CN114921145B - Modified graphene anticorrosive paint and preparation method thereof - Google Patents
Modified 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
Abstract
The invention provides a modified graphene anticorrosive paint and a preparation method thereof, and belongs to the technical field of paint. The modified graphene anticorrosive paint is characterized in that: the material is prepared from the following raw materials in parts by weight: 30-38 parts of aqueous polyurethane resin, 25-32 parts of acrylic ester emulsion, 15-23 parts of modified graphene, 1-3 parts of polydopamine, 0.01-1.2 parts of penetrating agent, 0.01-1 part of emulsifying agent, 0-0.05 part of defoaming agent, 0-10 parts of film forming auxiliary agent and 0-1 part of other auxiliary agents. According to the invention, through matching of the matrix, preparation of the modified graphene and selection optimization of the auxiliary agent, the dispersibility and compatibility of the graphene and the matrix are improved, and the corrosion resistance of the graphene added into the coating is improved, so that the coating can provide better corrosion protection for metals.
Description
Technical Field
The invention belongs to the technical field of coatings, and particularly relates to a modified graphene anticorrosive coating and a preparation method thereof.
Background
Most metals and their alloys, such as copper, nickel, magnesium and carbon steel, are often subject to corrosion in industrial processes. Corrosion, in addition to deteriorating the properties of the material, can also lead to loss of degraded material, and significant losses from damage to the contaminated material from surrounding materials have prompted considerable effort in developing new corrosion protection strategies. The corrosion-resistant coating may isolate the underlying metal from the corrosive medium, thereby reducing the risk of corrosion. Coating the metal surface with an anticorrosive coating is a cost effective method of corrosion protection. Therefore, it is very necessary to develop an anticorrosive paint having excellent protective properties, which effectively protects metals for a long period of time.
The water-based paint is an environment-friendly paint advocated to be used in the current country, but the emulsion mainly takes water as a dispersion medium because the emulsion mainly takes water as a main film forming substance, has poor water resistance and corrosion resistance, and limits the further application of the emulsion in the fields of high and new technology and the like. Graphene is used as a nano material with excellent comprehensive performance, has great potential in preparing functional water-based paint with corrosion resistance, conductivity, flame retardance, self-repairing property and the like, and is an ideal water-based paint modifier, but the maximum efficacy of the modified graphene is difficult to develop due to poor dispersibility and stability in water-based emulsion.
Patent document CN108384397a provides a heavy-duty coating, comprising a component a and a component B, wherein the component a comprises, by mass, 10-20% of epoxy resin, 25-45% of ceramic powder, 20-55% of zinc powder, 0.1-5% of graphene and 2-10% of organic bentonite, and the balance of organic solvent; the component B comprises 50-95% of curing agent, 3-10% of curing accelerator and the balance of organic solvent; the mass ratio of the component A to the component B is 7-10:1. The heavy anti-corrosion coating provided by the invention has higher hardness, wear resistance, high temperature resistance, water resistance and salt spray resistance, and is good in flexibility, high in adhesive force and better in anti-corrosion performance.
Patent document CN106243943a provides a modified white graphene composite anticorrosive paint, which comprises the following raw materials in parts by weight: 18-68.5 parts of matrix resin, 5-20 parts of pigment and filler, 0.4-1.5 parts of dispersing agent, 0.1-0.5 part of defoamer, 20-30 parts of solvent, 1-20 parts of white graphene and 0-10 parts of curing agent. The anticorrosive paint of the composite modified white graphene has excellent anticorrosive performance, higher strength and salt spray resistance, and the modified white graphene with atomic-level thickness can further reduce the thickness of the coating, increase the adhesive force to a substrate and improve the wear resistance of the paint.
Patent document CN113185906a provides a water-based anticorrosive paint, which comprises the following raw materials in parts by weight: 40-70 parts of aqueous composite emulsion, 10-30 parts of pigment and filler, 5-10 parts of multifunctional auxiliary agent, 0.1-1 part of thickener, 1-10 parts of curing agent and 0-10 parts of water. The multifunctional auxiliary agent provides the coating with various purposes such as corrosion resistance, dispersion performance, anti-sedimentation performance and the like, and reduces the unstable risk caused by excessive additive types; the water-based paint prepared by taking water as a dispersion medium meets the environmental protection requirement; the auxiliary dispersing agent in the auxiliary agent provides a stable dispersing system for the modified graphene on one hand, and is a dispersing agent of a coating system on the other hand, and can be firmly adsorbed by the electrostatic action of pigment and filler ions, so that the anti-sedimentation performance of the water-based coating is improved; the modified graphene has good dispersibility in the coating, greatly improves the film forming uniformity, has good anti-corrosion performance, and has strong adhesive force after the coating is sprayed, so that the coating is not easy to crack or peel.
In summary, the prior art has made many researches and improvements in aspects of dispersibility and compatibility of graphene, so that the corrosion resistance of the coating is improved greatly, and meanwhile, the improvement of the corrosion resistance of the coating with respect to graphene still has an improved direction and space worth researching and exploring.
Disclosure of Invention
The invention aims to solve the technical problem of providing a modified graphene anticorrosive paint for improving the corrosion resistance and ageing resistance of the paint aiming at the defects of the prior art.
The invention aims to provide a preparation method of the modified graphene anticorrosive paint.
In order to solve the technical problems, the invention adopts the following technical scheme:
a modified graphene anticorrosive paint is prepared from the following raw materials in parts by weight: 30-38 parts of aqueous polyurethane resin, 25-32 parts of acrylic ester emulsion, 15-23 parts of modified graphene, 1-3 parts of polydopamine, 0.01-1.2 parts of penetrating agent, 0.01-1 part of emulsifying agent, 0-0.05 part of defoaming agent, 0-10 parts of film forming auxiliary agent and 0-1 part of other auxiliary agents.
Preferably, the modified graphene is graphene oxide/ZnO/SiO 2 The composite material is prepared by the following steps:
s1: adding zinc salt into ethanol to prepare 1-1.2mol/L solution A, fully and uniformly stirring, heating the prepared solution A to 50-55 ℃, adding 100-150ml of silica sol emulsion with the mass content of 12-15%, controlling the temperature to 50-55 ℃, dropwise adding ammonia water, stirring, controlling the end pH value to 8.0-8.2, reacting the obtained slurry at 120-130 ℃ for 10-15h, filtering, washing, drying and calcining reactants to obtain a material I;
s2: dispersing graphene oxide in isopropanol to prepare 1.5-1.8g/L of solution B, then immersing a material I in the solution B for equal volume immersion for 1-2 times, filtering, performing hydrothermal reaction at 145-150 ℃ for 8-9h, cooling to room temperature, washing, filtering, drying, grinding to obtain graphene oxide/ZnO/SiO 2 A composite material.
Preferably, the zinc salt is zinc acetate or zinc nitrate.
Preferably, the temperature of the calcination is 400-420 ℃.
Preferably, the temperature of the impregnation is 75-80 ℃ and the time is 12-18h.
Preferably, the penetrating agent is fatty alcohol polyoxyethylene ether.
Preferably, the emulsifier is nonylphenol polyoxyethylene ether or cardanol polyoxyethylene ether.
Preferably, the weight portion of the defoaming agent is 0.003-0.05 portion, and the defoaming agent is tributyl phosphate or polyether defoaming agent DF-220.
Preferably, the weight portion of the film forming auxiliary agent is 3-10 portions, and the film forming auxiliary agent is Fexanol1951.
Preferably, the weight portion of the other auxiliary agent is 0.1-1 portion, the other auxiliary agent is more than one of sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, polyvinyl alcohol, sodium lignin sulfonate, cetyltrimethylammonium bromide and polyvinylpyrrolidone, and the mass concentration of the other auxiliary agent is 3-10g/L.
The invention also provides a preparation method of the modified graphene anticorrosive paint, which comprises the following steps:
weighing aqueous polyurethane resin and acrylic emulsion, mixing, heating to 45-50deg.C, stirring for 30-40min to obtain matrix;
weighing other auxiliary agents, dissolving in water to prepare a solution with the mass concentration of 3-10g/L, adding modified graphene and polydopamine, heating to 55-60 ℃, and magnetically stirring for 50-60min to obtain modified graphene dispersion;
adding the modified graphene dispersion liquid, the penetrating agent and the emulsifying agent into a matrix, stirring for 1.6-2h at 45-50 ℃, sequentially adding the defoaming agent and the film-forming auxiliary agent every 20min in the process, observing the number of bubbles, adding the defoaming agent or not, stopping stirring when no bubbles exist, and standing to obtain the product.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, through matching of the matrix, preparation of the modified graphene and selection optimization of the auxiliary agent, the dispersibility and compatibility of the graphene and the matrix are improved, and the corrosion resistance of the graphene added into the coating is improved, so that the coating can provide better corrosion protection for metals. The aqueous polyurethane resin and the acrylic emulsion are used together for the matrix, so that the adhesive force and flexibility of the coating can be enhanced, the dispersion of graphene is facilitated, and the corrosion resistance of the coating is improved. According to the invention, graphene oxide is selected and subjected to composite modification, so that on one hand, the problem that aggregation is easy to occur when components are dispersed in a matrix is greatly solved, and on the other hand, the weather resistance and corrosion resistance of the coating in the outdoor or severe environment are enhanced, so that the coating is more flexible, is more firmly attached, the water permeability is reduced, the corrosion of coated metal is prevented, and the self-cleaning capability of the coating is improved. In addition, the uniform dispersion of the graphene oxide composite material in the matrix coating is promoted by selecting and matching the polydopamine and other auxiliary agents, so that the graphene oxide composite material is better in dispersibility and not easy to agglomerate and lose effectiveness, and the comprehensive performance of the coating is improved. The penetrating agent can promote the coating to penetrate to the defect part of the coated metal, form a protective coating on the defect part, slow down the corrosion rate of the defect part and improve the corrosion resistance of the coating. Based on the corrosion-resistant coating disclosed by the invention, multiple protections can be provided for metal, a substrate provides a physical barrier coating for metal, a barrier mechanism of the wide specific surface area of the modified graphene composite material increases the tortuosity of an invasion path of a corrosive medium, and the improvement of the weather resistance and self-cleaning property of the coating prolongs the protection aging of the metal.
The coating can be used for protecting carbon steel structures/pipelines from outdoor corrosion, mainly plays a role of a physical barrier, prevents oxygen, water and other corrosive ions from entering the metal surface, enhances the permeability and adhesive force of the coating, and can prolong the protection timeliness of the coating to the metal.
It is known that the coating is inevitably scratched and bumped during use, damages the coating, and microcracks generated during aging of the coating also cause local defects of the coating, and the local defect areas are extremely easy to be permeated by corrosive media, so that the corrosion resistance and durability of the coating are tested. The invention uses aqueous polyurethane resin and acrylic emulsion as matrix resin, uses modified graphene as antiseptic additive, and prepares the organic-inorganic composite coating, graphene oxide and Zn 2+ And an adsorption protective film is formed on the metal surface and the defect part thereof in a cooperated manner to inhibit the cathode and anode reactions on the metal surface, so that the corrosion inhibition effect is achieved.
The coating of the invention has smooth and bright appearance, has no obvious defects of pinholes, bubble inclusion, flaking, cracks and the like which lead to the failure of the physical shielding effect of the coating, and can prolong the service life of the coating.
Detailed Description
For a better understanding of the present invention, the following examples are set forth to further illustrate the invention, but are not to be construed as limiting the invention. In the following description, numerous specific details are set forth in order to provide a more thorough understanding of the present invention. It will be apparent, however, to one skilled in the art that the invention may be practiced without one or more of these details.
All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of steps, operations, devices, components and/or combinations thereof.
Unless otherwise indicated, all starting materials are from commercially available products and unless otherwise indicated, they do not contain other components not explicitly indicated except for unavoidable impurities.
Example 1: preparation of modified graphene
Adding zinc nitrate into ethanol to prepare 1mol/L solution A, fully and uniformly stirring, heating the prepared solution A to 50 ℃, adding 100ml of silica sol emulsion with 12% of silica content, controlling the temperature to 50 ℃, dropwise adding ammonia water, stirring, controlling the end point pH value to 8.0, reacting the obtained slurry at 120 ℃ for 15 hours, filtering, washing, drying and calcining the reactant to obtain a material I;
dispersing graphene oxide in isopropanol to prepare a solution B with the concentration of 1.5g/L, soaking a material I in the solution B for 1 time in an equal volume, performing hydrothermal reaction for 9 hours at 145 ℃ after filtering, washing, filtering, drying and grinding to obtain graphene oxide/ZnO/SiO 2 A composite material.
Wherein the calcination temperature was 400 ℃.
The temperature of the impregnation was 75℃and the time was 18h.
Example 2: preparation of modified graphene
Adding zinc nitrate into ethanol to prepare 1.2mol/L solution A, fully and uniformly stirring, heating the prepared solution A to 55 ℃, adding 120ml of silica sol emulsion with 15% of silica content, controlling the temperature to 55 ℃, dropwise adding ammonia water, stirring, controlling the end point pH value to 8.2, reacting the obtained slurry at 130 ℃ for 10 hours, filtering, washing, drying and calcining the reactant to obtain a material I;
dispersing graphene oxide in isopropanol to prepare 1.8g/L solution B, soaking a material I in the solution B for 2 times with equal volume, filtering, performing hydrothermal reaction at 150 ℃ for 8 hours, cooling to room temperature, washing, filtering, drying, grinding to obtain graphene oxide/ZnO/SiO 2 A composite material.
Wherein the calcination temperature was 420 ℃.
The temperature of the impregnation was 80℃and the time was 12 hours.
Example 3: preparation of modified graphene
Adding zinc nitrate into ethanol to prepare 1.1mol/L solution A, fully and uniformly stirring, heating the prepared solution A to 52 ℃, adding 150ml of silica sol emulsion with 13% of silica content, controlling the temperature to 52 ℃, dropwise adding ammonia water, stirring, controlling the final pH value to 8.0, reacting the obtained slurry at 125 ℃ for 12 hours, filtering, washing, drying and calcining the reactant to obtain a material I;
dispersing graphene oxide in isopropanol to prepare 1.6g/L solution B, soaking the material I in the solution B for 1 time, filtering, and then adding water at 148 DEG CCarrying out thermal reaction for 8.5h, cooling to room temperature, washing, filtering, drying and grinding to obtain graphene oxide/ZnO/SiO 2 A composite material.
Wherein the calcination temperature was 410 ℃.
The temperature of the impregnation was 78℃and the time was 15 hours.
Example 4: preparation of modified graphene anticorrosive paint
The raw materials as shown in table 1 were provided,
weighing aqueous polyurethane resin and acrylic emulsion, mixing, heating to 45 ℃, and stirring for 40min to obtain a matrix;
weighing sodium dodecyl sulfate, dissolving in water to prepare a solution with the mass concentration of 10g/L, adding the modified graphene and polydopamine prepared in the example 1, heating to 55 ℃, and magnetically stirring for 60min to obtain a modified graphene dispersion;
adding the modified graphene dispersion liquid, the fatty alcohol polyoxyethylene ether and the nonylphenol polyoxyethylene ether into a matrix, stirring for 2 hours at 45 ℃, sequentially adding a polyether defoamer DF-220 and a film forming additive Fexanol1951 every 20 minutes in the process, observing the number of bubbles, adding the defoamer or not, stopping stirring when no bubbles exist, and standing to obtain the product.
Example 5: preparation of modified graphene anticorrosive paint
The raw materials as shown in table 1 were provided,
weighing aqueous polyurethane resin and acrylic emulsion, mixing, heating to 50 ℃, and stirring for 30min to obtain a matrix;
weighing polyvinyl alcohol, dissolving in water to prepare a solution with the mass concentration of 3g/L, adding the modified graphene and polydopamine prepared in example 1, heating to 60 ℃, and magnetically stirring for 50min to obtain a modified graphene dispersion;
adding the modified graphene dispersion liquid, the fatty alcohol polyoxyethylene ether and the cardanol polyoxyethylene ether into a matrix, stirring for 1.6 hours at 50 ℃, sequentially adding tributyl phosphate and a film forming additive Fexanol1951 every 20 minutes in the process, observing the number of bubbles, adding a defoaming agent or not, stopping stirring when no bubbles exist, and standing to obtain a product.
Example 6: preparation of modified graphene anticorrosive paint
The raw materials as shown in table 1 were provided,
weighing aqueous polyurethane resin and acrylic emulsion, mixing, heating to 46 ℃, and stirring for 38min to obtain a matrix;
cetyl trimethyl ammonium bromide is weighed and dissolved in water to prepare a solution with the mass concentration of 5g/L, modified graphene and polydopamine prepared in example 2 are added, the temperature is raised to 56 ℃, and magnetic stirring is carried out for 58min, so that modified graphene dispersion liquid is obtained;
adding the modified graphene dispersion liquid, the fatty alcohol polyoxyethylene ether and the cardanol polyoxyethylene ether into a matrix, stirring for 1.8 hours at 46 ℃, sequentially adding a polyether defoamer DF-220 and a film forming additive Fexanol1951 every 20 minutes in the process, observing the number of bubbles, adding the defoamer or not, stopping stirring when no bubbles exist, and standing to obtain the product.
Example 7: preparation of modified graphene anticorrosive paint
The raw materials as shown in table 1 were provided,
weighing aqueous polyurethane resin and acrylic emulsion, mixing, heating to 48 ℃, and stirring for 32min to obtain a matrix;
weighing sodium dodecyl benzene sulfonate, dissolving in water to prepare a solution with the mass concentration of 7g/L, adding the modified graphene and polydopamine prepared in the example 2, heating to 58 ℃, and magnetically stirring for 52min to obtain a modified graphene dispersion;
adding the modified graphene dispersion liquid, fatty alcohol polyoxyethylene ether and nonylphenol polyoxyethylene ether into a matrix, stirring for 1.7h at 48 ℃ under the condition of Fexanol1951, sequentially adding a polyether defoamer DF-220 and a film-forming auxiliary agent every 20min in the process, observing the number of bubbles, adding the defoamer or not, stopping stirring when no bubbles exist, and standing to obtain the product.
Example 8: preparation of modified graphene anticorrosive paint
The raw materials as shown in table 1 were provided,
weighing aqueous polyurethane resin and acrylic emulsion, mixing, heating to 47 ℃, and stirring for 35min to obtain a matrix;
weighing polyvinylpyrrolidone, dissolving the polyvinylpyrrolidone in water to prepare a solution with the mass concentration of 8g/L, adding the modified graphene and polydopamine prepared in the example 3, heating to 57 ℃, and magnetically stirring for 55min to obtain a modified graphene dispersion;
adding the modified graphene dispersion liquid, the fatty alcohol polyoxyethylene ether and the cardanol polyoxyethylene ether into a matrix, stirring for 1.8 hours at 47 ℃, sequentially adding a polyether defoamer DF-220 and a film forming additive Fexanol1951 every 20 minutes in the process, observing the number of bubbles, adding the defoamer or not, stopping stirring when no bubbles exist, and standing to obtain the product.
Table 1 raw material composition of examples 4 to 8
Comparative example 1: unlike example 4, the following is: graphene oxide is used for replacing modified graphene, and other conditions are unchanged.
Comparative example 2: unlike example 4, the following is: the aqueous polyurethane resin was omitted, and the weight part of the acrylic emulsion was 62 parts.
Comparative example 3: unlike example 4, the following is: the acrylate emulsion is omitted, and the weight part of the aqueous polyurethane resin is 62 parts.
Comparative example 4: unlike example 4, the following is: the penetrating agent is omitted, namely the addition of the fatty alcohol-polyoxyethylene ether is omitted.
Comparative example 5: unlike example 4, the following is: the modified graphene is obtained by the following preparation method: adding zinc acetate into ethanol to prepare 1mol/L solution A, fully and uniformly stirring, heating the prepared solution A to 50 ℃, dropwise adding ammonia water, stirring, controlling the pH value of the end point to 8.0, reacting the obtained slurry at 120 ℃ for 1.5h, filtering, washing and drying the reactant to obtain a material I'; dispersing graphene oxide in isopropanol to prepare a solution B with the concentration of 1.5g/L, then immersing a material I' in the solution B, carrying out isovolumetric immersion for 1 time, filtering, carrying out hydrothermal reaction for 9 hours at 145 ℃, cooling to room temperature, washing, filtering, drying and grinding to obtain the graphene oxide/ZnO composite material.
Comparative example 6: a modified graphene anticorrosive paint is prepared from the following raw materials in parts by weight: 30 parts of aqueous polyurethane resin, 32 parts of acrylic ester emulsion, 15 parts of graphene oxide, 1 part of polydopamine, 0.01 part of fatty alcohol polyoxyethylene ether, 0.12 part of nonylphenol polyoxyethylene ether, DF-2200.01 parts of polyether defoamer, fexanol1951 2 parts of film forming additive, 0.3 part of sodium dodecyl sulfate, 5 parts of nano zinc oxide and 2 parts of nano silicon dioxide;
the preparation method comprises the following steps: weighing aqueous polyurethane resin and acrylic emulsion, mixing, heating to 45 ℃, and stirring for 40min to obtain a matrix; weighing sodium dodecyl sulfate, dissolving in water to prepare a solution with the mass concentration of 10g/L, adding graphene oxide, nano zinc oxide, nano silicon dioxide and polydopamine, heating to 55 ℃, and magnetically stirring for 60min to obtain graphene dispersion; adding graphene dispersion liquid, fatty alcohol polyoxyethylene ether and nonylphenol polyoxyethylene ether into a matrix, stirring for 2 hours at 45 ℃, sequentially adding a polyether defoamer DF-220 and a film forming additive Fexanol1951 every 20 minutes in the process, observing the number of bubbles, adding the defoamer or not, stopping stirring when no bubbles exist, and standing to obtain the product.
Effect test example:
the anticorrosive paint prepared in example 4 to example 8 and comparative example 1 to comparative example 6 was applied to a substrate by bar coating after a tin plate having a size of 120mm×25mm× (0.2 mm to 0.3 mm) was treated as specified in GB/T9271, and left to stand at room temperature for 24 hours to cure, and the thickness of the coating was measured to be 100.+ -. 5. Mu.m.
The detection standard is according to the national recommended standard, and the results are shown in tables 2 and 3.
Table 2 example 4-example 8 test items and results
Note that: the aging resistance is regulated by GB/T16585-1996, a fluorescent ultraviolet/condensation cycle test method is adopted, and the light source is a UV-B (313 nm) lamp tube; the conditions for each cycle test were: UV illumination at 60 ℃ for 4 hours; condensing at 50 ℃ for 4 hours;
acid resistance and alkali resistance are carried out by adopting an A method, the sample is fully soaked, and the air blowing amount is 0.5m 3 And/h, maintaining the original concentration without stirring.
As can be seen from the data in Table 2, the coating of the invention has an adhesion of 0-1 level and shows a good adhesion effect; the flexibility test result is 1mm; impact resistance is 45-50cm; the aging resistance time is 18-20d (432-480 h), and the good coating performance can be maintained in a longer time; the wet heat resistance time is 40-42d, the acid resistance time is 21-23d, the alkali resistance time is 23-25d, the salt fog resistance time is 60-65d, and the stable and excellent corrosion resistance performance is shown.
Table 3 comparative example 1-comparative example 6 test items and results
Note that: the aging resistance is regulated by GB/T16585-1996, a fluorescent ultraviolet/condensation cycle test method is adopted, and the light source is a UV-B (313 nm) lamp tube; the conditions for each cycle test were: UV illumination at 60 ℃ for 4 hours; condensing at 50 ℃ for 4 hours;
acid resistance and alkali resistance are carried out by adopting an A method, the sample is fully soaked, and the air blowing amount is 0.5m 3 And/h, maintaining the original concentration without stirring.
From the data in table 3, the comparative example 1 uses graphene oxide to replace the modified graphene in the embodiment 4 of the present invention, and the aging resistance and corrosion resistance (wet heat resistance, acid resistance, alkali resistance and salt spray resistance) of the obtained coating are significantly reduced, which indicates that the modified graphene of the present invention has the effect of significantly improving the corrosion resistance of the coating. The single resin or emulsion is adopted in comparative example 2 and comparative example 3, the adhesive force and flexibility of the paint are obviously changed, and the degradation degree of other properties is smaller, but the invention also shows some descending trend, so that the combination of the two substrates is obviously beneficial to improving the comprehensive properties of the paint. Comparative example 4 omits the use of penetrant and the anti-aging and corrosion resistance properties of the coating show a more significant decrease than those of example 4, so that the use of penetrant can enhance the corrosion resistance of the coating of the invention to some extent, which is necessary to add. Comparative example 5 shows that the corrosion resistance of the modified graphene shows a degradation phenomenon by changing the preparation method of the modified graphene, particularly omitting the use of silica sol emulsion, and the composite preparation effect of the modified graphene is more remarkable. In comparative example 6, the conventional nano-filler is adopted to add nano-zinc oxide and nano-silicon dioxide into the coating, and experimental results show that the addition of the nano-zinc oxide and the nano-silicon dioxide does not have obvious promotion effect on ageing resistance and corrosion resistance of the coating compared with comparative example 1, and each performance of the coating of the comparative example is reduced compared with example 4, so that the effect of adding the nano-zinc oxide and the nano-silicon dioxide into the coating by adopting the modified composite mode of the invention is more obvious.
In conclusion, the anticorrosive paint has good comprehensive performance, has good adaptability to damp heat, acid and alkali and smoke environments, can keep good performance for a long time in the extreme environments, and has excellent corrosion resistance; the coating has excellent adhesion effect and flexibility, and can be suitable for corrosion prevention and rust prevention of steel structures such as railway vehicles, bridge wharf steel structures, shipbuilding, heavy machinery, electric machinery, mining machinery, petrochemical equipment, hydraulic steel structures and the like. The coating is also suitable for corrosion prevention of other base materials (nonferrous metals, ceramics and the like) and the like.
Finally, it is noted that the above-mentioned embodiments are merely for illustrating the technical solution of the present invention, and that other modifications and equivalents thereof by those skilled in the art should be included in the scope of the claims of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (8)
1. The modified graphene anticorrosive paint is characterized in that: the material is prepared from the following raw materials in parts by weight: 30-38 parts of aqueous polyurethane resin, 25-32 parts of acrylic ester emulsion, 15-23 parts of modified graphene, 1-3 parts of polydopamine, 0.01-1.2 parts of penetrating agent, 0.01-1 part of emulsifying agent, 0-0.05 part of defoaming agent, 0-10 parts of film forming auxiliary agent and 0-1 part of other auxiliary agents;
the modified graphene is graphene oxide/ZnO/SiO 2 The composite material is prepared by the following steps:
s1: adding zinc salt into ethanol to prepare 1-1.2mol/L solution A, fully and uniformly stirring, heating the prepared solution A to 50-55 ℃, adding 100-150ml of silica sol emulsion with the mass content of 12-15%, controlling the temperature to 50-55 ℃, dropwise adding ammonia water, stirring, controlling the end pH value to 8.0-8.2, reacting the obtained slurry at 120-130 ℃ for 10-15h, filtering, washing, drying and calcining reactants to obtain a material I;
s2: dispersing graphene oxide in isopropanol to prepare a solution B with the concentration of 1.5-1.8g/L, then immersing a material I in the solution B for equal volume immersion for 1-2 times, filtering, performing hydrothermal reaction at 145-150 ℃ for 8-9 hours, cooling to room temperature, washing, filtering, drying and grinding to obtain the graphene oxide/ZnO/SiO 2 composite material;
the penetrating agent is fatty alcohol polyoxyethylene ether;
the emulsifier is nonylphenol polyoxyethylene ether or cardanol polyoxyethylene ether;
the defoamer is tributyl phosphate or polyether defoamer DF-220;
the film forming additive is Fexanol1951;
the other auxiliary agent is more than one of sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate, polyvinyl alcohol, sodium lignin sulfonate, cetyltrimethylammonium bromide and polyvinylpyrrolidone.
2. The modified graphene anticorrosive paint as claimed in claim 1, wherein: the zinc salt is zinc acetate or zinc nitrate.
3. The modified graphene anticorrosive paint as claimed in claim 2, wherein: the calcination temperature is 400-420 ℃.
4. A modified graphene anti-corrosive coating as claimed in claim 3, wherein: the temperature of the soaking is 75-80 ℃ and the time is 12-18h.
5. The modified graphene anticorrosive paint as claimed in claim 1, wherein: the weight portion of the defoaming agent is 0.003-0.05 portion.
6. The modified graphene anticorrosive paint as claimed in claim 5, wherein: the film forming auxiliary agent is 3-10 parts by weight.
7. The modified graphene anticorrosive paint as claimed in claim 6, wherein: the weight portion of the other auxiliary agent is 0.1-1 portion, and the mass concentration of the other auxiliary agent is 3-10g/L.
8. The method for preparing the modified graphene anticorrosive paint as claimed in claim 7, which is characterized in that: the method comprises the following steps:
weighing aqueous polyurethane resin and acrylic emulsion, mixing, heating to 45-50deg.C, stirring for 30-40min to obtain matrix;
weighing other auxiliary agents, dissolving in water to prepare a solution with the mass concentration of 3-10g/L, adding modified graphene and polydopamine, heating to 55-60 ℃, and magnetically stirring for 50-60min to obtain modified graphene dispersion;
adding the modified graphene dispersion liquid, the penetrating agent and the emulsifying agent into a matrix, stirring for 1.6-2h at 45-50 ℃, sequentially adding the defoaming agent and the film-forming auxiliary agent every 20min in the process, observing the number of bubbles, adding the defoaming agent or not, stopping stirring when no bubbles exist, and standing to obtain the product.
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| CN116396636B (en) * | 2023-04-04 | 2023-11-14 | 佛山市三水区康立泰无机合成材料有限公司 | Black pigment for ceramic ink-jet printing and preparation method and application thereof |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018036422A1 (en) * | 2016-08-22 | 2018-03-01 | 广东纳路纳米科技有限公司 | Modified white graphene composite anti-corrosion coating and preparation thereof |
| CN110698616A (en) * | 2019-11-01 | 2020-01-17 | 河北科技大学 | Graphene/acrylic acid composite emulsion, anticorrosive water-based paint and preparation method thereof |
| CN111363443A (en) * | 2020-04-03 | 2020-07-03 | 杨海青 | Anticorrosive paint for building materials and preparation method thereof |
| CN112300652A (en) * | 2020-11-25 | 2021-02-02 | 福建农林大学 | Graphene oxide modified water-based acrylic coating and preparation method thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105062083A (en) * | 2015-08-16 | 2015-11-18 | 江龙 | Nano-zinc oxide doped high-performance silicone resin-polymethyl methacrylate composite material for LED packaging and preparation method of composite material |
| CN105419413A (en) * | 2015-12-25 | 2016-03-23 | 常州大学 | Anti-corrosion coating containing grapheme/zinc oxide/titanium oxide composite material and preparation method thereof |
| CN107266999A (en) * | 2017-05-17 | 2017-10-20 | 青岛瑞利特新材料科技有限公司 | A kind of watersoluble plumbago alkene anticorrosive paint and preparation method thereof |
| CN107473261A (en) * | 2017-09-01 | 2017-12-15 | 北京化工大学 | A kind of preparation method of zinc oxide/redox graphene composite |
| US11312630B2 (en) * | 2018-02-08 | 2022-04-26 | Tunghsu Technology Group Co., Ltd. | Modification method for graphene, modified graphene, and composition containing graphene |
| CN108997867B (en) * | 2018-09-17 | 2021-02-02 | 惠州市日大实业有限公司 | Water-based environment-friendly coating and preparation method thereof |
| CN111978771B (en) * | 2019-05-21 | 2022-03-01 | 中车唐山机车车辆有限公司 | Modified graphene oxide, preparation method thereof, anticorrosive paint containing modified graphene oxide and preparation method |
| CN111100512B (en) * | 2019-12-27 | 2021-07-30 | 杭州吉华高分子材料股份有限公司 | Preparation method of graphene modified water-based non-stick coating for iron cookers |
| CN113979466B (en) * | 2021-10-27 | 2023-04-28 | 烟台佳隆纳米产业有限公司 | ZnO@SiO 2 Method for preparing nanocapsules |
-
2022
- 2022-06-10 CN CN202210657616.0A patent/CN114921145B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018036422A1 (en) * | 2016-08-22 | 2018-03-01 | 广东纳路纳米科技有限公司 | Modified white graphene composite anti-corrosion coating and preparation thereof |
| CN110698616A (en) * | 2019-11-01 | 2020-01-17 | 河北科技大学 | Graphene/acrylic acid composite emulsion, anticorrosive water-based paint and preparation method thereof |
| CN111363443A (en) * | 2020-04-03 | 2020-07-03 | 杨海青 | Anticorrosive paint for building materials and preparation method thereof |
| CN112300652A (en) * | 2020-11-25 | 2021-02-02 | 福建农林大学 | Graphene oxide modified water-based acrylic coating and preparation method thereof |
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