CN113956745A - Weather-proof salt-mist corrosion-resistant coating with low VOC content, and preparation method and application thereof - Google Patents
Weather-proof salt-mist corrosion-resistant coating with low VOC content, and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
- C09D5/103—Anti-corrosive paints containing metal dust containing Al
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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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- 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
- C09D7/66—Additives characterised by particle size
- C09D7/67—Particle size smaller than 100 nm
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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
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08K2201/00—Specific properties of additives
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Abstract
The invention discloses a weather-proof salt-fog-corrosion-resistant coating with low VOC content, and a preparation method and application thereof, wherein the coating comprises the following components in percentage by mass: 30-50% of mixed resin; 10-30% of zinc powder; 0.2-1.5% of carbon nano material; 10-30% of a filler; 0.5-3% of an auxiliary agent and 10-20% of a solvent. The invention overcomes the problems of the existing heavy-duty zinc-rich paint, has lower zinc powder content than the zinc-rich paint, can greatly improve the salt spray corrosion resistance of the coating, has better anti-foaming performance and excellent adhesive force to the steel matrix, has better weather resistance, can realize effective corrosion protection of the coating under the environment of C5 or CX, has VOC content lower than 120g/L, and accords with the environmental protection development trend of the coating.
Description
Technical Field
The invention belongs to the technical field of paint production, and particularly relates to a weather-resistant salt spray corrosion-resistant paint with low zinc powder and low VOC content, which is used for corrosion protection of steel in coastal areas and marine environments, and a preparation method and application thereof.
Background
China is a large country with both sea and land, and the exploration of the ocean has entered a stage from shallow to deep from the first interest of fish salt to a series of ideas of developing ocean economy, innovating ocean technology, protecting ocean environment, building ocean ecological civilization and the like which are vigorously advocated in recent years. Meanwhile, with the progress of the technological level, the development and utilization of marine resources have been moving from shallow sea to deep sea, even ultra-deep sea. Especially in the industrial industries of ocean energy, submarine mining industry, ocean farming, etc. However, the severe corrosion result caused by the severe marine environment directly affects the use safety of the marine engineering structural steel and the like, and huge economic loss and potential safety hazard are caused. The zinc-rich heavy-duty anticorrosive coating is widely applied to corrosion protection of marine equipment, and the traditional zinc-rich heavy-duty anticorrosive coating provides corrosion protection for a base material based on a cathode protection mechanism of zinc powder, so that the content of the zinc powder is closely related to the corrosion protection effect, but the high-content zinc powder (60-85%) in a dry film also brings many disadvantages for the zinc-rich heavy-duty anticorrosive coating: (1) the high zinc powder content causes poor compactness and low strength of the coating; (2) the paint material can be precipitated after long-term storage due to the high content of the zinc powder, and the zinc powder is easy to block a spray gun in the spraying process, so that the storage and the construction are inconvenient; (3) the high zinc powder content has certain harm to the environment, which causes the problem of serious zinc pollution; (4) the consumption of zinc resources is large, and the zinc is consumed within 40 years according to the current use speed, and the zinc is statistically consumed.
With the rapid development of industrial science and technology, the industrial pollution of each country is serious, carbon dioxide is discharged in large quantity, greenhouse gases are increased dramatically, the world environment and biological systems are seriously damaged, the sustainable development under the earth ecological environment is vigorously advocated with the awareness of the human beings of each country on the environmental protection, and under the background, China puts forward the goals of carbon peak reaching and carbon neutralization. Of which the most important is the limitation of the VOC content of solvent-borne coatings in the coating. VOCs are Volatile Organic compounds (VOLATILE Organic Compounds) that are broadly any liquid or solid Organic Compound that can be volatilized in the atmosphere at ambient temperatures and pressures. Definition of the united states Environmental Protection Agency (EPA): all carbon compounds participating in atmospheric photochemical reaction, excluding CO and CO2Carbonic acid, metal carbides or carbonates, and ammonium carbonate. Definition of VOCs by the european union: an organic compound having an initial boiling point of 250 ℃ or lower at normal atmospheric pressure (101.3 kPa). At present, the mainstream heavy anti-corrosion paint is mainly solvent-based paint, the relevant standard is specified (GB30981-2020), the VOC limit value of the metal substrate anti-corrosion solvent-based inorganic workshop primer paint applied to the protection of buildings and structures is not more than 720g/L, the VOC limit value of the metal substrate anti-corrosion solvent-based organic workshop primer paint applied to the protection of buildings and structures is not more than 650g/L, the VOC content of the solvent-based spray workshop primer applied to containers and ships is not more than 700g/L, and the VOC content of the solvent-based roller coating workshop primer applied to containers and ships is not more than 700 g/L. The other coating is a water-based inorganic zinc-rich coating (wherein the content of metal zinc in a dry film is 60-80 wt%), according to the related standard (GB/T38597-The zinc powder is used in the environment of C5 and CX, and the high content of the zinc powder can cause damage to the environment. Therefore, the solvent type heavy anti-corrosion coating still needs to be used for corrosion protection under severe environment, the solvent type coating is widely used, the solvent content in the coating is high, the construction tools of the coating need to be cleaned by adopting volatile organic solvents, and in the process, harm is inevitably caused to human bodies or environment, so that the development of the solvent type heavy anti-corrosion coating with low VOC content is urgent.
Disclosure of Invention
In view of the above, the invention aims to provide a weather-resistant salt-spray corrosion-resistant coating with low VOC content, a preparation method and an application thereof, which overcome the problems of the existing zinc-rich heavy-duty anticorrosive coating, can reduce the coating quality, greatly reduce the content of zinc powder and VOC, and further reduce the pollution harm to the environment.
In order to achieve the aim, the invention provides a low-VOC-content weather-resistant salt-fog-corrosion-resistant coating which comprises the following components in percentage by mass: 30-50% of mixed resin; 10-30% of zinc powder; 0.2-1.5% of carbon nano material; 10-30% of a filler; 0.5-3% of an auxiliary agent and 10-20% of a solvent.
Further wherein the VOC content of the coating is not higher than 120 g/L.
Further, the mixed resin comprises the following components in percentage by mass: (1-3) the following (1-3): (0.5 to 1.5) the hydrogenated epoxy resin, the polyamide curing agent, the modified liquid polysulfide rubber and the silicone resin of (1 to 3); wherein the hydrogenated epoxy resin is EP-4080E, the epoxy equivalent is 200-230 g/eq, and the viscosity is 1500-3000 mPa.s/25 ℃; the polyamide curing agent has an amine value of 200 +/-20 (mgKOH/g) and a viscosity of 2000-4000 mpa.s; the liquid polysulfide rubber is JYL-121 in type, and the molecular weight is 800-6000; the type of the organic silicon resin is ME-8750, and the viscosity is 1000-2500 mPa.s/25 ℃.
Further, the zinc powder is first-grade zinc powder (GB/T6890-2012) with 99% of metal zinc content, and the particle size of the zinc powder is 30 μm.
Further, wherein the carbon nanomaterial is a carbon nanotube, graphene, or fullerene.
Further, the carbon nano tube is a multi-wall carbon nano tube with the purity of more than 95%, the outer diameter of 8-15 nm, the inner diameter of 3-5 nm and the length of 15-30 mu m.
Further, the graphene is multilayer graphene with the purity of more than 98%, the thickness of 3.4-8 nm, the sheet diameter of 5-50 microns and the number of layers of 5-10.
Further, the fullerene is a C60/C70 mixture with the purity of 98%, wherein the C60 accounts for 80%.
Further wherein the filler comprises at least one of titanium powder, ferrophosphorus powder, aluminum alloy powder, stainless steel powder, and hydrophobic silica.
Further, the filler is composed of titanium powder, phosphorus iron powder, aluminum alloy powder, stainless steel powder and hydrophobic silica, and the mass ratio of the five is as follows: (0.5-2): (0.5-2): (0.5-2): (0.5-2): (0.5-2).
Further, the solvent is a mixed solvent of butyl glycidyl ether and xylene, and the volume ratio of the mixed solvent to the mixed solvent is (1-3): (2-5).
In order to achieve the above object, the invention also provides a preparation method of the low-VOC weather-resistant salt-fog-corrosion-resistant coating, which comprises the following steps:
(1) adding zinc powder, a carbon nano material, a filler and an auxiliary agent into a solvent according to the formula ratio, and stirring at a high speed of 1000-2000 r/min for 20-40 minutes to obtain a uniformly dispersed base material;
(2) mixing the mixed resin with the base material in the step (1), sealing, introducing high-purity nitrogen, and performing ball milling for 10-12 hours to obtain uniformly dispersed first slurry;
(3) and (3) adding the polyamide curing agent with the mass ratio of 1:1 to the epoxy resin into the first slurry obtained in the step (2), and stirring at a high speed of 1000-2000 r/min for 20-40 minutes to obtain a second slurry which is uniformly dispersed, so as to obtain the coating.
Further, in the step (2), the mixed resin is prepared by the following steps: the mass ratio is as follows: (1-3), (0.5-1.5), (1-3) mixing the hydrogenated epoxy resin, the modified liquid polysulfide rubber and the organic silicon resin, stirring at a high speed of 1000-2000 r/min for 20-40 minutes, and dispersing uniformly to obtain the mixed resin.
Further wherein the modified liquid polysulfide rubber is prepared by the steps of: uniformly mixing the liquid polysulfide rubber, the coupling agent and xylene according to a mass ratio of (12-20) to (9-15) to (30-35), continuously stirring and heating to 120 ℃ in a high-purity nitrogen environment, reacting for 24-36 hours to obtain a transparent viscous liquid product, extracting with petroleum ether, and collecting lower-layer viscous liquid to obtain the modified liquid polysulfide rubber.
In order to achieve the above object, the present invention also provides a preparation method of the low-VOC-content weather-resistant salt-spray-corrosion-resistant coating, comprising the following steps:
coating the paint on a substrate by adopting a brushing process, naturally placing the paint at room temperature, and completely curing to obtain the low-VOC-content weather-resistant salt-fog-corrosion-resistant coating; wherein the temperature of the drying environment is 25-40 ℃; the humidity of the dry environment is 85% or less.
In order to achieve the above object, the present invention also provides a low-VOC, weather-resistant, salt-spray-corrosion-resistant coating, which has a zinc powder content of less than 30 wt% and a VOC content of not more than 120 g/l; the coating is prepared by the method.
According to the invention, the weather resistance of the coating is improved by adopting the hydrogenated epoxy resin, but the defects of large brittleness, poor adhesion and the like of the coating after curing caused by high benzene ring and crosslinking density in the epoxy resin are overcome, so that the polysulfide rubber is added to improve the elasticity of the coating and the adhesion of the coating; the zinc powder content in the finally prepared coating is lower than 30 wt%, the VOC content is not higher than 120g/L, the coating has excellent weather-resistant and salt spray corrosion-resistant performance, and meanwhile, the coating has excellent adhesive force to steel substrates, and can meet the corrosion protection coating for steel products under the C5 and CX environments.
Compared with the prior art, the weather-proof salt spray corrosion-resistant coating with low VOC content, the preparation method and the application thereof have the following beneficial effects:
the protective effect of the coating obtained after curing on steel can achieve the corrosion protection performance of a zinc-rich coating, effective cathodic protection is provided for the steel, the coating has excellent adhesion with the steel (the adhesion of a steel substrate reaches 10MPa), and the VOC content of the coating is lower than 120 g/L.
The coating provided by the invention adopts high-purity and low-content zinc powder, greatly reduces pollution to the marine environment, has excellent salt spray corrosion resistance, aging resistance and alternate dry-wet change resistance, is suitable for coastal areas with high requirements on corrosion resistance and weather resistance and steel using places in the marine environment, and has wide application prospect.
The zinc powder content of the coating provided by the invention is lower than 30 wt%, the VOC content is not higher than 120g/L, the coating has excellent weather-resistant and salt spray corrosion-resistant performance, and meanwhile, the coating has excellent adhesive force to steel substrates, and can meet the field of corrosion protection coatings for steel products under C5 and CX environments.
Drawings
FIG. 1 is an SEM topography of the cured low VOC, weather and salt spray resistant coatings of examples 1-3 of the present invention and the coatings of comparative examples 1-2;
FIG. 2 is a graph of electrochemical polarization of the cured low VOC, weather-resistant, salt-spray resistant coatings of examples 1-3 of the present invention and the coatings of comparative examples 1-2;
FIG. 3 is a graph of the electrochemical AC impedance of the cured low VOC, weather-resistant, salt-spray corrosion-resistant coatings of examples 1-3 of the present invention and the coatings of comparative examples 1-2;
FIG. 4 is a graph of the salt spray corrosion resistance effect of the cured low VOC, weather resistant salt spray corrosion resistant coatings of examples 1-3 of the present invention and the coatings of comparative examples 1-2.
Detailed Description
To further illustrate the technical means and effects of the present invention adopted to achieve the intended purpose, the following description is given with reference to the preferred embodiments. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions. The following materials or reagents, unless otherwise specified, are all commercially available.
The invention provides a weather-proof salt-spray corrosion-resistant coating with low VOC content, which comprises mixed resin, zinc powder, a carbon nano material, a filler, an auxiliary agent and a solvent; the mixed resin is selected to improve the defects of a single resin material, improve the defects of low adhesive force, large brittleness, poor weather resistance and corrosion resistance of a single coating, improve the strength, weather resistance and salt spray corrosion resistance and adhesive force of the coating, improve the salt spray corrosion resistance of the coating by zinc powder, play a role in cathodic protection on a base material, reduce the cost and the zinc content by adding the filler, improve the hardness, weather resistance and corrosion resistance of the coating, improve the binding force between the added filler and the mixed resin by adding the carbon material, improve the compactness of the coating, improve the hardness, weather resistance and corrosion resistance of the coating, prevent the problem caused by the reduction of the compactness of the coating by adding the filler, prepare the coating by more easily and uniformly dispersing all components by the aid and the mixed solvent, reduce the viscosity of slurry, make the coating more easily cured and be convenient to prepare uniformly, a flat weather-resistant salt-fog corrosion-resistant coating. In consideration of the above various factors, the coating may comprise the following components in percentage by mass: 30-50% of mixed resin; 10-30% of zinc powder; 0.2-1.5% of carbon nano material; 10-30% of a filler; 0.5-3% of an auxiliary agent and 10-20% of a solvent.
In some embodiments of the present invention, the mixed resin may be hydrogenated epoxy resin, polyamide curing agent, modified liquid polysulfide rubber, and silicone resin, in the following mass ratios: (1-3): (1-3): (0.5-1.5): (1-3) mixing; because the four resins mutually improve the weather resistance and the corrosion resistance among the resins, the cured resins have large brittleness and adhesive force, and the like, if the mass ratio of the four resins is lower than the lower limit value or higher than the upper limit value, the viscosity of the mixed resin is not suitable, the strength and the adhesive force of the mixed resin after curing, the brittleness and other properties of a coating layer are not good, and therefore, the preferable mass ratio of the three resins is selected as follows: (2-2.5): (2-2.5): (1-1.2): (1.5-2), so that the resin viscosity is more moderate after optimization, and the weather resistance and salt spray corrosion resistance of the coating are better.
It should be noted here that the polyamide curing agent can react with the hydrogenated epoxy resin to crosslink, so that the resin is cured; the flexible group is introduced by adding the modified polysulfide rubber, so that the characteristics of reduced mechanical property and brittleness of the coating caused by stress concentration in the coating after the hydrogenated epoxy resin is cured can be avoided; the elasticity of the coating is increased by adding the organic silicon resin, the weather resistance of the coating is improved, meanwhile, the adhesion performance of the organic silicon resin and the hydrogenated epoxy resin to a base material can be improved by the modified polysulfide rubber, and the four resins are improved in a synergistic manner, so that the mixed resin has excellent weather resistance and corrosion resistance and excellent adhesion to a substrate material.
In the embodiment, the type of the hydrogenated epoxy resin is EP-4080E, the epoxy equivalent is 200-230 g/eq, the viscosity is 1500-3000 mPa.s/25 ℃, and the weather resistance of the coating can be improved by selecting the hydrogenated epoxy resin; the polyamide curing agent has an amine value of 200 +/-20 (mgKOH/g) and a viscosity of 2000-4000 mpa.s, and is mainly used for curing hydrogenated epoxy resin; the type of the liquid polysulfide rubber is JYL-121, the molecular weight is 800-6000, and the polysulfide rubber is selected to improve the elasticity and the adhesive force of the coating; the type of the organic silicon resin is ME-8750, the viscosity is 1000-2500 mPa.s/25 ℃, and the organic silicon resin can reduce the surface energy of the coating and improve the weather resistance and salt spray corrosion resistance of the coating.
In some embodiments of the present invention, the filler is titanium powder, ferrophosphorus powder, aluminum alloy powder, stainless steel powder, and hydrophobic silica in a mass ratio of: (0.5-2): (0.5-2): (0.5-2): (0.5-2): (0.5-2) uniformly mixing and dispersing the mixture, wherein if the mass ratio of the five components is lower than the lower limit value, the action effect is not obvious, and the improvement of the strength, the hardness, the adhesive force, the corrosion resistance and the like of the coating cannot be limited; above the upper limit, too many metal particles in the coating can result in excessive coating viscosity, poor compactness, no film formation, cracking, etc. In order to improve the weather resistance and the corrosion resistance of the coating, the mass ratio of the powder, the phosphorus iron powder, the aluminum alloy powder, the stainless steel powder and the hydrophobic silicon dioxide is preferably (0.8-1): (1-1.3): (1.5-1.8): (1.5-1.8): (0.8 to 1).
In some embodiments of the present invention, the solvent is butyl glycidyl ether and xylene in a volume ratio of (1-3): if the volume ratio of the butyl glycidyl ether to the xylene is lower than the lower limit value, the zinc powder, the filler and the like in the mixed slurry are difficult to disperse, the viscosity of the slurry is high, and the coating is difficult to crack and reduce the performance of the coating; if the viscosity of the slurry is higher than the upper limit value, the viscosity of the slurry is too low, the adhesive force is reduced, the VOC content is increased, and the environment is polluted after long-term use. The volume ratio is preferably (2 to 2.5): (3-3.5), so that the preferable post-mixed solvent has proper volatilization speed, and the cured coating is flat and uniform.
In some embodiments of the present invention, the mass ratio of the hydrogenated epoxy resin, the modified liquid polysulfide rubber, and the silicone resin is: (1-3): (0.5-1.5): (1-3), the weather resistance and corrosion resistance of the three resins are improved mutually, the problems of high brittleness, adhesive force and the like of the cured resin of a single resin are solved, if the mass ratio of the three resins is lower than a lower limit value or higher than an upper limit value, the viscosity of the mixed resin is not suitable, the strength and adhesive force of the cured mixed resin are poor, the brittleness and other properties of a coating are poor, the viscosity of the mixed resin is more moderate after the mixed resin is optimized, the adhesive force and elasticity of the cured coating are better, and the weather resistance and salt spray corrosion resistance of the coating are better. The preferred mass ratio is: (2-2.5): (1-1.2): (1.5-2), so that the resin viscosity is more moderate after the optimization, and the weather resistance and the salt spray corrosion resistance of the coating are better.
In some embodiments of the invention, the zinc powder can be first-grade zinc powder with a zinc content of more than 99%, the particle size is about 30 μm, the first-grade zinc powder can be used as an important corrosion protection component in the coating, and has about cathodic protection to a substrate material, high-purity zinc powder ensures excellent protection capability, and the particle size is too low, so that the agglomeration of the zinc powder is caused, the dispersion in the preparation process is difficult, and the cost is increased; the zinc powder with large particle size can not be uniformly dispersed in the mixed resin due to large particle size, so that the corrosion resistance is unstable, or the zinc powder with large particle size can be uniformly dispersed only by increasing the content of the zinc powder; therefore, the proper particle size is beneficial to the uniform dispersion of the zinc powder in the coating, and simultaneously, the content of the zinc powder is reduced, so that the corrosion resistance of the coating is better.
In some embodiments of the present invention, the carbon nanomaterial can be a carbon nanotube, graphene or fullerene carbon material, wherein the carbon nanotube is a multi-walled carbon nanotube with a purity of more than 95%, an outer diameter of 8 to 15nm, an inner diameter of 3 to 5nm, and a length of 15 to 30 μm; the graphene is multilayer graphene with the purity of more than 98%, the thickness of 3.4-8 nm, the diameter of a lamella of 5-50 mu m and 5-10 layers; the fullerene is a C60/C70 mixture with the purity of 98 percent, wherein C60 accounts for about 80 percent, so that the hardness of the coating and the weather resistance and the salt mist corrosion resistance of the coating can be improved.
The test result shows that the volume solid content of the coating is not less than 95 percent, and the VOC content is not higher than 120 g/L.
The invention also provides a preparation method of the weather-resistant salt spray corrosion-resistant coating with low VOC content, which comprises the following steps:
(1) mixing hydrogenated epoxy resin, modified liquid polysulfide rubber and organic silicon resin according to the formula ratio, and stirring at a high speed of 1000-2000 r/min for 20-40 minutes to obtain uniformly dispersed mixed resin; the rotating speed and the time are preferably 1500r/min and 30min, so that the dispersing effect after the optimization is good, and the time is short;
(2) adding zinc powder, a carbon nano material, a filler and an auxiliary agent into a solvent according to the formula ratio, and stirring at a high speed of 1000-2000 r/min for 20-40 minutes to obtain a uniformly dispersed base material; the rotating speed and the time are preferably 1500r/min and 30min, so that the dispersing effect after the optimization is good, and the time is short;
(3) adding the mixed resin in the step (1) and the base material in the step (2) into a ball milling tank in which ball milling balls are placed in advance, wherein the ball milling balls are ball milling balls with the particle size of 15mm, the using amount of the ball milling balls is about two thirds of the volume of the ball milling tank, introducing high-purity nitrogen with the purity of more than 99.999% after sealing, enabling the ball milling tank to be in a nitrogen atmosphere, preventing metal powder from being oxidized, and carrying out ball milling in the ball milling machine for 10-12 hours to obtain uniformly dispersed first slurry;
(4) adding the first slurry obtained in the step (3) into hydrogenated epoxy resin according to a mass ratio of (1-1.5): (1-1.5) (the preferable mass ratio is 1:1, so that the preferable curing time is proper and the coating strength is better) of a polyamide curing agent, and stirring at a high speed of 1000-2000 r/min for 20-40 minutes to finally obtain uniformly dispersed second slurry, so that the coating can be obtained; the rotation speed and the time are preferably 1500r/min and 30min, so that the dispersing effect after optimization is good, and the time is short.
The invention also provides a preparation method of the weather-resistant salt-mist corrosion-resistant coating with low VOC content, which comprises the following steps:
coating the paint on a substrate by adopting a brushing process, naturally placing the paint at room temperature, and completely curing to obtain the low-VOC-content weather-resistant salt-fog-corrosion-resistant coating; wherein the natural placing temperature is 25-40 ℃; the humidity of the natural standing was 85% or less.
The invention also provides a weather-proof salt spray corrosion-resistant coating with low VOC content, wherein the zinc powder content is lower than 30 percent, and the VOC content is not higher than 120 g/L; the coating is prepared by the method.
The coating with low VOC content, weather resistance and salt mist corrosion resistance has good adhesive force with steel, and has excellent salt mist resistance, aging resistance and alternate dry and wet change performance.
The following is a further description with reference to specific examples.
Example 1
This example provides a low VOC, weather-resistant, salt-spray corrosion-resistant coating having the specific formulation shown in Table 1.
TABLE 1
The preparation method of the coating comprises the following steps:
(1) mixing hydrogenated epoxy resin, modified liquid polysulfide rubber and organic silicon resin according to the formula ratio, and stirring at a high speed of 1500r/min for 30 minutes to obtain a first base material which is uniformly dispersed;
(2) adding zinc powder, graphene, titanium powder, ferrophosphorus powder, aluminum alloy powder, stainless steel powder, hydrophobic silicon dioxide and a dispersing agent according to a formula ratio into a solvent (the mass ratio of butyl glycidyl ether to xylene is 1:1) according to a formula ratio for dispersing and mixing, and stirring at a high speed of 1500r/min for 30 minutes to obtain a second base material which is uniformly dispersed;
(3) adding the first base material in the step (1) and the second base material in the step (2) into a ball milling tank which is placed into ball milling balls in advance, wherein the ball milling balls are ball milling balls with the particle size of 15mm, the using amount of the ball milling balls is about two thirds of the volume of the ball milling tank, and introducing high-purity nitrogen with the purity of more than 99.999 percent after sealing, so that the ball milling tank is in a nitrogen atmosphere, the metal powder can be prevented from being oxidized, and the ball milling is carried out in the ball milling machine for 12 hours to obtain uniformly dispersed first slurry;
(4) and (4) adding the polyamide curing agent with the mass ratio of 1:1 to the hydrogenated epoxy resin into the first slurry obtained in the step (3), and stirring at a high speed of 1500r/min for 30 minutes to obtain uniformly dispersed second slurry, so as to obtain the coating.
The coating is coated on a substrate by adopting a brushing process, and the coating with low VOC content, weather resistance and salt spray corrosion resistance can be obtained after the coating is naturally placed for 7 days at room temperature; wherein the natural standing temperature is 30 ℃; the humidity of the natural standing was 50%.
Example 2
This example provides a low VOC, weather-resistant, salt-spray corrosion-resistant coating having the specific formulation shown in Table 2.
TABLE 2
The preparation method of the coating comprises the following steps:
(1) mixing hydrogenated epoxy resin, modified liquid polysulfide rubber and organic silicon resin according to the formula ratio, and stirring at a high speed of 1500r/min for 30 minutes to obtain a first base material which is uniformly dispersed;
(2) adding zinc powder, carbon nano tubes, titanium powder, ferrophosphorus powder, aluminum alloy powder, stainless steel powder, hydrophobic silicon dioxide and a dispersing agent according to the formula into a solvent (the mass ratio of butyl glycidyl ether to xylene is 1:1) according to the formula for dispersing and mixing, and stirring at a high speed of 1500r/min for 30 minutes to obtain a second base material which is uniformly dispersed;
(3) adding the first base material in the step (1) and the second base material in the step (2) into a ball milling tank which is placed into ball milling balls in advance, wherein the ball milling balls are ball milling balls with the particle size of 15mm, the using amount of the ball milling balls is about two thirds of the volume of the ball milling tank, and introducing high-purity nitrogen with the purity of more than 99.999 percent after sealing, so that the ball milling tank is in a nitrogen atmosphere, the metal powder can be prevented from being oxidized, and the ball milling is carried out in the ball milling machine for 12 hours to obtain uniformly dispersed first slurry;
(4) and (4) adding the polyamide curing agent with the mass ratio of 1:1 to the hydrogenated epoxy resin into the first slurry obtained in the step (3), and stirring at a high speed of 1500r/min for 30 minutes to obtain uniformly dispersed second slurry, so as to obtain the coating.
The coating is coated on a substrate by adopting a brushing process, and the coating with low VOC content, weather resistance and salt spray corrosion resistance can be obtained after the coating is naturally placed for 7 days at room temperature; wherein the natural standing temperature is 30 ℃; the humidity of the dry environment was 50%.
Example 3
This example provides a low VOC, weather-resistant, salt-spray corrosion-resistant coating having the specific formulation shown in Table 3.
TABLE 3
The preparation method of the coating comprises the following steps:
(1) mixing hydrogenated epoxy resin, modified liquid polysulfide rubber and organic silicon resin according to the formula ratio, and stirring at a high speed of 1500r/min for 30 minutes to obtain a first base material which is uniformly dispersed;
(2) adding zinc powder, fullerene, titanium powder, ferrophosphorus powder, aluminum alloy powder, stainless steel powder, hydrophobic silicon dioxide and a dispersing agent according to the formula amount into a solvent (the mass ratio of butyl glycidyl ether to xylene is 1:1) according to the formula amount for dispersing and mixing, and stirring at a high speed of 1500r/min for 30 minutes to obtain a second base material which is uniformly dispersed;
(3) adding the first base material in the step (1) and the second base material in the step (2) into a ball milling tank which is placed into ball milling balls in advance, wherein the ball milling balls are ball milling balls with the particle size of 15mm, the using amount of the ball milling balls is about two thirds of the volume of the ball milling tank, and introducing high-purity nitrogen with the purity of more than 99.999 percent after sealing, so that the ball milling tank is in a nitrogen atmosphere, the metal powder can be prevented from being oxidized, and the ball milling is carried out in the ball milling machine for 12 hours to obtain uniformly dispersed first slurry;
(4) and (4) adding the polyamide curing agent with the mass ratio of 1:1 to the hydrogenated epoxy resin into the first slurry obtained in the step (3), and stirring at a high speed of 1500r/min for 30 minutes to obtain uniformly dispersed second slurry, so as to obtain the coating.
The coating is coated on a substrate by adopting a brushing process, and the coating with low VOC content, weather resistance and salt spray corrosion resistance can be obtained after the coating is naturally placed for 7 days at room temperature; wherein the natural standing temperature is 30 ℃; the humidity of the dry environment was 50%.
Comparative example 1
The comparative example provides a low VOC, weather resistant, salt spray corrosion resistant coating having the specific formulation shown in Table 4.
TABLE 4
The preparation method of the coating comprises the following steps:
(1) mixing hydrogenated epoxy resin, modified liquid polysulfide rubber and organic silicon resin according to the formula ratio, and stirring at a high speed of 1500r/min for 30 minutes to obtain a first base material which is uniformly dispersed;
(2) adding zinc powder, fullerene, titanium powder, ferrophosphorus powder, aluminum alloy powder, stainless steel powder, hydrophobic silicon dioxide and a dispersing agent according to the formula amount into a solvent (the mass ratio of butyl glycidyl ether to xylene is 1:1) according to the formula amount for dispersing and mixing, and stirring at a high speed of 1500r/min for 30 minutes to obtain a second base material which is uniformly dispersed;
(3) adding the first base material in the step (1) and the second base material in the step (2) into a ball milling tank which is placed into ball milling balls in advance, wherein the ball milling balls are ball milling balls with the particle size of 15mm, the using amount of the ball milling balls is about two thirds of the volume of the ball milling tank, and introducing high-purity nitrogen with the purity of more than 99.999 percent after sealing, so that the ball milling tank is in a nitrogen atmosphere, the metal powder can be prevented from being oxidized, and the ball milling is carried out in the ball milling machine for 12 hours to obtain uniformly dispersed first slurry;
(4) and (4) adding the polyamide curing agent with the mass ratio of 1:1 to the hydrogenated epoxy resin into the first slurry obtained in the step (3), and stirring at a high speed of 1500r/min for 30 minutes to obtain uniformly dispersed second slurry, so as to obtain the coating.
The coating is coated on a substrate by adopting a brushing process, and the coating with low VOC content, weather resistance and salt spray corrosion resistance can be obtained after the coating is naturally placed for 7 days at room temperature; wherein the natural standing temperature is 30 ℃; the humidity of the dry environment was 50%.
Comparative example 2
The comparative example provides a low VOC, weather resistant, salt spray corrosion resistant coating having the specific formulation shown in Table 5.
TABLE 5
The preparation method of the coating comprises the following steps:
(1) mixing hydrogenated epoxy resin, modified liquid polysulfide rubber and organic silicon resin according to the formula ratio, and stirring at a high speed of 1500r/min for 30 minutes to obtain a first base material which is uniformly dispersed;
(2) adding zinc powder, fullerene, titanium powder, ferrophosphorus powder, aluminum alloy powder, stainless steel powder, hydrophobic silicon dioxide and a dispersing agent according to the formula amount into a solvent (the mass ratio of butyl glycidyl ether to xylene is 1:1) according to the formula amount for dispersing and mixing, and stirring at a high speed of 1500r/min for 30 minutes to obtain a second base material which is uniformly dispersed;
(3) adding the first base material in the step (1) and the second base material in the step (2) into a ball milling tank which is placed into ball milling balls in advance, wherein the ball milling balls are ball milling balls with the particle size of 15mm, the using amount of the ball milling balls is about two thirds of the volume of the ball milling tank, and introducing high-purity nitrogen with the purity of more than 99.999 percent after sealing, so that the ball milling tank is in a nitrogen atmosphere, the metal powder can be prevented from being oxidized, and the ball milling is carried out in the ball milling machine for 12 hours to obtain uniformly dispersed first slurry;
(4) and (4) adding the polyamide curing agent with the mass ratio of 1:1 to the hydrogenated epoxy resin into the first slurry obtained in the step (3), and stirring at a high speed of 1500r/min for 30 minutes to obtain uniformly dispersed second slurry, so as to obtain the coating.
The coating is coated on a substrate by adopting a brushing process, and the coating with low VOC content, weather resistance and salt spray corrosion resistance can be obtained after the coating is naturally placed for 7 days at room temperature; wherein the natural standing temperature is 30 ℃; the humidity of the dry environment was 50%.
The low VOC content, weather and salt spray resistant coatings of examples 1-3 of the present invention and the coatings of comparative examples 1-2 were tested using the following test methods and the results are shown in table 4.
Characterizing the coating by Fourier infrared spectroscopy (FT-IR), wherein the test condition is 4000-400 cm-1Resolution of 4cm-1。
And characterizing the surface appearance and the section appearance of the coating with low zinc powder, low VOC content, weather resistance and salt spray corrosion resistance by adopting a Scanning Electron Microscope (SEM).
The adhesion of the coating with low VOC content, weather resistance and salt mist corrosion resistance is tested by adopting GB/T5210 as a standard.
The salt spray corrosion resistance test of the coating with low VOC content, weather resistance and salt spray corrosion resistance tests the corrosion resistance according to the GB/T10125 standard.
And (3) carrying out electrochemical alternating current impedance spectroscopy (EIS) test and polarization curve test on the coating with low VOC content, weather resistance and salt spray corrosion resistance by using test and analysis instruments such as an AUTOLAB electrochemical workstation and the like.
TABLE 4
It can be seen from the test data in table 4 that the coatings prepared in examples 1 to 3 of the present invention have excellent adhesion and salt spray corrosion resistance, and the coatings still have good other properties under the condition of low VOC content, and the adhesion and other properties of the obtained coating are not significantly changed when the content of zinc powder in comparative examples 1 to 2 is greatly reduced to about 5% at the lowest, but the weather resistance and the salt spray corrosion resistance are sharply reduced, as shown in fig. 1 to 4.
In examples 1 to 3, the addition of the modified polysulfide rubber introduces a flexible group, which can avoid the characteristics of reduced mechanical properties and brittle coatings of the coatings caused by stress concentration in the coatings after the hydrogenated epoxy resins are cured, the addition of the silicone resin increases the elasticity of the coatings and improves the weather resistance of the coatings, and meanwhile, the modified polysulfide rubber can improve the adhesion properties of the silicone resin and the hydrogenated epoxy resins to the matrix material, and the three resins are synergistically improved, so that the mixed resin has excellent weather resistance and corrosion resistance and excellent adhesion to the matrix material. Zinc powder is an important anticorrosion component in the coating, and the anticorrosion mechanism is that the existence of the zinc powder provides cathodic protection capability for a matrix material, and a stable passive film generated by the easy oxidation of the zinc powder provides further anticorrosion protection. The addition of the filler reduces the cost on one hand, reduces the content of the zinc powder on the other hand, prevents high-content zinc powder from causing zinc pollution to the environment and damaging the ecological environment in actual long-term application, can improve the hardness strength and the salt spray corrosion resistance of the resin coating by adding the filler, increases the binding force between the resin coating and the added filler by adding the carbon material, improves the compactness of the coating, and prevents the cracking and other serious damages of the coating caused by the addition of the filler. In the comparative examples 1-2, under the condition that the content of zinc powder is greatly reduced under the condition that other components are not changed, the performances such as strength, hardness and adhesion of the obtained coating are not obviously changed, but the corrosion resistance is rapidly reduced (see fig. 4), electrochemical alternating current impedance and salt spray tests show that the corrosion resistance of the coating is reduced, and the content of the zinc powder plays an important role in corrosion protection of the coating, so that the common heavy-duty anticorrosive material mainly comprises the zinc-rich coating (60-80%), and the coating still has excellent weather resistance and salt spray corrosion resistance under the condition that the content of the zinc is greatly reduced (10-30%) compared with the zinc-rich anticorrosive coating.
As shown in FIGS. 1 to 4, by analyzing the test results of examples 1 to 3 and comparative examples 1 to 2 for reducing the zinc powder content, the SEM images of the coating shown in FIG. 1 are used for observing the compactness of the coating material under different component formulas, so as to prevent the failure of the coating material due to the compactness problem of the coating material, and the SEM images under high resolution show that all coatings have good compactness. FIG. 2 shows polarization curves for examples and comparative examples, with the polarization curves for examples 1-3 showing lower corrosion currents for all three coatings, illustrating that examples 1-3 have good corrosion resistance, and the results for comparative examples 1-2 showing higher corrosion currents than examples 1-3, illustrating that the corrosion resistance of the coating material is reduced due to the significant reduction in zinc powder content, since the uniform distribution of zinc powder in the coating provides cathodic protection for the substrate, protecting the coated material from corrosion. The electrochemical alternating current impedance (EIS) test results of FIG. 3 also verify the modified results, the EIS results show that the three coatings of examples 1-3 all have higher impedance values at the frequency of 0.01Hz, and the impedance values at the frequency of 0.01Hz are generally used to reflect the corrosion resistance of the coating material, which shows that the coating of the invention has excellent corrosion resistance, and the results of comparative examples 1-2 show that the impedance values of the coating are gradually reduced due to the obvious reduction of the content of zinc powder, which shows that the corrosion resistance of the coating is gradually reduced. The results of the salt spray test shown in fig. 4 visually show the salt spray corrosion resistance of the examples and the comparative examples, and the three coatings of examples 1 to 3 have excellent weather resistance and salt spray corrosion resistance in a salt spray environment, and have no obvious corrosion diffusion on the surface and no foaming of the coating material after 1440 hours of corrosion in the salt spray environment; in the comparative example, the corrosion resistance of the coating is obviously suddenly reduced due to the obvious reduction of the content of the zinc powder, the obvious corrosion diffusion phenomenon occurs after the test of 360 hours, and then serious problems of blistering and the like of the coating also occur, which are that the cathode protection capability of the substrate is reduced due to the low content of the zinc powder, the corrosion resistance is reduced, and then a series of serious problems are caused to the coating. Therefore, the coating is suitable for outdoor structures in the seaside chemical environment, and can also be used for other offshore wind power steel structures or other offshore structures with high requirements on corrosion resistance and weather resistance.
In summary, the test results of the examples 1 to 3 and the comparative examples 1 to 2 prove the preparation principle of the invention and the action mechanism of each component in the coating, the salt spray test shows that the coating has excellent salt spray corrosion resistance, and the electrochemical alternating current impedance (EIS) test result shows that the coating has excellent corrosion resistance.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
Claims (10)
1. The weather-resistant salt-spray-corrosion-resistant coating with low VOC content is characterized by comprising the following components in percentage by mass: 30-50% of mixed resin; 10-30% of zinc powder; 0.2-1.5% of carbon nano material; 10-30% of a filler; 0.5-3% of an auxiliary agent and 10-20% of a solvent.
2. The low VOC content, weather and salt spray resistant coating of claim 1, wherein the VOC content of the coating is not greater than 120 g/L.
3. The low VOC content, weather resistant, salt spray corrosion resistant coating of claim 1, wherein said hybrid resin comprises, by mass: (1-3): (1-3): (0.5-1.5): (1-3) a hydrogenated epoxy resin, a polyamide curing agent, a modified liquid polysulfide rubber and an organosilicon resin; wherein the hydrogenated epoxy resin is EP-4080E, the epoxy equivalent is 200-230 g/eq, and the viscosity is 1500-3000 mPa.s/25 ℃; the polyamide curing agent has an amine value of 200 +/-20 (mgKOH/g) and a viscosity of 2000-4000 mpa.s; the type of the modified liquid polysulfide rubber is JYL-121, and the molecular weight is 800-6000; the type of the organic silicon resin is ME-8750, and the viscosity is 1000-2500 mPa.s/25 ℃.
4. The low VOC, weather resistant, salt spray corrosion resistant coating of claim 1 wherein said zinc powder is a first grade zinc powder having a 99% metallic zinc content and a particle size of 30 μm; the carbon nano material is carbon nano tube, graphene or fullerene.
5. The low VOC, weather resistant, salt spray corrosion resistant coating of claim 4 wherein said carbon nanotubes are multi-walled carbon nanotubes having a purity of greater than 95%, an outer diameter of 8 to 15nm, an inner diameter of 3 to 5nm, and a length of 15 to 30 μm; the graphene is multilayer graphene with the purity of more than 98%, the thickness of 3.4-8 nm, the diameter of a lamella of 5-50 mu m and 5-10 layers; the fullerene is a C60/C70 mixture with the purity of 98%, wherein C60 accounts for 80 wt%.
6. The low VOC content, weather and salt spray resistant coating of claim 1, wherein the filler comprises at least one of titanium powder, ferrophosphorus powder, aluminum alloy powder, stainless steel powder, and hydrophobic silica; the solvent is a mixed solvent consisting of butyl glycidyl ether and xylene.
7. The preparation method of the low-VOC weather-resistant salt-fog-corrosion-resistant coating according to any one of claims 1 to 6, characterized by comprising the following steps:
(1) adding zinc powder, a carbon nano material, a filler and an auxiliary agent into a solvent according to the formula ratio, and stirring at a high speed of 1000-2000 r/min for 20-40 minutes to obtain a uniformly dispersed base material;
(2) mixing the mixed resin with the base material in the step (1), sealing, introducing high-purity nitrogen, and performing ball milling for 10-12 hours to obtain uniformly dispersed first slurry;
(3) and (3) adding the polyamide curing agent with the mass ratio of 1:1 to the epoxy resin into the first slurry obtained in the step (2), and stirring at a high speed of 1000-2000 r/min for 20-40 minutes to obtain a second slurry which is uniformly dispersed, so as to obtain the coating.
8. The method for preparing the low-VOC, weather-resistant and salt-spray-corrosion-resistant coating according to claim 7, wherein in the step (2), the mixed resin is prepared by the following steps: hydrogenated epoxy resin, modified liquid polysulfide rubber and organic silicon resin are mixed according to the mass ratio of (1-3): (0.5-1.5): (1-3), stirring at a high speed of 1000-2000 r/min for 20-40 minutes, and uniformly dispersing to obtain the mixed resin.
9. A preparation method of a coating with low VOC content, weather resistance and salt spray corrosion resistance is characterized by comprising the following steps:
coating the coating of any one of claims 1 to 6 on a substrate by a brush coating process, naturally standing at room temperature, and completely curing to obtain the low-VOC weather-resistant salt-fog-corrosion-resistant coating; wherein the natural standing temperature is 25-40 ℃; the humidity of the natural standing was 85% or less.
10. A low VOC content, weather-resistant and salt-spray corrosion-resistant coating is characterized in that the zinc powder content is lower than 30 wt%, and the VOC content is not higher than 120 g/L; the coating is made by the method of claim 7 or 8.
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