Polyaniline amorphous anticorrosive coating and preparation method thereof

Abstract

The present application provides a kind of polyaniline amorphous anticorrosive coating, including component A and component B, component A includes 25 mass parts-40 mass parts water-based epoxy resin, 20 mass parts-30 mass parts micrometre flaky amorphous alloy, 5 mass parts-10 mass parts doped polyaniline, 10 mass parts-20 mass parts filler and 4 mass parts-7 mass parts first auxiliary agent;Component B includes 10 mass parts-20 mass parts water-based curing agent and 1 mass parts-3 mass parts second auxiliary agent.The preparation method of polyaniline amorphous anticorrosive coating is also provided.The polyaniline amorphous anticorrosive coating of the present application has super high adhesion, hardness, acid resistance, alkali resistance and salt fog resistance on metal surface, and uses water-based formula, avoids the use of a large amount of organic solvent, green and environmental protection.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of coating, more particularly, to the technical field of anticorrosive coating, and particularly relates to a kind of polyaniline amorphous anticorrosive coating and preparation method thereof. BACKGROUND

[0002] The material that is coated on the surface of object and can be well bonded with base material and form complete and tough protective film is called coating. The function of coating can be summarized into three aspects: protective function, decorative function and special function.

[0003] Metal corrosion is a universal problem worldwide, especially in marine, chemical, construction and other environments, the problem of metal corrosion is particularly serious, resulting in huge economic losses and safety hazards.

[0004] Traditional anticorrosive coatings, such as zinc-rich epoxy primer, lack effective electrochemical protection mechanism and have low coating density. Although they can slow down corrosion to some extent, they have problems such as poor adhesion, low hardness, poor chemical resistance (acid, alkali) and poor salt spray resistance, resulting in short protection period of metal, easy to break during transportation and installation, and cannot meet the durability requirements of long-term exposure to harsh environments, frequent maintenance and updating are required. At the same time, most of the traditional anticorrosive coatings use organic solvents as solvent or dispersion medium, containing a large amount of VOC (volatile organic compounds), which not only affects the environment and human health, but also has the risk of fire and explosion during transportation, storage and use, so it faces the double problems of environmental protection and safety.

[0005] In order to solve these problems, the coating industry is actively developing new anticorrosive coatings, such as environmentally friendly and high durability anticorrosive coatings, to meet the higher requirements of modern industry for corrosion resistance. SUMMARY

[0006] In order to overcome the above-mentioned shortcomings of the prior art, one object of the present application is to provide a kind of polyaniline amorphous anticorrosive coating, which has super high adhesion, hardness, acid resistance, alkali resistance and salt spray resistance on the surface of metal, and uses water-based formula, avoids the use of a large amount of organic solvent, is green and environmentally friendly, and is suitable for large-scale popularization and application.

[0007] Another object of the present application is to provide a preparation method of polyaniline amorphous anticorrosive coating, which is ingenious in design, simple in process, easy to operate, low in production cost, and suitable for large-scale popularization and application.

[0008] To achieve the above objects, in the first aspect of the present application, a kind of polyaniline amorphous anticorrosive coating is provided, which is characterized by comprising component A and component B, wherein:

[0009] The A component comprises 25-40 parts by mass of an aqueous epoxy resin, 20-30 parts by mass of a micron flaky amorphous alloy, 5-10 parts by mass of doped polyaniline, 10-20 parts by mass of a filler, and 4-7 parts by mass of a first additive;

[0010] The B component comprises 10-20 parts by mass of an aqueous curing agent and 1-3 parts by mass of a second additive.

[0011] Preferably, the micron flaky amorphous alloy is selected from Fe α M β at least one of Cr, P, C, B, N, Co, Si, Cu, V, Al, Ti, Ta, Nb, Zr, Mo, and Ni, wherein α and β are atomic percentages, 55≤α≤80, 20≤β≤45, and α+β=100.

[0012] Preferably, the micron flaky amorphous alloy has a particle size of 20-50 microns.

[0013] Preferably, the aqueous epoxy resin has a solid content of 42-70% by weight.

[0014] Preferably, the filler is at least one of titanium dioxide, zinc oxide, precipitated barium sulfate, talc, and calcium carbonate; the first additive is at least one of a dispersant, a thickening agent, an antifoaming agent, an anti-tarnish agent, and a pH adjuster; and the second additive is an adhesion promoter.

[0015] Preferably, the aqueous curing agent has a solid content of 40-70% by weight.

[0016] Preferably, the doped polyaniline is prepared by the following steps:

[0017] (1) adding a polyaniline powder to an aqueous phytic acid solution and continuously stirring;

[0018] (2) repeatedly washing and filtering the mixture obtained in step (1) with deionized water until the pH of the filtrate is greater than 6, and drying the filter residue to obtain a doped polyaniline powder.

[0019] More preferably, in step (1), the polyaniline is 5-10 parts by mass, the aqueous phytic acid solution has a volume of 100 ml and a mass fraction of 5-10 wt%, the stirring speed is 300-1000 rpm, and the stirring time is 5-12 h; in step (2), the drying temperature is 50-100°C.

[0020] More preferably, in the step (1), the polyaniline is in an intrinsic state, and the molecular weight of the polyaniline is 10000 g / mol to 100000 g / mol.

[0021] In the second aspect of the present application, a preparation method of the above-mentioned polyaniline amorphous anticorrosive coating is provided, and the preparation method comprises the following steps:

[0022] The water-based epoxy resin, the micron flaky amorphous alloy, the doped polyaniline, the filler and the first additive are uniformly mixed to obtain the A component;

[0023] The water-based curing agent and the second additive are uniformly mixed to obtain the B component;

[0024] The B component is added into the A component and stirred uniformly to obtain the polyaniline amorphous anticorrosive coating.

[0025] The present application has the following advantages:

[0026] 1. The polyaniline amorphous anticorrosive coating comprises an A component and a B component, the A component comprises 25-40 parts by mass of a water-based epoxy resin, 20-30 parts by mass of a micron flaky amorphous alloy, 5-10 parts by mass of a doped polyaniline, 10-20 parts by mass of a filler and 4-7 parts by mass of a first additive, and the B component comprises 10-20 parts by mass of a water-based curing agent and 1-3 parts by mass of a second additive, the polyaniline amorphous anticorrosive coating has super high adhesion, hardness, acid resistance, alkali resistance and salt fog resistance on the surface of a metal, and is prepared by using a water-based formula, so that a large amount of organic solvents are avoided, the polyaniline amorphous anticorrosive coating is green and environmentally friendly, and is suitable for large-scale popularization and application.

[0027] 2. The preparation method of the polyaniline amorphous anticorrosive coating comprises the following steps: uniformly mixing a water-based epoxy resin, a micron flaky amorphous alloy, a doped polyaniline, a filler and a first additive to obtain an A component; uniformly mixing a water-based curing agent and a second additive to obtain a B component; and adding the B component into the A component and stirring uniformly to obtain the polyaniline amorphous anticorrosive coating, so that the preparation method is ingenious in design, simple in process, easy to operate, low in production cost and suitable for large-scale popularization and application.

[0028] These and other objects, features, and advantages of the present application will become apparent by reference to the following detailed description and drawings, in which: DETAILED DESCRIPTION

[0029] In order to provide a kind of anticorrosive coating, to solve the existing anticorrosive coating with low adhesion, VOC content is high, and poor acid, alkali, salt fog resistance, short service life and other problems, the present application is obtained by in-depth and extensive research, a kind of polyaniline amorphous anticorrosive coating, it has super high adhesion, hardness, acid, alkali and salt fog resistance on the metal surface, and using water-based formula, avoid the use of a large amount of organic solvent, green environmental protection.

[0030] The polyaniline amorphous anticorrosive coating of the present application comprises a component A and a component B, wherein:

[0031] The component A comprises 25-40 parts by mass of water-based epoxy resin, 20-30 parts by mass of micron flaky amorphous alloy, 5-10 parts by mass of doped polyaniline, 10-20 parts by mass of filler and 4-7 parts by mass of first additive;

[0032] The component B comprises 10-20 parts by mass of water-based curing agent and 1-3 parts by mass of second additive.

[0033] The micron flaky amorphous alloy can be any suitable micron flaky amorphous alloy, preferably, the micron flaky amorphous alloy is selected from Fe α M β Alloy, wherein M is at least one of elements Cr, P, C, B, N, Co, Si, Cu, V, Al, Ti, Ta, Nb, Zr, Mo, Ni, wherein α, β are atomic percentages, 55≤α≤80, 20≤β≤45, α+β=100.

[0034] The particle size of the micron flaky amorphous alloy can be determined as required, preferably, the particle size of the micron flaky amorphous alloy is 20-50 microns.

[0035] The solid content of the water-based epoxy resin can be determined as required, preferably, the solid content of the water-based epoxy resin is 42-70% by weight.

[0036] The filler can be any suitable filler, preferably, the filler is at least one of titanium dioxide, zinc oxide, precipitated barium sulfate, talc and calcium carbonate.

[0037] The first additive and the second additive can be any suitable additive, preferably, the first additive is at least one of dispersant, thickening agent, defoaming agent, anti-flash rust agent and pH regulator, and the second additive is adhesion promoter.

[0038] The solid content of the water-based curing agent can be determined as required, preferably, the solid content of the water-based curing agent is 40-70% by weight.

[0039] The doped polyaniline can be prepared by any suitable step, preferably, the doped polyaniline is prepared by the following steps:

[0040] (1) adding polyaniline powder into a water solution of phytic acid and continuously stirring;

[0041] (2) repeatedly washing and filtering the mixture obtained in the step (1) with deionized water until the pH value of the filtrate is greater than 6, and drying the filter residue to obtain doped polyaniline powder.

[0042] In the step (1), the mass fraction of the polyaniline, the volume of the water solution of phytic acid, the mass fraction of the water solution of phytic acid and the stirring condition can be determined as required, and in the step (2), the drying temperature can be determined as required, more preferably, in the step (1), the mass fraction of the polyaniline is 5-10 mass fraction, the volume of the water solution of phytic acid is 100 ml, the mass fraction of the water solution of phytic acid is 5wt%-10wt%, the stirring speed is 300 rpm-1000 rpm, and the stirring time is 5 h-12 h; in the step (2), the drying temperature is 50℃-100℃.

[0043] The polyaniline can be any suitable polyaniline, more preferably, in the step (1), the polyaniline is in an intrinsic state, and the molecular weight of the polyaniline is 10000 g / mol-100000 g / mol.

[0044] Also provided is a preparation method of the above-mentioned polyaniline amorphous anticorrosive coating, comprising the following steps:

[0045] mixing the water-based epoxy resin, the micrometer flaky amorphous alloy, the doped polyaniline, the filler and the first auxiliary agent uniformly to obtain the A component;

[0046] mixing the water-based curing agent and the second auxiliary agent uniformly to obtain the B component;

[0047] adding the B component into the A component and stirring uniformly to obtain the polyaniline amorphous anticorrosive coating.

[0048] The water-based epoxy resin in the A component and the water-based curing agent in the B component are cured by chemical reaction to form the film-forming material of the polyaniline amorphous anticorrosive coating film, and by using a water-based formula, the environmental protection performance of the anticorrosive coating is improved, and the coating is odorless, non-flammable, and safe in storage, transportation and use.

[0049] The doped polyaniline in the application is synthesized by doping the intrinsic state polyaniline with phytic acid, and the doped polyaniline has excellent conductive performance, when in contact with a metal substrate, the electrochemical corrosion of the metal substrate is moved from the original negative potential to the positive potential, and through the redox reaction with oxygen, the penetration of oxygen to the metal interface is prevented, thereby cutting off the rusting reaction on the metal surface. Moreover, one phytic acid molecule contains six phosphate groups, and the phosphate groups can passivate the surface of the metal substrate, forming a dense passivation film, improving the corrosion resistance of the metal material and the adhesion of the polyaniline amorphous anticorrosion coating film to the metal surface.

[0050] The microparticle-shaped amorphous alloy Fe α M β has high strength and high hardness, and the self-corrosion potential and polarization potential are more positive, the corrosion resistance is high, and there is a synergistic interaction between the doped polyaniline, which can provide excellent comprehensive performance for the anticorrosion coating film of the application.

[0051] The filler in the application not only can increase the volume of the coating, but also has the function of improving some properties of the coating or coating film, such as increasing the solid content, improving the hiding power, improving the aging resistance and corrosion resistance, etc.

[0052] The first auxiliary agent in the application is mainly used for dispersing the doped polyaniline and the filler, preventing the precipitation of the amorphous alloy, improving the anti-sagging property of the coating, reducing the surface tension of the coating, and enhancing the anti-flash rust performance of the wet film, etc.

[0053] The second auxiliary agent in the application is mainly used for enhancing the bonding force between the polyaniline amorphous anticorrosion coating film and the metal substrate, and improving the adhesion of the paint film to the metal substrate.

[0054] The polyphenylamine amorphous anticorrosion coating of the present application adopts micron sheet-shaped amorphous alloy and doped polyphenylamine to jointly form an anticorrosion functional component. Due to the doping of phytic acid, the intrinsic state polyphenylamine is converted into conductive state polyphenylamine with good conductivity, electrochemical activity and dispersibility. When the conductive state polyphenylamine contacts with the metal substrate and the amorphous alloy, the self-corrosion potential and polarization potential of the metal substrate and the amorphous alloy are moved from the original negative potential to the positive potential, and the conductive state polyphenylamine has high redox activity, reacts with corrosion media such as alkali, oxidizing agent or reducing agent, prevents the penetration of oxygen and other corrosion media to the metal interface, and thus cuts off the rusting reaction on the metal surface. Meanwhile, due to the rigid molecular chain structure and strong intermolecular force of the intrinsic state polyphenylamine, the dispersibility of the polyphenylamine in water is poor, and the doping of phytic acid can make the polyphenylamine easily dispersed in the aqueous system and present a coral shape. When the coating film is dried, the polyphenylamine has better compatibility with the epoxy resin as the film-forming material, thereby improving the anticorrosion performance of the paint film. And the polyphenylamine doped by phytic acid contains rich phosphate groups, which can passivate the surface of the metal substrate and the amorphous alloy to form a dense passivation film, thereby improving the corrosion resistance of the metal material and the adhesion of the paint film to the metal surface, and enhancing the compatibility of the amorphous alloy with the epoxy resin. Therefore, the synthesized doped polyphenylamine in the anticorrosion coating assumes four functions of improving the self-corrosion and polarization potential, blocking the corrosion medium, passivating the metal surface and enhancing the compatibility of the amorphous alloy, and under the synergistic interaction of the doped polyphenylamine and the amorphous alloy, the prepared coating has super high adhesion (more than 15 MPa), hardness (more than 5H), acid resistance (more than 720h in 5% sulfuric acid solution), alkali resistance (more than 720h in 5% sodium hydroxide solution) and salt spray resistance (more than 7000h) (see the performance test examples attached below).

[0055] In order to enable the technical content of the present application to be more clearly understood, the following examples are used for detailed description.

[0056] The experimental methods in the following examples not specified in the specific conditions are generally determined according to the national standards. If there is no corresponding national standard, the general international standards, conventional conditions, or the conditions suggested by the manufacturers are used.

[0057] Unless otherwise defined or specified, all professional and scientific terms used herein have the same meaning as familiar to those skilled in the art. In addition, any method and material similar or equivalent to the described content can be applied to the method of the present application.

[0058] In the following specific examples, the test samples were prepared according to the standard GB / T9271-2008 Standard Test Panels for Paints and Varnishes, and the hardness test, cross-hatch test, adhesion, and salt spray resistance test were carried out accordingly. The test used tinplate. The hardness test was based on GB / T6739-2022 Paints and Varnishes - Determination of Film Hardness by Pencil Method; the acid resistance (immersion in 5% sulfuric acid solution) and alkali resistance (immersion in 5% sodium hydroxide solution) tests were based on GB / T 9274-1988 Paints and Varnishes - Determination of Resistance to Liquid Media; the adhesion test was based on GB / T5210-2006 Paints and Varnishes - Adhesion Test by Pulling Apart Method; and the salt spray resistance test was based on GBT1771-2007 Paints and Varnishes - Determination of Resistance to Neutral Salt Spray. The volatile organic compound (VOC) content test was based on GB / T 23985-2009 Paints and Varnishes - Determination of the Content of Volatile Organic Compounds (VOC) - Difference Method.

[0059] The performance of the polyamine amorphous anticorrosive coating of the present application was tested by preparing it, and compared with that of the amorphous anticorrosive coating without doped polyamine, the polyamine anticorrosive coating without amorphous alloy, and the organic epoxy zinc-rich coating.

[0060] Example 1

[0061] In this example, the polyamine amorphous anticorrosive coating I was prepared by the following scheme

[0062] 1. The doped polyamine was synthesized by the following method:

[0063] 5 parts by mass of polyamine powder (COOLBJC, intrinsic state (molecular weight 10000-100000 g / mol)) was added to 100 mL of 6 wt% phytic acid aqueous solution, and continuous stirring was carried out at a speed of 1000 rpm for 5 h. The obtained mixture was repeatedly washed and filtered with deionized water until the pH value of the filtrate was greater than 6. The filter residue obtained by filtration was dried at 100°C to obtain doped polyamine powder (doped polyamine I).

[0064] 2. The Group A component included the following components by mass: 30 parts by mass of water-based epoxy resin (Yida Chemical F0704 (solid content 50%)), 25 parts by mass of micron flaky amorphous alloy (Fe 72 Cr8P5C 10 B5, 25 μm), 8 parts by mass of doped polyamine I, 15 parts by mass of filler (5 parts by mass of titanium dioxide and 10 parts by mass of calcium carbonate), and 5 parts by mass of first auxiliary agent (2 parts by mass of dispersing agent (Kewin KYC-9366), 2 parts by mass of anti-flash rust agent (Tusen TSF-802), 0.5 parts by mass of defoaming agent (Kewin KYC-750), 0.5 parts by mass of thickening agent (fumed silica)).

[0065] The dispersant, doped polyaniline I were added into the waterborne epoxy resin in turn according to the formulation, stirred at 2000 rpm for 30 min, then the filler was added and stirred for another 30 min, then the micrometer flaky amorphous alloy, anti-flash rust agent, defoaming agent, thickening agent were added in turn at 500 rpm and stirred for 15 min to obtain the A component of this example, which was ready for use.

[0066] 3. The B component included the following components by mass fraction: 15 parts by mass of waterborne curing agent (Yoshida Chemical F0705 (solid content 44%)) and 2 parts by mass of second auxiliary agent (adhesion promoter XUHUACAKN-6618).

[0067] The adhesion promoter was added into the waterborne curing agent according to the formulation, stirred at 1100 rpm for 12 min, and mixed thoroughly and uniformly to obtain the B component of this example, which was ready for use.

[0068] 4. Finally, the polyaniline amorphous anticorrosive coating was obtained by mixing.

[0069] The obtained A component and B component were mechanically stirred (1000 rpm, 8 min) and mixed uniformly to obtain the polyaniline amorphous anticorrosive coating I of this example.

[0070] Example 2

[0071] This example prepared a polyaniline amorphous anticorrosive coating II by the following scheme

[0072] 1. The doped polyaniline was synthesized by the following method:

[0073] 7 parts by mass of polyaniline powder (Adamas, intrinsic state (molecular weight > 15000 g / mol)) was added into 100 mL of 5 wt% phytic acid aqueous solution, and stirred continuously at 300 rpm for 12 h. The obtained mixture was repeatedly washed and filtered using deionized water until the pH value of the filtrate was greater than 6. The filter residue obtained by filtration was dried at 50°C to obtain the doped polyaniline powder (doped polyaniline I).

[0074] 2. The A component included the following components by mass fraction: 25 parts by mass of waterborne epoxy resin (Kester EP325 (solid content 52%)), 30 parts by mass of micrometer flaky amorphous alloy (Fe 72 Cr8P 10C5B5, 20 μιη), 5 parts by mass of doped polyaniline II, 20 parts by mass of fillers (4 parts by mass of titanium dioxide, 3 parts by mass of zinc oxide and 13 parts by mass of calcium carbonate) and 6 parts by mass of first auxiliary agents (2 parts by mass of dispersant (Clariant PLF100), 0.5 parts by mass of pH regulator (Dow AMP-95), 2 parts by mass of anti-flashing agent (A Strong Ralox-X151), 0.5 parts by mass of defoaming agent (Dikote Foamex 825), 1 part by mass of thickening agent (organic bentonite)).

[0075] The dispersant, the pH regulator and the doped polyaniline II were added into the waterborne epoxy resin in turn according to the formulation, and stirred at a speed of 1500 rpm for 45 min, then the fillers were added and stirred for 20 min, and then the micrometer flaky amorphous alloy, the anti-flashing agent, the defoaming agent and the thickening agent were added in turn at a speed of 800 rpm and stirred for 10 min to obtain the Part A component of the present example, which was ready for use.

[0076] 3. The Part B component comprises the following components in parts by mass: 11 parts by mass of waterborne curing agent (Baling Petrochemical CYDHD-220 (solid content of 70% after dilution)) and 3 parts by mass of second auxiliary agents (adhesion promoter (Dowlat BTB-04)).

[0077] The adhesion promoter was added into the waterborne curing agent according to the formulation, and stirred at a speed of 1500 rpm for 5 min, and then mixed thoroughly and uniformly to obtain the Part B component of the present example, which was ready for use.

[0078] 4. Finally, the polyaniline amorphous anticorrosive coating was obtained by mixing:

[0079] The obtained Part A component and Part B component were mixed uniformly by mechanical stirring (1500 rpm, 5 min) to obtain the polyaniline amorphous anticorrosive coating II of the present example.

[0080] Example 3

[0081] The polyaniline amorphous anticorrosive coating III of the present example was prepared by the following scheme:

[0082] 1. The doped polyaniline was synthesized by the following method:

[0083] 8 parts by mass of polyaniline powder (Ika Bio, intrinsic state (molecular weight 50000-60000 g / mol)) was added into 100 mL of 10 wt% phytic acid aqueous solution, and stirred continuously at a speed of 500 rpm for 9 h. The obtained mixture was repeatedly washed and filtered using deionized water until the pH value of the filtrate was greater than 6, and the filter residue obtained by filtration was dried at 60°C to obtain the doped polyaniline powder (doped polyaniline II).

[0084] 2、The A component comprises the following components by mass fraction: 35 parts by mass of water-based epoxy resin (Towen Polymer EP-6551 (solid content 55%)), 20 parts by mass of micron flaky amorphous alloy (Fe 72 Cr8P5C5B 10 , 50 μm), 10 parts by mass of doped polyaniline III, 11 parts by mass of filler (4 parts by mass of titanium dioxide and 7 parts by mass of precipitated barium sulfate), and 4 parts by mass of first auxiliary agent (1.5 parts by mass of dispersant (Dekor 755W), 0.3 parts by mass of pH regulator (Dow AMP-95), 1.2 parts by mass of anti-flashing agent (Enzhi Chemical HY-71), 0.7 parts by mass of defoaming agent (Ante Fu AFE-1267), and 0.3 parts by mass of thickening agent (Key Win KYC-426)).

[0085] The dispersant, the pH regulator, and the doped polyaniline III are sequentially added to the water-based epoxy resin according to the formulation, and stirring is performed at a rotation speed of 1300 rpm for 40 min, then the filler is added and stirring is continued for 24 min, and then the micron flaky amorphous alloy, the anti-flashing agent, the defoaming agent, and the thickening agent are sequentially added at a rotation speed of 400 rpm and stirring is performed for 20 min, to obtain the A component of the present example, which is ready for use.

[0086] 3、The B component comprises the following components by mass fraction: 18 parts by mass of water-based curing agent (Towen Polymer EH-3878 (solid content 50%)), and 2 parts by mass of second auxiliary agent (adhesion promoter (Shangzhou New Material LY-40)).

[0087] The adhesion promoter is added to the water-based curing agent according to the formulation, and stirring is performed at a rotation speed of 1300 rpm for 7 min, and after thorough mixing, the B component of the present example is obtained, which is ready for use.

[0088] 4、Finally, the polyaniline amorphous anticorrosive coating is obtained by mixing:

[0089] The obtained A component and B component are mechanically stirred (1300 rpm, 9 min) and uniformly mixed, to obtain the polyaniline amorphous anticorrosive coating III of the present example.

[0090] Example 4

[0091] The polyaniline amorphous anticorrosive coating IV of the present example is prepared by the following scheme:

[0092] 1、The doped polyaniline is synthesized by the following method:

[0093] Nine parts by weight of polyaniline powder (Kinu Bio, intrinsic state (molecular weight 10,000-100,000 g / mol)) were added to 100 mL of 8 wt% phytic acid aqueous solution and stirred continuously at 700 rpm for 8 h. The resulting mixture was repeatedly washed and filtered with deionized water until the pH of the filtrate was greater than 6. The filter residue was dried at 80 °C to obtain doped polyaniline powder (doped polyaniline IV).

[0094] 2. Component A comprises the following components in parts by weight: 38 parts by weight of waterborne epoxy resin (Tuochuang Polymer EP-6528 (70% solid content)), and 22 parts by weight of micron-sized flake-like amorphous alloy (Fe). 76 Si6B8P9Cu1 (30μm), 9 parts by mass of doped polyaniline IV, 10 parts by mass of filler (5 parts by mass of titanium dioxide and 5 parts by mass of zinc oxide) and 5 parts by mass of first additive (2.5 parts by mass of dispersant (BYK-190), 0.4 parts by mass of pH adjuster (Dow AMP-95), 1 part by mass of anti-flash rust agent (MC-907), 0.6 parts by mass of defoamer (BYK-024), 0.5 parts by mass of thickener (Acrysol RM-8W)).

[0095] According to the formula, the dispersant, pH adjuster, and doped polyaniline IV were added to the waterborne epoxy resin in sequence, and stirred at 1700 rpm for 35 min. Then, the filler was added and the mixture was stirred for another 40 min. Next, the micron-sized flake amorphous alloy, anti-flash rust agent, defoamer, and thickener were added in sequence at 900 rpm and the mixture was stirred for another 30 min to obtain component A of this embodiment, which is ready for use.

[0096] 3. Component B comprises the following components in parts by weight: 15 parts by weight of water-based curing agent (Tuochuang Polymer EH-3870 (solid content 40%)) and 1 part by weight of second auxiliary agent (adhesion promoter (Shirui M040)).

[0097] According to the formula, the adhesion promoter is added to the water-based curing agent and treated at 900 rpm for 16 minutes. After thorough mixing until homogeneous, component B of this embodiment is obtained and ready for use.

[0098] 4. Finally, the mixture yields a polyaniline amorphous anti-corrosion coating:

[0099] The obtained components A and B were mechanically stirred (1600 rpm, 5 min) to obtain the polyaniline amorphous anti-corrosion coating IV of this embodiment.

[0100] Example 5

[0101] This embodiment prepares polyaniline amorphous anti-corrosion coating V using the following method.

[0102] 1. Doped polyaniline is synthesized by the following method:

[0103] 10 parts by mass of polyaniline powder (Adamas, intrinsic state (molecular weight > 15000 g / mol)) is added to 100 mL of a 7 wt% phytic acid aqueous solution, and stirring is carried out at a rotation speed of 800 rpm for 6 h. The obtained mixture is repeatedly washed and filtered using deionized water until the pH value of the filtrate is greater than 6, and the filter residue obtained by filtration is dried at 90°C to obtain doped polyaniline powder (doped polyaniline V).

[0104] 2. The A component comprises the following components by mass: 27 parts by mass of an aqueous epoxy resin (EPICLON H-505-42W (solid content 42%)), 28 parts by mass of a micron flaky amorphous alloy (Fe 72 Cr8P5C5B 10 (30 μm): Fe 75 Si 10 B 15 (20 μm) = 1:2), 6 parts by mass of doped polyaniline V, 18 parts by mass of a filler (8 parts by mass of zinc oxide and 10 parts by mass of calcium carbonate), and 7 parts by mass of a first auxiliary agent (3 parts by mass of a dispersant (Nopco SN-5040), 2.5 parts by mass of an anti-flashing agent (Dykon MT5017), 0.5 parts by mass of an antifoaming agent (Dowfume DF-2665), and 1 part by mass of a thickening agent (BASF RHEOVIS AS1130)).

[0105] The dispersant, the pH adjuster, and the doped polyaniline V are sequentially added to the aqueous epoxy resin according to the formulation, and stirring is carried out at a rotation speed of 1400 rpm for 60 min, then the filler is added and stirring is carried out for another 30 min, and then the micron flaky amorphous alloy, the anti-flashing agent, the antifoaming agent, and the thickening agent are sequentially added at a rotation speed of 1000 rpm and stirring is carried out for 20 min, to obtain the A component of the present embodiment, which is ready for use.

[0106] 3. The B component comprises the following components by mass: 13 parts by mass of an aqueous curing agent (Shin-Etsu YK-60 (solid content 55%)), and 1 part by mass of a second auxiliary agent (an adhesion promoter (Dico AddBond DS1300)).

[0107] The adhesion promoter is added to the aqueous curing agent according to the formulation, and stirring is carried out at a rotation speed of 2000 rpm for 5 min, and the mixture is thoroughly mixed until uniform to obtain the B component of the present embodiment, which is ready for use.

[0108] 4. Finally, the polyaniline amorphous anticorrosive coating is obtained by mixing:

[0109] The obtained component A and component B were mixed by mechanical stirring (1000 rpm, 8 min) to obtain the non-crystalline anticorrosive coating of polyaniline without doping of this example.

[0110] Comparative Example 1

[0111] The non-crystalline anticorrosive coating without doping of polyaniline was prepared by the following scheme

[0112] 1, Component A includes the following components by mass fraction: 30 mass fraction of water-based epoxy resin (Yida Chemical F0704 (solid content 50%)), 25 mass fraction of micron flaky non-crystalline alloy (Fe 72 Cr8P5C 10 B5, 25 μm), 23 mass fraction of filler (7.7 mass fraction of titanium dioxide and 15.3 mass fraction of calcium carbonate), and 5 mass fraction of first auxiliary agent (2 mass fraction of dispersant (Kewin KYC-9366), 2 mass fraction of anti-flash rust agent (Tosoh TSF-802), 0.5 mass fraction of defoaming agent (Kewin KYC-750), 0.5 mass fraction of thickening agent (fumed silica)).

[0113] The dispersant was added into the water-based epoxy resin according to the formula, stirred at a speed of 2000 rpm for 30 min, then the filler was added and stirred for another 30 min, then the micron flaky non-crystalline alloy, the anti-flash rust agent, the defoaming agent, and the thickening agent were added in sequence at a speed of 500 rpm and stirred for 15 min to obtain component A of this example, which was ready for use.

[0114] 2, Component B includes the following components by mass fraction: 15 mass fraction of water-based curing agent (Yida Chemical F0705 (solid content 44%)), and 2 mass fraction of second auxiliary agent (adhesion promoter (XUHUACAKN-6618)).

[0115] The adhesion promoter was added into the water-based curing agent according to the formula, stirred at a speed of 1100 rpm for 12 min, and fully mixed to obtain component B of this example, which was ready for use.

[0116] 3, Finally, the non-crystalline anticorrosive coating without doping of polyaniline was obtained by mixing:

[0117] The obtained component A and component B were mixed by mechanical stirring (1000 rpm, 8 min) to obtain the non-crystalline anticorrosive coating of polyaniline without doping of this example.

[0118] Comparative Example 2

[0119] The non-crystalline anticorrosive coating without doping of polyaniline was prepared by the following scheme

[0120] 1, The doping polyaniline was the doping polyaniline I prepared in Example 1.

[0121] 2. The A component comprises the following components by mass parts: 30 mass parts of water-based epoxy resin (YIDAGONG F0704 (solid content 50%)), 8 mass parts of doped polyaniline I, 38 mass parts of filler (12.7 mass parts of titanium dioxide and 25.3 mass parts of calcium carbonate), and 5 mass parts of first auxiliary agent (2 mass parts of dispersant (KEQING KYC-9366), 2 mass parts of anti-flash rust agent (TOSHF TSF-802), 0.5 mass parts of defoaming agent (KEQING KYC-750), 0.5 mass parts of thickening agent (fumed silica)).

[0122] According to the formula, the dispersant and the doped polyaniline I are sequentially added to the water-based epoxy resin, stirred at a speed of 2000 rpm for 30 min, then the filler is added and stirred for another 30 min, and then the anti-flash rust agent, the defoaming agent, and the thickening agent are sequentially added at a speed of 500 rpm and stirred for 15 min to obtain the A component of the present example, which is ready for use.

[0123] 3. The B component comprises the following components by mass parts: 15 mass parts of water-based curing agent (YIDAGONG F0705 (solid content 44%)), and 2 mass parts of second auxiliary agent (adhesion promoter (XUHUACAKN-6618)).

[0124] According to the formula, the adhesion promoter is added to the water-based curing agent and stirred at a speed of 1100 rpm for 12 min, and then mixed uniformly to obtain the B component of the present example, which is ready for use.

[0125] 4. Finally, the amorphous alloy-free polyaniline anticorrosive coating is obtained by mixing:

[0126] The obtained A component and B component are mechanically stirred (1000 rpm, 8 min) and uniformly mixed to obtain the amorphous alloy-free polyaniline anticorrosive coating of the present comparative example.

[0127] Comparative Example 3

[0128] The organic epoxy zinc-rich coating of the present comparative example is prepared by the following scheme

[0129] 1. The A component comprises the following components by mass parts: 16 mass parts of epoxy resin (YIDAGONG, E44), 14 mass parts of organic solvent (xylene: n-butanol = 7:3), 60 mass parts of zinc powder, 1 mass parts of first auxiliary agent (0.5 mass parts of defoaming agent (BYK CHEMICAL BYK-1790), 0.5 mass parts of thickening agent (fumed silica)).

[0130] The organic solvent, dispersant were added into the epoxy resin according to the formula, stirred at 1500 rpm for 15 min, then the zinc powder, defoaming agent, thickening agent were added at 1000 rpm and treated for 20 min, to obtain the first component of the solvent type organic zinc-rich primer of the present comparative example.

[0131] 2. The second component includes the following components by mass fraction: 7 parts by mass of curing agent (Yida Chemical, T-31) and 2 parts by mass of second auxiliary agent (adhesion promoter (BYK-4510 of Pichem)).

[0132] 3. Finally, the organic epoxy zinc-rich coating was obtained by mixing:

[0133] The obtained first component and second component were mechanically stirred (1500 rpm, 3 min) to obtain the organic epoxy zinc-rich coating of the present comparative example.

[0134] Performance test example

[0135] The products prepared in examples 1-5 and the products prepared in comparative examples 1-3 were tested for relevant performance, and the results are shown in the following table:

[0136]

[0137]

[0138] From the results of the above tests, it can be seen that there is a synergistic interaction between the microparticle non-crystalline alloy and the doped polyaniline in the polyaniline non-crystalline corrosion-resistant coating, and both of them have a significant promoting effect on enhancing the comprehensive performance of the coating (such as hardness, adhesion, acid resistance, alkali resistance, salt spray resistance, etc.), and compared with the organic epoxy zinc-rich coating of comparative example 3, the polyaniline non-crystalline corrosion-resistant coating of examples 1-5 of the present application has significant performance and environmental protection advantages.

[0139] The polyaniline non-crystalline corrosion-resistant coating of the present application uses microparticle non-crystalline alloy and doped polyaniline to jointly form a corrosion-resistant functional component, and the coating formed on the metal surface has ultra-high adhesion (more than 15 MPa), hardness (more than 5H), acid resistance (more than 720h in 5% sulfuric acid solution), alkali resistance (more than 720h in 5% sodium hydroxide solution) and salt spray resistance (more than 7000h).

[0140] The polyaniline non-crystalline corrosion-resistant coating of the present application uses a water-based formula, avoiding the use of a large amount of organic solvent, and the VOC content is less than 50g / L, which is green and environmentally friendly.

[0141] Therefore, the polyphenylamine amorphous anticorrosive coating has excellent adhesion, hardness, acid resistance, alkali resistance and salt fog resistance, low VOC content, green environmental protection, solves the problems of easy falling off, poor acid and alkali resistance, short salt fog resistance time, high organic solvent content and the like of the existing anticorrosive paint, meanwhile, the preparation method is ingenious in design, simple in process, easy to operate and low in production cost.

[0142] In summary, the polyphenylamine amorphous anticorrosive coating has super high adhesion, hardness, acid resistance, alkali resistance and salt fog resistance on the metal surface, uses a water-based formula, avoids the use of a large amount of organic solvent, is green and environmentally friendly, ingenious in design, simple in process, easy to operate, low in production cost, and suitable for large-scale popularization and application.

[0143] In this specification, the application has been described with reference to its specific embodiments. However, it is obvious that various modifications and changes can be made without departing from the spirit and scope of the application. Therefore, the specification should be considered as illustrative rather than restrictive.

Claims

1. A polyaniline amorphous anti-corrosion coating, characterized in that, It includes component A and component B, wherein: The first component comprises 25 to 40 parts by weight of waterborne epoxy resin, 20 to 30 parts by weight of micron-sized sheet-like amorphous alloy, 5 to 10 parts by weight of doped polyaniline, 10 to 20 parts by weight of filler, and 4 to 7 parts by weight of a first additive. The B component comprises 10 to 20 parts by weight of an aqueous curing agent and 1 to 3 parts by weight of a second auxiliary agent. The micron-sized sheet-like amorphous alloy is selected from Fe. α M β At least one of the alloys, wherein M is at least one of the elements Cr, P, C, B, N, Co, Si, Cu, V, Al, Ti, Ta, Nb, Zr, Mo, and Ni, wherein α and β are atomic percentages, 55≤α≤80, 20≤β≤45, and α+β=100; The doped polyaniline was prepared using the following steps: (1) Add polyaniline powder to phytic acid aqueous solution and stir continuously; (2) The mixture obtained in step (1) is repeatedly washed and filtered with deionized water until the pH value of the filtrate is greater than 6. The filter residue obtained by filtration is dried to obtain polyaniline powder.

2. The polyaniline amorphous anti-corrosion coating according to claim 1, characterized in that, The particle size of the micron-sized sheet-like amorphous alloy is 20 micrometers to 50 micrometers.

3. The polyaniline amorphous anti-corrosion coating according to claim 1, characterized in that, The solid content of the waterborne epoxy resin is 42% to 70% by weight.

4. The polyaniline amorphous anti-corrosion coating according to claim 1, characterized in that, The filler is at least one of titanium dioxide, zinc oxide, precipitated barium sulfate, talc and calcium carbonate; the first additive is at least one of dispersant, thickener, defoamer, anti-flash rust agent and pH adjuster; and the second additive is an adhesion promoter.

5. The polyaniline amorphous anti-corrosion coating according to claim 1, characterized in that, The solid content of the water-based curing agent is 40% to 70% by weight.

6. The polyaniline amorphous anti-corrosion coating according to claim 1, characterized in that, In step (1), the polyaniline is 5 to 10 parts by mass, the volume of the phytic acid aqueous solution is 100 ml, the mass fraction of the phytic acid aqueous solution is 5 wt% to 10 wt%, the stirring speed is 300 rpm to 1000 rpm, and the stirring time is 5 h to 12 h; in step (2), the drying temperature is 50 °C to 100 °C.

7. The polyaniline amorphous anti-corrosion coating according to claim 1, characterized in that, In step (1), the polyaniline is in its intrinsic state and the molecular weight of the polyaniline is 10000g / mol to 100000g / mol.

8. A method for preparing a polyaniline amorphous anti-corrosion coating according to any one of claims 1 to 7, characterized in that, Includes the following steps: The aqueous epoxy resin, the micron-sized sheet-like amorphous alloy, the doped polyaniline, the filler, and the first additive are mixed evenly to obtain component A; The water-based curing agent and the second auxiliary agent are mixed evenly to obtain component B; The polyaniline amorphous anti-corrosion coating is prepared by adding component B to component A and stirring evenly.

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