CN116574549A - Thioether thiadiazole ionic liquid lubricating oil extreme pressure antiwear additive, preparation method and application - Google Patents
Thioether thiadiazole ionic liquid lubricating oil extreme pressure antiwear additive, preparation method and application Download PDFInfo
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- CN116574549A CN116574549A CN202310542166.5A CN202310542166A CN116574549A CN 116574549 A CN116574549 A CN 116574549A CN 202310542166 A CN202310542166 A CN 202310542166A CN 116574549 A CN116574549 A CN 116574549A
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- 239000010687 lubricating oil Substances 0.000 title claims abstract description 20
- 239000007866 anti-wear additive Substances 0.000 title claims abstract description 16
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 13
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 150000003568 thioethers Chemical class 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000002148 esters Chemical class 0.000 claims abstract description 26
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 25
- GAYUSSOCODCSNF-UHFFFAOYSA-N 1-(dodecyldisulfanyl)dodecane Chemical group CCCCCCCCCCCCSSCCCCCCCCCCCC GAYUSSOCODCSNF-UHFFFAOYSA-N 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 20
- 239000012263 liquid product Substances 0.000 claims abstract description 19
- BIGYLAKFCGVRAN-UHFFFAOYSA-N 1,3,4-thiadiazolidine-2,5-dithione Chemical compound S=C1NNC(=S)S1 BIGYLAKFCGVRAN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000002904 solvent Substances 0.000 claims abstract description 16
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 claims abstract description 13
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract 7
- 239000000654 additive Substances 0.000 claims description 25
- 230000000996 additive effect Effects 0.000 claims description 22
- 239000000314 lubricant Substances 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 3
- JJJPTTANZGDADF-UHFFFAOYSA-N thiadiazole-4-thiol Chemical compound SC1=CSN=N1 JJJPTTANZGDADF-UHFFFAOYSA-N 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 16
- 239000002199 base oil Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- 150000004867 thiadiazoles Chemical class 0.000 description 8
- 238000005299 abrasion Methods 0.000 description 6
- 230000001050 lubricating effect Effects 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 5
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 239000004519 grease Substances 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- FRQQKWGDKVGLFI-UHFFFAOYSA-N 2-methylundecane-2-thiol Chemical compound CCCCCCCCCC(C)(C)S FRQQKWGDKVGLFI-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 108010037444 diisopropylglutathione ester Proteins 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- -1 sulfhydryl thiadiazole Chemical compound 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
- C10M135/36—Heterocyclic sulfur, selenium or tellurium compounds the ring containing sulfur and carbon with nitrogen or oxygen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
- C07D285/01—Five-membered rings
- C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
- C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
- C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
- C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/2805—Esters used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
- C10M2219/104—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring containing sulfur and carbon with nitrogen or oxygen in the ring
- C10M2219/106—Thiadiazoles
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/045—Metal containing thio derivatives
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Lubricants (AREA)
Abstract
The invention discloses a thioether thiadiazole ionic liquid lubricating oil extreme pressure antiwear additive, a preparation method and application. The method comprises the following steps: mixing 2, 5-dimercapto-1, 3, 4-thiadiazole, ethanol and dodecyl mercaptan, and stirring to obtain a mixed solution A; dropwise adding hydrogen peroxide into the mixed solution A, heating to 75-80 ℃, and maintaining the temperature to stir for reaction; after stopping the reaction, distilling under reduced pressure to remove the solvent to obtain a tan transparent liquid product; mixing the yellow brown transparent liquid product with the ethyl iodide, heating to 70-75 ℃, maintaining the temperature and stirring for reaction; filtering, drying, washing, and distilling off the solvent under reduced pressure to obtain 2, 5-di (dodecyl disulfide group) -3-ethyl-1, 3, 4-thiadiazole iodized salt. The mercaptothiadiazole ionic liquid extreme pressure antiwear additive can be directly applied to synthetic ester lubricating oil and has good extreme pressure antiwear effect.
Description
Technical Field
The invention relates to a thioether thiadiazole ionic liquid extreme pressure antiwear additive for synthetic ester lubricating oil, a preparation method and application thereof, and belongs to the technical field of lubricating oil additives.
Background
The dimercaptothiadiazole can form a stronger adsorption film on a metal friction surface by complexing and coordinating with the metal surface, thereby effectively reducing the friction coefficient between the friction pair metal surfaces. As an extreme pressure antiwear additive of lubricating grease, the dimercaptothiadiazole derivative not only has the general property of the thiadiazole derivative-the complexing and passivating effect on metal, but also has very strong extreme pressure antiwear performance and synergistic antioxidant performance in lubricating grease; particularly, the lubricating grease has excellent bearing, antifriction and antiwear performances under the heavy-load working condition of mechanical equipment, and is widely applied to various high-end equipment and mechanical bearing lubricating grease.
By searching, no report is made on the synthesis of 2, 5-bis (dodecyl disulfide) -3-ethyl-1, 3, 4-thiadiazole iodized salt in the prior art.
Because the thiadiazole derivative has strong polarity and is difficult to dissolve in lubricating oil mainly containing aliphatic hydrocarbon, the application range of the thiadiazole derivative is greatly limited, and the thiadiazole derivative can be used as an extreme pressure antiwear additive in lubricating oil only by modifying or modifying the structure of the thiadiazole derivative and enhancing the oil solubility of the thiadiazole derivative. The sulfhydryl thiadiazole ionic liquid extreme pressure antiwear additive is synthesized and prepared by the invention, can be directly applied to synthetic ester lubricating oil, and has good extreme pressure antiwear effect.
Disclosure of Invention
The invention provides a thioether thiadiazole ionic liquid extreme pressure antiwear additive for synthetic ester lubricating oil, a preparation method and application thereof. According to the invention, 2, 5-di (dodecyl disulfide group) -3-ethyl-1, 3, 4-thiadiazole iodized salt is synthesized for the first time, and the 2, 5-di (dodecyl disulfide group) -3-ethyl-1, 3, 4-thiadiazole iodized salt is used as a lubricating additive to be added into synthetic ester lubricating oil, so that the extreme pressure wear resistance of the synthetic ester lubricating oil is improved. The invention uses 2, 5-dimercapto-1, 3, 4-thiadiazole, hydrogen peroxide, tertiary dodecyl mercaptan, ethyl iodide and the like as raw materials, and the additive product is obtained through two steps of reactions, and the synthetic route is shown in figure 1:
the invention adopts the following technical scheme:
a thioether thiadiazole ionic liquid lubricating oil extreme pressure antiwear additive has a structure shown in the following formula:
the preparation method of the additive comprises the following steps:
(1) Mixing 2, 5-dimercapto-1, 3, 4-thiadiazole, ethanol and dodecyl mercaptan, and stirring to obtain a mixed solution A; dropwise adding hydrogen peroxide into the mixed solution A, heating to 75-80 ℃, and maintaining the temperature to stir for reaction; after stopping the reaction, distilling under reduced pressure to remove the solvent to obtain a tan transparent liquid product;
(2) Mixing the yellow brown transparent liquid product with the ethyl iodide, heating to 70-75 ℃, maintaining the temperature and stirring for reaction; filtering, drying, washing, and distilling off the solvent under reduced pressure to obtain 2, 5-di (dodecyl disulfide group) -3-ethyl-1, 3, 4-thiadiazole iodized salt.
Further, the additive is 2, 5-di (dodecyl disulfide group) -3-ethyl-1, 3, 4-thiadiazole iodized salt.
Further, in the step (1), the mass ratio of the 2, 5-dimercapto-1, 3, 4-thiadiazole, ethanol and dodecyl mercaptan is 1:5.7 to 5.9:2.6 to 2.8. For example, in step (1), the mass ratio of 2, 5-dimercapto-1, 3, 4-thiadiazole, ethanol, and dodecyl mercaptan is 1:5.8:2.6 to 2.8, 1:5.7 to 5.9:2.6, 1:5.7 to 5.9:2.7 or 1:5.8:2.7.
further, in the step (1), the reaction is stirred for 2 to 4 hours.
Further, in the step (1), the mass ratio of the 2, 5-dimercapto-1, 3, 4-thiadiazole to the hydrogen peroxide is 1:0.7 to 0.9. For example, the mass ratio of the 2, 5-dimercapto-1, 3, 4-thiadiazole to the hydrogen peroxide is 1:0.8.
further, in the step (2), the molar ratio of the yellow brown transparent liquid product to the ethyl iodide is 1:1.0 to 1.1. For example, the molar ratio of tan clear liquid product to ethyl iodide is 1:1.05.
further, in the step (2), the reaction is stirred for 18 to 22 hours.
The use of the additives described above, said additives being incorporated into synthetic ester lubricating oils.
Further, the additive is added in an amount of 2% based on the mass of the synthetic ester lubricating oil.
The 2, 5-bis (dodecyl disulfide group) -3-ethyl-1, 3, 4-thiadiazole iodized salt is synthesized by the following steps:
specifically, the specific synthesis method of the 2, 5-bis (dodecyl disulfide group) -3-ethyl-1, 3, 4-thiadiazole iodized salt is as follows: adding 2, 5-dimercapto-1, 3, 4-thiadiazole into a three-necked flask, then adding ethanol into the system, and stirring at room temperature for 0.5-1.0 hour; dodecyl mercaptan is added into a three-necked flask and stirred at room temperature; dropwise adding hydrogen peroxide into the system, controlling the temperature of the system, avoiding rapid heating, slowly heating to 75-80 ℃, maintaining the temperature, and stirring for reaction for 2-4 hours; after the reaction was stopped, the solvent was distilled off under reduced pressure to give a tan clear liquid product.
Adding the yellow brown transparent liquid product and the ethyl iodide into another three-necked flask, slowly heating to 70-75 ℃, maintaining the temperature and stirring for reaction for 18-22 hours; filtering, drying, washing with petroleum ether, distilling under reduced pressure to remove solvent, and obtaining brown solid as additive target product.
The molecular structure is innovative, and 2, 5-di (dodecyl disulfide group) -3-ethyl-1, 3, 4-thiadiazole iodized salt is synthesized for the first time and used as an antiwear additive of lubricating oil.
The 2, 5-di (dodecyl disulfide group) -3-ethyl-1, 3, 4-thiadiazole iodized salt is used as an additive, so that the oil solubility of the thiadiazole derivative is enhanced, the thiadiazole derivative can be applied to the synthesis of ester base oil, and the extreme pressure antiwear performance of the thiadiazole derivative can be effectively improved. Meanwhile, the invention has the advantages of simple synthesis and preparation method, high product yield and the like.
Drawings
FIG. 1 is a synthetic route diagram of 2, 5-bis (dodecyl disulfide) -3-ethyl-1, 3, 4-thiadiazole iodisalt;
FIG. 2 is a nuclear magnetic resonance spectrum of 2, 5-bis (dodecyl disulfide) -3-ethyl-1, 3, 4-thiadiazole iodized salt.
Detailed Description
The invention will now be described in detail with reference to the accompanying drawings and specific embodiments thereof. The following examples are intended to be illustrative only and the scope of the invention is to be construed as including the full breadth of the claims and by the recitation of the following examples, the full breadth of the claims can be fully set forth by those skilled in the art.
The invention uses 2, 5-dimercapto-1, 3, 4-thiadiazole, hydrogen peroxide, tertiary dodecyl mercaptan, ethyl iodide and the like as raw materials, and the additive product is obtained through two steps of reactions, and the synthetic route is shown in figure 1.
The specific synthesis method is as follows: adding a certain amount of 2, 5-dimercapto-1, 3, 4-thiadiazole into a three-neck flask, then adding a proper amount of ethanol into the system, and stirring at room temperature for 0.5-1.0 hour; adding a certain amount of dodecyl mercaptan into a three-necked flask, and stirring at room temperature; dropwise adding hydrogen peroxide into the system, controlling the temperature of the system, avoiding rapid heating, slowly heating to 75-80 ℃, maintaining the temperature, and stirring for reaction for 2-4 hours; after the reaction was stopped, the solvent was distilled off under reduced pressure to give a tan clear liquid product.
Adding a proper amount of yellow brown transparent liquid product and ethyl iodide into another three-necked flask, slowly heating to 70-75 ℃, maintaining the temperature, and stirring for reaction for 18-22 hours; filtering, drying, washing with petroleum ether, distilling under reduced pressure to remove solvent, and obtaining brown solid as additive target product.
The following raw materials in the examples of the invention are as follows:
synthetic ester base oils (rayleigh, DIPE); traditional commercial antiwear additives ZDDP (Rate Feng Xincai, RF 2202).
Embodiment one:
15g of 2, 5-dimercapto-1, 3, 4-thiadiazole was added to the three-necked flask, followed by adding 110mL of ethanol to the system, and stirring at room temperature for 0.6 hours; 40.4g of dodecyl mercaptan was added to a three-necked flask and stirred at room temperature; dropwise adding hydrogen peroxide (11.4 g in total) into the system, controlling the temperature of the system, avoiding rapid heating, slowly heating to 75 ℃, maintaining the temperature and stirring for reaction for 2 hours; after the reaction was stopped, the solvent was distilled off under reduced pressure to give a tan clear liquid product.
Adding 0.1mol of a yellow brown transparent liquid product and 0.1mol of ethyl iodide into another three-necked flask, slowly heating to 70 ℃, maintaining the temperature and stirring for reaction for 18 hours; filtering, drying, washing with petroleum ether, distilling under reduced pressure to remove solvent, and obtaining the 2, 5-di (dodecyl disulfide group) -3-ethyl-1, 3, 4-thiadiazole iodized salt which is the target product of the additive. The molecular structure of the 2, 5-bis (dodecyl disulfide) -3-ethyl-1, 3, 4-thiadiazole iodized salt is determined by nuclear magnetic resonance spectroscopy (shown in figure 2). The number of hydrogen atoms in the molecular structure of the target product 2, 5-bis (dodecyl disulfide) -3-ethyl-1, 3, 4-thiadiazole iodized salt is consistent with the characteristic result of nuclear magnetic resonance spectroscopy, and the correctness of the molecular structure of the synthesized additive product is proved.
2, 5-bis (dodecyl disulfide) -3-ethyl-1, 3, 4-thiadiazole iodized salt is added into synthetic ester base oil (Rayleigh, DIPE), and the iodized salt accounts for 2.0% of the synthetic ester base oil by mass. The SRV test result shows that when the test load is 500N, the abrasion volume of the synthesized ester base oil sample is 14.36 multiplied by 10 after the ionic liquid additive is added 6 μm 3 Reduced to 2.92×10 6 μm 3 About, the abrasion volume of the synthetic ester base oil sample was measured from that of the conventional commercial antiwear additive ZDDP (Rayleigh Feng Xincai, RF 2202) added14.36×10 6 μm 3 Reduced to 6.35×10 6 μm 3 Left and right.
Embodiment two:
120g of 2, 5-dimercapto-1, 3, 4-thiadiazole was added to the three-necked flask, and then 685g of ethanol was added to the system, followed by stirring at room temperature for 1.0 hour; 325g of dodecyl mercaptan was added to a three-necked flask and stirred at room temperature; hydrogen peroxide (90 g) is added into the system dropwise, the temperature of the system is controlled, and rapid temperature rise is avoided.
Slowly heating to 80 ℃, maintaining the temperature and stirring for reaction for 4 hours; after the reaction was stopped, the solvent was distilled off under reduced pressure to give a tan clear liquid product.
Adding 0.2mol of a yellow brown transparent liquid product and 0.2mol of ethyl iodide into another three-necked flask, slowly heating to 75 ℃, maintaining the temperature and stirring for reaction for 22 hours; filtering, drying, washing with petroleum ether, distilling under reduced pressure to remove solvent, and obtaining the 2, 5-di (dodecyl disulfide group) -3-ethyl-1, 3, 4-thiadiazole iodized salt which is the target product of the additive. The molecular structure of the 2, 5-bis (dodecyl disulfide) -3-ethyl-1, 3, 4-thiadiazole iodized salt is determined by nuclear magnetic resonance spectroscopy (shown in figure 2).
The 2, 5-bis (dodecyl disulfide) -3-ethyl-1, 3, 4-thiadiazole iodized salt synthesized in the second embodiment is added into the synthetic ester base oil, and the iodized salt accounts for 2.0% of the mass of the synthetic ester base oil. The SRV test result shows that when the test load is 500N, the abrasion volume of the synthesized ester base oil sample is 15.19 multiplied by 10 after the ionic liquid additive is added 6 μm 3 Reduced to 2.76×10 6 μm 3 About, the abrasion volume of the synthetic ester base oil sample is 15.19X10 after adding the traditional commercial antiwear additive ZDDP 6 μm 3 Reduced to 6.61×10 6 μm 3 Left and right.
Embodiment III:
45g of 2, 5-dimercapto-1, 3, 4-thiadiazole was added to the three-necked flask, followed by adding 330mL of ethanol to the system, and stirring at room temperature for 0.6 hours; 118g of dodecyl mercaptan was added to a three-necked flask and stirred at room temperature; dropwise adding hydrogen peroxide (34.2 g in total) into the system, controlling the temperature of the system, avoiding rapid heating, slowly heating to 75 ℃, maintaining the temperature and stirring for reaction for 3 hours; after the reaction was stopped, the solvent was distilled off under reduced pressure to give a tan clear liquid product.
Adding 0.1mol of a yellow brown transparent liquid product and 0.1mol of ethyl iodide into another three-necked flask, slowly heating to 70 ℃, maintaining the temperature and stirring for reaction for 20 hours; filtering, drying, washing with petroleum ether, distilling under reduced pressure to remove solvent, and obtaining the 2, 5-di (dodecyl disulfide group) -3-ethyl-1, 3, 4-thiadiazole iodized salt which is the target product of the additive. The molecular structure of the 2, 5-bis (dodecyl disulfide) -3-ethyl-1, 3, 4-thiadiazole iodized salt is determined by nuclear magnetic resonance spectroscopy (shown in figure 2).
The 2, 5-bis (dodecyl disulfide) -3-ethyl-1, 3, 4-thiadiazole iodized salt synthesized in the third embodiment is added into the synthetic ester base oil, and the iodized salt accounts for 2.0% of the mass of the synthetic ester base oil. The SRV test result shows that when the test load is 500N, the abrasion volume of the synthesized ester base oil sample is 14.90 multiplied by 10 after the ionic liquid additive is added 6 μm 3 Reduced to 2.59X10 6 μm 3 About, the abrasion volume of the synthetic ester base oil sample is 14.90×10 after the traditional commercial antiwear additive ZDDP is added 6 μm 3 Reduced to 6.27×10 6 μm 3 Left and right.
The tribological property evaluation method (i.e., tribological property SRV test) employed in examples 1 to 3 of the present invention is as follows:
adding an ionic liquid additive product into the synthetic ester lubricating oil, and evaluating the tribological performance of the lubricating oil by adopting an Optimel-SRV IV friction and wear testing machine, wherein the friction coefficient is given by the testing machine; the surface topography of the plaque was detected using a microXAM-3D three-dimensional profiler and the wear volume was calculated using software. The test conditions were: the load is 500N, the temperature is 150 ℃, the amplitude is 1mm, the frequency is 25Hz, and the test time is 30min. The upper test ball and the lower test disc are GCr15 steel (SAE 52100, hardness is 59-61 HRC), and the diameter of the upper test ball is 10mm; the lower test disc had a diameter of 24mm and a thickness of 8.0mm. Three lubricant samples were added drop wise to the ball-and-disc contact sites prior to each test.
Table 1 wear volume of example lubricant samples
| Sample of | Synthetic ester base oils | Additive (2%) of the present invention | ZDDP(2％) |
| Example 1 | 14.36×10 6 μm 3 | 2.92×10 6 μm 3 | 6.35×10 6 μm 3 |
| Example 2 | 15.19×10 6 μm 3 | 2.76×10 6 μm 3 | 6.61×10 6 μm 3 |
| Example 3 | 14.90×10 6 μm 3 | 2.59×10 6 μm 3 | 6.27×10 6 μm 3 |
The present invention is not described in detail in part as being well known to those skilled in the art. The above examples are merely illustrative of preferred embodiments of the invention, which are not exhaustive of all details, nor are they intended to limit the invention to the particular embodiments disclosed. Various modifications and improvements of the technical scheme of the present invention will fall within the protection scope of the present invention as defined in the claims without departing from the design spirit of the present invention.
Claims (9)
1. The sulfide thiadiazole ionic liquid lubricating oil extreme pressure antiwear additive is characterized by having a structure shown in the following formula:
2. the method for preparing the additive as claimed in claim 1, comprising the steps of:
(1) Mixing 2, 5-dimercapto-1, 3, 4-thiadiazole, ethanol and dodecyl mercaptan, and stirring to obtain a mixed solution A; dropwise adding hydrogen peroxide into the mixed solution A, heating to 75-80 ℃, and maintaining the temperature to stir for reaction; after stopping the reaction, distilling under reduced pressure to remove the solvent to obtain a tan transparent liquid product;
(2) Mixing the yellow brown transparent liquid product with the ethyl iodide, heating to 70-75 ℃, maintaining the temperature and stirring for reaction; filtering, drying, washing, and distilling off the solvent under reduced pressure to obtain 2, 5-di (dodecyl disulfide group) -3-ethyl-1, 3, 4-thiadiazole iodized salt.
3. The method according to claim 2, wherein in the step (1), the mass ratio of 2, 5-dimercapto-1, 3, 4-thiadiazole, ethanol and dodecyl mercaptan is 1:5.7 to 5.9:2.6 to 2.8.
4. The method according to claim 2, wherein in the step (1), the reaction is stirred for 2 to 4 hours.
5. The method according to claim 1, wherein in the step (1), the mass ratio of the 2, 5-dimercapto-1, 3, 4-thiadiazole to the hydrogen peroxide is 1:0.7 to 0.9.
6. The process of claim 2, wherein in step (2), the molar ratio of tan clear liquid product to ethyl iodide is 1:1.0 to 1.1.
7. The method according to claim 1, wherein in the step (2), the reaction is stirred for 18 to 22 hours.
8. The use of an additive according to claim 1, wherein said additive is added to a synthetic ester lubricant.
9. The use according to claim 8, wherein the additive is added in an amount of 2% by mass of the synthetic ester lubricating oil.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4661273A (en) * | 1985-12-30 | 1987-04-28 | Mobil Oil Company | Mercapto-thiadiazole reaction products as multifunctional lubricant additives and compositions thereof |
| CN114507556A (en) * | 2022-01-14 | 2022-05-17 | 中国科学院兰州化学物理研究所 | Thiadiazole lubricating oil anti-wear additive and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4661273A (en) * | 1985-12-30 | 1987-04-28 | Mobil Oil Company | Mercapto-thiadiazole reaction products as multifunctional lubricant additives and compositions thereof |
| CN114507556A (en) * | 2022-01-14 | 2022-05-17 | 中国科学院兰州化学物理研究所 | Thiadiazole lubricating oil anti-wear additive and preparation method thereof |
Non-Patent Citations (2)
| Title |
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| CHEN, HUAN: "一些新型含羟基的二巯基噻二唑衍生物作为多功能润滑油添加剂在可生物降解锂基润滑脂中的摩擦学行为", INDUSTRIAL LUBRICATION AND TRIBOLOGY, vol. 66, no. 1, 1 January 2014 (2014-01-01), pages 51 - 61 * |
| V. S. GORBUNOV: "Immobilized Acid Catalysts in the Oxidation of Sulfur-Containing Compounds with Hydrogen Peroxide", PETROLEUM CHEMISTRY, vol. 61, no. 2021, 11 November 2021 (2021-11-11), pages 1260 - 1269, XP037646795, DOI: 10.1134/S0965544121110086 * |
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