A zinc powder composite anticorrosive coating and a preparation method thereof

Abstract

The application discloses a zinc powder composite anticorrosive paint and a preparation method thereof, and relates to the technical field of zinc powder composite anticorrosive paint.The zinc powder composite anticorrosive paint is composed of component A and component B, wherein component A is prepared from the following raw materials in mass fractions: 30-35 mass parts of epoxy resin, 8-12 mass parts of toughening diluent, 0.8-1.5 mass parts of carbon nanotubes, 7-10 mass parts of glass flake, 20-25 mass parts of zinc powder, 8-12 mass parts of pigment and filler, 1-1.5 mass parts of surface modifier, 3-4 mass parts of additive, and 10-13 mass parts of solvent; and component B is prepared from the following raw materials in mass fractions: 10-14 mass parts of curing agent and 1-2 mass parts of adhesion promoter.The zinc powder composite anticorrosive paint has good adhesion, wear resistance, impact resistance and salt spray resistance compared with the epoxy zinc-rich paint, and the preparation process is simple, so that the zinc powder composite anticorrosive paint is suitable for large-scale popularization and application.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of zinc powder composite anticorrosive paint, in particular to a zinc powder composite anticorrosive paint and a preparation method thereof. BACKGROUND

[0002] In the prior art, the epoxy zinc-rich primer occupies an important position in the domestic anticorrosive paint market. Due to its excellent corrosion protection performance, the epoxy zinc-rich primer is widely used in the anticorrosive coating of steel facilities and equipment, especially in the heavy-duty anticorrosive fields such as chemical industry, construction, offshore platform, ship, bridge, etc. The corrosion protection mechanism of the epoxy zinc-rich primer mainly depends on the zinc powder therein. The zinc powder protects the steel substrate by means of sacrificial anode in the corrosive environment, and the zinc salt protection film formed can also prevent the invasion of corrosive media;

[0003] The high content of zinc powder in the epoxy zinc-rich primer also brings a series of problems. First, the high content of zinc powder provides strong cathodic protection, but also means that only about 1 / 3 of the zinc powder in communication with the steel surface can participate in the cathodic protection, and about 2 / 3 of the isolated zinc powder has no activity. When corrosion occurs, the active zinc powder is gradually oxidized into insulating zinc salt, causing the conductive path to be damaged and the cathodic protection to fail. In addition, the use of a large amount of zinc powder reduces the proportion of film-forming substances and freely adjustable components in the formula, resulting in poor toughness and brittleness of the paint film, and the occurrence of paint film cracking, stress corrosion, weld corrosion and other failure phenomena. At the same time, the use of a large amount of zinc powder also leads to poor performance of the paint film in terms of density and adhesion, making the coated film prone to blistering, peeling, rusting and other phenomena.

[0004] In order to save resources and reduce energy consumption, in recent years, there has been an increasing trend of reducing the amount of zinc powder and replacing zinc powder by adding nano materials and sheet materials. The development of these technologies is expected to break through the limitations of existing technologies, change the existing anticorrosive market competition pattern, bring a new direction for the application of epoxy zinc-rich primer, and at the same time, it is also in line with the global trend of sustainable development, reducing dependence on limited resources and reducing environmental impact, bringing a more green and efficient solution to the anticorrosive paint industry. SUMMARY

[0005] The present application aims to solve the problems existing in the prior art and provides a zinc powder composite anticorrosive paint and a preparation method thereof.

[0006] In order to achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0007] A zinc powder composite anticorrosive paint, the paint is composed of component A and component B, the component A contains the following raw materials by mass:

[0008] Epoxy resin: 30-35 parts by mass, epoxy equivalent weight: 400-600 g / eq;

[0009] Toughening diluent: 8-12 parts by mass, viscosity of 30-1200 mPa·s (25℃);

[0010] Carbon nanotubes: 0.8-1.5 parts by mass, at least one of hydroxylated carbon nanotubes, carboxylated carbon nanotubes, hydroxyl or carboxyl content of 1-4wt%, length of 10-50μm;

[0011] Glass flake: 7-10 parts by mass, mesh of 300-400 mesh;

[0012] Zinc powder: 20-25 parts by mass, mesh of 500-1000 mesh;

[0013] Color filler: 8-12 parts by mass, at least one of titanium dioxide, barium sulfate, talc;

[0014] Surface modifier: 1-1.5 parts by mass, at least one of 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane;

[0015] Auxiliary agent: 3-4 parts by mass, at least one of dispersant, thickening agent, defoaming agent, leveling agent;

[0016] Solvent: 10-13 parts by mass, at least one of dibutyl ester, xylene, n-butanol;

[0017] The B component contains the following parts by mass of raw materials:

[0018] Curing agent: 10-14 parts by mass, at least one of phenolic amide curing agent, polyamide curing agent, phenolic amine curing agent;

[0019] Adhesion promoter: 1-2 parts by mass, at least one of 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane.

[0020] Preferably: the epoxy resin in the A component contains epoxy groups, the curing agent in the B component contains active hydrogen atoms, and when mixed, the epoxy groups and active hydrogen atoms in the curing agent undergo ring-opening addition reaction to form a three-dimensional network structure to form a resin matrix of the anticorrosive coating.

[0021] Further, the surface modifier contains epoxy groups and siloxy groups, wherein the siloxy groups can react with the hydroxyl groups and carboxyl groups on the surface of the hydroxylated carbon nanotubes (the surface mainly contains hydroxyl groups), the carboxylated carbon nanotubes (the surface mainly contains carboxyl groups), and the glass flake (the surface mainly contains hydroxyl groups) to form covalent bonds.

[0022] Further, the epoxy groups have affinity with the epoxy resin and can react with the curing agent in the B component to form covalent bonds.

[0023] As a preferred scheme of the present application, the solvent modifies the liquid matrix of the carbon nanotubes and the glass flake.

[0024] A preparation method of a zinc powder composite anticorrosive coating, comprising the following steps:

[0025] S1: sequentially adding a toughening diluent, a dispersant, and carbon nanotubes into a solvent, treating under ultrasonic frequency, then adding glass flake and a surface modifier, and stirring to obtain a modified carbon nanotube / glass flake mixture;

[0026] S2: adding an epoxy resin and pigments and fillers into the mixture obtained in step S1, stirring, then sequentially adding zinc powder, a thickening agent, a leveling agent, and a defoaming agent, and continuing to stir to obtain a A component;

[0027] S3: adding an adhesion promoter into a curing agent, and stirring to obtain a B component;

[0028] S4: mixing the A component obtained in step S2 and the B component obtained in step S3, and stirring to obtain a zinc powder composite anticorrosive coating.

[0029] As a further scheme of the present application, in step S1, the ultrasonic frequency is 40 kHz, the treatment time is 20-45 minutes, the stirring speed is 800-1200 rpm, and the stirring time is 30-60 minutes.

[0030] Based on the foregoing scheme, in step S2, the stirring speed is 1200-1500 rpm, and the stirring time is 50-100 minutes.

[0031] Based on the foregoing scheme, in step S3, the stirring speed is 1500-2000 rpm, and the stirring time is 5-10 minutes.

[0032] Based on the foregoing scheme, in step S4, the stirring speed is 1100-1500 rpm, and the stirring time is 3-5 minutes.

[0033] The present application has the following beneficial effects:

[0034] A zinc powder composite anti-corrosion coating and a preparation method thereof. By modifying carbon nanotubes, glass flakes, and zinc powder in the composite anti-corrosion coating, the modified carbon nanotubes, glass flakes, and zinc powder have a synergistic interaction, so that the coating has excellent comprehensive properties (including wear resistance, adhesion, impact resistance, salt spray resistance, etc.), and has significant performance advantages over traditional epoxy zinc-rich anti-corrosion coatings. At the same time, the coating uses a small amount of zinc powder and is low in cost, making it suitable for large-scale promotion and application.

[0035] A zinc powder composite anti-corrosion coating and a preparation method thereof are disclosed. The preparation process of the zinc powder composite anti-corrosion coating is simple and suitable for large-scale preparation by modifying carbon nanotubes, glass flakes and zinc powder. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 The present invention provides a schematic flow chart of a method for preparing a zinc powder composite anti-corrosion coating. DETAILED DESCRIPTION

[0037] The technical solution of this patent is further described in detail below in conjunction with specific implementation methods.

[0038] The following describes in detail embodiments of the present invention, examples of which are shown in the accompanying drawings, wherein the same or similar reference numerals throughout represent the same or similar elements or elements having the same or similar functions. The embodiments described below with reference to the accompanying drawings are exemplary and are only used to explain the present invention, and should not be construed as limiting the present invention.

[0039] Example 1:

[0040] A zinc powder composite anti-corrosion coating, comprising component A and component B, wherein component A is made from the following raw materials: 30-35 parts by mass of epoxy resin, 8-12 parts by mass of toughening diluent, 0.8-1.5 parts by mass of carbon nanotubes, 7-10 parts by mass of glass flakes, 20-25 parts by mass of zinc powder, 8-12 parts by mass of pigments and fillers, 1-1.5 parts by mass of surface modifiers, 3-4 parts by mass of additives, and 10-13 parts by mass of solvents;

[0041] Component B is made of the following raw materials: 10-14 parts by mass of curing agent and 1-2 parts by mass of adhesion promoter;

[0042] The epoxy equivalent weight of the epoxy resin is 400-600 g / eq;

[0043] The viscosity of the toughening diluent is 30-1200 mPa·s (25°C);

[0044] The carbon nanotubes are at least one of hydroxylated carbon nanotubes and carboxylated carbon nanotubes, with a hydroxyl or carboxyl content of 1-4 wt% and a length of 10-50 μm;

[0045] The glass flake has a mesh number of 300-400 mesh;

[0046] The zinc powder has a mesh number of 500-1000 mesh

[0047] The pigment and filler is at least one of titanium dioxide, barium sulfate, and talcum powder;

[0048] The surface modifier is at least one of 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane;

[0049] The auxiliary agent is at least one of a dispersing agent, a thickening agent, an antifoaming agent, and a leveling agent;

[0050] The solvent is at least one of dibutyl ester, dimethylbenzene, and n-butanol;

[0051] The curing agent is at least one of a phenolic amide curing agent, a polyamide curing agent, and a phenolic amine curing agent;

[0052] The adhesion promoter is at least one of 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane;

[0053] The epoxy resin in the A component contains epoxy groups, and the curing agent in the B component contains active hydrogen atoms, when the two components are mixed, the epoxy groups react with the active hydrogen atoms in the curing agent through ring-opening addition reaction to form a three-dimensional network structure, thereby forming the resin matrix of the anticorrosive coating of the present application;

[0054] The toughening diluent not only serves as a liquid matrix for modification of the carbon nanotubes and the glass flake together with the solvent, but also can reduce the viscosity of the coating and improve the toughness of the coating film;

[0055] The carbon nanotubes not only can enhance the toughness of the coating film, but also can form a stable conductive grid in the coating through its one-dimensional linear structure, effectively improve the utilization rate of the zinc powder, enhance the cathodic protection performance of the zinc powder, and reduce the amount of the zinc powder;

[0056] The glass flake has a two-dimensional sheet structure and high hardness, when arranged layer by layer in the coating, the formed labyrinth structure can enhance the compactness of the coating, reduce the pores formed by the stacking of the spherical zinc powder and the pigment and filler in the coating, and significantly improve the permeation resistance, corrosion resistance life, and wear resistance of the coating;

[0057] Zinc powder has a one-dimensional spherical structure and preferentially undergoes oxidation in a corrosive environment, thereby protecting the iron substrate from corrosion. Therefore, zinc powder in the coating provides cathodic protection for metals such as steel by sacrificing itself. Through the synergistic interaction with modified carbon nanotubes and glass flakes, the coating has excellent anti-corrosion properties.

[0058] Pigments and fillers can not only reduce the cost of coatings, provide the color and hiding power required by the coating, but also improve the mechanical and construction properties of the coating;

[0059] The surface modifier contains epoxy and silanoxy groups. The silanoxy groups can react with the hydroxyl and carboxyl groups on the surfaces of hydroxylated carbon nanotubes (mainly containing hydroxyl groups on the surface), carboxylated carbon nanotubes (mainly containing carboxyl groups on the surface), and glass flakes (mainly containing hydroxyl groups on the surface) to form covalent bonds. The epoxy groups not only have affinity with epoxy resins, thereby improving the dispersion properties of carbon nanotubes and glass flakes, but can also react with the curing agent in component B to form covalent bonds, further enhancing the bonding between carbon nanotubes and glass flakes and the epoxy resin base material, thereby transferring their excellent properties to the coating.

[0060] The additives in the present invention have the functions of promoting the dispersion of carbon nanotubes and pigments and fillers, adjusting the viscosity of the coating, promoting the parallel arrangement of glass flakes, and eliminating bubbles in the coating;

[0061] The solvent not only serves as a liquid matrix for the modification of carbon nanotubes and glass flakes, but also has the function of adjusting the viscosity of the coating and improving the processing and construction properties of the coating;

[0062] The adhesion promoter used in the present invention is used to improve the adhesion of the coating film on the surface of the steel substrate.

[0063] Example 2:

[0064] A method for preparing a zinc powder composite anti-corrosion coating comprises the following steps:

[0065] S1: 10 parts by weight of a toughening diluent (Cardolite LITE 547LV, 700 mPa·s), 1 part by weight of a dispersant (Aiketron ECO-2900), and 1.2 parts by weight of carbon nanotubes (Xianfeng Nano, hydroxylated multi-walled carbon nanotubes, hydroxyl content 3.06 wt%, length 10-30 μm) were added sequentially to 11 parts by weight of a solvent (xylene:n-butanol mass ratio of 4:1) and treated at a 40 kHz ultrasonic frequency for 30 minutes. Then, 8 parts by weight of glass flakes (Xuhan, 400 mesh) and 1.3 parts by weight of a surface modifier (2-(3,4-epoxycyclohexyl)ethyltriethoxysilane) were added, and the mixture was stirred at 1000 rpm for 45 minutes to obtain a modified carbon nanotube / glass flake mixture.

[0066] S2: 32 parts by mass of epoxy resin (Nanya NPES-901, 450-500 g / eq), 10 parts by mass of pigment and filler (mass ratio of titanium dioxide, barium sulfate and talc is 2:2:3) were added to the modified carbon nanotube / glass flake mixed solution described in step S1, stirred at 1300 rpm for 80 min, then 23 parts by mass of zinc powder (Xiangcheng Chemical, 1000 mesh), 0.5 parts by mass of thickening agent (Gida Chemical J0602), 1 part by mass of leveling agent (Bayer BYK-354), 1 part by mass of defoaming agent (Bayer BYK-1765) were added in turn at a stirring speed of 700 rpm, and after stirring for 20 min, the A component was obtained;

[0067] S3: 1.5 parts by mass of adhesion promoter (3-aminopropyl methyl dimethoxy silane) was added to 12 parts by mass of curing agent (Junjiang D8115A), stirred at 1800 rpm for 9 min to obtain the B component;

[0068] S4: The A component obtained in step S2 and the B component obtained in step S3 were mixed, and stirred at 1200 rpm for 5 min to obtain the modified carbon nanotube / glass flake / zinc powder composite anticorrosive coating.

[0069] Example 3:

[0070] A method for preparing a zinc powder composite anticorrosive coating, comprising the following steps:

[0071] S1: 8 parts by mass of toughening diluent (Caldic LITE 2100R, 500-1000 mPa·s), 0.8 parts by mass of dispersant (Eco-creative ECO-2900), 1 part by mass of carbon nanotube (Xianfeng nano, carboxylated multi-walled carbon nanotube, carboxyl content 2wt%, length 10-30 μm) were added to 13 parts by mass of solvent (mass ratio of dibutyl ester, xylene and n-butanol is 3:4:1) in turn, treated under 40 kHz ultrasonic frequency for 35 min, then 7 parts by mass of glass flake (Baijiang, 325 mesh) and 1 part by mass of surface modifier (3-glycidyl ether propyl methyl diethoxy silane) were added, and stirred at 800 rpm for 50 min to obtain a modified carbon nanotube / glass flake mixed solution;

[0072] S2: 34 parts by mass of epoxy resin (Dow DER 671, 475-550 g / eq), 8 parts by mass of pigment and filler (mass ratio of titanium dioxide to talc is 3:2) were weighed into the modified carbon nanotube / glass flake mixture solution described in step S1, stirred at 1200 rpm for 70 min, then 25 parts by mass of zinc powder (Xiangcheng Chemical, 800 mesh), 0.2 parts by mass of thickening agent (Gida Chemical J0602), 1 part by mass of leveling agent (BYK-354, BYK Chemical), 1 part by mass of defoaming agent (BYK-A530, BYK Chemical) were added in turn at 800 rpm, and stirred for 15 min to obtain component A;

[0073] S3: 2 parts by mass of adhesion promoter (3-aminopropylmethyldiethoxysilane) was added to 10 parts by mass of curing agent (Yingchuang Ancamide 350A), stirred at 1600 rpm for 5 min to obtain component B;

[0074] S4: The component A obtained in step S2 and the component B obtained in step S3 were mixed, and stirred at 1500 rpm for 3 min to obtain a modified carbon nanotube / glass flake / zinc powder composite anticorrosive coating.

[0075] Example 4:

[0076] A method for preparing a zinc powder composite anticorrosive coating, comprising the following steps:

[0077] S1: 12 parts by mass of toughening diluent (Huisheng Electronic Materials Co., Ltd. D-1217, 40-70 mPa·s), 1 part by mass of dispersant (BYK-9076, BYK Chemical), 1.5 parts by mass of carbon nanotube (Suzhou Carbon Fortune, hydroxylated multi-walled carbon nanotube, hydroxyl content ~2wt%, length 30-50 μm) were added in turn into 12 parts by mass of solvent (mass ratio of dibutyl ester to n-butanol is 5:1), treated under 40 kHz ultrasonic frequency for 45 min, then 10 parts by mass of glass flake (Xuhan, 400 mesh) and 1.5 parts by mass of surface modifier (3-glycidyloxypropylmethyldimethoxysilane) were added, and stirred at 500 rpm for 30 min to obtain a modified carbon nanotube / glass flake mixture solution;

[0078] S2: 30 parts by mass of epoxy resin (Nanya NPES-901, 450-500 g / eq), 9 parts by mass of pigment and filler (mass ratio of titanium dioxide to barium sulfate is 2:5) were added to the modified carbon nanotube / glass flake mixed solution described in step S1, stirred at 1500 rpm for 50 min, then 20 parts by mass of zinc powder (Xiangda Chemical, 500 mesh), 1 part by mass of thickening agent (Gida Chemical J0602), 1 part by mass of leveling agent (Bayer BYK-354), 1 part by mass of defoaming agent (Bayer BYK-A530) were added in turn at 600 rpm, and stirred for 30 min to obtain component A;

[0079] S3: 2 parts by mass of adhesion promoter (3-aminopropyltrimethoxysilane) was added to 14 parts by mass of curing agent (Caldery NX-2003D), stirred at 2000 rpm for 6 min to obtain component B;

[0080] S4: The component A obtained in step S2 and the component B obtained in step S3 were mixed, stirred at 1400 rpm for 4 min to obtain a modified carbon nanotube / glass flake / zinc powder composite anticorrosive coating.

[0081] Example 5:

[0082] A method for preparing a zinc powder composite anticorrosive coating, comprising the following steps:

[0083] S1: 9 parts by mass of toughening diluent (Huisheng Electronic Materials Co., Ltd. YM-004, 55-95 mPa·s), 1 part by mass of dispersant (Bayer BYK-9076), 0.8 parts by mass of carbon nanotube (Macklin, hydroxylated multi-walled carbon nanotube, hydroxyl content ~3.7wt%, length ~50μm) were added in turn to 10 parts by mass of solvent (mass ratio of dibutyl ester to xylene is 3:4), treated under 40 kHz ultrasonic frequency for 40 min, then 9 parts by mass of glass flake (Xingshui, 325 mesh) and 1.2 parts by mass of surface modifier (3-glycidyloxypropyltriethoxysilane) were added, and stirred at 600 rpm for 60 min to obtain a modified carbon nanotube / glass flake mixed solution;

[0084] S2: 35 parts by mass of epoxy resin (Balin Petrochemical CYD-011, 454-555 g / eq), 9 parts by mass of pigment and filler (mass ratio of barium sulfate to talc is 3:7) were added to the modified carbon nanotube / glass flake mixture solution described in step S1, stirred at 1400 rpm for 100 min, then 22 parts by mass of zinc powder (size chemical, 800 mesh), 1 part by mass of thickening agent (Gida Chemical J0602), 1 part by mass of leveling agent (BYK-354, BYK Chemical), 1 part by mass of defoaming agent (BYK-1765, BYK Chemical) were added in turn at a stirring speed of 700 rpm, and after stirring for 25 min, a component A was obtained;

[0085] S3: 1 part by mass of adhesion promoter (3-aminopropyl triethoxysilane) was added to 13 parts by mass of curing agent (Junjiang D650A), stirred at 1500 rpm for 8 min to obtain component B;

[0086] S4: The component A obtained in step S2 and the component B obtained in step S3 were mixed, and stirred at 1300 rpm for 3 min to obtain a modified carbon nanotube / glass flake / zinc powder composite anticorrosive coating.

[0087] Example 6:

[0088] A method for preparing a zinc powder composite anticorrosive coating, comprising the following steps:

[0089] S1: 10 parts by mass of toughening diluent (Caldic LITE 513DF, 90-200 mPa·s), 1 part by mass of dispersant (BASF Efka PX 4703), 1.3 parts by mass of carbon nanotube (Nanjing Suzhan Intelligent Technology, carboxylated multi-walled carbon nanotube, carboxyl content 1.28 wt%, length 10-50 μm) were added to 10 parts by mass of solvent (dibutyl ester, xylene and n-butanol in a mass ratio of 1:4:1) in turn, treated under ultrasonic frequency of 40 kHz for 35 min, then 10 parts by mass of glass flake (Hangshuai, 325 mesh) and 1.2 parts by mass of surface modifier (3-glycidyl ether propyl trimethoxysilane) were added, and stirred at a stirring speed of 700 rpm for 55 min to obtain a modified carbon nanotube / glass flake mixture solution;

[0090] S2: 31 parts by mass of epoxy resin (Nanya NPES-901, 450-500 g / eq), 12 parts by mass of pigment and filler (titanium dioxide, barium sulfate and talc in a mass ratio of 5:2:3) were weighed into the modified carbon nanotube / glass flake mixed solution described in step S1, stirred at a speed of 1300 rpm for 90 min, then 21 parts by mass of zinc powder (Size Chemical, 1000 mesh), 0.5 parts by mass of thickener (Gyoda Chemical J0602), 1 part by mass of leveling agent (BYK-354, BYK Chemical), 1 part by mass of defoaming agent (BYK-1765, BYK Chemical) were added in turn at a speed of 600 rpm, and after stirring for 20 min, the A component was obtained;

[0091] S3: 1.5 parts by mass of adhesion promoter (3-aminopropyl methyldiethoxysilane) was added to 11 parts by mass of curing agent (Caldic LITE 3040), stirred at a speed of 1700 rpm for 10 min to obtain the B component;

[0092] S4: The A component obtained in step S2 and the B component obtained in step S3 were mixed and stirred at a speed of 1100 rpm for 5 min to obtain the modified carbon nanotube / glass flake / zinc powder composite anticorrosive coating.

[0093] Comparative Example 1

[0094] This comparative example prepared a modified glass flake / zinc powder composite anticorrosive coating without carbon nanotubes by the following steps:

[0095] S1: 10 parts by mass of toughening diluent (Caldic LITE 547LV, 700 mPa·s), 1 part by mass of dispersant (ECO-2900, Eco-chem), 8 parts by mass of glass flake (Xuhan, 400 mesh) and 1.3 parts by mass of surface modifier (2- (3, 4-epoxycyclohexyl) ethyl triethoxysilane) were added in turn into 11 parts by mass of solvent (xylene and n-butanol in a mass ratio of 4:1), stirred at a speed of 1000 rpm for 45 min to obtain a modified glass flake mixed solution;

[0096] S2: 32 parts by mass of epoxy resin (Nanya NPES-901, 450-500 g / eq), 10 parts by mass of pigment and filler (titanium dioxide, barium sulfate and talc in a mass ratio of 2:2:3) were weighed into the modified glass flake mixed solution described in step S1, stirred at a speed of 1300 rpm for 80 min, then 24.2 parts by mass of zinc powder (Size Chemical, 1000 mesh), 0.5 parts by mass of thickener (Gyoda Chemical J0602), 1 part by mass of leveling agent (BYK-354, BYK Chemical), 1 part by mass of defoaming agent (BYK-1765, BYK Chemical) were added in turn at a speed of 700 rpm, and after stirring for 20 min, the A component was obtained;

[0097] S3: 1.5 parts by mass of an adhesion promoter (3-aminopropylmethyldimethoxysilane) was added to 12 parts by mass of a curing agent (Junjin D8115A), and stirred at 1800 rpm for 9 min to obtain Component B;

[0098] S4: Component A obtained in Step S2 and Component B obtained in Step S3 were mixed, and stirred at 1200 rpm for 5 min to obtain the modified glass flake / zinc powder composite anticorrosive coating without carbon nanotubes.

[0099] Comparative Example 2

[0100] The modified carbon nanotube / zinc powder composite anticorrosive coating without glass flakes was prepared by the following steps:

[0101] S1: 10 parts by mass of a toughening diluent (Kadox LITE 547LV, 700 mPa s), 1 part by mass of a dispersant (Eccoclean ECO-2900), 1.2 parts by mass of carbon nanotubes (Xianfeng Nanometer, hydroxylated multi-walled carbon nanotubes, hydroxyl content 3.06 wt%, length 10-30 pm) were sequentially added to 11 parts by mass of a solvent (dichlorobenzene and n-butanol in a mass ratio of 4:1), treated at an ultrasonic frequency of 40 kHz for 30 min, then 1.3 parts by mass of a surface modifier (2-(3,4-epoxycyclohexyl) ethyl triethoxysilane) was added, and stirred at 1000 rpm for 45 min to obtain a modified carbon nanotube mixture;

[0102] S2: 32 parts by mass of an epoxy resin (Nanya NPES-901, 450-500 g / eq), 10 parts by mass of pigments and fillers (titanium dioxide, barium sulfate, and talc in a mass ratio of 2:2:3) were added to the modified carbon nanotube mixture of Step S1, and stirred at 1300 rpm for 80 min, then 31 parts by mass of zinc powder (Size Chemical, 1000 mesh), 0.5 parts by mass of a thickening agent (Gyoda Chemical J0602), 1 part by mass of a leveling agent (BYK-354, BYK-Chemie), 1 part by mass of a defoaming agent (BYK-1765, BYK-Chemie) were sequentially added at a stirring speed of 700 rpm, and stirred for 20 min to obtain Component A;

[0103] S3: 1.5 parts by mass of an adhesion promoter (3-aminopropylmethyldimethoxysilane) was added to 12 parts by mass of a curing agent (Junjin D8115A), and stirred at 1800 rpm for 9 min to obtain Component B;

[0104] S4: Component A obtained in Step S2 and Component B obtained in Step S3 were mixed, and stirred at 1200 rpm for 5 min to obtain the modified carbon nanotube / zinc powder composite anticorrosive coating without glass flakes.

[0105] Comparative Example 3

[0106] The comparative example 1 was prepared by the following steps to prepare a traditional epoxy zinc-rich coating without carbon nanotubes and glass flake;

[0107] S1: 20 parts by mass of epoxy resin (Nanya NPES-901, 450-500 g / eq), 60 parts by mass of zinc powder (Xianghua Chemical, 1000 mesh), 0.5 parts by mass of thickening agent (Gida Chemical J0602), 1 part by mass of leveling agent (BYK-354, BYK Chemical), 1 part by mass of defoaming agent (BYK-1765, BYK Chemical) were added to 18.5 parts by mass of solvent (mass ratio of xylene to n-butanol was 4:1), and after stirring at 1200 rpm for 45 min, the A component was obtained;

[0108] S2: 1.5 parts by mass of adhesion promoter (3-aminopropyl methyldimethoxysilane) was added to 6 parts by mass of curing agent (Junjiang D8115A), and stirred at 1800 rpm for 9 min to obtain the B component;

[0109] S4: The A component obtained in step S2 and the B component obtained in step S3 were mixed and stirred at 1200 rpm for 5 min to obtain a traditional epoxy zinc-rich coating without carbon nanotubes and glass flake.

[0110] The anti-corrosion coatings prepared in Examples 2-6 and Comparative Examples 1-3 were used to prepare test samples according to the standard "GB / T 9271-2008 Standard Test Panels for Color Coatings", and the non-volatile content, adhesion, abrasion resistance, impact resistance, and salt spray resistance were tested according to the standard. The non-volatile content test was based on "GB / T 1725-2007 Determination of Non-volatile Content of Paints, Varnishes and Plastics"; the adhesion test was based on "GB / T 5210-2006 Adhesion Test of Paints and Varnishes by Pull-off Method"; the abrasion resistance test was based on "GB / T 1768-2006 Determination of Abrasion Resistance of Paints and Varnishes by Rotary Rubber Sanding Wheel Method" with 1000 g / 1000 r, and the sanding wheel type was CS-17; the impact resistance test was based on "GB / T 1732-2020 Paint Film Impact Resistance Test Method", and the weight of the weight was 1000 g; the salt spray resistance test was based on "GB / T 1771-2007 Determination of Neutral Salt Spray Resistance of Paints and Varnishes". The test results are shown in Table 1:

[0111] Table 1 Comparison of test properties of Examples 2-6 and Comparative Examples 1-3

[0112]

[0113] As can be seen from Table 1, the comparison between the modified carbon nanotube / glass flake / zinc powder composite anticorrosive coating of Examples 2-6 and the modified glass flake / zinc powder composite anticorrosive coating of Comparative Example 1 not containing carbon nanotubes, and the modified carbon nanotube / zinc powder composite anticorrosive coating of Comparative Example 2 not containing glass flakes, shows that there is a synergistic interaction between carbon nanotubes, glass flakes and zinc powder in the modified carbon nanotube / glass flake / zinc powder composite anticorrosive coating, and both of them have a promoting effect on enhancing the comprehensive performance (such as adhesion, wear resistance, impact resistance, salt spray resistance, etc.) of the coating;

[0114] Compared with the traditional epoxy zinc-rich coating of Comparative Example 3 not containing carbon nanotubes and glass flakes, the modified carbon nanotube / glass flake / zinc powder composite anticorrosive coating of Examples 2-6 of the present application has a significant performance advantage, and has a higher content of non-volatile matter and a lower amount of organic solvent.

[0115] The above describes the preferred specific embodiments of the present application, and the protection scope of the present application is not limited thereto, any modification, equivalent replacement and improvement made by any person skilled in the art within the technical scope disclosed by the present application, combining the prior art or public common knowledge, within the spirit and principle of the present application, should be covered within the protection scope of the present application.

Claims

1. A zinc powder composite anti-corrosion coating, characterized in that: The coating is composed of component A and component B, wherein component A contains the following raw materials in parts by mass: Epoxy resin: 30-35 parts by mass, epoxy equivalent weight 400-600 g / eq; Toughening diluent: 8-12 parts by mass, viscosity 30-1200 mPa·s (25°C); Carbon nanotubes: 0.8-1.5 parts by weight, at least one of hydroxylated carbon nanotubes and carboxylated carbon nanotubes, with a hydroxyl or carboxyl group content of 1-4 wt% and a length of 10-50 μm; Glass flakes: 7-10 parts by mass, 300-400 mesh; Zinc powder: 20-25 parts by mass, mesh size 500-1000 mesh; Pigment and filler: 8-12 parts by mass, at least one of titanium dioxide, barium sulfate, and talc; Surface modifier: 1-1.5 parts by mass, at least one selected from 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; Additives: 3-4 parts by mass, at least one of a dispersant, a thickener, a defoamer, and a leveling agent; Solvent: 10-13 parts by mass, at least one of dibutyl ether, xylene, and n-butanol; The second component comprises the following raw materials in parts by mass: Curing agent: 10-14 parts by mass, at least one of a phenolic amide curing agent, a polyamide curing agent, and a phenalkamine curing agent; Adhesion promoter: 1-2 parts by mass, at least one selected from 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, 3-aminopropyltrimethoxysilane, and 3-aminopropyltriethoxysilane.

2. A method for preparing the zinc powder composite anti-corrosion coating according to claim 1, characterized in that: The following steps are involved: S1: A toughening diluent, a dispersant, and carbon nanotubes are sequentially added to a solvent, treated under ultrasonic frequency, and then glass flakes and a surface modifier are added and stirred to obtain a modified carbon nanotube / glass flake mixture; S2: adding epoxy resin and pigments and fillers to the mixed solution obtained in step S1, stirring, then sequentially adding zinc powder, thickener, leveling agent, and defoaming agent, and continuing to stir to obtain component A; S3: adding the adhesion promoter to the curing agent and stirring to obtain component B; S4: Component A obtained in step S2 and component B obtained in step S3 are mixed and stirred to obtain a zinc powder composite anti-corrosion coating.

3. A zinc powder composite anti-corrosion coating and a preparation method thereof according to claim 2, characterized in that: In step S1, the ultrasonic frequency is 40 kHz, the treatment time is 20-45 minutes, the stirring speed is 800-1200 rpm, and the stirring time is 30-60 minutes.

4. A zinc powder composite anti-corrosion coating and a preparation method thereof according to claim 3, characterized in that: In step S2, the stirring speed is 1200-1500 rpm, and the stirring time is 50-100 minutes.

5. A zinc powder composite anti-corrosion coating and a preparation method thereof according to claim 4, characterized in that: In step S3, the stirring speed is 1500-2000 rpm, and the stirring time is 5-10 minutes.

6. A zinc powder composite anti-corrosion coating and a preparation method thereof according to claim 5, characterized in that: In step S4, the stirring speed is 1100-1500 rpm, and the stirring time is 3-5 minutes.

Images