CN115948067A - Functional filler, self-repairing anticorrosive coating and preparation method - Google Patents
Functional filler, self-repairing anticorrosive coating and preparation method Download PDFInfo
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- 238000005260 corrosion Methods 0.000 claims abstract description 60
- 230000007797 corrosion Effects 0.000 claims abstract description 59
- 239000003112 inhibitor Substances 0.000 claims abstract description 51
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 claims abstract description 50
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052621 halloysite Inorganic materials 0.000 claims abstract description 27
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- 238000000034 method Methods 0.000 claims description 12
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- 239000004593 Epoxy Substances 0.000 claims description 5
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 5
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- 239000007787 solid Substances 0.000 claims description 5
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 3
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical group C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 2
- LXOFYPKXCSULTL-UHFFFAOYSA-N 2,4,7,9-tetramethyldec-5-yne-4,7-diol Chemical compound CC(C)CC(C)(O)C#CC(C)(O)CC(C)C LXOFYPKXCSULTL-UHFFFAOYSA-N 0.000 claims description 2
- 229910014314 BYK190 Inorganic materials 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012964 benzotriazole Substances 0.000 claims description 2
- UUMXWUNNKCQWHS-UHFFFAOYSA-N benzotriazole-1-carboxamide Chemical compound C1=CC=C2N(C(=O)N)N=NC2=C1 UUMXWUNNKCQWHS-UHFFFAOYSA-N 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 claims description 2
- 229910000165 zinc phosphate Inorganic materials 0.000 claims description 2
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 2
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- 229910000831 Steel Inorganic materials 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
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- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 150000001448 anilines Chemical class 0.000 description 1
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Paints Or Removers (AREA)
Abstract
The invention discloses a functional filler, a self-repairing anticorrosive coating and a preparation method thereof, wherein the preparation method of the functional filler comprises the following steps: uniformly mixing the hydrochloric acid suspension of the halloysite nanotube and the hydrochloric acid solution of aniline, and stirring in an ice-water bath for a set time to obtain a first mixed solution; dropwise adding a hydrochloric acid solution of ammonium persulfate into the mixed solution I, continuing to stir in an ice-water bath for a set time, then recovering to 20-40 ℃, and reacting to obtain a polyaniline-modified halloysite nanotube; dispersing polyaniline modified halloysite nanotubes in a saturated aqueous solution of an organic corrosion inhibitor, and stirring for reaction for a set time; and after the reaction is finished, vacuumizing the reaction liquid to remove the solvent until the reaction liquid becomes viscous liquid, and washing and drying the viscous liquid to obtain the functional filler.
Description
Technical Field
The invention relates to the technical field of anticorrosive coatings, and particularly relates to a functional filler, a self-repairing anticorrosive coating and a preparation method thereof.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
The anticorrosive coating cannot avoid being damaged by external force in the service process. The damaged area is more vulnerable to the invasion of corrosion factors, resulting in local rapid corrosion. If the local corrosion part can not be found in time and repair measures are taken, the local corrosion part can quickly spread to cause the failure of a large-area coating, thereby bringing higher repair cost.
Microcapsule nanotechnology is an important research direction for the development of self-repairing coatings in recent years. The micromolecule corrosion inhibitor is loaded in the filler by a microcapsule coating technology, the release rate of the micromolecule corrosion inhibitor is controlled, and the long-acting protection function of the polymer antirust agent is combined, so that the functions of different types of corrosion inhibitors are exerted to the greatest extent in a service cycle, and the rapid corrosion of the damaged coating is inhibited.
The functions of the microcapsules reported at present are single, and most of the microcapsules are only used as carriers of small molecular corrosion inhibitors and do not have anticorrosion functions (such as porous silica, zirconia and the like). In addition, although the microcapsule synthesized by adopting the polymerization method can provide a stimulus-response release function, a compound (such as formaldehyde) with higher toxicity is used in the preparation method, and the residue of the compound can negatively influence the environmental protection property of the coating.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a functional filler, a self-repairing anticorrosive coating and a preparation method thereof.
In order to achieve the purpose, the invention is realized by the following technical scheme:
in a first aspect, the present invention provides a method for preparing a functional filler, comprising the steps of:
uniformly mixing the hydrochloric acid suspension of the halloysite nanotube and the hydrochloric acid solution of aniline, and stirring in an ice-water bath for a set time to obtain a mixed solution I;
dropwise adding a hydrochloric acid solution of ammonium persulfate into the mixed solution I, continuing to stir in an ice-water bath for a set time, then recovering to 20-40 ℃, and reacting to obtain a polyaniline-modified halloysite nanotube;
dispersing polyaniline modified halloysite nanotubes in a saturated aqueous solution of an organic corrosion inhibitor, and stirring for reaction for a set time;
and after the reaction is finished, vacuumizing the reaction liquid to remove the solvent until the reaction liquid becomes viscous liquid, and washing and drying the viscous liquid to obtain the functional filler.
In a second aspect, the invention provides a functional filler prepared by the preparation method, wherein the halloysite nanotube is filled with an organic slow-release agent, and the outer surface of the halloysite nanotube is modified with polyaniline.
In a third aspect, the invention provides a self-repairing anticorrosive coating, which comprises a component A, a component B and a component C, wherein the mass ratio of the component A to the component B to the component C is 1:0.1-0.5:0.01-0.1; wherein, the first and the second end of the pipe are connected with each other,
the component A comprises the following components in parts by weight: 80-100 parts of water-based epoxy resin, 40-60 parts of deionized water, 2-6 parts of wetting dispersant, 1-3 parts of defoaming agent, 0.5-1 part of surface wetting agent, 6-12 parts of corrosion inhibitor, 35-45 parts of pigment and filler and 4-8 parts of mica sheet;
the component B comprises the following components in parts by weight: 30-35 parts of waterborne epoxy resin curing agent and 4-8 parts of flash rust inhibitor;
the component C is the functional filler.
In a fourth aspect, the invention provides a preparation method of the self-repairing anticorrosive coating, which comprises the following steps: adding a wetting dispersant and a defoaming agent into deionized water under a stirring state, then adding a pigment, a filler and a corrosion inhibitor, adding a grinding medium, grinding, and stopping grinding when the fineness is below 10 mu m; removing the grinding medium, and adding the water-based epoxy resin, the surface wetting agent and the mica sheet; fully dispersing to obtain a component A;
uniformly mixing the waterborne epoxy resin curing agent and the anti-flash rust agent to obtain a component B;
quickly mixing the component A and the component C, and then mixing the component A and the component C with the component B.
The beneficial effects achieved by one or more of the embodiments of the invention described above are as follows:
1. the invention makes full use of different corrosion prevention effects of the micromolecule corrosion inhibitor and the polyaniline in different corrosion prevention stages. The micromolecule corrosion inhibitor is quickly released from the filler in the early corrosion prevention stage when the coating is damaged, and the corrosion rate is quickly inhibited. The polymer corrosion is inhibited to form a passivation protective layer in the middle and later corrosion prevention periods, so that the protective aging of the anticorrosive paint film is improved.
2. According to the invention, the micromolecular corrosion inhibitor is coated in the cavity of the halloysite nanotube, so that the micromolecular corrosion inhibitor can be prevented from reacting with epoxy groups in resin to reduce the crosslinking density in the stages of paint mixing and coating, and the micromolecular corrosion inhibitor can be released to inhibit corrosion when a coating is damaged.
3. According to the invention, polyaniline is modified on the surface of the halloysite nanotube, and the permeability resistance of a paint film is improved by increasing the surface area of the nano filler, so that the long-acting corrosion resistance of the paint film is enhanced. Meanwhile, the polymer modified on the surface of the halloysite nanotube can block openings at two ends of the nanotube to a certain degree, so that the diffusion rate of the small-molecule corrosion inhibitor is reduced, the release period of the small-molecule corrosion inhibitor is prolonged, and the process control of corrosion prevention is more accurately adjusted.
4. The synthetic process of the self-repairing anticorrosive functional filler is simple, and the equipment is conventional equipment. The paint is easy to use and can be mixed uniformly in the paint mixing stage. Because the self-repairing functional filler has a nano-scale size and certain hydrophilicity, no additional auxiliary agent and dispersing process are needed.
The polyaniline modified halloysite nanotube with the anticorrosion function is prepared by a mild method, and the micromolecule corrosion inhibitor is loaded in the polyaniline modified halloysite nanotube by a microcapsule technology. When the coating is damaged, the micromolecular corrosion inhibitor is released from the coating to quickly inhibit the corrosion at the damaged part. And the polyaniline can form a passivation layer on the metal surface in the long-term anticorrosion process so as to play an anticorrosion role. Organically combines the microcapsule technology and polymer anticorrosion, and enables the functions of different types of corrosion inhibitors to be exerted to the maximum extent in a service period so as to inhibit the rapid corrosion of the coating after damage.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a scanning electron microscope photograph of an unmodified halloysite nanotube and a scanning electron microscope photograph of a polyaniline-modified halloysite nanotube in example 1 of the present invention.
FIG. 2 is a graph showing the effects of the salt spray test and the salt water test of the anticorrosive paint of example 2 of the present invention, wherein (a) is the salt spray test for 120 hours, (b) is the salt water test for 120 hours, (c) is the salt spray test for 240 hours, and (d) is the salt water test for 240 hours.
FIG. 3 is a graph showing the effects of a salt spray test and a salt water test on an anticorrosive coating according to example 3 of the present invention, wherein (a) shows the salt spray test for 120 hours, (b) shows the salt water test for 120 hours, (c) shows the salt spray test for 240 hours, and (d) shows the salt water test for 240 hours.
FIG. 4 is a graph showing the effects of the salt spray test and the salt water test on the anticorrosive paint of example 4 of the present invention, wherein (a) shows the salt spray test for 120 hours, (b) shows the salt water test for 120 hours, (c) shows the salt spray test for 240 hours, and (d) shows the salt water test for 240 hours.
FIG. 5 is a graph showing the effects of the salt spray test and the salt water test of the anticorrosive paint of comparative example 1 of the present invention, wherein (a) is the salt spray test for 120 hours, (b) is the salt water test for 120 hours, (c) is the salt spray test for 240 hours, and (d) is the salt water test for 240 hours.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In a first aspect, the invention provides a preparation method of a functional filler for a self-repairing anticorrosive coating, which comprises the following steps:
uniformly mixing the hydrochloric acid suspension of the halloysite nanotube and the hydrochloric acid solution of aniline, and stirring in an ice-water bath for a set time to obtain a mixed solution I;
dropwise adding a hydrochloric acid solution of ammonium persulfate into the mixed solution I, continuing to stir in an ice-water bath for a set time, then recovering to 20-40 ℃, and reacting to obtain a polyaniline-modified halloysite nanotube;
dispersing polyaniline-modified halloysite nanotubes in a saturated aqueous solution of an organic corrosion inhibitor, and stirring for reaction for a set time;
and after the reaction is finished, vacuumizing the reaction liquid to remove the solvent until the reaction liquid becomes viscous liquid, and washing and drying the viscous liquid to obtain the functional filler.
Halloysite is a silicate mineral with spherical, sheet and tubular structures, with tubular structures being the most prevalent. The halloysite nanotube is a tubular structure formed by rolling twenty-few layers, the inner diameter of the tube is generally 15-100nm, and the length of the tube is generally 500-1000nm.
The hydrochloric acid solution is used for making the outer surface of the halloysite nanotube carry negative charges and facilitating the adsorption of protonated aniline on the surface.
The ice-water bath stirring is adopted to reduce the nucleation speed of the polyaniline, so that the polymerization reaction of the aniline is more likely to occur on the surface of the halloysite nanotube. Polymerization of polyaniline is carried out by filtration of the oxidation catalyst of ammonium sulfate.
Polyaniline is modified and then organic corrosion inhibitor is filled to avoid the inactivation of the organic corrosion inhibitor caused by the reaction under the oxidation condition.
In some embodiments, the mass ratio of halloysite nanotubes to aniline is 1:2 to 1:3.
preferably, in the mixed solution of the halloysite nanotubes and the aniline, the concentration of the halloysite nanotubes is 4-12g/L, and the concentration of the aniline is 8-36g/L. Excessive amounts of aniline can affect the morphology of the halloysite nanotubes, increase the amorphous structure, and a decrease in loading efficiency is observed, probably because excessive polyaniline can destroy the tubular structure, i.e., the seal, of the halloysite nanotubes themselves. Thereby affecting loading efficiency.
In some embodiments, the method further comprises the steps of centrifuging, washing and drying the prepared polyaniline-modified halloysite nanotubes, wherein the drying is low-temperature vacuum drying, and the drying temperature is 35-45 ℃.
In some embodiments, the organic corrosion inhibitor is 2-mercaptobenzimidazole, benzotriazole or benzotriazole-1-carboxamide.
In some embodiments, the viscous liquid is washed by first washing with acetone, then washing with deionized water, and vacuum-drying the washed product. The acetone washing is used for quickly washing off a large amount of uncoated corrosion inhibitor in the suspension, and the subsequent deionized water washing is used for removing the corrosion inhibitor adsorbed on the surface of the modified halloysite nanotube without influencing the corrosion inhibitor crystallized in the halloysite nanotube as much as possible.
In a second aspect, the invention provides a functional filler for a self-repairing anticorrosive coating, which is prepared by the preparation method, wherein the halloysite nanotube is filled with an organic slow-release agent, and the outer surface of the halloysite nanotube is modified with polyaniline.
In a third aspect, the invention provides a self-repairing anticorrosive coating, which comprises a component A, a component B and a component C, wherein the mass ratio of the component A to the component B to the component C is 1:0.1-0.5:0.01-0.1; wherein the content of the first and second substances,
the component A comprises the following components in parts by weight: 80-100 parts of water-based epoxy resin, 40-60 parts of deionized water, 2-6 parts of wetting dispersant, 1-3 parts of defoaming agent, 0.5-1 part of surface wetting agent, 6-12 parts of corrosion inhibitor, 35-45 parts of pigment and filler and 4-8 parts of mica sheet;
the component B comprises the following components in parts by weight: 30-35 parts of waterborne epoxy resin curing agent and 4-8 parts of flash rust inhibitor;
the component C is the functional filler.
In some embodiments, the solid content of the waterborne epoxy resin is 50-60%, and the epoxy equivalent is 500-700 g/eq.
In some embodiments, the wetting dispersant is BYK2010, BYK2080, or BYK190;
the defoaming agent is a Pasteur mineral oil defoaming agent MO2190, BYK024, BYK019 or BYK022;
the surface wetting agent is BYK-3455, BYK349 or Surfynol 104;
the corrosion inhibitor is modified aluminum tripolyphosphate, zinc phosphate or strontium phosphosilicate;
the pigment and filler is barium sulfate, zirconium silicate or talcum powder.
In a fourth aspect, the invention provides a preparation method of the self-repairing anticorrosive coating, which comprises the following steps:
adding a wetting dispersant and a defoaming agent into deionized water under a stirring state, then adding pigment, filler and a corrosion inhibitor, adding a grinding medium, grinding, and stopping grinding when the fineness is below 10 mu m; removing the grinding medium, and adding the water-based epoxy resin, the surface wetting agent and the mica sheet; fully dispersing to obtain a component A;
uniformly mixing the waterborne epoxy resin curing agent and the anti-flash rust agent to obtain a component B;
and quickly mixing the component A and the component C, and then mixing the component A and the component C with the component B.
The present invention will be further described with reference to the following examples.
Example 1
Synthesizing self-repairing anticorrosive functional filler:
step one, 8g halloysite nanotubes are dispersed in 1L of 1M hydrochloric acid aqueous solution, and magnetic stirring is carried out after ultrasonic treatment is carried out for 10 minutes. To the above solution was added 0.5L of a 1M hydrochloric acid solution containing 16g of aniline, and magnetic stirring was continued for 1 hour. Then stirred in an ice-water bath for 1 hour.
In the second step, 98g of ammonium persulfate was dissolved in 0.25L of a hydrochloric acid solution, and then the above solution was slowly dropped into the dispersion prepared in the first step. The dropping time was 0.5 hour, during which the temperature was kept low. After the addition was complete, the reaction was stirred in an ice-water bath for 2 hours and then returned to room temperature. After 12 hours of reaction, the reaction was centrifuged and washed with water. And drying the product in a 40 ℃ oven in vacuum to obtain the polyaniline modified halloysite nanotube.
And step three, dispersing 20g of polyaniline-modified halloysite nanotubes in 2L of saturated aqueous solution of organic corrosion inhibitor, and stirring at room temperature overnight. And (3) vacuumizing the dispersion liquid at 65 ℃ to remove the solvent, vacuumizing for 3 hours, standing for 1 hour, and repeating the circulation until the dispersion liquid becomes viscous liquid. The resulting concentrated dispersion was washed once with acetone, five times with deionized water and centrifuged. The obtained product is dried in a vacuum oven at 40 ℃ until the weight is stable, and the polyaniline modified halloysite nanotube loaded with the organic corrosion inhibitor is used as the self-repairing anti-corrosion functional filler.
In fig. 1, a is a scanning electron microscope photograph of an unmodified halloysite nanotube, and B is a scanning electron microscope photograph of a polyaniline-modified halloysite nanotube.
Example 2
A self-repairing water-based anticorrosive coating comprises three components A, B and C, wherein the mass ratio of the component A to the component B to the component C is 4:1:0.05; wherein, the first and the second end of the pipe are connected with each other,
the component A comprises the following raw materials in parts by weight: 90 parts of water-based epoxy resin, 50 parts of deionized water, 6 parts of wetting dispersant, 2 parts of defoamer, 1 part of surface wetting agent, 8 parts of corrosion inhibitor, 45 parts of pigment and filler and 4 parts of mica sheet;
the component B comprises the following raw materials in parts by weight: 30 parts of a water-based epoxy resin curing agent and 4 parts of a flash rust inhibitor.
The component C is the polyaniline-modified halloysite nanotubes loaded with organic corrosion inhibitors prepared in example 1.
Wherein the water-based epoxy resin is BECKOPOX EP 2387w/53WA, the solid content is 50 percent, and the epoxy equivalent is 500g/eq; the wetting dispersant is BYK2010; the defoaming agent is BYK022; the surface wetting agent is BYK-3455; the corrosion inhibitor is aluminum tripolyphosphate; the pigment and filler are precipitated barium sulfate and talcum powder, and the mass ratio is 1:1; the waterborne epoxy resin curing agent is BECKOPOX EH 2188w/55WA; the anti-FLASH rust agent is HALOX FLASH-X330.
The preparation method of the component A comprises the steps of adding the wetting dispersant and the defoaming agent into deionized water under the stirring state, then adding the pigment, the filler and the corrosion inhibitor, adding zirconium beads, grinding for 2 hours, and stopping grinding when the fineness is confirmed to be below 10 mu m. Removing zirconium beads, and adding water-based epoxy resin, a surface wetting agent and mica sheets; fully dispersing to obtain a component A;
the preparation method of the component B comprises the steps of uniformly mixing the waterborne epoxy resin curing agent and the flash rust inhibitor to obtain the component B;
the preparation method of the self-repairing water-based anticorrosive coating comprises the steps of adding the component C into the component A under the stirring condition, adding the component B, and mixing uniformly to obtain the self-repairing water-based anticorrosive coating.
Example 3
A self-repairing water-based anticorrosive coating comprises three components A, B and C, wherein the mass ratio of the component A to the component B to the component C is 1:0.5:0.1; wherein the content of the first and second substances,
the component A comprises the following raw materials in parts by weight: 100 parts of water-based epoxy resin, 40 parts of deionized water, 6 parts of wetting dispersant, 2 parts of defoaming agent, 0.5 part of surface wetting agent, 12 parts of corrosion inhibitor, 45 parts of pigment and filler and 4 parts of mica sheet;
the component B comprises the following raw materials in parts by weight: 32 parts of a water-based epoxy resin curing agent and 4 parts of a flash rust inhibitor.
Component C is the polyaniline-modified halloysite nanotubes loaded with organic corrosion inhibitors prepared in example 1.
Wherein the water-based epoxy resin is BECKOPOX EP 2387w/53WA, the solid content is 55 percent, and the epoxy equivalent is 600g/eq; the wetting dispersant is BYK2010; the defoaming agent is BYK022; the surface wetting agent is BYK-3455; the corrosion inhibitor is aluminum tripolyphosphate; the pigment and filler are precipitated barium sulfate and talcum powder, and the mass ratio is 1:1; the waterborne epoxy resin curing agent is BECKOPOX EH 2188w/55WA; the anti-FLASH rust agent is HALOX FLASH-X330.
The preparation methods of the component A, the component B and the self-repairing water-based anticorrosive coating are the same as example 2.
Example 4
A self-repairing water-based anticorrosive coating comprises three components A, B and C, wherein the mass ratio of the component A to the component B to the component C is 1:0.4:0.05; wherein the content of the first and second substances,
the component A comprises the following raw materials in parts by weight: 95 parts of water-based epoxy resin, 60 parts of deionized water, 2 parts of wetting dispersant, 1 part of defoamer, 1 part of surface wetting agent, 10 parts of corrosion inhibitor, 40 parts of pigment and filler and 8 parts of mica sheet;
the component B comprises the following raw materials in parts by weight: 35 parts of a water-based epoxy resin curing agent and 8 parts of an anti-flash rust agent.
Component C is the polyaniline-modified halloysite nanotubes loaded with organic corrosion inhibitors prepared in example 1.
Wherein the water-based epoxy resin is BECKOPOX EP 2387w/53WA, the solid content is 60 percent, and the epoxy equivalent is 700g/eq; the wetting dispersant is BYK2010; the defoaming agent is BYK022; the surface wetting agent is BYK-3455; the corrosion inhibitor is aluminum tripolyphosphate; the pigment and filler are precipitated barium sulfate and talcum powder, and the mass ratio is 1:1; the waterborne epoxy resin curing agent is BECKOPOX EH 2188w/55WA; the antiscratch agent is HALOX FLASH-X330.
The preparation methods of the component A, the component B and the self-repairing water-based anticorrosive coating are the same as example 2.
Comparative example 1
Compared with example 2, the difference is that: the C component was omitted, and the formulation and the coating were prepared in the same manner as in example 2.
The self-healing properties of the coatings obtained in example 2 and comparative example 1 were tested and the results are shown in table 1.
Salt spray corrosion test: the anticorrosive coatings obtained in examples 2 to 4 and comparative example 1 were applied to 50 × 100 × 5mm Q235 clean steel plates, the dry film thickness was 100 to 120 μm, the coating was cured for 7 days in a room temperature environment, the coating was scratched to the substrate with a carving tool, the width of the scratch was 0.3mm, the substrate was left to stand for 24 hours, and the rust on the scratch was observed after the salt spray test according to GB/T1771-2007, and the test results are shown in table 1.
Brine corrosion test: the anticorrosive coatings obtained in examples 2-4 and comparative example 1 were applied to a 50 × 100 × 5mm q235 clean steel plate to a dry film thickness of 100-120 μm, cured at room temperature for 7d, scribed with a scribing tool to break the coating to the substrate with a scribe width of 0.3mm, left to stand for 24h, and then applied with an aqueous NaCl solution with a concentration of 3.5% to the scribe to observe the rust on the scribe in experiments.
FIG. 2 is a graph showing the effects of the salt spray test and the salt water test of the anticorrosive paint of example 2 of the present invention, wherein (a) is the salt spray test for 120 hours, (b) is the salt water test for 120 hours, (c) is the salt spray test for 240 hours, and (d) is the salt water test for 240 hours.
FIG. 3 is a graph showing the effects of the salt spray test and the salt water test of the anticorrosive paint of example 3 of the present invention, wherein (a) is 120 hours in the salt spray test, (b) is 120 hours in the salt water test, (c) is 240 hours in the salt spray test, and (d) is 240 hours in the salt water test.
FIG. 4 is a graph showing the effects of a salt spray test and a salt water test on an anticorrosive coating according to example 4 of the present invention, wherein (a) shows the salt spray test for 120 hours, (b) shows the salt water test for 120 hours, (c) shows the salt spray test for 240 hours, and (d) shows the salt water test for 240 hours.
FIG. 5 is a graph showing the effects of the salt spray test and the salt water test of the anticorrosive paint of comparative example 1 of the present invention, wherein (a) is the salt spray test for 120 hours, (b) is the salt water test for 120 hours, (c) is the salt spray test for 240 hours, and (d) is the salt water test for 240 hours.
The test results are summarized in Table 1.
TABLE 1
As can be seen from the experimental results in Table 1, the paint films of examples 2-4 added with the self-repairing anticorrosive functional filler have obviously enhanced corrosive printing effect on the damaged part, which is far superior to that of comparative example 1. The self-repairing paint film has a certain self-repairing effect, and can effectively prevent rapid corrosion caused by crushing by external force.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a functional filler for a self-repairing anticorrosive coating is characterized by comprising the following steps: the method comprises the following steps:
uniformly mixing the hydrochloric acid suspension of the halloysite nanotube and the hydrochloric acid solution of aniline, and stirring in an ice-water bath for a set time to obtain a first mixed solution;
dropwise adding a hydrochloric acid solution of ammonium persulfate into the mixed solution I, continuing to stir in an ice-water bath for a set time, then recovering to 20-40 ℃, and reacting to obtain a polyaniline-modified halloysite nanotube;
dispersing polyaniline-modified halloysite nanotubes in a saturated aqueous solution of an organic corrosion inhibitor, and stirring for reaction for a set time;
and after the reaction is finished, vacuumizing the reaction liquid to remove the solvent until the reaction liquid becomes viscous liquid, and washing and drying the viscous liquid to obtain the functional filler.
2. The preparation method of the functional filler for the self-repairing anticorrosive coating according to claim 1, characterized in that: in the mixed solution of the halloysite nanotube and aniline, the concentration of the halloysite nanotube is 4-12g/L, and the concentration of the aniline is 8-36g/L.
3. The preparation method of the functional filler for the self-repairing anticorrosive coating according to claim 1, characterized in that: the method also comprises the steps of centrifuging, washing and drying the prepared polyaniline-modified halloysite nanotube, wherein the drying is low-temperature vacuum drying, and the drying temperature is 35-45 ℃.
4. The preparation method of the functional filler for the self-repairing anticorrosive coating according to claim 1, characterized in that: the organic corrosion inhibitor is 2-mercaptobenzimidazole, benzotriazole or benzotriazole-1-formamide.
5. The preparation method of the functional filler for the self-repairing anticorrosive coating according to claim 1, characterized in that: the method for washing the viscous liquid comprises the steps of washing with acetone, washing with deionized water, and drying the washed product in vacuum.
6. A functional filler for self-repairing anticorrosive paint is characterized in that: the halloysite nanotube polymer is prepared by the preparation method of any one of claims 1-5, wherein the halloysite nanotube is filled with an organic slow-release agent, and the outer surface of the halloysite nanotube polymer is modified with polyaniline.
7. A self-repairing anticorrosive coating is characterized in that: the paint comprises a component A, a component B and a component C, wherein the mass ratio of the component A to the component B to the component C is 1:0.1-0.5:0.01-0.1; wherein the component A comprises the following components in parts by weight: 80-100 parts of water-based epoxy resin, 40-60 parts of deionized water, 2-6 parts of wetting dispersant, 1-3 parts of defoaming agent, 0.5-1 part of surface wetting agent, 6-12 parts of corrosion inhibitor, 35-45 parts of pigment and filler and 4-8 parts of mica sheet;
the component B comprises the following components in parts by weight: 30-35 parts of waterborne epoxy resin curing agent and 4-8 parts of flash rust inhibitor;
the component C is the functional filler.
8. The self-repairing anticorrosive coating of claim 7, characterized in that: the solid content of the waterborne epoxy resin is 50-60%, and the epoxy equivalent is 500-700 g/eq.
9. The self-repairing anticorrosive coating of claim 7, characterized in that: the wetting dispersant is BYK2010, BYK2080 or BYK190;
the defoaming agent is a Pasteur mineral oil defoaming agent MO2190, BYK024, BYK019 or BYK022;
the surface wetting agent is BYK-3455, BYK349 or Surfynol 104;
the corrosion inhibitor is modified aluminum tripolyphosphate, zinc phosphate or strontium phosphosilicate;
the pigment and filler is barium sulfate, zirconium silicate or talcum powder.
10. The preparation method of the self-repairing anticorrosive coating of any one of claims 8 to 9, characterized by comprising the following steps: the method comprises the following steps: adding a wetting dispersant and a defoaming agent into deionized water under a stirring state, then adding a pigment, a filler and a corrosion inhibitor, adding a grinding medium, grinding, and stopping grinding when the fineness is below 10 mu m; removing the grinding medium, and adding the water-based epoxy resin, the surface wetting agent and the mica sheet; fully dispersing to obtain a component A;
uniformly mixing the waterborne epoxy resin curing agent and the anti-flash rust agent to obtain a component B;
and quickly mixing the component A and the component C, and then mixing the component A and the component C with the component B.
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