CN115725211A - Self-cleaning corrosion-resistant coating, preparation method thereof and self-cleaning corrosion-resistant metal plate - Google Patents

Self-cleaning corrosion-resistant coating, preparation method thereof and self-cleaning corrosion-resistant metal plate Download PDF

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Publication number
CN115725211A
CN115725211A CN202111014446.6A CN202111014446A CN115725211A CN 115725211 A CN115725211 A CN 115725211A CN 202111014446 A CN202111014446 A CN 202111014446A CN 115725211 A CN115725211 A CN 115725211A
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self
silicon dioxide
coating
mixed solution
resistant coating
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苗珍录
莫敏华
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Shanghai Balote New Material Research Co ltd
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Shanghai Balote New Material Research Co ltd
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Abstract

The application relates to a self-cleaning corrosion-resistant coating, which comprises: 70-80% of PVDF fluorocarbon resin, 5-15% of pigment, 1-2% of flatting agent, 10-20% of diluent and 1-5% of modified silicon dioxide calculated by mass fraction. The preparation method comprises the following steps: ultrasonically dispersing 1-3 parts of silicon dioxide into 7-9 parts of ethylene glycol to obtain a dispersion liquid; uniformly mixing 0.5-1.5% of coupling agent and 98.5-99.5% of dispersion liquid, standing for 4-8 hours at 110-120 ℃, filtering to obtain particles, and drying the particles for 0.5-1.5 hours at 30-50 ℃ to obtain modified silicon dioxide; mixing PVDF fluorocarbon resin, pigment, a flatting agent and a diluent, and stirring for 4-6 minutes to obtain a base solution; and adding the modified silicon dioxide into the base solution to obtain the self-cleaning corrosion-resistant coating. This application makes the automatically cleaning corrosion resistant coating that this application provided compare in ordinary corrosion resistant coating through add modified silicon dioxide in fluorocarbon coating, more has stronger hydrophobicity and corrosion resistance to make it have the automatically cleaning ability.

Description

Self-cleaning corrosion-resistant coating, preparation method thereof and self-cleaning corrosion-resistant metal plate
Technical Field
The application relates to an anticorrosive coating, belongs to the field of coating manufacturing, and particularly relates to a self-cleaning anticorrosive coating.
Background
With the development of economic society, the environmental pollution problem becomes more serious, and haze, industrial waste gas, automobile exhaust and the like bring serious pollution and corrosion to the outer wall of a building, so that the attractiveness and the service life of the building are influenced. To solve the above problems, there are generally two methods. Firstly, the manual high-altitude cleaning is carried out, and dust and attached dirt on the surface of the building outer wall are cleaned regularly. The method has high cost and high operation risk. Another method is to develop a stain resistant coating to reduce the number of exterior wall cleanings, even to achieve the effect of maintaining cleanliness without cleaning. In the stain-resistant coating, the protective coating with self-cleaning capability can take away dust and pollutants adsorbed on the surface by utilizing the scouring of rainwater, so that dangerous high-altitude cleaning operation is avoided, and the later maintenance cost of a building is reduced. And due to the hydrophobic effect, the coating reduces the contact with corrosive medium water and is more corrosion-resistant than the common coating. Therefore, it is necessary to provide a protective coating with self-cleaning capability.
Disclosure of Invention
The invention aims to provide a corrosion-resistant and hydrophobic coating and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
first, the present application provides a self-cleaning corrosion-resistant coating, comprising: 70-80% of PVDF fluorocarbon resin, 5-15% of pigment, 1-2% of flatting agent, 10-20% of diluent and 1-5% of modified silicon dioxide calculated by mass fraction.
Secondly, the present application provides a method for preparing the above coating, the method comprising:
a. ultrasonically dispersing 1-3 parts of silicon dioxide calculated by mass fraction into 7-9 parts of ethylene glycol to obtain a dispersion liquid;
b. uniformly mixing 0.5-1.5% of coupling agent and 98.5-99.5% of dispersion liquid by mass fraction, and standing for 4-8 hours at 110-120 ℃ to obtain a first mixed solution; filtering the first mixed solution to obtain particles, and drying the particles at the temperature of 30-50 ℃ for 0.5-1.5 hours to obtain modified silicon dioxide;
c. mixing the PVDF fluorocarbon resin, the pigment, the flatting agent and the diluent in mass fraction to obtain a second mixed solution, and stirring the second mixed solution for 4-6 minutes to obtain a base solution;
d. and adding the modified silicon dioxide with the mass fraction into a base solution to obtain the self-cleaning corrosion-resistant coating.
Preferably, the coupling agent is gamma-aminopropyltriethoxysilane.
On the other hand, the application also provides a self-cleaning corrosion-resistant metal plate, and the surface of the metal plate is coated with the self-cleaning corrosion-resistant coating.
The beneficial effect of this application lies in: the self-cleaning corrosion-resistant coating provided by the application is prepared by adding modified silicon dioxide into the coating, so that the self-cleaning corrosion-resistant coating provided by the application has stronger hydrophobicity compared with common corrosion-resistant coating, and the self-cleaning corrosion-resistant coating has self-cleaning capability. Meanwhile, PVDF fluorocarbon resin is adopted as a basic coating, so that the coating has stronger corrosion resistance compared with a common protective coating.
The foregoing description is only an overview of the technical solutions of the present application, and in order to make the technical solutions of the present application more clear and can be implemented according to the content of the specification, the following detailed description is given with reference to the preferred embodiments of the present application.
Detailed Description
The following examples are provided to further illustrate the embodiments of the present application. The following examples are intended to illustrate the present application, but are not intended to limit the scope of the present application.
Example 1
The preparation formula comprises: 76% of PVDF fluorocarbon resin, 10% of pigment, 1% of leveling agent, 13% of diluent and 1% of modified silicon dioxide.
The preparation method comprises the following steps:
a. 2 parts of silica particles were ultrasonically dispersed into 8 parts of ethylene glycol to obtain a dispersion liquid.
b. Adding 1% of gamma-aminopropyltriethoxysilane calculated by mass fraction into 99% of the dispersion, and standing at 115 ℃ for 6 hours to obtain a first mixed solution; and filtering the first mixed solution to obtain particles, washing the particles for 3 times, and drying the washed particles at 40 ℃ to obtain the modified silicon dioxide.
c. Uniformly mixing the PVDF fluorocarbon resin, the pigment, the flatting agent and the diluent in mass fraction, and stirring at the rotating speed of 100r/min for 5 minutes to obtain a second mixed solution.
d. And (3) adding the modified silicon dioxide prepared in the step (1) into the second mixed solution according to the mass fraction, and stirring at the rotating speed of 300r/min for 30min to obtain a coating finished product.
Example 2
The preparation formula comprises: 76% of PVDF fluorocarbon resin, 10% of pigment, 1% of leveling agent, 13% of diluent and 2% of modified silicon dioxide.
The preparation method comprises the following steps:
a. 2 parts of silica particles were ultrasonically dispersed into 8 parts of ethylene glycol to obtain a dispersion liquid.
b. Adding 1% of gamma-aminopropyltriethoxysilane calculated by mass fraction into 99% of the dispersion liquid, and standing for 6 hours at 115 ℃ to obtain a first mixed solution; and filtering the first mixed solution to obtain particles, washing the particles for 3 times, and drying the washed particles at 40 ℃ to obtain the modified silicon dioxide.
c. Uniformly mixing the PVDF fluorocarbon resin, the pigment, the flatting agent and the diluent in mass fraction, and stirring at the rotating speed of 100r/min for 5 minutes to obtain a second mixed solution.
d. And (3) adding the modified silicon dioxide prepared in the step (1) into the second mixed solution according to the mass fraction, and stirring at the rotating speed of 300r/min for 30min to obtain a coating finished product.
Example 3
The preparation formula comprises: 76% of PVDF fluorocarbon resin, 10% of pigment, 1% of leveling agent, 13% of diluent and 3% of modified silicon dioxide.
The preparation method comprises the following steps:
a. 2 parts of silica particles were ultrasonically dispersed into 8 parts of ethylene glycol to obtain a dispersion liquid.
b. Adding 1% of gamma-aminopropyltriethoxysilane calculated by mass fraction into 99% of the dispersion, and standing at 115 ℃ for 6 hours to obtain a first mixed solution; and filtering the first mixed solution to obtain particles, washing the particles for 3 times, and drying the washed particles at 40 ℃ to obtain the modified silicon dioxide.
c. Uniformly mixing the PVDF fluorocarbon resin, the pigment, the flatting agent and the diluent in mass fraction, and stirring at the rotating speed of 100r/min for 5 minutes to obtain a second mixed solution.
d. And (3) adding the modified silicon dioxide prepared in the step (1) into the second mixed solution according to the mass fraction, and stirring at the rotating speed of 300r/min for 30min to obtain a coating finished product.
Example 4
The preparation formula comprises: 76% of PVDF fluorocarbon resin, 10% of pigment, 1% of leveling agent, 13% of diluent and 4% of modified silicon dioxide.
The preparation method comprises the following steps:
a. 2 parts of silica particles were ultrasonically dispersed into 8 parts of ethylene glycol to obtain a dispersion liquid.
b. Adding 1% of gamma-aminopropyltriethoxysilane calculated by mass fraction into 99% of the dispersion, and standing at 115 ℃ for 6 hours to obtain a first mixed solution; and filtering the first mixed solution to obtain particles, washing the particles for 3 times, and drying the washed particles at 40 ℃ to obtain the modified silicon dioxide.
c. Uniformly mixing the PVDF fluorocarbon resin, the pigment, the flatting agent and the diluent in mass fraction, and stirring at the rotating speed of 100r/min for 5 minutes to obtain a second mixed solution.
d. And (3) adding the modified silicon dioxide prepared in the step (1) into the second mixed solution according to the mass fraction, and stirring at the rotating speed of 300r/min for 30min to obtain a coating finished product.
Example 5
The preparation formula comprises: 76% of PVDF fluorocarbon resin, 10% of pigment, 1% of leveling agent, 13% of diluent and 5% of modified silicon dioxide.
The preparation method comprises the following steps:
a. 2 parts of silica particles were ultrasonically dispersed into 8 parts of ethylene glycol to obtain a dispersion liquid.
b. Adding 1% of gamma-aminopropyltriethoxysilane calculated by mass fraction into 99% of the dispersion, and standing at 115 ℃ for 6 hours to obtain a first mixed solution; and filtering the first mixed solution to obtain particles, washing the particles for 3 times, and drying the washed particles at 40 ℃ to obtain the modified silicon dioxide.
c. Uniformly mixing the PVDF fluorocarbon resin, the pigment, the flatting agent and the diluent in mass fraction, and stirring at the rotating speed of 100r/min for 5 minutes to obtain a second mixed solution.
d. And (3) adding the modified silicon dioxide prepared in the step (1) into the second mixed solution according to the mass fraction, and stirring at the rotating speed of 300r/min for 30min to obtain a coating finished product.
Test experiment 1
To test the effect of varying the concentration of modified silica in the coating on the hydrophobicity of the coating, the coatings provided in examples 1-5 were selected for separate testing. In order to distinguish the experimental groups, the coatings prepared in the above 5 examples are named as coating 1, coating 2, coating 3, coating 4 and coating 5 in sequence. Among them, the coating 1, the coating 2, the coating 3, the coating 4, and the coating 5 are different only in the proportion of the modified silica added to the coating. 5 same metal plates are selected, degreased liquid medicine is used for cleaning the metal plates, and a layer of epoxy primer with the thickness of 50 mu m is coated on the metal plates. The 5 coating materials were applied to the 5 treated metal plates, and dried at 220 ℃ for 60 seconds to cure the surface coating materials into a film, thereby forming a coating layer having a thickness of about 20 μm. Here, the designation of the metal plate coated with the paint 1 is test plate 1, the metal plate coated with the paint 2 is test plate 2, the metal plate coated with the paint 3 is test plate 3, the metal plate coated with the paint 4 is test plate 4, and the metal plate coated with the paint 5 is paint 5.
The contact angle of the surfaces of the above 5 test boards were tested separately, and the specific data were recorded as follows:
percentage of modified silica Contact angle
Test board 1 1% 97°
Test board 2 2% 103°
Test board 3 3% 114°
Test board 4 4% 137°
Test board 5 5% 139°
TABLE 1
As can be seen from Table 1, in the above 5 sheets, the contact angles of the coating surfaces were all larger than 90 °, and the metal sheet surfaces were all hydrophobic, i.e., the liquid did not easily wet the solid. And as the content ratio of the modified silicon dioxide in the coating is increased, the contact angle of the coating is larger after the coating is coated on a metal plate, and the hydrophobic property is better. The hydrophobic property of the coating is high, and the retention time of the liquid on the surface of the coating is short. Then as the liquid moves, dust on the surface of the coating is carried away with the flow of the liquid.
As shown in table 1, the contact angles of the test boards 4 and 5 are greatly increased compared to the contact angles of the test boards 1, 2 and 3, i.e. the hydrophobicity is better than that of the test boards 1, 2 and 3. That is, the test boards 4 and 5 have better self-cleaning ability than the test boards 1 and 2 and 3. Alternatively, one skilled in the art can select the actual amount of modified silica in the coating formulation based on the actual self-cleaning capability requirements.
Example 6
The preparation formula comprises: 70% of PVDF fluorocarbon resin, 10% of pigment, 1% of leveling agent, 19% of diluent and 1% of modified silicon dioxide.
The preparation method comprises the following steps:
a. 2 parts of silica particles were ultrasonically dispersed into 8 parts of ethylene glycol to obtain a dispersion liquid.
b. Adding 1% of gamma-aminopropyltriethoxysilane calculated by mass fraction into 99% of the dispersion, and standing at 115 ℃ for 6 hours to obtain a first mixed solution; and filtering the first mixed solution to obtain particles, washing the particles for 3 times, and drying the washed particles at 40 ℃ to obtain the modified silicon dioxide.
c. Uniformly mixing the PVDF fluorocarbon resin, the pigment, the flatting agent and the diluent in mass fraction, and stirring at the rotating speed of 100r/min for 5 minutes to obtain a second mixed solution.
d. And (3) adding the modified silicon dioxide prepared in the step (1) into the second mixed solution according to the mass fraction, and stirring at the rotating speed of 300r/min for 30min to obtain a coating finished product.
Example 7
The preparation formula comprises the following steps: 70% of PVDF fluorocarbon resin, 10% of pigment, 1% of leveling agent, 19% of diluent and 2% of modified silicon dioxide.
The preparation method comprises the following steps:
a. 2 parts of silica particles were ultrasonically dispersed into 8 parts of ethylene glycol to obtain a dispersion liquid.
b. Adding 1% of gamma-aminopropyltriethoxysilane calculated by mass fraction into 99% of the dispersion, and standing at 115 ℃ for 6 hours to obtain a first mixed solution; and filtering the first mixed solution to obtain particles, washing the particles for 3 times, and drying the washed particles at 40 ℃ to obtain the modified silicon dioxide.
c. Uniformly mixing the PVDF fluorocarbon resin, the pigment, the flatting agent and the diluent in mass fraction, and stirring at the rotating speed of 100r/min for 5 minutes to obtain a second mixed solution.
d. And (3) adding the modified silicon dioxide prepared in the step (1) into the second mixed solution according to the mass fraction, and stirring at the rotating speed of 300r/min for 30min to obtain a coating finished product.
Example 8
The preparation formula comprises: 70% of PVDF fluorocarbon resin, 10% of pigment, 1% of leveling agent, 19% of diluent and 3% of modified silicon dioxide.
The preparation method comprises the following steps:
a. 2 parts of silica particles were ultrasonically dispersed into 8 parts of ethylene glycol to obtain a dispersion liquid.
b. Adding 1% of gamma-aminopropyltriethoxysilane calculated by mass fraction into 99% of the dispersion liquid, and standing for 6 hours at 115 ℃ to obtain a first mixed solution; and filtering the first mixed solution to obtain particles, washing the particles for 3 times, and drying the washed particles at 40 ℃ to obtain the modified silicon dioxide.
c. Uniformly mixing the PVDF fluorocarbon resin, the pigment, the flatting agent and the diluent in mass fraction, and stirring at the rotating speed of 100r/min for 5 minutes to obtain a second mixed solution.
d. And (3) adding the modified silicon dioxide prepared in the step (1) into the second mixed solution according to the mass fraction, and stirring at the rotating speed of 300r/min for 30min to obtain a coating finished product.
Example 9
The preparation formula comprises: 70% of PVDF fluorocarbon resin, 10% of pigment, 1% of leveling agent, 19% of diluent and 4% of modified silicon dioxide.
The preparation method comprises the following steps:
a. 2 parts of silica particles were ultrasonically dispersed into 8 parts of ethylene glycol to obtain a dispersion liquid.
b. Adding 1% of gamma-aminopropyltriethoxysilane calculated by mass fraction into 99% of the dispersion, and standing at 115 ℃ for 6 hours to obtain a first mixed solution; and filtering the first mixed solution to obtain particles, washing the particles for 3 times, and drying the washed particles at 40 ℃ to obtain the modified silicon dioxide.
c. Uniformly mixing the PVDF fluorocarbon resin, the pigment, the flatting agent and the diluent in mass fraction, and stirring at the rotating speed of 100r/min for 5 minutes to obtain a second mixed solution.
d. And (3) adding the modified silicon dioxide prepared in the step (1) into the second mixed solution according to the mass fraction, and stirring at the rotating speed of 300r/min for 30min to obtain a coating finished product.
Example 10
The preparation formula comprises: 70% of PVDF fluorocarbon resin, 10% of pigment, 1% of leveling agent, 19% of diluent and 5% of modified silicon dioxide.
The preparation method comprises the following steps:
a. 2 parts of silica particles were ultrasonically dispersed into 8 parts of ethylene glycol to obtain a dispersion liquid.
b. Adding 1% of gamma-aminopropyltriethoxysilane calculated by mass fraction into 99% of the dispersion liquid, and standing for 6 hours at 115 ℃ to obtain a first mixed solution; and filtering the first mixed solution to obtain particles, washing the particles for 3 times, and drying the washed particles at 40 ℃ to obtain the modified silicon dioxide.
c. Uniformly mixing the PVDF fluorocarbon resin, the pigment, the flatting agent and the diluent in mass fraction, and stirring at the rotating speed of 100r/min for 5 minutes to obtain a second mixed solution.
d. And (2) adding the modified silicon dioxide prepared in the step (1) into the second mixed solution according to the mass fraction, and stirring at the rotating speed of 300r/min for 30min to obtain a coating finished product.
Test experiment 2
The coatings provided in examples 6 to 10 were selected to test the hydrophobicity of the coatings, and the coatings prepared in the above 5 examples were named as coating 6, coating 7, coating 8, coating 9, and coating 10 in order to distinguish the experimental groups. Among them, the coating materials 6, 7, 8, 9, and 10 are different only in the proportion of the modified silica added to the coating material. 5 same metal plates are selected, degreased liquid medicine is used for cleaning the metal plates, and a layer of epoxy primer with the thickness of 50 mu m is coated on the metal plates. The 5 coating materials were applied to the 5 treated metal plates, and dried at 220 ℃ for 60 seconds to cure the surface coating materials into a film, thereby forming a coating layer having a thickness of about 20 μm. Here, the designation of the metal plate coated with the paint 6 is test plate 6, the metal plate coated with the paint 7 is test plate 7, the metal plate coated with the paint 8 is test plate 8, the metal plate coated with the paint 9 is test plate 9, and the metal plate coated with the paint 10 is paint 10.
The contact angle of the surfaces of the above 5 test boards were tested separately, and the specific data were recorded as follows:
modified silica content Contact angle
Test board 6 1% 99°
Test board 7 2% 112°
Test board 8 3% 125°
Test board 9 4% 151°
Test board 10 5% 152°
TABLE 2
As can be seen from table 2, in the above 5 plates, the contact angles of the coating surfaces are all larger than 90 °, and the metal plate surfaces are all hydrophobic, i.e., the liquid is not easy to wet the solid. And as the proportion of the modified silicon dioxide content in the coating is increased, the contact angle of the coating is larger and the hydrophobic property is better after the coating is coated on a metal plate. The hydrophobic property of the coating is high, and the retention time of the liquid on the surface of the coating is short. Then as the liquid moves, dust on the surface of the coating is carried away as the liquid flows away.
5 parts of equal amounts of fly ash were scattered on the test boards 6 to 10, respectively, and then washed with water to test the self-cleaning ability of the test boards 6 to 10. Wherein, the dust on the test boards 9 and 10 is washed by water, and the residual amount of the coal dust is less. Alternatively, one skilled in the art can select the actual amount of modified silica in the coating formulation based on the actual self-cleaning capability requirements.
In conclusion, the self-cleaning corrosion-resistant coating provided by the application has stronger hydrophobicity compared with the common corrosion-resistant coating by adding the modified silicon dioxide in the coating, so that the self-cleaning corrosion-resistant coating has self-cleaning capability. Meanwhile, PVDF fluorocarbon resin is adopted as the basic coating, so that the paint has stronger corrosion resistance compared with common protective coatings.
For relevant details reference is made to the above-described method embodiments.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present application, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the concept of the present application, which falls within the scope of protection of the present application. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (6)

1. The self-cleaning corrosion-resistant coating is characterized by comprising 70-80% of PVDF fluorocarbon resin, 5-15% of pigment, 1-2% of flatting agent, 10-20% of diluent and 1-5% of modified silicon dioxide in percentage by mass.
2. The self-cleaning corrosion-resistant coating material of claim 1, wherein said modified silica is silica modified with γ -aminopropyltriethoxysilane.
3. A method of preparing a self-cleaning corrosion resistant coating as recited in claim 1, said method comprising:
a. ultrasonically dispersing 1-3 parts of silicon dioxide into 7-9 parts of ethylene glycol to obtain a dispersion liquid;
b. uniformly mixing 0.5-1.5% of coupling agent and 98.5-99.5% of dispersion liquid by mass percent, and standing for 4-8 hours at 110-120 ℃ to obtain a first mixed solution; filtering the first mixed solution to obtain particles, and drying the particles at the temperature of 30-50 ℃ for 0.5-1.5 hours to obtain modified silicon dioxide;
c. mixing the PVDF fluorocarbon resin, the pigment, the flatting agent and the diluent in mass fraction to obtain a second mixed solution, and stirring the second mixed solution for 4-6 minutes to obtain a base solution;
d. and adding the modified silicon dioxide with the mass fraction into the base liquid to obtain the self-cleaning corrosion-resistant coating.
4. The method of claim 3, wherein the coupling agent is gamma-aminopropyltriethoxysilane.
5. The self-cleaning corrosion-resistant coating material of claim 3, wherein after filtering the first mixed solution to obtain particles and before drying the particles in step b, the method further comprises: washing the particulate matter.
6. A self-cleaning corrosion-resistant metal sheet coated with the self-cleaning corrosion-resistant coating of claim 1.
CN202111014446.6A 2021-08-31 2021-08-31 Self-cleaning corrosion-resistant coating, preparation method thereof and self-cleaning corrosion-resistant metal plate Pending CN115725211A (en)

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