Composite nanometer material with corrosion resistance, corrosion-resistant material and preparation method of composite nanometer material and corrosion-resistant material

Abstract

The invention discloses a composite nano material with anti-corrosion performance, an anti-corrosion material and a preparation method thereof, and the method comprises the following steps: taking organic zinc as a zinc source, taking a pyrrole monomer as an organic ligand, and synthesizing first nano particles through a one-step method; ammonia monomer modified zirconium phosphate and sulfo-salicylaldehyde are adopted, and second nano particles are prepared through a chemical oxidation polymerization method; and by taking the second nano particles as a template, growing the first nano particles on the surfaces of the second nano particles in situ to obtain the composite nano material with corrosion resistance. The material prepared by the invention has a good metal anti-corrosion effect.

Description

Technical Field

[0001] The present invention relates to the technical field of metal anti-corrosion, and in particular to a composite nano material with anti-corrosion performance, an anti-corrosion material and a preparation method thereof. Background Art

[0002] Metal materials are widely used in important industrial production fields such as petrochemical pipelines, construction, shipbuilding, and aviation, and play an extremely important role in my country's social development. However, in actual use, metal materials and their alloys are easily affected by the surrounding humid environment or microbial bacteria, causing a series of physical, chemical, or electrochemical reactions, resulting in varying degrees of corrosion, which significantly reduces mechanical properties, shortens service life, and even causes catastrophic accidents, bringing huge harm and economic losses to the development of various countries and the metal industry. According to incomplete statistics, approximately 20% of metal materials in the world cannot be recycled each year due to corrosion. In addition, metal corrosion also poses a huge threat to the natural environment. The heavy metal ions produced by corrosion not only pollute the soil, plants, water and other environments, but also threaten human life and health. Therefore, it is imperative to find a method to improve the corrosion resistance of metals.

[0003] Organic polymer coatings are the most common corrosion protection method in the related art due to their high efficiency, low cost, and ease of use. Typically, organic polymer coatings form a protective layer on the metal surface to block the diffusion of corrosive media in the hope of achieving corrosion protection. However, the actual corrosion protection performance of organic polymer coatings needs to be further improved. Summary of the Invention

[0004] In view of at least one technical problem in the prior art, the object of the present invention is to provide a composite nanomaterial with anti-corrosion performance, an anti-corrosion material and a preparation method thereof.

[0005] In order to solve the above technical problems, on the one hand, the present invention provides a method for preparing a composite nanomaterial with anti-corrosion performance, comprising the following steps:

[0006] The first nanoparticles were synthesized by a one-step method using organozinc as the zinc source and pyrrole monomers as the organic ligand;

[0007] Zirconium phosphate and sulfosalicylaldehyde are modified with amino monomers and the second nanoparticles are prepared by chemical oxidative polymerization.

[0008] The first nanoparticles are grown in situ on the surface of the second nanoparticles as a template to obtain a composite nanomaterial with anti-corrosion performance.

[0009] Preferably, the preparation method of the composite nanomaterial satisfies at least one of the following conditions:

[0010] The organic zinc is one of zinc diethyldithiocarbamate, zinc stearate and zinc phytate;

[0011] The pyrrole monomer is one of 2,4-dimethylpyrrole, 2-(trichloroacetyl)pyrrole, and pyrrole-2,6-dicarboxylic acid;

[0012] The amino monomer is one of (R)-3-aminobutanol, aminomethylphosphonic acid or tromethamine;

[0013] The particle size of the first nanoparticles is 10 nm to 20 nm, the particle size of the second nanoparticles is 420 nm to 480 nm, and the particle size of the composite nanomaterial is 430 nm to 500 nm.

[0014] Preferably, the step of synthesizing the first nanoparticles by a one-step method comprises:

[0015] Dispersing zinc diethyldithiocarbamate in distilled water with ultrasonication to obtain a first solution;

[0016] Dissolve 2,4-dimethylpyrrole in distilled water, place in a constant temperature water bath and stir to obtain a second solution;

[0017] Under vigorous stirring, the first solution is rapidly added dropwise to the second solution to carry out a reaction;

[0018] The reaction product was collected by centrifugation, washed and dried to obtain white product ZDC@Dp nanoparticles, namely the first nanoparticles.

[0019] Preferably, the synthesized first nanoparticles satisfy at least one of the following conditions:

[0020] The mass ratio of zinc diethyldithiocarbamate to 2,4-dimethylpyrrole is (4-6):(1-3);

[0021] The mass volume ratio of the zinc diethyldithiocarbamate and the distilled water in which it is dissolved is (4-6) g: (50-60) mL;

[0022] The mass and volume ratio of the 2,4-dimethylpyrrole and the distilled water in which it is dissolved is (1-3) g: (30-40) mL;

[0023] The ultrasonic time of the first solution is 10 min to 20 min;

[0024] The ultrasonic time of the second solution is 20 min to 30 min.

[0025] The reaction time of rapidly adding the first solution dropwise to the second solution is 5 hours to 6 hours.

[0026] Preferably, the step of preparing the second nanoparticles by chemical oxidative polymerization comprises:

[0027] ZrOCl2·8H2O and 12.0 mol / L H3PO4 were mixed evenly and then placed in a forced air drying oven for reaction. After the reaction was stopped, the crude product was poured out, washed until the pH was neutral, and dried to obtain ammonia monomer-modified zirconium phosphate;

[0028] Dissolving (R)-3-aminobutanol in dichloromethane, adding ammonia monomer-modified zirconium phosphate thereto, and ultrasonically treating the resulting suspension to obtain a third solution;

[0029] Adjusting the pH of the third solution to be weakly acidic, adding sulfosalicylaldehyde and stirring to react;

[0030] The reaction product was centrifuged and washed with deionized water, and then freeze-dried to obtain 3R / SSA-α-ZrP nanoparticles, ie, the second nanoparticles.

[0031] Preferably, the second nanoparticles obtained by the preparation satisfy at least one of the following conditions:

[0032] The mass volume ratio of the ZrOCl2·8H2O and H3PO4 is (10-15) g: (100-120) mL;

[0033] The mass ratio of the (R)-3-aminobutanol, α-ZrP and sulfosalicylaldehyde is (4-5):(2-3):(1-2);

[0034] The reaction time for preparing α-ZrP is 2h to 3h, and the reaction temperature is 150°C to 160°C;

[0035] The suspension ultrasonic time is 30min to 40min;

[0036] The stirring time is 30min to 40min;

[0037] The pH value of the third solution is adjusted to be between 6 and 7.

[0038] Preferably, the step of using the second nanoparticles as a template and in-situ growing the first nanoparticles on the surface thereof to obtain a composite nanomaterial with anti-corrosion properties comprises:

[0039] Dissolve the second nanoparticles in distilled water, slowly add the first nanoparticles under ultrasonic conditions, and continue ultrasonication;

[0040] Adding a catalyst, reacting under heating conditions, collecting the product by centrifugation, washing and drying, thereby obtaining a composite nanomaterial with anti-corrosion performance;

[0041] Wherein, the preparation of the composite nanomaterial satisfies at least one of the following conditions:

[0042] The mass ratio of the second nanoparticles, the first nanoparticles and the catalyst is (2-3):(4-5):(0.2-0.4);

[0043] The catalyst is one of dibutyltin dilaurate, platinum-divinyltetramethyldisiloxane, and molybdenum disulfide;

[0044] The heating condition temperature is 80℃~90℃, and the reaction time is 1h~2h;

[0045] The mass volume ratio of the second nanoparticles to distilled water is (2-3) g: (50-60) mL;

[0046] The ultrasonic time is 30 min to 40 min.

[0047] On the other hand, the present invention also provides a composite nanomaterial with anti-corrosion performance, wherein the composite nanomaterial is prepared by any of the methods described above.

[0048] On the other hand, the present invention also provides a method for preparing an anti-corrosion material, comprising the following steps:

[0049] A physical blending method is adopted to introduce any of the above-mentioned composite nanomaterials into a water-based epoxy resin emulsion, and a composite anti-corrosion coating is prepared after the reaction, and the composite anti-corrosion coating is used as the anti-corrosion material.

[0050] On the other hand, the present invention also provides a method for preparing an anti-corrosion material, comprising the following steps: introducing any of the above-mentioned composite nanomaterials into a water-based epoxy resin emulsion by a physical blending method, and obtaining a composite anti-corrosion coating after the reaction;

[0051] The composite anti-corrosion coating is sprayed on the surface of the pretreated metal substrate by a spraying method, and a metal anti-corrosion layer is prepared after curing and drying. The metal anti-corrosion layer is used as the anti-corrosion material.

[0052] On the other hand, the present invention also provides an anti-corrosion material, which is prepared by the above-mentioned method.

[0053] The composite nanomaterial with anti-corrosion performance, the anti-corrosion material and the preparation method thereof of the present invention have at least the following beneficial effects:

[0054] In this embodiment of the present invention, a first nanoparticle is synthesized in a one-step process using organozinc as a zinc source and a pyrrole monomer as an organic ligand. Zirconium phosphate and sulfosalicylaldehyde are modified with an ammonia monomer and then prepared via chemical oxidative polymerization to obtain a second nanoparticle. The first nanoparticle is then grown in situ on the surface of the second nanoparticle, using it as a template, to produce a composite nanomaterial with corrosion resistance. Two nanoparticles, a first nanoparticle (ZDC@Dp) and a second nanoparticle (3R / SSA-α-ZrP), are synthesized and then combined to form a composite material with corrosion resistance. The organozinc in the first nanoparticle ZDC@Dp is a green and environmentally friendly corrosion inhibitor. It can complex with metals to form a dense monomolecular protective film, preventing corrosive media from entering the metal substrate surface. Furthermore, the active groups in the structure react chemically with the organic coating, creating strong adhesion between the metal surface and the organic coating, thereby reducing metal corrosion. Furthermore, the zinc in the organozinc structure coordinates with the nitrogen-containing groups in the pyrrole, enabling controlled release of the corrosion inhibitor. In addition, the nitrogen atoms in the pyrrole molecule contain lone pairs of electrons, which can not only form a film on the metal surface by adsorption, but also react with certain oxidants in the medium to form complexes, thereby effectively inhibiting metal corrosion. On the other hand, the synthesized second nanoparticle 3R / SSA-α-ZrP not only achieves a higher aspect ratio and better dispersibility in the water-based epoxy polymer matrix, but also effectively improves the adhesion of the composite coating to the substrate and the cross-linking density within the composite coating, prolonging the anti-corrosion effect.

[0055] In addition, the micro size of the composite nanomaterial synthesized by the present invention can fill the defects of the water-soluble polymer coating and improve the barrier shielding effect of the coating; on the other hand, when corrosion occurs, the composite nanoparticles are stimulated by the surrounding corrosive medium to decompose and release organic zinc and pyrrole, which participate in the reaction in the damaged area and form a dense protective film, thereby inhibiting further corrosion of the metal.

[0056] In addition, the preparation method of the present invention has a simple process, mild conditions, and is easy to control. The raw materials used are all non-toxic or low-toxic raw materials. The raw material consumption during the reaction is small, the cost is low, and no toxic by-products are generated. It is an environmentally friendly synthesis method. BRIEF DESCRIPTION OF THE DRAWINGS

[0057] In order to more clearly illustrate the technical solutions and advantages of the embodiments of the present invention or the prior art, the following briefly introduces the drawings required for use in the embodiments or the prior art descriptions. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0058] Figure 1This is a flow chart of a method for preparing a composite nanomaterial with anti-corrosion properties provided by an embodiment of the present invention;

[0059] Figure 2 3 is a scanning electron microscope image of the composite nanomaterial prepared in an embodiment of the present invention. DETAILED DESCRIPTION

[0060] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts shall fall within the scope of protection of the present invention.

[0061] In related technologies, organic polymer coatings have become the most common anti-corrosion method due to their high efficiency, low cost, and ease of operation. Typically, organic polymer coatings form a protective layer on the metal surface to block the diffusion of corrosive media in the hope of achieving the purpose of corrosion prevention.

[0062] However, the inventors found that organic polymer coatings inevitably produce some defects during the curing process, and corrosive media will penetrate into the coating through these defects, resulting in a decrease in the corrosion resistance of the coating. Therefore, the actual corrosion resistance of organic polymer coatings needs to be further improved.

[0063] The present invention provides a method for preparing a composite nanomaterial with anti-corrosion performance, such as Figure 1 As shown, the following steps are included.

[0064] S1, synthesizing the first nanoparticles by a one-step method using organic zinc as a zinc source and pyrrole monomers as organic ligands;

[0065] S2, using an ammonia monomer to modify zirconium phosphate and sulfosalicylaldehyde to prepare second nanoparticles by chemical oxidative polymerization;

[0066] S3. Using the second nanoparticles as a template, in situ growing the first nanoparticles on the surface of the second nanoparticles to obtain a composite nanomaterial with anti-corrosion properties.

[0067] Preferably, the preparation method of the composite nanomaterial satisfies at least one of the following conditions:

[0068] The organic zinc is one of zinc diethyldithiocarbamate, zinc stearate and zinc phytate;

[0069] The pyrrole monomer is one of 2,4-dimethylpyrrole, 2-(trichloroacetyl)pyrrole, and pyrrole-2,6-dicarboxylic acid;

[0070] The amino monomer is one of (R)-3-aminobutanol, aminomethylphosphoric acid or tromethamine.

[0071] Preferably, the step of synthesizing the first nanoparticles by a one-step method comprises:

[0072] Dispersing zinc diethyldithiocarbamate in distilled water with ultrasonication to obtain a first solution;

[0073] Dissolve 2,4-dimethylpyrrole in distilled water, place in a constant temperature water bath and stir to obtain a second solution;

[0074] Under vigorous stirring, the first solution is rapidly added dropwise to the second solution to carry out a reaction;

[0075] The reaction product was collected by centrifugation, washed and dried to obtain white product ZDC@Dp nanoparticles, namely the first nanoparticles.

[0076] Preferably, the synthesized first nanoparticles satisfy at least one of the following conditions:

[0077] The mass ratio of zinc diethyldithiocarbamate to 2,4-dimethylpyrrole is (4-6):(1-3);

[0078] The mass volume ratio of the zinc diethyldithiocarbamate and the distilled water in which it is dissolved is (4-6) g: (50-60) mL;

[0079] The mass and volume ratio of the 2,4-dimethylpyrrole and the distilled water in which it is dissolved is (1-3) g: (30-40) mL;

[0080] The ultrasonic time of the first solution is 10 min to 20 min;

[0081] The ultrasonic time of the second solution is 20 min to 30 min.

[0082] The reaction time of rapidly adding the first solution dropwise to the second solution is 5 hours to 6 hours.

[0083] Preferably, the step of preparing the second nanoparticles by chemical oxidative polymerization comprises:

[0084] ZrOCl2·8H2O and 12.0 mol / L H3PO4 were mixed evenly and then placed in a forced air drying oven for reaction. After the reaction was stopped, the crude product was poured out, washed until the pH was neutral, and dried to obtain ammonia monomer-modified zirconium phosphate;

[0085] Dissolving (R)-3-aminobutanol in dichloromethane, adding ammonia monomer-modified zirconium phosphate thereto, and ultrasonically treating the resulting suspension to obtain a third solution;

[0086] Adjusting the pH of the third solution to be weakly acidic, adding sulfosalicylaldehyde and stirring to react;

[0087] The reaction product was centrifuged and washed with deionized water, and then freeze-dried to obtain 3R / SSA-α-ZrP nanoparticles, ie, the second nanoparticles.

[0088] Preferably, the second nanoparticles obtained by the preparation satisfy at least one of the following conditions:

[0089] The mass volume ratio of the ZrOCl2·8H2O and H3PO4 is (10-15) g: (100-120) mL;

[0090] The mass ratio of the (R)-3-aminobutanol, α-ZrP and sulfosalicylaldehyde is (4-5):(2-3):(1-2);

[0091] The reaction time for preparing α-ZrP is 2h to 3h, and the reaction temperature is 150°C to 160°C;

[0092] The ultrasonic time of the suspension is 30min to 40min;

[0093] The stirring time is 30min to 40min;

[0094] The pH value of the third solution is adjusted to be between 6 and 7.

[0095] Preferably, the step of using the second nanoparticles as a template and in-situ growing the first nanoparticles on the surface thereof to obtain a composite nanomaterial with anti-corrosion properties comprises:

[0096] Dissolve the second nanoparticles in distilled water, slowly add the first nanoparticles under ultrasonic conditions, and continue ultrasonication;

[0097] A catalyst is added, reacted under heating conditions, the product is collected by centrifugation, washed and dried, and thus a composite nano material with anti-corrosion performance is obtained.

[0098] Preferably, the preparation of the composite nanomaterial satisfies at least one of the following conditions:

[0099] The mass ratio of the second nanoparticles, the first nanoparticles and the catalyst is (2-3):(4-5):(0.2-0.4);

[0100] The catalyst is one of dibutyltin dilaurate, platinum-divinyltetramethyldisiloxane, and molybdenum disulfide;

[0101] The heating condition temperature is 80℃~90℃, and the reaction time is 1h~2h;

[0102] The mass volume ratio of the second nanoparticles to distilled water is (2-3) g: (50-60) mL;

[0103] The ultrasonic time is 30 min to 40 min.

[0104] Preferably, the particle size of the first nanoparticles is 10 nm to 20 nm, the particle size of the second nanoparticles is 420 nm to 480 nm, and the particle size of the composite nanomaterial is 430 nm to 500 nm.

[0105] An embodiment of the present invention further provides a composite nanomaterial with anti-corrosion properties, wherein the composite nanomaterial with anti-corrosion properties is prepared using the preparation method described in any of the above embodiments.

[0106] An embodiment of the present invention also provides a method for preparing an anti-corrosion material, comprising the following steps:

[0107] Any of the above composite nanomaterials is introduced into a waterborne epoxy resin emulsion by a physical blending method, and a composite anti-corrosion coating is prepared after the reaction, and the composite anti-corrosion coating is used as the anti-corrosion material.

[0108] Another method for preparing an anti-corrosion material provided in an embodiment of the present invention includes the following steps:

[0109] A physical blending method is used to introduce any of the above composite nanomaterials into a waterborne epoxy resin emulsion, and a composite anti-corrosion coating is obtained after the reaction;

[0110] The composite anti-corrosion coating is sprayed on the surface of the pretreated metal substrate by a spraying method, and a metal anti-corrosion layer is prepared after curing and drying. The metal anti-corrosion layer is used as the anti-corrosion material.

[0111] An embodiment of the present invention further provides an anti-corrosion material, which is prepared by any of the above methods, wherein the anti-corrosion material can be a composite anti-corrosion coating or a metal anti-corrosion layer.

[0112] As a preferred overall solution, an embodiment of the present invention provides a method for preparing an anti-corrosion material, comprising the following steps:

[0113] 1) Disperse 4g-6g of zinc diethyldithiocarbamate in 50mL-60mL of distilled water and sonicate for 10-20 minutes to obtain a first solution. Dissolve 1g-3g of 2,4-dimethylpyrrole in a separate beaker containing 30mL-40mL of distilled water and stir in a constant-temperature water bath at 40°C-50°C for 20-30 minutes to obtain a second solution. Under vigorous stirring, the first solution is rapidly added dropwise to the second solution and allowed to react for 5-6 hours. The reaction product is collected by centrifugation, washed with distilled water, and dried to obtain white ZDC@Dp nanoparticles, i.e., the first nanoparticles.

[0114] 2) 10g-15g of ZrOCl2·8H2O and 100mL-120mL of 12.0mol / L H3PO4 were stirred in a beaker for 30-40min, then reacted in a forced air drying oven at 150°C-160°C for 2-3h. After the reaction was terminated, the crude product was decanted, rinsed with distilled water several times until the pH was neutral, and dried in a vacuum oven at 70°C for 5h to obtain ammonia-modified zirconium phosphate (α-ZrP). 4g-5g of (R)-3-aminobutanol (3R) was dissolved in 30mL-40mL of dichloromethane, followed by the addition of 2g-3g of α-ZrP. The suspension was ultrasonically treated for 30-40min to obtain a third solution. Then, a 1 mol / L aqueous HCl solution was added to adjust the pH of the solution to between 6 and 7. Subsequently, 1 g to 2 g of sulfosalicylaldehyde (SSA) was added and stirred for 30 to 40 minutes to obtain a product. The reaction product was centrifuged and washed with deionized water, followed by freeze-drying to obtain 3R / SSA-α-ZrP nanoparticles, i.e., the second nanoparticles.

[0115] 3) 2 g to 3 g of 3R / SSA-α-ZrP nanoparticles were dissolved in 50 mL to 60 mL of distilled water, and 4 g to 5 g of ZDC@Dp nanoparticles were slowly added under ultrasonic conditions, and ultrasonication was continued for 30 min to 40 min; 0.2 g to 0.4 g of catalyst was added, and then reacted under heating conditions for 1 h to 2 h. The product was collected by centrifugation, washed with distilled water 3 to 6 times, and dried in a vacuum oven at 60°C for 2 h to obtain a composite nanomaterial with corrosion resistance.

[0116] The catalyst is one of dibutyltin dilaurate, platinum-divinyltetramethyldisiloxane, and molybdenum disulfide; and the heating temperature is 80° C. to 90° C.

[0117] 4) 5g to 7g of the composite nanomaterial is dissolved in 50mL to 60mL of distilled water and ultrasonicated for 30min to 40min, then poured into 30mL to 40mL of a waterborne epoxy resin (WEP) emulsion, stirred for 30min to 40min, and mixed evenly to obtain a composite anti-corrosion coating. The composite anti-corrosion coating is sprayed on the surface of the pretreated metal substrate by a spraying method, cured and dried at 60°C to 70°C for 30min to 40min, and then dried at room temperature for 8h to 10h to obtain a metal anti-corrosion layer.

[0118] The following is further described in detail with reference to specific embodiments to help those skilled in the art to have a more complete, accurate and in-depth understanding of the inventive concept and technical solution of the present invention.

[0119] Example 1

[0120] (1) Disperse 4 g of zinc diethyldithiocarbamate (ZDC) in 50 mL of distilled water and ultrasonicate for 10 min to obtain the first solution. Dissolve 1 g of 2,4-dimethylpyrrole (Dp) in another beaker containing 30 mL of distilled water and stir in a 40°C constant temperature water bath for 20 min to obtain the second solution. Under vigorous stirring, the first solution was quickly added dropwise to the second solution and reacted for 5 h. The reaction product was collected by centrifugation, washed 6 times with distilled water, and dried in a vacuum oven at 60°C for 24 h to obtain a white product, namely ZDC@Dp nanoparticles.

[0121] (2) 10 g of ZrOCl2·8H2O and 100 mL of 12.0 mol / L H3PO4 were stirred in a beaker for 30 min and then placed in a 150°C forced air drying oven for 2 h. After stopping the reaction, the crude product was poured out and rinsed with distilled water several times until the pH was neutral. It was then dried in a 70°C vacuum oven for 5 h to obtain α-ZrP. 4 g of (R)-3-aminobutanol (3R) was dissolved in 30 mL of dichloromethane. Subsequently, 2 g of α-ZrP was added and the suspension was sonicated for 30 min to obtain a third solution. 1 mol / L aqueous HCl was then added to adjust the pH of the solution to 6. Subsequently, 1 g of sulfosalicylaldehyde (SSA) was added and stirred for 30 min to obtain the product. The reaction product was centrifuged and washed with deionized water, then freeze-dried to obtain 3R / SSA-α-ZrP nanoparticles.

[0122] (3) 2g of 3R / SSA-α-ZrP nanoparticles were dissolved in 50mL of distilled water, and 4g of ZDC@Dp nanoparticles were slowly added under ultrasonic conditions, and ultrasonication was continued for 30min. 0.2g of dibutyltin dilaurate catalyst was added, and then the reaction was carried out under heating conditions for 1h. The product was collected by centrifugation and washed with distilled water 3 times. It was dried in a vacuum oven at 60℃ for 2h to obtain a composite nanomaterial with anti-corrosion properties. The scanning electron microscope image of the prepared composite nanomaterial is shown in Figure 2. Figure 2 shown.

[0123] (4) 5 g of the composite nanomaterial was dissolved in 50 mL of distilled water and ultrasonicated for 30 min, then poured into 30 mL of water-based epoxy resin and stirred for 30 min. After mixing evenly, the composite anti-corrosion coating was sprayed on the surface of the pretreated metal substrate by spraying, cured and dried at 60 ° C for 30 min, and then dried at room temperature for 8 h to obtain a metal anti-corrosion layer.

[0124] Example 2

[0125] (1) Disperse 5 g of zinc diethyldithiocarbamate (ZDC) in 55 mL of distilled water and ultrasonicate for 15 min to obtain the first solution. Dissolve 2 g of 2,4-dimethylpyrrole (Dp) in another beaker containing 35 mL of distilled water and stir in a 45°C constant temperature water bath for 25 min to obtain the second solution. Under vigorous stirring, the first solution was quickly added dropwise to the second solution and reacted for 5.5 h. The product was collected by centrifugation, washed with distilled water 6 times, and dried in a vacuum oven at 60°C for 24 h to obtain a white product, namely ZDC@Dp nanoparticles.

[0126] (2) 12 g of ZrOCl2·8H2O and 110 mL of 12.0 mol / L H3PO4 were stirred in a beaker for 35 min and then placed in a forced air drying oven at 155°C for 2.5 h. After stopping the reaction, the crude product was poured out and rinsed with distilled water several times until the pH was neutral. It was then dried in a vacuum oven at 70°C for 5 h to obtain α-ZrP. 4.5 g of (R)-3-aminobutanol (3R) was dissolved in 35 mL of dichloromethane. Subsequently, 2.5 g of α-ZrP was added and the suspension was sonicated for 35 min. 1 mol / L aqueous HCl was then added to adjust the pH of the solution to 6.5. 1.5 g of sulfosalicylaldehyde (SSA) was then added and stirred for 35 min to obtain the product. The reaction product was centrifuged and washed with deionized water, then freeze-dried to obtain 3R / SSA-α-ZrP nanoparticles.

[0127] (3) 2.5 g of 3R / SSA-α-ZrP nanoparticles were dissolved in 55 mL of distilled water, and 4.5 g of ZDC@Dp nanoparticles were slowly added under ultrasonic conditions, and ultrasonication was continued for 35 min; 0.3 g of platinum-divinyltetramethyldisiloxane catalyst was added, and then the reaction was carried out under heating conditions for 1.5 h; the product was collected by centrifugation, washed three times with distilled water, and dried in a vacuum oven at 60 ° C for 2 h to obtain a composite nanomaterial with anti-corrosion properties.

[0128] (4) 6 g of the composite nanomaterial was dissolved in 55 mL of distilled water and ultrasonicated for 35 min, then poured into 35 mL of water-based epoxy resin and stirred for 35 min. After mixing evenly, the composite anti-corrosion coating was sprayed on the surface of the pretreated metal substrate by spraying, cured and dried at 65 ° C for 35 min, and then dried at room temperature for 9 h to obtain a metal anti-corrosion layer.

[0129] Example 3

[0130] (1) Disperse 6 g of zinc diethyldithiocarbamate (ZDC) in 60 mL of distilled water and ultrasonicate for 20 min to obtain the first solution. Dissolve 3 g of 2,4-dimethylpyrrole (Dp) in another beaker containing 40 mL of distilled water and stir in a 50°C constant temperature water bath for 30 min to obtain the second solution. Under vigorous stirring, the first solution was quickly added dropwise to the second solution and reacted for 6 h. Finally, the reaction product was collected by centrifugation, washed 6 times with distilled water, and dried in a vacuum oven at 60°C for 24 h to obtain a white product, namely ZDC@Dp nanoparticles.

[0131] (2) 15 g of ZrOCl2·8H2O and 120 mL of 12.0 mol / L H3PO4 were stirred in a beaker for 40 min and then placed in a 160°C forced air drying oven for 3 h. After stopping the reaction, the crude product was poured out and rinsed with distilled water several times until the pH was neutral. It was then dried in a 70°C vacuum oven for 5 h to obtain α-ZrP. 5 g of (R)-3-aminobutanol (3R) was dissolved in 40 mL of dichloromethane. Subsequently, 3 g of α-ZrP was added and the suspension was sonicated for 40 min to obtain a third solution. 1 mol / L aqueous HCl was then added to adjust the pH of the solution to 7. 2 g of sulfosalicylaldehyde (SSA) was then added and stirred for 40 min to obtain the product. After centrifugation and washing several times with deionized water, 3R / SSA-α-ZrP nanoparticles were obtained by freeze-drying.

[0132] (3) 3 g of 3R / SSA-α-ZrP nanoparticles were dissolved in 60 mL of distilled water, and 5 g of ZDC@Dp nanoparticles were slowly added under ultrasonic conditions, and ultrasonication was continued for 40 min; 0.4 g of molybdenum disulfide catalyst was added, and then reacted under heating conditions for 2 h. The product was collected by centrifugation, washed three times with distilled water, and dried in a vacuum oven at 60 °C for 2 h to obtain a composite nanomaterial.

[0133] (4) 7 g of the composite nanomaterial was dissolved in 60 mL of distilled water and ultrasonicated for 40 min, then poured into 40 mL of water-based epoxy resin and stirred for 40 min. After mixing evenly, the composite anti-corrosion coating was sprayed on the surface of the pretreated metal substrate by spraying, cured and dried at 70 ° C for 40 min, and then dried at room temperature for 10 h to obtain a metal anti-corrosion layer.

[0134] Comparative Example 1

[0135] ZDC@Dp is not synthesized

[0136] (1) 15 g of ZrOCl2·8H2O and 120 mL of 12.0 mol / L H3PO4 were stirred in a beaker for 40 min and then placed in a forced air drying oven at 160°C for 3 h. After stopping the reaction, the crude product was poured out, rinsed with distilled water several times until the pH was neutral, and dried in a vacuum oven at 70°C for 5 h to obtain α-ZrP. 5 g of (R)-3-aminobutanol (3R) was dissolved in 40 mL of dichloromethane, followed by the addition of 3 g of α-ZrP, and the suspension was sonicated for 40 min. Then, 1 mol / L aqueous HCl was added to adjust the pH of the solution to 7, followed by the addition of 2 g of sulfosalicylaldehyde (SSA) and stirring for 40 min to obtain the product. The reaction product was centrifuged, washed with deionized water, and freeze-dried to obtain 3R / SSA-α-ZrP nanoparticles.

[0137] (2) 7 g of 3R / SSA-α-ZrP was dissolved in 60 mL of distilled water and ultrasonicated for 40 min. Then, the solution was poured into 40 mL of water-based epoxy resin and stirred for 40 min. After mixing evenly, the coating was obtained. The coating was sprayed on the surface of the pretreated metal substrate by spraying, cured and dried at 70 ° C for 40 min, and then dried at room temperature for 10 h to obtain a metal coating.

[0138] Comparative Example 2

[0139] 3R / SSA-α-ZrP is not synthesized

[0140] (1) 6 g of zinc diethyldithiocarbamate (ZDC) was dispersed in 60 mL of distilled water and ultrasonicated for 20 min. At the same time, 3 g of 2,4-dimethylpyrrole (Dp) was dissolved in another beaker containing 40 mL of distilled water and stirred in a 50°C constant temperature water bath for 30 min. Then, the ZDC solution was rapidly added dropwise to the Dp solution under vigorous stirring and reacted for 6 h. Finally, the product was collected by centrifugation, washed 6 times with distilled water, and dried in a vacuum oven at 60°C for 24 h to obtain a white product, namely ZDC@Dp nanoparticles.

[0141] (2) 7 g of ZDC@Dp was dissolved in 60 mL of distilled water and ultrasonicated for 40 min. Then, the solution was poured into 40 mL of water-based epoxy resin and stirred for 40 min. After mixing evenly, the coating was obtained. The coating was sprayed on the surface of the pretreated metal substrate by spraying, cured and dried at 70 °C for 40 min, and then dried at room temperature for 10 h to obtain a metal coating.

[0142] The anti-corrosion performance of the metal anti-corrosion layer or metal coating prepared above was tested, and the test results showed that the anti-corrosion performance of the metal anti-corrosion layer prepared in Examples 1-3 was significantly higher than that of the gold coating prepared in Comparative Examples 1-2.

[0143] Analysis shows that the present invention synthesizes two nanoparticles, ZDC@Dp and 3R / SSA-α-ZrP, and then combines the two nanoparticles into a composite nanomaterial with corrosion resistance. The organic zinc selected in ZDC@Dp is a green and environmentally friendly corrosion inhibitor. On the one hand, it can complex with metals to form a dense monomolecular protective film, preventing corrosive media from entering the surface of the metal substrate. On the other hand, the active groups contained in its structure can chemically react with the organic coating, creating a strong adhesion between the metal surface and the organic coating, thereby achieving the purpose of slowing metal corrosion. At the same time, the zinc in the organic zinc structure can coordinate with the nitrogen-containing groups in pyrrole, achieving controlled release of the corrosion inhibitor. In addition, the nitrogen atoms in the pyrrole molecule contain lone pairs of electrons, which can not only adsorb to form a film on the metal surface, but also react with certain oxidants in the medium to form complexes, thereby effectively inhibiting metal corrosion. On the other hand, the synthesized 3R / SSA-α-ZrP can not only obtain a higher aspect ratio and better dispersibility in the waterborne epoxy polymer matrix, but also effectively improve the adhesion between the composite coating and the substrate and the cross-linking density within the composite coating, thereby prolonging the anti-corrosion effect.

[0144] Furthermore, the tiny size of the synthesized composite nanomaterials can fill defects in the hydrophilic polymer coating, improving the barrier effect of the coating. Furthermore, when corrosion occurs, stimulated by the surrounding corrosive medium, the composite nanoparticles decompose to release organic zinc and pyrrole, which react in the damaged area and form a dense protective film, thereby inhibiting further corrosion of the metal.

[0145] In addition, the metal anticorrosion layers obtained in Examples 1-3 and the metal coatings obtained in Comparative Examples 1-2 were subjected to relevant performance tests, and the test results are shown in Table 1 below:

[0146] Table 1

[0147]

[0148] Based on the above Table 1, it can be seen that compared with Comparative Examples 1-2, the metal anti-corrosion layers prepared in Examples 1-3 not only have better corrosion resistance, but also have higher impedance modulus and hardness, as well as better adhesion, and have good comprehensive performance.

[0149] The preparation method of the present invention has a simple process, mild conditions, and is easy to control. The raw materials used are all non-toxic or low-toxic raw materials. The raw material consumption during the reaction is small, the cost is low, and no toxic by-products are generated. Therefore, it is an environmentally friendly synthesis method.

[0150] The above description fully discloses the specific embodiments of the present invention. It should be noted that any modifications made by those skilled in the art to the specific embodiments of the present invention do not depart from the scope of the claims. Accordingly, the scope of the claims of the present invention is not limited solely to the foregoing specific embodiments.

Claims

1. A method for preparing a composite nanomaterial with anti-corrosion properties, characterized in that: The following steps are involved: The first nanoparticles were synthesized by a one-step method using organozinc as the zinc source and pyrrole monomers as the organic ligand; Zirconium phosphate and sulfosalicylaldehyde are modified with amino monomers and the second nanoparticles are prepared by chemical oxidative polymerization. The first nanoparticles are grown in situ on the surface of the second nanoparticles as a template to obtain a composite nanomaterial with anti-corrosion performance.

2. The method according to claim 1, characterized in that The preparation method of the composite nanomaterial satisfies at least one of the following conditions: The organic zinc is one of zinc diethyldithiocarbamate, zinc stearate and zinc phytate; The pyrrole monomer is one of 2,4-dimethylpyrrole, 2-(trichloroacetyl)pyrrole, and pyrrole-2,6-dicarboxylic acid; The amino monomer is one of (R)-3-aminobutanol, aminomethylphosphonic acid or tromethamine; The particle size of the first nanoparticles is 10 nm to 20 nm, the particle size of the second nanoparticles is 420 nm to 480 nm, and the particle size of the composite nanomaterial is 430 nm to 500 nm.

3. The method according to claim 1, characterized in that The step of synthesizing the first nanoparticles by a one-step method comprises: Dispersing zinc diethyldithiocarbamate in distilled water with ultrasonication to obtain a first solution; Dissolve 2,4-dimethylpyrrole in distilled water, place in a constant temperature water bath and stir to obtain a second solution; Under vigorous stirring, the first solution is rapidly added dropwise to the second solution to carry out a reaction; The reaction product was collected by centrifugation, washed and dried to obtain white product ZDC@Dp nanoparticles, namely the first nanoparticles.

4. The method according to claim 3, characterized in that The synthesized first nanoparticles satisfy at least one of the following conditions: The mass ratio of zinc diethyldithiocarbamate to 2,4-dimethylpyrrole is (4-6):(1-3); The mass volume ratio of the zinc diethyldithiocarbamate and the distilled water in which it is dissolved is (4-6) g: (50-60) mL; The mass and volume ratio of the 2,4-dimethylpyrrole and the distilled water in which it is dissolved is (1-3) g: (30-40) mL; The ultrasonic time of the first solution is 10 min to 20 min; The ultrasonic time of the second solution is 20 min to 30 min. The reaction time of rapidly adding the first solution dropwise to the second solution is 5 hours to 6 hours.

5. The method according to claim 1, wherein The step of preparing the second nanoparticles by chemical oxidative polymerization comprises: ZrOCl2·8H2O and 12.0 mol / L H3PO4 were mixed evenly and then placed in a forced air drying oven for reaction. After the reaction was stopped, the crude product was poured out, washed until the pH was neutral, and dried to obtain ammonia monomer-modified zirconium phosphate; Dissolving (R)-3-aminobutanol in dichloromethane, adding ammonia monomer-modified zirconium phosphate thereto, and ultrasonically treating the resulting suspension to obtain a third solution; Adjusting the pH of the third solution to be weakly acidic, adding sulfosalicylaldehyde and stirring to react; The reaction product was centrifuged and washed with deionized water, and then freeze-dried to obtain 3R / SSA-α-ZrP nanoparticles, ie, the second nanoparticles.

6. The method according to claim 5, characterized in that The second nanoparticles obtained by the preparation satisfy at least one of the following conditions: The mass volume ratio of the ZrOCl2·8H2O and H3PO4 is (10-15) g: (100-120) mL; The mass ratio of the (R)-3-aminobutanol, α-ZrP and sulfosalicylaldehyde is (4-5):(2-3):(1-2); The reaction time for preparing α-ZrP is 2h to 3h, and the reaction temperature is 150°C to 160°C; The ultrasonic time of the suspension is 30min to 40min; The stirring time is 30min to 40min; The pH value of the third solution is adjusted to be between 6 and 7.

7. The method according to claim 1, characterized in that The step of using the second nanoparticles as a template and in-situ growing the first nanoparticles on the surface of the second nanoparticles to obtain a composite nanomaterial with anti-corrosion performance comprises: Dissolve the second nanoparticles in distilled water, slowly add the first nanoparticles under ultrasonic conditions, and continue ultrasonication; Adding a catalyst, reacting under heating conditions, collecting the product by centrifugation, washing and drying, thereby obtaining a composite nanomaterial with anti-corrosion performance; Wherein, the preparation of the composite nanomaterial satisfies at least one of the following conditions: The mass ratio of the second nanoparticles, the first nanoparticles and the catalyst is (2-3):(4-5):(0.2-0.4); The catalyst is one of dibutyltin dilaurate, platinum-divinyltetramethyldisiloxane, and molybdenum disulfide; The heating condition temperature is 80℃~90℃, and the reaction time is 1h~2h; The mass volume ratio of the second nanoparticles to distilled water is (2-3) g: (50-60) mL; The ultrasonic time is 30 min to 40 min.

8. A composite nanomaterial with anti-corrosion properties, characterized in that: The composite nanomaterial is prepared by the method according to any one of claims 1 to 7.

9. A method for preparing an anti-corrosion material, characterized in that: The following steps are involved: The composite nanomaterial according to claim 8 is introduced into a waterborne epoxy resin emulsion by a physical blending method, and a composite anti-corrosion coating is prepared after the reaction, and the composite anti-corrosion coating is used as the anti-corrosion material; or, The composite nanomaterial according to claim 8 is introduced into a waterborne epoxy resin emulsion by a physical blending method, and a composite anti-corrosion coating is obtained after the reaction; The composite anti-corrosion coating is sprayed on the surface of the pretreated metal substrate by a spraying method, and a metal anti-corrosion layer is prepared after curing and drying. The metal anti-corrosion layer is used as the anti-corrosion material.

10. An anti-corrosion material, characterized in that: The anti-corrosion material is prepared by the method according to claim 9.

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