rich paint and the like is high, so that the cost of the paint is also high. The inventor of the invention finds that the dispersion uniformity and stability of graphene in the heavy-duty anticorrosive coating can be greatly improved by adopting a specific dispersant to carry out covalent modification on the graphene; the two-dimensional sheet structure of the graphene is uniformly dispersed and laminated layer by layer in the graphene modified heavy-duty anticorrosive coating, and is supplemented with pigments and fillers in the coating to form a blocking layer, so that corrosion factors such as oxygen molecules, water molecules and chloride ions are greatly delayed from entering, a coating prepared from the graphene modified heavy-duty anticorrosive coating has good water resistance and salt spray resistance, and the overall anticorrosive efficiency of the coating is improved; due to the addition of the graphene, the content of zinc powder in the anticorrosive coating can be further reduced, and the coating cost is greatly reduced. In addition, the graphene modified heavy-duty anticorrosive coating adopts an environment-friendly solvent, so that the emission of organic volatile matters is greatly reduced, and the coating is more environment-friendly.
In some embodiments, preferably, the graphene-modified heavy anti-corrosion coating contains 20% to 40% of resin by mass, for example, 20%, 22%, 25%, 30%, 38%, 40%, and the like; pigment and filler content of 45% to 65%, for example, 45%, 48%, 50%, 52%, 56%, 60%, etc.; the content of the graphene dispersion slurry is 1% to 10%, for example, 1%, 4%, 5%, 7%, 10%, or the like; the content of the auxiliary agent is 2% to 6%, for example, 2%, 3%, 5%, 5.2%, 6%, etc.; the solvent content is 8% to 12%, for example, 8%, 9%, 10%, 11%, 12%, etc. Wherein the solvent is selected from one or more of n-butanol, acetone, ethylene glycol butyl ether, propylene glycol methyl ether acetate and ethanol. As for the solvent, a plurality of substances are preferably selected and used in combination to improve the compatibility and stability of the resin and the graphene dispersion slurry.
According to the invention, the graphene dispersion slurry comprises graphene, a dispersing agent and a dispersing medium, wherein the dispersing medium is selected from one or more of n-butyl alcohol, acetone, ethylene glycol butyl ether, propylene glycol methyl ether acetate and ethanol, the dispersing agent is selected from one or more of polyacrylate copolymer, polyether tertiary amine polymer, polyethylene oxide, polyurethane modified acrylic polymer, sodium lignosulfonate, gallic acid and polycarboxylate, and is commercially available, such as dispersing agent 9200 of Shanghai Kangcheng International trade company, new dispersing agent Additol VX L6212, dispersing agent KYC-926 of the science chemistry, and the like.
In some embodiments, the mass fraction of graphene in the graphene dispersion slurry is 0.1% to 10%, e.g., 0.1%, 0.5%, 0.8%, 1%, 2.6%, 3%, 3.4%, 4%, 5%, 6%, 6.7%, 8%, 8.5%, 9%, 9.5%, etc., the mass fraction of dispersant in the graphene dispersion slurry is 0.1% to 10%, e.g., 0.1%, 0.4%, 1%, 2.2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 9.6%, etc., and the mass fraction of dispersion medium in the graphene dispersion slurry is 80% to 90%, e.g., 80%, 81%, 84%, 85%, 87%, 88%, 89%, etc. Preferably, the mass ratio of the dispersant to the graphene is 3:1 to 1:3, for example, 3:1, 3:2, 1:1, 1:1.5, 1:2, and the like.
The graphene structure of the present invention is not limited, and may be a graphene nanosheet, a graphene nanoribbon, a graphene film, a graphene quantum dot, a few-layer graphene, a multi-layer graphene, and derivatives of these graphene materials. The thickness of the graphene is less than or equal to 15 nm. The graphene material provided by the invention is a graphene product provided by Baotailong. The graphene material can be prepared by mechanical stripping, electrochemical stripping and liquid phase stripping, and can also be obtained by adopting an oxidation-reduction method, and the obtained graphene material has different groups and properties according to different preparation methods. The diameter of the graphene is 5-30 μm.
In some embodiments, the aforementioned resin is selected from one or more of epoxy resin, acrylic resin, polyurethane resin, silicone resin and amino resin, the pigment and filler is selected from one or more of zinc powder, zinc phosphate, aluminum tripolyphosphate, talcum powder, ceramic powder, titanium dioxide and iron oxide powder; the auxiliary agent is selected from one or more of a wetting agent, an antifoaming agent, a leveling agent and an anti-settling agent, wherein the wetting agent is selected from one or more of polyether modified silicone oil, organic modified silicone oil and non-silicon surfactant, the antifoaming agent is selected from one or more of modified polysiloxane, mineral oil compound, ethylene copolymer and non-silicon polymer solution, the leveling agent is selected from one or more of polyether modified silicone oil, modified polysiloxane and acrylic acid copolymer, and the anti-settling agent is selected from one or more of fumed silica, organic bentonite and polyamide wax.
The following specifically explains the preparation method of the graphene modified inorganic anticorrosive coating of the present invention, fig. 1 shows a flow chart of a preparation process of the graphene modified inorganic anticorrosive coating according to an embodiment of the present invention, and the preparation method shown in fig. 1 includes: the method comprises the following steps: putting the resin into a solvent for primary mixing to obtain resin slurry; placing graphene and a dispersing agent in a dispersion medium for secondary mixing to obtain graphene dispersion slurry; and adding pigment, filler, auxiliary agent and graphene dispersion slurry into the resin slurry, and mixing for three times to obtain the graphene modified heavy-duty anticorrosive coating.
First, the resin is placed in a solvent to be mixed at one time, and a resin slurry is obtained. Specifically, the resin is placed in the solvent and stirred at a speed of 800rad/min to 1200rad/min, such as 800rad/min, 820rad/min, 860rad/min, 900rad/min, 910rad/min, 1050rad/min, or the like, for 20min to 40min, such as 20min, 22min, 25min, 30min, 35min, or the like, to obtain a resin slurry.
And then placing the graphene and the dispersing agent in a dispersing medium for secondary mixing to obtain the graphene dispersion slurry. The graphene dispersion slurry may be prepared first, and then the resin slurry may be prepared, but the present invention is not limited to the preparation sequence described above.
In some embodiments, the second mixing comprises: placing the dispersing agent in a dispersing medium for primary stirring; adding graphene into the solution after primary stirring, and sequentially performing secondary stirring and grinding to obtain graphene dispersion slurry; wherein the grinding is selected from one or more of sand grinding, ball milling and three-roll grinding.
Wherein, the speed of one-time stirring is 800rad/min to 1200rad/min, such as 800rad/min, 810rad/min, 860rad/min, 900rad/min, 910rad/min, 950rad/min, 1000rad/min, 1100rad/min and the like, and the time of one-time stirring is 20min to 40min, such as 20min, 30min, 35min, 40min and the like; the secondary stirring speed is 1000rad/min to 1300rad/min, for example, 1000rad/min, 1060rad/min, 1100rad/min, 1150rad/min, 1200rad/min, 1260rad/min, 1300rad/min, etc.; the time of the secondary stirring is 20min to 40min, for example, 20min, 25min, 30min, 37min and the like; the grinding time is 40min to 80min, for example, 40min, 42min, 50min, 55min, 70min, 80min, etc.
And finally, adding the pigment, the filler, the auxiliary agent and the graphene dispersion slurry into the resin slurry, and mixing for three times to obtain the graphene modified heavy-duty anticorrosive coating. Wherein the third mixing specifically comprises: and sequentially adding the auxiliary agent, the pigment filler and the graphene dispersion slurry into the resin slurry, and stirring at the speed of 1200 rad/min-1500 rad/min, such as 1200rad/min, 1250rad/min, 1300rad/min, 1350rad/min, 1500rad/min and the like for 30 min-60 min, such as 30min, 34min, 45min, 50min, 60min and the like to obtain the graphene modified heavy-duty anticorrosive coating.
The invention also provides a graphene modified heavy-duty anticorrosive coating obtained by the graphene modified heavy-duty anticorrosive coating, wherein the mass ratio of graphene in the graphene modified heavy-duty anticorrosive coating is 0.01-5%.
In conclusion, the graphene modified heavy-duty anticorrosive coating is prepared in a specific dispersion medium by adopting a specific dispersing agent and a dispersion process, the dispersion uniformity and the chemical stability of graphene are improved by utilizing the pi-pi covalence of the dispersing agent and the graphene, the graphene can stably exist in the coating for a long time, and the coating has good water resistance and salt spray resistance due to the two-dimensional sheet structure of the graphene, so that the overall anticorrosive effect of the coating is improved. Due to the addition of the graphene, the content of zinc powder in the anticorrosive coating can be further reduced, and the coating cost is greatly reduced. Meanwhile, the environment-friendly solvent adopted by the graphene modified heavy-duty anticorrosive coating improves the anticorrosive effect of the coating, greatly reduces the emission of organic volatile matters, and is more environment-friendly. According to the preparation method of the graphene modified heavy-duty anticorrosive coating, the cost is further reduced by renovating the preparation process, the graphene modified heavy-duty anticorrosive coating with good dispersibility is obtained, and the industrial application of graphene is facilitated.
The invention will be further illustrated by the following examples, but is not to be construed as being limited thereto. Unless otherwise specified, reagents, materials and the like used in the present invention are commercially available.
Example 1
1) 10g of a polyether tertiary amine polymer (Shanghai Kangchen International trade Co., Ltd., 9200) and 80g of n-butanol were stirred at a high speed of 1150rad/min for 20min to obtain a mixture A. Then 10g of graphene powder (Baotailong, 5-15 μm in diameter and 10-15 nm in thickness) obtained by a mechanical stripping method is added into the mixture A, stirred at a high speed of 1250rad/min for 30min, and then sanded for 60min to obtain uniform and stable graphene dispersion slurry.
2) 25g of amino resin (CYME L1158, Zhan Miao USA) is added into a paint can, 3g of n-butanol and 2g of ethylene glycol butyl ether are added, and the mixture is stirred at 1000rad/min for 20min at high speed and stirred uniformly to obtain a mixture B.
3) To the mixture B, 1.6g of an organic modified silicone oil (diko-4000), 0.6g of a modified polysiloxane (BYK-066N, BYK-085), 0.6g of a polyether modified silicone oil (BYK-331, diko-435), 1g of fumed silica, 0.6g of an organobentonite and 0.6g of a polyamide wax were added, and stirring was continued for 10 minutes to obtain a mixture C. And adding 50g of zinc powder, 5g of talcum powder and 5g of ceramic powder into the mixture C, and continuously stirring for 30min to obtain a mixture D. And adding 5g of the mixture A into the mixture D, and stirring at a high speed of 1350rad/min for 40min to obtain the graphene modified heavy anti-corrosion coating.
4) And (3) coating the obtained graphene modified heavy-duty anticorrosive coating on a 150 x 70 x 0.8mm test-grade steel plate by using a wire bar coater with the thickness of 100 microns, and curing for 7 days to obtain the graphene modified heavy-duty anticorrosive coating.
Example 2:
1) 3g of polyacrylate copolymer (Zhanxin, Additol VX L6212) and 96g of acetone are stirred at a high speed of 1000rad/min for 20min to obtain a mixture A, 1g of graphene powder (Taylon, 10-30 μm in diameter and 10nm in thickness) obtained through oxidation reduction is added into the mixture A, the mixture is stirred at a high speed of 1150rad/min for 30min, and ultrasonic dispersion is carried out for 60min to obtain uniform and stable graphene dispersion slurry.
2) Adding 25g of organic silicon resin (Dongguan, Glucona nanomaterial Co., Ltd., GR-5001) into a coating tank, adding 2g of acetone, 3g of n-butanol and 4g of ethylene glycol butyl ether, stirring at a high speed of 1000rad/min for 20min, and stirring uniformly to obtain a mixture B.
3) To the mixture B were added 1.5g of polyether-modified silicone oil (BYK-346), 0.5g of mineral oil, 0.5g of acrylic copolymer (BYK-381, BYK-361N), 1g of fumed silica, 0.5g of organobentonite and 0.5g of polyamide wax, and the mixture was stirred for 10 minutes to obtain a mixture C. 50g of zinc powder and 5g of zinc phosphate were added to the mixture C, and the mixture was further stirred for 30min to obtain a mixture D. And adding 3.5g of the mixture A into the mixture D, and stirring at a high speed of 1400rad/min for 40min to obtain the graphene modified heavy-duty anticorrosive coating.
4) And (3) coating the obtained graphene modified heavy-duty anticorrosive coating on a 150 x 70 x 0.8mm test-grade steel plate by using a wire bar coater with the thickness of 100 microns, and curing for 7 days to obtain the graphene modified heavy-duty anticorrosive coating.
Example 3:
1) 1g of a urethane-modified acrylic polymer (Kongsu chemical, KYC-926) and 96g of butyl cellosolve were stirred at high speed at 900rad/min for 20min to give a mixture A. And then 3g of graphene powder (Taylon, Inc., diameter 15-30 μm, thickness 5-15 nm) obtained by electrochemical stripping is added into the mixture A, stirred at high speed for 30min at 1100rad/min, and then subjected to ultrasonic dispersion for 60min to obtain uniform and stable graphene dispersion slurry.
2) 25g of epoxy resin (Sanko, E44) was put into a coating pot, 3g of n-butanol and 2g of butyl cellosolve were added, and the mixture was stirred at 1200rad/min for 20min at a high speed and stirred uniformly to obtain a mixture B.
3) 1g of wetting agent (BYK-349, BYK-163), 0.4g of defoaming agent (BYK-055, Digao-932), 0.4g of flatting agent (Digao-2300, BYK-333), 0.8g of fumed silica, 0.5g of organic bentonite and 0.4g of polyamide wax are added into the mixture B, and the mixture C is obtained after continuous stirring for 10 min. And adding 60g of zinc powder and 3g of talcum powder into the mixture C, and continuing stirring for 30min to obtain a mixture D. And adding 3.5g of the mixture A into the mixture D, and stirring at a high speed of 1500rad/min for 40min to obtain the graphene modified heavy-duty anticorrosive coating.
4) And (3) coating the obtained graphene modified heavy-duty anticorrosive coating on a 150 x 70 x 0.8mm test-grade steel plate by using a wire bar coater with the thickness of 100 microns, and curing for 7 days to obtain the graphene modified heavy-duty anticorrosive coating.
Comparative example 1
The graphene modified heavy-duty anticorrosive coating is prepared by the method in example 3, except that the step 1) is not performed, that is, the graphene dispersion slurry is not added to the coating.
Test example 1
The salt spray resistance of the coatings of example 3 and comparative example 1 was determined according to GB/T1771-2007 for 1000 hours. Fig. 2 shows the coating layer without graphene of comparative example 1 after 1000 hours of salt spray, and fig. 3 shows the heavy anti-corrosion coating layer without graphene of example 3 after 1000 hours of salt spray, and it can be seen from fig. 2 and 3 that a small amount of bubbles appear at the scratch of the coating layer of comparative example 1, and a significant corrosion phenomenon occurs and slightly spreads. The graphene modified heavy-duty anticorrosive coating of example 3 has a good surface, and scratches are not expanded. Therefore, the graphene modified heavy-duty anticorrosive coating has good salt spray resistance.
Test example 2
The coatings obtained in examples 1-3 and comparative example 1 were subjected to a cross cut test to determine the adhesion of the coating according to GB9286-1998, pencil hardness according to GB/T6739-2006, flexibility according to GB/T1731-93, and impact resistance according to GB/T1732-93, respectively. The results are shown in Table 1 below. As can be seen from table 1, the graphene modified heavy anti-corrosion coating of the present invention has superior mechanical properties compared to a coating without graphene.
TABLE 1
Figure BDA0002504686610000101
Test example 3
The coatings of example 3 and comparative example 1 were each subjected to an electrochemical performance test, i.e., the corrosion resistance of the coatings were tested by immersion in a 3.5 wt% sodium chloride solution. The method comprises the following specific operation steps: electrochemical Impedance (EIS) spectrum of the coating was tested using the electrochemical workstation of CHI 660E: 3.5 wt% sodium chloride solution is used as corrosion medium, and three electrodes are adoptedTesting the electrode system, wherein the working electrode is a coating sample, and the electrode area is 1cm2The counter electrode is a metal platinum sheet, and the reference electrode is a saturated calomel electrode with a luggin capillary tube. The frequency range of EIS test is 105Hz～10-2Hz, sine wave amplitude of 10mV, from high frequency to low frequency.
FIG. 4 is an AC impedance spectrum of the coating of comparative example 1 without added graphene after being soaked in a 3.5 wt% sodium chloride solution for 5 days; FIG. 5 is an AC impedance spectrum of the graphene modified heavy duty coating of example 3 immersed in a 3.5 wt% sodium chloride solution for 5 days; FIG. 6 is a comparison graph of AC impedance spectra of the graphene modified heavy duty coating of example 3 and the coating of comparative example 1 without added graphene after being soaked in 3.5 wt% sodium chloride solution for 16 days; wherein the a curve corresponds to the coating of comparative example 1 and the b curve corresponds to the graphene modified heavy duty coating of example 3.
As can be seen from fig. 4 to 6, the addition of graphene can increase the electrochemical impedance of the coating by one order of magnitude when the coating is soaked in a 3.5 wt% sodium chloride solution for 5 days. After being soaked in a 3.5 wt% sodium chloride solution for 16 days, the resistance of the graphene modified heavy anti-corrosion coating is still several times that of an epoxy coating without graphene. This shows that the graphene modified heavy-duty anticorrosive coating has better corrosion resistance.
In conclusion, the graphene is subjected to covalent modification by using the specific dispersant, so that the dispersion uniformity and stability of the graphene in the heavy anti-corrosion coating are greatly improved, and the protective effects of the prepared coating, such as mechanical property, salt spray resistance and the like, are greatly improved. According to the preparation method of the graphene modified heavy-duty anticorrosive coating, the cost is further reduced by renovating the preparation process, the graphene modified heavy-duty anticorrosive coating with good dispersibility is obtained, and the industrial application of graphene is facilitated.
It should be noted by those skilled in the art that the described embodiments of the present invention are merely exemplary and that various other substitutions, alterations, and modifications may be made within the scope of the present invention. Accordingly, the present invention is not limited to the above-described embodiments, but is only limited by the claims.

Claims (10)

1. The graphene modified heavy-duty anticorrosive coating is characterized by comprising the following components in parts by weight based on the total mass of the graphene modified heavy-duty anticorrosive coating: 20-50% of resin, 20-80% of pigment and filler, 1-20% of graphene dispersion slurry, 2-10% of auxiliary agent and 5-20% of solvent.
2. The graphene-modified heavy anti-corrosion coating according to claim 1, wherein the graphene dispersion slurry comprises graphene, a dispersant and a dispersion medium, the dispersant is selected from one or more of polyacrylate copolymer, polyether tertiary amine polymer, polyethylene oxide, polyurethane-modified acrylic polymer, sodium lignosulfonate, gallic acid and polycarboxylate, and the solvent and the dispersion medium are each independently selected from one or more of n-butanol, acetone, ethylene glycol butyl ether, propylene glycol methyl ether acetate and ethanol.
3. The graphene modified heavy-duty anticorrosive coating according to claim 2, wherein the mass ratio of the graphene in the graphene dispersion slurry is 0.1% to 10%, the mass ratio of the dispersant in the graphene dispersion slurry is 0.1% to 10%, and the mass ratio of the dispersion medium in the graphene dispersion slurry is 80% to 90%; the mass ratio of the dispersing agent to the graphene is 3: 1-1: 3.
4. The graphene-modified heavy-duty anticorrosive coating according to claim 1, wherein the diameter of the graphene is 5 μm to 30 μm, and the thickness of the graphene is less than or equal to 15 nm.
5. The graphene-modified heavy-duty anticorrosive coating according to claim 1, wherein the resin is selected from one or more of epoxy resin, acrylic resin, polyurethane resin, silicone resin, and amino resin; the pigment and filler is selected from one or more of zinc powder, zinc phosphate, aluminum tripolyphosphate, talcum powder, ceramic powder, titanium dioxide and iron oxide powder; the auxiliary agent is selected from one or more of a wetting agent, an antifoaming agent, a leveling agent and an anti-settling agent, wherein the wetting agent is selected from one or more of polyether modified silicone oil, organic modified silicone oil and non-silicon surfactant, the antifoaming agent is selected from one or more of modified polysiloxane, mineral oil compound, ethylene copolymer and non-silicon polymer solution, the leveling agent is selected from one or more of polyether modified silicone oil, modified polysiloxane and acrylic acid copolymer, and the anti-settling agent is selected from one or more of fumed silica, organic bentonite and polyamide wax.
6. The preparation method of the graphene modified heavy-duty anticorrosive coating as claimed in any one of claims 1 to 5, characterized by comprising:
putting the resin into a solvent for primary mixing to obtain resin slurry;
placing graphene and a dispersing agent in a dispersion medium for secondary mixing to obtain graphene dispersion slurry; and
and adding pigment and filler, an auxiliary agent and the graphene dispersion slurry into the resin slurry, and mixing for three times to obtain the graphene modified heavy-duty anticorrosive coating.
7. The method of manufacturing according to claim 6, wherein the primary mixing includes: placing the resin in a solvent, and stirring for 20-40 min at 800-1200 rad/min to obtain the resin slurry; the three times of mixing comprises: and adding the pigment filler, the auxiliary agent and the graphene dispersion slurry into the resin slurry, and stirring for 30-60 min at 1200-1500 rad/min to obtain the graphene modified heavy anti-corrosion coating.
8. The method of claim 6, wherein the secondary mixing comprises:
placing the dispersing agent in the dispersing medium for primary stirring;
adding the graphene into the solution after primary stirring, and sequentially performing secondary stirring and grinding to obtain the graphene dispersion slurry;
wherein the grinding is selected from one or more of sand grinding, ball milling and three-roll grinding.
9. The method according to claim 8, wherein the one-time stirring speed is 800rad/min to 1200rad/min, and the one-time stirring time is 20min to 40 min; the secondary stirring speed is 1000rad/min to 1300rad/min, and the secondary stirring time is 20min to 40 min; the grinding time is 40-80 min.
10. A graphene modified heavy-duty anticorrosive coating is obtained from the graphene modified heavy-duty anticorrosive coating of any one of claims 1 to 5, wherein the mass ratio of graphene in the graphene modified heavy-duty anticorrosive coating is 0.01-5%.
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CN112812605A (en) * 2020-12-29 2021-05-18 有研工程技术研究院有限公司 Preparation method of graphene modified heavy-duty anticorrosive paint
CN113185892A (en) * 2021-01-18 2021-07-30 中国人民解放军陆军勤务学院 Graphene modified epoxy coating and preparation method thereof
CN115093769A (en) * 2022-06-23 2022-09-23 有研工程技术研究院有限公司 Organic hydrogen permeation resistant coating and preparation method and application thereof
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CN115353793A (en) * 2022-03-14 2022-11-18 低维新材料科技(苏州)有限公司 Heavy-duty anticorrosive paint based on few-layer graphene and preparation method and application thereof
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CN112812605A (en) * 2020-12-29 2021-05-18 有研工程技术研究院有限公司 Preparation method of graphene modified heavy-duty anticorrosive paint
CN113185892A (en) * 2021-01-18 2021-07-30 中国人民解放军陆军勤务学院 Graphene modified epoxy coating and preparation method thereof
CN115181472A (en) * 2021-04-02 2022-10-14 上海新池能源科技有限公司 Anticorrosive paint and preparation method thereof
CN115353793A (en) * 2022-03-14 2022-11-18 低维新材料科技(苏州)有限公司 Heavy-duty anticorrosive paint based on few-layer graphene and preparation method and application thereof
CN115093769A (en) * 2022-06-23 2022-09-23 有研工程技术研究院有限公司 Organic hydrogen permeation resistant coating and preparation method and application thereof
CN115895428A (en) * 2022-11-27 2023-04-04 中国特种飞行器研究所 Intrinsic self-healing anticorrosive paint and preparation method thereof
CN116535929A (en) * 2023-04-03 2023-08-04 百氏高涂料（苏州）有限公司 Graphene high-temperature-resistant and oxidation-resistant water-based paint and preparation method thereof
CN116769390A (en) * 2023-06-01 2023-09-19 徐州卧牛山新型防水材料有限公司 Graphene quantum dot modified antibacterial mildew-proof waterproof coating and preparation method thereof
CN118325450A (en) * 2024-05-14 2024-07-12 青岛中净益环保科技有限公司 Ocean anti-corrosion coating based on waterborne graphene and preparation and application thereof
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