CN111073463A - Low-zinc heavy-duty anticorrosive paint and preparation method thereof - Google Patents
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- CN111073463A CN111073463A CN201911337052.7A CN201911337052A CN111073463A CN 111073463 A CN111073463 A CN 111073463A CN 201911337052 A CN201911337052 A CN 201911337052A CN 111073463 A CN111073463 A CN 111073463A
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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
- 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
- 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
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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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
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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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
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Abstract
The invention discloses a low-zinc heavy-duty anticorrosive paint and a preparation method thereof, belongs to the technical field of paint production, overcomes the problems of zinc-rich heavy-duty anticorrosive paint in the prior art, reduces the quality of a coating, further improves the performance of a paint film, can realize the protection of the coating on the corrosion of marine equipment, reduces the quality of a ship body, improves the cruising speed, and is green and low in pollution in the coating production and preparation process. The coating comprises a main agent and a curing agent, wherein the main agent comprises epoxy resin, modified carbon fiber, self-ground carbon powder, high-purity zinc powder, a functional assistant and a solvent; the preparation method of the coating comprises the steps of zinc powder surface treatment, preparation of a main agent and mixing treatment. The prepared coating adopts high-purity and low-content zinc powder on the basis of not changing the corrosion resistance of common zinc-rich paint, thereby greatly reducing the pollution to the marine environment, and the preparation process is simple, green and low in pollution.
Description
Technical Field
The invention belongs to the technical field of paint production, and particularly relates to a low-zinc heavy-duty anticorrosive paint and a preparation method thereof.
Background
With the progress of scientific technology and the continuous improvement of the cognitive level of human beings on marine resources, the development of marine industries such as marine petroleum, submarine mining industry, marine chemical industry, marine culture, marine energy and the like has been moved from shallow sea to deep sea, even ultra-deep sea. The ocean engineering steel structure is fixed in the sea for a long time, the severe corrosion caused by the severe ocean environment directly influences the use safety of the steel structure, the zinc-rich heavy-duty anticorrosive paint is widely applied to corrosion protection of ocean equipment, but the high zinc content of a dry film causes poor mechanical property of a paint film, paint precipitation can be caused by long-term placement, a spray gun is easily blocked by zinc powder in the spraying process, inconvenience is brought to storage and construction, and the excessive zinc powder content has certain harm to the environment. The current coating protection technology has poor binding force widely, and the hull is difficult to effectively protect along with the depletion of zinc in the use process, and can reach better anticorrosive effect through increasing the coating thickness, but easily make the paint film drying process produce the crackle because of the shrink and initiate inefficacy to increase the hull quality, influence speed of cruising scheduling problem, consequently be difficult to satisfy product property demand and economy, environmental protection, sustainable requirement.
Disclosure of Invention
The invention provides a low-zinc heavy-duty anticorrosive paint and a preparation method thereof, which overcome the problems of a zinc-rich heavy-duty anticorrosive paint in the prior art, reduce the quality of a coating, further improve the performance of the paint film, realize the protection of the coating on corrosion of marine equipment, simultaneously reduce the quality of a ship body, improve the cruising speed, and realize green and low pollution in the production and preparation process of the coating.
In order to achieve the purpose, the invention adopts the following technical scheme:
a low-zinc heavy-duty anticorrosive coating comprises a main agent and a curing agent; the main agent comprises: the coating comprises epoxy resin, modified carbon fiber, self-grinding carbon powder, high-purity zinc powder, a functional assistant and a solvent, wherein the mass fraction of each substance in the main agent in the coating is as follows: 20-40% of epoxy resin, 0-5% of modified carbon fiber, 0-10% of self-ground carbon powder, 30-50% of solvent, and the fineness of the high-purity zinc powder is 150-600 meshes, and the dosage is selected according to the fineness; the curing agent is a phenolic aldehyde curing agent, and the proportion of the curing agent to the epoxy resin is selected according to different curing agent types.
In the coating, the epoxy resin is bisphenol A epoxy resin, specifically E-44 epoxy resin, E-51 epoxy resin and E-54 epoxy resin, preferably E-51 epoxy resin;
the modified carbon fiber is formed by coating carbon fiber with metallic nickel, and the mass fraction of the modified carbon fiber in the coating is 1-3%, preferably 2%;
the mass fraction of the self-grinding carbon powder in the coating is 2-8%, preferably 5%; the preparation method of the self-grinding carbon powder comprises the following steps: performing high-temperature pyrolysis on bamboo at 600 ℃, and crushing the bamboo after ball milling for 48 hours to obtain self-grinding carbon powder;
the fineness of the high-purity zinc powder is 200-400 meshes, preferably 400 meshes, and the mass fraction of the 400-mesh zinc powder in the total system is 5-20%, preferably 10%;
the functional assistant comprises a silane coupling agent, wherein the silane coupling agent is an epoxy silane coupling agent, specifically epoxy methoxysilane, epoxy ethoxysilane, 3-glycidyl ether oxypropyl trimethoxysilane or derivatives of different substituents of the epoxy silane coupling agent, and preferably 3-glycidyl ether oxypropyl trimethoxysilane (KH 560);
the mass fraction of the solvent is 20-40%, the solvent is aromatic hydrocarbon, alcohol, ketone, ester or a mixture of aromatic hydrocarbon and alcohol, preferably a mixed solvent of xylene and n-butanol with the mass ratio of 3: 1;
the curing agent is phenolic aldehyde amine, and the mass ratio of the epoxy resin to the phenolic aldehyde amine is 10:5-10:3, preferably 10:4, calculated on the basis of 100% of solid content.
A preparation method of a low-zinc heavy-duty anticorrosive coating comprises the following steps:
(1) zinc powder surface treatment: completely immersing high-purity zinc powder by using a solvent so as to fully soak the zinc powder; filtering to remove the solvent, and adding 1/4 mass of silane coupling agent into the zinc powder; fully oscillating the mixture of the zinc powder and the silane coupling agent to disperse the zinc powder; standing the mixture of the zinc powder and the silane coupling agent for 12 hours, and filtering to remove the silane coupling agent to obtain the treated zinc powder;
(2) preparation of the main agent: sequentially adding a solvent and a silane coupling agent into epoxy resin, pre-dispersing for 2-3min, then adding the treated zinc powder obtained in the step (1), self-made carbon powder and modified carbon fiber, and dispersing for 20min to obtain a coating main agent;
(3) mixing treatment: and (3) diluting the curing agent to 20% by using the solvent, mixing the curing agent with the main agent obtained in the step (2), and uniformly stirring to obtain the coating.
In the above steps, the pre-dispersion in step (2) is performed at a high speed disperser rotation speed of 1000rpm, and the dispersion is performed at a high speed disperser rotation speed of 3000 rpm.
Has the advantages that: the invention provides a low-zinc heavy-duty anticorrosive coating and a preparation method thereof, wherein the low-zinc heavy-duty anticorrosive coating is an epoxy group light-duty low-zinc coating, the protective effect of the coating on aluminum alloy can reach the protective effect of a zinc-rich coating, and the coating provides cathodic protection for a steel substrate; the light carbon-based functional filler adopted by the invention is beneficial to reducing the coating quality under unit volume, is beneficial to realizing light weight of marine navigation equipment such as ships and the like, improves the cruising speed and can further improve the paint film performance; as shown in fig. 1, compared with a pure epoxy coating, a network structure formed by irregular carbon powder and modified carbon fiber in the coating can increase a permeation path, increase the density of the coating and prevent a corrosive medium from permeating; in addition, electrons lost by the zinc powder as an anode can be transferred through the conductive network, so that anode metal is protected from corrosion, and the anti-corrosion performance of the coating is improved; and the carbon-based functional filler has the characteristics of wide source, low cost, reproducibility and the like, realizes green production of the anticorrosive coating, and has the characteristics of high curing speed, convenience and quickness in construction and the like. The solvent type epoxy group light low-zinc coating provided by the invention has good fluidity, low zinc powder content, low cost, long-term stable storage and simple preparation process, and simultaneously, the coating formed by the coating is firmly combined with a base material, the adhesive force grade can reach 0 grade, and the coating has excellent corrosion resistance and mechanical property and wide application prospect.
Drawings
FIG. 1 is a schematic diagram of the electrochemical reaction mechanism and corrosion medium permeation path extension of the light low-zinc filler of the present invention;
FIG. 2 is an SEM topography of the light low-zinc mixed filler of the invention;
FIG. 3 is a diagram showing the effect of the light low-zinc coating on the heavy corrosion resistance of a tin plate.
Detailed Description
The invention is described in detail below with reference to the following figures and specific examples:
example 1
A low-zinc heavy-duty anticorrosive coating comprises a main agent and a curing agent; the main agent comprises: 150g E-51 epoxy resin, 10g of modified carbon fiber, 25g of self-grinding carbon powder, 50g of 400-mesh high-purity zinc powder, 8g of BYK161 dispersing agent, 1g of BYK358 leveling agent and 200g of mixed solvent of xylene and n-butanol, wherein the mass ratio of the xylene to the n-butanol is 3: 1; the curing agent is phenolic aldehyde amine, and the mass ratio of the epoxy resin to the phenolic aldehyde amine is 10: 4.
The preparation method of the coating comprises the following steps:
(1) zinc powder surface treatment: firstly, soaking metal zinc powder of 400 meshes in sufficient dimethylbenzene to ensure that the dimethylbenzene is completely immersed in the zinc powder, filtering to remove redundant dimethylbenzene when in use, adding a silane coupling agent KH560 with the mass of about 1/4 zinc powder, fully oscillating and dispersing the zinc powder in the silane coupling agent to carry out zinc powder surface treatment, standing for 12 hours, and filtering to remove redundant silane coupling agent for later use;
(2) preparation of the main agent: sequentially adding 200g of a mixed solvent of xylene and n-butanol (the mass ratio of the xylene to the n-butanol is 3:1), 10g of a BYK161 dispersant and 1g of a BYK358 leveling agent into 150g of E-51 epoxy resin, pre-dispersing for 2min by using a high-speed dispersing machine 1000rmp, then adding 20g of zinc powder, modified carbon fiber and self-grinding carbon powder subjected to surface treatment in the step (1), dispersing for 20min by using a high-speed dispersing machine 3000rmp to obtain a main agent, and allowing a hard precipitate to appear in the standing process;
(3) mixing treatment: and (3) diluting the curing agent to 20% by using the solvent, mixing the diluted curing agent with the main agent obtained in the step (2), and uniformly stirring to obtain the epoxy light low-zinc coating.
The prepared epoxy group light low-zinc coating is sprayed, dried and cured at room temperature, the volume concentration (PVC%) of zinc powder in the coating after the drying and curing of the formula system is about 10%, and a white corrosion product appears on the surface of the coating after a neutral salt spray experiment for 3000 hours; after the xenon lamp is aged for 1000 hours in an accelerated manner, the coating is pulverized; the experiment proves that the adhesion strength is 0 grade by adopting a Baige method; the impact test shows that the coating can bear the impact of a heavy hammer with the height of 50cm and no peeling of the coating occurs.
Example 2
A low-zinc heavy-duty anticorrosive coating comprises a main agent and a curing agent; the main agent comprises: 100g E-44 epoxy resin, 7g of modified carbon fiber, 17g of self-ground carbon powder, 33g of 400-mesh high-purity zinc powder, 6g of BYK161 dispersing agent, 1g of BYK358 leveling agent and 150g of xylene-n-butanol mixed solvent, wherein the mass ratio of xylene to n-butanol is 3: 1; the curing agent is phenolic aldehyde amine, and the mass ratio of the epoxy resin to the phenolic aldehyde amine is 10: 5.
The preparation method of the coating comprises the following steps:
(1) zinc powder surface treatment: firstly, soaking metal zinc powder of 400 meshes in sufficient dimethylbenzene to ensure that the dimethylbenzene is completely immersed in the zinc powder, filtering to remove redundant dimethylbenzene when in use, adding a silane coupling agent KH560 with the mass of about 1/4 zinc powder, fully oscillating and dispersing the zinc powder in the silane coupling agent to carry out zinc powder surface treatment, standing for 12 hours, and filtering to remove redundant silane coupling agent for later use;
(2) preparation of the main agent: sequentially adding 150g of a mixed solvent of xylene and n-butanol (the mass ratio of the xylene to the n-butanol is 3:1), 10g of a BYK161 dispersant and 1g of a BYK358 leveling agent into 150g of E-51 epoxy resin, pre-dispersing for 2min by using a high-speed dispersing machine 1000rmp, then adding 10g of zinc powder, modified carbon fiber and self-grinding carbon powder subjected to surface treatment in the step (1), dispersing for 20min by using a high-speed dispersing machine 3000rmp to obtain a main agent, and allowing hard precipitates to appear in the standing process;
(3) mixing treatment: and (3) diluting the curing agent to 20% by using the solvent, mixing the diluted curing agent with the main agent obtained in the step (2), and uniformly stirring to obtain the epoxy light low-zinc coating.
Example 3
A low-zinc heavy-duty anticorrosive coating comprises a main agent and a curing agent; the main agent comprises: 200g E-44 epoxy resin, 13g of modified carbon fiber, 33g of self-grinding carbon powder, 66g of 400-mesh high-purity zinc powder, 11g of BYK161 dispersing agent, 1g of BYK358 leveling agent and 200g of mixed solvent of xylene and n-butanol, wherein the mass ratio of the xylene to the n-butanol is 3: 1; the curing agent is phenolic aldehyde amine, and the mass ratio of the epoxy resin to the phenolic aldehyde amine is 10: 3.
The preparation method of the coating comprises the following steps:
(1) zinc powder surface treatment: firstly, soaking metal zinc powder of 400 meshes in sufficient dimethylbenzene to ensure that the dimethylbenzene is completely immersed in the zinc powder, filtering to remove redundant dimethylbenzene when in use, adding a silane coupling agent KH560 with the mass of about 1/4 zinc powder, fully oscillating and dispersing the zinc powder in the silane coupling agent to carry out zinc powder surface treatment, standing for 12 hours, and filtering to remove redundant silane coupling agent for later use;
(2) preparation of the main agent: sequentially adding 200g of a mixed solvent of xylene and n-butanol (the mass ratio of the xylene to the n-butanol is 3:1), 10g of a BYK161 dispersant and 1g of a BYK358 leveling agent into 200g of E-51 epoxy resin, pre-dispersing for 2min by using a high-speed dispersion machine 1000rmp, then adding 10g of zinc powder, modified carbon fiber and self-grinding carbon powder subjected to surface treatment in the step (1), dispersing for 20min by using a high-speed dispersion machine 3000rmp to obtain a main agent, and allowing a hard precipitate to appear in the standing process;
(3) mixing treatment: and (3) diluting the curing agent to 20% by using the solvent, mixing the diluted curing agent with the main agent obtained in the step (2), and uniformly stirring to obtain the epoxy light low-zinc coating.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. The low-zinc heavy-duty anticorrosive paint is characterized by comprising a main agent and a curing agent; the main agent comprises: the coating comprises epoxy resin, modified carbon fiber, self-grinding carbon powder, high-purity zinc powder, a functional assistant and a solvent, wherein the mass fraction of each substance in the main agent in the coating is as follows: 20-40% of epoxy resin, 0-5% of modified carbon fiber, 0-10% of self-ground carbon powder, 30-50% of solvent, and the fineness of the high-purity zinc powder is 150-600 meshes, and the dosage is selected according to the fineness; the functional assistant comprises a silane coupling agent; the curing agent is a phenolic aldehyde curing agent, and the proportion of the curing agent to the epoxy resin is selected according to different curing agent types.
2. The low-zinc heavy-duty anticorrosive coating according to claim 1, wherein the epoxy resin is bisphenol a type cyclic ester; the modified carbon fiber is formed by coating carbon fiber with metallic nickel; the self-grinding carbon powder is formed by sintering bamboo charcoal and then carrying out surface treatment; the fineness of the high-purity zinc powder is 200-400 meshes; the silane coupling agent is an epoxy silane coupling agent; the solvent is aromatic hydrocarbon, alcohol, ketone, ester or a mixture of aromatic hydrocarbon and alcohol; the curing agent is phenolic aldehyde amine.
3. The low-zinc heavy-duty anticorrosive coating according to claim 1 or 2, characterized in that the mass fraction of the solvent in the coating is 20% -40%; the mass fraction of the modified carbon fiber in the coating is 1-3%; the mass fraction of the self-grinding carbon powder in the coating is 2-8%; the mass fraction of the 400-mesh high-purity zinc powder in the coating is 5-20%, and the mass ratio of the epoxy resin to the phenol aldehyde amine is 10:5-10:3 calculated by 100% of solid content.
4. The low-zinc heavy-duty anticorrosive coating according to claim 2, wherein the epoxy resin is E-12 epoxy resin, E-44 epoxy resin, E-51 epoxy resin, E-54 epoxy resin; the solvent is a mixed solvent of dimethylbenzene and n-butyl alcohol in a mass ratio of 3: 1; the epoxy silane coupling agent is epoxy methoxy silane, epoxy ethoxy silane, 3-glycidyl ether oxygen propyl trimethoxy silane or derivatives of different substituents of the epoxy silane coupling agent.
5. The low-zinc heavy-duty anticorrosive coating according to claim 4, wherein the epoxy resin is an E-51 epoxy resin; the epoxy silane coupling agent is 3-glycidyl ether oxypropyl trimethoxy silane (KH 560).
6. The low-zinc heavy-duty anticorrosive coating according to claim 1, wherein the mass fraction of the epoxy resin in the coating is 30%.
7. The low-zinc heavy-duty anticorrosive coating according to claim 3, wherein the mass fraction of the modified carbon fiber in the coating is 2%; the mass fraction of the self-grinding carbon powder in the coating is 5 percent; the mass fraction of the 400-mesh zinc powder in the total system is 10 percent; the mass ratio of epoxy resin to phenalkamine was 10:4 based on 100% solids.
8. The preparation method of the low-zinc heavy-duty anticorrosive paint is characterized by comprising the following steps of:
(1) zinc powder surface treatment: completely immersing high-purity zinc powder by using a solvent so as to fully soak the zinc powder; filtering to remove the solvent, and adding 1/4 mass of silane coupling agent into the zinc powder; fully oscillating the mixture of the zinc powder and the silane coupling agent to disperse the zinc powder; standing the mixture of the zinc powder and the silane coupling agent for 12 hours, and filtering to remove the silane coupling agent to obtain the treated zinc powder;
(2) preparation of the main agent: sequentially adding a solvent and a silane coupling agent into epoxy resin, pre-dispersing for 2-3min, then adding the treated zinc powder obtained in the step (1), modified carbon fiber and self-ground carbon powder, and dispersing for 20min to obtain a coating main agent;
(3) mixing treatment: and (3) diluting the curing agent to 20% by using the solvent, mixing the curing agent with the main agent obtained in the step (2), and uniformly stirring to obtain the coating.
9. The method for preparing a low-zinc heavy-duty anticorrosive paint according to claim 8, characterized in that the pre-dispersion in step (2) is performed at a high-speed disperser rotation speed of 1000rpm, and the dispersion of the added treated zinc powder is performed at a high-speed disperser rotation speed of 3000 rpm.
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