Preparation method of water-based succinic anhydride derivative anti-corrosion lubricant
The preparation of water-based succinic anhydride derivative anti-corrosion lubricant has solved the problems of environmental pollution and performance instability of aluminum alloy additives, and achieved high-efficiency anti-corrosion and lubrication of aluminum alloys, which is suitable for metal processing under various working conditions.
Patent Information
- Application Number
- CN202511479516.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-10-16
- Publication Date
- 2026-01-13
AI Technical Summary
In existing aluminum alloy corrosion-resistant additives, the use of phosphorus and silicon leads to environmental pollution and unstable performance, making it difficult to meet environmental regulations and process requirements. In particular, their corrosion resistance is insufficient in high-salt and humid environments, affecting coating adhesion and welding performance.
A method for preparing a water-based succinic anhydride derivative anti-corrosion lubricant is adopted, which involves reacting saturated alkyl succinic anhydride with mercapto polyethylene glycol monomethyl ether to form a compound with excellent anti-corrosion and lubrication properties, which can be used for surface treatment of aluminum and aluminum alloys.
It provides environmentally friendly and stable corrosion protection and lubrication, reduces processing costs, improves the surface roughness of aluminum alloys and tool life, meets environmental regulations, and is suitable for metal processing under various working conditions.
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Abstract
Description
TECHNICAL FIELD
[0001] The present invention relates to the field of corrosion protection lubricants, in particular to a method for the production of a water-based succinic anhydride derivative corrosion protection lubricant and its use in protecting aluminum and / or aluminum alloys from corrosion and in providing lubrication during metal processing. BACKGROUND
[0002] The search for corrosion protection additives for aluminum and / or aluminum alloys has always been an important topic in the field of materials science and engineering, especially in the context of increasingly stringent environmental regulations and the diversification of industrial needs, the development of additives without phosphorus and silicon has significant scientific and application value.
[0003] Firstly, the driving force of environmental and health regulations. Traditional corrosion protection additives (such as phosphates, silicates) may cause water eutrophication (phosphorus) or soil pollution (silicon compounds) after production and disposal, the EU REACH Regulation, the US Clean Water Act, etc. limit the use of harmful substances; phosphorus / silicon-containing wastewater needs additional treatment to meet the discharge standard, increasing the cost of enterprises. Phosphorus-free and silicon-free formulations are easier to pass environmental certification (such as the EU Ecolabel).
[0004] Secondly, the special needs of aluminum alloy application fields. In the fields of aerospace and transportation, aluminum alloys need to maintain corrosion resistance in harsh environments (such as high salt, heat and humidity), but phosphorus / silicon may affect the adhesion of subsequent coatings or welding performance; in the miniaturization of electronic devices, the insulating property of silicon may interfere with the conductivity of electronic components, and silicon-free additives are more suitable for precision parts (such as mobile phone cases, heat sinks).
[0005] Secondly, the optimization needs of technical performance. The limitations of phosphorus / silicon: phosphorus-based additives may form hydrogen gas in acidic environments, leading to hydrogen embrittlement of aluminum alloys; silicates are prone to gel formation, poor stability, affecting process consistency.
[0006] Finally, the market and industry chain drive. Apple, Tesla and other companies require suppliers to use environmentally friendly materials, forcing upstream to develop phosphorus-free and silicon-free solutions.
[0007] Some maleic anhydride-derived mixtures and amino acid derivatives have certain corrosion protection properties and hard water stability, but are still less efficient. Therefore, further improvements are needed.
[0008] It is an object of the present invention to provide corrosion protection additives for manufacturing processes which are free of phosphorus and silicon, which are simple and inexpensive to prepare and at least as effective as the phosphorus- and silicon-containing additives to be replaced. In addition, the corrosion protection additives should be storage-stable, have good lubricity. SUMMARY
[0009] To address the problems existing in the prior art, this invention provides a method for preparing a water-based succinic anhydride derivative anti-corrosion lubricant and its application in protecting aluminum and / or aluminum alloys from corrosion and in providing lubrication during metal processing.
[0010] This invention selects saturated alkyl succinic anhydride and mercapto polyethylene glycol monomethyl ether as raw materials in molecular design. The invention adjusts the properties of the final succinate ester from the molecular structure based on at least one saturated alkyl succinic anhydride and at least one mercapto polyethylene glycol monomethyl ether raw material. The resulting water-based succinic anhydride derivative anti-corrosion lubricant has excellent anti-corrosion and lubrication properties for aluminum and / or aluminum alloys, and is an excellent water-based fluid anti-corrosion additive.
[0011] To achieve the above objectives, the present invention provides a method for preparing a water-based succinic anhydride derivative anti-corrosion lubricant, comprising the following steps: Under inert gas protection and a slightly positive pressure of 500–2000 Pa, at 60–120 °C, and without solvent, at least one saturated alkyl succinic anhydride is esterified with at least one mercapto-polyethylene glycol monomethyl ether at a molar ratio of 1:(0.8–1.5). The reaction endpoint is reached when the acid value of the reactants no longer changes, yielding a succinate compound. The saturated alkyl succinic anhydride is selected from one or more of linear or branched octyl succinic anhydride, nonyl succinic anhydride, decyl succinic anhydride, dodecyl succinic anhydride, tetradecyl succinic anhydride, hexadecyl succinic anhydride, or octadecyl succinic anhydride. The mercapto-polyethylene glycol monomethyl ether has the structural formula: CH3(OCH2CH2). n SH, where n is an integer from 2 to 20.
[0012] Preferably, the inert gas is argon or nitrogen.
[0013] Preferably, the reaction raw materials are added in any of the following ways: First, add saturated alkyl succinic anhydride, then add mercapto polyethylene glycol monomethyl ether, and then maintain the reaction system at 80°C until the acid value of the reactants no longer changes; First, add mercapto polyethylene glycol monomethyl ether, then add saturated alkyl succinic anhydride, and then maintain the reaction system at 80°C until the acid value of the reactants no longer changes; Saturated alkyl succinic anhydride and mercapto polyethylene glycol monomethyl ether were added to the reaction system simultaneously for esterification.
[0014] Preferably, the mercapto polyethylene glycol monomethyl ether is selected from one or more of mercaptodiethylene glycol methyl ether, mercaptotriethylene glycol methyl ether, mercaptotetraethylene glycol methyl ether, mercaptopentethylene glycol methyl ether, mercaptohexaethylene glycol methyl ether, mercaptoheptaethylene glycol methyl ether, mercaptooctaethylene glycol methyl ether, mercaptononethylene glycol methyl ether, mercaptodeethylene glycol methyl ether, mercaptododecylethylene glycol methyl ether, mercaptotridecylethylene glycol methyl ether, mercaptotetradecylethylene glycol methyl ether, mercaptodedecylethylene glycol methyl ether, mercaptohexadecylethylene glycol methyl ether, mercaptoheptaethylene glycol methyl ether, mercaptooctadecylethylene glycol methyl ether, mercaptononadecanylethylene glycol methyl ether, and mercaptoeicosylethylene glycol methyl ether.
[0015] The present invention also provides the application of a water-based succinic anhydride derivative anti-corrosion lubricant in protecting aluminum and / or aluminum alloys from corrosion.
[0016] Preferably, the aluminum alloy includes cast aluminum alloy and forged aluminum alloy.
[0017] Preferably, the water-based succinic anhydride derivative anti-corrosion lubricant is applied to the surface of aluminum and / or aluminum alloy by means of pouring, impregnation or spraying.
[0018] This invention also provides an application of a water-based succinic anhydride derivative anti-corrosion lubricant in providing lubrication during metal processing. Preferably, the metal processing includes metal cutting, grinding, and forming; the metal includes ferrous metals and non-ferrous metals.
[0019] Preferably, the water-based succinic anhydride derivative anti-corrosion lubricant is applied to the processing area by pouring, impregnation, or spraying.
[0020] The technical solution of this invention has the following beneficial effects: This invention utilizes the reaction product of at least one saturated alkyl succinic anhydride and mercapto polyethylene glycol monomethyl ether. The prepared product can be used as a water-based anti-corrosion lubricant in the manufacturing process of aluminum and / or aluminum alloys. It not only provides excellent aluminum corrosion inhibition and lubrication but also meets environmental protection requirements. This water-based succinic anhydride derivative anti-corrosion lubricant is free of silicates and phosphorus, overcoming the problems of silicate-based corrosion inhibitors causing scratches on machined surfaces and insufficient durability, as well as the environmental problems of phosphate-based corrosion inhibitors. This water-based succinic anhydride derivative anti-corrosion lubricant not only possesses excellent anti-corrosion properties for aluminum and / or aluminum alloys but is also suitable for long-lasting anti-biological formulations. It is safe, environmentally friendly, and easy to dispose of as waste. Furthermore, it provides lubrication, reducing the amount of lubricating additives needed and saving costs.
[0021] The preparation process of this invention is solvent-free, the product is free of phosphorus and silicon, has low volatile organic compound emissions, and requires minimal post-treatment, which is in line with environmental regulations. The preparation conditions are mild and controllable: the reaction is carried out at 60-120°C under an inert atmosphere and a slight positive pressure, with the endpoint being when the acid value no longer changes. There are few side reactions, the color is light, the batch stability is good, and it is easy to scale up industrially.
[0022] The reaction product of this invention has an amphiphilic structure consisting of an alkyl succinic acid group, a PEG ether chain, and a sulfur bond. The long alkyl chain provides boundary lubrication and film-forming ability, reducing interfacial shear. The hydrophilic PEG chain enhances affinity for the aqueous phase and spreading on the metal surface. The sulfur-containing groups and carboxylic acid / ester groups adsorb and coordinate with the metal / oxide film, enhancing the density of the corrosion-inhibiting film. Therefore, a stable adsorption / lubricating film can be formed in the aqueous phase, achieving integrated corrosion prevention and lubrication.
[0023] The lubricant of this invention is suitable for various working conditions such as cutting, grinding, and forming. In working conditions where boundary lubrication is dominant, such as tapping, drilling, reaming, and extrusion forming of aluminum alloys, it can reduce cutting force / torque and wear, improve surface roughness, and extend tool life. Detailed Implementation
[0024] The present invention will be further described below with reference to specific embodiments.
[0025] Example 1 In a 2000 mL four-necked flask equipped with a thermometer, electric stirrer, gas delivery tube, and condenser, 424.6 g (2 mol) of octyl succinic anhydride and 299.7 g (2.2 mol) of mercaptodiethylene glycol glycidyl ether were added. High-purity argon gas was introduced to maintain a slight positive pressure of 1050 Pa throughout the system. The stirring was started, and the temperature was raised to 80 °C to initiate the reaction. After maintaining the reaction temperature for 2–4 hours, the acid value no longer changed, and the reaction was terminated. The product was discharged, thus obtaining the target succinic anhydride derivative compound.
[0026] Example 2 In a 2000mL four-necked flask equipped with a thermometer, electric stirrer, gas delivery tube, and condenser, 424.6g (2mol) of octyl succinic anhydride and 656g (2.1mol) of mercaptohexaethylene glycol glycidyl ether were added. High-purity argon gas was introduced to maintain a slight positive pressure of 1050Pa throughout the system. The stirring was started and the temperature was raised to 80℃ to initiate the reaction. After maintaining the reaction temperature for 2-4 hours, the acid value essentially stopped decreasing, and the reaction was terminated. The product was discharged, thus obtaining the target succinic anhydride derivative compound.
[0027] Example 3 In a 2000mL four-necked flask equipped with a thermometer, electric stirrer, gas delivery tube, and condenser, 536.8g (2mol) of isomeric dodecyl succinic anhydride, 586g (1.2mol) of mercaptodecaethylene glycol glycidyl ether, and 312g (1mol) of mercaptohexaethylene glycol glycidyl ether were added. High-purity argon gas was introduced to maintain a slight positive pressure of 1050Pa throughout the system. The stirring was started, and the temperature was raised to 80℃ to initiate the reaction. After maintaining the reaction temperature for 2-4 hours, the acid value essentially stopped decreasing, and the reaction was terminated. The product was discharged, thus obtaining the target succinic anhydride derivative compound.
[0028] Example 4 In a 2000mL four-necked flask equipped with a thermometer, electric stirrer, gas delivery tube, and condenser, 212.3g (1mol) of octyl succinic anhydride, 268.4g (1mol) of isomeric dodecyl succinic anhydride, and 625g (2mol) of mercaptohexaethylene glycol glycidyl ether were added. High-purity argon gas was introduced to maintain a slight positive pressure of 1050Pa throughout the system. The stirring was started, and the temperature was raised to 80℃ to initiate the reaction. After maintaining the reaction temperature for 2-4 hours, the acid value essentially stopped decreasing, and the reaction was terminated. The product was discharged, thus obtaining the target succinic anhydride derivative compound.
[0029] Example 5 In a 2000 mL four-necked flask equipped with a thermometer, electric stirrer, gas delivery tube, and condenser, 212.3 g (1 mol) of octyl succinic anhydride, 268.4 g (1 mol) of isomeric dodecyl succinic anhydride, 224 g (1 mol) of mercaptotetraethylene glycol glycidyl ether, and 401 g (1 mol) of mercaptooctaethylene glycol glycidyl ether were added. High-purity argon gas was introduced to maintain a slight positive pressure of 1050 Pa throughout the system. The stirring was started, and the temperature was raised to 80 °C to initiate the reaction. After maintaining the reaction temperature for 2–4 hours, the acid value essentially stopped decreasing, and the reaction was terminated. The product was discharged, thus obtaining the target succinic anhydride derivative compound.
[0030] The experiments used, and a brief description of each experiment, are as follows: I. In order to evaluate the anti-corrosion performance of the succinic anhydride derivative compound obtained in the embodiments of the present invention, it was added to a fully synthetic cutting fluid for evaluation. The formulation ratio of the cutting fluid is shown in Table 1.
[0031] Table 1 Cutting Fluid Formulation Table
[0032] Note: Silicon-containing corrosion inhibitors 1022C: siloxane ketones, such as those from Chimba Chemical Materials Co., Ltd.; 1008: isomeric tridecyl phosphate, such as those from Chimba Chemical Materials Co., Ltd.; DEA: diethanolamine, available from Dow Chemical Co., Ltd.; TEA: triethanolamine, available from Dow Chemical Co., Ltd.; neodecanoic acid: 2-ethyl-2,5-dimethylhexanoic acid, available from Shanghai Yingtai Trading Co., Ltd.; 3089: tricarboxylic acid amine type rust inhibitor, such as those from Chimba Chemical Materials Co., Ltd.; RPE-1740: trans-block polyether, available from BASF.
[0033] The aluminum corrosion test method in the following experiment was conducted according to the "Synthetic Cutting Fluids" (GB / T6144-2010): The aluminum test piece was sanded to a new surface using sandpaper, and a 5% working solution was prepared. The sanded LY12 aluminum test piece was cleaned with alcohol and air-dried, then placed in the prepared working solution in a semi-immersion state. It was then placed in an oven at a set temperature of 55℃ for 3 hours. After 3 hours, the aluminum test piece was removed from the oven, and the observed phenomena were recorded and evaluated. A grade of A is defined as follows: both the immersed and unimmersioned surfaces are bright and new; grade B is defined as slightly darkened; grade C is defined as moderately darkened; and grade D is defined as severely darkened.
[0034] The test results are shown in Table 2. The results show that after the aluminum corrosion inhibitors in Examples 1-5 are well-matched with other additives in the cutting fluid formulation, they have a good aluminum corrosion inhibitor effect, and their corrosion inhibition effect is comparable to that of silicon-containing and phosphate ester-type corrosion inhibitors.
[0035] Table 2. Results of aluminum corrosion resistance tests for the examples and comparative examples.
[0036] II. The lubricating properties of the succinic anhydride derivative compounds obtained in the embodiments of the present invention were evaluated by adding them to a fully synthetic cutting fluid. Conventional lubricants RPE-1740 and RPE-1740 were used as references. The formulation ratios of the cutting fluid are shown in Table 3. The cutting fluid was prepared as a 10% working fluid, and P was tested. B And the average torque value for tapping.
[0037] Table 3 Cutting Fluid Formulation Table
[0038] Note: TEA: Triethanolamine, available from Dow Chemical Company; RPE-1720 and RPE-1740: Trans-block polyethers, available from BASF.
[0039] P B Value determination: The P value of the sample was evaluated using an MRS-10A four-ball friction tester, in accordance with SH / T0762-2005 (four-ball method).B The test used 12.7mm diameter steel balls specifically designed for four-ball testing machines, with a hardness of HRC64-66. The test conditions were 1450 rpm for 10 seconds.
[0040] Average tapping torque value determination: The value was measured using a Microtap tapping torque tester (Germany). Test conditions: M4 tap, 1500 rpm, 20mm hole depth, and 7075 aluminum alloy hole. (Note: A lower average tapping torque value is better.) As can be seen from Table 4, P in Examples 1-5 B The values are significantly higher than those of conventional lubricants RPE-1720 and RPE-1740, and the average tapping torque values of Examples 1 to 5 are also lower than those of conventional lubricants RPE-1720 and RPE-1740, indicating that the water-based succinic anhydride derivative anti-corrosion lubricant prepared in this invention has excellent lubricity.
[0041] Table 4. Experimental results of lubrication performance of several cutting fluids
[0042] In summary, this invention is based on the reaction of saturated alkyl succinic anhydride with mercapto polyethylene glycol monomethyl ether in molecular design. The invention adjusts the properties of the final succinate ester from a molecular structure perspective, using at least one saturated alkyl succinic anhydride and at least one mercapto polyethylene glycol monomethyl ether raw material. The resulting water-based succinic anhydride derivative anti-corrosion lubricant exhibits excellent anti-corrosion and lubrication properties for aluminum and / or aluminum alloys, making it an excellent water-based fluid anti-corrosion lubricant additive.
[0043] The above description is merely a preferred embodiment of the present invention and does not limit the patent scope of the present invention. Any equivalent structural transformations made using the contents of the present invention under the inventive concept of the present invention, or direct / indirect applications in other related technical fields, are included within the patent protection scope of the present invention.
Claims
1. A method for preparing a water-based succinic anhydride derivative anti-corrosion lubricant, characterized in that, Includes the following steps: Under inert gas protection and a slightly positive pressure of 500–2000 Pa, at 60–120 °C, and without solvent, at least one saturated alkyl succinic anhydride is esterified with at least one mercapto-polyethylene glycol monomethyl ether at a molar ratio of 1:(0.8–1.5). The reaction endpoint is reached when the acid value of the reactants no longer changes, yielding a succinate compound. The saturated alkyl succinic anhydride is selected from one or more of linear or branched octyl succinic anhydride, nonyl succinic anhydride, decyl succinic anhydride, dodecyl succinic anhydride, tetradecyl succinic anhydride, hexadecyl succinic anhydride, or octadecyl succinic anhydride. The mercapto-polyethylene glycol monomethyl ether has the structural formula: CH3(OCH2CH2). n SH, where n is an integer from 2 to 20.
2. The preparation method of the water-based succinic anhydride derivative anti-corrosion lubricant according to claim 1, characterized in that, The inert gas is argon or nitrogen.
3. The preparation method of the water-based succinic anhydride derivative anti-corrosion lubricant according to claim 1, characterized in that, The reaction raw materials can be added in any of the following ways: First, add saturated alkyl succinic anhydride, then add mercapto polyethylene glycol monomethyl ether, and then maintain the reaction system at 80°C until the acid value of the reactants no longer changes; First, add mercapto polyethylene glycol monomethyl ether, then add saturated alkyl succinic anhydride, and then maintain the reaction system at 80°C until the acid value of the reactants no longer changes; Saturated alkyl succinic anhydride and mercapto polyethylene glycol monomethyl ether were added to the reaction system simultaneously for esterification.
4. The preparation method of the water-based succinic anhydride derivative anti-corrosion lubricant according to claim 3, characterized in that, The thiol polyethylene glycol monomethyl ether is selected from one or more of the following: thiol diethylene glycol methyl ether, thiol triethylene glycol methyl ether, thiol tetraethylene glycol methyl ether, thiol pentaethylene glycol methyl ether, thiol hexaethylene glycol methyl ether, thiol heptaethylene glycol methyl ether, thiol octaethylene glycol methyl ether, thiol nonaethylene glycol methyl ether, thiol decaethylene glycol methyl ether, thiol undecaethylene glycol methyl ether, thiol dodecaethylene glycol methyl ether, thiol tridecaethylene glycol methyl ether, thiol tetradecaethylene glycol methyl ether, thiol decadecylethylene glycol methyl ether, thiol decadecylethylene glycol methyl ether, thiol hexadecylethylene glycol methyl ether, thiol heptaethylene glycol methyl ether, thiol octadecylethylene glycol methyl ether, thiol nonadecylethylene glycol methyl ether, and thiol eicosylethylene glycol methyl ether.
5. The use of a water-based succinic anhydride derivative anti-corrosion lubricant as described in any one of claims 1-4 in protecting aluminum and / or aluminum alloys from corrosion.
6. The application of the water-based succinic anhydride derivative anti-corrosion lubricant according to claim 5 in protecting aluminum and / or aluminum alloys from corrosion, characterized in that, The aluminum alloys include cast aluminum alloys and forged aluminum alloys.
7. The application of the water-based succinic anhydride derivative anti-corrosion lubricant according to claim 5 in protecting aluminum and / or aluminum alloys from corrosion, characterized in that, When applying, the water-based succinic anhydride derivative anti-corrosion lubricant is applied to the surface of aluminum and / or aluminum alloy by pouring, impregnation or spraying.
8. The application of a water-based succinic anhydride derivative anti-corrosion lubricant as described in any one of claims 1-4 in providing lubrication during metal processing.
9. The application of the water-based succinic anhydride derivative anti-corrosion lubricant according to claim 8 in providing lubrication during metal processing, characterized in that, The metal processing includes metal cutting, grinding and forming; the metals include ferrous metals and non-ferrous metals.
10. The application of the water-based succinic anhydride derivative anti-corrosion lubricant according to claim 8 in providing lubrication during metal processing, characterized in that, When applying, the water-based succinic anhydride derivative anti-corrosion lubricant is applied to the processing area by pouring, impregnation, or spraying.