Lubricating oil additive and preparation method thereof
By introducing organic amines and alkyl sulfonic acids into 5-chlorobenzotriazole, a lubricating oil additive was synthesized, which solved the problem of limited dispersibility of alkyl sulfonates in non-polar base oils and achieved excellent anti-corrosion, anti-rust, and anti-wear properties of lubricating oil under high temperature and high pressure.
Patent Information
- Application Number
- CN202511438454.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-10-10
- Publication Date
- 2025-11-14
AI Technical Summary
Existing alkyl sulfonates have limited dispersibility in non-polar base oils, making it difficult to meet the corrosion prevention, rust prevention, and wear resistance requirements of mechanical equipment under high temperature and high pressure environments.
Organic amines and alkyl sulfonic acids are introduced into 5-chlorobenzotriazole via the Mannich reaction to synthesize Mannich bases containing benzotriazole alkyl sulfonic acid derivatives and 5-chlorobenzotriazole, which are then used to prepare lubricating oil additives to improve their oil solubility and overall performance.
The prepared lubricating oil additives exhibit excellent anti-corrosion, anti-rust, and anti-wear properties under high temperature and high pressure, improving the load-bearing capacity and anti-wear performance of lubricating oil, and significantly reducing copper sheet corrosion and liquid phase rust.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of lubricating oil additives, and relates to a lubricating oil additive and its preparation method. The additive can be used as an anti-corrosion, anti-rust and anti-wear additive for lubricating oils. Background Technology
[0002] As more and more mechanical equipment needs to operate under conditions such as high temperature, high speed, and heavy load, the requirements for lubricating oil are becoming increasingly stringent. Additives are the essence of lubricating oil and play an increasingly important role in improving mechanical performance.
[0003] Alkyl sulfonates (such as sodium dodecyl sulfonate and sodium petroleum sulfonate) are a class of environmentally friendly anionic surfactants with excellent chemical stability, widely used in lubricating oils, metalworking fluids, and industrial cleaning agents. Their molecules contain sulfonic acid groups (-SO3). - Alkyl sulfonates possess unique performance advantages: excellent extreme pressure and anti-wear properties, good corrosion and rust inhibition properties, and environmental friendliness. However, alkyl sulfonates still have certain limitations when used alone; the strong polarity of the sulfonic acid group limits their dispersibility in non-polar base oils. Therefore, there is an urgent need in the field to develop a lubricating oil additive with excellent oil solubility, and excellent anti-corrosion, rust prevention, and anti-wear properties. Summary of the Invention
[0004] The purpose of this invention is to provide a novel lubricating oil additive and its preparation method. This type of additive is biodegradable and has excellent anti-corrosion, anti-rust and anti-wear properties.
[0005] To achieve the above objectives, a lubricating oil additive is provided, the preparation method of which includes the following steps: (1) Preparation of Mannich base containing 5-chlorobenzotriazole: 5-Chlorobenzotriazole, organic amine and solvent are added to a reactor, along with aliphatic aldehyde or aromatic aldehyde. The mixture is stirred and homogenized, heated to 50-100°C, and water is removed by gas stripping. After the reaction continues for 3-9 hours, the solvent is removed by vacuum distillation to obtain Mannich base containing 5-chlorobenzotriazole. (2) Preparation of multifunctional additives: Add the 5-chlorobenzotriazole Mannich base and solvent from step (1) to a reaction vessel, stir and mix evenly, add alkyl sulfonate, heat to 80-130℃ and reflux for 3-6 hours, add deionized water after the reaction is completed, separate the oil and water phases, and evaporate the solvent to obtain the lubricating oil additive. In step (2), the molar ratio of the mannice base and the alkyl sulfonate of 5-chlorobenzotriazole is 1: (0.1~0.5).
[0006] As a preferred embodiment of the above technical solution, the organic amine mentioned in step (1) is any one of tert-dodecylamine, dodecylamine, or n-octylamine.
[0007] As a preferred embodiment of the above technical solution, the solvent in step (1) is one or a mixture of two or more of water, petroleum ether, benzene, toluene, xylene, cyclohexane, and ethanol.
[0008] As a preferred embodiment of the above technical solution, the aliphatic aldehyde or aromatic aldehyde mentioned in step (1) is any one of formaldehyde, paraformaldehyde, acetaldehyde, butyraldehyde, pentanal, hexanal, octanal, decanal, benzaldehyde, and phenylacetaldehyde.
[0009] As a preferred embodiment of the above technical solution, in step (1), the molar ratio of 5-chlorobenzotriazole, organic amine and fatty aldehyde or aromatic aldehyde is 1:1:(1.0~1.6).
[0010] As a preferred embodiment of the above technical solution, the solvent in step (2) is one or a mixture of two or more of petroleum ether, n-heptane, benzene, toluene, xylene, and cyclohexane.
[0011] As a preferred embodiment of the above technical solution, the alkyl sulfonate in step (2) is an alkyl sulfonate represented by the following formula (4). , R4 represents a straight-chain or branched C1-C24 hydrocarbon group, and R5 represents sodium or potassium.
[0012] Secondly, the present invention provides an application of the above-mentioned additive in the preparation of lubricating oil, wherein the amount of the additive added to the base oil is 0.2wt% to 5wt%.
[0013] Beneficial effects of the invention: 5-Chlorobenzotriazole (5-Cl-BTA) is an important class of nitrogen-containing heterocyclic compounds. The triazole ring and chlorine substituents in its molecule endow it with excellent metal adsorption capacity and chemical activity. Compared with benzotriazole, chlorobenzotriazole has better metal protection performance, and its copper slow-release effect is several times that of benzotriazole. However, as a solid additive, the poor oil solubility of 5-chlorobenzotriazole and its compatibility with other additives limit its application in the field of lubricating oil. This invention comprehensively considers the performance advantages of 5-chlorobenzotriazole. First, an organic amine is introduced into benzotriazole via the Mannich reaction. Then, an alkyl sulfonic acid is introduced into benzotriazole via a nucleophilic substitution reaction, synthesizing an additive containing a benzotriazole alkyl sulfonic acid derivative and a Mannich base of 5-chlorobenzotriazole. When applied to lubricating oils, it exhibits excellent oil solubility, excellent anti-corrosion, anti-rust, and anti-wear properties, making it a lubricating oil additive with superior comprehensive performance. Its preparation process is simple, the reaction conditions are mild, the raw materials used are inexpensive and readily available, and the synthesis yield is high. Detailed Implementation
[0014] The present invention will be further described in detail below with reference to specific embodiments.
[0015] Example 1 1 mol of 5-chlorobenzotriazole (154 g), 1 mol of tert-dodecylamine (185 g), and 150 mL of toluene were added to a 500 mL four-necked flask. The mixture was stirred until homogeneous, and the temperature was raised to 80 °C. 1 mol of paraformaldehyde (30 g) was added to the four-necked flask, and the mixture was refluxed for 6 h until no water was generated. The solvent toluene was removed by vacuum distillation to obtain the Mannich base M1 of chlorobenzotriazole. 0.5 mol of the Mannich base M1 of chlorobenzotriazole (176 g) and 100 mL of petroleum ether were added to a 500 mL four-necked flask. The mixture was stirred until homogeneous, and 79 g of sodium tetradecyl sulfonate was added. The mixture was refluxed at 100 °C for 6 h. After the reaction was completed, a certain amount of deionized water was added, the oil and water phases were separated, and the solvent petroleum ether was evaporated to obtain the lubricating oil additive.
[0016] Example 2 1 mol of 5-chlorobenzotriazole (154 g), 1 mol of dodecylamine (185 g), and 100 mL of benzene were added to a 500 mL four-necked flask and stirred until homogeneous. The mixture was heated to 75 °C, and 1 mol of formaldehyde (30 g) was added to the flask. The mixture was refluxed for 5 h until no water was generated. The solvent benzene was removed by vacuum distillation to obtain the Mannich base M2 of chlorobenzotriazole. 0.5 mol of 176 g of the Mannich base M2 of chlorobenzotriazole and 150 mL of xylene were added to a 500 mL four-necked flask and stirred until homogeneous. 36 g of sodium octadecyl sulfonate was added, and the mixture was refluxed at 110 °C for 5 h. After the reaction was completed, a certain amount of deionized water was added, the oil and water phases were separated, and the solvent xylene was removed by distillation to obtain the lubricating oil additive.
[0017] Example 3 1 mol of 5-chlorobenzotriazole (119 g), 1 mol of n-octylamine (129 g), and 100 mL of petroleum ether were added to a 500 mL four-necked flask. The mixture was stirred until homogeneous, and the temperature was raised to 70 °C. 1.2 mol of benzaldehyde (127 g) was added dropwise to the four-necked flask. The mixture was refluxed for 4 h until no water was generated. The solvent petroleum ether was removed by vacuum distillation to obtain the Mannich base M3 of chlorobenzotriazole. 0.5 mol of 168 g of the Mannich base M3 of chlorobenzotriazole and 150 mL of n-heptane were added to a 500 mL four-necked flask. The mixture was stirred until homogeneous, and 40 g of sodium petroleum sulfonate was added. The mixture was refluxed at 130 °C for 5 h. After the reaction was completed, a certain amount of deionized water was added, the oil and water phases were separated, and the solvent n-heptane was evaporated to obtain the lubricating oil additive.
[0018] Example 4 0.5 mol of 176 g of 5-chlorobenzotriazole Mannich base M1 and 150 mL of petroleum ether were added to a 500 mL four-necked flask and stirred until homogeneous. 45 g of potassium petroleum sulfonate was added, and the mixture was heated to 120 °C and refluxed for 5 hours. After the reaction was completed, a certain amount of deionized water was added, the oil and water phases were separated, and the solvent n-heptane was evaporated to obtain the lubricating oil additive.
[0019] Comparative Example 1 Add 1 mol benzotriazole (119 g), 1 mol tert-dodecylamine (185 g) and 150 mL toluene to a 500 mL four-necked flask, stir and mix well, heat to 80 °C, add 1 mol paraformaldehyde (30 g) dropwise to the four-necked flask, and reflux for 6 h until no water is generated. Remove the solvent toluene by vacuum distillation to obtain the Mannich base M4 of benzotriazole.
[0020] Comparative Example 2 0.5 mol of 158 g of benzotriazole Mannich base M4 and 100 mL of petroleum ether were added to a 500 mL four-necked flask and stirred until homogeneous. 79 g of sodium tetradecyl sulfonate was added, and the mixture was heated to 100 °C and refluxed for 6 hours. After the reaction was completed, a certain amount of deionized water was added, the oil and water phases were separated, and the solvent petroleum ether was evaporated to obtain comparative additive 2.
[0021] Comparative Example 3 0.5 mol of 176 g of 5-chlorobenzotriazole Mannich base M1 and 100 mL of petroleum ether were added to a 500 mL four-necked flask and stirred until homogeneous. Then, 126 g of sodium tetradecyl sulfonate was added, and the mixture was heated to 100 °C and refluxed for 6 hours. After the reaction was completed, a certain amount of deionized water was added, the oil and water phases were separated, and the solvent petroleum ether was evaporated to obtain the comparative additive 3.
[0022] The additives obtained in the examples and comparative examples were added at a rate of 1.0 wt% to HVIS 150BS base oil containing 1 wt% sulfurized isobutylene (T321H). Subsequently, the wear scar diameter and sintering load (P) of the lubricating oil under a load of 392 N were measured. D The corrosion performance of copper sheets and liquid phase corrosion were measured.
[0023] The maximum non-seize load (P) was determined according to the method of GB / T 3142-1982. D The wear scar diameter of the steel ball was determined according to the method of NB / SH / T 0189-2017, the copper sheet corrosion was determined according to the method of GB / T 5096-2017, and the liquid phase corrosion was determined according to the method of GB / T11143.
[0024] Table 1. Performance Evaluation of Additives
[0025] As can be seen from Table 1, after adding the additives prepared in Examples 1-4, the load-carrying capacity P of the lubricating oil was increased. D The wear scar diameter was significantly improved compared to 1.0% T321H base oil. Compared to additives in Comparative Examples 1 and 2, the additives in this example showed a better synergistic effect with T321H and were able to better improve P. D The additives prepared in Examples 1-4 all exhibit good resistance to copper corrosion, reducing the copper corrosion of lubricating oil from 4C to 1b-2a. In contrast, the copper corrosion of additives in Comparative Examples 1-3 remained at 2e-3b. This demonstrates that the additives with specific structures and proportions of this invention play a crucial role in reducing copper corrosion. Another outstanding performance characteristic of the additives with specific structures and proportions of this invention is their ability to significantly improve the liquid phase corrosion resistance of oils. The additives in Examples 1-4 are all rust-free.
[0026] The embodiments described above are merely preferred embodiments of this application and are not intended to limit this application. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of this application should be included within the scope of protection of this application.
Claims
1. A lubricating oil additive, characterized in that, The preparation method of the lubricating oil additive includes the following steps: (1) Preparation of Mannich base containing chlorobenzotriazole: 5-Chlorobenzotriazole, organic amine and solvent are added to a reactor, along with aliphatic aldehyde or aromatic aldehyde. The mixture is stirred and homogenized, heated to 50-100°C, and water is removed by gas stripping. After the reaction continues for 3-9 hours, the solvent is removed by vacuum distillation to obtain Mannich base containing 5-chlorobenzotriazole. (2) Preparation of multifunctional additives: Add the 5-chlorobenzotriazole Mannich base and solvent from step (1) to a reaction vessel, stir and mix evenly, add alkyl sulfonate, heat to 80-130℃ and reflux for 3-6 hours, add deionized water after the reaction is completed, separate the oil and water phases, and evaporate the solvent to obtain the lubricating oil additive. In step (2), the molar ratio of the mannice base and the alkyl sulfonate of 5-chlorobenzotriazole is 1: (0.1~0.5).
2. The lubricating oil additive according to claim 1, characterized in that: The organic amine mentioned in step (1) is any one of tert-dodecylamine, dodecylamine, or n-octylamine.
3. The lubricating oil additive according to claim 1, characterized in that: The solvent mentioned in step (1) is one or a mixture of two or more of the following: water, petroleum ether, benzene, toluene, xylene, cyclohexane, and ethanol.
4. The lubricating oil additive according to claim 1, characterized in that: The aliphatic or aromatic aldehydes mentioned in step (1) are any one of formaldehyde, paraformaldehyde, acetaldehyde, butyraldehyde, pentanaldehyde, hexanal, octanaldehyde, decanal, benzaldehyde, and phenylacetaldehyde.
5. The lubricating oil additive according to claim 1, characterized in that: In step (1), the molar ratio of 5-chlorobenzotriazole, organic amine and aliphatic aldehyde or aromatic aldehyde is 1:1:(1.0~1.6).
6. The lubricating oil additive according to claim 1, characterized in that: The solvent mentioned in step (2) is one or a mixture of two or more of petroleum ether, n-heptane, benzene, toluene, xylene, and cyclohexane.
7. The lubricating oil additive according to claim 1, characterized in that: The alkyl sulfonate mentioned in step (2) is an alkyl sulfonate represented by the following formula (4). ， R4 represents a straight-chain or branched C1-C24 hydrocarbon group, and R5 represents sodium or potassium.
8. The use of the additive according to any one of claims 1-7 in a lubricating oil, characterized in that, The additive is added to the base oil in an amount of 0.2 wt% to 5 wt%.