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CN120230443B - Wear-resistant anticorrosive paint and preparation method thereof - Google Patents

Wear-resistant anticorrosive paint and preparation method thereof

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Publication number
CN120230443B
CN120230443BCN202510717349.5ACN202510717349ACN120230443BCN 120230443 BCN120230443 BCN 120230443BCN 202510717349 ACN202510717349 ACN 202510717349ACN 120230443 BCN120230443 BCN 120230443B
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wear
component
preparation
magnesium sulfate
quaternary
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CN120230443A (en
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廖鑫宇
柴娅宁
张茜
邱先慧
张欣潼
陈诗雨
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Shandong University of Technology
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Shandong University of Technology
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Abstract

The invention belongs to the technical field of paint preparation, and particularly relates to a wear-resistant anticorrosive paint and a preparation method thereof. The wear-resistant anticorrosive paint consists of a component A and a component B, wherein the weight ratio of the component A to the component B is 10:1, the component A consists of quaternary fluorocarbon resin, hydroxyl-terminated perfluoropolyether resin, hydrogenated bisphenol A epoxy resin, poly (perfluoromethyl isopropyl ether), di-n-butyltin dilaurate, dimethyl carbonate, methyl isobutyl ketone, modified sillimanite, a mixture of nano chromium diboride and basic magnesium sulfate whisker, trifluoropropyl methyl silicone oil and polyamide wax, and the component B is hexamethylene diisocyanate trimer. The raw materials of the wear-resistant anticorrosive paint disclosed by the invention have synergistic effect, so that the prepared paint has excellent salt spray resistance, acid and alkali resistance, and lower wet friction coefficient and wear rate.

Description

Wear-resistant anticorrosive paint and preparation method thereof
Technical Field
The invention belongs to the technical field of paint preparation, and particularly relates to a wear-resistant anticorrosive paint and a preparation method thereof.
Background
The sucker rod is an important part of sucker rod pumping equipment, and transmits the power of a pumping unit to a downhole oil pump, and when a rod pipe contacts, the sucker rod and an oil pipe are worn by relatively moving, which is called eccentric wear. The eccentric wear makes the sucker rod wear, has reduced the intensity of sucker rod, causes the sucker rod fracture, grinds the oil pipe wall, influences the normal work of oil well, brings great economic loss for the oil field.
In the petroleum exploitation process, the pumping well medium environment where the pumping rod is located belongs to the severe environment of high temperature, high mineralization degree and high water content accompanied by corrosive mediums such as CO2, H2 S gas, bacteria and the like. The high temperature, high mineralization and high water content all play a role in catalyzing and promoting the corrosion reaction rate. The high Cl- content provides conditions and opportunities for the sucker rod to develop pitting. Therefore, a large-cathode small-anode area ratio structure is easily formed on the outer surface of the sucker rod, a closed cathode-anode loop is formed, the ratio of the corrosion reaction rate to the corrosion area is increased along with the extension of time, and the sucker rod is corroded and broken in time.
In order to improve the wear resistance and corrosion resistance of the sucker rod, a surface coating technology is generally adopted to carry out modification treatment on the sucker rod. The types of paint which are frequently adopted are epoxy resin paint, inorganic ceramic paint, polyurethane/polytetrafluoroethylene paint and graphene composite paint. The epoxy resin coating is high in brittleness, cracking or layering is easily caused by reciprocating motion of the sucker rod, the inorganic ceramic coating has severe treatment requirements on the surface of a substrate, and cracks are easily generated due to mechanical impact or deformation, so that local corrosion is accelerated, the wear resistance of the polyurethane/polytetrafluoroethylene coating is insufficient, and the durability of the graphene composite coating in a hypersalinity environment is insufficient. Therefore, it is necessary to explore a novel wear-resistant anticorrosive paint.
Disclosure of Invention
The invention aims to provide a wear-resistant anticorrosive paint, the prepared paint has corrosion resistance and wear resistance, and the invention also provides a preparation method of the wear-resistant anticorrosive paint.
The wear-resistant anticorrosive paint comprises, by weight, 30-32 parts of quaternary fluorocarbon resin, 10-12 parts of hydroxyl-terminated perfluoropolyether resin, 13-15 parts of hydrogenated bisphenol A epoxy resin, 3-5 parts of poly (perfluoromethyl isopropyl ether), 0.05 part of di-n-butyltin dilaurate, 10-10.5 parts of dimethyl carbonate, 3-3.5 parts of methyl isobutyl ketone, 15-17 parts of a mixture of modified sillimanite, nano chromium diboride and basic magnesium sulfate whisker, 0.2-0.4 part of trifluoropropyl methyl silicone oil and 0.8-1.0 part of polyamide wax, and B is hexamethylene diisocyanate trimer.
The preparation method of the quaternary fluorocarbon resin comprises the following steps of firstly vacuumizing a high-pressure reaction kettle, introducing argon gas, keeping the high-pressure reaction kettle in an anhydrous and anaerobic environment, then controlling the pressure of the high-pressure reaction kettle to be 1.5MPa, firstly adding a solvent which is a mixture of 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether and dimethylbenzene, then adding 1-octene-3-alcohol acetate, 4-hydroxybutyl vinyl ether, itaconic acid and azodiisobutyronitrile, then introducing trifluoro vinyl chloride gas into the high-pressure reaction kettle, reacting for 7 hours at 73-75 ℃, cooling the reaction kettle to room temperature, depressurizing and discharging unreacted trifluoro vinyl chloride gas, precipitating the obtained liquid by adopting ethanol, filtering, and performing Soxhlet extraction and drying to obtain the quaternary fluorocarbon resin.
In the preparation method of the quaternary fluorocarbon resin, the molar ratio of the chlorotrifluoroethylene to the 4-hydroxybutyl vinyl ether to the itaconic acid to the 1-octene-3-alcohol acetate is 50:30:10:10.
The mass of the azodiisobutyronitrile in the preparation method of the quaternary fluorocarbon resin accounts for 0.7 percent of the sum of the mass of the chlorotrifluoroethylene, the 4-hydroxybutyl vinyl ether, the itaconic acid and the 1-octene-3-alcohol acetate.
The solvent volume in the preparation method of the quaternary fluorocarbon resin accounts for 60 percent of the volume of the solvent including 4-hydroxybutyl vinyl ether, itaconic acid, 1-octene-3-alcohol acetate, azodiisobutyronitrile and the like.
In the preparation method of the quaternary fluorocarbon resin, the volume ratio of the 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether to the dimethylbenzene is 3:1.
The manufacturer of the hydroxyl-terminated perfluoropolyether resin is Kaimei chemical technology (Nantong) Co., ltd, the model is FB-800, the fluorine content is 42%, the functionality is 2, and the viscosity at 25 ℃ is 600mPa.s.
The preparation method of the mixture of the modified sillimanite, the nano chromium diboride and the basic magnesium sulfate whisker comprises the following steps of mixing ethanol and deionized water to prepare a mixed solution, adding a KH-550 silane coupling agent, stirring for 1.0h at a rotating speed of 600r/min, adding the mixture of the sillimanite powder, the nano chromium diboride and the basic magnesium sulfate whisker, shearing for 50min at a high speed, reacting for 3h at 55 ℃, vacuum-filtering, and finally drying under a vacuum condition to prepare the mixture of the modified sillimanite, the nano chromium diboride and the basic magnesium sulfate whisker.
Wherein the volume ratio of KH-550 silane coupling agent, ethanol and deionized water is 5:18:2.
The mass of KH-550 silane coupling agent is 2.0% of the sum of the mass of sillimanite powder, nanometer chromium diboride and basic magnesium sulfate whisker.
The mass ratio of the sillimanite powder to the nano chromium diboride to the basic magnesium sulfate whisker is 3:0.9-1.1:0.8-1.0.
The vacuum drying temperature is 70 ℃ and the vacuum drying time is 3 hours in the preparation process of the mixture of the modified sillimanite, the nano chromium diboride and the basic magnesium sulfate whisker.
The preparation method of the wear-resistant anticorrosive paint provided by the invention comprises the following steps:
(1) Firstly, uniformly mixing hydrogenated bisphenol A epoxy resin, dimethyl carbonate and methyl isobutyl ketone, then adding quaternary fluorocarbon resin, hydroxyl-terminated perfluoropolyether resin and poly-perfluoromethyl isopropyl ether for blending, then adding a mixture of modified sillimanite, nano chromium diboride and basic magnesium sulfate whisker for high-speed dispersion for 23-25min, adding polyamide wax and di-n-butyltin dilaurate for mixing for 1.5h, and finally adding trifluoropropyl methyl silicone oil for stirring for 3-5min to prepare a component A;
(2) And uniformly mixing the component A and the component B according to the weight ratio of 10:1 to prepare the wear-resistant anticorrosive paint.
Wherein the stirring rotating speed of the step (1) is 700r/min when the component A is prepared.
In the step (2), the stirring speed is 800r/min, the stirring time is 25-27min, and the stirring temperature is 25 ℃.
And (3) spraying the wear-resistant anticorrosive paint in the step (2), and then curing for 36 hours at room temperature.
Compared with the prior art, the invention has the following beneficial effects:
(1) The wear-resistant anticorrosive paint disclosed by the invention is prepared from quaternary fluorocarbon resin, hydroxyl-terminated perfluoropolyether resin, hydrogenated bisphenol A epoxy resin and poly-perfluoromethyl isopropyl ether serving as main components, wherein the molecular chain of the quaternary fluorocarbon resin contains hydroxyl, carboxyl and other active groups, the groups can be subjected to addition reaction with isocyanate groups-NCO of an HDI trimer to form a urethane bond crosslinking network, so that the coating is cured, the fluorocarbon chain section of the wear-resistant anticorrosive paint endows the coating with high corrosion resistance and hydrophobicity, and the rigid structure of the quaternary fluorocarbon resin enables the anticorrosive coating to have good mechanical properties. The hydroxyl-terminated perfluoropolyether resin has the advantages that the hydroxyl-terminated groups can react with the component B to form a three-dimensional crosslinked network, the mechanical strength and adhesive force of the coating are improved, the low friction characteristic of the hydroxyl-terminated perfluoropolyether resin can reduce the surface abrasion of the anti-corrosion coating, in addition, the hydroxyl-terminated groups are physically adsorbed on the surface of the metal matrix, the adhesive force between the coating and the matrix is enhanced, the anti-corrosion layer can be firmly adhered on the surface of the metal matrix, the anti-corrosion layer is not easy to fall off or crack, and the stability of the anti-corrosion effect is ensured. The hydrogenated bisphenol A epoxy resin has good flexibility and impact resistance, can interact with other components such as quaternary fluorocarbon resin and the like to form a network structure with excellent toughness in the coating, so that the modified fluorocarbon anticorrosive coating has good hardness and wear resistance, can resist the influence of external mechanical stress to a certain extent, and avoids the reduction of the anticorrosive performance of the coating caused by brittle fracture of the coating. The poly-perfluoromethyl isopropyl ether can provide fluorine element and ether bond group, the existence of the ether bond enables the modified fluorocarbon anticorrosive layer to have lower surface energy, which is beneficial to reducing the adhesion of pollutants such as dirt and oil stain on the surface of the coating, further enhancing the durability and effectiveness of the anticorrosive layer, dispersing the anticorrosive layer in the coating, filling the micropore defects of other resins, and enhancing the compactness of the coating. Therefore, the lubricity of the hydroxyl-terminated perfluoropolyether resin and the toughness of the hydrogenated bisphenol A epoxy resin jointly improve the wear resistance, the low surface tension of the poly (perfluoromethyl isopropyl ether) promotes the uniform dispersion of other components and reduces the coating pores, the rigid structure of the quaternary fluorocarbon resin supports the compressive strength of the coating to form a wear-resistant system with hardness and softness, the interaction of the four components enables the coating to have a compact structure, and the coating has high fluorine content, so that the wear resistance and the corrosion resistance of the prepared coating are fundamentally ensured. The dimethyl carbonate and the methyl isobutyl ketone are used as solvents, the two solvents are compounded to avoid pinholes in a paint film caused by too fast evaporation of a single solvent, sagging phenomenon of the methyl isobutyl ketone when the methyl isobutyl ketone is singly used can be prevented, balance of spraying leveling property and curing speed is realized, trifluoropropyl methyl silicone oil is used as a defoaming agent, polyamide wax is used as a leveling agent, a mixture of modified sillimanite, chromium diboride and basic magnesium sulfate whisker is used as a filler, and the wear resistance of the paint is improved, so that the raw materials are cooperated to ensure the corrosion resistance and the wear resistance of the prepared wear-resistant anticorrosive paint.
(2) The wear-resistant anticorrosive paint disclosed by the invention takes the mixture of modified sillimanite, chromium diboride and basic magnesium sulfate whisker as a filler, a unique crystal structure of the sillimanite forms a rigid framework in the coating, the embedding and the plow effect of abrasive particles in the friction process can be resisted, the chromium diboride crystal structure forms hard wear-resistant particles in the coating and directly resists mechanical wear and abrasive particle cutting, the basic magnesium sulfate whisker is a needle-shaped single crystal fiber, a three-dimensional network structure is formed in the coating by the high length-diameter ratio of the basic magnesium sulfate whisker, and crack expansion is restrained through crack bridging, deflection and pulling effects, so that the three cooperate to further improve the wear resistance of the paint.
(3) When the wear-resistant anticorrosive paint disclosed by the invention is used for preparing quaternary fluorocarbon resin, 1-octene-3-alcohol acetate, 4-hydroxybutyl vinyl ether, itaconic acid and chlorotrifluoroethylene are adopted as raw materials, chlorotrifluoroethylene is used as fluorine-containing monomers to form a rigid structure of a molecular main chain, fluorine atoms are tightly arranged on the outer layer of a carbon chain to form a shielding effect, corrosion of acid alkali and salt mist is prevented, hydroxyl is introduced into the 4-hydroxybutyl vinyl ether to serve as a crosslinking site, the hydroxyl reacts with-NCO of an HDI trimer to form a compact three-dimensional network structure, and carboxyl groups of the itaconic acid can enhance compatibility of the prepared quaternary fluorocarbon resin with a filler, and meanwhile, the adhesive force of the coating is improved through hydrogen bonding, so that the prepared quaternary fluorocarbon resin has certain flexibility, and the improvement of flexibility can avoid the cracking of the coating due to internal stress. The four raw materials interact with each other, the rigid framework with high fluorine content is provided by the chlorotrifluoroethylene, chemical erosion is resisted, the 4-hydroxybutyl vinyl ether is introduced into a crosslinking site, the polarity of the prepared quaternary fluorocarbon resin is enhanced by itaconic acid, and the 1-octene-3-alcohol acetate ensures that the prepared quaternary fluorocarbon resin has certain flexibility, so that the prepared quaternary fluorocarbon resin has excellent corrosion resistance.
(4) The raw materials of the wear-resistant anticorrosive paint disclosed by the invention have synergistic effect, so that the prepared paint has excellent salt spray resistance, acid and alkali resistance, and lower wet friction coefficient and wear rate.
(5) The preparation method of the wear-resistant anticorrosive paint has the advantages of simple process, easy parameter control, realization of normal-temperature solidification and stable performance of the paint after spraying.
Detailed Description
The invention is further described below with reference to examples.
Example 1
The wear-resistant anticorrosive paint disclosed by the embodiment 1 comprises, by weight, 31 parts of quaternary fluorocarbon resin, 11 parts of hydroxyl-terminated perfluoropolyether resin, 14 parts of hydrogenated bisphenol A epoxy resin, 4 parts of poly (perfluoromethyl isopropyl ether), 0.05 part of di-n-butyltin dilaurate, 10.3 parts of dimethyl carbonate, 3.3 parts of methyl isobutyl ketone, 16 parts of a mixture of modified sillimanite, nano chromium diboride and basic magnesium sulfate whisker, 0.3 part of trifluoropropyl methyl silicone oil and 0.9 part of polyamide wax, and B is hexamethylene diisocyanate trimer.
The preparation method of the quaternary fluorocarbon resin comprises the following steps of firstly vacuumizing a high-pressure reaction kettle, introducing argon to enable the high-pressure reaction kettle to keep an anhydrous and anaerobic environment, then controlling the pressure of the high-pressure reaction kettle to be 1.5MPa, firstly adding a solvent which is a mixture of 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether and dimethylbenzene, then adding 1-octene-3-alcohol acetate, 4-hydroxybutyl vinyl ether, itaconic acid and azodiisobutyronitrile, then introducing chlorotrifluoroethylene gas into the high-pressure reaction kettle, reacting for 7 hours at 74 ℃, cooling the reaction kettle to room temperature, depressurizing and discharging unreacted chlorotrifluoroethylene gas, precipitating the obtained liquid by adopting ethanol, filtering, and performing Soxhlet extraction and drying to obtain the quaternary fluorocarbon resin.
In the preparation method of the quaternary fluorocarbon resin, the molar ratio of the chlorotrifluoroethylene to the 4-hydroxybutyl vinyl ether to the itaconic acid to the 1-octene-3-alcohol acetate is 50:30:10:10.
The mass of the azodiisobutyronitrile in the preparation method of the quaternary fluorocarbon resin accounts for 0.7 percent of the sum of the mass of the chlorotrifluoroethylene, the 4-hydroxybutyl vinyl ether, the itaconic acid and the 1-octene-3-alcohol acetate.
The solvent volume in the preparation method of the quaternary fluorocarbon resin accounts for 60 percent of the volume of the solvent including 4-hydroxybutyl vinyl ether, itaconic acid, 1-octene-3-alcohol acetate, azodiisobutyronitrile and the like.
In the preparation method of the quaternary fluorocarbon resin, the volume ratio of the 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether to the dimethylbenzene is 3:1.
The manufacturer of the hydroxyl-terminated perfluoropolyether resin is Kaimei chemical technology (Nantong) Co., ltd, the model is FB-800, the fluorine content is 42%, the functionality is 2, and the viscosity at 25 ℃ is 600mPa.s.
The preparation method of the mixture of the modified sillimanite, the nano chromium diboride and the basic magnesium sulfate whisker comprises the following steps of mixing ethanol and deionized water to prepare a mixed solution, adding a KH-550 silane coupling agent, stirring for 1.0h at a rotating speed of 600r/min, adding the mixture of the sillimanite powder, the nano chromium diboride and the basic magnesium sulfate whisker, shearing for 50min at a high speed, reacting for 3h at 55 ℃, vacuum-filtering, and finally drying under a vacuum condition to prepare the mixture of the modified sillimanite, the nano chromium diboride and the basic magnesium sulfate whisker.
Wherein the volume ratio of KH-550 silane coupling agent, ethanol and deionized water is 5:18:2.
The mass of KH-550 silane coupling agent is 2.0% of the sum of the mass of sillimanite powder, nanometer chromium diboride and basic magnesium sulfate whisker.
The mass ratio of the sillimanite powder to the nano chromium diboride to the basic magnesium sulfate whisker is 3:1.0:0.9.
The vacuum drying temperature is 70 ℃ and the vacuum drying time is 3 hours in the preparation process of the mixture of the modified sillimanite, the nano chromium diboride and the basic magnesium sulfate whisker.
The preparation method of the wear-resistant anticorrosive paint of the embodiment 1 comprises the following steps:
(1) Firstly, uniformly mixing hydrogenated bisphenol A epoxy resin, dimethyl carbonate and methyl isobutyl ketone, then adding quaternary fluorocarbon resin, hydroxyl-terminated perfluoropolyether resin and poly-perfluoromethyl isopropyl ether for blending, then adding a mixture of modified sillimanite, nano chromium diboride and basic magnesium sulfate whisker for high-speed dispersion for 24min, adding polyamide wax and di-n-butyltin dilaurate for mixing for 1.5h, and finally adding trifluoropropyl methyl silicone oil for stirring for 4min to prepare a component A;
(2) And uniformly mixing the component A and the component B according to the weight ratio of 10:1 to prepare the wear-resistant anticorrosive paint.
Wherein the stirring rotating speed of the step (1) is 700r/min when the component A is prepared.
In the step (2), the stirring speed is 800r/min, the stirring time is 26min, and the stirring temperature is 25 ℃.
And (3) spraying the wear-resistant anticorrosive paint in the step (2), and then curing for 36 hours at room temperature.
Example 2
The wear-resistant anticorrosive paint disclosed by the embodiment 2 comprises, by weight, 32 parts of quaternary fluorocarbon resin, 10 parts of hydroxyl-terminated perfluoropolyether resin, 13 parts of hydrogenated bisphenol A epoxy resin, 5 parts of poly (perfluoromethyl isopropyl ether), 0.05 part of di-n-butyltin dilaurate, 10.5 parts of dimethyl carbonate, 3 parts of methyl isobutyl ketone, 17 parts of a mixture of modified sillimanite, nano chromium diboride and basic magnesium sulfate whisker, 0.2 part of trifluoropropyl methyl silicone oil and 1.0 part of polyamide wax, and B is hexamethylene diisocyanate trimer.
The preparation method of the quaternary fluorocarbon resin comprises the following steps of firstly vacuumizing a high-pressure reaction kettle, introducing argon to enable the high-pressure reaction kettle to keep an anhydrous and anaerobic environment, then controlling the pressure of the high-pressure reaction kettle to be 1.5MPa, firstly adding a solvent which is a mixture of 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether and dimethylbenzene, then adding 1-octene-3-alcohol acetate, 4-hydroxybutyl vinyl ether, itaconic acid and azodiisobutyronitrile, then introducing chlorotrifluoroethylene gas into the high-pressure reaction kettle, reacting for 7 hours at 75 ℃, cooling the reaction kettle to room temperature, depressurizing and discharging unreacted chlorotrifluoroethylene gas, precipitating the obtained liquid by adopting ethanol, filtering, and performing Soxhlet extraction and drying to obtain the quaternary fluorocarbon resin.
In the preparation method of the quaternary fluorocarbon resin, the molar ratio of the chlorotrifluoroethylene to the 4-hydroxybutyl vinyl ether to the itaconic acid to the 1-octene-3-alcohol acetate is 50:30:10:10.
The mass of the azodiisobutyronitrile in the preparation method of the quaternary fluorocarbon resin accounts for 0.7 percent of the sum of the mass of the chlorotrifluoroethylene, the 4-hydroxybutyl vinyl ether, the itaconic acid and the 1-octene-3-alcohol acetate.
The solvent volume in the preparation method of the quaternary fluorocarbon resin accounts for 60 percent of the volume of the solvent including 4-hydroxybutyl vinyl ether, itaconic acid, 1-octene-3-alcohol acetate, azodiisobutyronitrile and the like.
In the preparation method of the quaternary fluorocarbon resin, the volume ratio of the 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether to the dimethylbenzene is 3:1.
The manufacturer of the hydroxyl-terminated perfluoropolyether resin is Kaimei chemical technology (Nantong) Co., ltd, the model is FB-800, the fluorine content is 42%, the functionality is 2, and the viscosity at 25 ℃ is 600mPa.s.
The preparation method of the mixture of the modified sillimanite, the nano chromium diboride and the basic magnesium sulfate whisker comprises the following steps of mixing ethanol and deionized water to prepare a mixed solution, adding a KH-550 silane coupling agent, stirring for 1.0h at a rotating speed of 600r/min, adding the mixture of the sillimanite powder, the nano chromium diboride and the basic magnesium sulfate whisker, shearing for 50min at a high speed, reacting for 3h at 55 ℃, vacuum-filtering, and finally drying under a vacuum condition to prepare the mixture of the modified sillimanite, the nano chromium diboride and the basic magnesium sulfate whisker.
Wherein the volume ratio of KH-550 silane coupling agent, ethanol and deionized water is 5:18:2.
The mass of KH-550 silane coupling agent is 2.0% of the sum of the mass of sillimanite powder, nanometer chromium diboride and basic magnesium sulfate whisker.
The mass ratio of the sillimanite powder to the nano chromium diboride to the basic magnesium sulfate whisker is 3:1.1:0.8.
The vacuum drying temperature is 70 ℃ and the vacuum drying time is 3 hours in the preparation process of the mixture of the modified sillimanite, the nano chromium diboride and the basic magnesium sulfate whisker.
The preparation method of the wear-resistant anticorrosive paint of the embodiment 2 comprises the following steps:
(1) Firstly, uniformly mixing hydrogenated bisphenol A epoxy resin, dimethyl carbonate and methyl isobutyl ketone, then adding quaternary fluorocarbon resin, hydroxyl-terminated perfluoropolyether resin and poly-perfluoromethyl isopropyl ether for blending, then adding a mixture of modified sillimanite, nano chromium diboride and basic magnesium sulfate whisker for high-speed dispersion for 25min, adding polyamide wax and di-n-butyltin dilaurate for mixing for 1.5h, and finally adding trifluoropropyl methyl silicone oil for stirring for 5min to prepare a component A;
(2) And uniformly mixing the component A and the component B according to the weight ratio of 10:1 to prepare the wear-resistant anticorrosive paint.
Wherein the stirring rotating speed of the step (1) is 700r/min when the component A is prepared.
In the step (2), the stirring speed is 800r/min, the stirring time is 27min, and the stirring temperature is 25 ℃.
And (3) spraying the wear-resistant anticorrosive paint in the step (2), and then curing for 36 hours at room temperature.
Example 3
The wear-resistant anticorrosive paint of the embodiment 3 comprises, by weight, 30 parts of quaternary fluorocarbon resin, 12 parts of hydroxyl-terminated perfluoropolyether resin, 15 parts of hydrogenated bisphenol A epoxy resin, 3 parts of poly (perfluoromethyl isopropyl ether), 0.05 part of di-n-butyltin dilaurate, 10 parts of dimethyl carbonate, 3.5 parts of methyl isobutyl ketone, 15 parts of a mixture of modified sillimanite, nano chromium diboride and basic magnesium sulfate whisker, 0.4 part of trifluoropropyl methyl silicone oil and 0.8 part of polyamide wax, and B is hexamethylene diisocyanate trimer.
The preparation method of the quaternary fluorocarbon resin comprises the following steps of firstly vacuumizing a high-pressure reaction kettle, introducing argon gas, keeping the high-pressure reaction kettle in an anhydrous and anaerobic environment, then controlling the pressure of the high-pressure reaction kettle to be 1.5MPa, firstly adding a solvent which is a mixture of 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether and dimethylbenzene, then adding 1-octene-3-alcohol acetate, 4-hydroxybutyl vinyl ether, itaconic acid and azodiisobutyronitrile, then introducing chlorotrifluoroethylene gas into the high-pressure reaction kettle, reacting for 7 hours at 73 ℃, cooling the reaction kettle to room temperature, depressurizing and discharging unreacted chlorotrifluoroethylene gas, precipitating the obtained liquid by adopting ethanol, filtering, and performing Soxhlet extraction and drying to obtain the quaternary fluorocarbon resin.
In the preparation method of the quaternary fluorocarbon resin, the molar ratio of the chlorotrifluoroethylene to the 4-hydroxybutyl vinyl ether to the itaconic acid to the 1-octene-3-alcohol acetate is 50:30:10:10.
The mass of the azodiisobutyronitrile in the preparation method of the quaternary fluorocarbon resin accounts for 0.7 percent of the sum of the mass of the chlorotrifluoroethylene, the 4-hydroxybutyl vinyl ether, the itaconic acid and the 1-octene-3-alcohol acetate.
The solvent volume in the preparation method of the quaternary fluorocarbon resin accounts for 60 percent of the volume of the solvent including 4-hydroxybutyl vinyl ether, itaconic acid, 1-octene-3-alcohol acetate, azodiisobutyronitrile and the like.
In the preparation method of the quaternary fluorocarbon resin, the volume ratio of the 1, 2-tetrafluoroethyl-2, 2-trifluoroethyl ether to the dimethylbenzene is 3:1.
The manufacturer of the hydroxyl-terminated perfluoropolyether resin is Kaimei chemical technology (Nantong) Co., ltd, the model is FB-800, the fluorine content is 42%, the functionality is 2, and the viscosity at 25 ℃ is 600mPa.s.
The preparation method of the mixture of the modified sillimanite, the nano chromium diboride and the basic magnesium sulfate whisker comprises the following steps of mixing ethanol and deionized water to prepare a mixed solution, adding a KH-550 silane coupling agent, stirring for 1.0h at a rotating speed of 600r/min, adding the mixture of the sillimanite powder, the nano chromium diboride and the basic magnesium sulfate whisker, shearing for 50min at a high speed, reacting for 3h at 55 ℃, vacuum-filtering, and finally drying under a vacuum condition to prepare the mixture of the modified sillimanite, the nano chromium diboride and the basic magnesium sulfate whisker.
Wherein the volume ratio of KH-550 silane coupling agent, ethanol and deionized water is 5:18:2.
The mass of KH-550 silane coupling agent is 2.0% of the sum of the mass of sillimanite powder, nanometer chromium diboride and basic magnesium sulfate whisker.
The mass ratio of the sillimanite powder to the nano chromium diboride to the basic magnesium sulfate whisker is 3:0.9:1.0.
The vacuum drying temperature is 70 ℃ and the vacuum drying time is 3 hours in the preparation process of the mixture of the modified sillimanite, the nano chromium diboride and the basic magnesium sulfate whisker.
The preparation method of the wear-resistant anticorrosive paint of the embodiment 3 comprises the following steps:
(1) Firstly, uniformly mixing hydrogenated bisphenol A epoxy resin, dimethyl carbonate and methyl isobutyl ketone, then adding quaternary fluorocarbon resin, hydroxyl-terminated perfluoropolyether resin and poly-perfluoromethyl isopropyl ether for blending, then adding a mixture of modified sillimanite, nano chromium diboride and basic magnesium sulfate whisker for high-speed dispersion for 23min, adding polyamide wax and di-n-butyltin dilaurate for mixing for 1.5h, and finally adding trifluoropropyl methyl silicone oil for stirring for 3min to prepare a component A;
(2) And uniformly mixing the component A and the component B according to the weight ratio of 10:1 to prepare the wear-resistant anticorrosive paint.
Wherein the stirring rotating speed of the step (1) is 700r/min when the component A is prepared.
In the step (2), the stirring speed is 800r/min, the stirring time is 25min, and the stirring temperature is 25 ℃.
And (3) spraying the wear-resistant anticorrosive paint in the step (2), and then curing for 36 hours at room temperature.
Comparative example 1
The method for preparing the abrasion-resistant anticorrosive paint of comparative example 1 is the same as that of example 1, except that the raw material composition of the abrasion-resistant anticorrosive paint is different from that of example 1, the mixture of the modified sillimanite of component a, the nano chromium diboride and the basic magnesium sulfate whisker is replaced with the modified sillimanite, and the method for preparing the modified sillimanite is the same as that of example 1.
Comparative example 2
The preparation method of the wear-resistant anticorrosive paint of the comparative example 2 is the same as that of example 1, except that the raw material composition of the wear-resistant anticorrosive paint is different from that of example 1, the mixture of the modified sillimanite, the nano chromium diboride and the basic magnesium sulfate whisker of the A component is replaced by the modified nano chromium diboride, and the preparation method of the modified nano chromium diboride is the same as that of the mixture of the modified sillimanite, the nano chromium diboride and the basic magnesium sulfate whisker of example 1.
Comparative example 3
The preparation method of the wear-resistant anticorrosive paint of comparative example 3 is the same as that of example 1, except that the raw material composition of the wear-resistant anticorrosive paint is different from that of example 1, the mixture of the modified sillimanite, the nano chromium diboride and the basic magnesium sulfate whisker of the component a is replaced with the modified basic magnesium sulfate whisker, and the preparation method of the modified basic magnesium sulfate whisker is the same as that of the mixture of the modified sillimanite, the nano chromium diboride and the basic magnesium sulfate whisker of example 1.
Comparative example 4
The preparation method of the wear-resistant anticorrosive paint of comparative example 4 is the same as that of example 1, except that the raw material composition of the wear-resistant anticorrosive paint is different from that of example 1, and the quaternary fluorocarbon resin is not added to the raw material of comparative example 4.
The abrasion-resistant anticorrosive coatings prepared in examples 1 to 3 and comparative examples 1 to 4 were sprayed on the surface of a sucker rod to perform performance tests, the results of which are shown in the following table 1, wherein the salt spray resistance test standard is GB/T1771-2007, the acid and alkali resistance test standard is GB/T9274-1988, the corrosive medium adopts 10% H2SO4 solution and 10% NaOH solution, the coating hardness test standard is GB/T6739-2022, the coating adhesion test standard is GB/T9286-2021, the coating impact resistance test standard is GB/T1732-2020, the coating frictional wear performance is evaluated by a linear reciprocating test using a CFT-I frictional tester, the test adopts a ball-disc structure, a steel ball with a diameter of 4mm, the load is 3N, wet friction is performed at a constant rotation speed of 400r/min, a saline simulated wetting environment is injected at a frictional interface, and the test time is 30min. All friction pairs were washed several times with ethanol before the test to remove surface impurities. Each test was repeated 4 times under the same conditions.
TABLE 1 results of the performance test of the abrasion-resistant anticorrosive coatings of examples 1 to 3 and comparative examples 1 to 4

Claims (8)

Translated fromChinese
1.一种耐磨防腐涂料,其特征在于:由A组分和B组分组成,A组分与B组分的重量比为10:1,A组分以重量份数计,由以下原料组成:四元氟碳树脂30-32份、端羟基全氟聚醚树脂10-12份、氢化双酚A环氧树脂13-15份、聚全氟甲基异丙基醚3-5份、二月桂酸二正丁基锡0.05份、碳酸二甲酯10-10.5份、甲基异丁基酮3-3.5份、改性硅线石、纳米二硼化铬以及碱式硫酸镁晶须的混合物15-17份、三氟丙基甲基硅油0.2-0.4份以及聚酰胺蜡0.8-1.0份;B组分为六亚甲基二异氰酸酯三聚体;1. A wear-resistant and anti-corrosion coating, characterized in that it consists of component A and component B, the weight ratio of component A to component B is 10:1, component A is composed of the following raw materials in parts by weight: 30-32 parts of quaternary fluorocarbon resin, 10-12 parts of hydroxyl-terminated perfluoropolyether resin, 13-15 parts of hydrogenated bisphenol A epoxy resin, 3-5 parts of polyperfluoromethyl isopropyl ether, 0.05 parts of di-n-butyltin dilaurate, 10-10.5 parts of dimethyl carbonate, 3-3.5 parts of methyl isobutyl ketone, 15-17 parts of a mixture of modified sillimanite, nano-chromium diboride and basic magnesium sulfate whiskers, 0.2-0.4 parts of trifluoropropyl methyl silicone oil and 0.8-1.0 parts of polyamide wax; component B is hexamethylene diisocyanate trimer;其中:in:所述四元氟碳树脂的制备方法,由以下步骤组成:首先对高压反应釜抽真空、通氩气,使高压反应釜保持无水无氧环境,然后控制高压反应釜的压力为1.5MPa,先向其中加入溶剂,所述溶剂为1,1,2,2-四氟乙基-2,2,2-三氟乙基醚和二甲苯的混合物,然后加入1-辛烯-3-醇乙酸酯、4-羟丁基乙烯基醚、衣康酸以及偶氮二异丁腈,随后向高压反应釜中通入三氟氯乙烯气体,于73-75℃反应7h,待反应釜冷却至室温降压排出未反应的三氟氯乙烯气体,将所得液体采用乙醇沉淀并过滤,经索氏提取、烘干制备得到四元氟碳树脂;The preparation method of the quaternary fluorocarbon resin comprises the following steps: first, evacuating a high-pressure reactor and passing argon gas to maintain an anhydrous and oxygen-free environment in the high-pressure reactor; then controlling the pressure of the high-pressure reactor to 1.5 MPa; first, adding a solvent into the high-pressure reactor, wherein the solvent is a mixture of 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether and xylene; then, adding 1-octen-3-ol acetate, 4-hydroxybutyl vinyl ether, itaconic acid, and azobisisobutyronitrile; then, passing chlorotrifluoroethylene gas into the high-pressure reactor, reacting at 73-75° C. for 7 hours; cooling the reactor to room temperature, reducing the pressure, and discharging unreacted chlorotrifluoroethylene gas; precipitating the resulting liquid with ethanol, filtering, and performing Soxhlet extraction and drying to obtain the quaternary fluorocarbon resin;四元氟碳树脂的制备方法中三氟氯乙烯、4-羟丁基乙烯基醚、衣康酸、1-辛烯-3-醇乙酸酯四者的摩尔比为50:30:10:10;In the preparation method of the quaternary fluorocarbon resin, the molar ratio of trifluorochloroethylene, 4-hydroxybutyl vinyl ether, itaconic acid, and 1-octen-3-ol acetate is 50:30:10:10;所述端羟基全氟聚醚树脂的氟含量为42%,官能度为2,25℃的粘度为600mPa.s。The fluorine content of the hydroxyl-terminated perfluoropolyether resin is 42%, the functionality is 2, and the viscosity at 25° C. is 600 mPa.s.2.根据权利要求1所述的耐磨防腐涂料,其特征在于:四元氟碳树脂的制备方法中偶氮二异丁腈的质量占三氟氯乙烯、4-羟丁基乙烯基醚、衣康酸以及1-辛烯-3-醇乙酸酯四者质量和的0.7%。2. The wear-resistant and anti-corrosion coating according to claim 1, characterized in that the mass of azobisisobutyronitrile in the preparation method of the quaternary fluorocarbon resin accounts for 0.7% of the total mass of trifluorochloroethylene, 4-hydroxybutyl vinyl ether, itaconic acid and 1-octen-3-ol acetate.3.根据权利要求1所述的耐磨防腐涂料,其特征在于:四元氟碳树脂的制备方法中溶剂的体积占4-羟丁基乙烯基醚、衣康酸、1-辛烯-3-醇乙酸酯、偶氮二异丁腈以及溶剂体积和的60%;3. The wear-resistant and anti-corrosion coating according to claim 1, wherein the volume of the solvent in the preparation method of the quaternary fluorocarbon resin is 60% of the total volume of 4-hydroxybutyl vinyl ether, itaconic acid, 1-octen-3-ol acetate, azobisisobutyronitrile and the solvent;四元氟碳树脂的制备方法中1,1,2,2-四氟乙基-2,2,2-三氟乙基醚与二甲苯的体积比为3:1。In the preparation method of the tetrafluorocarbon resin, the volume ratio of 1,1,2,2-tetrafluoroethyl-2,2,2-trifluoroethyl ether to xylene is 3:1.4.根据权利要求1所述的耐磨防腐涂料,其特征在于:改性硅线石、纳米二硼化铬以及碱式硫酸镁晶须的混合物的制备方法,由以下步骤组成:将乙醇与去离子水混合制备得到混合液,加入KH-550硅烷偶联剂,于600r/min的转速下搅拌1.0h,然后加入硅线石粉末、纳米二硼化铬以及碱式硫酸镁晶须的混合物高速剪切50min,于55℃反应3h后真空抽滤,最后在真空条件下干燥处理,制备得到改性硅线石、纳米二硼化铬以及碱式硫酸镁晶须的混合物。4. The wear-resistant and anti-corrosion coating according to claim 1 is characterized in that the preparation method of the mixture of modified sillimanite, nano-chromium diboride and basic magnesium sulfate whisker comprises the following steps: mixing ethanol and deionized water to prepare a mixed solution, adding KH-550 silane coupling agent, stirring at a speed of 600 r/min for 1.0 h, then adding sillimanite powder, nano-chromium diboride and basic magnesium sulfate whisker to the mixture, high-speed shearing for 50 min, reacting at 55° C. for 3 h, vacuum filtering, and finally drying under vacuum conditions to prepare the mixture of modified sillimanite, nano-chromium diboride and basic magnesium sulfate whisker.5.根据权利要求4所述的耐磨防腐涂料,其特征在于:KH-550硅烷偶联剂、乙醇、去离子水的体积比为5:18:2;5. The wear-resistant and anti-corrosion coating according to claim 4, wherein the volume ratio of KH-550 silane coupling agent, ethanol, and deionized water is 5:18:2;KH-550硅烷偶联剂的质量占硅线石粉末、纳米二硼化铬以及碱式硫酸镁晶须质量和的2.0%;The mass of KH-550 silane coupling agent accounts for 2.0% of the total mass of sillimanite powder, nano-chromium diboride and basic magnesium sulfate whiskers;硅线石粉末、纳米二硼化铬、碱式硫酸镁晶须的质量比为3 : 0.9-1.1 : 0.8-1.0;The mass ratio of sillimanite powder, nano-chromium diboride, and basic magnesium sulfate whiskers is 3:0.9-1.1:0.8-1.0;改性硅线石、纳米二硼化铬以及碱式硫酸镁晶须的混合物制备过程中真空干燥温度为70℃,真空干燥时间为3h。During the preparation of the mixture of modified sillimanite, nano-chromium diboride and basic magnesium sulfate whiskers, the vacuum drying temperature is 70° C. and the vacuum drying time is 3 h.6.一种权利要求1所述的耐磨防腐涂料的制备方法,其特征在于:由以下步骤组成:6. A method for preparing the wear-resistant and anti-corrosion coating according to claim 1, characterized in that it comprises the following steps:(1)首先将氢化双酚A环氧树脂、碳酸二甲酯以及甲基异丁基酮混匀,然后加入四元氟碳树脂、端羟基全氟聚醚树脂以及聚全氟甲基异丙基醚进行共混,随后加入改性硅线石、纳米二硼化铬以及碱式硫酸镁晶须的混合物高速分散23-25min,加入聚酰胺蜡和二月桂酸二正丁基锡混合1.5h,最后加入三氟丙基甲基硅油搅拌3-5min,制备得到A组分;(1) First, hydrogenated bisphenol A epoxy resin, dimethyl carbonate and methyl isobutyl ketone are mixed, and then quaternary fluorocarbon resin, terminal hydroxyl perfluoropolyether resin and polyperfluoromethyl isopropyl ether are added and blended, and then a mixture of modified sillimanite, nano chromium diboride and basic magnesium sulfate whiskers is added and dispersed at high speed for 23-25 minutes, polyamide wax and di-n-butyltin dilaurate are added and mixed for 1.5 hours, and finally trifluoropropyl methyl silicone oil is added and stirred for 3-5 minutes to prepare component A;(2)将A组分与B组分按照重量比10:1混匀,制备得到耐磨防腐涂料。(2) Component A and component B were mixed in a weight ratio of 10:1 to prepare a wear-resistant and anti-corrosion coating.7.根据权利要求6所述的耐磨防腐涂料的制备方法,其特征在于:步骤(1)在制备A组分时搅拌转速为700r/min;7. The method for preparing the wear-resistant and anti-corrosion coating according to claim 6, characterized in that: in step (1), the stirring speed is 700 r/min when preparing component A;步骤(2)中搅拌转速为800r/min,搅拌时间为25-27min,搅拌温度为25℃。In step (2), the stirring speed is 800 r/min, the stirring time is 25-27 min, and the stirring temperature is 25°C.8.根据权利要求6所述的耐磨防腐涂料的制备方法,其特征在于:步骤(2)中喷涂耐磨防腐涂料后于室温下固化36h。8. The method for preparing the wear-resistant and anti-corrosion coating according to claim 6, characterized in that: after spraying the wear-resistant and anti-corrosion coating in step (2), the coating is cured at room temperature for 36 hours.
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