A kind of anti-corrosion and anti-fouling coating and preparation method thereof

Abstract

The present invention provides an anti-corrosion and anti-fouling coating and a preparation method thereof, wherein the anti-corrosion and anti-fouling coating comprises the following components by mass: 20-40 parts of hydrophilic acrylic resin, 20-30 parts of epoxy resin, 5-10 parts of modified polyacrylate, 5-10 parts of silane polymer, 5-15 parts of filler, 1-10 parts of auxiliary agent, and 20-70 parts of solvent; wherein the modified polyacrylate is a polymerization product of carbitol acrylate, hydroxyalkyl acrylate and modified acrylate; and the modified acrylate is a reaction product of alkyl halide and aminoalkyl acrylate. The present invention not only improves the stability and anti-corrosion of the coating, but also gives the product good hydrophilicity, achieves better self-cleaning and anti-fouling effects, and overcomes the defects of the prior art.

Description

Technical Field

[0001] The invention belongs to the technical field of coatings, and in particular relates to an anti-corrosion and anti-fouling coating and a preparation method thereof. Background Art

[0002] Acrylic resin coating is a commonly used coating product. This type of coating uses acrylic resin as the main film-forming substance, compounded with fillers, additives, solvents and other ingredients. Acrylic resin coating has been widely used in furniture, electrical appliances, machine tools, light industry, ships, construction, bridges, aviation, automobiles and other fields, mainly for the protection of material surfaces and decorative topcoat.

[0003] As the coatings industry develops towards high-tech products, the market is paying more and more attention to acrylic resin products, and the demand for research on acrylic resin is gradually increasing. Traditional acrylic coatings have good technical effects in terms of waterproofness and adhesion, but due to the continuous improvement of protection requirements and the continuous increase in specific requirements put forward by different industries, the strength, weather resistance, dirt resistance and self-cleaning properties of conventional coatings are difficult to meet the needs of current applications, and ideal protection effects cannot be achieved, which urgently needs to be improved.

[0004] In summary, it is necessary to develop a new technical solution to solve the problems existing in the prior art. Summary of the invention

[0005] In order to solve the deficiencies in the prior art, the present invention provides an anti-corrosion and anti-fouling coating and a preparation method thereof. The present invention uses hydrophilic acrylic resin and epoxy resin as base resins, and is compounded with modified polyacrylate obtained by polymerization of carbitol acrylate, hydroxyalkyl acrylate and modified acrylate, as well as silane polymer, filler and other components, which not only improves the stability and anti-corrosion of the coating, but also gives the product good hydrophilic properties, achieves better self-cleaning and anti-fouling effects, and overcomes the defects of the prior art.

[0006] One object of the present invention is to provide an anti-corrosion and anti-fouling coating, wherein the anti-corrosion and anti-fouling coating comprises the following components in parts by weight:

[0007]

[0008] in,

[0009] The modified polyacrylate is a polymerization product of carbitol acrylate, hydroxyalkyl acrylate and modified acrylate;

[0010] The modified acrylate is a reaction product of an alkyl halide and an aminoalkyl acrylate.

[0011] Furthermore, the filler is a filler that has been surface hydroxylated.

[0012] Furthermore, the auxiliary agent is selected from one or more of a dispersant, a defoamer, a leveling agent, an emulsifier, a thickener, a curing agent, a film-forming agent, an antioxidant and a photoinitiator.

[0013] Furthermore, the hydrophilic acrylic resin is methyl etherified amino acrylic resin.

[0014] Furthermore, the filler is selected from one or more of montmorillonite, silicon dioxide, calcined kaolin, talc, calcium carbonate, diatomaceous earth and metal oxides.

[0015] Another object of the present invention is to provide a method for preparing the above-mentioned anti-corrosion and anti-fouling coating, wherein the method for preparing the anti-corrosion and anti-fouling coating comprises the following steps:

[0016] S1, mixing an alkyl halide and aminoalkyl acrylate, heating and reacting the mixture to obtain a modified acrylate;

[0017] S2, blending carbitol acrylate, hydroxyalkyl acrylate and the modified acrylate, then adding an initiator and a dispersant, and heating the mixture under the protection of an inert gas to react, thereby obtaining a modified polyacrylate;

[0018] S3, adding silane to a solvent, then adding an acid catalyst and water, stirring and heating to react, to obtain a silane polymer;

[0019] S4, blending and evenly stirring the modified polyacrylate, silane polymer and other ingredients to obtain the anti-corrosion and anti-fouling coating.

[0020] Furthermore, in step S1, the heating reaction temperature is 20-60°C and the time is 2-5h.

[0021] Furthermore, in step S2, the initiator is azobisisobutyronitrile, and the dispersant is polyethylene glycol.

[0022] Furthermore, in step S2, the heating reaction temperature is 60-90°C and the time is 4-6h.

[0023] Furthermore, in step S2, the mass ratio of carbitol acrylate, hydroxyalkyl acrylate and modified acrylate is (1-5):(1-10):(1-10).

[0024] Furthermore, in step S3, the stirring and heating reaction is carried out at a temperature of 50-70° C. and for a time of 2-5 h.

[0025] Furthermore, the silane is selected from one or more of methyl silicate, ethyl silicate, propyl silicate and butyl silicate.

[0026] The present invention has the following beneficial effects:

[0027] In the anti-corrosion and dirt-resistant coating of the present invention, hydrophilic acrylic resin and epoxy resin are used as matrix resin, and are compounded with components such as modified polyacrylate, silane polymer and hydroxylated filler. Wherein, modified polyacrylate first reacts alkyl halide with aminoalkyl acrylate to obtain a hydrophobic monomer, and then polymerizes with carbides and hydroxyalkyl acrylate to obtain a product, which has good compatibility with the matrix resin, and because it contains hydrophilic and hydrophobic groups at the same time, it has a certain surface activity, is conducive to enhancing the dispersibility of hydroxylated filler, improves the stability of the composition, and also helps to strengthen the film-forming effect. The silane polymer is obtained by polycondensation reaction of small molecule silane, improves the density and content of silane alkoxy, enhances the hydrophilic function, and after compounding with a matrix resin containing a large amount of hydroxyl groups and ether bonds, modified polyacrylate, and filler, it can not only promote the coating to absorb moisture to form a water film, enhance anti-fouling, self-cleaning effects, but also promote a variety of active groups to be cross-linked, and produce intermolecular forces, obtain a more three-dimensional network structure, and significantly improve the stability and strength of the coating. DETAILED DESCRIPTION

[0028] The present invention is further described below with reference to specific examples, but the examples do not limit the present invention in any form. Unless otherwise specified, the reagents, methods and equipment used in the present invention are conventional reagents, methods and equipment in the art.

[0029] Unless otherwise specified, the reagents and materials used in the following examples are commercially available.

[0030] The hydrophilic acrylic resin in the embodiment of the present invention is Jiangsu Sanmu 6121 methyl etherified amino acrylic resin.

[0031] The epoxy resin in the embodiment of the present invention is E44 bisphenol A epoxy resin.

[0032] The auxiliary agents in the embodiment of the present invention are photoinitiator Irgacure 2959, curing agent MHG-80B, hydroxyethyl cellulose ether (Dow) and film-forming auxiliary agent propylene glycol butyl ether in a mass ratio of 1:1:1:1.

[0033] The filler in the embodiment of the present invention is hydroxylated silicon dioxide, and the preparation method of the hydroxylated silicon dioxide comprises the following steps:

[0034] Silicon dioxide and glucose in a mass ratio of 1:5 were mixed and ball-milled (ball-to-material ratio 5:1), and hydroxylated silicon dioxide was obtained through washing, centrifugation and drying.

[0035] The solvent in the embodiment of the present invention is butyl acetate.

[0036] Example 1

[0037] An anti-corrosion and anti-fouling coating comprises the following components in parts by weight:

[0038]

[0039] The preparation method of the anti-corrosion and anti-fouling coating comprises the following steps:

[0040] S1. Using acetone as solvent, hexadecane bromide and dimethylaminoethyl methacrylate in a mass ratio of 2:1 were mixed, added into a reaction kettle, reacted at 30° C. for 4 h, filtered, washed, and dried to obtain modified acrylate;

[0041] S2, using water as solvent, blending carbitol acrylate, hydroxyethyl methacrylate and the modified acrylate in a mass ratio of 5:5:8, then adding azobisisobutyronitrile (system 0.5wt%) and polyethylene glycol 1000 (system 0.5wt%), stirring evenly, reacting at 85°C under a nitrogen atmosphere for 5h, centrifuging and drying to obtain modified polyacrylate;

[0042] S3, using ethanol as solvent, adding ethyl silicate, then adding deionized water (ethyl silicate: deionized water = 1:1, n / n) with stirring, adjusting the pH to 4 with 15wt% hydrochloric acid, stirring and reacting at 60°C for 4h, and removing the solvent by distillation under reduced pressure to obtain a silane polymer;

[0043] S4. Blend and evenly stir the modified polyacrylate, silane polymer and other ingredients according to the above-mentioned mass fractions to obtain the anti-corrosion and anti-fouling coating.

[0044] Example 2

[0045] An anti-corrosion and anti-fouling coating comprises the following components in parts by weight:

[0046]

[0047] The preparation method of the anti-corrosion and anti-fouling coating comprises the following steps:

[0048] S1. Using acetone as solvent, hexadecane bromide and dimethylaminoethyl methacrylate in a mass ratio of 2:1 were mixed, added into a reaction kettle, reacted at 30° C. for 4 h, filtered, washed, and dried to obtain modified acrylate;

[0049] S2, using water as solvent, blending carbitol acrylate, hydroxyethyl methacrylate and the modified acrylate in a mass ratio of 5:5:8, then adding azobisisobutyronitrile (system 0.5wt%) and polyethylene glycol 1000 (system 0.5wt%), stirring evenly, reacting at 85°C under a nitrogen atmosphere for 5h, centrifuging and drying to obtain modified polyacrylate;

[0050] S3, using ethanol as solvent, adding ethyl silicate, then adding deionized water (ethyl silicate: deionized water = 1:1, n / n) with stirring, adjusting the pH to 4 with 15wt% hydrochloric acid, stirring and reacting at 60°C for 4h, and removing the solvent by distillation under reduced pressure to obtain a silane polymer;

[0051] S4. Blend and evenly stir the modified polyacrylate, silane polymer and other ingredients according to the above-mentioned mass fractions to obtain the anti-corrosion and anti-fouling coating.

[0052] Example 3

[0053] An anti-corrosion and anti-fouling coating comprises the following components in parts by weight:

[0054]

[0055]

[0056] The preparation method of the anti-corrosion and anti-fouling coating comprises the following steps:

[0057] S1. Using acetone as solvent, hexadecane bromide and dimethylaminoethyl methacrylate in a mass ratio of 2:1 were mixed, added into a reaction kettle, reacted at 30° C. for 4 h, filtered, washed, and dried to obtain modified acrylate;

[0058] S2, using water as solvent, blending carbitol acrylate, hydroxyethyl methacrylate and the modified acrylate in a mass ratio of 5:5:8, then adding azobisisobutyronitrile (system 0.5wt%) and polyethylene glycol 1000 (system 0.5wt%), stirring evenly, reacting at 85°C under a nitrogen atmosphere for 5h, centrifuging and drying to obtain modified polyacrylate;

[0059] S3, using ethanol as solvent, adding ethyl silicate, then adding deionized water (ethyl silicate: deionized water = 1:1, n / n) with stirring, adjusting the pH to 4 with 15wt% hydrochloric acid, stirring and reacting at 60°C for 4h, and removing the solvent by distillation under reduced pressure to obtain a silane polymer;

[0060] S4. Blend and evenly stir the modified polyacrylate, silane polymer and other ingredients according to the above-mentioned mass fractions to obtain the anti-corrosion and anti-fouling coating.

[0061] Comparative Example 1

[0062] A corrosion-resistant and dirt-resistant coating. The difference between this comparative example and Example 1 is that step S1 is omitted, the modified acrylate is replaced by methyl acrylate of equal mass in step S2, and other components and preparation methods are the same as those in Example 1.

[0063] Comparative Example 2

[0064] A corrosion-resistant and dirt-resistant coating. The difference between this comparative example and Example 1 is that in step S2, the carbitol acrylate is replaced by methyl acrylate of equal mass, and the other ingredients and preparation method are the same as those in Example 1.

[0065] Comparative Example 3

[0066] A corrosion-resistant and dirt-resistant coating. The difference between this comparative example and Example 1 is that step S3 is omitted, and in step S4, the silane polymer is replaced by ethyl silicate of equal mass, and other components and preparation methods are the same.

[0067] Test Case

[0068] The performance tests were performed on the products obtained in Examples 1-3 and Comparative Examples 1-3.

[0069] Corrosion resistance: After the surface of the tinplate was polished and cleaned, the sample coating was applied and cured at 60℃ for 5h. Then, the sample was treated with 395nm, 400mJ / cm 2 The coating was irradiated with ultraviolet light to obtain the coating. The acid and alkali corrosion resistance test was carried out by soaking in 10wt% HCl and 10wt% NaOH.

[0070] Adhesion, stain resistance, and resistance to artificial climate acceleration: tested in accordance with GB / T 9286, GB / T 9780, and GB / T 14522 standards.

[0071] The test results are shown in Table 1.

[0072] Table 1 Performance test results

[0073] project Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Comparative Example 3 Acid resistance / 96h No abnormality No abnormality No abnormality No abnormality No abnormality A few rust spots Alkali resistance / 96h No abnormality No abnormality No abnormality A few rust spots A few rust spots Obvious rust spots Adhesion Level 0 Level 0 Level 0 Level 1 Level 1 Level 1 Stain resistance / % 0.8 0.8 0.8 1.9 2.5 7.6 Weather resistance / 4000h No abnormality No abnormality No abnormality A small amount of bubbles A small amount of bubbles A small amount of bubbles

[0074] According to Table 1, the anti-corrosion and anti-fouling coatings of Examples 1-3 of the present invention, after being placed in an acidic or alkaline environment for a long time, did not rust, had excellent corrosion resistance, and had good adhesion and anti-fouling properties. However, in Comparative Examples 1-3, due to the replacement of modified polyacrylate or silane polymer, the stability, strength and other properties of the coatings decreased, and the synergistic effect between the components was weakened, and the corrosion resistance and anti-fouling properties were significantly reduced. In summary, the present invention overcomes the defects existing in the prior art and has good application prospects.

[0075] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be equivalent replacement methods and are included in the protection scope of the present invention.

Claims

1. An anti-corrosion and anti-fouling coating, characterized in that: The anti-corrosion and anti-fouling coating comprises the following components in parts by mass: 20-40 parts of methyl etherified amino acrylic resin Epoxy resin 20-30 parts Modified polyacrylate 5-10 parts Silane polymer 5-10 parts Filler 5-15 parts 1-10 parts of additives 20-70 parts of solvent; in, The modified polyacrylate is a polymerization product of carbitol acrylate, hydroxyalkyl acrylate and modified acrylate; The modified acrylate is a reaction product of an alkyl halide and aminoalkyl acrylate; The preparation method of the anti-corrosion and anti-fouling coating comprises the following steps: S1, mixing an alkyl halide and aminoalkyl acrylate, heating and reacting the mixture to obtain a modified acrylate; S2, blending carbitol acrylate, hydroxyalkyl acrylate and the modified acrylate, then adding an initiator and a dispersant, and heating the mixture under the protection of an inert gas to react, thereby obtaining a modified polyacrylate; S3, adding silane to a solvent, then adding an acid catalyst and water, stirring and heating to react, to obtain a silane polymer; S4, blending and evenly stirring the modified polyacrylate, silane polymer and other ingredients to obtain the anti-corrosion and anti-fouling coating.

2. The anti-corrosion and anti-fouling coating according to claim 1, characterized in that: The filler is a filler after surface hydroxylation treatment.

3. The anti-corrosion and anti-fouling coating according to claim 1, characterized in that: The auxiliary agent is selected from one or more of a dispersant, a defoamer, a leveling agent, an emulsifier, a thickener, a curing agent, a film-forming agent, an antioxidant and a photoinitiator.

4. The anti-corrosion and anti-fouling coating according to claim 2, characterized in that: The filler is selected from one or more of montmorillonite, silicon dioxide, calcined kaolin, talc, calcium carbonate, diatomaceous earth and metal oxides.

5. The anti-corrosion and anti-fouling coating according to claim 1, characterized in that: In step S1, the heating reaction temperature is 20-60°C and the time is 2-5 h.

6. The anti-corrosion and anti-fouling coating according to claim 1, characterized in that: In step S2, the heating reaction temperature is 60-90°C and the time is 4-6 h.

7. The anti-corrosion and anti-fouling coating according to claim 1, characterized in that: In step S2, the mass ratio of carbitol acrylate, hydroxyalkyl acrylate and modified acrylate is (1-5):(1-10):(1-10).

8. The anti-corrosion and anti-fouling coating according to claim 1, characterized in that: In step S3, the stirring and heating reaction is carried out at a temperature of 50-70° C. and for a time of 2-5 h.

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