CN115874186B - Preparation method and application of water-based siloxane aluminum copper corrosion inhibitor - Google Patents
Preparation method and application of water-based siloxane aluminum copper corrosion inhibitor Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a water-based siloxane aluminum copper corrosion inhibitor. The sodium dihydrogen phosphate modified organic epoxy silane is used as a main film forming agent by taking water as a solvent, and is added as a stabilizer, and sodium silicate and an azole compound are used as auxiliary film forming agents for reinforcement. The water-based siloxane aluminum copper corrosion inhibitor provided by the invention has the corrosion inhibition property on aluminum materials in a water-based environment, has a very good corrosion inhibition function on metal copper, has the characteristics of good storage stability, low volatility and no smell, is a green water-based siloxane aluminum copper corrosion inhibitor, can meet the high corrosion inhibition processing requirements on aluminum materials and copper materials, is especially suitable for processing multiple metals such as aluminum materials and copper materials in the same equipment and other metal processing requirements, and can also be used for corrosion prevention on aluminum copper metals and ferrous metals in cleaning agents.
Description
Technical Field
The invention belongs to the field of chemical industry, and particularly relates to a preparation method and application of a water-based siloxane aluminum copper corrosion inhibitor.
Background
When the machine tool is used for processing aluminum and copper materials by using metal processing liquid, a large number of workpieces are unqualified due to oxidation corrosion, blackening and discoloration of the workpieces, and waste and loss are large. At present, most of aluminum corrosion inhibitors in the market are organic phosphorus ester aluminum corrosion inhibitors, and the aluminum corrosion inhibitors which are added into alkaline cutting fluid at the beginning have good effect, but the corrosion inhibition capability of the aluminum corrosion inhibitors is slowly deteriorated after a period of use. The preparation method and application of the water-based siloxane aluminum copper corrosion inhibitor solve the problem of oxidation corrosion during processing of aluminum and copper materials, and prolong the use corrosion inhibition capability of cutting fluid. The core technology utilizes the hydrolysis of organosilane in water to form a large number of silanol bonds (Si-OH), the silanol bonds with high activity are dehydrated with Metal-OH on the Metal surface to form a large number of Si-O-Metal bonds, and in addition, si-O-Si bonds can be formed by dehydration condensation between the silanol bonds and the silanol bonds. Thus, a network-like silane film structure is formed on the metal surface. And adding sodium silicate and an azole compound to carry out doping modification on the silane film, wherein the sodium silicate is an anode corrosion inhibitor, and is mainly used for inhibiting pitting corrosion of aluminum alloy by promoting passivation of the aluminum alloy or forming a conversion film on the surface of the aluminum alloy, so that the generation of crack sources is reduced, the pitting corrosion resistance and the corrosion fatigue life of the aluminum alloy are improved, the corrosion inhibition effect is achieved, and the azole compound can form a complex protective film of copper ions on the surface of copper, so that further corrosion of copper can be prevented. After the silane film is doped and modified by the sodium silicate and the azole compound, a compact protective film can be rapidly formed on the surfaces of gold materials such as aluminum, copper and the like.
The core principle of the water-based siloxane corrosion inhibitor technology is that water is used as a solvent, the acidic condition (pH is 3.5-5.0) of a sodium dihydrogen phosphate aqueous solution is utilized, after a stabilizer is added, the organic epoxy silane is not easy to polymerize in the water, and at the moment, after the sodium dihydrogen phosphate and the organic epoxy silane undergo an addition reaction, the defects of unstable and easy polymerization of organic silicon molecules in the aqueous solution are further overcome, and then sodium silicate and an azole compound are added to dope and modify a silane film, so that a compact protective film is rapidly formed on the surfaces of gold materials such as aluminum, copper and the like.
Similar reports are also reported, namely, the addition reaction of the organic epoxy silane and sodium bisulphite under the anhydrous condition utilizes methanol and ethanol as solvents, and finally the methanol and the ethanol are removed by reduced pressure distillation, so that the organic epoxy silane belongs to a third type of flammable liquid dangerous goods, has high transportation and storage requirements, has high requirements on large-scale industrial production, and is not beneficial to industrial safe production. The sodium dihydrogen phosphate used in the invention has the passivation protection effect on metal processing accessories and machine tools.
Disclosure of Invention
In order to avoid the defects existing in the prior art, the invention provides a preparation method and application of a water-based siloxane aluminum copper corrosion inhibitor.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention firstly discloses a preparation method of a water-based siloxane aluminum copper corrosion inhibitor, which comprises the following steps: the preparation method comprises the steps of taking water as a solvent, taking sodium dihydrogen phosphate modified organic epoxy silane as a main film forming agent, adding the organic epoxy silane as a stabilizing agent, taking sodium silicate and an azole compound as auxiliary film forming agents for reinforcement, firstly, completely dissolving the water, the stabilizing agent and the sodium dihydrogen phosphate, then slowly dropwise adding the organic epoxy silane, dropwise adding the organic epoxy silane for about 1 hour, and then slowly heating the mixture to 80-85 ℃ for reflux reaction for 3 hours to obtain a clear solution. And secondly, adding sodium silicate and an azole compound, and continuing stirring and reacting for 5 hours to obtain the water-based siloxane aluminum copper corrosion inhibitor.
Further, the preparation method according to the invention is characterized in that: the water is purified water; the stabilizer is one or more of methanol, ethanol, glycol, glycerol and butanediol; the organic epoxy silane is one or more than one of gamma-glycidol ether oxypropyl trimethoxysilane and gamma-glycidol ether oxypropyl triethoxysilane; the azole compound is one or more than one mixture of benzotriazole, methylbenzotriazole, 2-methyl-5-mercapto-1, 3, 4-thiadiazole and mercaptobenzothiazole; the chemical formula of the sodium silicate is Na 2 O·nSiO 2 N is silicon dioxide and Na 2 The ratio of the weight ratio of O can be one or a mixture of more than one of n=2.4, n=2. n =3.4.
According to the preparation method of the present invention, preferably, the water is purified water; the sodium dihydrogen phosphate is anhydrous sodium dihydrogen phosphate, and the organic epoxy silane is gamma-glycidol ether oxypropyl triethoxy silane; the stabilizer is glycerol; the sodium silicate has a chemical formula of r2o.nso2, n=2.4; the azole compound is benzotriazole; sodium dihydrogen phosphate and gamma-glycidol ether oxypropyl triethoxysilane in a molar ratio of 1.1:1.
the preparation method is characterized in that: 40-65 parts of water, 0.5-3 parts of stabilizer, 5-15 parts of sodium dihydrogen phosphate, 10-20 parts of organic epoxy silane, 15-20 parts of sodium silicate and 2-5 parts of azole compound.
A water-based silicone aluminum copper corrosion inhibitor obtainable by the method of any one of the preceding claims of the present invention.
The invention further discloses an aluminum copper corrosion inhibitor composition which is characterized by comprising the water-based siloxane aluminum copper corrosion inhibitor obtained by the preparation method according to any one of the above.
The invention further discloses application of the water-based siloxane aluminum copper corrosion inhibitor obtained by the preparation method. The water-based siloxane aluminum copper corrosion inhibitor provided by the invention is used for replacing an organic phosphate aluminum corrosion inhibitor, replacing an inorganic silicate aluminum corrosion inhibitor and replacing a water-insoluble benzotriazole copper corrosion inhibitor in cutting fluid, so that the problem of oxidation corrosion in the processing process of nonferrous metal materials aluminum and copper is solved, different materials can be processed in the same machine tool equipment, and one agent can be multifunctional.
Compared with the prior art, the invention has the beneficial effects that:
1. the water-based siloxane aluminum copper corrosion inhibitor prepared by the preparation method and application thereof have the characteristics of excellent aluminum copper corrosion inhibition property, excellent high-temperature stability, low volatility, no smell, difficult putrefaction and stink and the like, is environment-friendly, can meet the high aluminum copper material corrosion inhibition requirement, and is particularly suitable for application in the cutting fluid industry.
2. The preparation method and application of the water-based siloxane aluminum copper corrosion inhibitor can be widely used as aluminum copper corrosion inhibitors in cast iron, aluminum copper processing, stainless steel processing and other metal processing liquids and cleaning agents.
Drawings
FIG. 1 is a schematic illustration of corrosion inhibition of an aluminum material;
fig. 2 is a schematic representation of corrosion inhibition of copper.
Detailed Description
The following describes in detail the examples of the present invention, which are implemented on the premise of the technical solution of the present invention, and detailed embodiments and specific operation procedures are given, but the scope of protection of the present invention is not limited to the following examples.
Example 1
52g of purified water, 9.5g of sodium dihydrogen phosphate and 1.5g of methanol are weighed into a 250ml flat-bottomed flaskIn the process, the mixture is completely dissolved by a magnetic stirrer, 17g of gamma-glycidol ether oxypropyl trimethoxy silane is slowly added dropwise, the mixture is completely added dropwise in about 1 hour, and then the mixture is slowly heated to 83 ℃ for reflux reaction for 3 hours, so that a clear solution is obtained. Adding sodium silicate with chemical formula of Na 2 O·nSiO 2 16g of sodium silicate with n=2.8 and 4g of benzotriazole are stirred and reacted for 5 hours. The final product 1 is obtained.
Example 2
49g of purified water, 9.5g of sodium dihydrogen phosphate and 1.5g of methanol are weighed into a 250ml flat-bottomed flask, the mixture is completely dissolved by a magnetic stirrer, 20g of gamma-glycidol ether oxypropyl triethoxysilane is slowly added dropwise after about 1 hour, and then the mixture is slowly heated to 83 ℃ for reflux reaction for 3 hours, so that a clear solution is obtained. Adding sodium silicate with chemical formula of Na 2 O·nSiO 2 16g of sodium silicate with n=2.8 and 4g of benzotriazole are stirred and reacted for 5 hours. The final product 2 is obtained.
Example 3
52g of purified water, 9.5g of sodium dihydrogen phosphate and 1.5g of ethanol are weighed into a 250ml flat-bottomed flask, the mixture is completely dissolved by a magnetic stirrer, 17g of gamma-glycidol ether oxypropyl trimethoxysilane is slowly added dropwise after about 1 hour, and then the mixture is slowly heated to 83 ℃ for reflux reaction for 3 hours to obtain a clear solution. Adding sodium silicate with chemical formula of Na 2 O·nSiO 2 16g of sodium silicate with n=2.8 and 4g of benzotriazole are stirred and reacted for 5 hours. The final product 3 is obtained.
Example 4
49g of purified water, 9.5g of sodium dihydrogen phosphate and 1.5g of ethanol are weighed into a 250ml flat-bottomed flask, the mixture is completely dissolved by a magnetic stirrer, 20g of gamma-glycidol ether oxypropyl triethoxysilane is slowly added dropwise after about 1 hour, and then the mixture is slowly heated to 83 ℃ for reflux reaction for 3 hours, so that a clear solution is obtained. Adding sodium silicate with chemical formula of Na 2 O·nSiO 2 16g of sodium silicate with n=2.8 and 4g of benzotriazole are stirred and reacted for 5 hours. The final product 4 is obtained.
Example 5
52g of purified water and sodium dihydrogen phosphate are weighed9.5g of ethylene glycol 1.5g is added into a 250ml flat-bottomed flask, the mixture is completely dissolved by a magnetic stirrer, 17g of gamma-glycidol ether oxypropyl trimethoxy silane is slowly added dropwise, the dropwise addition is completed for about 1 hour, and then the mixture is slowly heated to 83 ℃ for reflux reaction for 3 hours, so that a clear solution is obtained. Adding sodium silicate with chemical formula of Na 2 O·nSiO 2 16g of sodium silicate with n=3.0 and 4g of benzotriazole are stirred and reacted for 5 hours. The final product 5 is obtained.
Example 6
49g of purified water, 9.5g of sodium dihydrogen phosphate and 1.5g of ethylene glycol are weighed into a 250ml flat-bottomed flask, the mixture is completely dissolved by a magnetic stirrer, 20g of gamma-glycidol ether oxypropyl triethoxysilane is slowly added dropwise after about 1 hour, and then the mixture is slowly heated to 83 ℃ for reflux reaction for 3 hours, so that a clear solution is obtained. Adding sodium silicate with chemical formula of Na 2 O·nSiO 2 16g of sodium silicate with n=2.8 and 4g of benzotriazole are stirred and reacted for 5 hours. The final product 6 is obtained.
Example 7
52g of purified water, 9.5g of sodium dihydrogen phosphate and 1.5g of glycerol are weighed into a 250ml flat-bottomed flask, the mixture is completely dissolved by a magnetic stirrer, 17g of gamma-glycidol ether oxypropyl trimethoxysilane is slowly added dropwise after about 1 hour, and then the mixture is slowly heated to 83 ℃ for reflux reaction for 3 hours to obtain a clear solution. Adding sodium silicate with chemical formula of Na 2 O·nSiO 2 16g of sodium silicate with n=2.8 and 4g of benzotriazole are stirred and reacted for 5 hours. The final product 7 is obtained.
Example 8
49g of purified water, 9.5g of sodium dihydrogen phosphate and 1.5g of glycerol are weighed into a 250ml flat-bottomed flask, the mixture is completely dissolved by a magnetic stirrer, 20g of gamma-glycidol ether oxypropyl triethoxysilane is slowly added dropwise after about 1 hour, and then the mixture is slowly heated to 83 ℃ for reflux reaction for 3 hours, so that a clear solution is obtained. Adding sodium silicate with chemical formula of Na 2 O·nSiO 2 16g of sodium silicate with n=2.8 and 4g of benzotriazole are stirred and reacted for 5 hours. The final product 8 is obtained.
Comparative example 1
49g of purified water, 8.2g of sodium bisulphite and 1.5g of glycerol are weighed into a 250ml flat-bottomed flask, the mixture is completely dissolved by a magnetic stirrer, 20g of gamma-glycidol ether oxypropyl triethoxysilane is slowly added dropwise after about 1 hour, and then the mixture is slowly heated to 83 ℃ for reflux reaction for 3 hours, so that a clear solution is obtained. Adding sodium silicate with chemical formula of Na 2 O·nSiO 2 16g of sodium silicate with n=2.8 and 4g of benzotriazole are stirred and reacted for 5 hours. Obtaining the final product A.
Application example 1 cutting fluid stability test
Table 1:
note that: amide emulsifier NEUF183-2, rust inhibitor NEUF727-2, rust inhibitor NEUF316-2 from North Biotechnology (joint fertilizer) Co., ltd; triethanolamine is from the dow chemical; oleic acid is derived from Feng Yi plant oleic acid in Yihaijia 55; the bactericide BK is from the company of Hefei green ester metal protection materials; isononanoic acid is from the company of the chemical industry, ltd, tokyo.
From the test data in table 1, the organoepoxysilane gamma-glycidol ether oxypropyl triethoxysilane has longer stability time than gamma-glycidol ether oxypropyl trimethoxysilane in an alkaline water system, the polymerization time is prolonged, and the stabilizer glycerol is clarified to be the most stable time of 210 days after becoming turbid. Therefore, gamma-glycidol ether oxypropyl triethoxysilane is preferable under the same conditions as glycerol. The aqueous solution of sodium bisulphite has unpleasant smell of sulfur dioxide, affects human health and severely corrodes equipment, and has a large amount of sulfite ions and serious corrosiveness.
Example 9
49g of purified water, 9.5g of sodium dihydrogen phosphate and 1.5g of glycerol are weighed into a 250ml flat-bottomed flask, the mixture is completely dissolved by a magnetic stirrer, 20g of gamma-glycidol ether oxypropyl triethoxysilane is slowly added dropwise after about 1 hour, and then the mixture is slowly heated to 83 ℃ and returnedFlow reaction for 3 hours to give a clear solution. Adding sodium silicate with chemical formula of Na 2 O·nSiO 2 16g of sodium silicate with n=2.4 g of benzotriazole are reacted for 5 hours with stirring. The final product 9 is obtained.
Example 10
49g of purified water, 9.5g of sodium dihydrogen phosphate and 1.5g of glycerol are weighed into a 250ml flat-bottomed flask, the mixture is completely dissolved by a magnetic stirrer, 20g of gamma-glycidol ether oxypropyl triethoxysilane is slowly added dropwise after about 1 hour, and then the mixture is slowly heated to 83 ℃ for reflux reaction for 3 hours, so that a clear solution is obtained. Adding sodium silicate with chemical formula of Na 2 O·nSiO 2 16g of sodium silicate with n=3.4 g of benzotriazole are reacted for 5 hours with stirring. The final product 10 is obtained.
Application example 2 aluminium, copper corrosiveness test
In the cutting fluid, the water-based siloxane aluminum copper corrosion inhibitor can improve the service performance of the cutting fluid. The preparation method and application of the water-based siloxane aluminum copper corrosion inhibitor obtained in the example are taken as examples below to verify the effect of the water-based siloxane aluminum copper corrosion inhibitor in cutting fluid.
Aluminium corrosiveness test
● Main experimental instrument
Constant temperature drying cabinet, beaker and glass cover dish
● Experimental method
Immersing the prepared aluminum sheet in the test liquid (usually 5% diluent of cutting liquid), covering with glass cover, transferring to a drying oven with constant temperature of 55deg.C+ -2deg.C, continuously testing for 8 hr, taking out test piece, and checking (standard GB/T6144-2010)
B. Copper corrosiveness test
● Main experimental instrument
Constant temperature drying cabinet, beaker and glass cover dish
● Experimental method
Immersing the prepared copper sheet in the test sample, displacing the copper sheet in a drying oven with a certain temperature according to the type of the test sample product, continuously testing for a certain time, and taking out the test piece for inspection (the execution standard is GB/T5096-2017)
● The corrosion results are as follows
Copper corrosion test (80 ℃ C., 8 h)
C. Rust inhibitive performance test
The physical and chemical indexes and the rust resistance test of cast iron filings are carried out by the following method: putting filter paper into a culture dish, weighing 2 g+/-0.1 g of GG25 cast iron filings, dispersing on the filter paper, transferring 2mL of liquid to be tested, wetting all the iron filings, covering the culture dish, standing at room temperature (18-28 ℃) for 2 hours, removing the cast iron filings, flushing with tap water, immersing the filter paper in acetone solution for 5s, and naturally drying at room temperature (18-28 ℃). The rust point state on the filter paper was observed, and the rust grade was determined. (execution standard is JBT 9189-2016 Water-based material rust prevention test method cast iron filings test)
Table 2:
the grade of the national standard aluminum corrosion test result of the 5% tap water solution of the stock solution of the cutting fluid is grade D, the grade of the national standard aluminum corrosion test result of the 5% tap water solution is grade A after 2% of the water-based siloxane aluminum copper corrosion inhibitor products of the products A, rhodafac ASI80, sodium silicate and the examples 8-9-10 are added, and the grade of the national standard aluminum corrosion test result of the 5% tap water solution is grade D after 2% of the benzotriazole product is added, because benzotriazole has no aluminum corrosion inhibition performance. After 90 days, the national standard aluminum corrosion test result of the 5% tap water solution is measured, the corrosion inhibition performance of the aluminum product corrosion inhibitor Rhodafac ASI80 is obviously reduced, the aluminum product corrosion inhibitor Rhodafac ASI80 is organic phosphate, the corrosion inhibition performance of the aluminum product is slowly lost after the aluminum product is decomposed in an alkaline system, flocculent precipitate appears when sodium silicate is added into the system, and the corrosion inhibition performance of the aluminum product is lost. The product A still has the corrosion inhibition performance of aluminum materials, but the product A has a large amount of sulfite ions and serious corrosiveness, and the grade of the rust resistance test result of the 3% tap water solution is reduced to 1/2 grade.
Similarly, the copper sheet corrosion test results of 5% tap water solution added with benzotriazole with copper corrosion inhibition performance and the products of examples 8-9-10 are all 1a grade, and the copper sheet corrosion test results of 5% tap water solution added with corrosion inhibitor without copper corrosion inhibition performance are all 3b grade.
Therefore, after the water-based siloxane aluminum copper corrosion inhibitor is added into the common microemulsion cutting fluid, ferrous metals such as cast iron, carbon steel, alloy steel and the like can be processed, and nonferrous metals such as aluminum materials, copper materials and the like can also be processed.
Claims (7)
1. The preparation method of the water-based siloxane aluminum copper corrosion inhibitor is characterized by comprising the following steps of:
the preparation method comprises the steps of taking water as a solvent, taking sodium dihydrogen phosphate modified organic epoxy silane as a main film forming agent, adding the organic epoxy silane as a stabilizing agent, taking sodium silicate and an azole compound as auxiliary film forming agents for reinforcement, firstly, completely dissolving the water, the stabilizing agent and the sodium dihydrogen phosphate, then slowly dropwise adding the organic epoxy silane, after 1 hour of dropwise adding, then slowly heating to 80-85 ℃ for reflux reaction for 3 hours, and obtaining a clear solution. Adding sodium silicate and an azole compound, and continuing stirring and reacting for 5 hours to obtain the water-based siloxane aluminum copper corrosion inhibitor;
wherein, the water is 40-65 parts, the stabilizer is 0.5-3 parts, the sodium dihydrogen phosphate is 5-15 parts, the organic epoxy silane is 10-20 parts, the sodium silicate is 15-20 parts, and the azole compound is 2-5 parts.
2. The method of claim 1, wherein the water is purified water; the stabilizer is one or more of methanol, ethanol, glycol, glycerol and butanediol; the organic epoxy silane is one or more than one of gamma-glycidol ether oxypropyl trimethoxysilane and gamma-glycidol ether oxypropyl triethoxysilane; the azole compound is one or more than one mixture of benzotriazole, methylbenzotriazole, 2-methyl-5-mercapto-1, 3, 4-thiadiazole and mercaptobenzothiazole; the chemical formula of the sodium silicate is Na 2 O·nSiO 2 N is silicon dioxide and Na 2 The ratio of the weight ratio of O can be one or a mixture of more than one of n=2.4, n=2. n =3.4.
3. The method of claim 2, wherein the water is purified water; the sodium dihydrogen phosphate is anhydrous sodium dihydrogen phosphate, and the organic epoxy silane is gamma-glycidol ether oxypropyl triethoxy silane; the stabilizer is glycerol; the sodium silicate has a chemical formula of Na 2 O·nsio2, n=2.4; the azole compound is benzotriazole; sodium dihydrogen phosphate and gamma-glycidol ether oxypropyl triethoxysilane in a molar ratio of 1.1:1.
4. a water-based silicone aluminum copper corrosion inhibitor obtained by the process of any one of claims 1-3.
5. An aluminum copper corrosion inhibitor composition, characterized in that it contains a water-based silicone aluminum copper corrosion inhibitor obtained by the preparation method according to any one of claims 1 to 3.
6. Use of a water-based silicone aluminum copper corrosion inhibitor obtained by the method according to any one of claims 1-3 or an aluminum copper corrosion inhibitor composition according to claim 5, in cutting fluids for corrosion inhibition of aluminum and copper materials.
7. The method according to claim 6, wherein the cutting fluid is used for replacing organic phosphate aluminum corrosion inhibitors, inorganic silicate aluminum corrosion inhibitors or water-insoluble benzotriazole copper corrosion inhibitors in the cutting fluid for corrosion inhibition of aluminum materials and copper materials.
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| US6228283B1 (en) * | 1998-05-22 | 2001-05-08 | Ashland Inc. | Aqueous corrosion inhibitor |
| CN1565993A (en) * | 2003-06-25 | 2005-01-19 | 中国人民解放军海军工程大学 | Long acting phosphorusless corrosion inhibitor for recirculating cooling water |
| JP5744654B2 (en) * | 2011-07-15 | 2015-07-08 | 日本パーカライジング株式会社 | Metal surface treatment agent and metal material treated with the treatment agent |
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| CN105086720A (en) * | 2015-07-11 | 2015-11-25 | 合肥正浩机械科技有限公司 | Anticorrosive metal surface treating agent and preparation method thereof |
| EP3484976B1 (en) * | 2016-07-12 | 2024-05-29 | Prestone Products Corporation | Heat transfer fluids and methods for preventing corrosion in heat transfer systems |
| CN106756923A (en) * | 2016-12-15 | 2017-05-31 | 天长市润达金属防锈助剂有限公司 | A kind of water base brass antioxidant of uvioresistant for adding BTA and preparation method thereof |
| CN106756964A (en) * | 2016-12-15 | 2017-05-31 | 天长市润达金属防锈助剂有限公司 | It is a kind of to add good water base brass antioxidant of benzimidazole solderability and preparation method thereof |
| CN109468620A (en) * | 2018-11-09 | 2019-03-15 | 苏州铂韬新材料科技有限公司 | A kind of process of flaky metallic material surface silanization processing |
| CN110219005B (en) * | 2019-07-09 | 2020-11-06 | 北京航空航天大学 | Copper-based material corrosion inhibition liquid, preparation method thereof and corrosion inhibition method |
| CN114231289A (en) * | 2021-12-23 | 2022-03-25 | Tcl华星光电技术有限公司 | Thin film etching solution, etching method and application thereof |
| CN115161643B (en) * | 2022-06-28 | 2023-09-05 | 哈尔滨工业大学(深圳)(哈尔滨工业大学深圳科技创新研究院) | Nanometer silicon corrosion inhibitor containing benzotriazole and preparation method thereof |
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