CN110066999B - Cleaning agent for 3003 aluminum material - Google Patents
Cleaning agent for 3003 aluminum material Download PDFInfo
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- CN110066999B CN110066999B CN201910449701.6A CN201910449701A CN110066999B CN 110066999 B CN110066999 B CN 110066999B CN 201910449701 A CN201910449701 A CN 201910449701A CN 110066999 B CN110066999 B CN 110066999B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/04—Cleaning or pickling metallic material with solutions or molten salts with acid solutions using inhibitors
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
- C23G1/12—Light metals
- C23G1/125—Light metals aluminium
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Abstract
The invention relates to the field of chemical cleaning agents, in particular to a cleaning agent for 3003 aluminum materials. The invention provides a cleaning agent for 3003 aluminum material, which at least comprises 0.5-4 parts by weight of acid, 0.1-2 parts by weight of surfactant and 0.1-2 parts by weight of corrosion inhibitor, wherein the surfactant comprises dimer sulfonate and fluorine surfactant.
Description
Technical Field
The invention relates to the field of chemical cleaning agents, in particular to a cleaning agent for 3003 aluminum materials.
Background
The 3003 aluminum alloy is Al-Mn alloy, mainly contains Al, Si, Cu, Zn, Mn and Fe, and is a widely used antirust aluminum, the strength of the alloy is slightly higher than that of industrial pure aluminum, and the alloy can not be strengthened by heat treatment, so the mechanical property of the alloy is improved by a cold working method: has high plasticity in an annealing state, good plasticity in semi-cold-work hardening, low plasticity in cold-work hardening, good corrosion resistance, good weldability and poor machinability. 3003 the aluminium alloy is mainly used for low-load parts which require high plasticity and good weldability and work in liquid or gaseous medium, such as oil tanks, gasoline or lubricant oil conduits, various liquid containers and other small-load parts made by deep drawing, and the wire is used as rivet.
Because aluminum is an active metal, aluminum products are very easy to oxidize or mildew under certain temperature and humidity conditions, the existing cleaning agent is an alkaline cleaning agent and an acidic cleaning agent for obvious cleaning effect, the aluminum materials are easy to discolor after the alkaline cleaning agent cleans the aluminum materials, white spots are easy to appear on the surfaces of the aluminum materials, white spots can appear after the acidic cleaning agent cleans the aluminum materials, and mildew spots can appear in humid climates. And aluminum scraps can be generated in the process of stretching the aluminum material, and the use of the aluminum material is limited due to the existence of the aluminum scraps.
Disclosure of Invention
Aiming at some problems in the prior art, the invention provides a cleaning agent for 3003 aluminum material, which at least comprises 0.5-4 parts by weight of acid, 0.1-2 parts by weight of surfactant and 0.1-2 parts by weight of corrosion inhibitor, wherein the surfactant comprises dimer sulfonate and fluorine surfactant.
In a preferred embodiment of the present invention, the acid is a mixture of nitric acid, hydroxyethylidene diphosphonic acid, citric acid, and hydrofluoric acid.
As a preferable technical scheme of the invention, the weight ratio of the dimer sulfonate to the fluorine surfactant is (1-4): 1.
as a preferred embodiment of the present invention, the raw material for preparing the dimer sulfonate comprises a polyhydric alcohol, and the polyhydric alcohol is selected from any one of n-nonanol, n-decanol, n-undecanol, and n-dodecanol.
As a preferable technical scheme of the invention, the corrosion inhibitor comprises any one of phytic acid, boric acid and sebacic acid.
As a preferred technical solution of the present invention, the corrosion inhibitor further includes a bisamide type corrosion inhibitor.
As a preferable technical scheme of the invention, the weight ratio of the phytic acid to the diamide-type corrosion inhibitor is (10-15): 1.
as a preferable technical scheme of the invention, the raw material for preparing the diamide corrosion inhibitor comprises long-chain fatty acid, and the long-chain fatty acid is pelargonic acid or capric acid.
According to a preferable technical scheme of the invention, the weight ratio of the acid to the surfactant to the corrosion inhibitor is (1-5): 1: 1.
the second aspect of the invention provides a preparation method of the cleaning agent, which at least comprises the following steps:
(1) adding the corrosion inhibitor into water for dissolving;
(2) adding acid and surfactant, stirring and dissolving.
Compared with the prior art, the invention has the following beneficial effects:
aluminum scraps are generated in the aluminum material in the stretching process, the aluminum scraps can be peeled by the cleaning agent, the diameter of the peeled aluminum scraps is larger than 200 mu m, and the original color of the aluminum material is not changed and the aluminum material is not corroded; the use temperature of the cleaning agent is 35-40 ℃, and the cleaned aluminum product can be used for a new energy battery box to prevent explosion and combustion of the battery.
Drawings
FIG. 1 is a schematic view of the largest area metal on the filter membrane after the aluminum material is cleaned in example 3;
FIG. 2 is a schematic diagram of the largest area metal on the filter membrane after the aluminum material of example 1 is cleaned.
Detailed Description
The present invention is illustrated by the following specific embodiments, but is not limited to the specific examples given below.
The invention provides a cleaning agent for 3003 aluminum material, which at least comprises 0.5-4 parts by weight of acid, 0.1-2 parts by weight of surfactant and 0.1-2 parts by weight of corrosion inhibitor, wherein the surfactant comprises dimer sulfonate and fluorine surfactant.
Preferably, the cleaning agent further comprises an antifoaming agent, silicon dioxide and water.
Preferably, the cleaning agent at least comprises 0.5-4 parts by weight of acid, 0.1-2 parts by weight of surfactant, 0.1-2 parts by weight of corrosion inhibitor, 0.1-1 part by weight of defoaming agent, 0.1-1 part by weight of silicon dioxide and 85-95 parts by weight of water.
Further preferably, the cleaning agent at least comprises 2 parts of acid, 1 part of surfactant, 1 part of corrosion inhibitor, 0.5 part of defoaming agent, 0.5 part of silicon dioxide and 90 parts of water in parts by weight.
Acid(s)
Examples of the acid include nitric acid, hydrochloric acid, sulfuric acid, sulfamic acid, hydroxyethylidene diphosphonic acid, citric acid, tartaric acid, ethylenediaminetetraacetic acid, glycolic acid, hydrofluoric acid, and silicofluoric acid.
Preferably, the acid is a mixture of nitric acid, hydroxyethylidene diphosphonic acid, citric acid, hydrofluoric acid, and the acid is not particularly limited by the manufacturer of the acid.
Preferably, the weight ratio of the nitric acid to the hydroxyethylidene diphosphonic acid to the citric acid to the hydrofluoric acid is 1: 1: 1: 1.
surface active agent
The surfactant is a substance which is added in a small amount and can cause the interface state of a solution system to change obviously. Has fixed hydrophilic and lipophilic groups and can be directionally arranged on the surface of the solution. The molecular structure of the surfactant has amphipathy: one end is a hydrophilic group, and the other end is a hydrophobic group; the hydrophilic group is often a polar group, such as carboxylic acid, sulfonic acid, sulfuric acid, amino or amino groups and salts thereof, hydroxyl, amide, ether linkages, and the like may also be used as the polar hydrophilic group; and the hydrophobic group is often a non-polar hydrocarbon chain, such as a hydrocarbon chain of 8 or more carbon atoms. The surfactant is divided into ionic surfactant (including cationic surfactant and anionic surfactant), nonionic surfactant, amphoteric surfactant, compound surfactant, other surfactants, etc.
As the surfactant, triethanolamine oleate, polyoxyethylene phenol ether, fatty alcohol-polyoxyethylene ether, dimer sulfonate, sodium dodecyl sulfate, fluorosurfactant and the like can be exemplified.
Preferably, the surfactant comprises a dimer sulfonate and a fluorosurfactant.
Further preferably, the weight ratio of the dimer sulfonate to the fluorine surfactant is (1-4): 1.
further preferably, the weight ratio of the dimer sulfonate to the fluorosurfactant is 2: 1.
more preferably, the raw material for preparing the dimer sulfonate comprises a polyol selected from any one of n-nonanol, n-decanol, n-undecanol and n-dodecanol.
In one embodiment, the process for preparing the dimer sulfonate comprises the steps of:
sequentially adding 0.2mol of polyethylene glycol, maleic anhydride, anhydrous sodium acetate and 150mL of acetone into a three-neck bottle, stirring and heating to T1Reaction t1Recrystallizing to obtain polyethylene glycol monoester products; taking a certain amount of polyethylene glycol monoester product, adding polyalcohol, taking p-toluenesulfonic acid as a catalyst, and heating to T2Reaction t2Washing and purifying to obtain polyethylene glycol diester products; neutralizing the diester product of polyethylene glycol series, adding a certain amount of sodium bisulfite, and heating at temperature T3Reaction t3And (4) hours.
Preferably, the polyethylene glycol has a relative molecular weight of 600, and the polyethylene glycol is not particularly limited to a purchaser.
Preferably, the molar ratio of the polyethylene glycol to the maleic anhydride is 1: 2, the maleic anhydride is not particularly limited to the purchasing manufacturer.
Preferably, the anhydrous sodium acetate accounts for 1% of the total mass of the polyethylene glycol, the maleic anhydride, the anhydrous sodium acetate and the acetone, and the anhydrous sodium acetate is not particularly limited to a purchasing manufacturer.
Preferably, the polyol is selected from any one of n-nonanol, n-decanol, n-undecanol and n-dodecanol, and the molar ratio of the polyol to the polyethylene glycol monoester product is 2: 1, the polyol is not particularly limited to the purchasing manufacturer.
More preferably, the polyol is n-decanol.
Preferably, the p-toluenesulfonic acid accounts for 1.5% of the total mass of the polyethylene glycol monoester products and the polyhydric alcohols, and the p-toluenesulfonic acid is not particularly limited by a purchasing manufacturer.
Preferably, said T1Is 80-85 ℃.
Preferably, said t1Is 4 to 6.
Preferably, said T2Is 100 to 110 ℃.
Preferably, said t2Is 4 to 5.
Preferably, the molar ratio of the polyethylene glycol series diester product to sodium bisulfite is 1: 2, the sodium bisulfite is not particularly limited to the purchasing manufacturer.
Preferably, said T3Is 90 to 100 ℃.
Preferably, said t3Is 3 to 4.
The two sulfonic acid groups of the dimer sulfonate pass through-CH2The O-CO-connection ensures that hydrocarbon chains have stronger interaction and are closely arranged among molecules, and a certain amount of hydrogen bonds exist in the dimer sulfonate, so that the close arrangement among the molecules is further promoted, the dimer sulfonate has higher surface activity, can be quickly diffused to the interface of the aluminum material and the cleaning agent, and is cooperated with the fluorine surfactantThe surface tension of an oil-water interface is reduced in a short time, so that stains on the surface of the aluminum material are quickly stripped and dispersed in the cleaning agent.
If the alkyl alcohol carbon chain in the dimer sulfonate is too short or too long, the cleaning efficiency is reduced, and if the carbon chain is too long, the alkyl alcohol carbon chain is easy to intertwine and curl, so that the intermolecular repulsion force is increased, and the quick cleaning of the oil stains is not facilitated.
Preferably, the fluorine surfactant is at least one of a perfluor alcohol acrylate compound, a perfluor alkyl sulfonamide derivative, a perfluor alkyl amine compound or a perfluor carboxylic acid chromium complex; more preferably, the fluorosurfactant is a perfluoroalkyl sulfonamide derivative.
Examples of the perfluoroalkyl sulfonamide derivatives include N-ethylperfluorooctane sulfonamide, N- (3' -trichlorosilylpropyl) -3-oxaperfluoroalkyl sulfonamide, and 5-halo-3-oxaperfluoropentyl diethyl sulfonamide; preferably, the perfluoroalkyl sulfonamide derivative is N-ethyl perfluorooctane sulfonamide, which is not particularly limited to the manufacturer.
The fluorine surfactant can reduce the surface tension of the aluminum scrap to the maximum extent, and is favorable for accelerating the peeling of the aluminum scrap, so that the reaction of a formula system is more thorough.
In one embodiment, the surfactant further comprises an amphoteric surfactant.
Preferably, the weight ratio of amphoteric surfactant to dimer sulfonate is 1: (3-5); more preferably, the weight ratio of amphoteric surfactant to dimer sulfonate is 1: 4.
preferably, the amphoteric surfactant is a betaine type amphoteric surfactant and/or an imidazoline type amphoteric surfactant; more preferably, the amphoteric surfactant is an imidazoline type amphoteric surfactant.
Preferably, the imidazoline type surfactant is at least one of 1-hydroxyethyl-2-cocoimidazoline acetate, disodium caprylamidoethyl-N-hydroxyethylaminoethoxypropionate and sodium stearamidoethyl-N-hydroxyethylaminoacetate; more preferably, the imidazoline type surfactant is 1-hydroxyethyl-2-cocoimidazoline acetate, and the 1-hydroxyethyl-2-cocoimidazoline acetate is not particularly limited to the purchasing manufacturer.
The amphoteric surfactant can form an antistatic adsorption layer on the solid surface, can reduce the electrostatic adsorption of aluminum scraps on the surface of the aluminum shell, enables the aluminum scraps to be easy to separate from the surface of the aluminum shell, can remove the aluminum scraps to the maximum extent, and has a corrosion inhibition effect.
Corrosion inhibitor
Chemicals or compounds that, when present in the environment (medium) in appropriate concentrations and forms, can prevent or slow the corrosion of materials, and therefore corrosion inhibitors may also be referred to as corrosion inhibitors. Its dosage is very small (0.1% -1%), but its effect is obvious. This method of protecting metals is known as corrosion inhibitor protection. The corrosion inhibitor is used for neutral media (water for boilers and circulating cooling water), acidic media (hydrochloric acid for removing scale of boilers, acid leaching solution for removing rust of plated parts before electroplating) and gas media (vapor phase corrosion inhibitor).
Examples of the corrosion inhibitor include amines, aldehydes, heterocyclic compounds, alkynols, quaternary ammonium salts, organic sulfur compounds, organic phosphorus compounds, and the like.
Preferably, the corrosion inhibitor comprises any one of phytic acid, boric acid and sebacic acid; more preferably, the corrosion inhibitor is phytic acid, which is not particularly limited by the manufacturer.
Phytic acid: phytic acid, also known as creatine, inositol hexakis-dihydrogen phosphate, is found mainly in seeds, roots and stems of plants, with the highest content among seeds of leguminous plants, bran and germs of cereals. The application of the phytic acid is very wide. In the food industry, phytic acid can be used as a food additive, can be used as a metal removing agent in the wine industry, can be used for treating diseases such as diabetes, kidney stone and the like in the medical industry, has wide application in the chemical industry, the petroleum industry, the metallurgy industry and the daily chemical industry, can be used as an antioxidant of grease, a preservative of food and fruits, an anti-sticking agent of a polyvinyl chloride polymerization kettle, a quenching agent in medicine and an additive of feed, can be used as an antirust, cleaning, antistatic and metal surface treating agent and the like, and can be particularly used as one of important raw materials for producing inositol.
Further preferably, the corrosion inhibitor further comprises a bisamide type corrosion inhibitor.
Further preferably, the weight ratio of the phytic acid to the diamide corrosion inhibitor is (10-15): 1.
further preferably, the weight ratio of the phytic acid to the diamide-type corrosion inhibitor is 12: 1.
more preferably, the raw material for preparing the diamide-type corrosion inhibitor comprises long-chain fatty acid which is pelargonic acid or capric acid.
In one embodiment, the method for preparing the bisamide type corrosion inhibitor includes the steps of:
mixing long-chain fatty acid with N, N-di (3-aminopropyl) -methylamine, stirring, and heating to T1And (4) reacting, stopping the reaction when no water is generated, and purifying to obtain the product.
Preferably, the long-chain fatty acid is pelargonic acid or capric acid, and the long-chain fatty acid is not particularly limited to the vendor.
More preferably, the long chain fatty acid is pelargonic acid.
Preferably, the molar ratio of the long chain fatty acid to N, N-bis (3-aminopropyl) -methylamine is 2: 1, the N, N-bis (3-aminopropyl) -methylamine is not particularly limited to the purchasing manufacturer.
Preferably, said T1Is 160 to 170 ℃.
In the application, the added corrosion inhibitor phytic acid acts on the surface of aluminum through a complexing reaction to generate a plurality of chelate rings and form a protective film layer on the surface of the aluminum, but the added corrosion inhibitor phytic acid is limited by the structure of the phytic acid, and the continuity of the protective film layer formed on the surface of the aluminum is poor. (10-15): 1, the corrosion inhibition effect of the cleaning agent can be improved. The possible reasons for guessing are: unpaired nitrogen atoms on the diamide corrosion inhibitor can be adsorbed on the surface of aluminum, and active groups on the diamide corrosion inhibitor interact with active groups on phytic acid to form a compact continuous protective layer, so that adsorption of phytic acid molecules on the surface of the aluminum is stabilized, and the effect of enhancing corrosion inhibition is achieved.
When the amount of the phytic acid is large, the formed protective film has uneven thickness and poor continuity; when the amount of the diamide corrosion inhibitor is large, the diamide corrosion inhibitor competes with phytic acid to be adsorbed on the surface of aluminum, so that the produced film is unstable and is easy to fall off.
Preferably, the weight ratio of the acid to the surfactant to the corrosion inhibitor is (1-5): 1: 1.
more preferably, the weight ratio of the acid, the surfactant and the corrosion inhibitor is 2: 1: 1.
the cleaning agent can remove aluminum scraps on the surface of the aluminum material by adding acid, but only small-particle-size aluminum scraps can be removed in a short time, and the aluminum material is corroded by increasing the acid amount, so that the application of the cleaning agent is limited. The applicant finds that the weight ratio of the acid to the surfactant to the corrosion inhibitor is (1-5): 1: 1, the aluminum scrap with large diameter is quickly stripped, and the surface of the aluminum material is prevented from being corroded. The possible reasons for guessing are: the citric acid, the nitric acid, the hydroxyethylidene diphosphonic acid and the hydrofluoric acid are mutually cooperated, on one hand, hydrogen ions interact with aluminum scraps, and on the other hand, the citric acid and the hydroxyethylidene diphosphonic acid quickly form a hydrophilic chelate with the aluminum scraps; the corrosion inhibitor can quickly permeate into the interface of the stain and the aluminum under the cooperation of the surfactant, the binding force of the stain and the aluminum is weakened, and secondary power is provided for removing aluminum scraps; meanwhile, in the acid medium, nitrogen atoms which are not formed into electron pairs in the cleaning agent are combined with hydrogen ions so as to carry some positive charges, and a protective layer can be formed on the surface of the aluminum metal in the moment after the aluminum scraps are removed, so that the hydrogen ions in the acid liquid can not generate corrosion reaction with the metal, and the corrosion aggravation caused by the removal of the aluminum scraps can be avoided.
When the weight part of the acid is larger, more hydrogen ions are contained in the acid liquor, so that the corrosion is increased; when the weight of the acid is less, the cleaning effect cannot be effectively realized; too much surfactant can lead to increased corrosion.
Defoaming agent
Defoamers, also known as defoamers, are additives that reduce surface tension during processing, inhibit foam generation or eliminate foam already generated.
Examples of the defoaming agent include silicone emulsion, higher alcohol fatty acid ester complex, polyoxyethylene polyoxypropylene pentaerythritol ether, polyoxyethylene polyoxypropylene amine ether, polyoxypropylene glycerol ether, polyoxypropylene polyoxyethylene glycerol ether, and polydimethylsiloxane.
Preferably, the defoaming agent is polyether modified organic silicon which is purchased from field chemistry and has the model of WT-55.
Silicon dioxide
Silica, chemical term, pure silica is colorless, solid at room temperature, and has the chemical formula SiO2It is insoluble in water and acid, but soluble in hydrofluoric acid and hot concentrated phosphoric acid, and can react with molten alkali. Both crystalline silica and amorphous silica exist in nature. Silica has a wide application range and is mainly used for manufacturing glass, water glass, pottery, enamel, refractory materials, aerogel felts, ferrosilicon, molding sand, simple substance silicon, cement and the like. Silica has also been used in ancient times to make glaze and carcass for porcelain. The general stone is mainly composed of silicon dioxide and calcium carbonate.
Preferably, the silica is single-layer organic chain modified nano-silica, available from the eastern Shen petrochemical Co., Ltd. of Zheng, and has the model of MGS-2.
Preferably, the weight ratio of the defoaming agent to the silicon dioxide is (1-2): 1.
more preferably, the weight ratio of the defoamer to silica is 1: 1.
in the application, after polyether modified organic silicon is added, a siloxane chain segment with hydrophobicity can be curled inside, a polyether chain segment with hydrophilicity extends outside, an antifoaming agent continuously diffuses and permeates among liquid films, the permeation depth of the antifoaming agent continuously increases to form a water-oil-water bridge, the bridge is dragged in the radial direction by high surface tension liquid on two sides, the bridge is continuously thinned and thinned, stress imbalance is finally caused, foam is caused to be broken, the steps are continuously repeated, and finally all foams are caused to be covered and extinguished. The applicant unexpectedly finds that when the weight of the polyether modified organic silicon is 1-2 times of that of silicon dioxide, the defoaming time can be greatly shortened. The possible reasons for guessing are: the hydrophobic groups of the surfactant foaming in the cleaning agent interact with silicon dioxide, and the hydrophilic groups extend into the water phase; the silicon dioxide causes the surfactant originally adsorbed on the surface of the liquid film to be pulled down from the surface of the liquid film and enter the water phase of the liquid film, thereby destroying the stability of the foam, and simultaneously reducing the resistance of the defoaming agent entering the foam to establish the bridge, thereby greatly shortening the defoaming time.
The second aspect of the invention provides a preparation method of the cleaning agent, which at least comprises the following steps:
(1) adding the corrosion inhibitor into water for dissolving;
(2) adding acid and surfactant, stirring and dissolving.
Preferably, the preparation method of the cleaning agent at least comprises the following steps:
(1) adding the corrosion inhibitor into water for dissolving;
(2) adding acid, silicon dioxide and surfactant for dissolving;
(3) adding the defoaming agent, stirring and dissolving.
Examples
Example 1
Embodiment 1 of the invention provides a cleaning agent for 3003 aluminum material, which comprises, by weight, 0.5 part of acid, 0.1 part of surfactant, 0.1 part of corrosion inhibitor, 0.1 part of defoaming agent, 0.1 part of silica and 85 parts of water.
The acid is a mixture of nitric acid, hydroxyethylidene diphosphonic acid, citric acid and hydrofluoric acid, and the weight ratio of the nitric acid to the hydroxyethylidene diphosphonic acid to the citric acid to the hydrofluoric acid is 1: 1: 1: 1. the nitric acid is purchased from Shih Shu Biotech, Inc., the hydroxyethylidene diphosphonic acid is purchased from Fulu Biotech, Inc., Suzhou, the citric acid is purchased from Shanghai Yi En chemical technology, Inc., and the hydrofluoric acid is purchased from Tian Hua chemical industry, Inc., Jiangxi.
The surfactants include dimer sulfonates and fluorosurfactants. The weight ratio of the dimer sulfonate to the fluorine surfactant is 1: 1.
the fluorine surfactant is N-ethyl perfluorooctane sulfonamide and is purchased from Shanghai Jiachen chemical Co.
The preparation method of the dimer sulfonate comprises the following steps:
sequentially adding 0.2mol of polyethylene glycol, maleic anhydride, anhydrous sodium acetate and 150mL of acetone into a three-neck bottle, stirring and heating to T1Reaction t1Recrystallizing to obtain polyethylene glycol monoester products; taking a certain amount of polyethylene glycol monoester product, adding polyalcohol, taking p-toluenesulfonic acid as a catalyst, and heating to T2Reaction t2Washing and purifying to obtain polyethylene glycol diester products; neutralizing the diester product of polyethylene glycol series, adding a certain amount of sodium bisulfite, and heating at temperature T3Reaction t3And (4) hours.
The polyethylene glycol has a relative molecular weight of 600, and is available from Changzhou Guxu chemical industry Co., Ltd.
The molar ratio of the polyethylene glycol to the maleic anhydride is 1: 2, the maleic anhydride is available from Shanghai Pont chemical industries, Ltd.
The anhydrous sodium acetate accounts for 1% of the total mass of the polyethylene glycol, the maleic anhydride, the anhydrous sodium acetate and the acetone, and the anhydrous sodium acetate is purchased from Touchuang Tianke Biotech limited.
The polyol is n-decanol, and the molar ratio of the n-decanol to the polyethylene glycol monoester products is 2: 1, the n-decanol is purchased from Jiangtai Tahua chemical Co., Ltd, Hubei.
The p-toluenesulfonic acid accounts for 1.5% of the total mass of the polyethylene glycol monoester products and the polyhydric alcohols, and is purchased from Shanghai Yi En chemical technology Co.
The T is1Is 80-85 ℃.
Said t is1Is 4 to 6.
The T is2Is 100 to 110 ℃.
Said t is2Is 4 to 5.
The molar ratio of the polyethylene glycol series diester product to the sodium bisulfite is 1: 2, the sodium bisulfite is available from good industries, chemical, ltd, changzhou.
The T is3Is 90 to 100 ℃.
Said t is3Is 3 to 4.
The corrosion inhibitor is phytic acid and a diamide corrosion inhibitor, and the weight ratio of the phytic acid to the diamide corrosion inhibitor is 10: 1.
the phytic acid was purchased from Shanghai Xicheng Chemicals, Inc.
The preparation method of the diamide corrosion inhibitor comprises the following steps:
mixing long-chain fatty acid with N, N-di (3-aminopropyl) -methylamine, stirring, and heating to T1And (4) reacting, stopping the reaction when no water is generated, and purifying to obtain the product.
The long chain fatty acid is pelargonic acid, which is available from Nanjing Sikh Vanck chemical Co.
The molar ratio of the nonanoic acid to the N, N-bis (3-aminopropyl) -methylamine is 2: 1, said N, N-bis (3-aminopropyl) -methylamine is available from golden malol chemical co.
The T is1The temperature was 170 ℃.
The defoaming agent is polyether modified organic silicon.
The silica was purchased from Zhengzhou Dongshu petrochemical Co., Ltd, and was designated MGS-2.
The preparation method of the cleaning agent comprises the following steps:
(1) adding the corrosion inhibitor into water for dissolving;
(2) adding acid, silicon dioxide and surfactant, stirring and dissolving;
(3) add antifoam and stir for 1 hour.
Example 2
The embodiment 2 of the invention provides a cleaning agent for 3003 aluminum material, which comprises, by weight, 4 parts of acid, 2 parts of surfactant, 2 parts of corrosion inhibitor, 1 part of defoaming agent, 1 part of silicon dioxide and 95 parts of water.
The acid is a mixture of nitric acid, hydroxyethylidene diphosphonic acid, citric acid and hydrofluoric acid, and the weight ratio of the nitric acid to the hydroxyethylidene diphosphonic acid to the citric acid to the hydrofluoric acid is 1: 1: 1: 1. the nitric acid is purchased from Shih Shu Biotech, Inc., the hydroxyethylidene diphosphonic acid is purchased from Fulu Biotech, Inc., Suzhou, the citric acid is purchased from Shanghai Yi En chemical technology, Inc., and the hydrofluoric acid is purchased from Tian Hua chemical industry, Inc., Jiangxi.
The surfactants include dimer sulfonates and fluorosurfactants. The weight ratio of the dimer sulfonate to the fluorosurfactant is 4: 1.
the fluorine surfactant is N-ethyl perfluorooctane sulfonamide and is purchased from Shanghai Jiachen chemical Co. The specific embodiment of the preparation method of the dimer sulfonate is the same as that of example 1.
The corrosion inhibitor is phytic acid and a diamide corrosion inhibitor, and the weight ratio of the phytic acid to the diamide corrosion inhibitor is 15: 1, phytic acid was purchased from Shanghai Soxichem chemical Co., Ltd, and a specific embodiment of the method for preparing the bisamide-type corrosion inhibitor was the same as in example 1.
The defoaming agent is polyether modified organic silicon.
The silica was purchased from Zhengzhou Dongshu petrochemical Co., Ltd.
The specific implementation mode of the preparation method of the cleaning agent is the same as that of the example 1.
Example 3
Embodiment 3 of the invention provides a cleaning agent for 3003 aluminum material, which comprises, by weight, 2 parts of acid, 1 part of surfactant, 1 part of corrosion inhibitor, 0.5 part of defoaming agent, 0.5 part of silicon dioxide and 90 parts of water.
The acid is a mixture of nitric acid, hydroxyethylidene diphosphonic acid, citric acid and hydrofluoric acid, and the weight ratio of the nitric acid to the hydroxyethylidene diphosphonic acid to the citric acid to the hydrofluoric acid is 1: 1: 1: 1. the nitric acid is purchased from Shih Shu Biotech, Inc., the hydroxyethylidene diphosphonic acid is purchased from Fulu Biotech, Inc., Suzhou, the citric acid is purchased from Shanghai Yi En chemical technology, Inc., and the hydrofluoric acid is purchased from Tian Hua chemical industry, Inc., Jiangxi.
The surfactants include dimer sulfonates and fluorosurfactants. The weight ratio of the dimer sulfonate to the fluorine surfactant is 2: 1.
the fluorine surfactant is N-ethyl perfluorooctane sulfonamide and is purchased from Shanghai Jiachen chemical Co. The specific embodiment of the preparation method of the dimer sulfonate is the same as that of example 1.
The corrosion inhibitor is phytic acid and a diamide corrosion inhibitor, and the weight ratio of the phytic acid to the diamide corrosion inhibitor is 12: 1, phytic acid was purchased from Shanghai Soxichem chemical Co., Ltd, and a specific embodiment of the method for preparing the bisamide-type corrosion inhibitor was the same as in example 1.
The defoaming agent is polyether modified organic silicon.
The silica was purchased from Zhengzhou Dongshu petrochemical Co., Ltd.
The specific implementation mode of the preparation method of the cleaning agent is the same as that of the example 1.
Example 4
The embodiment 4 of the invention provides a cleaning agent for 3003 aluminum material, which is the same as the embodiment 3 in specific implementation manner, and is characterized in that the surfactant further comprises an amphoteric surfactant, and the weight ratio of the amphoteric surfactant to dimer sulfonate is 1: 4; the amphoteric surfactant is 1-hydroxyethyl-2-cocoimidazoline acetate available from Hill of Huizhii, Guangzhou, science and technology development, Inc.
The specific embodiment of the preparation method of the dimer sulfonate is the same as that of example 1.
The specific embodiment of the preparation method of the diamide corrosion inhibitor is the same as that of example 1.
The specific implementation mode of the preparation method of the cleaning agent is the same as that of the example 1.
Example 5
The embodiment 5 of the invention provides a cleaning agent for 3003 aluminum material, which is the same as the embodiment 3 in the specific implementation manner, and is characterized in that the weight ratio of the dimer sulfonate to the fluorine surfactant is 1: 10.
the specific embodiment of the preparation method of the dimer sulfonate is the same as that of example 1.
The specific embodiment of the preparation method of the diamide corrosion inhibitor is the same as that of example 1.
The specific implementation mode of the preparation method of the cleaning agent is the same as that of the example 1.
Example 6
The embodiment 6 of the invention provides a cleaning agent for 3003 aluminum material, which is the same as the embodiment 3 in the specific implementation manner, and is characterized in that the weight ratio of the dimer sulfonate to the fluorine surfactant is 10: 1.
the specific embodiment of the preparation method of the dimer sulfonate is the same as that of example 1.
The specific embodiment of the preparation method of the diamide corrosion inhibitor is the same as that of example 1.
The specific implementation mode of the preparation method of the cleaning agent is the same as that of the example 1.
Example 7
Example 7 of the present invention provides a cleaning agent for 3003 aluminum material, and the specific embodiment thereof is the same as example 3.
The dimer sulfonate is prepared in the same manner as in example 1, except that the polyol used in the preparation of the dimer sulfonate is n-pentanol, which is available from puhua chemical technology ltd.
The specific embodiment of the preparation method of the diamide corrosion inhibitor is the same as that of example 1.
The specific implementation mode of the preparation method of the cleaning agent is the same as that of the example 1.
Example 8
Example 8 of the present invention provides a cleaning agent for 3003 aluminum material, and the specific embodiment thereof is the same as example 3.
The specific implementation manner of the preparation method of the dimer sulfonate is the same as that of example 1, except that the polyol in the preparation method of the dimer sulfonate is n-octadecanol, which is purchased from Shanghai Bingsui Biotech Co.
The specific embodiment of the preparation method of the diamide corrosion inhibitor is the same as that of example 1.
The specific implementation mode of the preparation method of the cleaning agent is the same as that of the example 1.
Example 9
The embodiment 9 of the invention provides a cleaning agent for 3003 aluminum material, which has the same specific implementation manner as the embodiment 3, and is characterized in that the corrosion inhibitor is phytic acid.
The specific embodiment of the preparation method of the dimer sulfonate is the same as that of example 1.
The specific embodiment of the preparation method of the diamide corrosion inhibitor is the same as that of example 1.
The specific implementation mode of the preparation method of the cleaning agent is the same as that of the example 1.
Example 10
The embodiment 10 of the invention provides a cleaning agent for 3003 aluminum material, which has the same specific implementation manner as the embodiment 3, and is characterized in that the weight ratio of the phytic acid to the diamide-type corrosion inhibitor is 30: 1.
the specific embodiment of the preparation method of the dimer sulfonate is the same as that of example 1.
The specific embodiment of the preparation method of the diamide corrosion inhibitor is the same as that of example 1.
The specific implementation mode of the preparation method of the cleaning agent is the same as that of the example 1.
Example 11
The embodiment 11 of the invention provides a cleaning agent for 3003 aluminum material, which has the same specific implementation manner as the embodiment 3, and is characterized in that the weight ratio of the phytic acid to the diamide-type corrosion inhibitor is 1: 10.
the specific embodiment of the preparation method of the dimer sulfonate is the same as that of example 1.
The specific embodiment of the preparation method of the diamide corrosion inhibitor is the same as that of example 1.
The specific implementation mode of the preparation method of the cleaning agent is the same as that of the example 1.
Example 12
Example 12 of the present invention provides a cleaning agent for 3003 aluminum material, which is prepared in the same manner as example 3, except that the weight ratio of the acid, the surfactant and the corrosion inhibitor is 1: 2: 2.
the specific embodiment of the preparation method of the dimer sulfonate is the same as that of example 1.
The specific embodiment of the preparation method of the diamide corrosion inhibitor is the same as that of example 1.
The specific implementation mode of the preparation of the cleaning agent is the same as that of example 1.
Example 13
Embodiment 13 of the present invention provides a cleaning agent for 3003 aluminum material, which is the same as embodiment 3 in specific implementation manner, except that the acid is nitric acid or citric acid, and the weight ratio of nitric acid to citric acid is 1: 1.
the specific embodiment of the preparation method of the dimer sulfonate is the same as that of example 1.
The specific embodiment of the preparation method of the diamide corrosion inhibitor is the same as that of example 1.
The specific implementation mode of the preparation method of the cleaning agent is the same as that of the example 1.
Example 14
Example 14 of the present invention provides a cleaning agent for 3003 aluminum material, which is the same as example 3 except that the content of the surfactant is 0.
The specific embodiment of the preparation method of the diamide corrosion inhibitor is the same as that of example 1.
The specific implementation mode of the preparation method of the cleaning agent is the same as that of the example 1.
Example 15
Example 15 of the present invention provides a cleaning agent for 3003 aluminum material, which is the same as example 3 in the following specific embodiment, wherein the weight ratio of the acid, the surfactant and the corrosion inhibitor is 10: 1: 1.
the specific embodiment of the preparation method of the dimer sulfonate is the same as that of example 1.
The specific embodiment of the preparation method of the diamide corrosion inhibitor is the same as that of example 1.
The specific implementation mode of the preparation method of the cleaning agent is the same as that of the example 1.
Example 16
Example 16 of the present invention provides a cleaning agent for 3003 aluminum material, which is the same as example 3 except that the content of the defoaming agent is 0.
The specific embodiment of the preparation method of the dimer sulfonate is the same as that of example 1.
The specific embodiment of the preparation method of the diamide corrosion inhibitor is the same as that of example 1.
The specific implementation mode of the preparation method of the cleaning agent is the same as that of the example 1.
Example 17
Example 17 of the present invention provides a cleaning agent for 3003 aluminum material, which is prepared in the same manner as example 3, except that the silica is obtained from Shanghai Pongjing industries, Inc., CAS No: 60676-86-0, cat # BJ 021427.
The specific embodiment of the preparation method of the dimer sulfonate is the same as that of example 1.
The specific embodiment of the preparation method of the diamide corrosion inhibitor is the same as that of example 1.
The specific implementation mode of the preparation method of the cleaning agent is the same as that of the example 1.
Example 18
Example 18 of the present invention provides a cleaning agent for 3003 aluminum material, which is the same as example 3 in the following specific embodiment, except that the weight ratio of the defoaming agent to silica is 4: 1.
the specific embodiment of the preparation method of the dimer sulfonate is the same as that of example 1.
The specific embodiment of the preparation method of the diamide corrosion inhibitor is the same as that of example 1.
The specific implementation mode of the preparation method of the cleaning agent is the same as that of the example 1.
Example 19
Example 19 of the present invention provides a cleaning agent for 3003 aluminum material, which is the same as example 3 in the following specific embodiment, except that the weight ratio of the defoaming agent to silica is 1: 4.
the specific embodiment of the preparation method of the dimer sulfonate is the same as that of example 1.
The specific embodiment of the preparation method of the diamide corrosion inhibitor is the same as that of example 1.
The specific implementation mode of the preparation method of the cleaning agent is the same as that of the example 1.
Performance evaluation
1. And (3) testing the cleaning efficiency: the cleaning agent obtained in the embodiment 1-18 is subjected to a cleaning efficiency test according to HG/T2387-92, and the test conditions are as follows: 3003 soaking the aluminum material in the cleaning agent for 5 h. The cleaning rate B (%) was calculated by the following formula:
B＝(S0-S1)/S0×100％；
in the formula, S0Mm area covered by dirt before cleaning2，
S1Area covered by dirt after cleaning, mm2。
2. And (3) corrosion inhibition effect testing: the cleaning agent obtained in the embodiment 1-18 is heated to 50 +/-2 ℃, poured into a wide-mouth bottle, added with 3003 aluminum material, covered, placed at the constant temperature of 50 +/-2 ℃ for 10 hours, taken out of the 3003 aluminum material when the material is hot, cleaned by distilled water, dried and compared with the freshly polished and cleaned 3003 aluminum material, the appearance of the aluminum material is checked.
The evaluation of the corrosion inhibition effect is carried out according to the experimental method of the JB4322-86 water-based metal cleaner.
3. And (3) testing the cleaning effect: the metal on the filter membrane cleaned by the 3003 aluminum material is measured by using the cleaning agent obtained in the embodiment 1-18, and the area of the maximum metal on the filter membrane is calculated.
4. And (3) defoaming time test: 240mL of tap water was put into a 250mL measuring cylinder with a plug, 10mL of the cleaning agent obtained in examples 1 to 18 was added, and the mixture was gently shaken to prepare a 4 vol% diluted solution. The cylinder was shaken vigorously for 5 seconds, and then allowed to stand. The time at which the foam disappeared was recorded.
Table 1 results of performance testing
As can be seen from the test results in Table 1, the cleaning agent provided by the invention has excellent cleaning efficiency, corrosion inhibition effect, cleaning effect and defoaming effect.
The attached figure 1 of the specification is a schematic diagram of the metal with the largest area on the filter membrane after the aluminum material is cleaned in the embodiment 3, and the size is 219 micrometers 77 micrometers, the attached figure 2 of the specification is a schematic diagram of the metal with the largest area on the filter membrane after the aluminum material is cleaned in the embodiment 1, the size is 157 micrometers 104 micrometers, and the metal after cleaning is all larger, which shows that the cleaning effect is good.
The foregoing examples are merely illustrative and serve to explain some of the features of the method of the present invention. The appended claims are intended to claim as broad a scope as is contemplated, and the examples presented herein are merely illustrative of selected implementations in accordance with all possible combinations of examples. Accordingly, it is applicants' intention that the appended claims are not to be limited by the choice of examples illustrating features of the invention. Also, where numerical ranges are used in the claims, subranges therein are included, and variations in these ranges are also to be construed as possible being covered by the appended claims.
Claims (3)
1. The cleaning agent for the 3003 aluminum material is characterized by comprising, by weight, 0.5-4 parts of acid, 0.1-2 parts of surfactant, 0.1-2 parts of corrosion inhibitor, 0.1-1 part of defoaming agent, 0.1-1 part of silicon dioxide and 85-95 parts of water, wherein the surfactant comprises dimer sulfonate and fluorine surfactant; the raw material for preparing the dimer sulfonate comprises a polyol, wherein the polyol is any one of n-nonanol, n-decanol, n-undecanol and n-dodecanol; the acid is a mixture of nitric acid, hydroxyethylidene diphosphonic acid, citric acid and hydrofluoric acid; the weight ratio of the dimer sulfonate to the fluorine surfactant is (1-4): 1; the corrosion inhibitor comprises phytic acid and a diamide corrosion inhibitor, wherein the weight ratio of the phytic acid to the diamide corrosion inhibitor is (10-15): 1; the weight ratio of the acid to the surfactant to the corrosion inhibitor is (1-5): 1: 1; the weight ratio of the defoaming agent to the silicon dioxide is (1-2): 1.
2. the cleaning agent as claimed in claim 1, wherein the raw material for preparing the diamide corrosion inhibitor comprises long-chain fatty acid, and the long-chain fatty acid is pelargonic acid or capric acid.
3. The preparation method of the cleaning agent according to any one of claims 1 to 2, characterized by comprising at least the following steps:
(1) adding the corrosion inhibitor into water for dissolving;
(2) adding acid, silicon dioxide and surfactant, stirring and dissolving;
(3) adding the defoaming agent, stirring and dissolving.
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| CN113278979B (en) * | 2021-04-30 | 2023-04-11 | 厦门普诺尔新材料科技有限公司 | Magnetic grinding cleaning agent and preparation method thereof |
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