CN-122012153-A - Phosphorothioate proton ionic liquid additive and preparation method and application thereof

Abstract

The invention relates to a phosphorothioate proton ionic liquid additive, which has the following structural formula: Wherein R C 1 ~C 20 is alkyl. Meanwhile, the invention also discloses a preparation method and application of the additive. The additive disclosed by the invention has excellent antifriction and antiwear properties and bearing capacity in composite lithium-based lubricating grease, and solves the technical problem that the key performance of the lubricating grease is not improved enough by the conventional additive.

Inventors

• ZHANG SONGWEI
• LI YI
• HU LITIAN

Assignees

• 中国科学院兰州化学物理研究所
• 青岛市资源化学与新材料研究中心

Dates

Publication Date

20260512

Application Date

20260204

Claims (5)

1. 1. The phosphorothioate ionic liquid additive is characterized in that the structural formula of the additive is shown as follows: wherein R represents C 1 ~C 20 alkyl.
2. 2. The preparation method of the phosphorothioate proton type ionic liquid additive according to claim 1, comprising the following steps: s1, synthesizing a cation precursor: sequentially adding n-butylamine, triethylamine and excessive dichloromethane solvent into a container A at the temperature of minus 20 ℃ to minus 5 ℃, then dropwise adding diphenyl chlorophosphate, reacting at room temperature for 12-24 hours after the dropwise adding is finished, removing the dichloromethane solvent, and then placing the mixture into a 70 ℃ vacuum drying box for 12-24 hours to obtain a cation precursor, wherein the mass ratio of the n-butylamine to the triethylamine is 1:1.0-1.2, and the mass ratio of the n-butylamine to the diphenyl chlorophosphate is 1:1.0-1.1; s2, synthesizing an anion precursor: Adding phosphorus pentasulfide and excessive toluene into a container B with a tail gas treatment device, then adding alkylphenol, reacting for 24-48 hours at 80-100 ℃, and removing toluene solvent and unreacted raw materials by reduced pressure distillation after the reaction is completed to obtain an anion precursor, wherein the mass ratio of the phosphorus pentasulfide to the alkylphenol is 1:3.3-4.0; S3, synthesizing target ionic liquid: Sequentially adding a cationic precursor and an excessive anhydrous ethanol solvent into a container C, then, quickly dripping an anionic precursor, stirring at room temperature for 24-48 h, performing rotary evaporation to remove the ethanol solvent after reaction, and then, performing vacuum drying at 70 ℃ for 12-24 h to obtain the target ionic liquid, wherein the mass ratio of the cationic precursor to the anionic precursor is 1:0.98-1.02.
3. 3. The method for preparing a phosphorothioate proton type ionic liquid additive according to claim 2, wherein the alkylphenol in the step S2 is one of C 1 ~C 20 alkylphenols.
4. 4. The application of the phosphorothioate proton type ionic liquid additive according to claim 1, which is characterized in that the additive is used for preparing composite lithium-based grease.
5. 5. The application of the phosphorothioate proton type ionic liquid additive according to claim 4, wherein the composite lithium-based lubricating grease is prepared by the following method: Dissolving 12-hydroxystearic acid and azelaic acid in 2/3 base oil at 60-80 ℃, adding lithium hydroxide aqueous solution with the mass concentration of 9-11%, carrying out saponification reaction at 60-80 ℃ for 2h, continuously heating the mixed system to 200-220 ℃ for high-temperature refining, adding the rest 1/3 base oil after 5-10 min, naturally cooling to room temperature, grinding for three times by using a three-roller grinder to obtain base grease, adding an additive with the mass of 1-5% into the base grease, and grinding for three times by using the three-roller grinder to obtain the composite lithium-based grease containing the additive, wherein the mass ratio of azelaic acid, 12-hydroxystearic acid, the base oil and the lithium hydroxide aqueous solution is 1:12.5-13.0:160-165:13-14.

Description

Phosphorothioate proton ionic liquid additive and preparation method and application thereof Technical Field The invention relates to the technical field of lubricating additives, in particular to a phosphorothioate proton ionic liquid additive, a preparation method and application thereof. Background The need for high-end mechanical equipment for efficient, environmentally friendly and long-life lubrication techniques is increasing, grease being a critical lubricant, the performance of which depends to a large extent on the effectiveness of the additives. The antiwear and extreme pressure additives form a protective film by acting on the surface of the friction pair, and directly determine the bearing capacity and reliability of the lubricating system under severe working conditions. However, the traditional halogen-containing additive is easy to generate corrosive substances in the friction process, and is potentially harmful to the environment and equipment, so that the strict requirements of high-end equipment such as wind power bearings on green and high-reliability lubrication are difficult to meet. Therefore, the development of novel high-performance additives with antifriction, antiwear and extreme pressure properties has become an important research direction in the lubrication field. The proton type ionic liquid as a structurally programmable additive has great potential due to its excellent physicochemical properties and controllable tribochemical activity. However, by rational molecular design, the grease can effectively exert extreme pressure anti-wear function in a complex system of the grease, and is a key problem for breaking through the application bottleneck of the grease. Disclosure of Invention The invention aims to provide a phosphorothioate proton type ionic liquid additive with good performance. The invention aims to provide a preparation method of the phosphorothioate proton type ionic liquid additive. The third technical problem to be solved by the invention is to provide the application of the phosphorothioate proton type ionic liquid additive. In order to solve the problems, the phosphorothioate proton type ionic liquid additive is characterized by having the following structural formula: wherein R represents C 1~C20 alkyl. The preparation method of the phosphorothioate proton type ionic liquid additive comprises the following steps: s1, synthesizing a cation precursor: Sequentially adding n-butylamine, triethylamine and excessive dichloromethane solvent into a container A at the temperature of minus 20 ℃ to minus 5 ℃, then dropwise adding diphenyl chlorophosphate, reacting at room temperature for 12-24 hours after the dropwise adding is finished, removing the dichloromethane solvent, and then placing the mixture into a 70 ℃ vacuum drying box for 12-24 hours to obtain a cation precursor, wherein the mass ratio of the n-butylamine to the triethylamine is 1:1.0-1.2, and the mass ratio of the n-butylamine to the diphenyl chlorophosphate is 1:1.0-1.1; s2, synthesizing an anion precursor: Adding phosphorus pentasulfide and excessive toluene into a container B with a tail gas treatment device, then adding alkylphenol, reacting for 24-48 hours at 80-100 ℃, and removing toluene solvent and unreacted raw materials by reduced pressure distillation after the reaction is completed to obtain an anion precursor, wherein the mass ratio of the phosphorus pentasulfide to the alkylphenol is 1:3.3-4.0; S3, synthesizing target ionic liquid: Sequentially adding a cationic precursor and an excessive anhydrous ethanol solvent into a container C, then, quickly dripping an anionic precursor, stirring at room temperature for 24-48 h, performing rotary evaporation to remove the ethanol solvent after reaction, and then, performing vacuum drying at 70 ℃ for 12-24 h to obtain the target ionic liquid, wherein the mass ratio of the cationic precursor to the anionic precursor is 1:0.98-1.02. The alkylphenol in the step S2 refers to one of C 1~C20 alkylphenols. The application of the phosphorothioate proton type ionic liquid additive is characterized in that the additive is used for preparing composite lithium-based lubricating grease. The composite lithium-based lubricating grease is prepared by the following method: Dissolving 12-hydroxystearic acid and azelaic acid in 2/3 base oil at 60-80 ℃, adding lithium hydroxide aqueous solution with the mass concentration of 9-11%, carrying out saponification reaction at 60-80 ℃ for 2h, continuously heating the mixed system to 200-220 ℃ for high-temperature refining, adding the rest 1/3 base oil after 5-10 min, naturally cooling to room temperature, grinding for three times by using a three-roller grinder to obtain base grease, adding an additive with the mass of 1-5% into the base grease, and grinding for three times by using the three-roller grinder to obtain the composite lithium-based grease containing the additive, wherein the mass ratio of azelaic acid, 12-hydroxyst