CN115491105A - Chitosan-gallic acid synergistically modified water-based rusty paint and preparation method thereof - Google Patents
Chitosan-gallic acid synergistically modified water-based rusty paint and preparation method thereof Download PDFInfo
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- CN115491105A CN115491105A CN202211217723.8A CN202211217723A CN115491105A CN 115491105 A CN115491105 A CN 115491105A CN 202211217723 A CN202211217723 A CN 202211217723A CN 115491105 A CN115491105 A CN 115491105A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/084—Inorganic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/327—Aluminium phosphate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/328—Phosphates of heavy metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/14—Gas barrier composition
Abstract
The invention discloses a chitosan-gallic acid synergistically modified water-based rusty paint and a preparation method thereof. Dispersing chitosan-gallic acid solution and a dispersing agent in aqueous epoxy emulsion at a high speed to obtain chitosan-gallic acid dispersion slurry; adding the aqueous epoxy emulsion, the chitosan-gallic acid dispersion slurry, the antirust filler, the dispersing agent, the defoaming agent and the anti-settling agent into a stirrer according to a certain mass ratio, and dispersing and grinding at a high speed to obtain a component A of the chitosan-gallic acid aqueous rusty paint; the component B is composed of an amine addition curing agent and a proper amount of water, and the component A and the component B are fully mixed according to a proportion to obtain the coating. The invention utilizes the polyhydroxy structures of chitosan and gallic acid, has good stabilizing and transforming effects on a rust layer, avoids a complex rust removal process, shows good construction performance, has the advantages of safety, environmental protection, quick drying, good adhesive force, excellent corrosion resistance and the like, and has wide application prospect.
Description
Technical Field
The invention belongs to the field of coatings, relates to an embroidery coating technology, and particularly relates to a chitosan-gallic acid synergistically modified water-based rust coating and a preparation method thereof.
Background
The corrosion is commonly existed in steel structure equipment, and according to statistics, the steel substrate with nearly 1/4 of total production generates corrosion every year in the world, and the coating is one of the most efficient and direct methods for protecting the steel substrate. However, when the surface of the rusted equipment is coated, the traditional coating process can be constructed only by carrying out rust removal treatment on the surface of the rusted equipment to be more than Sa2.5 grade, the working procedure is complicated, the operation period is long, a large amount of economic cost and time cost are consumed, the economic cost of general surface treatment is about 30-40% of the total engineering cost, the time cost accounts for about 50% of the total coating workload, and meanwhile, a large amount of smoke and dust are generated in the surface treatment process, so that the serious damage is caused to the surrounding environment and constructors. Therefore, if the rusty coating directly constructed on the surface of the rusty steel base material can be developed, the workload and the coating cost can be greatly reduced or saved in a rust removing link, and meanwhile, the health hazard of a rust layer to constructors can be reduced. The chitosan and the gallic acid have polyhydroxy structures, have good stabilizing and converting effects on a rust layer, have good biocompatibility when used in a coating, and can improve the adhesive force, the stability and the corrosion resistance of the coating. Meanwhile, compared with a solvent type coating, the water-based rusty coating has the advantages of safety, environmental protection and the like, and has wide application prospect. The chitosan-gallic acid is used for synergistically modifying the water-based rusty paint to prepare the corrosion-resistant rusty coating with excellent performance, and the chitosan-gallic acid modified water-based rusty paint has important significance for recycling the rusty steel base material and prolonging the service life.
Disclosure of Invention
The invention aims to provide a chitosan-gallic acid synergistically modified waterborne rusty coating and a preparation method thereof, so that the prepared rusty coating is safe and environment-friendly, is quick to dry and has good adhesive force, the harm of a rust layer to constructors and the environmental pollution can be effectively reduced, and the corrosion resistance of the waterborne rusty coating is improved.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the invention provides a chitosan-gallic acid synergistically modified waterborne rusty paint, which is prepared by uniformly mixing a component A and a component B according to a certain proportion;
the component A comprises the following components in parts by weight:
the component B comprises the following components in parts by weight:
10-30 parts of water-based epoxy curing agent
0 to 30 portions of deionized water
Preferably, the chitosan-gallic acid dispersion slurry is composed of chitosan with the molecular weight of 500-20000, gallic acid solution, a dispersing agent and aqueous epoxy emulsion.
Preferably, the waterborne epoxy emulsion is any one or a combination of more of bisphenol A waterborne epoxy resin emulsion, bisphenol F waterborne epoxy resin emulsion and waterborne acrylic modified epoxy emulsion with the epoxy equivalent of 300-800 g/eq.
Preferably, the filler is any one or a combination of talcum powder, mica powder, titanium dioxide, zinc phosphate and aluminum tripolyphosphate.
Preferably, the dispersant is a block polymer copolymer dispersant.
Preferably, the defoaming agent is a polyether modified organic silicon defoaming agent.
Preferably, the anti-settling agent is any one or a combination of fumed silica, organic bentonite and polyamide wax slurry.
Preferably, the curing agent is a modified amine adduct waterborne epoxy curing agent.
The invention also provides a preparation method of the chitosan-gallic acid synergistically modified water-based rusty paint, which comprises the following steps:
step (1), preparation of chitosan-gallic acid dispersion slurry: preparing 3-6 parts of gallic acid into 30-60 wt% aqueous solution, adding 1-3 parts of chitosan with the molecular weight of 500-20000 into the solution, stirring at 25-60 ℃ for 0.5h, adding 0.3-1 part of dispersant and 5-10 parts of aqueous epoxy emulsion, and grinding for 1-4 h by using a high-speed dispersion machine to obtain chitosan-gallic acid dispersion slurry;
step (2), preparation of chitosan-gallic acid synergistically modified water-based rust paint A component: adding the chitosan-gallic acid dispersion slurry, the waterborne epoxy emulsion, the antirust filler, the dispersant, the defoaming agent, the anti-settling agent and the like into a high-speed dispersion machine according to the mass ratio of the coating formula, wherein the defoaming agent is added for 3 times, and grinding and dispersing to obtain a component A of the chitosan-gallic acid synergistically modified waterborne rusty coating;
step (3), preparation of chitosan-gallic acid synergistically modified water-based rust paint component B: mixing and diluting 10-30 parts of waterborne epoxy curing agent and 0-30 parts of deionized water to obtain a chitosan-gallic acid synergistically modified waterborne rusty paint component B;
and (4) mixing the component A and the component B to obtain the chitosan-gallic acid synergistically modified water-based rust paint, and coating.
Preferably, in the step (2), the component A is obtained by dispersing and grinding at high speed by using a high-speed dispersing machine until the fineness is less than 50 μm.
The invention has the following beneficial effects:
according to the chitosan-gallic acid synergistically modified water-based rusty coating, the o-phenolic hydroxyl group of gallic acid can generate a good chelation reaction with a rust layer, a fluffy rust layer is quickly converted into a stable compact layer, and the rusty coating performance is far better than that of a common hydroxyl group; the abundant amino and hydroxyl polar groups of the chitosan can be self-crosslinked to optimize the network structure of the resin and inhibit the cathodic hydrogen evolution reaction, and can be adsorbed on an anode site on the surface of the metal through the interaction with an iron empty d-rail to inhibit the dissolution reaction of the anode metal, namely inhibit the generation of new rust, so that the invention synergistically improves the protective performance of the coating on the base material from two aspects of converting an old rust layer and inhibiting the generation of new rust, avoids a complex rust removal process, can be directly coated with rust, and prolongs the service life of the rusty base material; meanwhile, the water-based epoxy emulsion is used as a film forming substance, and a coating film of the water-based epoxy emulsion has the characteristics of excellent adhesive force, quick drying, outstanding environmental protection and the like.
The invention takes the talcum powder, the mica powder, the zinc phosphate and the aluminum tripolyphosphate as the anti-rust pigment and filler, has good barrier property and corrosion resistance, and the chitosan-gallic acid synergistically modified waterborne rusty coating can be coated on the surface of a rusty steel base material and can also be used on the surface of a rustless steel structure as an anti-corrosive coating.
Drawings
Fig. 1 is an SEM image of an unmodified waterborne rusty coating.
Fig. 2 is an SEM image of chitosan-gallic acid synergistically modified aqueous rusty coating.
FIG. 3 is a macro-topography of a rusted steel plate prepared according to the Standard waterborne primer for rusted coating.
FIG. 4 is a neutral salt spray macro-topography of an unmodified waterborne rusty coating.
FIG. 5 is a macro topography diagram of neutral salt spray of chitosan-gallic acid synergistically modified waterborne over-rust coating.
Fig. 6 is an electrochemical test nyquist plot of unmodified coating and chitosan-gallic acid synergistically modified aqueous rusty coating.
Fig. 7 is a diagram of electrochemical test baud for unmodified coating and chitosan-gallic acid synergistically modified aqueous rusty coating.
Detailed Description
The following describes embodiments of a chitosan-gallic acid synergistically modified waterborne rusty paint and a preparation method thereof in detail with reference to the accompanying drawings and examples. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
The following is a detailed description of the embodiments.
Example 1
A chitosan-gallic acid synergistically modified water-based rusty paint is prepared by preparing 3 parts of gallic acid into a 30wt% aqueous solution, adding 1 part of chitosan with the molecular weight of 500 into the solution, stirring at 25 ℃ for 0.5h, adding 0.3 part of a dispersing agent and 10 parts of a water-based epoxy emulsion, and grinding for 1h by using a high-speed dispersion machine to obtain chitosan-gallic acid dispersion slurry. According to the mass ratio, 20 parts of chitosan-gallic acid dispersion slurry, 30 parts of bisphenol A type waterborne epoxy resin emulsion, 5 parts of talcum powder, 5 parts of mica powder, 5 parts of zinc phosphate, 5 parts of aluminum tripolyphosphate, 1 part of dispersing agent, 0.5 part of defoaming agent and 2 parts of fumed silica are added, wherein the defoaming agent is added for 3 times (the adding amount is the same for each time), and the components are dispersed at high speed and ground until the fineness reaches below 50 mu m, so that the chitosan-gallic acid synergistic modified waterborne rusty paint A component is obtained. Meanwhile, 10 parts of amine adduct aqueous epoxy curing agent and 10 parts of deionized water are diluted and mixed to obtain the chitosan-gallic acid synergistically modified aqueous rusty paint B component. And (4) testing the qualified indexes of the component A and the component B, and packaging after the qualified indexes are tested. And mixing the component A and the component B according to the proportion to obtain the chitosan-gallic acid synergistically modified water-based rust paint capable of being coated.
Corresponding performance tests are carried out on the chitosan-gallic acid synergistically modified waterborne rusty paint and the coating film, and the test results are shown in the following table.
Table 1 example 1 chitosan-gallic acid synergistically modified waterborne rusty paint and coating film performance evaluation
Example 2
A chitosan-gallic acid synergistically modified water-based rust paint is prepared by preparing 5 parts of gallic acid into a 50wt% aqueous solution, adding 3 parts of chitosan with the molecular weight of 1000 into the solution, stirring at 40 ℃ for 0.5h, adding 0.5 part of dispersing agent and 9 parts of water-based epoxy emulsion, and grinding for 2h by using a high-speed dispersion machine to obtain chitosan-gallic acid dispersion slurry. According to the mass ratio, 15 parts of chitosan-gallic acid dispersion slurry, 35 parts of bisphenol A type waterborne epoxy resin emulsion, 10 parts of mica powder, 5 parts of zinc phosphate, 10 parts of aluminum tripolyphosphate, 1 part of dispersing agent, 0.8 part of defoaming agent and 3 parts of organic bentonite are added in 3 times, dispersed at high speed and ground until the fineness reaches below 50 mu m, so that the component A of the chitosan-gallic acid synergistically modified waterborne rusty coating is obtained. And simultaneously diluting and mixing 15 parts of amine adduct waterborne epoxy curing agent and 20 parts of deionized water to obtain the chitosan-gallic acid synergistically modified waterborne rusty paint B component. And testing the qualified indexes of the component A and the component B, and packaging after the component A and the component B are qualified. And mixing the component A and the component B according to the proportion to obtain the chitosan-gallic acid synergistically modified waterborne rusty paint capable of being coated.
Corresponding performance tests are carried out on the chitosan-gallic acid synergistically modified waterborne rusty paint and the coating film, and the test results are shown in the following table.
Table 2 example 2 chitosan-gallic acid synergistically modified aqueous rust paint and coating film performance evaluation
Example 3
A chitosan-gallic acid synergistically modified water-based rusty paint is prepared by preparing 6 parts of gallic acid into a 60wt% aqueous solution, adding 2 parts of chitosan with the molecular weight of 10000 into the solution, stirring at 40 ℃ for 0.5h, adding 1 part of dispersing agent and 15 parts of aqueous epoxy emulsion, and grinding for 2.5h by using a high-speed dispersion machine to obtain chitosan-gallic acid dispersion slurry. According to the mass ratio, 10 parts of chitosan-gallic acid dispersed slurry, 40 parts of bisphenol A type waterborne epoxy resin emulsion, 10 parts of talcum powder, 10 parts of aluminum tripolyphosphate, 1.5 parts of dispersing agent, 1 part of defoaming agent, 1 part of fumed silica and 1 part of organic bentonite are added in 3 times, and the mixture is dispersed at high speed and ground until the fineness reaches below 50 mu m, so that the chitosan-gallic acid synergistically modified waterborne rusty coating A component is obtained. And simultaneously diluting and mixing 20 parts of amine adduct waterborne epoxy curing agent and 20 parts of deionized water to obtain the chitosan-gallic acid synergistically modified waterborne rusty paint B component. And testing the qualified indexes of the component A and the component B, and packaging after the component A and the component B are qualified. And mixing the component A and the component B according to the proportion to obtain the chitosan-gallic acid synergistically modified water-based rust paint capable of being coated.
Corresponding performance tests are carried out on the chitosan-gallic acid synergistically modified waterborne rusty paint and the coating film, and the test results are shown in the table below.
Table 3 example 3 chitosan-gallic acid synergistically modified aqueous rust paint and coating film performance evaluation
Example 4
A chitosan-gallic acid synergistically modified water-based rust paint is prepared by preparing 4 parts of gallic acid into 40wt% aqueous solution, adding 2 parts of chitosan with the molecular weight of 20000 into the solution, stirring at 50 ℃ for 0.5h, adding 1.5 parts of dispersant and 10 parts of water-based epoxy emulsion, and grinding for 4h by using a high-speed dispersion machine to obtain chitosan-gallic acid dispersion slurry. 8 parts of chitosan-gallic acid dispersed slurry, 42 parts of bisphenol A type waterborne epoxy resin emulsion, 12 parts of mica powder, 12 parts of zinc phosphate, 6 parts of aluminum tripolyphosphate, 2 parts of a dispersing agent, 1.5 parts of an antifoaming agent and 4 parts of gas polyamide wax slurry according to the mass ratio, wherein the antifoaming agent is added for 3 times, and is dispersed at a high speed and ground until the fineness reaches below 50 mu m, so as to obtain the chitosan-gallic acid synergistically modified waterborne rusty coating A component. And simultaneously diluting and mixing 15 parts of amine adduct waterborne epoxy curing agent and 15 parts of deionized water to obtain the chitosan-gallic acid synergistically modified waterborne rusty paint B component. And testing the qualified indexes of the component A and the component B, and packaging after the component A and the component B are qualified. And mixing the component A and the component B according to the proportion to obtain the chitosan-gallic acid synergistically modified waterborne rusty paint capable of being coated.
Corresponding performance tests are carried out on the chitosan-gallic acid synergistically modified waterborne rusty paint and the coating film, and the test results are shown in the following table.
Table 4 example 4 chitosan-gallic acid synergistically modified aqueous rust paint and coating film performance evaluation
From examples 1 to 4, it can be seen that: the chitosan-gallic acid synergistically modified waterborne rusty coating has the characteristics of low VOCs content, no heavy metal, high drying speed, capability of being directly coated on a rusty steel substrate and being coated on a rustless steel substrate, and the like, and also has the advantages of good adhesive force, impact resistance, corrosion resistance and the like. From the comparison of the neutral salt spray macro-topography of the unmodified coating and the chitosan-gallic acid synergistically modified waterborne rusty coating and the electrochemical test result, the corrosion resistance of the chitosan-gallic acid synergistically modified waterborne rusty coating is better than that of the unmodified coating. From the SEM image in fig. 2, it can be observed that the filler in the chitosan-gallic acid synergistically modified aqueous rusty coating has better compatibility with the base material, the surface morphology is smoother and smoother, a better physical barrier can be provided for a rusty base material, and the occurrence of the rust returning phenomenon is reduced.
The above examples are only for illustrating the embodiments of the present invention, but not for limiting the scope of the present invention, and other various substitutions, combinations, modifications, and simplifications may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention, which is also intended to be covered by the claims of the present invention.
Claims (10)
1. The chitosan-gallic acid synergistically modified water-based rusty paint is characterized in that a paint formula consists of a component A and a component B, and the components are calculated in parts by mass as follows:
the component A comprises the following components in percentage by weight:
the component B comprises the following components in percentage by weight:
10 to 30 portions of waterborne epoxy curing agent
0 to 30 portions of deionized water
Wherein the molecular weight of the chitosan in the chitosan-gallic acid dispersed slurry is 500-20000.
2. The chitosan-gallic acid synergistically modified aqueous rust paint of claim 1, wherein: the chitosan-gallic acid dispersion slurry is formed by uniformly mixing chitosan with the molecular weight of 500-20000, gallic acid solution, a dispersing agent and aqueous epoxy emulsion.
3. The chitosan-gallic acid synergistically modified aqueous rust coating according to claim 1, wherein: the waterborne epoxy emulsion is any one or a combination of a plurality of bisphenol A waterborne epoxy resin emulsion, bisphenol F waterborne epoxy resin emulsion and waterborne acrylic acid modified epoxy emulsion with the epoxy equivalent of 300-800 g/eq.
4. The chitosan-gallic acid synergistically modified aqueous rust paint of claim 1, wherein: the antirust filler is any one or a combination of talcum powder, mica powder, zinc phosphate and aluminum tripolyphosphate.
5. The chitosan-gallic acid synergistically modified aqueous rust paint of claim 1, wherein: the dispersant is a block polymer copolymer dispersant.
6. The chitosan-gallic acid synergistically modified aqueous rust paint of claim 1, wherein: the defoaming agent is a polyether modified organic silicon defoaming agent.
7. The chitosan-gallic acid synergistically modified aqueous rust paint of claim 1, wherein: the anti-settling agent is any one or a combination of gas-phase silicon dioxide, organic bentonite and polyamide wax slurry.
8. The chitosan-gallic acid synergistically modified aqueous rust coating according to claim 1, wherein: the waterborne epoxy curing agent is a modified amine adduct waterborne epoxy curing agent.
9. The preparation method of the chitosan-gallic acid synergistically modified waterborne rusty paint of any one of claims 1-8, comprising the steps of:
step (1), preparation of chitosan-gallic acid dispersion slurry: preparing 30-60 wt% aqueous solution by 3-6 parts of gallic acid according to the mass part, simultaneously adding 1-3 parts of chitosan with the molecular weight of 500-20000 into the aqueous solution, stirring for 0.5h at 25-60 ℃, then adding 0.3-1 part of dispersing agent and 5-10 parts of aqueous epoxy emulsion, and grinding for 1-4 h by using a high-speed dispersion machine to obtain chitosan-gallic acid dispersed slurry;
step (2), preparation of chitosan-gallic acid synergistically modified water-based rust paint A component: adding the chitosan-gallic acid dispersion slurry, aqueous epoxy emulsion, antirust filler, dispersant, defoaming agent, anti-settling agent and the like into a high-speed dispersion machine according to the mass ratio of the coating formula, wherein the defoaming agent is added for 3 times, and grinding and dispersing to obtain a component A of the chitosan-gallic acid synergistic modified aqueous rusty coating;
step (3), preparation of chitosan-gallic acid synergistically modified water-based rust paint component B: mixing and diluting 10-30 parts of waterborne epoxy curing agent and 0-30 parts of deionized water to obtain a chitosan-gallic acid synergistically modified waterborne rusty paint component B;
and (4) mixing the component A and the component B to obtain the chitosan-gallic acid synergistically modified water-based rust paint, and coating.
10. The preparation method of the chitosan-gallic acid synergistically modified waterborne rusty coating according to claim 9, wherein the preparation method comprises the following steps: in the step (2), a high-speed dispersion machine is used for high-speed dispersion and grinding until the fineness reaches below 50 mu m, and the component A is obtained.
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