CN114921145A - Modified graphene anticorrosive paint and preparation method thereof - Google Patents

Modified graphene anticorrosive paint and preparation method thereof Download PDF

Info

Publication number
CN114921145A
CN114921145A CN202210657616.0A CN202210657616A CN114921145A CN 114921145 A CN114921145 A CN 114921145A CN 202210657616 A CN202210657616 A CN 202210657616A CN 114921145 A CN114921145 A CN 114921145A
Authority
CN
China
Prior art keywords
modified graphene
parts
anticorrosive paint
stirring
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202210657616.0A
Other languages
Chinese (zh)
Other versions
CN114921145B (en
Inventor
赵娜
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Luoyang Dayu Industrial Co ltd
Original Assignee
Luoyang Dayu Industrial Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Luoyang Dayu Industrial Co ltd filed Critical Luoyang Dayu Industrial Co ltd
Priority to CN202210657616.0A priority Critical patent/CN114921145B/en
Publication of CN114921145A publication Critical patent/CN114921145A/en
Application granted granted Critical
Publication of CN114921145B publication Critical patent/CN114921145B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D133/00Coating 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
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/65Additives macromolecular
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2296Oxides; Hydroxides of metals of zinc
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/08Stabilised 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 paints. The modified graphene anticorrosive paint is characterized in that: the feed is prepared from the following raw materials in parts by weight: 30-38 parts of waterborne polyurethane resin, 25-32 parts of acrylate 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 emulsifier, 0-0.05 part of defoaming agent, 0-10 parts of film-forming assistant and 0-1 part of other assistant. According to the invention, through the matching of the matrix, the preparation of the modified graphene and the selection optimization of the auxiliary agent, the dispersibility and compatibility of the graphene and the matrix are improved, the corrosion resistance of the coating added with the graphene is improved, and the coating can provide better corrosion protection for metals.

Description

Modified graphene anticorrosive paint and preparation method thereof
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. In addition to deterioration of material properties, corrosion can also lead to loss of degraded material, and the significant loss of contaminating material damage to surrounding materials has prompted considerable effort in developing new corrosion protection strategies. The corrosion resistant coating can isolate the underlying metal from the corrosive medium, thereby reducing the risk of corrosion. The coating of the metal surface with the anticorrosive paint is an economic and effective anticorrosive method. Therefore, it is necessary to develop an anticorrosive coating having excellent protective properties and effectively protecting metals for a long period of time.
The water-based paint is an environment-friendly paint advocated by the current country, but the water-based emulsion is mainly used as a main film forming substance, most of the emulsion takes water as a dispersion medium, and the water resistance and the corrosion resistance of the emulsion are poor, so that the further application of the emulsion in the fields of high and new technologies and the like is limited. Graphene, as a nano material with excellent comprehensive performance, has great potential in the aspect of preparing functional water-based coatings with corrosion resistance, conductivity, flame retardance, self-repairability and the like, and is an ideal water-based coating modifier, but the graphene is difficult to exert the maximum effect of modification due to poor dispersibility and stability in a water-based emulsion.
Patent document CN108384397A provides a heavy-duty anticorrosive paint, which comprises a component a and a component B, wherein the component a comprises, by mass, 10 to 20% of epoxy resin, 25 to 45% of ceramic powder, 20 to 55% of zinc powder, 0.1 to 5% of graphene and 2 to 10% of organobentonite, and the balance is an 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-duty anticorrosive coating provided by the invention has the advantages of high hardness, wear resistance, high temperature resistance, water resistance, salt spray resistance, good flexibility, high adhesion and better anticorrosive 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 defoaming agent, 20-30 parts of solvent, 1-20 parts of white graphene and 0-10 parts of curing agent. The anticorrosive coating of the composite modified white graphene has excellent anticorrosive performance, high strength and salt spray resistance, and the modified white graphene with atomic-scale thickness can further reduce the thickness of the coating, increase the adhesive force to a base material and improve the wear resistance of the coating.
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 thickening agent, 1-10 parts of curing agent and 0-10 parts of water. The multifunctional additive provides multiple purposes such as corrosion resistance, dispersibility, anti-settling property and the like for the coating, and reduces unstable risks caused by excessive additive types; the water-based paint prepared by taking water as a dispersion medium meets the requirement of environmental protection; the auxiliary dispersing agent in the auxiliary agent provides a stable dispersing system for the modified graphene on one hand, and is also a dispersing agent of a coating system on the other hand, and can be firmly adsorbed through the electrostatic interaction with pigment and filler ions, so that the anti-settling property of the water-based coating is improved; the modified graphene has good dispersibility in the coating, greatly improves the film forming uniformity, has good corrosion resistance, has strong adhesive force after the coating is sprayed, and is not easy to crack or peel.
In conclusion, the prior art is researched and improved in many aspects such as graphene dispersibility and compatibility, so that the anticorrosive performance of the coating is greatly improved, and the improvement of the anticorrosive performance of the coating by the graphene is still in an improved direction and a space worth researching and exploring.
Disclosure of Invention
The invention aims to solve the technical problem of providing a modified graphene anticorrosive coating aiming at the defects of the prior art so as to improve the corrosion resistance and aging resistance of the coating.
The invention aims to solve another technical problem of providing a preparation method of the modified graphene anticorrosive paint.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the modified graphene anticorrosive paint is prepared from the following raw materials in parts by weight: 30-38 parts of waterborne polyurethane resin, 25-32 parts of acrylate 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 emulsifier, 0-0.05 part of defoaming agent, 0-10 parts of film-forming assistant and 0-1 part of other assistant.
Preferably, the modified graphene is graphene oxide/ZnO/SiO 2 The composite material is prepared by the following method, and the specific steps are as follows:
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 150ml of 100-plus silica sol emulsion with the mass content of 12-15% of silicon dioxide, controlling the temperature to be 50-55 ℃, dropwise adding ammonia water, stirring, controlling the end pH value to be 8.0-8.2, reacting the obtained slurry at the temperature of 120-plus 130 ℃ for 10-15h, filtering, washing, drying and calcining the reactant to obtain a material I;
s2: dispersing graphene oxide in isopropanol to prepare a solution B of 1.5-1.8g/L, then soaking the material I in the solution B for 1-2 times in equal volume, performing hydrothermal reaction at the temperature of 145-150 ℃ for 8-9h after filtering, cooling to room temperature, washing, filtering, drying and 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 12-18 h.
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 to 0.05, and the defoaming agent is tributyl phosphate or polyether defoaming agent DF-220.
Preferably, the film-forming assistant is 3-10 parts by weight, and the film-forming assistant is Fexanol 1951.
Preferably, the weight portion of the other auxiliary agent is 0.1-1 part, the other auxiliary agent is more than one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, polyvinyl alcohol, sodium lignosulfonate, cetyl trimethyl ammonium bromide and polyvinylpyrrolidone, and the mass concentration of the other auxiliary agent is 3-10 g/L.
The invention also provides a preparation method of the modified graphene anticorrosive paint, which comprises the following steps:
weighing aqueous polyurethane resin, mixing with acrylic emulsion, heating to 45-50 ℃, and stirring for 30-40min to obtain a matrix;
weighing other additives, dissolving the other additives 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 a modified graphene dispersion liquid;
and adding the modified graphene dispersion liquid, the penetrating agent and the emulsifier 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, supplementing 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 the matching of the matrix, the preparation of the modified graphene and the optimization of the selection of the auxiliary agent, the dispersibility and compatibility of the graphene and the matrix are improved, and the corrosion resistance of the coating added with the graphene is improved, so that the coating can provide better corrosion protection for metals. The matrix is matched with the waterborne polyurethane resin and the acrylic emulsion, so that the adhesive force and the 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 compositely modified, so that on one hand, the problem that all components are dispersed in a matrix and are easy to agglomerate is greatly solved, and on the other hand, the weather resistance and corrosion resistance of the coating in outdoor or severe environment are enhanced, so that the coating is more flexible and firmer in adhesion, 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 graphene oxide composite material is promoted to be uniformly dispersed in the matrix coating by selecting and matching polydopamine and other auxiliary agents, so that the graphene oxide composite material has better dispersibility and is not easy to agglomerate and lose efficacy, and the comprehensive performance of the coating is improved. The penetrant can promote the paint to permeate into 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 situation, the anticorrosive coating can provide multiple protection for metal, the matrix provides a physical barrier coating for the metal, the specific surface area-to-width barrier mechanism of the modified graphene composite material increases the tortuosity of a corrosive medium invasion path, and the weather resistance and self-cleaning performance of the coating are improved, so that the protective aging of the metal is prolonged.
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 surface of metal, strengthens the permeability and adhesive force of the coating, and can also prolong the protective aging of the coating on the metal.
It is known that the coating is inevitably scratched and collided in the using process, so that the coating is damaged, meanwhile, microcracks generated in the aging process of the coating also cause local defects of the coating, the local defect areas are extremely easy to permeate corrosive media, and the corrosion resistance and durability of the coating are tested. The invention takes aqueous polyurethane resin and acrylic emulsion as matrix resin and modified graphene as an anticorrosive additive to prepare an organic-inorganic composite coating, and graphene oxide and Zn 2+ And an adsorption protective film is formed on the metal surface and the defect part thereof in a synergistic manner, and the reaction of the cathode and the anode on the metal surface is inhibited, so that the corrosion inhibition effect is achieved.
The coating of the invention has smooth and bright appearance, has no obvious defects of failure of physical shielding effect of the coating caused by pinholes, bubble inclusion, peeling, cracks and the like, and can prolong the service life of the coating.
Detailed Description
In order to better understand the present invention, the following examples are further used to clearly illustrate the content of the present invention, but the content of the present invention is not limited to the following examples. 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 present invention may be practiced without one or more of these specific details.
All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present 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 invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
Unless otherwise specified, all starting materials are derived from commercially available products, and if not specified, contain no other components not specifically specified except for unavoidable impurities.
Example 1: preparation of modified graphene
Adding zinc nitrate into ethanol to prepare a 1mol/L solution A, fully and uniformly stirring, heating the prepared solution A to 50 ℃, adding 100ml of silica sol emulsion with the silicon dioxide content of 12%, 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 1.5g/L solution B, then soaking the material I in the solution B for equal volume for 1 time, filtering, carrying out hydrothermal reaction at 145 ℃ for 9 hours, cooling to room temperature, washing, filtering, drying, and grinding to obtain graphene oxide/ZnO/SiO 2 A composite material.
Wherein the calcining temperature is 400 ℃.
The impregnation temperature was 75 ℃ and the time 18 h.
Example 2: preparation of modified graphene
Adding zinc nitrate into ethanol to prepare a 1.2mol/L solution A, fully and uniformly stirring, heating the prepared solution A to 55 ℃, adding 120ml of silica sol emulsion with the content of 15% of silicon dioxide, controlling the temperature to be 55 ℃, dropwise adding ammonia water, stirring, controlling the pH value at the end point to be 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 a solution B of 1.8g/L, then soaking the material I in the solution B for 2 times of equal volume soaking, filtering, and carrying out hydrothermal reaction at 150 ℃ for 8hCooling to room temperature, washing, filtering, drying and grinding to obtain the graphene oxide/ZnO/SiO 2 A composite material.
Wherein the calcining temperature is 420 ℃.
The impregnation temperature was 80 ℃ and the time was 12 h.
Example 3: preparation of modified graphene
Adding zinc nitrate into ethanol to prepare a 1.1mol/L solution A, fully and uniformly stirring, heating the prepared solution A to 52 ℃, adding 150ml of silica sol emulsion with 13 percent of silicon dioxide content, controlling the temperature to 52 ℃, dropwise adding ammonia water, stirring, controlling the end point 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, then soaking the material I in the solution B for equal volume for 1 time, filtering, carrying out hydrothermal reaction at 148 ℃ for 8.5h, cooling to room temperature, washing, filtering, drying and grinding to obtain graphene oxide/ZnO/SiO 2 A composite material.
Wherein the temperature of calcination is 410 ℃.
The impregnation temperature was 78 ℃ and the time was 15 h.
Example 4: preparation of modified graphene anticorrosive paint
The raw materials as shown in table 1 were provided,
weighing and mixing the aqueous polyurethane resin and the acrylic emulsion, heating to 45 ℃, and stirring for 40min to obtain a matrix;
weighing sodium dodecyl sulfate, dissolving the sodium dodecyl sulfate in water to prepare a solution with the mass concentration of 10g/L, adding the modified graphene and the polydopamine prepared in the embodiment 1, heating to 55 ℃, and magnetically stirring for 60min to obtain a modified graphene dispersion liquid;
adding the modified 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 aid Fexanol1951 every 20 minutes in the process, observing the number of bubbles, supplementing 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, mixing with acrylic emulsion, heating to 50 ℃, and stirring for 30min to obtain a matrix;
weighing polyvinyl alcohol, dissolving the polyvinyl alcohol in water to prepare a solution with the mass concentration of 3g/L, adding the modified graphene and the polydopamine prepared in the embodiment 1, heating to 60 ℃, and magnetically stirring for 50min to obtain a modified graphene dispersion liquid;
adding the modified graphene dispersion liquid, fatty alcohol-polyoxyethylene ether and cardanol polyoxyethylene ether into a matrix, stirring for 1.6h at 50 ℃, sequentially adding tributyl phosphate and a film forming aid, namely, Fexanol1951 every 20min in the process, observing the number of bubbles, supplementing a defoaming agent or not, stopping stirring when no bubbles exist, and standing to obtain the product.
Example 6: preparation of modified graphene anticorrosive paint
The raw materials as shown in table 1 were provided,
weighing aqueous polyurethane resin, mixing with acrylic emulsion, heating to 46 ℃, and stirring for 38min to obtain a matrix;
weighing hexadecyl trimethyl ammonium bromide, dissolving the hexadecyl trimethyl ammonium bromide in water to prepare a solution with the mass concentration of 5g/L, adding the modified graphene and the polydopamine prepared in the embodiment 2, heating to 56 ℃, and magnetically stirring for 58min to obtain a modified graphene dispersion liquid;
adding the modified graphene dispersion liquid, fatty alcohol-polyoxyethylene ether and cardanol polyoxyethylene ether into a matrix, stirring for 1.8 hours at 46 ℃, sequentially adding a polyether defoamer DF-220 and a film forming aid Fexanol1951 every 20 minutes in the process, observing the number of bubbles, supplementing 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 and mixing the aqueous polyurethane resin and the acrylic emulsion, heating to 48 ℃, and stirring for 32min to obtain a matrix;
weighing sodium dodecyl benzene sulfonate, dissolving the sodium dodecyl benzene sulfonate in water to prepare a solution with the mass concentration of 7g/L, adding the modified graphene and the polydopamine prepared in the embodiment 2, heating to 58 ℃, and magnetically stirring for 52min to obtain a modified graphene dispersion liquid;
adding the modified graphene dispersion liquid, fatty alcohol-polyoxyethylene ether and nonylphenol polyoxyethylene ether into a matrix, stirring for 1.7h under the condition of Fexanol1951 at 48 ℃, adding a polyether defoamer DF-220 and a film-forming aid in sequence every 20min in the process, observing the number of bubbles, supplementing 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, mixing with acrylic emulsion, 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 embodiment 3, heating to 57 ℃, and magnetically stirring for 55min to obtain a modified graphene dispersion liquid;
adding the modified graphene dispersion liquid, fatty alcohol-polyoxyethylene ether and cardanol polyoxyethylene ether into a matrix, stirring for 1.8h at 47 ℃, sequentially adding a polyether defoamer DF-220 and a film forming aid Fexanol1951 every 20min in the process, observing the number of bubbles, supplementing the defoamer or not, stopping stirring when no bubbles exist, and standing to obtain the product.
Table 1 raw material compositions of example 4 to example 8
Figure BDA0003688861160000081
Figure BDA0003688861160000091
Comparative example 1: the difference from example 4 is: the graphene oxide is used for replacing modified graphene, and other conditions are unchanged.
Comparative example 2: the difference from example 4 is: the waterborne polyurethane resin is omitted, and the weight portion of the acrylic emulsion is 62 portions.
Comparative example 3: the difference from example 4 is: the acrylic ester emulsion is omitted, and the weight portion of the waterborne polyurethane resin is 62 portions.
Comparative example 4: the difference from example 4 is: omitting the penetrant, i.e. omitting the addition of fatty alcohol-polyoxyethylene ether.
Comparative example 5: the difference from example 4 is: the modified graphene is obtained by the following preparation method: adding zinc acetate into ethanol to prepare a 1mol/L solution A, fully and uniformly stirring, heating the prepared solution A to 50 ℃, dropwise adding ammonia water, stirring, controlling the end point pH value to be 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 1.5g/L solution B, then soaking the material I' in the solution B for equal volume for 1 time, filtering, carrying out hydrothermal reaction at 145 ℃ for 9 hours, cooling to room temperature, washing, filtering, drying, and grinding to obtain the graphene oxide/ZnO composite material.
Comparative example 6: the modified graphene anticorrosive paint is prepared from the following raw materials in parts by weight: 30 parts of waterborne polyurethane resin, 32 parts of acrylate 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, 0.3 part of polyether defoamer DF-2200.01, 19512 parts of film-forming assistant Fexanol, 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, mixing with acrylic emulsion, heating to 45 ℃, and stirring for 40min to obtain a matrix; weighing sodium dodecyl sulfate, dissolving the sodium dodecyl sulfate 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 a graphene dispersion liquid; adding the graphene dispersion liquid, fatty alcohol-polyoxyethylene ether and nonylphenol polyoxyethylene ether into a matrix, stirring for 2 hours at 45 ℃, sequentially adding a polyether defoaming agent DF-220 and a film-forming aid, namely, Fexanol1951 every 20 minutes in the process, observing the number of bubbles, supplementing the defoaming agent or not, stopping stirring when no bubbles exist, and standing to obtain the product.
Example of effect test:
using a galvanized iron plate having a size of 120 mm. times.25 mm. times. (0.2mm to 0.3mm) as a substrate after treatment as specified in GB/T9271, the anticorrosive coatings prepared in examples 4 to 8 and comparative examples 1 to 6 were applied to the substrate by bar coating, respectively, and left to stand at room temperature for 24 hours for curing, and the coating thickness was measured to be 100. + -. 5. mu.m.
The test standards were in accordance with the national recommendations, and the results are shown in tables 2 and 3.
Table 2 examples 4 to 8 test items and results
Figure BDA0003688861160000101
Note: the aging resistance is determined according to GB/T16585-1996, a fluorescent ultraviolet/condensation cycle test method is adopted, and a light source is a UV-B (313nm) lamp tube; the test conditions for each cycle were: UV light irradiation is carried out for 4h at 60 ℃; condensing for 4 hours at 50 ℃;
acid resistance and alkali resistance are carried out by adopting a method A, the sample is fully soaked, and the air blowing amount is 0.5m 3 And h, keeping the original concentration without stirring.
As can be seen from the data in Table 2, the paint of the invention has an adhesive force of 0-1 grade, and shows a good adhesive effect; the flexibility test result is 1 mm; impact resistance is 45-50 cm; the aging resistance time is 18-20d (432h-480h), and good coating performance can be kept for a long time; the wet heat resistance time is 40-42d, the acid resistance time is 21-23d, the alkali resistance time is 23-25d, and the salt spray resistance time is 60-65d, so that the corrosion-resistant paint has stable and excellent corrosion resistance.
Table 3 items and results of examination of comparative examples 1 to 6
Figure BDA0003688861160000111
Note: the aging resistance is determined according to GB/T16585-1996, a fluorescent ultraviolet/condensation cycle test method is adopted, and a light source is a UV-B (313nm) lamp tube; the test conditions for each cycle were: UV light irradiation is carried out for 4h at 60 ℃; condensing for 4 hours at 50 ℃;
acid resistance and alkali resistance are carried out by adopting a method A, the sample is fully soaked, and the air blowing amount is 0.5m 3 And h, keeping the original concentration without stirring.
As can be seen from the data in table 3, in comparative example 1, graphene oxide is used to replace the modified graphene in example 4 of the present invention, and the aging resistance and the corrosion resistance (moisture-heat resistance, acid resistance, alkali resistance, and salt-fog 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 comparative examples 2 and 3 adopt single resin or emulsion, the adhesive force and flexibility of the coating are obviously changed, the deterioration degree of other properties is smaller, but the deterioration tendency is shown, and the method shows that the improvement of the comprehensive properties of the coating is obviously beneficial to the matching use of two substrates. Comparative example 4 omits the use of a penetrant, and the aging resistance and corrosion resistance of the coating show a more significant decrease than those of example 4, and therefore, it is necessary to add a penetrant that can enhance the corrosion resistance of the coating of the present invention to some extent. Comparative example 5 changes the preparation method of the modified graphene, specifically, omits the use of the silica sol emulsion, and the result shows that the corrosion resistance of the modified graphene shows a deterioration phenomenon, which indicates that the composite preparation effect of the modified graphene of the invention is more significant. Comparative example 6 is that the nano zinc oxide and the nano silicon dioxide are added into the coating by adopting a conventional nano filler mode, and the experimental result shows that compared with comparative example 1, the addition of the two nano fillers does not play a remarkable role in improving the aging resistance and the corrosion resistance of the coating, and compared with example 4, the coating of the comparative example has all performances reduced, so that the effect of adding the coating by adopting the modified composite mode of the invention is more remarkable.
In conclusion, the anticorrosive coating has good comprehensive performance, shows good adaptability to damp-heat, acid-base and smoke environments, can maintain good performance for a long time in the extreme environment, and has excellent corrosion resistance; and 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 and wharf steel structures, ship building, heavy machinery, electric machinery, mining machinery, petrochemical equipment, hydraulic steel structures and the like. It is also suitable for corrosion prevention of other base materials (nonferrous metal, ceramics, etc.) and the like.
Finally, the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting, and other modifications or equivalent substitutions made by the technical solutions of the present invention by those of ordinary skill in the art should be covered within the scope of the claims of the present invention as long as they do not depart from the spirit and scope of the technical solutions of the present invention.

Claims (10)

1. The modified graphene anticorrosive paint is characterized in that: the feed is prepared from the following raw materials in parts by weight: 30-38 parts of waterborne polyurethane resin, 25-32 parts of acrylate 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 emulsifier, 0-0.05 part of defoaming agent, 0-10 parts of film-forming assistant and 0-1 part of other assistant.
2. The modified graphene anticorrosive paint according to claim 1, characterized in that: the modified graphene is graphene oxide/ZnO/SiO 2 The composite material is prepared by the following method, and the specific steps are as follows:
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 150ml of 100-plus silica sol emulsion with the mass content of 12-15% of silicon dioxide, controlling the temperature to be 50-55 ℃, dropwise adding ammonia water, stirring, controlling the end pH value to be 8.0-8.2, reacting the obtained slurry at the temperature of 120-plus 130 ℃ for 10-15h, filtering, washing, drying and calcining the reactant to obtain a material I;
s2: dispersing graphene oxide in isopropanol to prepare a solution B of 1.5-1.8g/L, and then preparing the materialSoaking the graphene oxide/ZnO/SiO in the solution B for 1-2 times in equal volume, filtering, performing hydrothermal reaction at the temperature of 145-150 ℃ for 8-9h, cooling to room temperature, washing, filtering, drying and grinding to obtain the graphene oxide/ZnO/SiO 2 A composite material.
3. The modified graphene anticorrosive paint of claim 2, wherein: the zinc salt is zinc acetate or zinc nitrate.
4. The modified graphene anticorrosive paint of claim 3, wherein: the temperature of the calcination is 400-420 ℃.
5. The modified graphene anticorrosive paint of claim 4, wherein: the dipping temperature is 75-80 ℃ and the time is 12-18 h.
6. The modified graphene anticorrosive paint of claim 5, wherein: the penetrating agent is fatty alcohol-polyoxyethylene ether.
7. The modified graphene anticorrosive paint of claim 6, wherein: the emulsifier is nonylphenol polyoxyethylene ether or cardanol polyoxyethylene ether.
8. The modified graphene anticorrosive paint according to claim 7, characterized in that: the defoaming agent is 0.003 to 0.05 part by weight, and the defoaming agent is tributyl phosphate or polyether defoaming agent DF-220.
9. The modified graphene anticorrosive paint of claim 8, wherein: the film-forming assistant is 3-10 parts by weight, and the film-forming assistant is a film-forming assistant Fexanol 1951;
preferably, the weight portion of the other auxiliary agent is 0.1-1 part, the other auxiliary agent is more than one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, polyvinyl alcohol, sodium lignosulfonate, cetyl trimethyl ammonium bromide and polyvinylpyrrolidone, and the mass concentration of the other auxiliary agent is 3-10 g/L.
10. The preparation method of the modified graphene anticorrosive paint according to claim 9, characterized by comprising the following steps: the method comprises the following steps:
weighing and mixing the aqueous polyurethane resin and the acrylic emulsion, heating to 45-50 ℃, and stirring for 30-40min to obtain a matrix;
weighing other additives, 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 a modified graphene dispersion liquid;
and adding the modified graphene dispersion liquid, the penetrating agent and the emulsifier 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, supplementing the defoaming agent or not, stopping stirring when no bubbles exist, and standing to obtain the product.
CN202210657616.0A 2022-06-10 2022-06-10 Modified graphene anticorrosive paint and preparation method thereof Active CN114921145B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202210657616.0A CN114921145B (en) 2022-06-10 2022-06-10 Modified graphene anticorrosive paint and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202210657616.0A CN114921145B (en) 2022-06-10 2022-06-10 Modified graphene anticorrosive paint and preparation method thereof

Publications (2)

Publication Number Publication Date
CN114921145A true CN114921145A (en) 2022-08-19
CN114921145B CN114921145B (en) 2023-07-18

Family

ID=82813725

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202210657616.0A Active CN114921145B (en) 2022-06-10 2022-06-10 Modified graphene anticorrosive paint and preparation method thereof

Country Status (1)

Country Link
CN (1) CN114921145B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115851058A (en) * 2022-12-26 2023-03-28 江苏绿能电力科技有限公司 Anti-corrosion coating for surface of distributed photovoltaic module
CN116396636A (en) * 2023-04-04 2023-07-07 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
CN116515353A (en) * 2023-05-08 2023-08-01 速维工程技术股份有限公司 High-temperature-resistant high-strength pressure pipeline and production process thereof

Citations (13)

* Cited by examiner, † Cited by third party
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
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
CN108997867A (en) * 2018-09-17 2018-12-14 深圳市心版图科技有限公司 A kind of Environmental Protective Water-paint and preparation method 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
CN111100512A (en) * 2019-12-27 2020-05-05 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
CN111363443A (en) * 2020-04-03 2020-07-03 杨海青 Anticorrosive paint for building materials and preparation method thereof
CN111978771A (en) * 2019-05-21 2020-11-24 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
US20210017436A1 (en) * 2018-02-08 2021-01-21 Tunghsu Technology Group Co., Ltd. Modification method for graphene, modified graphene, and composition containing graphene
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
CN113979466A (en) * 2021-10-27 2022-01-28 烟台佳隆纳米产业有限公司 ZnO@SiO2Preparation method of nano capsule

Patent Citations (13)

* Cited by examiner, † Cited by third party
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
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
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
US20210017436A1 (en) * 2018-02-08 2021-01-21 Tunghsu Technology Group Co., Ltd. Modification method for graphene, modified graphene, and composition containing graphene
CN108997867A (en) * 2018-09-17 2018-12-14 深圳市心版图科技有限公司 A kind of Environmental Protective Water-paint and preparation method thereof
CN111978771A (en) * 2019-05-21 2020-11-24 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
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
CN111100512A (en) * 2019-12-27 2020-05-05 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
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
CN113979466A (en) * 2021-10-27 2022-01-28 烟台佳隆纳米产业有限公司 ZnO@SiO2Preparation method of nano capsule

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115851058A (en) * 2022-12-26 2023-03-28 江苏绿能电力科技有限公司 Anti-corrosion coating for surface of distributed photovoltaic module
CN116396636A (en) * 2023-04-04 2023-07-07 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
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
CN116515353A (en) * 2023-05-08 2023-08-01 速维工程技术股份有限公司 High-temperature-resistant high-strength pressure pipeline and production process thereof

Also Published As

Publication number Publication date
CN114921145B (en) 2023-07-18

Similar Documents

Publication Publication Date Title
CN114921145B (en) Modified graphene anticorrosive paint and preparation method thereof
CN106189677B (en) A kind of low surface treatment epoxy coating and its manufacture method
CN108192403B (en) Solvent type zinc-aluminum coating
CN113265185B (en) Self-repairing graphene composite titanium nano heavy-duty anticorrosive material and preparation and use methods thereof
CN110218504B (en) Steel structure anticorrosive paint
KR20110026956A (en) Aqueous rust-resisting paint composition
CN110938350A (en) Epoxy primer for rail transit and preparation method thereof
JPWO2020045487A1 (en) Anti-corrosive paint composition and its uses
CN113897115B (en) Protective basalt flake coating capable of improving corrosion resistance of concrete and preparation method thereof
CN103588443A (en) Nano water-based functional ceramic composite coating and preparation method thereof
CN110845879A (en) Novel environment-friendly water-based paint and preparation method thereof
KR101130297B1 (en) Two component zinc type water base paint composition
CN110819193A (en) Self-flame-retardant acrylic resin water-based anticorrosive paint
CN111518451B (en) Epoxy micaceous iron intermediate paint
CN109762455B (en) Water-based weather-resistant anticorrosive paint and preparation method thereof
CN108610881A (en) Aqueous heavy anti-corrosion paint and preparation method thereof
CN110643210A (en) High-performance anti-corrosion coating for metal surface treatment
CN111423752A (en) Water-based inorganic zinc-rich primer for heavy corrosion protection
WO2016175367A1 (en) Aqueous colored pigment composition mixed with plate-like zinc powder
CN114891409A (en) Single-coating water-based ceramic heat-insulating anticorrosive paint for metal material and preparation method thereof
CN115353795A (en) High-resistance water-based epoxy zinc-rich primer and preparation method thereof
WO2016024653A1 (en) Pigment separable type aqueous paint composition mixed with plate-like zinc powder
CN113416467A (en) Epoxy ester antirust water paint and preparation method thereof
CN114058246A (en) High-strength corrosion-resistant water-based epoxy coating and preparation method thereof
CN106380998A (en) Polyaniline-chopped glass fiber-phenolic resin paint and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant