Normal-temperature water-based rust-proof cleaning agent for black metal and preparation method thereof

Abstract

The invention discloses a normal-temperature water-based ferrous metal anti-rust cleaning agent and a preparation method thereof.The cleaning agent is prepared from, by mass, 2.5%-6.0% of an anti-rust additive, 2.5%-9.0% of organic alcohol amine, 1.0%-4.5% of polycarboxylic acid, 0.5%-3.0% of an enhancer, 4.5%-12.0% of an alcohol solvent, 2.5%-7.5% of composite inorganic base, 9.0%-22.5% of a nonionic surfactant, 3.0%-7.5% of an auxiliary and the balance deionized water, the antirust additive is prepared by reacting benzotriazole and a derivative thereof with phytic acid. The cleaning agent has good anti-rust performance, excellent water resistance, strong cleaning ability and no peculiar smell, and is mainly used for improving the anti-rust performance of the cleaning agent.

Description

Technical Field

[0001] The present invention relates to the technical field of cleaning agents, and in particular to a room-temperature water-based ferrous metal anti-rust cleaning agent and a preparation method thereof. Background Art

[0002] Water-based cleaning agents primarily rely on the wetting, emulsifying, penetrating, and dispersing properties of their surfactants, along with the synergistic effects of certain additives, to remove surface dirt. To date, these environmentally friendly water-based cleaning agents have been widely used to remove various contaminants from the surfaces of metal and non-metal products, such as metalworking fluids, dust, and sweat.

[0003] Advantages of water-based cleaning agents: (1) Strong cleaning and decontamination capabilities, and a large amount of oil dissolving capacity; (2) No flash point, non-flammable and non-explosive, safe to use; (3) Non-toxic and harmless, water-based cleaning agents will not harm the physical and mental health of operators.

[0004] However, in the process of cleaning ferrous metals, especially iron-based metals with high carbon content, if a cleaning agent without anti-rust functional components is used, a common problem will be encountered. That is, during the cleaning process, especially the rinsing process, the presence of water and oxygen will easily cause the product to rust, seriously affecting the product's performance and increasing the company's costs.

[0005] The current standard practice for cleaning ferrous metals is to add high concentrations of nitrites or the reaction products of polycarboxylic acids and alcoholamines to the cleaning agent as rust inhibitors. Nitrites are known to be environmentally unfriendly, while the reaction products of polycarboxylic acids and alcoholamines can easily leave significant residue. Furthermore, due to their poor water resistance, they can render the rust inhibitor ineffective after rinsing, losing its effectiveness.

[0006] At present, the cleaning agents for ferrous metals are mainly Ridoline RT-1020 from Henkel of Germany, FC-4362 from Parker Sekin of Japan, and Chemetall of Germany. 1553. Ridoline RT-1020 from Henkel of Germany has good emulsification and solubilization ability, and is suitable for cleaning ferrous metals before painting. It has excellent cleaning power, but its anti-rust performance will be lost after rinsing. Generally, when cleaning rust-prone materials, corresponding rust inhibitors are added to the cleaning agent for adjustment. The cleaning agent FC-4362 from Paka Sekin of Japan has good emulsification and dispersing ability, and is widely used for cleaning ferrous metals before painting. It has good painting applicability, but like Henkel's cleaning agent, its anti-rust performance will be lost after rinsing. Therefore, when cleaning ferrous metals, corresponding rust inhibitors are added to the cleaning agent for adjustment. The cleaning agent from Chemetall of Germany 1553 has good emulsification and solubilization capabilities and is suitable for cleaning ferrous metals before painting. It has excellent cleaning power and still has certain anti-rust properties after rinsing, but its main problem is that it is relatively expensive.

[0007] Therefore, the cleaning agents in the prior art either do not have an anti-rust function or have an anti-rust function but are expensive, resulting in excessively high investment costs for enterprises and reducing their economic benefits. It is necessary to provide a cleaning agent with an anti-rust function that can improve the economic benefits of enterprises. Summary of the Invention

[0008] To achieve the above technical objectives, the present invention provides a low-cost, room-temperature, water-based, ferrous metal anti-rust cleaning agent with excellent rust prevention properties. The agent combines excellent rust prevention properties with low cost, excellent water resistance, strong cleaning power, and lacks odor. Another object of the present invention is to provide a method for preparing the above product.

[0009] On the one hand, the present invention provides a room temperature water-based ferrous metal anti-rust cleaning agent, comprising an anti-rust additive, an organic alcohol amine, a polycarboxylic acid, a strengthening agent, an alcohol solvent, a composite inorganic base, a nonionic surfactant, an auxiliary agent and deionized water.

[0010] Furthermore, the anti-rust additive is prepared by reacting benzotriazole and its derivatives with phytic acid.

[0011] Furthermore, the room temperature water-based ferrous metal anti-rust cleaning agent includes, by mass percentage, 2.5-6.0% of anti-rust additives, 2.5-9.0% of organic alcohol amines, 1.0-4.5% of polycarboxylic acids, 0.5-3.0% of strengtheners, 4.5-12.0% of alcohol solvents, 2.5-7.5% of composite inorganic bases, 9.0-22.5% of non-ionic surfactants, 3.0-7.5% of additives, and the balance is deionized water.

[0012] Furthermore, the rust-proof additive is preferably 2.5-4%, such as 2.9%, 3%, 3.5%, or 4%.

[0013] Further, the organic alkanolamine is preferably 2.5 to 6%, such as 2.9%, 3%, 5%, 5.3%, 5.8%.

[0014] Further, the polycarboxylic acid is preferably 1.5 to 3%, such as 1.9%, 2%, 2.45%, 3%.

[0015] Further, the strengthening agent is preferably 0.5 to 2.5%, such as 0.9%, 1.5%, 1%, 1.9%, 2%.

[0016] Further, the alcohol solvent is preferably 4.5 to 10%, such as 4.5%, 4.8%, 5%, 5.8%, 6%, 7%, 7.8%.

[0017] Further, the composite inorganic base is preferably 2.5 to 7.5%, such as 2.5%, 2.9%, 4.5%, 4.8%, 5%, 7%, 7.5%.

[0018] Further, the non-ionic surfactant is preferably 9 to 15%, such as 9.5%, 10%, 14%, 14.5%.

[0019] Further, the auxiliary agent is preferably 3 to 6%, such as 3.8%, 4.4%, 4.8%, 5%.

[0020] Further, the benzotriazole and its derivatives are selected from at least one of benzotriazole, methylbenzotriazole, and mercaptobenzotriazole. Due to the presence of the amino functional group, benzotriazole and its derivatives can react with phytic acid under certain conditions to produce amide organic compounds. Due to the existence of the lone pair electrons of the nitrogen atom on the amide group, the stability of the phytic acid adsorption film layer on the workpiece surface is further enhanced. And due to the existence of the heterocyclic structure among benzotriazole and its derivatives, superimposing the electronic effect of the nitrogen atom in benzotriazole, the adsorption effect with the metal surface is strengthened, thereby improving the adsorption capacity of the rust prevention film layer, and thus increasing its water resistance.

[0021] Further, the organic alkanolamine is one or a mixture of monoethanolamine, diethanolamine, triethanolamine, dicyclohexylamine, and diisopropanolamine. Its function is not only to provide the alkalinity of the cleaning agent to ensure the cleaning effect, but also to react with the polycarboxylic acid in the cleaning agent to produce amide compounds, thereby further supplementing the rust prevention additive (cyclohexanehexol hexaphosphate amide containing the heterocyclic structure among benzotriazole and its derivatives, also known as cyclohexanehexol hexaphosphate amide derivative), and forming a three-dimensional rust prevention network structure.

[0022] Furthermore, the polycarboxylic acid is one or a mixture of several of decanedicarboxylic acid, undecanedicarboxylic acid, tricarboxylic acid, octadecatrienoic acid, and hexadecanedicarboxylic acid. Its main function is to react with organic alkanolamines to form amide compounds.

[0023] Furthermore, the intensifier is one or a mixture of several of sodium molybdate, sodium titanate, sodium zirconate, zinc nitrate, and potassium hexafluorozirconate. The main function of the intensifier is that under alkaline conditions with a pH greater than 7, sodium molybdate will form a complex with iron ions in steel, and can form a dense precipitation film layer on the surface of the substrate. For the blank spaces in the above three-dimensional anti-rust network structure, it can be well filled to form a denser structure.

[0024] Furthermore, the alcohol solvent is one or a mixture of several of ethanol, methanol, diethylene glycol, propylene glycol, glycerol, and isohexanediol. Its main function is to act as a coupling agent during the reaction, and also to increase the cleaning capacity of the cleaning agent and improve the cleaning ability of the cleaning agent.

[0025] Furthermore, the non-ionic surfactant is one or a mixture of several of secondary alcohol polyoxyethylene ether, isomeric alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, and castor oil polyoxyethylene ether. Its main function is to make the cleaning agent have extremely strong penetration, dispersion, solubilization, and emulsification capabilities through scientific compounding. Different from other cleaning agents that generally need to be used at temperatures above 50°C, the cleaning agent added with non-ionic surfactant has an efficient cleaning effect on the dirt on the material surface at room temperature. During cleaning, it can effectively protect the surface of the cleaning material from erosion, effectively improve the cleaning efficiency, and greatly reduce the cleaning cost.

[0026] Furthermore, the auxiliary agent is one or a mixture of several of sodium ethylenediaminetetraacetate, sodium gluconate, sodium citrate, and disodium ethylenediaminetetraacetate. Its main function is to improve the hard water resistance of the cleaning agent and reduce the influence of water hardness on the surface of the workpiece, so that the cleaning agent can be used well in different regions.

[0027] Furthermore, the composite inorganic base is one or a mixture of several of sodium metasilicate pentahydrate, sodium silicate, potassium silicate, potassium water glass, sodium carbonate, potassium hydroxide, and sodium bicarbonate. Its main purpose is to provide the appropriate alkalinity for the cleaning agent to ensure good cleaning effect on oil stains.

[0028] On the other hand, the present invention provides a preparation method of the room temperature water-based black metal anti-rust type cleaning agent described in the present invention, including the following steps:

[0029] (1) Under stirring conditions, phytic acid is slowly added to an alcoholic solution of benzotriazole and its derivatives, and heated until the alcoholic solution is evaporated to dryness to obtain a cyclohexanehexol hexaphosphoramide derivative.

[0030] (2) First, deionized water is added to a reactor. After heating up, a cyclohexanehexol hexaphosphoramide derivative, a strengthening agent, a composite inorganic base, an organic alkanolamine, and an alcoholic solvent are added in sequence. Under stirring conditions, a polycarboxylic acid and an auxiliary agent are added, and after they are fully dissolved, a nonionic surfactant is added under stirring conditions and mixed evenly to obtain a cleaning agent.

[0031] Further, in step (1), the heating temperature for evaporating the alcoholic solvent to dryness is 70 - 75 °C.

[0032] Further, in step (2), the temperature is raised to 60 - 70 °C.

[0033] Principle: Phytic acid, also known as inositol hexaphosphoric acid or cyclohexanehexol hexakis-dihydrogen phosphate, mainly exists in the seeds, roots, and stems of plants, with the highest content in the seeds of leguminous plants, the bran, and germ of grains. Phytic acid has a very wide range of applications. In the molecular structure of phytic acid, only one of the six phosphate groups is in the a-position, and the other five are in the e-position, with four phosphate groups in the same plane. Therefore, when phytic acid complexes with a metal on the metal surface, it is easy to form a dense monolayer protective film on the metal surface, which can effectively prevent O2, etc. from entering the metal surface, thus resisting the corrosion of the metal.

[0034] React phytic acid with the benzotriazole series to synthesize a cyclohexanehexol hexaphosphoramide derivative, thereby successfully introducing the heterocyclic structure of benzotriazole onto the phosphate group of phytic acid. Furthermore, utilize the self-assembly ability of the heterocyclic structure to form a three-dimensional network structure, thereby improving the water resistance of the organic film layer and the stability of adsorption on the workpiece.

[0035] The N atom in the amide compound formed by the reaction between the organic alkanolamine and the polycarboxylic acid will also combine with the hydrogen atom in the above-mentioned cyclohexanehexol hexaphosphoramide to form a more compact and three-dimensional rust-proof network structure, thereby better preventing the influence of oxygen and water.

[0036] The presence of the strengthening agent during the same period can fill the blank defects of the network structure, forming a better sealing effect, thereby enhancing the anti-oxidation effect.

[0037] The nonionic surfactant effectively removes stains and, in cooperation with the auxiliary agent, cleans the metal surface, effectively and quickly stripping and cleaning oil stains, dirt, carbon deposits, etc.

[0038] React phytic acid with benzotriazole and its series of compounds to synthesize cyclohexanehexol hexaphosphoramide and its series of derivatives, and then add them to the aqueous cleaning agent, and compound with other organic alkanolamines, polycarboxylic acids and strengthening agents at the same time. Therefore, it has a good rust prevention effect on ferrous metals, especially steel parts during the cleaning process. In particular, the introduction of the benzotriazole series of compounds plays a key role in improving the rust prevention film layer. The self-assembled structure of the heterocyclic compound is like the finishing touch, not only improving the water resistance of the protective film layer, but also enhancing the adsorption performance on the workpiece surface. Even after rinsing with water, it still has good rust prevention performance; even if it is not rinsed, no obvious drug residues visible to the naked eye will appear on the surface.

[0039] Under the combined action of cyclohexanehexol hexaphosphoramide derivatives, polyol amides, strengthening agents and composite inorganic bases (such as sodium zirconate), after rinsing and drying, it still has good rust prevention effect, or even if it is not rinsed, no drug residues visible to the naked eye will form on the workpiece surface after natural drying.

[0040] In short, the cleaning agent of the present invention has good cleaning effect at room temperature, and at the same time has good water resistance and excellent rust prevention performance. It is mainly used to improve the rust prevention performance of the cleaning agent while cleaning at room temperature; it has the application properties of expensive imported cleaning agents (such as the corresponding products of Chemetall GmbH in Germany), but greatly reduces the use cost of enterprises and meets the actual needs of the industry. Specific embodiments

[0041] To further understand the content of the present invention, the present invention will be described in detail in combination with the embodiments.

[0042] The following further illustrates the present invention in combination with the embodiments:

[0043] Example 1

[0044] (1) Under stirring conditions, slowly add 0.75 Kg of phytic acid to a 10 Kg ethanol (low-boiling alcohol) solution of 4.5 Kg of benzotriazole. After stirring and reacting at 70 - 75 °C for 2 hours, evaporate the ethanol (low-boiling alcohol) solution to dryness to obtain 5.25 Kg of cyclohexanehexol hexaphosphoramide derivatives.

[0045] (2) First add 86.25 Kg of deionized water to the reactor, heat up to 50 - 65 °C, and sequentially add 5.25 Kg of cyclohexanehexol hexaphosphoramide derivatives, 2.25 Kg of sodium molybdate, 11.25 Kg of sodium metasilicate pentahydrate, 8.25 Kg of triethanolamine, and 9.0 Kg of ethanol. Under stirring conditions, add 3.75 Kg of undecanedicarboxylic acid and 6.75 Kg of sodium gluconate, stir and react for 30 min until it is fully dissolved. Under stirring conditions, add 21.75 Kg of fatty alcohol polyoxyethylene ether to obtain the cleaning agent.

[0046] Example 2

[0047] (1) Under stirring conditions, 0.25 Kg of phytic acid was slowly added to a solution of 4.125 Kg of methylbenzotriazole in 15.0 Kg of ethanol (low-boiling alcohol). After stirring and reacting at 70 - 75 °C for 2 hours, the ethanol (low-boiling alcohol) solution was evaporated to dryness, and 4.5 Kg of cyclohexanehexol hexaphosphamide derivative was obtained.

[0048] (2) First, 103.5 Kg of deionized water was added to the reactor and heated to 65 - 70 °C. Then, 4.5 Kg of cyclohexanehexol hexaphosphamide derivative, 1.5 Kg of sodium titanate, 4.5 Kg of sodium carbonate, 4.5 Kg of diethanolamine, and 7.5 Kg of diethylene glycol were added in sequence. Under stirring conditions, 3.0 Kg of tricarboxylic acid and 6.0 Kg of sodium citrate were added, and the mixture was stirred and reacted for 30 min until it was fully dissolved. Then, 15.0 Kg of isomeric alcohol polyoxyethylene ether was added under stirring conditions to obtain a cleaning agent.

[0049] Example 3

[0050] (1) Under stirring conditions, 11.25 Kg of phytic acid was slowly added to a solution of 4.875 Kg of mercaptobenzotriazole in 15 Kg of ethanol (low-boiling alcohol). After stirring and reacting at 70 - 75 °C for 2 hours, the ethanol (low-boiling alcohol) solution was evaporated to dryness, and 6.0 Kg of cyclohexanehexol hexaphosphamide derivative was obtained.

[0051] (2) First, 78 Kg of deionized water was added to the reactor and heated to 65 - 70 °C. Then, 6.0 Kg of cyclohexanehexol hexaphosphamide derivative, 3.0 Kg of sodium zirconate, 7.5 Kg of potassium silicate, 9.0 Kg of monoethanolamine, and 12.0 Kg of glycerol were added in sequence. Under stirring conditions, 4.5 Kg of octadecatrienoic acid and 7.5 Kg of ethylenediaminetetraacetic acid tetrasodium were added, and the mixture was stirred and reacted for 30 min until it was fully dissolved. Then, 22.5 Kg of castor oil acid polyoxyethylene ether was added under stirring conditions to obtain a cleaning agent.

[0052] Comparative Example 1

[0053] The difference from Example 1 is that KH550 was used to replace benzotriazole.

[0054] Example 2

[0055] The difference from Example 2 is that KH540 was used to replace methylbenzotriazole.

[0056] Comparative Example 3

[0057] The difference from Example 3 is that KH792 was used to replace mercaptobenzotriazole.

[0058] Effect Example 1

[0059] The comparison between the cleaning agent obtained according to the example and the cleaning agent of Chemetall is shown in Table 1. It can be clearly seen from the data in the table that the physical and chemical indexes of the black metal cleaning agent prepared in the embodiment of the present invention are almost similar to those of the products of Chemetall GmbH in Germany. In particular, the anti-corrosion performance of the cleaning agent prepared in the embodiment of the present invention for cast iron and LY12 aluminum is one level better than that of the German products.

[0060] Table 1

[0061]

[0062] The black metal cleaning agent of the present invention has performance equivalent to that of well-known global brand products, with good comprehensive performance. It can replace imports, meet the needs of the black metal products processing industry, effectively reduce costs, and improve economic benefits.

[0063] Effect Example 2

[0064] The first-grade cast iron cleaned by the cleaning agent obtained according to the example and the cleaning agent of the comparative example was subjected to a salt spray test. The detection method refers to the standard GB / T6144-2010.5.8; the test results are shown in Table 2.

[0065] Table 2

[0066]

[0067] It can be clearly seen from Table 2 that after cleaning the black metal with the embodiment of the present invention, the rust prevention effect of the black metal is significantly better than that of the comparative example.

Claims

1. A room-temperature water-based rust-proof cleaning agent for ferrous metals, characterized in that, Including anti-rust additives, organic alcohol amines, polycarboxylic acids, strengthening agents, alcohol solvents, composite inorganic bases, non-ionic surfactants, additives and deionized water; The anti-rust additive is prepared by reacting benzotriazole and its derivatives with phytic acid.

2. The cleaning agent according to claim 1, characterized in that, The room temperature water-based ferrous metal anti-rust cleaning agent includes, by mass percentage, 2.5-6.0% of an anti-rust additive, 2.5-9.0% of an organic alcohol amine, 1.0-4.5% of a polycarboxylic acid, 0.5-3.0% of a strengthening agent, 4.5-12.0% of an alcohol solvent, 2.5-7.5% of a composite inorganic base, 9.0-22.5% of a non-ionic surfactant, 3.0-7.5% of an auxiliary agent, and the balance being deionized water.

3. The cleaning agent according to claim 1, characterized in that, The benzotriazole and its derivatives are at least one selected from benzotriazole, methylbenzotriazole, and mercaptobenzotriazole.

4. The cleaning agent according to claim 1, characterized in that The organic alcohol amine is one or a mixture of monoethanolamine, diethanolamine, triethanolamine, dicyclohexylamine and diisopropanolamine.

5. The cleaning agent according to claim 1, wherein The polycarboxylic acid is one of deca-dioic acid, undeca-dioic acid, tricarboxylic acid, octadecatrienoic acid, and hexadeca-dioic acid, or a mixture of several of them.

6. The cleaning agent according to claim 1, wherein, The strengthening agent is one or a mixture of sodium molybdate, sodium titanate, sodium zirconate, zinc nitrate, and potassium fluorozirconate.

7. The cleaning agent according to claim 1, wherein The alcohol solvent is one or a mixture of ethanol, methanol, diethylene glycol, propylene glycol, glycerol, and isohexylene glycol. The nonionic surfactant is one or a mixture of secondary alcohol polyoxyethylene ether, isomeric alcohol polyoxyethylene ether, alkylphenol polyoxyethylene ether, and castor oil polyoxyethylene ether.

8. The cleaning agent according to claim 1, characterized in that, The auxiliary agent is one of tetrasodium EDTA, sodium gluconate, sodium citrate, and disodium EDTA, or a mixture of several of them.

9. The cleaning agent according to claim 1, characterized in that The composite inorganic alkali is one or a mixture of sodium metasilicate pentahydrate, sodium silicate, potassium silicate, potassium water glass, sodium carbonate, potassium hydroxide, and sodium bicarbonate.

10. A method for preparing the room-temperature water-based rust inhibitor for ferrous metals according to any one of claims 1 to 9, characterized in that, The following steps are involved: (1) Slowly adding phytic acid to an alcohol solution of benzotriazole and its derivatives under stirring conditions, and heating until the alcohol solution is evaporated to dryness, thereby obtaining cyclohexanehexol hexaphosphoramide derivatives; (2) Deionized water is first added to the reactor. After heating, cyclohexane hexamethylenetetramine derivative, enhancer, composite inorganic base, organic alcohol amine and alcohol solvent are added in sequence. Polycarboxylic acid and auxiliary agent are added under stirring. After they are fully dissolved, non-ionic surfactant is added under stirring and mixed evenly to obtain a cleaning agent.

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