Reconfigurable intelligent anti-corrosion coating and preparation method thereof

Abstract

The invention discloses a reconfigurable intelligent anti-corrosion coating and a preparation method thereof. The preparation method comprises the following steps: dispersing a filler in deionized water, adjusting the pH value to 8-10, adding a pH buffer agent, adding a modifier A at room temperature, and carrying out a stirring reaction to obtain a precursor; a modifier B is dissolved in ethyl alcohol, then the precursor is added for a reaction, and a modified filler is obtained after centrifugation, washing and drying; dispersing the modified filler in ethanol, performing ultrasonic dispersion treatment, adding epoxy resin, polydimethylsiloxane, a flatting agent, an adhesion promoter and an ultraviolet light absorber, and uniformly dispersing; and adding a curing agent, and uniformly dispersing to obtain the reconfigurable intelligent anti-corrosion coating. The coating of the reconfigurable intelligent anticorrosive paint has a super-hydrophobic surface, efficient photothermal conversion performance, excellent ultraviolet resistance and excellent corrosion resistance, and is especially suitable for corrosion protection of carbon steel.

Description

Technical Field

[0001] The present invention relates to the field of epoxy composite coatings, and in particular to a reconfigurable intelligent anti-corrosion coating and a preparation method thereof. Background Art

[0002] Although traditional epoxy resin (EP) anti-corrosion coatings have good chemical inertness and mechanical strength, their inherent defects (such as microcracks and irreversible medium penetration) lead to insufficient long-term protection capabilities, making it difficult to meet the requirements of complex working conditions. The existing technology usually incorporates inorganic functional fillers into EP resins to enhance the corrosion protection capabilities of composite coatings by extending the diffusion path of corrosive media (barrier effect and maze effect), improving chemical inertness (acid resistance, alkali resistance and salt resistance, etc.), and enhancing the density of the coating (filling gaps and forming a dense structure). Although certain progress has been made, the problem of water droplet infiltration on the coating surface under complex working conditions still needs to be further solved. Superhydrophobic surface technology provides a new idea for breaking through this bottleneck. Inspired by the "lotus effect", superhydrophobic coatings with micro / nanostructures and low surface energy can form a gas-liquid composite interface, significantly delaying the diffusion of corrosive media to the metal substrate.

[0003] However, the surface properties of super-hydrophobic coatings can be reduced with the change of external environment and the extension of time, and super-hydrophobic function may be completely lost when serious. Especially, when affected by external load, interfacial adhesion or harsh operating conditions, due to the destruction of surface micro-nano structure or chemical composition, super-hydrophobic surface is difficult to maintain, and this instability limits their practical application. Chinese patent CN119500522A discloses a preparation method of a wear-regenerated super-hydrophobic durable type anti-corrosion coating. A mechanical robustness super-hydrophobic coating with bulk consistency is constructed by the reverse filling of self-similar structure; wherein, oily binder solution undergoes phase separation and is mixed with fluorinated nanoparticles under the action of alcoholic solvents, is sprayed on the metal substrate surface, constructs a self-similar super-hydrophobic coating, and the low surface energy nanoparticles and high hardness oily binder uniform dispersion sprayed on its surface; especially, the good oil absorption of oily binder enables the self-similar structure of super-hydrophobic coating to be effectively filled by high hardness oily binder, finally forming a wear-regenerated durable type super-hydrophobic anti-corrosion coating. This patent restores superhydrophobic properties by sanding the coating for 2.0 m with 800-grit sandpaper under a 200g load. However, mechanical sanding is time-consuming and labor-intensive, and can cause irreversible damage to the coating, significantly shortening its service life. Furthermore, the patent introduces fluorinated silicones to create the superhydrophobic surface. The long-term accumulation of fluorine atoms can harm the ecological environment and even affect human health. Summary of the Invention

[0004] In order to overcome the above-mentioned shortcomings and deficiencies of the prior art, the purpose of the present invention is to provide a method for preparing a reconfigurable intelligent anti-corrosion coating, by modifying the filler and introducing a long-chain alkyl group with low surface energy into the surface of the two-dimensional filler through chemical grafting technology. At the same time, the modified filler has photothermal conversion performance, and the solar energy absorbed by it can be converted into the heat required to stimulate the migration of low-surface energy substances (long-chain alkyl groups on the surface of the modified filler and the added polydimethylsiloxane) to the coating surface, thereby realizing the reconstruction of the hydrophobic surface; at the same time, the addition of an ultraviolet absorber enhances the ability of the composite coating to resist ultraviolet degradation, thereby avoiding the degradation effect of ultraviolet rays in sunlight on the polymer chain segments of the coating during the photothermal conversion process, and extending the service life of the reconfigurable intelligent anti-corrosion coating.

[0005] Another object of the present invention is to provide a reconfigurable intelligent anti-corrosion coating prepared by the preparation method of the above-mentioned reconfigurable intelligent anti-corrosion coating.

[0006] The purpose of the present invention is achieved through the following technical solutions:

[0007] The present invention provides a method for preparing a reconfigurable intelligent anti-corrosion coating, comprising the following steps:

[0008] (1) Preparation of modified filler: The filler is dispersed in deionized water, and then the pH is adjusted to 8-10, a pH buffer is added, and modifier A is added at room temperature, and stirred for reaction for 8-20 hours to obtain a precursor; modifier B is dissolved in ethanol at 30-50°C, and then the precursor is added, and the reaction is carried out at 40-50°C for 5-15 hours. After centrifugation, washing, and drying, the modified filler is obtained;

[0009] The filler is at least one of graphene nanosheets, boron nitride nanosheets, and nano-montmorillonite;

[0010] The modifier A is at least one of dopamine hydrochloride and tannic acid;

[0011] The modifier B is at least one of octadecyl mercaptan and octadecylamine;

[0012] (2) Preparation of reconfigurable intelligent anti-corrosion coating: The modified filler is dispersed in ethanol, and after ultrasonic dispersion treatment, epoxy resin and polydimethylsiloxane, leveling agent, adhesion promoter, and ultraviolet absorber are added and evenly dispersed; then a curing agent is added and evenly dispersed to obtain a reconfigurable intelligent anti-corrosion coating.

[0013] Preferably, in step (1), the mass ratio of the filler to the modifier A is: (1-5): (4-10).

[0014] Preferably, in step (1), the mass ratio of the filler to the modifier B is: (1-5): (2-10).

[0015] Preferably, in step (1), the mass ratio of the filler, deionized water, and pH buffer is: (1-5): (20-50): (0.5-1.5).

[0016] Preferably, in step (1), the mass ratio of the modifier B to ethanol is (2 to 10 parts): (30 to 100).

[0017] Preferably, in step (2), the mass ratio of the modified filler, epoxy resin, polydimethylsiloxane, leveling agent, adhesion promoter, and ultraviolet absorber is: (1-10): (50-120): (20-50): (1-5): (0.8-2.5): (0.5-1.8).

[0018] Preferably, in step (2), the mass ratio of the modified filler to ethanol is: (1-10): (20-100).

[0019] Preferably, the epoxy resin is one of E20, E44, E51, and E55;

[0020] The curing agent is composed of 10 to 30 parts of curing agent A and 2 to 5 parts of curing agent B, wherein the curing agent A is at least one of diethylenetriamine and polyamide YK651; and the curing agent B is a matching curing agent with the brand name Dow Corning Sylgard 184.

[0021] Preferably, the pH buffer is at least one of Tris buffer, MES buffer and PBS phosphate buffer.

[0022] Preferably, the leveling agent is a polyether-modified silicone oil leveling agent; more preferably, it is at least one of BYK-333, BYK-346 and Glide 450.

[0023] Preferably, the adhesion promoter is at least one of AKN-6105, YB-201D, BYK-4510 and BYK-4511.

[0024] Preferably, the ultraviolet absorber is at least one of UV531, UV329, UV234 and UV327.

[0025] The present invention also provides a reconfigurable intelligent anti-corrosion coating, which is prepared by the preparation method of the reconfigurable intelligent anti-corrosion coating.

[0026] The present invention also provides a reconfigurable intelligent anti-corrosion coating, which is prepared by coating the reconfigurable intelligent anti-corrosion coating on a metal surface and then curing it at room temperature for 6 to 12 hours; the superhydrophobicity of the surface of the reconfigurable intelligent anti-corrosion coating can be restored through photothermal conversion after being destroyed.

[0027] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0028] (1) The reconfigurable intelligent anti-corrosion coating of the present invention modifies the filler and introduces long-chain alkyl groups with low surface energy into the surface of the two-dimensional filler through chemical grafting technology. At the same time, the modified filler has photothermal conversion performance and can use the solar energy absorbed by it to convert it into the heat required to stimulate the migration of low-surface-energy substances (long-chain alkyl groups on the surface of the modified filler and added polydimethylsiloxane) to the coating surface, thereby realizing the reconstruction of the hydrophobic surface.

[0029] (2) The present invention combines super-hydrophobic surface technology with anti-corrosion coatings to reduce the wettability of the coating surface to water droplets, effectively preventing the aggregation of water droplets on the coating surface, and significantly improving the anti-corrosion performance of the composite coating. The long-chain alkyl groups on the surface of the modified filler and the added polydimethylsiloxane provide low surface energy for the coating, while the filler provides a micro-nanostructure for the composite coating, synergistically strengthening the super-hydrophobic properties of the coating.

[0030] (3) The present invention introduces a photothermal conversion function to make the coating reconfigurable and intelligent. On the one hand, the heat generated by the photothermal conversion can promote the diffusion and migration of low-surface-energy materials on the bottom to the coating surface, thus achieving the reconfigurable function of the coating's superhydrophobic properties. On the other hand, compared with traditional heating methods, photothermal activation is simpler to operate and more conducive to industrial applications, which is conducive to promoting the development of anti-corrosion coatings towards intelligentization.

[0031] (4) The present invention strengthens the ability of the composite coating to resist ultraviolet degradation by adding an ultraviolet absorber, thereby avoiding the degradation effect of ultraviolet rays in sunlight on the polymer chain segments of the coating during the photothermal conversion process, and extending the service life of the reconfigurable intelligent anti-corrosion coating. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 This is an infrared spectrum of the modified filler of Example 1 of the present invention.

[0033] Figure 2 1 is an X-ray photoelectron spectrum of the modified filler of Example 1 of the present invention, wherein (a) is the full spectrum and (b) is the X-ray photoelectron spectrum of N1s.

[0034] Figure 3 This is a contact angle diagram of the coating of Example 1 of the present invention after salt spray destruction and photothermal reconstruction.

[0035] Figure 4 This is a rolling angle diagram of the coating of Example 1 of the present invention after salt spray damage and photothermal reconstruction. DETAILED DESCRIPTION

[0036] To better understand the present invention, the present invention is further described below with reference to specific examples. It should be understood that these examples are intended only to illustrate the present invention and are not intended to limit the scope of protection of the present invention. Any modifications to the present invention that are readily implemented by a person of ordinary skill in the art without departing from the technical solution of the present invention are intended to fall within the scope of the claims of the present invention.

[0037] In the following examples and comparative examples, the hardness of the anti-corrosion coatings was measured according to the standard GB / T6739-2006. The adhesion of the anti-corrosion coatings was measured according to the standard GB / T1720-1979. The surface contact angle and rolling angle of the anti-corrosion coatings were measured according to the standard ASTM D7334.

[0038] In the following examples and comparative examples, the photothermal conversion performance of the anti-corrosion coatings was measured using the following procedures: a thermocouple thermometer and an infrared thermal imager (Testo AG, Germany) were used to record the surface temperature changes and infrared thermal images of the coating samples, respectively. A xenon lamp (XE 300F, China) without an optical filter was used to simulate sunlight irradiation at an intensity of 200 mW / cm 2 .

[0039] In the following examples and comparative examples, the initial impedance modulus values of the anti-corrosion coatings were measured according to the following steps: The electrochemical tests of the coating samples were evaluated by electrochemical impedance spectroscopy (EIS) and recorded using an electrochemical workstation (CHI-660E, China) after immersion in a 3.5 wt% NaCl solution at room temperature for 30 days. The electrochemical tests were performed in a conventional three-electrode system, in which a saturated calomel electrode was used as the reference electrode, a platinum electrode was used as the auxiliary electrode, and the exposed area was 1 cm 2 Q235 steel was used as the working electrode. Before the experiment, all samples were placed in 3.5wt% NaCl solution until a stable open circuit potential was reached at an interference potential of 10mV and a range of 100kHz to 10 -2 The EIS curves were recorded at Hz. The EIS results of different samples were analyzed using ZSimpWin software, and the initial impedance modulus after immersion for 30 days was recorded.

[0040] In the following examples and comparative examples, the UV resistance of the anti-corrosion coatings was measured according to the following steps: UV radiation testing was performed on the coating samples using an accelerated climate tester (Xenotest Beta LM Atlas) according to ASTM-D 6695. The coatings were exposed to UV radiation (300-400 nm, 65 Wm -2 ), the first 18 minutes of UV irradiation were accompanied by water spray, followed by 102 minutes of UV irradiation alone. The number of UV irradiation cycles was adjusted to meet the test requirements for different UV irradiation durations. The 60° gloss of the coatings before and after UV irradiation was measured using a WGG60-Y4 glossmeter (KSJ Optoelectronic Instrument Co., Ltd.) according to GB / T 9574-2007.

[0041] In the following examples and comparative examples, the reconfigurable performance of the anti-corrosion coating was measured according to the following steps: after exposure to salt spray conditions for 10 days, the super-hydrophobicity of the coating was lost, and then the damaged coating was exposed to 200 mW / cm 2 After irradiation under simulated sunlight for 15 minutes, the surface contact angle and rolling angle of the anti-corrosion coating after xenon lamp irradiation were measured according to standard ASTM D7334.

[0042] Example 1

[0043] A method for preparing a reconfigurable intelligent anti-corrosion coating comprises the following steps:

[0044] 1) Preparation of modified filler: Disperse 2 parts graphene nanosheets in 30 parts deionized water, adjust the pH to 9 with sodium hydroxide, and then add 1.2 parts tris (hydroxymethyl)aminomethane buffer. Add 8 parts tannic acid and stir at room temperature for 10 hours to obtain a precursor. Dissolve 6 parts octadecylamine in 60 parts ethanol at 40°C, then add the precursor and react at 50°C for 10 hours. Centrifuge, wash, and dry to obtain the modified filler.

[0045] 2) Preparation of a reconfigurable intelligent anti-corrosion coating: Disperse 5 parts by mass of the modified filler in 50 parts by mass of ethanol and ultrasonicate for 1.5 hours. Subsequently, add 80 parts of epoxy resin E44, 40 parts of polydimethylsiloxane, 3 parts of leveling agent BYK-333, 1.5 parts of adhesion promoter YB-201D, and 1.2 parts of UV absorber UV531, and disperse them evenly. Then, add 20 parts of curing agent polyamide YK651 and 2.5 parts of Dow Corning Sylgard 184, a matching curing agent, and disperse them evenly to obtain the coating.

[0046] Preparation method of reconfigurable intelligent anti-corrosion coating: The coating is evenly coated on pretreated Q235 steel by an automatic coating machine and cured at room temperature for 10 hours to obtain a reconfigurable intelligent anti-corrosion coating. The coating has excellent anti-corrosion performance and super-hydrophobicity, and the super-hydrophobicity can be restored through photothermal conversion after it is destroyed. That is, when the super-hydrophobicity of the coating is destroyed, under sunlight conditions, the coating absorbs light and converts it into heat, causing the surface temperature of the coating to rise to above 50°C, driving the long-chain alkyl and polydimethylsiloxane inside the coating to migrate to the interface between the coating and the air, and reconstructing the super-hydrophobic surface; the coating reconstructs the super-hydrophobic surface more than 5 times through photothermal conversion, extending the anti-corrosion life of the coating.

[0047] Example 2

[0048] A method for preparing a reconfigurable intelligent anti-corrosion coating comprises the following steps:

[0049] 1) Preparation of modified filler: Disperse 1 part boron nitride nanosheets in 20 parts deionized water, adjust the pH to 8 with ammonia, and then add 0.5 parts PBS phosphate buffer. Add 4 parts tannic acid and stir at room temperature for 8 hours to obtain a precursor. Dissolve 2 parts octadecylamine in 30 parts ethanol at 30°C, then add the precursor and react at 40°C for 5 hours. Centrifuge, wash, and dry to obtain the modified filler.

[0050] 2) Preparation of reconfigurable intelligent anti-corrosion coating: Disperse 1 part of modified filler in 20 parts of ethanol by mass and ultrasonicate for 0.5h. Then, add 50 parts of epoxy resin E51 and 20 parts of polydimethylsiloxane, 1 part of leveling agent Glide 450, 0.8 parts of adhesion promoter BYK-4511, and 0.5 parts of ultraviolet absorber UV327 and disperse them evenly. Then add 10 parts of a mixture of diethylenetriamine and polyamide YK651 and 2 parts of a matching curing agent named Dow Corning Sylgard 184 and disperse them evenly.

[0051] Preparation method of reconfigurable intelligent anti-corrosion coating: The coating is evenly coated on pretreated Q235 steel by an automatic coating machine and cured at room temperature for 6 hours to obtain a reconfigurable intelligent anti-corrosion coating. The coating has excellent anti-corrosion performance and super-hydrophobicity, and the super-hydrophobicity can be restored through photothermal conversion after it is destroyed. That is, when the super-hydrophobicity of the coating is destroyed, under sunlight conditions, the coating absorbs light and converts it into heat, causing the surface temperature of the coating to rise to above 60°C, driving the long-chain alkyl and polydimethylsiloxane inside the coating to migrate to the interface between the coating and the air, and reconstructing the super-hydrophobic surface; the coating reconstructs the super-hydrophobic surface more than 5 times through photothermal conversion, extending the anti-corrosion life of the coating.

[0052] Example 3

[0053] A method for preparing a reconfigurable intelligent anti-corrosion coating comprises the following steps:

[0054] 1) Preparation of modified filler: Disperse 5 parts of nano-montmorillonite in 50 parts of deionized water, adjust the pH to 10 with sodium hydroxide, and then add 1.5 parts of MES buffer. Add 10 parts of dopamine hydrochloride at room temperature and stir for 20 hours to obtain a precursor. Dissolve 10 parts of octadecylamine in 100 parts of ethanol at 50°C, then add the precursor and react at 50°C for 15 hours. Centrifuge, wash, and dry to obtain the modified filler.

[0055] 2) Preparation of reconfigurable intelligent anti-corrosion coating: Disperse 10 parts of modified filler in 100 parts of ethanol by mass and ultrasonicate for 2 hours. Then, add 120 parts of epoxy resin E55, 50 parts of polydimethylsiloxane, 5 parts of leveling agent BYK-346, 2.5 parts of adhesion promoter AKN-6105, and 1.8 parts of ultraviolet absorber UV329 and disperse them evenly. Then, add 30 parts of a mixture of diethylenetriamine and polyamide YK651 and 5 parts of a matching curing agent, Dow Corning Sylgard 184, and disperse them evenly.

[0056] Preparation method of reconfigurable intelligent anti-corrosion coating: The coating is evenly coated on pretreated Q235 steel by an automatic coating machine and cured at room temperature for 12 hours to obtain a reconfigurable intelligent anti-corrosion coating. The coating has excellent anti-corrosion performance and super-hydrophobicity, and the super-hydrophobicity can be restored through photothermal conversion after it is destroyed. That is, when the super-hydrophobicity of the coating is destroyed, under sunlight conditions, the coating absorbs light and converts it into heat, causing the surface temperature of the coating to rise to above 65°C, driving the long-chain alkyl and polydimethylsiloxane inside the coating to migrate to the interface between the coating and the air, and reconstructing the super-hydrophobic surface; the coating reconstructs the super-hydrophobic surface more than 5 times through photothermal conversion, extending the anti-corrosion life of the coating.

[0057] Example 4

[0058] A method for preparing a reconfigurable intelligent anti-corrosion coating comprises the following steps:

[0059] 1) Preparation of modified filler: 3 parts by mass of graphene nanosheets were dispersed in 40 parts of deionized water. Sodium hydroxide was added to adjust the pH to 9, followed by the addition of 1.4 parts of tris(hydroxymethyl)aminomethane buffer. 9 parts of dopamine hydrochloride were added at room temperature, and the mixture was stirred for 10 hours to obtain a precursor. 8 parts of octadecanethiol were dissolved in 70 parts of ethanol at 40°C, and the precursor was added. The mixture was reacted at 50°C for 10 hours. The modified filler was obtained after centrifugation, washing, and drying.

[0060] 2) Preparation of a reconfigurable intelligent anti-corrosion coating: Disperse 6 parts of modified filler in 60 parts of ethanol and ultrasonicate for 1.5 hours. Then, add 90 parts of epoxy resin E44, 30 parts of polydimethylsiloxane, 4 parts of leveling agent BYK-333, 1.5 parts of adhesion promoter YB-201D, and 1.3 parts of UV absorber UV531, and disperse evenly. Then, add 22 parts of curing agent polyamide YK651 and 2.0 parts of Dow Corning Sylgard 184, and disperse evenly.

[0061] Preparation method of reconfigurable intelligent anti-corrosion coating: The coating is evenly coated on pretreated Q235 steel by an automatic coating machine and cured at room temperature for 10 hours to obtain a reconfigurable intelligent anti-corrosion coating. The coating has excellent anti-corrosion performance and super-hydrophobicity, and the super-hydrophobicity can be restored through photothermal conversion after it is destroyed. That is, when the super-hydrophobicity of the coating is destroyed, under sunlight conditions, the coating absorbs light and converts it into heat, causing the surface temperature of the coating to rise to above 60°C, driving the long-chain alkyl and polydimethylsiloxane inside the coating to migrate to the interface between the coating and the air, and reconstructing the super-hydrophobic surface; the coating reconstructs the super-hydrophobic surface more than 5 times through photothermal conversion, extending the anti-corrosion life of the coating.

[0062] Example 5

[0063] A method for preparing a reconfigurable intelligent anti-corrosion coating comprises the following steps:

[0064] 1) Preparation of modified filler: 4 parts by mass of graphene nanosheets were dispersed in 45 parts of deionized water. Sodium hydroxide was then added to adjust the pH to 9, followed by the addition of 1.3 parts of tris(hydroxymethyl)aminomethane buffer. Dopamine hydrochloride (10 parts) was then added and stirred at room temperature for 10 hours to obtain a precursor. Octadecanethiol (7 parts) was dissolved in 80 parts of ethanol at 40°C, and the precursor was added. The mixture was reacted at 50°C for 10 hours. The modified filler was obtained after centrifugation, washing, and drying.

[0065] 2) Preparation of a reconfigurable intelligent anti-corrosion coating: Disperse 7 parts of modified filler in 70 parts of ethanol, ultrasonically treating for 1.5 hours. Then, add 100 parts of epoxy resin E44, 40 parts of polydimethylsiloxane, 5 parts of leveling agent BYK-333, 2.0 parts of adhesion promoter YB-201D, and 1.4 parts of UV absorber UV531, and disperse evenly. Then, add 25 parts of curing agent polyamide YK651 and 2.3 parts of Dow Corning Sylgard 184, and disperse evenly.

[0066] Preparation method of reconfigurable intelligent anti-corrosion coating: The coating is evenly coated on pretreated Q235 steel by an automatic coating machine and cured at room temperature for 10 hours to obtain a reconfigurable intelligent anti-corrosion coating. The coating has excellent anti-corrosion performance and super-hydrophobicity, and the super-hydrophobicity can be restored through photothermal conversion after it is destroyed. That is, when the super-hydrophobicity of the coating is destroyed, under sunlight conditions, the coating absorbs light and converts it into heat, causing the surface temperature of the coating to rise to above 60°C, driving the long-chain alkyl and polydimethylsiloxane inside the coating to migrate to the interface between the coating and the air, and reconstructing the super-hydrophobic surface; the coating reconstructs the super-hydrophobic surface more than 5 times through photothermal conversion, extending the anti-corrosion life of the coating.

[0067] Example 6

[0068] A method for preparing a reconfigurable intelligent anti-corrosion coating comprises the following steps:

[0069] 1) Preparation of modified filler: Disperse 2.5 parts of graphene nanosheets in 25 parts of deionized water, adjust the pH to 9 with sodium hydroxide, and then add 1.4 parts of tris (hydroxymethyl)aminomethane buffer. Add 5 parts of dopamine hydrochloride and stir at room temperature for 10 hours to obtain a precursor. Dissolve 5 parts of octadecanethiol in 90 parts of ethanol at 40°C, then add the precursor and react at 50°C for 10 hours. Centrifuge, wash, and dry to obtain the modified filler.

[0070] 2) Preparation of a reconfigurable intelligent anti-corrosion coating: Disperse 8 parts of modified filler in 20 parts of ethanol and ultrasonicate for 1.5 hours. Then, add 110 parts of epoxy resin E44, 20 parts of polydimethylsiloxane, 1 part of leveling agent BYK-333, 0.8 parts of adhesion promoter YB-201D, and 0.5 parts of UV absorber UV531, and disperse evenly. Then, add 27 parts of curing agent polyamide YK651 and 3.5 parts of Dow Corning Sylgard 184, and disperse evenly.

[0071] Preparation method of reconfigurable intelligent anti-corrosion coating: The coating is evenly coated on pretreated Q235 steel by an automatic coating machine and cured at room temperature for 10 hours to obtain a reconfigurable intelligent anti-corrosion coating. The coating has excellent anti-corrosion performance and super-hydrophobicity, and the super-hydrophobicity can be restored through photothermal conversion after it is destroyed. That is, when the super-hydrophobicity of the coating is destroyed, under sunlight conditions, the coating absorbs light and converts it into heat, causing the surface temperature of the coating to rise to above 60°C, driving the long-chain alkyl and polydimethylsiloxane inside the coating to migrate to the interface between the coating and the air, and reconstructing the super-hydrophobic surface; the coating reconstructs the super-hydrophobic surface more than 5 times through photothermal conversion, extending the anti-corrosion life of the coating.

[0072] Example 7

[0073] A method for preparing a reconfigurable intelligent anti-corrosion coating comprises the following steps:

[0074] 1) Preparation of modified filler: 3.5 parts by mass of graphene nanosheets were dispersed in 38 parts of deionized water. Sodium hydroxide was then added to adjust the pH to 9, followed by the addition of 1.5 parts of tris(hydroxymethyl)aminomethane buffer. Four parts of dopamine hydrochloride were added and stirred at room temperature for 10 hours to obtain a precursor. Nine parts of octadecanethiol were dissolved in 60 parts of ethanol at 40°C, and the precursor was added. The mixture was reacted at 50°C for 10 hours. The modified filler was obtained after centrifugation, washing, and drying.

[0075] 2) Preparation of reconfigurable intelligent anti-corrosion coating: Disperse 9 parts of modified filler in 60 parts of ethanol by mass and ultrasonicate for 1.5 hours. Then, add 100 parts of epoxy resin E44 and 45 parts of polydimethylsiloxane, 3 parts of leveling agent BYK-333, 1.0 part of adhesion promoter YB-201D, and 1.0 part of ultraviolet absorber UV531 and disperse them evenly. Then add 25 parts of curing agent polyamide YK651 and 5.0 parts of Dow Corning Sylgard 184 supporting curing agent and disperse them evenly to obtain.

[0076] Preparation method of reconfigurable intelligent anti-corrosion coating: The coating is evenly coated on pretreated Q235 steel by an automatic coating machine and cured at room temperature for 10 hours to obtain a reconfigurable intelligent anti-corrosion coating. The coating has excellent anti-corrosion performance and super-hydrophobicity, and the super-hydrophobicity can be restored through photothermal conversion after it is destroyed. That is, when the super-hydrophobicity of the coating is destroyed, under sunlight conditions, the coating absorbs light and converts it into heat, causing the surface temperature of the coating to rise to above 60°C, driving the long-chain alkyl and polydimethylsiloxane inside the coating to migrate to the interface between the coating and the air, and reconstructing the super-hydrophobic surface; the coating reconstructs the super-hydrophobic surface more than 5 times through photothermal conversion, extending the anti-corrosion life of the coating.

[0077] Example 8

[0078] A method for preparing a reconfigurable intelligent anti-corrosion coating comprises the following steps:

[0079] 1) Preparation of modified filler: 4.5 parts by mass of graphene nanosheets were dispersed in 40 parts of deionized water. Sodium hydroxide was then added to adjust the pH to 9, followed by the addition of 1.2 parts of tris (hydroxymethyl)aminomethane buffer. Six parts of dopamine hydrochloride were added and stirred at room temperature for 10 hours to obtain a precursor. Eight parts of octadecanethiol were dissolved in 90 parts of ethanol at 40°C, and the precursor was added. The mixture was reacted at 50°C for 10 hours. The modified filler was obtained after centrifugation, washing, and drying.

[0080] 2) Preparation of a reconfigurable intelligent anti-corrosion coating: Disperse 10 parts by mass of the modified filler in 90 parts by mass of ethanol and ultrasonicate for 1.5 hours. Then, add 120 parts of epoxy resin E44, 50 parts of polydimethylsiloxane, 5 parts of leveling agent BYK-333, 2.5 parts of adhesion promoter YB-201D, and 1.8 parts of UV absorber UV531, and disperse evenly. Then, add 30 parts of curing agent polyamide YK651 and 4.5 parts of Dow Corning Sylgard 184, and disperse evenly.

[0081] Preparation method of reconfigurable intelligent anti-corrosion coating: The coating is evenly coated on pretreated Q235 steel by an automatic coating machine and cured at room temperature for 10 hours to obtain a reconfigurable intelligent anti-corrosion coating. The coating has excellent anti-corrosion performance and super-hydrophobicity, and the super-hydrophobicity can be restored through photothermal conversion after it is destroyed. That is, when the super-hydrophobicity of the coating is destroyed, under sunlight conditions, the coating absorbs light and converts it into heat, causing the surface temperature of the coating to rise to above 60°C, driving the long-chain alkyl and polydimethylsiloxane inside the coating to migrate to the interface between the coating and the air, and reconstructing the super-hydrophobic surface; the coating reconstructs the super-hydrophobic surface more than 5 times through photothermal conversion, extending the anti-corrosion life of the coating.

[0082] Example 9

[0083] A method for preparing a reconfigurable intelligent anti-corrosion coating comprises the following steps:

[0084] 1) Preparation of modified filler: Disperse 5 parts by mass of graphene nanosheets in 50 parts of deionized water. Then, add sodium hydroxide to adjust the pH to 9, followed by the addition of 1.5 parts of tris(hydroxymethyl)aminomethane buffer. Add 7 parts of dopamine hydrochloride at room temperature, and stir for 10 hours to obtain a precursor. Dissolve 10 parts of octadecanethiol in 100 parts of ethanol at 40°C, then add the precursor, and react at 50°C for 10 hours. Centrifuge, wash, and dry to obtain the modified filler.

[0085] 2) Preparation of a reconfigurable intelligent anti-corrosion coating: Disperse 8 parts of modified filler in 100 parts of ethanol by mass and ultrasonicate for 1.5 hours. Then, add 120 parts of epoxy resin E44, 50 parts of polydimethylsiloxane, 5 parts of leveling agent BYK-333, 2.5 parts of adhesion promoter YB-201D, and 1.7 parts of UV absorber UV531, and disperse evenly. Then, add 30 parts of curing agent polyamide YK651 and 1.5 parts of Dow Corning Sylgard 184, and disperse evenly.

[0086] Preparation method of reconfigurable intelligent anti-corrosion coating: The coating is evenly coated on pretreated Q235 steel by an automatic coating machine and cured at room temperature for 10 hours to obtain a reconfigurable intelligent anti-corrosion coating. The coating has excellent anti-corrosion performance and super-hydrophobicity, and the super-hydrophobicity can be restored through photothermal conversion after it is destroyed. That is, when the super-hydrophobicity of the coating is destroyed, under sunlight conditions, the coating absorbs light and converts it into heat, causing the surface temperature of the coating to rise to above 80°C, driving the long-chain alkyl and polydimethylsiloxane inside the coating to migrate to the interface between the coating and the air, and reconstructing the super-hydrophobic surface; the coating reconstructs the super-hydrophobic surface more than 5 times through photothermal conversion, extending the anti-corrosion life of the coating.

[0087] Comparative Example 1

[0088] An anti-corrosion coating and a preparation method thereof, comprising the following steps:

[0089] 1) Preparation of modified filler: 2 parts by mass of graphene nanosheets were dispersed in 30 parts of deionized water. Sodium hydroxide was then added to adjust the pH to 9, followed by the addition of 1.2 parts of tris buffer. Dopamine hydrochloride (8 parts) was then added at room temperature, and the mixture was stirred for 10 hours. The modified filler was then centrifuged, washed, and dried.

[0090] 2) Preparation of the anti-corrosion coating: Disperse 5 parts by mass of the modified filler in 50 parts by mass of ethanol and ultrasonicate for 1.5 hours. Then, add 80 parts of epoxy resin E44, 40 parts of polydimethylsiloxane, 3 parts of leveling agent BYK-333, 1.5 parts of adhesion promoter YB-201D, and 1.2 parts of UV absorber UV531, and disperse evenly. Then, add 20 parts of curing agent polyamide YK651 and 2.5 parts of Dow Corning Sylgard 184, and disperse evenly.

[0091] Preparation method of the anti-corrosion coating: The coating is evenly applied on pretreated Q235 steel using an automatic coating machine and cured at room temperature for 10 hours to obtain a reconfigurable intelligent anti-corrosion coating.

[0092] Comparative Example 2

[0093] A method for preparing an anti-corrosion coating comprises the following steps:

[0094] 1) Preparation of modified filler: 2 parts by mass of graphene nanosheets were dispersed in 30 parts of deionized water. Sodium hydroxide was then added to adjust the pH to 9, followed by the addition of 1.2 parts of tris (hydroxymethyl)aminomethane buffer. Dopamine hydrochloride (8 parts) was then added and stirred at room temperature for 10 hours to obtain a precursor. Octadecanethiol (6 parts) was dissolved in ethanol (60 parts) at 40°C, and the precursor was added. The mixture was reacted at 50°C for 10 hours. The modified filler was obtained after centrifugation, washing, and drying.

[0095] 2) Preparation of the anti-corrosion coating: Disperse 5 parts by weight of the modified filler in 50 parts by weight of ethanol and sonicate for 1.5 hours. Then, add 80 parts of epoxy resin E44, 3 parts of leveling agent BYK-333, 1.5 parts of adhesion promoter YB-201D, and 1.2 parts of UV absorber UV531 and disperse evenly. Then, add 20 parts of curing agent polyamide YK651 and 2.5 parts of Dow Corning Sylgard 184, and disperse evenly.

[0096] Preparation method of anti-corrosion coating: evenly coat the coating on pretreated Q235 steel using an automatic coating machine and cure it at room temperature for 10 hours to obtain the anti-corrosion coating.

[0097] Comparative Example 3

[0098] A method for preparing a reconfigurable intelligent anti-corrosion coating comprises the following steps:

[0099] 1) Preparation of modified filler: 2 parts by mass of graphene nanosheets were dispersed in 30 parts of deionized water. Sodium hydroxide was then added to adjust the pH to 9, followed by the addition of 1.2 parts of tris (hydroxymethyl)aminomethane buffer. Dopamine hydrochloride (8 parts) was then added and stirred at room temperature for 10 hours to obtain a precursor. Octadecanethiol (6 parts) was dissolved in ethanol (60 parts) at 40°C, and the precursor was added. The mixture was reacted at 50°C for 10 hours. The modified filler was obtained after centrifugation, washing, and drying.

[0100] 2) Preparation of a reconfigurable intelligent anti-corrosion coating: Disperse 5 parts of modified filler in 50 parts of ethanol and sonicate for 1.5 hours. Then, add 80 parts of epoxy resin E44, 40 parts of polydimethylsiloxane, 3 parts of leveling agent BYK-333, and 1.5 parts of adhesion promoter YB-201D, and disperse evenly. Then, add 20 parts of curing agent polyamide YK651 and 2.5 parts of Dow Corning Sylgard 184, and disperse evenly.

[0101] Preparation method of the anti-corrosion coating: The coating is evenly applied on pretreated Q235 steel using an automatic coating machine and cured at room temperature for 10 hours to obtain a reconfigurable intelligent anti-corrosion coating.

[0102] Comparative Example 4

[0103] A method for preparing an anti-corrosion coating comprises the following steps:

[0104] Preparation of the reconfigurable intelligent anti-corrosion coating: By weight, evenly disperse 80 parts of epoxy resin E44, 40 parts of polydimethylsiloxane, 3 parts of leveling agent BYK-333, and 1.5 parts of adhesion promoter YB-201D. Then, add 20 parts of curing agent polyamide YK651 and 2.5 parts of Dow Corning Sylgard 184, and evenly disperse.

[0105] Preparation method of the anti-corrosion coating: The coating is evenly applied on pretreated Q235 steel using an automatic coating machine and cured at room temperature for 10 hours to obtain a reconfigurable intelligent anti-corrosion coating.

[0106] The reconfigurable intelligent anti-corrosion coatings in Examples 1 to 9 and Comparative Examples 1 to 4 were cured and left for 4 hours to a film thickness of 70 to 80 μm, and then their performance parameters were tested. The performance parameter results measured according to the above test method are shown in Table 1:

[0107] Table 1

[0108]

[0109]

[0110] The data in comparison table 1 show that the introduction of long-chain alkyl on filler surface and the addition of polydimethylsiloxane have improved the super-hydrophobicity of coating, thereby strengthening the corrosion protection ability of composite coating to metal, resulting in the increase of its initial impedance modulus. In addition, adding ultraviolet absorber effectively improves the anti-ultraviolet performance of composite coating, resulting in it after ultraviolet accelerated aging test, its glossiness variation is smaller. This illustrates that the composite coating prepared by the present invention has excellent super-hydrophobicity and good anti-ultraviolet performance. More importantly, composite coating is after xenon lamp irradiation, and the temperature on its surface significantly rises, and the heat of this photothermal conversion is that low-surface energy material (long-chain alkyl and polydimethylsiloxane) migrates to coating surface from coating interior and provides heat. After salt spray test, the low-surface energy material on coating surface is destroyed under adverse conditions, and after photothermal irradiation, promotes the low-surface energy material to move to coating surface, rebuilds super-hydrophobic surface, shows obvious intelligence, and repair time only needs 15 minutes, more efficient than prior art.

[0111] according to Figure 1 As shown, graphene nanosheets are at 3400 cm -1 and 1657cm -1 The characteristic peaks at 755 cm-1 correspond to the stretching vibration of the OH bond and the carbon skeleton vibration. -1 The bending vibration of the C=C bond in the benzene ring appeared at 1442cm -1 and 1532cm-1 The stretching vibration of the C—C bond in the aromatic group appears at 2847 cm, which indicates that the graphene nanosheet / tannic acid has been successfully synthesized. After further functionalization with octadecylamine, the graphene nanosheet / tannic acid / octadecylamine -1 (-CH2) and 2922cm -1 There is an obvious characteristic peak at (-CH3) and at 1642cm -1 The broad peak near 1466 cm is attributed to the stretching vibration of the C=N bond, while the peak at 1466 cm -1 The peak at comes from the bending vibration of the NH bond, which indicates that the long-chain alkyl of octadecylamine is grafted onto the graphene nanosheet / tannic acid surface through Schiff base reaction and Michael addition reaction. Figure 2 As shown, the O1s peak intensity at 533.71 eV for the graphene nanosheet / tannic acid composite is higher than that for the graphene nanosheet, demonstrating that the graphene nanosheet surface is coated with tannic acid. On the other hand, a new N1s peak at 400.01 eV appears for the graphene nanosheet / tannic acid / octadecylamine composite, confirming the successful grafting of octadecylamine onto the graphene nanosheet / tannic acid composite. These results confirm the successful synthesis of the graphene nanosheet / tannic acid / octadecylamine composite.

[0112] according to Figure 3 and Figure 4 As shown in Figure 2, the low surface energy materials graphene nanosheets / tannic acid / octadecylamine on the surface of the prepared composite coating were damaged in the salt spray test, resulting in a decrease in contact angle and an increase in rolling angle, and the coating lost its superhydrophobicity. However, at 200 mW·cm -2 After 15 minutes of simulated sunlight exposure, the contact angle of the composite coating recovered to over 150°, and the sliding angle dropped below 10°, re-exhibiting superhydrophobicity. This indicates that, under the stimulation of elevated temperature, the long alkyl chain octadecylamine migrated to the surface of the composite coating. Therefore, the excellent photothermal conversion capability of the graphene nanosheets / tannic acid / octadecylamine composite restored the superhydrophobicity of the composite coating, endowing it with long-term corrosion protection.

[0113] In summary, the present invention prepares a composite filler with superhydrophobic and photothermal conversion properties, endowing the composite coating with excellent corrosion resistance, photothermal conversion, and superhydrophobic properties. The added UV absorber enhances the coating's UV resistance. The resulting anticorrosion coating, due to its intelligent and reconfigurable properties, can be applied to metal corrosion protection.

[0114] The above embodiments are preferred implementation modes of the present invention, but the implementation modes of the present invention are not limited to the embodiments. Any other changes, modifications, substitutions, combinations, and simplifications that do not deviate from the spirit and principles of the present invention should be considered as equivalent replacement methods and are included in the scope of protection of the present invention.

Claims

1. A method for preparing a reconfigurable intelligent anti-corrosion coating, characterized in that: The following steps are involved: (1) Preparation of modified filler: The filler is dispersed in deionized water, and then the pH is adjusted to 8-10, a pH buffer is added, and modifier A is added at room temperature, and stirred for reaction for 8-20 hours to obtain a precursor; modifier B is dissolved in ethanol at 30-50°C, and then the precursor is added, and the reaction is carried out at 40-50°C for 5-15 hours. After centrifugation, washing, and drying, the modified filler is obtained; The filler is at least one of graphene nanosheets, boron nitride nanosheets, and nano-montmorillonite; The modifier A is at least one of dopamine hydrochloride and tannic acid; The modifier B is at least one of octadecyl mercaptan and octadecylamine; (2) Preparation of reconfigurable intelligent anti-corrosion coating: The modified filler is dispersed in ethanol, and after ultrasonic dispersion treatment, epoxy resin and polydimethylsiloxane, leveling agent, adhesion promoter, and ultraviolet absorber are added and evenly dispersed; then a curing agent is added and evenly dispersed to obtain a reconfigurable intelligent anti-corrosion coating.

2. The method for preparing the reconfigurable intelligent anti-corrosion coating according to claim 1, characterized in that: In step (1), the mass ratio of the filler to the modifier A is: (1-5): (4-10).

3. The method for preparing the reconfigurable intelligent anti-corrosion coating according to claim 1, characterized in that: In step (1), the mass ratio of the filler to the modifier B is: (1-5): (2-10).

4. The method for preparing the reconfigurable intelligent anti-corrosion coating according to claim 1, characterized in that: In step (1), the mass ratio of the filler, deionized water, and pH buffer is: (1-5): (20-50): (0.5-1.5).

5. The method for preparing the reconfigurable intelligent anti-corrosion coating according to claim 1, characterized in that: In step (1), the mass ratio of the modifier B to ethanol is (2 to 10 parts): (30 to 100).

6. The method for preparing the reconfigurable intelligent anti-corrosion coating according to claim 1, characterized in that: In step (2), the mass ratio of the modified filler, epoxy resin, polydimethylsiloxane, leveling agent, adhesion promoter and ultraviolet absorber is: (1-10): (50-120): (20-50): (1-5): (0.8-2.5): (0.5-1.8).

7. The method for preparing a reconfigurable intelligent anti-corrosion coating according to claim 1, characterized in that: In step (2), the mass ratio of the modified filler to ethanol is: (1-10): (20-100).

8. The method for preparing a reconfigurable intelligent anti-corrosion coating according to claim 1, characterized in that: The epoxy resin is one of E20, E44, E51, and E55; The curing agent is composed of 10 to 30 parts of curing agent A and 2 to 5 parts of curing agent B, wherein the curing agent A is at least one of diethylenetriamine and polyamide YK651; and the curing agent B is a matching curing agent with the brand name Dow Corning Sylgard 184.

9. Reconfigurable intelligent anti-corrosion coating, characterized by: The reconfigurable intelligent anti-corrosion coating is prepared by the preparation method of any one of claims 1 to 8.

10. Reconfigurable intelligent anti-corrosion coating, characterized in that: The reconfigurable intelligent anti-corrosion coating according to claim 9 is coated on a metal surface and then cured at room temperature for 6 to 12 hours; the superhydrophobicity of the surface of the reconfigurable intelligent anti-corrosion coating can be restored by photothermal conversion after being destroyed.

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