A cucurbituril-modified organosilicon-based metal antirust water and its preparation method and application

Abstract

The present invention discloses a cucurbituril-modified organosilicon metal antirust water and its preparation method and application. The method uses water as a solvent, cucurbituril-modified organosilane as the main film-forming agent, fluoro zirconic acid / salt as the auxiliary film-forming agent, and adds acid, accelerator and stabilizer to reinforce the film layer. Due to the introduction of the macrocyclic host molecule - cucurbituril, the storage time of the organosilane in the organosilicon metal antirust water of the present invention is significantly prolonged, and the film formation is more uniform and dense, realizing better storage stability and film-forming sealing property of the organosilicon metal antirust water.

Description

Technical Field

[0001] The present invention relates to the field of metal rust prevention, and particularly to a cucurbituril-modified organosilicon metal rust preventive solution, a preparation method thereof and an application thereof. Background Art

[0002] The emergence and rapid development of metal materials have promoted the continuous progress of human civilization. In the actual application process of metal materials, corrosion often occurs. On the one hand, the corrosion of metals will cause changes in the mechanical, electrical and other properties of the materials, greatly shortening the service life of metals; on the other hand, the corrosion of metals is also accompanied by huge economic losses. Therefore, exploring and developing environmentally friendly and efficient metal rust prevention technologies has great practical application value.

[0003] The main reason for metal corrosion is that at the interface of the metal, the metal contacts with oxygen, water, etc. and further undergoes chemical or electrochemical reactions, resulting in the transformation of the elemental metal into an oxidized state. The main principle of the method for slowing down metal corrosion is to isolate the metal from contact with oxygen and water, and the isolation methods are mainly divided into passivation, alloying, applying a coating layer, etc. Applying a coating layer is the most commonly used method in the actual application process.

[0004] Traditional metal surface rust prevention treatments are mainly chemical conversion film methods, such as phosphating processes, zirconating processes, etc., but these technologies all have some significant defects. A large amount of phosphorus-containing wastewater and other pollution sources such as heavy metals and other harmful substances will be generated in the phosphating process, greatly limiting the application of the phosphating process. The zirconating process refers to the zirconium conversion film process. Compared with the phosphating process, the zirconating process can form a denser zirconium dioxide film layer, but it has obvious film-forming defects and requires additional processes for secondary treatment.

[0005] Silanization treatment of metal surfaces is a new type of rust prevention process. Compared with the high pollution of the phosphating process and the complexity of the zirconating process, the silanization technology represents a new, environmentally friendly and friendly technical route. The core principle of the silanization rust prevention technology is to utilize the hydrolysis of organosilanes in water to form a large number of silanol bonds (Si-OH). These highly active silanol bonds undergo dehydration reactions with metal-OH on the metal surface to form a large number of Si-O-Metal bonds. In addition, the silanol bonds can also undergo dehydration condensation with each other to form Si-O-Si bonds. In this way, a network-like silane film structure is formed on the metal surface. In addition, the R group connected to Si in the organosilicon has strong modifiability and can be coupled with the film-forming substance (resin) in the paint, which is beneficial to the subsequent painting of the paint.

[0006] The biggest problems encountered in the practical application of the process based on silicone anti-rust are reflected in three aspects: 1) Silicone molecules are prone to hydrolysis and polymerization, with poor stability; 2) There are void defects in the simple silane film; 3) The film-forming time of the silane film is relatively long. Therefore, how to solve the storage stability of organosilanes, shorten the film-forming time, and fill the film-forming defects is the key to promoting the development of this new type of metal anti-rust technology. Summary of the Invention

[0007] The purpose of the present invention is to solve the above-mentioned deficiencies of the prior art, and provide an organosilane modified with cucurbituril as the main film-forming substance, and fluoro zirconic acid / salt as the auxiliary film-forming substance. Under the combined action of acid, stabilizer, and film-forming accelerator, a dense protective film can be rapidly formed on the surfaces of different metal substrates such as cast iron, tinplate, cold-rolled plate, hot-rolled plate, aluminum alloy, etc.

[0008] The technical solution provided by the present invention is specifically as follows:

[0009] An organosilicon-based metal anti-rust water modified with cucurbituril uses water as the solvent, a cucurbituril-modified organosilane complex as the main film-forming agent, fluoro zirconic acid / salt as the auxiliary film-forming agent, and adds acid, film-forming accelerator, and stabilizer as reinforcing agents.

[0010] The composition of the cucurbituril-modified organosilicon-based metal anti-rust water includes: 0.05 - 20 parts of cucurbituril-modified organosilane, 0.05 - 20 parts of fluoro zirconic acid / salt, 0.1 - 5 parts of acid, 0.1 - 0.5 parts of film-forming accelerator, 0.1 - 5 parts of stabilizer, 40 - 80 parts of water; optionally, it may also include 0.05 - 10 parts of organosilane.

[0011] The cucurbituril is one or a mixture of more than one of cucurbit[5]uril, cucurbit[6]uril, cucurbit[7]uril, cucurbit[8]uril; the organosilane in the cucurbituril-modified organosilane is one or a mixture of more than one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, N-aminoethyl-3-aminopropylmethyldiethoxysilane, glycidoxypropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, glycidoxypropylmethyldimethoxysilane, glycidoxypropylmethyldiethoxysilane, 1,2-bis(trimethoxysilyl)ethane, 1,2-bis(triethoxysilyl)ethane, and at least one of them is an amino silane.

[0012] The organosilane is one or a mixture of more than one of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-aminoethyl-3-aminopropyltrimethoxysilane, N-aminoethyl-3-aminopropyltriethoxysilane, 3-aminopropylmethyldimethoxysilane, 3-aminopropylmethyldiethoxysilane, N-aminoethyl-3-aminopropylmethyldimethoxysilane, N-aminoethyl-3-aminopropylmethyldiethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropylmethyldimethoxysilane, glycidoxypropylmethyldiethoxysilane, 1,2-bis(trimethoxysilyl)ethane, and 1,2-bis(triethoxysilyl)ethane.

[0013] The preparation method of the cucurbituril-modified organosilane complex is as follows: Cucurbituril and amino silane are blended in a molar ratio of 1-5:1, and the reaction temperature is 25-80 °C to obtain the cucurbituril-modified organosilane complex.

[0014] The acid is one or a mixture of more than one of hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid, tartaric acid, and citric acid; the film-forming promoter is one or a mixture of more than one of copper chloride, copper sulfate, copper nitrate, zinc chloride, zinc nitrate, cerium chloride, barium chloride, and iron chloride; the stabilizer is one or a mixture of more than one of methanol, ethanol, ethylene glycol, glycerol, and butanol.

[0015] The fluoro zirconic acid / salt is selected from one or a mixture of more than one of fluoro zirconic acid, ammonium fluoro zirconate, potassium fluoro zirconate, and sodium fluoro zirconate.

[0016] The preparation method of the cucurbituril-modified organosilicon metal antirust water mainly includes the following steps:

[0017] (1) Using water as a solvent, adding a stabilizer and cucurbituril-modified organosilane, and adjusting the pH with an acid, denoted as component A;

[0018] (2) Using water as a solvent, adding fluoro zirconic acid / salt, acid, and film-forming promoter, heating and stirring until completely dissolved, denoted as component B;

[0019] (3) Mixing components A and B to obtain the cucurbituril-modified organosilicon metal antirust water.

[0020] The present invention provides an application method of cucurbituril-modified organosilicon metal antirust water, specifically: Diluting the cucurbituril-modified organosilicon antirust water by 50-1000 times, controlling the pH within the range of 4-5, and using the immersion method to carry out antirust treatment on the metal substrate. The metal substrate can be cast iron, tinplate, cold-rolled plate, hot-rolled plate, or aluminum alloy.

[0021] Compared with the current technology, the present invention has the following advantages:

[0022] (1) Through host-guest interaction, cucurbituril molecules are introduced into amino silane, and the storage stability of the formed cucurbituril@amino silane complex in aqueous systems is greatly improved, effectively slowing down the dehydration condensation reaction between silanols, thereby extending the service life of silane;

[0023] (2) Defects are likely to occur after the film formation of pure organosilane. In the present invention, zirconium fluoride / salt is used as an auxiliary film-forming agent, enabling cross-linking between organosilane and zirconium film, improving the denseness of the film formation. At the same time, multiple carbonyl sites at the ports of cucurbituril further enhance the interaction force of metal surface atoms, effectively improving the adhesion;

[0024] (3) In the present invention, a film-forming accelerator of transition metal cation type is innovatively introduced, which can promote the rapid film formation of organosilane, greatly shortening the workpiece treatment time;

[0025] (4) A wide range of metal substrates can be treated, including cast iron, tinplate, cold-rolled sheet, hot-rolled sheet, and aluminum alloy. DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 is the structural diagram of cucurbituril molecule.

[0027] Figure 2 is the schematic diagram of the host-guest complex formed by organosilane and cucurbituril. DETAILED DESCRIPTION OF THE INVENTION

[0028] The present invention will be further described in detail below with reference to the drawings and examples, but the protection scope of the present invention is not limited to the content described.

[0029] EXAMPLE 1

[0030] A cucurbituril-modified organosilicon-based metal rust preventive water, the composition of which is: 10 parts of cucurbituril@3-aminopropyltriethoxysilane complex, 5 parts of 1,2-bis(triethoxysilyl)ethane, 1 part of ammonium zirconium fluoride, 0.5 part of tartaric acid, 2 parts of phosphoric acid, 0.1 part of copper chloride, 1 part of glycerol, and 80.4 parts of water.

[0031] The specific preparation steps are as follows:

[0032] (1) Take 20.4 parts of water, add 2 parts of phosphoric acid, 1 part of glycerol, and 10 parts of cucurbituril@3-aminopropyltriethoxysilane complex, stir at room temperature until clear and transparent, and then continue to dropwise add 5 parts of 1,2-bis(triethoxysilyl)ethane (BTSE), continuously stir for 8 hours until completely dissolved, denoted as component A.

[0033] (2) Take 60 parts of water, add 0.5 part of tartaric acid, 0.1 part of copper chloride, and 1 part of ammonium zirconium fluoride, stir until the solution is clear and transparent, denoted as component B.

[0034] (3) Slowly add Component A to Component B while stirring. After mixing, the cucurbituril-modified organosilicon metal antirust water is obtained.

[0035] Application method:

[0036] Take a cold-rolled plate, degrease it, wash it with water, and set it aside for later use. Then dilute the above-prepared cucurbituril-modified organosilicon metal antirust water 500 times with water, and control the pH between 4 - 4.5 with phosphoric acid or sodium acetate. Immerse the prepared cold-rolled plate in the diluted antirust water by the immersion method, control the immersion time within 1 - 2 minutes, take it out, rinse it with water 2 - 3 times, and dry it.

[0037] Performance test:

[0038] Refer to GB / T 1720 - 2020 (Cross-cut test for paint films) to determine the adhesion of the organosilane film on the surface of the above-prepared cold-rolled plate; refer to GB / T 6461 - 2002 (Rating of specimens and test pieces of metals and other inorganic coatings on metallic substrates after corrosion tests) and GB / T 10125 - 2012 (Artificial atmosphere corrosion test - Salt spray test) to determine the neutral salt spray corrosion resistance of the above-prepared cold-rolled plate. The test results are shown in Summary Table 1.

[0039] Example 2

[0040] A cucurbituril-modified organosilicon metal antirust water, whose composition is: 7 parts of cucurbituril@aminopropyltrimethoxysilane complex, 5 parts of 1,2-bis(trimethoxysilyl)ethane, 3 parts of 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane, 0.3 part of zirconium fluoride, 0.7 part of ammonium zirconium fluoride, 0.5 part of hydrochloric acid, 1.5 parts of nitric acid, 0.2 part of zinc chloride, 1 part of ethylene glycol, and 81.8 parts of water.

[0041] The specific preparation steps are as follows:

[0042] (1) Take 11.8 parts of water, add 0.5 part of hydrochloric acid, 1 part of ethylene glycol, and 7 parts of cucurbituril@aminopropyltrimethoxysilane complex, stir at room temperature until clear and transparent, then continue to dropwise add 5 parts of 1,2-bis(triethoxysilyl)ethane (BTSE) and 3 parts of 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane, and continuously stir for 8 hours until completely dissolved, denoted as Component A.

[0043] (2) Take 70 parts of water, add 1.5 parts of nitric acid, 0.2 part of zinc chloride, 0.3 part of zirconium fluoride, and 0.7 part of ammonium zirconium fluoride, stir until the solution is clear and transparent, denoted as Component B.

[0044] (3) Slowly add Component A to Component B while stirring. After mixing, the cucurbituril-modified organosilicon metal antirust water is obtained.

[0045] Application method:

[0046] Take a cold-rolled plate, degrease it, wash it with water, and set it aside for use. Then dilute the cucurbituril-modified organosilicon metal antirust water prepared above 500 times with water, and control the pH between 4 and 4.5 with phosphoric acid or sodium acetate. Immerse the prepared cold-rolled plate in the diluted antirust water by the immersion method, control the immersion time within 1 - 2 minutes, take it out, rinse it with water 2 - 3 times, and dry it.

[0047] Performance test:

[0048] Refer to GB / T 1720-2020 (Cross-cut test for paint films) to determine the adhesion of the organosilane film on the surface of the cold-rolled plate prepared above; refer to GB / T 6461-2002 (Rating of specimens and test pieces of metals and other inorganic coatings on metallic substrates after corrosion tests) and GB / T 10125-2012 (Artificial atmosphere corrosion test - Salt spray test) to determine the neutral salt spray corrosion resistance of the cold-rolled plate prepared above. The test results are shown in Summary Table 1.

[0049] Example 3

[0050] A cucurbituril-modified organosilicon metal antirust water, whose composition is: 5 parts of cucurbituril@3-aminopropylmethyldimethoxysilane complex, 8 parts of γ-glycidoxypropyltrimethoxysilane, 4 parts of 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane, 0.5 part of ammonium hexafluorozirconate, 0.8 part of potassium hexafluorozirconate, 1 part of citric acid, 0.6 part of tartaric acid, 0.1 part of cerium chloride, 2 parts of ethanol, and 78 parts of water.

[0051] The specific preparation steps are as follows:

[0052] (1) Take 15 parts of water, add 0.6 part of tartaric acid, 2 parts of ethanol, and 5 parts of cucurbituril@3-aminopropylmethyldimethoxysilane complex, stir at room temperature until clear and transparent, and then continue to dropwise add 8 parts of γ-glycidoxypropyltrimethoxysilane and 4 parts of 3-(2,3-epoxypropoxy)propylmethyldimethoxysilane, and continuously stir for 10 hours until completely dissolved, denoted as Component A.

[0053] (2) Take 63 parts of water, add 1 part of citric acid, 0.2 part of zinc chloride, 0.3 part of hexafluorozirconic acid, and 0.7 part of ammonium hexafluorozirconate, and stir until the solution is clear and transparent, denoted as Component B.

[0054] (3) Slowly add Component A to Component B while stirring. After mixing, the cucurbituril-modified organosilicon metal antirust water is obtained.

[0055] Application method:

[0056] Take a cold-rolled plate, degrease it, wash it with water, and set it aside for later use. Then dilute the cucurbituril-modified organosilicon metal antirust water prepared above 500 times with water, and control the pH between 4 and 4.5 with phosphoric acid or sodium acetate. Immerse the prepared cold-rolled plate in the diluted antirust water by the immersion method, control the immersion time within 1 - 2 minutes, take it out, rinse it with water 2 - 3 times, and dry it.

[0057] Performance test:

[0058] Refer to GB / T 1720 - 2020 (Cross - cut test for paint films) to determine the adhesion of the organosilane film on the surface of the prepared cold-rolled plate; refer to GB / T 6461 - 2002 (Rating of specimens and test pieces of metallic and other inorganic coatings on metallic substrates after corrosion tests) and GB / T 10125 - 2012 (Artificial atmosphere corrosion test - Salt spray test) to determine the neutral salt spray corrosion resistance of the prepared cold-rolled plate. The test results are shown in Summary Table 1.

[0059] Example 4

[0060] A cucurbituril-modified organosilicon metal antirust water, whose composition is: 5 parts of cucurbituril@N-aminoethyl-3-aminopropylmethyldimethoxysilane complex, 5 parts of cucurbituril@3-aminopropyltrimethoxysilane complex, 5 parts of γ-glycidoxypropyltrimethoxysilane, 4.8 parts of sodium hexafluorozirconate, 1 part of tartaric acid, 0.7 part of phosphoric acid, 0.3 part of ferric chloride, 3 parts of methanol, and 75.2 parts of water.

[0061] The specific preparation steps are as follows:

[0062] (1) Take 15.2 parts of water, add 1 part of tartaric acid, 3 parts of methanol, 5 parts of cucurbituril@N-aminoethyl-3-aminopropylmethyldimethoxysilane complex, and 5 parts of cucurbituril@3-aminopropyltrimethoxysilane complex. Stir at room temperature until it becomes clear and transparent, then continue to dropwise add 5 parts of γ-glycidoxypropyltrimethoxysilane, and continuously stir for 8 hours until completely dissolved, denoted as Component A.

[0063] (2) Take 60 parts of water, add 0.7 part of phosphoric acid, 0.3 part of ferric chloride, and 0.8 part of sodium hexafluorozirconate, and stir until the solution is clear and transparent, denoted as Component B.

[0064] (3) Slowly add Component A to Component B while stirring. After mixing, the cucurbituril-modified organosilicon metal antirust water is obtained.

[0065] Application method:

[0066] Take a cold-rolled plate, degrease it, wash it with water, and set it aside for later use. Then dilute the cucurbituril-modified organosilicon metal antirust water prepared above 500 times with water, and control the pH between 4 and 4.5 with phosphoric acid or sodium acetate. Immerse the prepared cold-rolled plate in the diluted antirust water by the immersion method, control the immersion time within 1 - 2 minutes, take it out, rinse it with water 2 - 3 times, and dry it.

[0067] Performance test:

[0068] Refer to GB / T 1720-2020 (Cross-cut test for paint films) to determine the adhesion of the organosilane film on the surface of the prepared cold-rolled plate; refer to GB / T 6461-2002 (Rating of specimens and test pieces of metals and other inorganic coatings on metallic substrates after corrosion tests) and GB / T 10125-2012 (Artificial atmosphere corrosion test - Salt spray test) to determine the neutral salt spray corrosion resistance of the prepared cold-rolled plate. The test results are shown in Summary Table 1.

[0069] Example 5

[0070] A cucurbituril-modified organosilicon metal antirust water, whose composition is: 20 parts of cucurbituril@N-aminoethyl-3-aminopropylmethyldiethoxysilane complex, 3 parts of sodium hexafluorozirconate, 2 parts of ammonium hexafluorozirconate, 1.5 parts of tartaric acid, 2 parts of phosphoric acid, 0.3 parts of barium chloride, 4 parts of butanol, and 67.2 parts of water.

[0071] The specific preparation steps are as follows:

[0072] (1) Take 10.2 parts of water, add 1.5 parts of tartaric acid, 4 parts of butanol, and 20 parts of cucurbituril@N-aminoethyl-3-aminopropylmethyldiethoxysilane complex, and stir at room temperature until it is clear and transparent, denoted as Component A.

[0073] (2) Take 57 parts of water, add 2 parts of phosphoric acid, 0.3 parts of barium chloride, 3 parts of sodium hexafluorozirconate, and 2 parts of ammonium hexafluorozirconate, and stir until the solution is clear and transparent, denoted as Component B.

[0074] (3) Slowly add Component A to Component B while stirring. After mixing, the cucurbituril-modified organosilicon metal antirust water is obtained.

[0075] Application method:

[0076] Take a cold-rolled plate, degrease it, wash it with water, and set it aside for later use. Then dilute the cucurbituril-modified organosilicon metal antirust water prepared above 500 times with water, and control the pH between 4 and 4.5 with phosphoric acid or sodium acetate. Immerse the prepared cold-rolled plate in the diluted antirust water by the immersion method, control the immersion time within 1 - 2 minutes, take it out, rinse it with water 2 - 3 times, and dry it.

[0077] Performance test:

[0078] The adhesion of the silicone alkane film on the surface of the cold-rolled plate prepared above was determined with reference to GB / T 1720-2020 (Cross-Cut Test for Paint Films); the neutral salt spray corrosion resistance of the cold-rolled plate prepared above was determined with reference to GB / T 6461-2002 (Rating of Specimens and Test Pieces of Metals and Other Inorganic Coatings on Metallic Substrates after Corrosion Tests) and GB / T 10125-2012 (Artificial Atmosphere Corrosion Tests - Salt Spray Tests). The test results are shown in Summary Table 1.

[0079] Reference Example 1

[0080] An organosilane metal antirust water, whose composition is: 10 parts of 3-aminopropyltrimethoxysilane, 5 parts of γ-glycidyletheroxypropyltrimethoxysilane, 5 parts of ammonium hexafluorozirconate, 2 parts of tartaric acid, and 68 parts of water.

[0081] The specific preparation method is as follows:

[0082] (1) Take 18 parts of water, add 2 parts of tartaric acid and 10 parts of 3-aminopropyltrimethoxysilane, stir at room temperature until clear and transparent, then continue to dropwise add 5 parts of γ-glycidyletheroxypropyltrimethoxysilane, and continuously stir for 8 hours until completely dissolved, denoted as Component A.

[0083] (2) Take 50 parts of water, add 5 parts of ammonium hexafluorozirconate, and stir until the solution is clear and transparent, denoted as Component B.

[0084] (3) Slowly add Component A to Component B while stirring. After mixing, the organosilane metal antirust water is obtained.

[0085] Application method:

[0086] Take a cold-rolled plate, degrease it, wash it with water, and set it aside for use. Then dilute the cucurbituril-modified organosilane-based metal antirust water prepared above 500 times with water, and control the pH between 4 - 4.5 with phosphoric acid or sodium acetate. Immerse the prepared cold-rolled plate in the diluted antirust water by the immersion method, control the immersion time within 1 - 2 minutes, take it out, rinse it with water 2 - 3 times, and dry it.

[0087] Performance test:

[0088] The adhesion of the silicone alkane film on the surface of the cold-rolled plate prepared above was determined with reference to GB / T 1720-2020 (Cross-Cut Test for Paint Films); the neutral salt spray corrosion resistance of the cold-rolled plate prepared above was determined with reference to GB / T 6461-2002 (Rating of Specimens and Test Pieces of Metals and Other Inorganic Coatings on Metallic Substrates after Corrosion Tests) and GB / T 10125-2012 (Artificial Atmosphere Corrosion Tests - Salt Spray Tests). The test results are shown in Summary Table 1.

[0089] The performance test results in the examples and reference examples are shown in Table 1:

[0090] Example 1 2 3 4 5 Reference Example 1 Adhesion 0 0 0 0 0 1 Neutral salt spray / minute 55 40 44 42 39 19

[0091] As can be seen from Table 1, when the cucurbituril-modified organosilane rust preventive water is applied to the surface rust prevention of cold-rolled sheets, it has good adhesion and good neutral salt spray resistance. Among them, the best salt spray resistance can be achieved according to Example 1. Comparing with Reference Example 1, it is not difficult to find that the performance of the silane film can be effectively improved by introducing the cucurbituril-modified organosilane complex and the film-forming promoter. The above results show that the introduction of the supramolecular host molecule - cucurbituril can improve the uniformity of the organosilane during film formation. At the same time, due to the multiple carbonyl (-CO-) sites at both ends of cucurbituril, the coupling coordination between the silane film and the metal surface can be enhanced.

[0092] The storage stability data of the organosilicon metal rust preventive water prepared according to the examples and reference examples are shown in Table 2 (experimental method: in a constant temperature and humidity box at 25 °C and 50% humidity, record the time from clear to turbid):

[0093] Example 1 2 3 4 5 Reference Example 1 Time from clear to turbid / hour 1421 1159 1327 996 955 528

[0094] As can be seen from Table 2, compared with Reference Example 1, the cucurbituril-modified organosilane metal rust preventive water shows very prominent storage stability performance, which confirms the effectiveness of the host-guest strategy: the cavity of cucurbituril forms an inclusion with the amino group in the amino silane, and the formed supramolecular assembly can effectively inhibit the condensation reaction of the organosilane, thus greatly prolonging the stability of the organosilane in the water system.

Claims

1. A cucurbituril-modified organosilicon-based metal antirust water, characterized in that, The components include: 0.05 - 20 parts of cucurbituril - modified organosilane, 0.05 - 20 parts of zirconium fluoride or zirconium fluoridate, 0.1 - 5 parts of acid, 0.1 - 0.5 parts of film - forming accelerator, 0.1 - 5 parts of stabilizer, and 40 - 80 parts of water; The cucurbituril is one or a mixture of more than one of cucurbit[5]uril, cucurbit[6]uril, cucurbit[7]uril, and cucurbit[8]uril; the organosilane in the cucurbituril - modified organosilane is one or a mixture of more than one of 3 - aminopropyltrimethoxysilane, 3 - aminopropyltriethoxysilane, 3 - aminopropylmethyldimethoxysilane, N - aminoethyl - 3 - aminopropylmethyldimethoxysilane, and N - aminoethyl - 3 - aminopropylmethyldiethoxysilane; The preparation method of the cucurbituril - modified organosilane complex is as follows: Cucurbituril and organosilane are blended at a molar ratio of 1 - 5:1, and the reaction temperature is 25 - 80 °C to obtain the cucurbituril - modified organosilane complex; The acid is one or a mixture of more than one of hydrochloric acid, phosphoric acid, nitric acid, sulfuric acid, tartaric acid, and citric acid; the film - forming accelerator is one or a mixture of more than one of copper chloride, copper sulfate, copper nitrate, zinc chloride, zinc nitrate, cerium chloride, barium chloride, and iron chloride; the stabilizer is one or a mixture of more than one of methanol, ethanol, ethylene glycol, glycerol, and butanol.

2. The cucurbituril-modified organosilicon-based metal antirust water according to claim 1, wherein The components further include 0.05 - 10 parts of organosilane.

3. The cucurbituril-modified organosilicon-based metal antirust water according to claim 2, characterized in that, The organosilane is one or a mixture of more than one of 3 - aminopropyltrimethoxysilane, 3 - aminopropyltriethoxysilane, N - aminoethyl - 3 - aminopropyltrimethoxysilane, N - aminoethyl - 3 - aminopropyltriethoxysilane, 3 - aminopropylmethyldimethoxysilane, 3 - aminopropylmethyldiethoxysilane, N - aminoethyl - 3 - aminopropylmethyldimethoxysilane, N - aminoethyl - 3 - aminopropylmethyldiethoxysilane, glycidoxypropyltriethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxypropylmethyldimethoxysilane, glycidoxypropylmethyldiethoxysilane, 1,2 - bis(trimethoxysilyl)ethane, and 1,2 - bis(triethoxysilyl)ethane.

4. The cucurbituril-modified organosilicon-based metal antirust water according to any one of claims 1-2, characterized in that, The zirconium fluoride or zirconium fluoridate is selected from one or a mixture of more than one of zirconium fluoride, ammonium zirconium fluoride, potassium zirconium fluoride, and sodium zirconium fluoride.

5. The preparation method of the cucurbituril-modified organosilicon-based metal antirust water according to claim 1, characterized in that, It includes the following steps: (1) Using water as a solvent, adding a stabilizer and a cucurbituril - modified organosilane complex, and adjusting the pH with acid, denoted as component A; (2) Using water as a solvent, adding zirconium fluoride or zirconium fluoridate, acid, and a film - forming accelerator, heating and stirring until completely dissolved, denoted as component B; (3) Mixing components A and B to obtain the cucurbituril - modified organosilicon - based metal antirust water.

6. The application method of the cucurbituril-modified organosilicon-based metal antirust water according to any one of claims 1-4, characterized in that Dilute the cucurbituril - modified organosilicon - based antirust water by 50 - 1000 times, control the pH within the range of 4 - 5, and use the immersion method to conduct antirust treatment on the metal.

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