CN115595045A - Graphene-substrate two-in-one epoxy anticorrosive paint and preparation method thereof - Google Patents
Graphene-substrate two-in-one epoxy anticorrosive paint and preparation method thereof Download PDFInfo
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- CN115595045A CN115595045A CN202211410399.1A CN202211410399A CN115595045A CN 115595045 A CN115595045 A CN 115595045A CN 202211410399 A CN202211410399 A CN 202211410399A CN 115595045 A CN115595045 A CN 115595045A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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
- C09D5/10—Anti-corrosive paints containing metal dust
- C09D5/106—Anti-corrosive paints containing metal dust containing Zn
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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
- C09D5/24—Electrically-conducting 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
- C09D7/20—Diluents or solvents
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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
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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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
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0893—Zinc
Abstract
The invention discloses a graphene-substrate two-in-one epoxy anticorrosive paint and a preparation method thereof. The paint film coating prepared by the invention combines the primer paint and the intermediate paint into a whole, and simplifies the construction process while maintaining the corrosion resistance, thereby saving the cost.
Description
Technical Field
The invention belongs to the field of anticorrosive coatings, and particularly relates to a primer-in-primer two-in-one anticorrosive coating suitable for a steel structure.
Background
Corrosion is the phenomenon that objects such as metal, concrete, wood, etc. are damaged by the chemical or electrochemical action of the surrounding environment medium. According to relevant statistics, the economic loss caused by corrosion is about 7000 hundred million to 10000 million dollars each year around the world, and is about 6 times of the total economic loss caused by natural disasters such as earthquake, flood, typhoon and the like. In China, the loss caused by corrosion on a steel structure is about 5000 billion yuan each year, and accounts for about 2% of GDP. For a long time, various techniques have been used to slow the rate of corrosion.
At present, epoxy anticorrosive paint is widely used for the anticorrosion of outdoor steel structures, and in order to achieve an excellent anticorrosion effect on the outdoor steel structures, three layers of anticorrosive paint are generally sprayed on the steel structures, wherein the bottom layer is epoxy zinc-rich paint, the middle layer is epoxy intermediate paint, and the finish paint is polyurethane or fluorocarbon paint. The primer containing a large amount of zinc powder plays a role in electrochemical protection, the intermediate paint has a sealing effect to block water vapor from permeating, the finish paint has weather resistance and a decorative effect, the three effects are different, the heavy-duty anticorrosion effect cannot be achieved, but the construction process and time are long, and the corresponding cost is increased due to the fact that three layers of anticorrosion paints need to be coated on a steel structure to achieve the ideal heavy-duty anticorrosion effect. However, the coating has a common anticorrosion effect (the salt spray resistance time is generally 500-1500 h), cannot achieve the salt spray resistance time required by heavy anticorrosion, and can only be used for light anticorrosion of indoor steel structures.
The traditional anticorrosive paint has the salt spray resistant service life of 2000-3000 hours. The salt spray resistant time of the heavy duty anticorrosion system with graphene zinc provided by patent CN 208328675U can reach about 6000h, but the anticorrosion time is required to be reached, and the structure of the heavy duty anticorrosion system is sequentially a modified graphene zinc primer layer, a laminated graphene intermediate paint layer, a micaceous iron epoxy intermediate paint layer and a sixth or seventh set of anticorrosion system finish paint layer of a railway from inside to outside, so that four paint films are required to be coated, the construction process is complex, and the time cost is high. The patent CN103173095A introduces a graphene epoxy zinc-rich paint using xylene and isobutanol as solvents, the maximum anticorrosion time reaches about 1000h while the thickness of the paint is reduced, but the solvent used by the paint contains xylene which is harmful to the environment and human bodies, and with the development of society and technology, the requirement of people on steel structure anticorrosion is higher and higher, the anticorrosion time of the paint introduced by the patent reaches 2000-3000h to the maximum under the condition of coating intermediate paint and finish paint, the performance of the paint is not much different from that of the traditional anticorrosion paint, only the content of zinc powder is reduced, and zinc oxide mist generated during welding is reduced. Patent CN 102604533A introduces an anticorrosive coating of polyaniline and graphene composite material, which is prepared by mixing aniline and graphene oxide of hydrochloric acid together, preparing the polyaniline and graphene composite material through an oxidation-reduction process and a series of centrifugation, washing, filtration and drying processes, and grinding and doping the polyaniline and graphene composite material into the coating, thereby preparing the anticorrosive coating of the polyaniline and graphene composite material. Therefore, there is a need in the art to develop a paint film coating that has an excellent anticorrosive effect and can simplify the production and construction processes and time, thereby achieving a cost-saving effect.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a graphene primer and intermediate epoxy anticorrosive paint, and the paint film effect formed after the paint is coated is equivalent to the effect which can be achieved by the traditional primer and intermediate paint, so that the excellent anticorrosive effect is ensured, the construction process flow is simplified, the construction time is shortened, and the production cost is reduced.
The purpose of the invention is realized by the following technical scheme:
the graphene-substrate two-in-one epoxy anticorrosive paint is characterized by comprising a component A capable of being cured to form a film and a component B containing a curing agent. The component A comprises the following raw materials in percentage by mass: 0.1-3wt% of graphene, 0.01-1.5wt% of polyaniline, 10-40wt% of zinc powder, 10-30wt% of filler, 20-40wt% of a bisphenol A type epoxy resin solution with the solid content of 75%, and the balance of a first solvent. The component B comprises the following raw materials in percentage by mass: 40-60wt% of curing agent and 40-60wt% of second solvent.
Further, the graphene is redox graphene. The graphene has excellent conductivity and physical shielding property, and is added into the paint, so that the use amount of zinc powder is reduced while the anti-corrosion performance of the paint is improved, and the content of resin is increased, so that the primer-in-primer two-in-one paint prepared by the invention has excellent anti-corrosion performance, and simultaneously the toughness, hardness and sealing performance of a paint film are improved, and the performance of the primer-in-primer two-in-one paint is even superior to that of the traditional primer-intermediate paint epoxy anti-corrosion paint. The invention sets the mass percentage of graphene in the component A to be 0.1-3wt%: the content of the graphene is too much, and the agglomeration is easy to occur, so that the corrosion resistance is reduced; the content of the graphene is too small, the content of zinc powder must be increased in order to achieve the same anti-corrosion effect, and the increase of the resin content is not facilitated, so that the sealing effect is reduced, and the performance of the two-in-one coating in the bottom is reduced.
Further, the polyaniline is intrinsic polyaniline or conductive polyaniline, preferably conductive polyaniline. Polyaniline has excellent conductivity and passivation performance on metal, and can improve the performance of the epoxy anticorrosive paint by doping the polyaniline into the paint.
Further, the mass ratio of graphene to polyaniline is 9. Polyaniline and graphene form a circuit in the coating, the circuit is respectively connected with zinc powder and a metal substrate to form a positive electrode and a negative electrode, when corrosion occurs, the function of protecting the negative electrode by sacrificing the positive electrode is achieved, the zinc powder is preferentially corroded, the polyaniline plays a role of passivating the metal substrate along with the further deepening of the corrosion so as to prevent or slow down the corrosion, and the coating provides excellent corrosion resistance for the protected metal substrate through a synergistic action mechanism of the graphene and the polyaniline.
Further, the zinc powder is at least one of granular zinc powder, flaky zinc powder and Dacromet-grade flaky zinc powder, and preferably the Dacromet-grade flaky zinc powder. The excellent physical covering property of the flaky zinc powder improves the shielding effect of a metal base material, the zinc powder replaces the metal base material to be corroded in one step by virtue of the metal activity when corrosion occurs, and the graphene, polyaniline and the metal base material are matched to form a battery anode and cathode, so that the zinc powder is preferentially corroded to protect the metal base material when the corrosion occurs.
Further, the first solvent and the second solvent are mixed solvents consisting of ethylene glycol butyl ether and isobutanol with the weight ratio of 1-4. The two solvents have good intermiscibility with the filler and the resin, have moderate flash points, are small in harm to the environment and human bodies, belong to green environment-friendly solvents, and the addition of the two solvents ensures that the prepared coating has proper viscosity and dispersity, so that the excellent performance of the solvent-based coating is ensured, and the pollution and harm to the environment and personnel in the production, construction and use processes of the coating are greatly reduced.
Further, the filler is selected from at least one of barium sulfate, sericite, talc, organic bentonite, zinc phosphate and titanium dioxide, preferably sericite.
Furthermore, the solution of bisphenol A epoxy resin with the solid content of 75% is prepared by using ethylene glycol butyl ether as a solvent, and bisphenol A epoxy resin SM-601 is preferred. Bisphenol a epoxy resin has strong adhesion to various materials, particularly metals, strong chemical resistance, high mechanical strength, good electrical insulation, corrosion resistance, and can be cured in a relatively wide temperature range, and the volume shrinkage is small during curing.
Further, the curing agent in the component B is at least one of an acrylic resin curing agent or a polyamide resin curing agent, preferably a polyamide resin curing agent, and more preferably a polyamide resin curing agent 2741.
The preparation method of the two-in-one epoxy anticorrosive paint in the graphene substrate comprises the following steps:
step 1, preparing a component A
Mixing graphene and polyaniline, adding a proper amount of first solvent, and performing ball milling and uniform dispersion to obtain a mixed dispersion liquid of graphene and polyaniline;
sequentially adding the rest first solvent, zinc powder, mixed dispersion liquid and filler into a solution of bisphenol A type epoxy resin with the solid content of 75% at the rotating speed of 1000-1500r/min, stirring uniformly at the rotating speed of 2000-3000 r/min after the addition is finished, and adding into a three-roll grinder to grind the mixture until the granularity is 20-60 mu m to obtain a component A;
step 2, preparing a component B
Uniformly mixing and stirring the curing agent and the second solvent at the rotating speed of 1000-1500r/min to obtain a component B;
step 3, preparing two-in-one epoxy anticorrosive paint in graphene substrate
Mixing the prepared component A and the component B according to a mass ratio of 4-8 (preferably 6).
Compared with the prior art, the invention has the beneficial effects that:
1. the epoxy anticorrosive coating prepared by the invention has excellent anticorrosive effect, can reach or even be superior to the anticorrosive effect of the primer and the intermediate coating of the traditional steel structure heavy anticorrosive coating (the salt spray resistance time of the primer-intermediate two-in-one anticorrosive coating of the invention reaches 3500h when the spraying thickness is 150 mu m and 80 mu m fluorocarbon finish paint is matched, the spraying thickness is 250 mu m, and the salt spray resistant time of the fluorocarbon finish paint with the thickness of 80 mu m reaches 6000 h), so the coating can replace the bottom layer and the middle layer of the existing epoxy anticorrosive coating, thereby simplifying the construction process and the flow of the coating and achieving the effect of reducing the production cost.
2. The graphene is added into the anticorrosive coating, so that the anticorrosive coating has excellent conductivity and physical shielding property, the usage amount of zinc powder is reduced, the thickness of a coating is reduced, an anticorrosive mode that the zinc powder is sacrificed in the traditional zinc-rich coating is overcome, zinc oxide mist generated in welding is greatly reduced, and the anticorrosive coating is environment-friendly.
3. The solvent adopted by the anticorrosive coating is a green environment-friendly solvent, so that the coating greatly reduces the harm to the environment and personnel in production, construction and use.
4. The polyaniline is added into the anticorrosive coating, the anticorrosive coating has a flaky structure, has an excellent physical shielding effect, and has a passivation effect on a metal substrate, with the further progress of corrosion, when corrosive gas or liquid enters the bottom layer of the coating through the barrier of graphene and zinc powder, the progress of corrosion of the metal substrate is prevented or slowed down due to the passivation effect of the polyaniline, and the coating provides excellent anticorrosive performance for the protected metal substrate due to the synergistic action mechanism of the graphene, the polyaniline and the flaky zinc powder.
Detailed Description
The following examples are given for the detailed implementation and the specific operation procedures, but the scope of the present invention is not limited to the following examples.
The preparation method of the two-in-one epoxy anticorrosive paint in the graphene substrate in the following embodiment comprises the following steps:
step 1, preparing a component A
Mixing graphene and polyaniline, adding a proper amount of a first solvent, and performing ball milling and uniform dispersion to obtain a mixed dispersion liquid of the graphene and the polyaniline;
and at the rotating speed of 1500r/min, sequentially adding the rest first solvent, zinc powder, mixed dispersion liquid and filler (barium sulfate, sericite and talcum powder) into a solution of bisphenol A type epoxy resin with the solid content of 75%, stirring uniformly at the rotating speed of 2500r/min after the addition is finished, and adding into a three-roll grinder to grind the mixture until the granularity is 60 mu m to obtain the component A.
Step 2, preparing a component B
And (3) uniformly mixing and stirring the curing agent and the second solvent at the rotating speed of 1500r/min to obtain the component B.
Step 3, preparing graphene primer-intermediate two-in-one epoxy anticorrosive paint
Mixing the prepared component A and component B according to the mass ratio of 6.
Examples 1 to 6
The anticorrosive epoxy resin coating provided in examples 1 to 6 includes a component a capable of being cured to form a film and a component b containing a curing agent, and the components of the component a and the component b are shown in table 1 by mass percentage. In the table: the epoxy resin is bisphenol A type epoxy resin SM-601 with the solid content of 75% (the dispersion solvent is ethylene glycol butyl ether); the first solvent is a mixed solvent of ethylene glycol butyl ether and isobutanol with the mass ratio of 1; graphene is oxidized by a Hummers method and then is prepared by thermal reduction; the curing agent is polyamide resin 2741 curing agent.
Table 1 components of corrosion resistant epoxy coating provided in examples 1-6
To verify the performance of the anticorrosive coatings obtained in the examples: the coatings of examples 1-6 were sprayed to a controlled thickness of 150 μm, and were tested with 80 μm thick fluorocarbon topcoat, with the properties shown in table 2 below. The coatings of examples 1-6 were sprayed to a thickness of 250 μm, and tested with an 80 μm thick fluorocarbon topcoat, with the properties shown in Table 3 below.
TABLE 2 results of performance tests of examples 1 to 6 (two-in-one primer coating thickness of 150 μm, fluorocarbon topcoat thickness of 80 μm)
TABLE 3 results of the performance tests of examples 1-6 (two-in-one primer spray thickness of 250 μm, fluorocarbon topcoat thickness of 80 μm)
As can be seen from tables 2 and 3: it can be seen from comparison of examples 1 and 2 that the Dacromet grade zinc powder has a much improved anti-corrosion effect on the coating compared to the conventional granular zinc powder. It can be seen from comparison of examples 3 and 4 that the conductive polyaniline has a greater improvement in performance over the intrinsic polyphenylene towards the coating. It can be seen from comparative examples 1-6 that the best performance of the coating of the present invention can be achieved only under the combined action of the conductive polyaniline, graphene and dacromet-grade zinc powder. The salt spray resistance of the graphene primer two-in-one epoxy anticorrosive coating (with the spraying thickness of 150 mu m) matched with the fluorocarbon finish (with the spraying thickness of 80 mu m) can reach more than 3500h, and the performance requirements of the traditional steel structure heavy-duty anticorrosive primer and intermediate paint are met or even surpassed, so that the primer two-in-one coating can replace the traditional primer and intermediate paint, thereby simplifying the production and construction process, shortening the construction time and reducing the production cost.
The above description is only a preferred embodiment of the present invention, and not intended to limit the present invention, and the scope of the present invention is defined by the appended claims, and all changes that come within the meaning and range of equivalency of the specification are therefore intended to be embraced therein.
Claims (10)
1. The graphene primer-in-two-in-one epoxy anticorrosive paint is characterized by comprising a component A capable of being cured to form a film and a component B containing a curing agent;
the component A comprises the following raw materials in percentage by mass: 0.1-3wt% of graphene, 0.01-1.5wt% of polyaniline, 10-40wt% of zinc powder, 10-30wt% of filler, 20-40wt% of a bisphenol A epoxy resin solution with a solid content of 75%, and the balance of a first solvent;
the component B comprises the following raw materials in percentage by mass: 40-60wt% of curing agent and 40-60wt% of second solvent.
2. The graphene primer in-two-in-one epoxy anticorrosive paint according to claim 1, characterized in that: the graphene is redox graphene, and the polyaniline is eigen-state polyaniline or conductive polyaniline.
3. The graphene in-ground two-in-one epoxy anticorrosive coating of claim 1, wherein the zinc powder is at least one of a particulate zinc powder, a flake zinc powder, and a dacromet-grade flake zinc powder.
4. The two-in-one epoxy anticorrosive paint in a graphene substrate according to claim 1, characterized in that: the mass ratio of the graphene to the polyaniline is 9.
5. The two-in-one epoxy anticorrosive paint in a graphene substrate according to claim 1, characterized in that: the first solvent and the second solvent are mixed solvents consisting of ethylene glycol butyl ether and isobutanol according to the weight ratio of 1-4.
6. The graphene primer in-two-in-one epoxy anticorrosive paint according to claim 1, characterized in that: the filler is at least one selected from barium sulfate, sericite, talcum powder, organic bentonite, zinc phosphate and titanium dioxide.
7. The graphene primer in-two-in-one epoxy anticorrosive paint according to claim 1, characterized in that: the solution of bisphenol A type epoxy resin with the solid content of 75 percent is prepared by taking ethylene glycol monobutyl ether as a solvent.
8. The graphene primer in-two-in-one epoxy anticorrosive paint according to claim 1, characterized in that: the curing agent is at least one of an acrylic resin curing agent or a polyamide resin curing agent.
9. The graphene primer in-two-in-one epoxy anticorrosive paint according to claim 1, characterized in that: before use, the component A and the component B are mixed according to the mass ratio of 4-8.
10. A preparation method of the two-in-one epoxy anticorrosive paint in the graphene substrate according to any one of claims 1 to 9 is characterized by comprising the following steps:
step 1, preparing a component A
Mixing graphene and polyaniline, adding a proper amount of first solvent, and performing ball milling and uniform dispersion to obtain a mixed dispersion liquid of graphene and polyaniline;
sequentially adding the rest first solvent, zinc powder, mixed dispersion liquid and filler into a solution of bisphenol A type epoxy resin with the solid content of 75% at the rotating speed of 1000-1500r/min, stirring uniformly at the rotating speed of 2000-3000 r/min after the addition is finished, and adding into a three-roll grinder to grind the mixture until the granularity is 20-60 mu m to obtain a component A;
step 2, preparing a component B
Uniformly mixing and stirring the curing agent and the second solvent at the rotating speed of 1000-1500r/min to obtain a component B;
step 3, preparing two-in-one epoxy anticorrosive paint in graphene substrate
Mixing the prepared component A and component B according to a mass ratio of 4-8.
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2022
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| CN105400373A (en) * | 2015-12-16 | 2016-03-16 | 常州大学 | Graphene/deimpurity polyaniline-containing anticorrosive coating and preparation method thereof |
| CN107163826A (en) * | 2017-06-30 | 2017-09-15 | 邹亚静 | A kind of nano ceramics polymer anticorrosive paint and preparation method thereof |
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