Modified hyperbranched polymer metal surface treatment liquid and preparation method thereof

Abstract

The invention belongs to the technical field of surface treatment, and relates to a modified hyperbranched polymer metal surface treatment fluid and a preparation method thereof.The modified hyperbranched polymer metal surface treatment fluid is characterized by being mainly composed of, by mass, 10-80 parts of hyperbranched polymer film forming matter dispersion liquid; 1 to 10 parts of a silane coupling agent; 0.1 to 5 parts of a complexing agent; 0.1 to 5 parts of a corrosion inhibitor; 0.1 to 2 parts of a pH regulator; and 1-90 parts of a solvent. The hyperbranched polymer in the metal surface treatment liquid obtained by the invention has a highly branched three-dimensional structure and contains a large number of functional groups at the tail end of a molecular chain, so that the hyperbranched polymer is easily subjected to strong cross-linking reaction with molecules such as a silane coupling agent and a complexing agent, and a strong cross-linking structure can be formed with the metal surface; and the physical and chemical shielding performance is enhanced. Meanwhile, cavities exist in hyperbranched polymer molecules and can adsorb and contain the corrosion inhibitor, so that the corrosion resistance is enhanced. The synergistic effect of the silane coupling agent and the green corrosion inhibitor can provide electrochemical corrosion resistance and salt spray resistance for metal, so that the metal corrosion inhibitor has an extremely high application prospect.

Description

Technical Field

[0001] The invention belongs to the technical field of surface treatment and relates to a modified hyperbranched polymer metal surface treatment liquid and a preparation method thereof. Technical Background

[0002] During short-term storage before paint coating, metal workpieces are subject to a certain degree of corrosion, which can affect the coating and reduce the service life of the metal material. Among the many preventative measures, the use of metal surface treatment fluids is the most widely used. Metal surface treatment fluids feature simple preparation processes, low raw material costs, and convenient application. They effectively block the erosion of metal workpieces by external corrosive factors in the short term, improving corrosion resistance and enhancing coating adhesion, thereby reducing initial maintenance costs. Currently, traditional metal surface treatment fluids carry heavy metal salts and phosphates, which pose a serious threat to water and soil. Volatile organic solvents (such as trichloroethylene and carbon tetrachloride) emit toxic gases, which damage the ozone layer and exacerbate air pollution. The high-temperature treatment environment required by traditional phosphating processes also results in high energy consumption and costs. However, new environmentally friendly metal surface treatment fluids (such as silane treatment agents, green corrosion inhibitors, and water-based solvents) are gradually replacing traditional products. Their low-toxicity formulations and ambient temperature processes effectively mitigate these shortcomings, aligning with the trend toward green manufacturing.

[0003] Since their discovery by Kim et al. at DuPont in 1988, hyperbranched polymers have garnered widespread attention. Hyperbranched polymers possess a highly branched three-dimensional structure, with numerous functional groups at the ends of the molecular chains and cavities within the molecules. Their advantages include simple synthesis, good molecular mobility, and low solution viscosity. The large number of functional groups at the ends also makes them easy to modify, allowing them to be used in modified materials, thus holding great promise for application in metal corrosion protection.

[0004] The research and development of new green and environmentally friendly metal surface treatment fluids has become a leading focus for enterprises. Silane coupling agents have significant advantages in environmental protection: they are inherently low-toxic and non-irritating, and their volatility during use is extremely low, which not only reduces the health hazards to operators, but also significantly reduces the risk of volatile organic compounds (VOCs) being emitted into the atmosphere. From a chemical stability perspective, it is not easy to decompose into toxic and harmful substances, making wastewater treatment less difficult and reducing the environmental pressure on the water treatment process. In terms of material compatibility, silane coupling agents are well-matched with various environmentally friendly materials, especially water-based systems, which can effectively reduce the use of organic solvents. In addition, some silane coupling agents are biodegradable, which is in line with the concept of green development. In metal surface treatment applications, silane coupling agents can significantly improve the corrosion resistance of metals and extend their service life.

[0005] In recent years, green corrosion inhibitors are gradually replacing traditional chromate, nitrite, phosphorus-containing, cyanide-containing corrosion inhibitors. The amino and carboxyl groups in the amino acid and its derivative molecules can chemically adsorb on the metal surface, and have good biocompatibility and easy solubility. Amino acids and their derivatives also have low or no toxicity, biodegradable and less impact on the ecosystem, and are environmentally friendly.

[0006] It should be noted that the information disclosed in the foregoing background section is only for strengthening the understanding of the background of the present application, and therefore it can include information which does not constitute prior art known to those of ordinary skill in the art. SUMMARY

[0007] The main purpose of the present application is to provide a modified hyperbranched polymer metal surface treatment fluid and a preparation method thereof. It can solve the problem of rust return before metal workpiece spraying.

[0008] To achieve the above-mentioned purpose, the technical scheme provided by the present application is as follows: a modified hyperbranched polymer metal surface treatment fluid, characterized in that it mainly comprises the following components in mass fraction: 10-80 parts of hyperbranched polymer film-forming material dispersion liquid; 1-10 parts of silane coupling agent; 0.1-5 parts of complexing agent; 0.1-5 parts of corrosion inhibitor; 0.1-2 parts of pH adjuster; 1-90 parts of solvent.

[0009] As a preferred modified hyperbranched polymer metal surface treatment fluid of the present application, the hyperbranched polymer film-forming material dispersion liquid is obtained by reacting N,N'-methylenebisacrylamide (MBA) and 1,4-butanediamine (BDA) in a solvent.

[0010] As a preferred modified hyperbranched polymer metal substrate surface treatment fluid of the present application, the silane coupling agent is one of dimethyldimethoxysilane, tetramethoxysilane, gamma-(2,3-epoxypropoxy) propyl trimethoxysilane (KH560), 1,2 bis(triethoxysilyl) ethane, methyl-trimethoxysilane (MTMS).

[0011] As a preferred modified hyperbranched polymer metal substrate surface treatment fluid of the present application, the complexing agent is one of disodium ethylenediaminetetraacetate, sodium gluconate, L(+)-tartaric acid, benzimidazole, 2-methylimidazole.

[0012] As a preferred modified hyperbranched polymer metal substrate surface treatment fluid of the present application, the corrosion inhibitor is one of sodium molybdate, L-histidine, L-proline, L-glutamic acid.

[0013] As a preferred modified hyperbranched polymer metal substrate surface treatment liquid of the present invention, the pH regulator is one of sodium carbonate, sodium bicarbonate, triethylamine, triethanolamine, and tris(hydroxymethyl)aminomethane (Tris).

[0014] As a preferred modified hyperbranched polymer metal substrate surface treatment liquid of the present invention, the solvent is one or more of methanol, ethanol, and distilled water.

[0015] A method for preparing a modified hyperbranched polymer metal surface treatment liquid mainly comprises the following steps:

[0016] Step 1: Prepare N,N'-methylenebisacrylamide (MBA) solution by dispersing MBA in solvent and stirring at 30°C for 30 minutes to obtain an MBA concentration of 0.137 g / mL, followed by cooling to room temperature for use;

[0017] Step 2: Prepare a 1,4-butanediamine (BDA) solution by dispersing BDA in a solvent and stirring at 30°C for 30 minutes to obtain a MBA concentration of 0.267 g / mL, followed by cooling to room temperature for later use;

[0018] Step 3: Prepare a hyperbranched polymer film-forming material dispersion by mixing the MBA solution prepared in step 1 with the BDA solution prepared in step 2 in a volume ratio of 1:1, and stirring at 30°C for 24 hours to obtain a hyperbranched polymer film-forming material dispersion, which is then cooled to room temperature for use;

[0019] Step 4. Weigh each material according to mass, first pour the hyperbranched polymer film-forming material dispersion into a beaker, add the silane coupling agent while stirring, and continue stirring for 3-5 minutes after it is completely dissolved; then continue to add the complexing agent while stirring, and continue stirring for 3-5 minutes after it is completely dissolved; then continue to add the corrosion inhibitor while stirring, and continue stirring for 3-5 minutes after it is completely dissolved; then continue to add the pH adjuster while stirring, and continue stirring for 3-5 minutes after it is completely dissolved; finally, fill it up to 100 parts with solvent, continue stirring and dispersing for 3-5 minutes to obtain a modified hyperbranched polymer metal surface treatment liquid.

[0020] The components mainly include, by mass fraction: 10-80 parts of hyperbranched polymer film-forming material dispersion; 1-10 parts of silane coupling agent; 0.1-5 parts of complexing agent; 0.1-5 parts of corrosion inhibitor; 0.1-2 parts of pH regulator; and 1-90 parts of solvent.

[0021] Compared with the prior art, the present invention has the following beneficial effects: the hyperbranched polymer in the metal surface treatment liquid obtained by the present invention, due to its highly branched three-dimensional structure and the large number of functional groups at the ends of the molecular chain, easily undergoes strong cross-linking reactions with molecules such as silane coupling agents and complexing agents, thereby forming a strong cross-linked structure with the metal surface and enhancing physical and chemical shielding properties. Furthermore, the presence of cavities within the hyperbranched polymer molecules can adsorb and accommodate corrosion inhibitors, enhancing corrosion resistance. The synergistic effect of the silane coupling agent and the green corrosion inhibitor can provide electrochemical corrosion protection and salt spray resistance to metals, and has extremely high application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 Figure 1 is a salt spray test graph of carbon steel. Figure a shows a steel plate immersed in a metal surface treatment liquid containing a modified hyperbranched polymer and a silane coupling agent and then dried at 80°C. Figure b shows a steel plate immersed in a metal surface treatment liquid without the addition of a hyperbranched polymer dispersion and a silane coupling agent and then dried at 80°C.

[0023] Figure 2 Figure 3 is the Tafel polarization curve of carbon steel after immersion in a 3.5 wt.% NaCl solution for one day. Curve a is the steel plate immersed in a metal surface treatment solution containing a modified hyperbranched polymer and a silane coupling agent and dried at 80°C. Curve b is the steel plate immersed in a metal surface treatment solution without the addition of a hyperbranched polymer dispersion and a silane coupling agent and dried at 80°C.

[0024] Specific implementation

[0025] The following is a clear and complete description of the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only some embodiments of the present invention, not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making any creative efforts are within the scope of protection of the present invention.

[0026] The present invention provides a modified hyperbranched polymer metal surface treatment liquid and a preparation method thereof. The modified hyperbranched polymer metal substrate surface treatment liquid comprises the following components, measured by mass: 10-80 parts of a hyperbranched polymer film-forming material dispersion; 1-10 parts of a silane coupling agent; 0.1-5 parts of a complexing agent; 0.1-5 parts of a corrosion inhibitor; 0.1-2 parts of a pH adjuster; and 1-90 parts of a solvent.

[0027] The metal surface treatment liquid obtained by the present invention utilizes a pre-dispersion process to fully dissolve each substance, avoiding unnecessary side reactions. Furthermore, the synergistic mechanism between the hyperbranched polymer and the silane coupling agent and corrosion inhibitor provides an electrochemical anti-corrosion effect, inhibiting the intrusion of chloride ions, oxygen, and water molecules in the air, thereby delaying corrosion of metals during storage.

[0028] In some embodiments, the modified hyperbranched polymer metal substrate surface treatment liquid preferably comprises, by mass, 10-80 parts of a hyperbranched polymer film-forming material dispersion, for example, 20 parts, 40 parts, 60 parts, 80 parts, etc.; 1-10 parts of a silane coupling agent, for example, 1.5 parts, 2.5 parts, 5 parts, 10 parts, etc.; 0.1-5 parts of a complexing agent, for example, 0.5 parts, 1.5 parts, 3 parts, 4 parts, 5 parts, etc.; 0.1-5 parts of a corrosion inhibitor, for example, 0.5 parts, 1 part, 1.5 parts, 3 parts, 5 parts, etc.; 0.1-2 parts of a pH adjuster, for example, 0.2 parts, 0.5 parts, 1 part, 1.5 parts, 2 parts, etc.; and 1-90 parts of a solvent, for example, 2 parts, 5 parts, 10 parts, 20 parts, 30 parts, 40 parts, 50 parts, 60 parts, 80 parts, 90 parts, etc.

[0029] According to the present invention, the mass concentration of the aforementioned N,N'-methylenebisacrylamide (MBA) solution is 0.137 g / mL; the mass concentration of the 1,4-butanediamine (BDA) solution is 0.267 g / mL.

[0030] In some embodiments, the aforementioned hyperbranched polymer film-forming material dispersion is obtained by reacting N,N'-methylenebisacrylamide (MBA) and 1,4-butanediamine (BDA) in a solvent.

[0031] In some embodiments, the silane coupling agent is one of dimethyldimethoxysilane, tetramethoxysilane, γ-(2,3-epoxypropyloxy)propyltrimethoxysilane (KH560), 1,2-bis(triethoxysilyl)ethane, and methyltrimethoxysilane (MTMS).

[0032] In some embodiments, the complexing agent is one of disodium edetate, sodium gluconate, L(+)-tartaric acid, benzimidazole, and 2-methylimidazole.

[0033] In some embodiments, the corrosion inhibitor is one of sodium molybdate, L-histidine, L-proline, and L-glutamic acid.

[0034] In some embodiments, the pH adjuster is one of sodium carbonate, sodium bicarbonate, triethylamine, triethanolamine, and tris(hydroxymethyl)aminomethane (Tris).

[0035] In some embodiments, the solvent is one or more of methanol, ethanol, and distilled water.

[0036] The present invention will be further described below by way of examples, but the present invention is not limited thereto. Unless otherwise specified, the reagents or materials used in the present invention can be purchased from commercial sources.

[0037] Example 1

[0038] Step 1: Prepare N,N'-methylenebisacrylamide (MBA) solution by dispersing MBA in solvent and stirring at 30°C for 30 minutes to obtain an MBA concentration of 0.137 g / mL, followed by cooling to room temperature for use;

[0039] Step 2: Prepare a 1,4-butanediamine (BDA) solution by dispersing BDA in a solvent and stirring at 30°C for 30 minutes to obtain a MBA concentration of 0.267 g / mL, followed by cooling to room temperature for later use;

[0040] Step 3: Prepare a hyperbranched polymer film-forming material dispersion by mixing the MBA solution prepared in step 1 with the BDA solution prepared in step 2 in a volume ratio of 1:1, and stirring at 30°C for 24 hours to obtain a hyperbranched polymer film-forming material dispersion, and then cooling to room temperature for use;

[0041] Step 4. Weigh each material according to mass, first pour 50 parts of hyperbranched polymer film-forming material dispersion into a beaker, add 4 parts of silane coupling agent under stirring, and continue stirring for 3-5 minutes after complete dissolution; then continue to add 1 part of complexing agent under stirring, and continue stirring for 3-5 minutes after complete dissolution; then continue to add 0.5 parts of corrosion inhibitor under stirring, and continue stirring for 3-5 minutes after complete dissolution; then continue to add 0.1 parts of pH regulator under stirring, and continue stirring for 3-5 minutes after complete dissolution; finally, fill up to 100 parts with solvent, continue stirring and dispersing for 3-5 minutes to obtain a modified hyperbranched polymer metal surface treatment liquid.

[0042] Example 2

[0043] Step 1: Prepare N,N'-methylenebisacrylamide (MBA) solution by dispersing MBA in solvent and stirring at 30°C for 30 minutes to obtain an MBA concentration of 0.137 g / mL, followed by cooling to room temperature for use;

[0044] Step 2: Prepare a 1,4-butanediamine (BDA) solution by dispersing BDA in a solvent and stirring at 30°C for 30 minutes to obtain a MBA concentration of 0.267 g / mL, followed by cooling to room temperature for later use;

[0045] Step 3: Prepare a hyperbranched polymer film-forming material dispersion by mixing the MBA solution prepared in step 1 with the BDA solution prepared in step 2 in a volume ratio of 1:1, and stirring at 30°C for 24 hours to obtain a hyperbranched polymer film-forming material dispersion, and then cooling to room temperature for use;

[0046] Step 4. Weigh each material according to mass, first pour 40 parts of hyperbranched polymer film-forming material dispersion into a beaker, add 4 parts of silane coupling agent under stirring, and continue stirring for 3-5 minutes after complete dissolution; then continue to add 1 part of complexing agent under stirring, and continue stirring for 3-5 minutes after complete dissolution; then continue to add 0.5 parts of corrosion inhibitor under stirring, and continue stirring for 3-5 minutes after complete dissolution; then continue to add 0.1 parts of pH regulator under stirring, and continue stirring for 3-5 minutes after complete dissolution; finally, fill up to 100 parts with solvent, continue stirring and dispersing for 3-5 minutes to obtain a modified hyperbranched polymer metal surface treatment liquid.

[0047] Example 3

[0048] Step 1: Prepare N,N'-methylenebisacrylamide (MBA) solution by dispersing MBA in solvent and stirring at 30°C for 30 minutes to obtain an MBA concentration of 0.137 g / mL, followed by cooling to room temperature for use;

[0049] Step 2: Prepare a 1,4-butanediamine (BDA) solution by dispersing BDA in a solvent and stirring at 30°C for 30 minutes to obtain a MBA concentration of 0.267 g / mL, followed by cooling to room temperature for later use;

[0050] Step 3: Prepare a hyperbranched polymer film-forming material dispersion by mixing the MBA solution prepared in step 1 with the BDA solution prepared in step 2 in a volume ratio of 1:1, and stirring at 30°C for 24 hours to obtain a hyperbranched polymer film-forming material dispersion, and then cooling to room temperature for use;

[0051] Step 4. Weigh each material according to mass, first pour 30 parts of hyperbranched polymer film-forming material dispersion into a beaker, add 4 parts of silane coupling agent under stirring, and continue stirring for 3-5 minutes after complete dissolution; then continue to add 1 part of complexing agent under stirring, and continue stirring for 3-5 minutes after complete dissolution; then continue to add 0.5 parts of corrosion inhibitor under stirring, and continue stirring for 3-5 minutes after complete dissolution; then continue to add 0.1 parts of pH regulator under stirring, and continue stirring for 3-5 minutes after complete dissolution; finally, fill up to 100 parts with solvent, continue stirring and dispersing for 3-5 minutes to obtain a modified hyperbranched polymer metal surface treatment liquid.

[0052] Example 4

[0053] Step 1: Prepare N,N'-methylenebisacrylamide (MBA) solution by dispersing MBA in solvent and stirring at 30°C for 30 minutes to obtain an MBA concentration of 0.137 g / mL, followed by cooling to room temperature for use;

[0054] Step 2: Prepare a 1,4-butanediamine (BDA) solution by dispersing BDA in a solvent and stirring at 30°C for 30 minutes to obtain a MBA concentration of 0.267 g / mL, followed by cooling to room temperature for later use;

[0055] Step 3: Prepare a hyperbranched polymer film-forming material dispersion by mixing the MBA solution prepared in step 1 with the BDA solution prepared in step 2 in a volume ratio of 1:1, and stirring at 30°C for 24 hours to obtain a hyperbranched polymer film-forming material dispersion, and then cooling to room temperature for use;

[0056] Step 4. Weigh each material according to mass, first pour 20 parts of hyperbranched polymer film-forming material dispersion into a beaker, add 4 parts of silane coupling agent under stirring, and continue stirring for 3-5 minutes after complete dissolution; then continue to add 1 part of complexing agent under stirring, and continue stirring for 3-5 minutes after complete dissolution; then continue to add 0.5 parts of corrosion inhibitor under stirring, and continue stirring for 3-5 minutes after complete dissolution; then continue to add 0.1 parts of pH regulator under stirring, and continue stirring for 3-5 minutes after complete dissolution; finally, fill up to 100 parts with solvent, continue stirring and dispersing for 3-5 minutes to obtain a modified hyperbranched polymer metal surface treatment liquid.

[0057] Example 5

[0058] Step 1: Prepare N,N'-methylenebisacrylamide (MBA) solution by dispersing MBA in solvent and stirring at 30°C for 30 minutes to obtain an MBA concentration of 0.137 g / mL, followed by cooling to room temperature for use;

[0059] Step 2: Prepare a 1,4-butanediamine (BDA) solution by dispersing BDA in a solvent and stirring at 30°C for 30 minutes to obtain a MBA concentration of 0.267 g / mL, followed by cooling to room temperature for later use;

[0060] Step 3: Prepare a hyperbranched polymer film-forming material dispersion by mixing the MBA solution prepared in step 1 with the BDA solution prepared in step 2 in a volume ratio of 1:1, and stirring at 30°C for 24 hours to obtain a hyperbranched polymer film-forming material dispersion, and then cooling to room temperature for use;

[0061] Step 4. Weigh each material according to mass, first pour 10 parts of hyperbranched polymer film-forming material dispersion into a beaker, add 4 parts of silane coupling agent under stirring, and continue stirring for 3-5 minutes after complete dissolution; then continue to add 1 part of complexing agent under stirring, and continue stirring for 3-5 minutes after complete dissolution; then continue to add 0.5 parts of corrosion inhibitor under stirring, and continue stirring for 3-5 minutes after complete dissolution; then continue to add 0.1 parts of pH regulator under stirring, and continue stirring for 3-5 minutes after complete dissolution; finally, fill up to 100 parts with solvent, continue stirring and dispersing for 3-5 minutes to obtain a modified hyperbranched polymer metal surface treatment liquid.

[0062] Example 6

[0063] Step 1: Prepare N,N'-methylenebisacrylamide (MBA) solution by dispersing MBA in solvent and stirring at 30°C for 30 minutes to obtain an MBA concentration of 0.137 g / mL, followed by cooling to room temperature for use;

[0064] Step 2: Prepare a 1,4-butanediamine (BDA) solution by dispersing BDA in a solvent and stirring at 30°C for 30 minutes to obtain a MBA concentration of 0.267 g / mL, followed by cooling to room temperature for later use;

[0065] Step 3: Prepare a hyperbranched polymer film-forming material dispersion by mixing the MBA solution prepared in step 1 with the BDA solution prepared in step 2 in a volume ratio of 1:1, and stirring at 30°C for 24 hours to obtain a hyperbranched polymer film-forming material dispersion, and then cooling to room temperature for use;

[0066] Step 4. Weigh each material according to mass, first pour 40 parts of hyperbranched polymer film-forming material dispersion into a beaker, add 5 parts of silane coupling agent under stirring, and continue stirring for 3-5 minutes after complete dissolution; then continue to add 1 part of complexing agent under stirring, and continue stirring for 3-5 minutes after complete dissolution; then continue to add 0.5 parts of corrosion inhibitor under stirring, and continue stirring for 3-5 minutes after complete dissolution; then continue to add 0.1 parts of pH regulator under stirring, and continue stirring for 3-5 minutes after complete dissolution; finally, fill up to 100 parts with solvent, continue stirring and dispersing for 3-5 minutes to obtain a modified hyperbranched polymer metal surface treatment liquid.

[0067] Example 7

[0068] Step 1: Prepare N,N'-methylenebisacrylamide (MBA) solution by dispersing MBA in solvent and stirring at 30°C for 30 minutes to obtain an MBA concentration of 0.137 g / mL, followed by cooling to room temperature for use;

[0069] Step 2: Prepare a 1,4-butanediamine (BDA) solution by dispersing BDA in a solvent and stirring at 30°C for 30 minutes to obtain a MBA concentration of 0.267 g / mL, followed by cooling to room temperature for later use;

[0070] Step 3: Prepare a hyperbranched polymer film-forming material dispersion by mixing the MBA solution prepared in step 1 with the BDA solution prepared in step 2 in a volume ratio of 1:1, and stirring at 30°C for 24 hours to obtain a hyperbranched polymer film-forming material dispersion, and then cooling to room temperature for use;

[0071] Step 4. Weigh each material according to mass, first pour 30 parts of hyperbranched polymer film-forming material dispersion into a beaker, add 6 parts of silane coupling agent under stirring, and continue stirring for 3-5 minutes after complete dissolution; then continue to add 1 part of complexing agent under stirring, and continue stirring for 3-5 minutes after complete dissolution; then continue to add 0.5 parts of corrosion inhibitor under stirring, and continue stirring for 3-5 minutes after complete dissolution; then continue to add 0.1 parts of pH regulator under stirring, and continue stirring for 3-5 minutes after complete dissolution; finally, fill up to 100 parts with solvent, continue stirring and dispersing for 3-5 minutes to obtain a modified hyperbranched polymer metal surface treatment liquid.

[0072] Example 8

[0073] Step 1: Prepare N,N'-methylenebisacrylamide (MBA) solution by dispersing MBA in solvent and stirring at 30°C for 30 minutes to obtain an MBA concentration of 0.137 g / mL, followed by cooling to room temperature for use;

[0074] Step 2: Prepare a 1,4-butanediamine (BDA) solution by dispersing BDA in a solvent and stirring at 30°C for 30 minutes to obtain a MBA concentration of 0.267 g / mL, followed by cooling to room temperature for later use;

[0075] Step 3: Prepare a hyperbranched polymer film-forming material dispersion by mixing the MBA solution prepared in step 1 with the BDA solution prepared in step 2 in a volume ratio of 1:1, and stirring at 30°C for 24 hours to obtain a hyperbranched polymer film-forming material dispersion, and then cooling to room temperature for use;

[0076] Step 4. Weigh each material according to mass, first pour 20 parts of hyperbranched polymer film-forming material dispersion into a beaker, add 7 parts of silane coupling agent under stirring, and continue stirring for 3-5 minutes after complete dissolution; then continue to add 1 part of complexing agent under stirring, and continue stirring for 3-5 minutes after complete dissolution; then continue to add 0.5 parts of corrosion inhibitor under stirring, and continue stirring for 3-5 minutes after complete dissolution; then continue to add 0.1 parts of pH regulator under stirring, and continue stirring for 3-5 minutes after complete dissolution; finally, fill up to 100 parts with solvent, continue stirring and dispersing for 3-5 minutes to obtain a modified hyperbranched polymer metal surface treatment liquid.

[0077] Example 9

[0078] Step 1: Prepare N,N'-methylenebisacrylamide (MBA) solution by dispersing MBA in solvent and stirring at 30°C for 30 minutes to obtain an MBA concentration of 0.137 g / mL, followed by cooling to room temperature for use;

[0079] Step 2: Prepare a 1,4-butanediamine (BDA) solution by dispersing BDA in a solvent and stirring at 30°C for 30 minutes to obtain a MBA concentration of 0.267 g / mL, followed by cooling to room temperature for later use;

[0080] Step 3: Prepare a hyperbranched polymer film-forming material dispersion by mixing the MBA solution prepared in step 1 with the BDA solution prepared in step 2 in a volume ratio of 1:1, and stirring at 30°C for 24 hours to obtain a hyperbranched polymer film-forming material dispersion, and then cooling to room temperature for use;

[0081] Step 4. Weigh each material according to mass, first pour 10 parts of hyperbranched polymer film-forming material dispersion into a beaker, add 8 parts of silane coupling agent under stirring, and continue stirring for 3-5 minutes after complete dissolution; then continue to add 1 part of complexing agent under stirring, and continue stirring for 3-5 minutes after complete dissolution; then continue to add 0.5 parts of corrosion inhibitor under stirring, and continue stirring for 3-5 minutes after complete dissolution; then continue to add 0.1 parts of pH regulator under stirring, and continue stirring for 3-5 minutes after complete dissolution; finally, fill up to 100 parts with solvent, continue stirring and dispersing for 3-5 minutes to obtain a modified hyperbranched polymer metal surface treatment liquid.

[0082] Comparative Example 1

[0083] Weigh each material according to mass, first pour 98.4 parts of solvent into a beaker, add 1 part of complexing agent while stirring, and continue stirring for 3-5 minutes after it is completely dissolved; then continue to add 0.5 parts of corrosion inhibitor while stirring, and continue stirring for 3-5 minutes after it is completely dissolved; then continue to add 0.1 parts of pH adjuster while stirring, and continue stirring for 3-5 minutes after it is completely dissolved; finally, fill up to 100 parts with solvent, continue stirring and dispersing for 3-5 minutes to obtain a modified hyperbranched polymer metal surface treatment liquid.

[0084] The hyperbranched polymer in the metal surface treatment liquid obtained by the present invention, due to its highly branched three-dimensional structure and the large number of functional groups contained at the end of the molecular chain, easily undergoes strong cross-linking reactions with molecules such as silane coupling agents and complexing agents, thereby forming a strong cross-linked structure with the metal surface and enhancing physical and chemical shielding properties. At the same time, the presence of cavities within the hyperbranched polymer molecules can adsorb and accommodate corrosion inhibitors, enhancing corrosion resistance. The synergistic effect of silane coupling agents and green corrosion inhibitors can provide electrochemical corrosion protection and salt spray resistance to metals, thus having extremely high application prospects.

[0085] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art will be able to modify the technical solutions described in the aforementioned embodiments or substitute equivalents for some of the technical features. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention shall be included within the scope of protection of the present invention.

Claims

1. A modified hyperbranched polymer metal surface treatment liquid, characterized in that: The composition mainly comprises the following components by mass fraction: 10-80 parts of hyperbranched polymer film-forming material dispersion; 1-10 parts of silane coupling agent; 0.1-5 parts of complexing agent; 0.1-5 parts of corrosion inhibitor; 0.1-2 parts of pH adjuster; 1-90 parts of solvent.

2. A modified hyperbranched polymer metal surface treatment liquid according to claim 1, characterized in that: The hyperbranched polymer film-forming material dispersion is obtained by reacting N,N'-methylenebisacrylamide (MBA) and 1,4-butanediamine (BDA) in a solvent.

3. The modified hyperbranched polymer metal surface treatment liquid according to claim 1, characterized in that: The silane coupling agent is one of dimethyldimethoxysilane, tetramethoxysilane, γ-(2,3-epoxypropoxy)propyltrimethoxysilane (KH560), 1,2-bis(triethoxysilyl)ethane, and methyl-trimethoxysilane (MTMS).

4. The modified hyperbranched polymer metal surface treatment liquid according to claim 1, characterized in that: The complexing agent is one of disodium edetate, sodium gluconate, L(+)-tartaric acid, benzimidazole and 2-methylimidazole.

5. The modified hyperbranched polymer metal surface treatment liquid according to claim 1, characterized in that: The corrosion inhibitor is one of sodium molybdate, L-histidine, L-proline and L-glutamic acid.

6. The modified hyperbranched polymer metal surface treatment liquid according to claim 1, characterized in that: The pH regulator is one of sodium carbonate, sodium bicarbonate, triethylamine, triethanolamine, and tris(hydroxymethyl)aminomethane (Tris).

7. The modified hyperbranched polymer metal surface treatment liquid according to claim 1, characterized in that: The solvent is one or more of methanol, ethanol and distilled water.

8. The method for preparing a modified hyperbranched polymer metal surface treatment solution according to claim 1, wherein: The main steps are as follows: Step 1: Prepare N,N'-methylenebisacrylamide (MBA) solution by dispersing MBA in solvent and stirring at 30°C for 30 minutes to obtain an MBA concentration of 0.137 g / mL, followed by cooling to room temperature for use; Step 2: Prepare a 1,4-butanediamine (BDA) solution by dispersing BDA in a solvent and stirring at 30°C for 30 minutes to obtain an MBA concentration of 0.267 g / mL, followed by cooling to room temperature for later use; Step 3: Prepare a hyperbranched polymer film-forming material dispersion by mixing the MBA solution prepared in step 1 with the BDA solution prepared in step 2 in a volume ratio of 1:1, and stirring at 30°C for 24 hours to obtain a hyperbranched polymer film-forming material dispersion, which is then cooled to room temperature for use; Step 4. Weigh each material according to mass, first pour the hyperbranched polymer film-forming material dispersion into a beaker, add the silane coupling agent while stirring, and continue stirring for 3-5 minutes after it is completely dissolved; then continue to add the complexing agent while stirring, and continue stirring for 3-5 minutes after it is completely dissolved; then continue to add the corrosion inhibitor while stirring, and continue stirring for 3-5 minutes after it is completely dissolved; then continue to add the pH adjuster while stirring, and continue stirring for 3-5 minutes after it is completely dissolved; finally, fill it up to 100 parts with solvent, continue stirring and dispersing for 3-5 minutes to obtain a modified hyperbranched polymer metal surface treatment liquid. The components mainly include, by mass fraction: 10-80 parts of hyperbranched polymer film-forming material dispersion; 1-10 parts of silane coupling agent; 1-5 parts of complexing agent; 0.1-5 parts of corrosion inhibitor; 0.1-2 parts pH regulator; 1 part to 90 parts of solvent.

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