CN115073393B - Preparation of halogen-free heterocyclic sulfonic acid ionic liquid and application of halogen-free heterocyclic sulfonic acid ionic liquid as titanium alloy lubricant - Google Patents
Preparation of halogen-free heterocyclic sulfonic acid ionic liquid and application of halogen-free heterocyclic sulfonic acid ionic liquid as titanium alloy lubricant Download PDFInfo
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 67
- 239000000314 lubricant Substances 0.000 title claims abstract description 45
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 41
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 title claims abstract description 26
- 125000000623 heterocyclic group Chemical group 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- 230000001681 protective effect Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229920013639 polyalphaolefin Polymers 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- YPKOTWSAVCIFAM-UHFFFAOYSA-N [Na].CCC Chemical compound [Na].CCC YPKOTWSAVCIFAM-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005461 lubrication Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- RELCDTAIQCOHIQ-UHFFFAOYSA-N C(CCC)[P+](CCCC)(CCCC)CCCC.[Na+] Chemical compound C(CCC)[P+](CCCC)(CCCC)CCCC.[Na+] RELCDTAIQCOHIQ-UHFFFAOYSA-N 0.000 description 2
- 101000686227 Homo sapiens Ras-related protein R-Ras2 Proteins 0.000 description 2
- 102100025003 Ras-related protein R-Ras2 Human genes 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000007810 chemical reaction solvent Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- 239000002480 mineral oil Substances 0.000 description 2
- MQVMJSWYKLYFIG-UHFFFAOYSA-N propane-1-sulfonic acid;sodium Chemical compound [Na].CCCS(O)(=O)=O MQVMJSWYKLYFIG-UHFFFAOYSA-N 0.000 description 2
- 239000013074 reference sample Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- -1 tetrafluoroborate Chemical compound 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 description 1
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D277/70—Sulfur atoms
- C07D277/74—Sulfur atoms substituted by carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/86—Separation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/62—Quaternary ammonium compounds
- C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/54—Quaternary phosphonium compounds
- C07F9/5407—Acyclic saturated phosphonium compounds
-
- 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
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/56—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing nitrogen
- C10M105/58—Amines, e.g. polyalkylene polyamines, quaternary amines
- C10M105/60—Amines, e.g. polyalkylene polyamines, quaternary amines having amino groups bound to an acyclic or cycloaliphatic carbon atom
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- 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
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/72—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing sulfur, selenium or tellurium
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- 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
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/74—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing phosphorus
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- 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
- C10M2215/041—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms used as base material
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- 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
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- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/06—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds
- C10M2223/0603—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-carbon bonds used as base material
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- 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
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/20—Metal working
- C10N2040/244—Metal working of specific metals
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Abstract
The invention provides a halogen-free heterocyclic sulfonic acid ionic liquid and application thereof as a titanium alloy lubricant, wherein the ionic liquid has a structure shown in a general formula (I), X is P element or N element, R 1 、R 2 、R 3 And R is 4 Independently selected from alkyl groups having 1 to 16 carbon atoms. The ionic liquid can form a physical adsorption protective film and a chemical reaction protective film with firm sequences on the surface of a titanium alloy friction pair in the friction process, and shows excellent antifriction and antiwear performance when being used as a titanium alloy lubricant.
Description
Technical Field
The invention belongs to the technical field of lubricants, and particularly relates to an ionic liquid lubricant, in particular to a halogen-free heterocyclic sulfonic acid ionic liquid lubricant with excellent tribological properties on titanium alloy, and a preparation method and application thereof.
Background
It is known that the titanium element is widely distributed in the earth crust and is located in the tenth position of the metal element. Despite such abundance of titanium, titanium alloys were not developed for the first time in 1954 for use in industry. From this point on, titanium alloys are widely used in various industries such as aerospace, chemical industry, sports, etc. Titanium alloys have been developed so widely and rapidly, mainly due to the many advantages of titanium alloy materials, such as: has the highest specific strength in the metal material and also has excellent performances of heat resistance, toughness, corrosion resistance, fatigue resistance and the like. However, as titanium alloys are increasingly used, defects thereof are gradually exposed, such as: the hardness is low, and the adhesive wear is easy to cause; poor heat conduction performance, easy occurrence of cutter sticking phenomenon, etc. These inherent defects have greatly limited the development and use of titanium alloys. Therefore, research and development of lubricants that improve the tribological properties of titanium alloys have become necessary.
Studies have shown that titanium alloy materials are prone to forming a dense oxide film on the surface in air due to the active nature of titanium, resulting in many liquid lubricants that are difficult to form a stable lubricating film on titanium alloy surfaces, particularly untreated alloy surfaces. For example, conventional lubricant mineral oils, polyalphaolefins, and the like have difficulty in achieving good lubrication effects on titanium alloys. Therefore, attempts have been made to apply ionic liquids to titanium alloys, and it is desirable to improve the poor tribological properties of titanium alloys. Jimenez et al report the use of imidazole-based ionic liquids as lubricants for steel/titanium friction pairs, indicating that: in comparison with conventional mineral oils, in Cl - 、BF 4 - Or PF (physical pattern) 6 - 、TFSI - The imidazole ionic liquid which is anions can effectively reduce the friction and abrasion of titanium alloy (TribolLett, 2009,33 (2): 111-126). Li et al report the effect of tetrafluoroborate and perfluorosulfonate and other different fluorine-containing ionic liquid lubricants on the tribological properties of TC21 titanium alloys, and the results indicate that: the perfluorosulfonate ionic liquid is an excellent lubricant for TC21 titanium/Si 3N4 friction pairs (J.Allys Compd.2018, 743:576-585).
However, the ionic liquid lubricants are all halogen-containing compounds, and the use thereof is difficult to meet the current environmental protection requirements. Along with the continuous enhancement of human environmental awareness, the development of halogen-free green environment-friendly ionic liquid lubricants for improving the tribological properties of titanium alloys has become one of the important contents of the current research in the lubrication field.
Disclosure of Invention
In view of the shortcomings of the prior art, the first object of the invention is to provide a halogen-free heterocyclic sulfonic acid ionic liquid which has excellent antifriction and antiwear properties as a lubricant of a titanium alloy friction pair, and can remarkably reduce the friction coefficient of a titanium alloy friction piece and reduce the abrasion volume of the titanium alloy friction piece in the friction process.
In order to achieve the technical purpose, the inventor has conducted extensive experimental research and diligent research, and finally obtains the following technical scheme: the halogen-free heterocyclic sulfonic acid ionic liquid has a structure shown in the following general formula (I):
wherein X is P element or N element, R 1 、R 2 、R 3 And R is 4 Independently selected from alkyl groups having 1 to 16 carbon atoms.
Further preferred is a halogen-free heterocyclic sulfonic acid ionic liquid as described above, wherein X is a P element or an N element, R 1 、R 2 、R 3 And R is 4 Is an alkyl group having the same structure and is selected from alkyl groups having 4 to 8 carbon atoms.
Still further preferablyThe halogen-free heterocyclic sulfonic acid ionic liquid as described above, wherein X is a P element or an N element, R 1 、R 2 、R 3 And R is 4 Are structurally identical alkyl groups and are each selected from alkyl groups having 4 or 8 carbon atoms.
In a most preferred embodiment of the present invention, a halogen-free heterocyclic sulfonic acid ionic liquid as described above, wherein when X is the element P, R 1 、R 2 、R 3 And R is 4 Are straight-chain butyl groups; when X is N element, R 1 、R 2 、R 3 And R is 4 Are all straight-chain octyl groups.
In addition, a second object of the present invention is to provide a method for preparing the halogen-free heterocyclic sulfonic acid ionic liquid, which comprises the following steps: mixing tetraalkyl phosphonium bromide or tetraalkyl amine bromide and 3- (benzothiazole-2-mercapto) propane sodium sulfonate in a reaction solvent, stirring and reacting for 24-48 hours at 58-62 ℃, extracting reaction liquid with dichloromethane after the reaction is finished, washing an extraction layer with deionized water for 1-5 times, decompressing and steaming out the solvent, dissolving and filtering with acetonitrile, decompressing and steaming out the solvent again, and drying to obtain a target product.
Further preferred is a process for the preparation of a halogen-free heterocyclic sulfonic acid ionic liquid as described above, wherein the molar ratio of tetraalkylphosphonium bromide or tetraalkylphosphonium bromide to sodium 3- (benzothiazole-2-mercapto) propane sulfonate is between 1:2 and 1:3.
Further preferably, the preparation method of the halogen-free heterocyclic sulfonic acid ionic liquid as described above, wherein the reaction solvent is selected from one or more than two of the following: methanol, water and acetone.
Finally, as the ionic liquid is used as the lubricant of the titanium alloy friction pair, the friction coefficient of the titanium alloy friction piece can be obviously reduced, and the abrasion volume of the titanium alloy friction piece in the friction process can be reduced. Accordingly, a third object of the present invention is to provide a novel use of the halogen-free heterocyclic sulfonic acid ionic liquid as a lubricant for titanium alloy.
Compared with a commercial lubricant PAO10, the halogen-free heterocyclic sulfonic acid ionic liquid provided by the invention has the following advantages and remarkable progress:
(1) The ionic liquid with the cation of tetraalkylphosphonium has ideal thermal stability, the decomposition temperature of the ionic liquid is up to 359.0 ℃, and the thermal decomposition temperature of the ionic liquid is improved by 17.1% compared with that of PAO10, and the ionic liquid has excellent thermal stability.
(2) In the friction process, the ionic liquid prepared by the invention can form a physical adsorption protective film and a chemical reaction protective film with firm sequence on the surface of a titanium alloy friction pair, thereby showing excellent antifriction and antiwear properties.
Drawings
FIG. 1 shows the PAO10 and two lubricants of the halogen-free heterocyclic sulfonic acid ionic liquid lubricant of the invention, tetra-n-butyl phosphonium 3- (benzothiazole-2-mercapto) propane sulfonic acid sodium ionic liquid (P) 4444 ZPS) and sodium tetra-N-octylamine 3- (benzothiazole-2-mercapto) propane sulfonate ionic liquid (N) 8888 ZPS) as a function of temperature.
FIG. 2 shows the PAO10 and the sodium tetra-n-butylphosphonium 3- (benzothiazole-2-mercapto) propane sulfonate ionic liquid (P) as two lubricants in the halogen-free heterocyclic sulfonic acid ionic liquid lubricant provided by the invention 4444 ZPS) and sodium tetra-N-octylamine 3- (benzothiazole-2-mercapto) propane sulfonate ionic liquid (N) 8888 ZPS) as a lubricant for a titanium alloy friction pair.
FIG. 3 shows the PAO10 and the sodium tetra-n-butylphosphonium 3- (benzothiazole-2-mercapto) propane sulfonate ionic liquid (P) as two lubricants in the halogen-free heterocyclic sulfonic acid ionic liquid lubricant provided by the invention 4444 ZPS) and sodium tetra-N-octylamine 3- (benzothiazole-2-mercapto) propane sulfonate ionic liquid (N) 8888 ZPS) as lubricant for titanium alloy friction pairs.
Detailed Description
In order that those skilled in the art will better understand the technical solution of the present invention and implement it, the present invention will be further described with reference to specific examples, but the examples are not intended to limit the scope of the present invention.
Example 1: ionic liquid lubricant P 4444 Preparation of ZPS
Mixing 50mmol of 3- (benzothiazole-2-mercapto) propane sodium sulfonate and 25mmol of tetrabutylphosphonium bromide, stirring at 60 ℃ for reaction for 24-48 hours, extracting the reaction liquid with dichloromethane after the reaction is finished, washing an extraction layer with water, evaporating the solvent under reduced pressure, repeating for 3 times, dissolving and filtering with 50-100g of acetonitrile, distilling under reduced pressure again, and drying the product in a vacuum drying oven for 12-24 hours to obtain the halogen-free ionic liquid lubricant (P) 4444 ZPS)。
Characterization of ionic liquids (P) using nuclear magnetic resonance spectroscopy 4444 ZPS), the specific data are as follows:
P 4444 ZPS： 1 H NMR(400MHz,CDCl 3 )δ(ppm)7.74-7.65(dd,2H),7.33–7.16(dd,2H),3.46(m,2H),2.9–2.86(m,2H),2.29(m,2H),2.25–2.16(m,8H),1.46-1.40(m,16H),0.92–0.84(m,12H). 13 C NMR(100MHz,CDCl 3 )δ(ppm)167.40,153.43,135.21,126.00,124.13,121.44,120.97,50.42,33.03,25.70,24.10,23.95,23.82,23.77,18.98,18.51,13.54。
example 2: ionic liquid lubricant N 8888 Preparation of ZPS
Mixing 50mmol of 3- (benzothiazole-2-mercapto) propane sodium sulfonate and 25mmol of tetraoctylammonium bromide, stirring in methanol at 60 ℃ for reaction for 24-48 hours, extracting the reaction liquid with dichloromethane after the reaction is finished, washing an extraction layer with water, evaporating the solvent under reduced pressure, repeating for 3 times, dissolving and filtering with 50-100g of acetonitrile, distilling under reduced pressure again, and drying the product in a vacuum drying oven for 12-24 hours to obtain the halogen-free ionic liquid lubricant (N) 8888 ZPS)。
Characterization of ionic liquids (N) using Nuclear magnetic resonance Spectrometry 8888 ZPS), the specific data are as follows:
N 8888 ZPS: 1 H NMR(400MHz,CDCl3)δ(ppm)7.61–7.40(m,2H),7.20–6.84(m,2H),3.40–3.23(m,2H),3.11–2.92(m,8H),2.78–2.60(m,2H),2.19–2.01(m,2H),1.44–1.28(m,8H),1.14–0.93(m,40H),0.68–0.54(m,12H). 13 C NMR(100MHz,CDCl3)δ(ppm)166.54,152.70,134.44,125.28,123.45,120.65,120.24,58.07,49.66,32.33,30.97,28.38,28.27,25.65,25.04,21.90,21.28,13.39。
example 3: stability study of ionic liquid lubricants
To evaluate the thermal stability of the ionic liquid lubricant, the present inventors measured its thermal stability using a (DSC/DTA-TG) STA449F3 simultaneous thermal analyzer.
Fig. 1 is a graph showing the thermal weight loss of PAO10 and halogen-free heterocyclic sulfonic acid ionic liquid lubricants prepared in example 1 and example 2. As can be seen from FIG. 1, P 4444 ZPS and N 8888 ZPS has good thermal stability. Wherein P is 4444 The decomposition temperature of ZPS is up to above 350 ℃, which is improved by 17.1% compared with the thermal decomposition temperature of PAO10, and the thermal stability is excellent.
Example 4: antifriction and antiwear performance research of ionic liquid lubricant
The frictional wear performance of the ionic liquid is evaluated by adopting an SRV-V micro-vibration frictional wear testing machine. The friction pair contact mode of the SRV-V micro-vibration friction wear testing machine is ball-checking contact, and the testing conditions are as follows: load 50N, temperature 25 ℃, frequency 25Hz, amplitude 1mm, experiment time 30min; the upper test ball in the test is AISI52100 steel ball with the diameter of phi 10 mm; the lower sample is Ti6Al4V titanium alloy with phi 24mm and thickness of 7.9mm, and the hardness is 32-35HRC; the wear volume of the lower sample was measured by BRUKER-NPFLEX three-dimensional optical profiler.
The invention adopts PAO10 as a reference sample, and the average friction coefficient and the wear volume of the titanium alloy friction pair lubricant at 50N and 25 ℃ are respectively as follows: 0.512 and 76.564 x 10 -2 mm 3 (Table 1, FIG. 3) whose coefficient of friction varies with time is shown in FIG. 2. As can be seen from the data in Table 1 and FIG. 3, PAO10 was used as a lubricant for the titanium alloy friction pair, and was synthesized with P 4444 ZPS、N 8888 ZPS ionic liquid lubricants have a poorer lubrication effect than others.
Ionic liquids (P) 4444 ZPS) as a titanium alloy friction pair lubricant at 50N,25 ℃ the average coefficient of friction and wear volume were respectively: 0.092 and 1.008 x 10 -2 mm 3 (Table 1, FIG. 3) whose coefficient of friction varies with time is shown in FIG. 2. From table 1 data and graphs2. As can be seen in fig. 3, the ionic liquid (P 4444 ZPS) as a lubricant of the titanium alloy friction pair, the friction coefficient is reduced by 82.0% and the wear volume is reduced by 98.7% compared with a reference PAO 10.
Ionic liquid (N) 8888 ZPS) as a titanium alloy friction pair lubricant at 50N,25 ℃ the average coefficient of friction and wear volume were respectively: 0.085 and 0.712 x 10 -2 mm 3 (Table 1, FIG. 3) whose coefficient of friction varies with time is shown in FIG. 2. As can be seen from the data in table 1 and fig. 2 and 3, the ionic liquid (N 8888 ZPS) as a lubricant for a titanium alloy friction pair, has excellent antifriction and antiwear effects, and has a friction coefficient reduced by 83.4% and a wear volume reduced by 99.1% as compared with a reference PAO 10.
Table 1: tribological properties of PAO10 and ionic liquid provided by the invention as titanium alloy lubricant
| Lubricant | Average coefficient of friction | Average wear volume/10 -2 mm 3 |
| Reference sample (PAO 10) | 0.512 | 76.564 |
| Ionic liquids (P) 4444 ZPS) | 0.092 | 1.008 |
| Ionic liquid (N) 8888 ZPS) | 0.085 | 0.712 |
As can be seen from tables 1, 2 and 3, the halogen-free heterocyclic sulfonic acid ionic liquid provided by the invention, in particular to tetra-N-octylamine 3- (benzothiazole-2-mercapto) propane sulfonic acid sodium ionic liquid (N) 8888 ZPS) as a lubricant for titanium alloy friction pairs, has excellent antifriction and antiwear properties.
The above-described embodiments are merely preferred embodiments for fully explaining the present invention, and the scope of protection is not limited thereto. Equivalent substitutions and modifications are intended to be within the scope of the present invention, as will be apparent to those skilled in the art based upon the present disclosure.
Claims (5)
1. The halogen-free heterocyclic sulfonic acid ionic liquid has a structure shown in the following general formula (I):
；
（Ⅰ）
wherein X is P element or N element, R 1 、R 2 、R 3 And R is 4 Independently selected from alkyl groups having 1 to 16 carbon atoms.
2. The halogen-free heterocyclic sulfonic acid ionic liquid as described in claim 1, wherein R 1 、R 2 、R 3 And R is 4 Is an alkyl group of the same structure and is selected from alkyl groups with 4-8 carbon atoms.
3. The halogen-free heterocyclic sulfonic acid ionic liquid as described in claim 2, wherein R 1 、R 2 、R 3 And R is 4 Are structurally identical alkyl groups and are each selected from alkyl groups having 4 or 8 carbon atoms.
4. A halogen-free heterocyclic sulfonic acid ionic liquid as described in claim 3, wherein R 1 、R 2 、R 3 And R is 4 Are both straight-chain butyl or straight-chain octyl.
5. Use of the halogen-free heterocyclic sulfonic acid ionic liquid as described in any one of claims 1-4 as a lubricant for titanium alloys.
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| CN109651434A (en) * | 2019-01-02 | 2019-04-19 | 宝鸡文理学院 | A kind of titanium alloy ion liquid lubricant and its preparation method and application |
| CN113549108A (en) * | 2021-08-25 | 2021-10-26 | 宝鸡文理学院 | Preparation of halogen-free quaternary phosphonium alkylbenzene sulfonic acid ionic liquid and application of ionic liquid as titanium alloy lubricant |
| CN115555514A (en) * | 2022-10-26 | 2023-01-03 | 柳晶科技集团股份有限公司 | Environment-friendly high-temperature-resistant precoated sand and preparation process thereof |
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| CN109651434A (en) * | 2019-01-02 | 2019-04-19 | 宝鸡文理学院 | A kind of titanium alloy ion liquid lubricant and its preparation method and application |
| CN113549108A (en) * | 2021-08-25 | 2021-10-26 | 宝鸡文理学院 | Preparation of halogen-free quaternary phosphonium alkylbenzene sulfonic acid ionic liquid and application of ionic liquid as titanium alloy lubricant |
| CN115555514A (en) * | 2022-10-26 | 2023-01-03 | 柳晶科技集团股份有限公司 | Environment-friendly high-temperature-resistant precoated sand and preparation process thereof |
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