CN116218310A - Silica sol modified acrylic acid anticorrosive paint and preparation method thereof - Google Patents

Silica sol modified acrylic acid anticorrosive paint and preparation method thereof Download PDF

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Publication number
CN116218310A
CN116218310A CN202310366183.8A CN202310366183A CN116218310A CN 116218310 A CN116218310 A CN 116218310A CN 202310366183 A CN202310366183 A CN 202310366183A CN 116218310 A CN116218310 A CN 116218310A
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silica sol
modified acrylic
anticorrosive paint
coating
acrylic acid
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Inventor
刘月涛
蒋玉洁
邱航
姜华
高传慧
王传兴
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Qingdao Energy Technology Co ltd
Qingdao University of Science and Technology
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Qingdao Energy Technology Co ltd
Qingdao University of Science and Technology
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Priority to CN202310366183.8A priority Critical patent/CN116218310A/en
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D133/00Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04Homopolymers or copolymers of esters
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/61Additives non-macromolecular inorganic
    • C09D7/62Additives non-macromolecular inorganic modified by treatment with other compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/80Processes for incorporating ingredients

Abstract

The invention discloses a silica sol modified acrylic acid anticorrosive paint and a preparation method thereof, wherein the anticorrosive paint comprises large-particle-size silica sol, acrylic acid emulsion, corrosion inhibitor and water-based flash rust inhibitor, wherein the mass fraction of the large-particle-size silica sol is 10% -30% of that of the acrylic acid emulsion; the particle size of the large-particle-size silica sol is 20-100nm. The silica sol modified acrylic acid anti-corrosion coating can be cured at room temperature, and has higher mechanical and physical stability. The addition of the silica sol not only improves the mechanical strength and the adhesive property of the coating, but also improves the corrosion resistance of the coating.

Description

Silica sol modified acrylic acid anticorrosive paint and preparation method thereof
Technical Field
The invention belongs to the technical field of water-based anti-corrosion coatings, and particularly relates to a silica sol modified acrylic anti-corrosion coating and a preparation method thereof.
Background
The statements herein merely provide background information related to the present disclosure and may not necessarily constitute prior art.
The metallic material is easily affected by the natural environment to cause corrosion. In order to effectively protect the metal substrate from corrosion, methods of spraying or brushing an anticorrosive coating are widely used in the industry, wherein solvent type anticorrosive coatings are mainly used. Because of containing a large amount of organic solvents, the environment is seriously polluted, the human health is endangered, and meanwhile, the resources are greatly wasted. The water-based paint has good environmental protection and low VOC content, and is an important direction for the future development of the anti-corrosion coating.
The aqueous acrylic resin is a low-VOC environment-friendly anticorrosive coating product, has better glossiness, weather resistance, chemical resistance and high stability, and has the advantages of no pollution, no toxicity, no irritation, stable production and low price. However, the conventional acrylate resin has the defects of high film forming temperature, low coating hardness, poor water resistance, poor adhesive force and the like, so that the conventional acrylate resin needs to be modified to improve the performance.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a silica sol modified acrylic acid anticorrosive paint and a preparation method thereof. The invention relates to a preparation method of silica sol with large particle size and high concentration and a product thereof. The high-adhesion acrylic acid anticorrosive coating is prepared by mixing the high-adhesion acrylic acid anticorrosive coating with pure acrylic acid emulsion as a film forming substrate of the anticorrosive coating and adding a water-based anti-flash rust agent and a corrosion inhibitor zinc phosphate.
In order to achieve the above object, the present invention is realized by the following technical scheme:
in a first aspect, the invention provides a silica sol modified acrylic acid anticorrosive paint, which comprises a large-particle-size silica sol, an acrylic acid emulsion, a corrosion inhibitor and a water-based flash rust inhibitor, wherein the mass fraction of the large-particle-size silica sol is 10% -30% of that of the acrylic acid emulsion;
the particle size of the large-particle-size silica sol is 20-100nm.
The chemical formula of the large-particle-size silica sol is shown as follows:
Figure BDA0004166887630000021
in some embodiments, the method for preparing the large particle size silica sol comprises: and adding the activated silicon powder into alkali liquor to perform multistage growth of particles, so as to obtain the silica sol with large particle size.
Preferably, the alkali liquor is sodium hydroxide or potassium hydroxide solution, and the mass concentration of the alkali liquor is 0.5% -1.5%.
Preferably, the temperature of each stage of growth is 80-90 ℃, and the time of growth is 5-10h.
Preferably, the activating method of the silicon powder is to place the silicon powder into hot water with the temperature of 60-80 ℃ for activating treatment.
In some embodiments, the corrosion inhibitor is zinc phosphate, and the zinc phosphate accounts for 3-7% of the mass fraction of the mixed solution of the silica sol with large particle size and the acrylic emulsion.
Preferably, the water-based flash rust inhibitor accounts for 0.2 to 0.5 percent of the mass of the coating.
In a second aspect, the invention provides a preparation method of the silica sol modified acrylic anti-corrosive paint, which comprises the following steps:
adding large-particle-size silica sol into acrylic emulsion according to a certain proportion, uniformly mixing, adding corrosion inhibitor and water-based anti-flash rust agent into the mixture, and uniformly dispersing to obtain the product.
In a third aspect, the invention provides a silica sol modified acrylic acid anticorrosive coating, which is obtained by uniformly coating the silica sol modified acrylic acid anticorrosive coating on a substrate and curing.
The beneficial effects achieved by one or more embodiments of the present invention described above are as follows:
the large-particle-size high-concentration silica sol is synthesized by a simple-substance silica powder hydrolysis method, and the preparation method is simple and has less wastewater discharge; the silica sol with large particle size and high concentration has better adhesive property, can be mixed with acrylic emulsion, and ensures that organic polymers are uniformly distributed in gaps of the silicon-oxygen-silicon inorganic coating, so that the formed coating has both inorganic and organic characteristics and complementary performance advantages.
In addition, the silica sol has the characteristics of good water resistance, alkali resistance, weather resistance and air permeability, and the organic polymer has the characteristics of good film forming property, strong adhesiveness, high gloss and the like. Therefore, the silica sol modified acrylic coating can further improve the mechanical strength, adhesion properties, and corrosion resistance of the coating, while allowing the silica sol modified acrylic corrosion resistant coating to cure at room temperature.
In the preparation method of the silica sol, the silica sol is prepared by adopting a mode of adding silicon powder in batches and slowly, so that the particle size of the prepared silica sol is uniform, and the silica sol with large particle size is prepared by multistage growth of particles. In the preparation process of the silica sol modified acrylic emulsion, chemical reaction is not involved, and a homogenizer is adopted for physical blending, so that the silica sol modified acrylic emulsion is uniform in mixing and good in modification effect.
Compared with the existing emulsion, the prepared silica sol modified acrylic emulsion has higher tensile strength of a coating formed by the emulsion, which reaches more than 10 MPa; the adhesive has higher adhesive force to the base material, and the adhesive force on the carbon steel reaches 4.3MPa; the anti-corrosion agent has excellent anti-corrosion effect on carbon steel, and the impedance modulus value of the EIS low-frequency area is 3 orders of magnitude higher than that of pure carbon steel.
The method has the advantages of simple reaction conditions, simple preparation process and environment friendliness, and can be popularized on a large scale.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a graph showing the particle size distribution of silica sols having different particle sizes prepared in example 1 of the present invention.
FIG. 2 is a Fourier infrared spectrum of silica sols of different particle sizes prepared in example 1 of the present invention.
FIG. 3 is a drawing showing the tensile strength of the silica sol modified acrylic anticorrosive coatings prepared in examples 2 to 8 and comparative example 1 according to the present invention.
Fig. 4 is an adhesion force diagram of the silica sol modified acrylic anti-corrosion coating prepared in examples 4, 7 and comparative example 1 of the present invention.
Fig. 5 is an electrochemical test chart of the silica sol modified acrylic anti-corrosive coating prepared in examples 4 and 7 and comparative example 1 of the present invention.
Detailed Description
It should be noted that the following detailed description is illustrative and is intended to provide further explanation of the invention. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The invention is further illustrated below with reference to examples.
Example 1
Firstly, 20g of silicon powder is activated in hot water at 70 ℃, then, the activated silicon powder is slowly added into a three-neck flask containing 180g of deionized water and 2.0g of sodium hydroxide, the reaction is carried out for 8 hours at 85 ℃, the reaction is cooled and the filtration is carried out, and the filtrate is the silica sol serving as primary particles. And taking the obtained primary particles as mother solution, carrying out multi-stage growth of the particles, and evaporating and concentrating to obtain the high-concentration silica sol with the concentration of 20-100nm.
Example 2
Weighing a certain mass of pure acrylic emulsion, adding 10% of the silica sol of the embodiment 1 and 0.2-0.5% of the water-based flash rust inhibitor into the pure acrylic emulsion, uniformly dispersing the pure acrylic emulsion for 1h under a homogenizer of 1500r/min, coating the pure acrylic emulsion on a substrate, and curing.
Example 3
Weighing a certain mass of pure acrylic emulsion, adding 15% of the silica sol of the embodiment 1 and 0.2-0.5% of the water-based flash rust inhibitor into the pure acrylic emulsion, uniformly dispersing the pure acrylic emulsion for 1h under a homogenizer of 1500r/min, coating the pure acrylic emulsion on a substrate, and curing.
Example 4
Weighing a certain mass of pure acrylic emulsion, adding 20% of the silica sol of the embodiment 1 and 0.2-0.5% of the water-based flash rust inhibitor into the pure acrylic emulsion, uniformly dispersing the pure acrylic emulsion for 1h under a homogenizer of 1500r/min, coating the pure acrylic emulsion on a substrate, and curing.
Example 5
Weighing a certain mass of pure acrylic emulsion, adding 30% of the silica sol of the embodiment 1 and 0.2-0.5% of the water-based flash rust inhibitor into the pure acrylic emulsion, uniformly dispersing the pure acrylic emulsion for 1h under a homogenizer of 1500r/min, coating the pure acrylic emulsion on a substrate, and curing.
Example 6
Weighing a certain mass of pure acrylic emulsion, adding 20% of the silica sol of the embodiment 1 and 0.2-0.5% of the water-based flash rust inhibitor into the pure acrylic emulsion, uniformly dispersing for 1h under a homogenizer of 1500r/min, adding 3% of high-purity Bai Linsuan zinc into the mixed emulsion, uniformly dispersing for 1h under the homogenizer of 1500r/min, coating the mixture on a substrate, and curing.
Example 7
Weighing a certain mass of pure acrylic emulsion, adding 20% of the silica sol of the embodiment 1 and 0.2-0.5% of the water-based flash rust inhibitor into the pure acrylic emulsion, uniformly dispersing for 1h under a homogenizer of 1500r/min, adding 5% of high-purity Bai Linsuan zinc into the mixed emulsion, uniformly dispersing for 1h under the homogenizer of 1500r/min, coating the mixture on a substrate, and curing.
Example 8
Weighing a certain mass of pure acrylic emulsion, adding 20% of the silica sol of the embodiment 1 and 0.2-0.5% of the water-based flash rust inhibitor into the pure acrylic emulsion, uniformly dispersing for 1h under a homogenizer of 1500r/min, adding 7% of high-purity white zinc phosphate into the mixed emulsion, uniformly dispersing for 1h under the homogenizer of 1500r/min, coating the mixture on a substrate, and curing.
Comparative example 1
To better illustrate the effect of the silica sol and the corrosion inhibitor zinc phosphate on the composite coating, in the comparative example, a pure acrylic emulsion was applied to a substrate and cured to give a pure acrylic coating.
Test example 1
The silica sol obtained in example 1 was tested for average particle size as shown in FIG. 1. The average particle diameter is 20nm-100nm. The particle size distribution broadens with increasing particle size, but the variation is not significant.
The silica sols of different particle sizes obtained in example 1 were tested for fourier infrared spectra as shown in figure 2. In the figure, 3480cm -1 The left and right peaks can be attributed to the stretching vibration of the O-H groups and Si-OH groups of the water adsorbed on the silica sol surface. 1634cm -1 Is the absorption peak of Si-OH bending vibration. And 1110cm -1 And 800cm -1 The anti-symmetrical stretching vibration peak and the symmetrical stretching vibration absorption peak of Si-O-Si are respectively. 470cm -1 The absorption peak at this point is caused by bending vibration of the Si-O bond. From the above analysis of the data, it can be seen that the silica sol was successfully prepared.
Tensile diagrams of the corrosion-resistant coatings prepared in examples 2 to 8 and comparative example 1 were tested, as shown in fig. 3. The tensile strength of the coating can be enhanced by adding the silica sol, the addition amount of the silica sol is below 20%, and the tensile strength of the coating is higher than 10MPa, because the organic and inorganic particles in the coating have better crosslinking degree and fewer microdefects, and a more complete space network continuous structure is formed. The addition of silica sol significantly reduces the elongation at break of the coating because the coating is rigid and less flexible after the addition of silica sol.
The adhesion force diagrams of the corrosion-resistant coatings prepared in examples 4, 7 and comparative example 1 were tested, as shown in fig. 4. The addition of silica sol to the acrylic emulsion can increase the adhesion of the coating to the substrate. When the silica sol is added to be 20%, the coating adhesion can reach 4MPa, and after the zinc phosphate is added, the coating adhesion reaches 4.3MPa, because the emulsion without the silica sol is low in solid content, more pores are formed by volatilization of water and solvent in the drying process, residual stress is generated, and a plurality of micro defects are formed in the coating. When the coating is subjected to drawing stress, the stress concentration at the micro defects is easy to develop into micro cracks, so that fracture zones are formed, and the adhesive force of the coating is reduced. The silica sol with certain amount is added to fill the micropores of the coating well, so that the strength of the matrix and the external stress of the dispersion coating are enhanced, and the adhesion of the coating is enhanced. The silica sol has strong binding force between a large number of silicon hydroxyl groups and the base material, and has the function of improving the adhesion.
Electrochemical test patterns of the anticorrosive coatings prepared in examples 4 and 7 and comparative example 1 were tested as shown in fig. 5. Example 7 EIS spectrum of composite coating on Q235 carbon steel, impedance at low frequency region was about 10 6 Ω·cm 2 The silica sol with proper addition amount is selected, and the synergistic effect of the corrosion inhibitor is added, so that the corrosion resistance of the coating in the early stage of corrosion can be enhanced.
In the polarization curve, the pure acrylic emulsion coating I corr 1.26X10 -7 A·cm -2 ,E corr I of the composite coating at-0.78V corr 6.31X10 -10 A·cm -2 ,E corr The corrosion current is reduced to-0.24V, the potential is positively moved, the shielding performance is improved by the silica sol and the zinc phosphate, and the zinc phosphate can also effectively transfer electrons generated in the corrosion process of the alloy, so that the surface of the Q235 steel is passivated, and the corrosion resistance of the coating is improved.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A silica sol modified acrylic acid anticorrosive paint is characterized in that: the anti-flash rust agent comprises large-particle-size silica sol, acrylic emulsion, a corrosion inhibitor and a water-based anti-flash rust agent, wherein the mass fraction of the large-particle-size silica sol is 10% -30% of that of the acrylic emulsion;
the particle size of the large-particle-size silica sol is 20-100nm.
2. The silica sol modified acrylic anticorrosive paint according to claim 1, wherein: the preparation method of the silica sol with large particle size comprises the following steps: and adding the activated silicon powder into alkali liquor to perform multistage growth of particles, so as to obtain the silica sol with large particle size.
3. The silica sol modified acrylic anticorrosive paint according to claim 2, wherein: the alkali liquor is sodium hydroxide or potassium hydroxide solution.
4. A silica sol modified acrylic anticorrosive paint according to claim 3, wherein: the mass concentration of the alkali liquor is 0.5% -1.5%.
5. The silica sol modified acrylic anticorrosive paint according to claim 2, wherein: the growth temperature of each stage is 80-90 ℃, and the growth time is 5-10h.
6. The silica sol modified acrylic anticorrosive paint according to claim 2, wherein: the activating method of the silicon powder is to place the silicon powder into hot water with the temperature of 60-80 ℃ for activating treatment.
7. The silica sol modified acrylic anticorrosive paint according to claim 1, wherein: the corrosion inhibitor is zinc phosphate, and the mass fraction of the zinc phosphate in the mixed solution of the silica sol with large particle size and the acrylic emulsion is 3-7%.
8. The silica sol modified acrylic anticorrosive paint according to claim 1, wherein: the water-based flash rust inhibitor accounts for 0.2 to 0.5 percent of the mass of the coating.
9. The method for preparing the silica sol modified acrylic acid anticorrosive paint according to any one of claims 1 to 8, which is characterized in that: the method comprises the following steps:
adding large-particle-size silica sol into acrylic emulsion according to a certain proportion, uniformly mixing, adding corrosion inhibitor and water-based anti-flash rust agent into the mixture, and uniformly dispersing to obtain the product.
10. The silica sol modified acrylic acid anticorrosive coating is characterized in that: uniformly coating the silica sol modified acrylic acid anticorrosive paint according to any one of claims 1-8 on a substrate, and curing to obtain the silica sol modified acrylic acid anticorrosive paint.
CN202310366183.8A 2023-04-07 2023-04-07 Silica sol modified acrylic acid anticorrosive paint and preparation method thereof Pending CN116218310A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102181231A (en) * 2011-04-20 2011-09-14 杭州灯塔涂料玻璃有限公司 Preparation method of water-based environmentally-friendly anticorrosion paint
CN102816486A (en) * 2011-06-10 2012-12-12 上海建冶科技工程股份有限公司 Rust-removing-free environment-friendly acrylic acid zinc phosphate organic composite ceramic anticorrosive paint and preparation method thereof
CN103937353A (en) * 2014-05-20 2014-07-23 重庆海联水性涂料有限公司 Application of nano silicon dioxide sol in water-based steel structure anticorrosive paint and protective paint
CN107936783A (en) * 2017-12-26 2018-04-20 黄作鹏 One kind is used for steel structure aqueous rust-proof antiseptic paint
CN109627872A (en) * 2018-11-26 2019-04-16 河北晨阳工贸集团有限公司 A kind of water soluble acrylic acid anticorrosive paint of containing graphene and preparation method thereof
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CN103937353A (en) * 2014-05-20 2014-07-23 重庆海联水性涂料有限公司 Application of nano silicon dioxide sol in water-based steel structure anticorrosive paint and protective paint
CN107936783A (en) * 2017-12-26 2018-04-20 黄作鹏 One kind is used for steel structure aqueous rust-proof antiseptic paint
CN109627872A (en) * 2018-11-26 2019-04-16 河北晨阳工贸集团有限公司 A kind of water soluble acrylic acid anticorrosive paint of containing graphene and preparation method thereof
CN111234627A (en) * 2020-01-21 2020-06-05 山东七维新材料有限公司 High-performance water-based acrylic coating

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