Anticorrosive paint as well as preparation method and application thereof

Abstract

The invention belongs to the technical field of coatings, and particularly relates to an anticorrosive coating as well as a preparation method and application thereof. The anticorrosive paint comprises the following raw materials in parts by weight: 60-80 parts of acrylic acid modified polysiloxane resin, 4-20 parts of MXene / polyaniline and 6-15 parts of a curing agent. The anticorrosive paint has the beneficial effects that MXene contained in the anticorrosive paint can form a compact barrier layer in a coating to effectively block permeation of water, oxygen and corrosive media, and can also be used as a polyaniline carrier to inhibit aggregation of polyaniline chains, enhance dispersion uniformity of the polyaniline chains in a resin matrix and reduce coating microcracks and other defects; and the metal surface passivation film is better promoted to be formed through electrochemical activity, the anodic oxidation process is inhibited, and finally the anti-corrosion performance of the coating is enhanced.

Description

Technical Field

[0001] The present application belongs to the field of coating technology, and specifically relates to an anti-corrosion coating and a preparation method and application thereof. Background Art

[0002] In modern industrial protection, demand for highly effective and durable anticorrosion coatings is growing. Polysiloxane anticorrosion coatings, with their exceptional weather resistance and chemical stability, have become the preferred material for numerous applications. These coatings, based on the abundant Si-O bonds in the polysiloxane resin molecular structure, impart exceptional thermal stability and oxidation resistance, while also ensuring good flexibility and water resistance. To further enhance the performance of these coatings, acrylic polysiloxane anticorrosion coatings have emerged. These coatings combine the advantages of acrylic resins and polysiloxanes, exhibiting superior overall performance. Firstly, they excel in improving the coating's weather resistance, particularly its resistance to UV aging, enabling the coating to maintain excellent gloss and color stability even after long-term outdoor use. Furthermore, these coatings exhibit excellent adhesion, forming a robust protective layer on a variety of substrates. However, these coatings still face numerous challenges in extreme environments. For example, in environments with high temperature, high humidity, strong acidity, strong alkali, or high salinity, their durability and long-term protection can be compromised. Furthermore, these coatings often lack effective electrochemical mechanisms, failing to effectively inhibit corrosion reactions on metal surfaces.

[0003] In view of the above problems existing in the prior art, it is particularly necessary to develop a new material that can overcome the shortcomings of acrylic polysiloxane anti-corrosion coatings and provide stronger anti-corrosion protection. Summary of the Invention

[0004] The present application provides an anti-corrosion coating, a preparation method and application thereof, aiming to solve the problem that the existing acrylic modified polysiloxane resin anti-corrosion coating has degraded application performance in high temperature, high humidity and highly corrosive environments and lacks an electrochemical protection mechanism.

[0005] In a first aspect, the present application provides an anti-corrosion coating comprising the following raw materials in parts by weight: 60-80 parts of acrylic modified polysiloxane resin, 4-20 parts of MXene / polyaniline, and 6-15 parts of a curing agent.

[0006] According to some embodiments of the anti-corrosion coating described in the present application, the coating includes the following raw materials in parts by weight: 5-8 parts of acrylic modified polysiloxane resin, 1 part of MXene / polyaniline, and 1-4 parts of curing agent.

[0007] According to some embodiments of the anti-corrosion coating described in the present application, the acrylic modified polysiloxane resin includes acrylic modified polysiloxane resin SH-309.

[0008] According to some embodiments of the anticorrosive coating described in the present application, the curing agent comprises one or more of isophorone diamine, 4,4'-diaminodiphenyl methane and methyltetrahydrophthalic anhydride.

[0009] According to some embodiments of the anticorrosive coating described in the present application, the mass ratio of MXene to aniline in the MXene / polyaniline is 1:(0.5-20).

[0010] According to some embodiments of the anticorrosive coating described in the present application, the mass ratio of MXene to aniline in the MXene / polyaniline is 1:(2-10).

[0011] According to some embodiments of the anticorrosive coating described in the present application, the particle size of the MXene / polyaniline is 2-20um.

[0012] According to some embodiments of the anticorrosive coating described in the present application, the particle size of the MXene / polyaniline is 5-15um.

[0013] According to some embodiments of the anticorrosive coating described in the present application, the MXene comprises transition metal Ti and / or V.

[0014] According to some embodiments of the anticorrosive coating described in the present application, the MXene comprises transition metal Ti.

[0015] According to some embodiments of the anticorrosive coating described in the present application, the number of layers of the MXene is ≤20.

[0016] According to some embodiments of the anticorrosive coating described in the present application, the lateral size of the MXene is 2-10um.

[0017] According to some embodiments of the anticorrosive coating described in the present application, the MXene is MXene modified by γ-aminopropyl triethoxysilane.

[0018] The second aspect of the present application provides a preparation method of the anticorrosive coating of the first aspect of the present application, comprising the following steps: mixing the acrylic modified polysiloxane resin, the MXene / polyaniline and the curing agent to obtain the anticorrosive coating.

[0019] According to some embodiments of the preparation method of the anticorrosive coating described in the present application, further comprising the step of preparing the MXene / polyaniline: mixing MXene, aniline, ammonium persulfate and hydrochloric acid to form a reaction solution, and reacting to obtain the MXene / polyaniline.

[0020] According to some embodiments of the preparation method of the anticorrosive coating described in the present application, the concentration of aniline in the reaction solution is (1-2) mol / L.

[0021] According to some embodiments of the method for preparing the anti-corrosion coating described in the present application, the molar ratio of the aniline to the ammonium persulfate is 1:1.

[0022] According to some embodiments of the method for preparing the anti-corrosion coating described in the present application, the reaction temperature is 0-5°C, and the reaction time is 6-12 hours.

[0023] The third aspect of the present application provides an application of the anti-corrosion coating described in the first aspect of the present application or the anti-corrosion coating obtained by the preparation method described in the second aspect of the present application in the corrosion resistance of steel parts.

[0024] The beneficial effects of the present application include: the MXene contained in the anti-corrosion coating described in the present application can form a dense barrier layer in the coating, effectively blocking the penetration of water, oxygen and corrosive media, and can also serve as a polyaniline carrier to inhibit the agglomeration of polyaniline chains, enhance its dispersion uniformity in the resin matrix, reduce defects such as microcracks in the coating, and enable it to better promote the formation of a passivation film on the metal surface through electrochemical activity, inhibit the anodic oxidation process, and ultimately enhance the anti-corrosion performance of the coating. DETAILED DESCRIPTION

[0025] The embodiments of the present invention are described in detail below. The examples of the embodiments are exemplary and intended to be used to explain the present invention, but should not be understood as limiting the present invention.

[0026] In the present invention, the terms "one embodiment", "some embodiments", "examples", "specific examples", or "some examples" mean that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic expressions of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described can be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine different embodiments or examples described in this specification and the features of different embodiments or examples without contradiction.

[0027] The embodiment of the present application provides an anti-corrosion coating, comprising the following raw materials in parts by weight: 60-80 parts of acrylic modified polysiloxane resin, 4-20 parts of MXene / polyaniline, and 6-15 parts of a curing agent.

[0028] MXene is a two-dimensional transition metal carbide or nitride with a large surface area and excellent mechanical strength. When combined with polyaniline (PAI), which exhibits excellent electrical conductivity and environmental stability, MXene not only effectively blocks the penetration of corrosive media but also inhibits surface oxidation on the metal through its electrochemical activity. The synergistic effect of MXene and PAI forms a dual anti-corrosion mechanism: physical shielding and chemical passivation. MXene, as a carrier for PAI, effectively inhibits PAI aggregation, enhancing its dispersion and further strengthening its protective capabilities. Furthermore, the pseudocapacitive properties of MXene combined with PAI impart excellent electrostatic dissipation to the coating, preventing localized electrochemical corrosion caused by charge accumulation. Furthermore, the abundant functional groups (such as -OH and -O) on the MXene surface enhance interfacial bonding with polysiloxane resins, improve the dispersion of the composite, and reduce defects such as microcracks in the coating, thereby increasing density and adhesion.

[0029] The anti-corrosion coating described in this application utilizes the unique advantages of MXene / polyaniline composite materials to overcome the limitations of existing acrylic modified polysiloxane resin anti-corrosion coatings and promote the development of high-performance anti-corrosion coatings.

[0030] In some embodiments of the present application, the following raw materials are included in parts by weight: 5-8 parts of acrylic modified polysiloxane resin, 1 part of MXene / polyaniline, and 1-4 parts of curing agent.

[0031] In some embodiments of the present application, the acrylic modified polysiloxane resin includes acrylic modified polysiloxane resin SH-309. The acrylic modified polysiloxane resin SH-309 described in the embodiments of the present application was purchased from Kaifeng Quark New Materials Co., Ltd.

[0032] In some embodiments of the present application, the curing agent includes one or more of isophoronediamine, 4,4′-diaminodiphenylmethane, and methyltetrahydrophthalic anhydride.

[0033] In some embodiments of the present application, the mass ratio of MXene to aniline in the MXene / polyaniline is 1:(0.5-20), for example, 1:0.5, 1:1, 1:5, 1:8, 1:12, 1:14, 1:16, 1:20, etc.

[0034] In some embodiments of the present application, the mass ratio of MXene to aniline in the MXene / polyaniline is 1:(2-10).

[0035] If the aniline content is too high, it is easy to cause agglomeration; if the aniline content is too low, more MXene / polyaniline composite materials need to be added, otherwise it is difficult to form a stable passivation film.

[0036] In some embodiments of the present application, the particle size of the MXene / polyaniline is 2-20 μm, such as 2 μm, 5 μm, 8 μm, 10 μm, 12 μm, 16 μm, 20 μm, etc. If the MXene / polyaniline particle size is too small, it is easy to cause agglomeration, resulting in poor resin fluidity, while if it is too large, it is easy to cause coating defects.

[0037] In some embodiments of the present application, the particle size of the MXene / polyaniline is 5-15 μm.

[0038] In some embodiments of the present application, the MXene contains transition metals Ti and / or V.

[0039] In some embodiments of the present application, the MXene contains the transition metal Ti.

[0040] In some embodiments of the present application, the number of MXene layers is ≤ 20, such as 20, 18, 13, 10, 8, 6, 3, etc. If the number of MXene layers is too large, its specific surface area decreases, reducing the shielding effect and the dispersion of polyaniline on the MXene.

[0041] In some embodiments of the present application, the lateral size of the MXene is 2-10 μm, for example, 2-3 μm, 3-5 μm, 4-6 μm, 4-7 μm, 4-10 μm, etc. If the lateral size of the MXene is too large, the effective specific surface area will be significantly reduced, the loading amount and dispersibility of the polyaniline will be limited, and the shielding effect of the MXene and the passivation effect of the polyaniline in the coating will be reduced.

[0042] In some embodiments of the present application, the MXene is modified with γ-aminopropyltriethoxysilane. The modification process includes adding 10g of γ-aminopropyltriethoxysilane and 1g of MXene to 100ml of anhydrous ethanol solution, stirring for 24 hours, filtering, washing the residue with ethanol, and drying.

[0043] An embodiment of the present application also provides a method for preparing the anti-corrosion coating described in the first aspect of the present application, comprising the following steps: mixing acrylic modified polysiloxane resin, MXene / polyaniline and a curing agent to obtain an anti-corrosion coating.

[0044] Some embodiments of this application also include the step of preparing MXene / polyaniline: mixing MXene, aniline, ammonium persulfate, and hydrochloric acid to form a reaction solution, and reacting to obtain MXene / polyaniline. The MXene / polyaniline preparation process described herein is simple and highly tunable, providing new possibilities and technical support for the development of a new generation of multifunctional anti-corrosion coatings.

[0045] In some embodiments of the present application, the concentration of aniline in the reaction solution is (1-2) mol / L; for example, 1 mol / L, 1.2 mol / L, 1.5 mol / L, 1.8 mol / L, 2 mol / L, etc.

[0046] In some embodiments of the present application, the molar ratio of the aniline to the ammonium persulfate is 1:(0.8-1.2).

[0047] In some embodiments of the present application, the reaction temperature is 0-5°C, such as 0°C, 2°C, 3°C, 5°C, etc., and the reaction time is 6-12h, such as 6h, 8h, 9h, 12h, etc.

[0048] The present application also provides an embodiment of the present application providing an application of the anti-corrosion coating described in the first aspect of the present application or the anti-corrosion coating prepared by the preparation method described in the second aspect of the present application for corrosion resistance of steel parts. The anti-corrosion coating described in the present application still has good corrosion resistance and strong adhesion under extreme environments.

[0049] The technical solution of this application is further described below with reference to specific embodiments.

[0050] Example 1

[0051] A method for preparing an anti-corrosion coating comprises the following steps:

[0052] (1) Preparation of MXene / polyaniline composites:

[0053] 2 g of γ-aminopropyltriethoxysilane-modified MXene (the transition metal contained in MXene is Ti) with a single layer and a lateral size of 2-10 μm was dispersed in 220 ml of a mixed solution of 1 mol / L hydrochloric acid and aniline monomer (wherein the mass ratio of γ-aminopropyltriethoxysilane-modified MXene to aniline is 1:1). 20 ml of a mixed solution of 1 mol / L hydrochloric acid and 4.9 g of ammonium sulfate was slowly added to the above solution. After the addition was completed, the mixture was reacted at a temperature of 0-5°C for 10 h. After the reaction was completed, the mixture was centrifuged, and the centrifuged product was washed until neutral, dried, and ground to obtain MXene / polyaniline with a particle size of 5-15 μm.

[0054] (2) 1 g of the above-mentioned MXene / polyaniline, 20 g of acrylic modified polysiloxane resin SH-309, and 3.33 g of isophorone diamine were mixed to obtain an anticorrosive coating.

[0055] Example 2

[0056] The preparation method of the anti-corrosion coating described in Example 2 is different from that of Example 1 only in that the dosage ratio of MXene / polyaniline and acrylic modified polysiloxane resin in the preparation process of the anti-corrosion coating described in Example 2 is different.

[0057] The specific steps include:

[0058] 2.5 g of the above MXene / polyaniline, 20 g of acrylic modified polysiloxane resin SH-309, and 3.33 g of isophorone diamine were mixed to obtain an anti-corrosion coating.

[0059] Example 3

[0060] The preparation method of the anti-corrosion coating described in Example 3 is different from that of Example 1 only in that the dosage ratio of MXene / polyaniline and acrylic modified polysiloxane resin in the preparation process of the anti-corrosion coating described in Example 3 is different.

[0061] The specific steps include:

[0062] 3.5 g of the above-mentioned MXene / polyaniline, 20 g of acrylic modified polysiloxane resin SH-309, and 3.33 g of isophorone diamine were mixed to obtain an anti-corrosion coating.

[0063] Example 4

[0064] The only difference between the preparation method of the anti-corrosion coating described in Example 4 and that of Example 1 is that the mass ratio of γ-aminopropyltriethoxysilane-modified MXene and aniline in the MXene / polyaniline used in the preparation process of the anti-corrosion coating described in Example 4 is 1:2, that is, the amount of γ-aminopropyltriethoxysilane-modified MXene added is 2 g, and the amount of aniline added is 4 g.

[0065] Example 5

[0066] The only difference between the preparation method of the anti-corrosion coating described in Example 5 and that of Example 1 is that the mass ratio of γ-aminopropyltriethoxysilane-modified MXene and aniline in the MXene / polyaniline used in the preparation process of the anti-corrosion coating described in Example 5 is 1:5, that is, the amount of γ-aminopropyltriethoxysilane-modified MXene added is 2 g, and the amount of aniline added is 10 g.

[0067] Example 6

[0068] The only difference between the preparation method of the anti-corrosion coating described in Example 6 and that in Example 1 is that the MXene used in the preparation process of the anti-corrosion coating described in Example 6 is not modified by γ-aminopropyltriethoxysilane.

[0069] Comparative Example 1

[0070] The preparation method of the anti-corrosion coating described in Comparative Example 1 is different from that of Example 1 only in that MXene is used instead of MXene / polyaniline in the preparation process of the anti-corrosion coating described in Comparative Example 1.

[0071] The specific operation steps include:

[0072] 1g MXene, 20g acrylic modified polysiloxane resin SH-309 and 3.33g isophorone diamine were mixed to obtain the anticorrosive coating.

[0073] Comparative Example 2

[0074] The preparation method of the anticorrosive coating of Comparative Example 2 is different from that of Example 1 only in that polyaniline is used instead of MXene / polyaniline in the preparation process of the anticorrosive coating of Comparative Example 2.

[0075] The specific operation steps include:

[0076] 1g polyaniline, 20g acrylic modified polysiloxane resin SH-309 and 3.33g isophorone diamine were mixed to obtain the anticorrosive coating.

[0077] Comparative Example 3

[0078] The preparation method of the anticorrosive coating of Comparative Example 3 is different from that of Example 1 only in that MXene / polyaniline is not used in the preparation process of the anticorrosive coating of Comparative Example 3.

[0079] The specific operation steps include:

[0080] 20g acrylic modified polysiloxane resin SH-309 and 3.33g isophorone diamine were mixed to obtain the anticorrosive coating.

[0081] The performance of the anticorrosive coatings prepared by the preparation methods of Examples 1-6 of the present application and the anticorrosive coatings of Comparative Examples 1-3 was studied.

[0082] The haze rate test of the present application is based on ASTM D6577;

[0083] The test method for corrosion resistance of the present application is based on ISO 9227.

[0084] The test results are shown in Table 1.

[0085] Table 1

[0086] Gloss loss rate (%) 1000 hours Salt spray resistance (days) Example 1 8.3％ 77 Example 2 7.4％ 83 Example 3 8.6％ 81 Example 4 8.1％ 80 Example 5 8.8％ 76 Example 6 8.1％ 52 Comparative Example 1 8.1％ 69 Comparative Example 2 10.3％ 64 Comparative Example 3 11.7％ 56

[0087] As can be seen from Table 1, the anticorrosive coating of the present application has better anticorrosive performance and weather resistance.

[0088] Comparing Examples 1-3 of the present application, it can be seen that when the mass ratio of MXene / polyaniline and acrylic modified polysiloxane resin is 1:8, the anticorrosive coating prepared has better corrosion resistance.

[0089] By comparing Example 1 and Examples 4-5 of the present application, it can be seen that when the mass ratio of MXene and aniline in the raw material MXene / polyaniline is 1:2, the prepared anti-corrosion coating has better corrosion resistance.

[0090] By comparing Example 1 of the present application with Comparative Examples 1-3, it can be seen that compared with the anti-corrosion coatings obtained by preparing raw materials without adding or only adding MXene or polyaniline, the anti-corrosion coatings described in the present application have obvious advantages in weather resistance and corrosion resistance.

[0091] Although the above embodiments have been shown and described, it is understood that the above embodiments are illustrative and are not to be construed as limitations on the present invention. Changes, modifications, substitutions and variations of the above embodiments by those skilled in the art are all within the scope of protection of the present invention.

Claims

1. An anti-corrosion coating, characterized in that: The method comprises the following raw materials in parts by weight: 60-80 parts of acrylic modified polysiloxane resin, 4-20 parts of MXene / polyaniline, and 6-15 parts of curing agent.

2. The anti-corrosion coating according to claim 1, characterized in that: The method comprises the following raw materials in parts by weight: 5-8 parts of acrylic modified polysiloxane resin, 1 part of MXene / polyaniline, and 1-4 parts of curing agent.

3. The anti-corrosion coating according to claim 1, characterized in that: The acrylic acid modified polysiloxane resin includes acrylic acid modified polysiloxane resin SH-309; And / or, the curing agent includes one or more of isophoronediamine, 4,4′-diaminodiphenylmethane and methyltetrahydrophthalic anhydride.

4. The anti-corrosion coating according to claim 1, characterized in that: The mass ratio of MXene to aniline in the MXene / polyaniline is 1:(0.5-20), preferably 1:(2-10).

5. The anti-corrosion coating according to claim 1, characterized in that: The particle size of the MXene / polyaniline is 2-20 μm, preferably 5-15 μm.

6. The anti-corrosion coating according to claim 1, characterized in that: The MXene comprises transition metals Ti and / or V, preferably Ti; and / or, the number of layers of the MXene is ≤20; and / or, the lateral size of the MXene is 2-10 μm; And / or, the MXene is MXene modified with γ-aminopropyltriethoxysilane.

7. The method for preparing the anticorrosive coating according to any one of claims 1 to 6, characterized in that: The following steps are involved: The anti-corrosion coating is obtained by mixing acrylic modified polysiloxane resin, MXene / polyaniline and a curing agent.

8. The method for preparing the anticorrosive coating according to claim 7, characterized in that: The method further includes the steps of preparing MXene / polyaniline: mixing MXene, aniline, ammonium persulfate and hydrochloric acid to form a reaction solution, and reacting to obtain MXene / polyaniline.

9. The method for preparing the anticorrosive coating according to claim 8, characterized in that: The concentration of aniline in the reaction solution is (1-2) mol / L; and / or, the molar ratio of the aniline to the ammonium persulfate is 1:(0.8-1.2); And / or, the reaction temperature is 0-5°C, and the reaction time is 6-12 hours.

10. Use of the anti-corrosion coating according to any one of claims 1 to 6 or the anti-corrosion coating obtained by the preparation method according to any one of claims 7 to 9 in the corrosion resistance of steel parts.