CN115073393A - 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 68
- 239000000314 lubricant Substances 0.000 title claims abstract description 44
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 40
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 title claims abstract description 29
- 125000000623 heterocyclic group Chemical group 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- YPKOTWSAVCIFAM-UHFFFAOYSA-N [Na].CCC Chemical compound [Na].CCC YPKOTWSAVCIFAM-UHFFFAOYSA-N 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 7
- 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 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- -1 amine bromide Chemical class 0.000 claims description 5
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 239000007810 chemical reaction solvent Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 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
- 230000001681 protective effect Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 239000000956 alloy Substances 0.000 description 5
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000001050 lubricating effect Effects 0.000 description 3
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 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
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000007613 environmental effect Effects 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
- 235000010446 mineral oil Nutrition 0.000 description 2
- 239000013074 reference sample Substances 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000010959 steel Substances 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
- 150000001450 anions Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 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
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000005461 lubrication Methods 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
- 229920013639 polyalphaolefin Polymers 0.000 description 1
- 230000001360 synchronised effect Effects 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
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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
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- C07C209/86—Separation
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- 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
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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
- C10M105/56—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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- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
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- 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
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Abstract
The invention provides halogen-free heterocyclic sulfonic acid ionic liquid and application thereof as a titanium alloy lubricantThe ionic liquid has a structure shown in a general formula (I), wherein X is P element or N element, and R is 1 、R 2 、R 3 And R 4 Each independently selected from alkyl groups having 1 to 16 carbon atoms. The ionic liquid can form a firm and ordered physical adsorption protective film and a chemical reaction protective film on the surface of a titanium alloy friction pair in the friction process, and shows excellent friction reduction and wear resistance 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 performance 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 place of the metal element. Despite such abundance of titanium element, titanium alloy for industrial use was not developed for the first time until 1954. Therefore, the titanium alloy is widely applied to various industries such as aerospace, chemical engineering, sports and the like. The titanium alloy can be developed widely and rapidly, and is mainly due to the advantages of the titanium alloy material, such as: has the highest specific strength in metal materials, and has excellent performances of heat resistance, toughness, corrosion resistance, fatigue resistance and the like. However, as titanium alloys are used more and more widely, their drawbacks become increasingly revealed, such as: the hardness is low, and the adhesive wear is easy to cause; poor heat conductivity, easy occurrence of knife sticking phenomenon and the like. These inherent drawbacks have greatly limited the development and application of titanium alloys. Therefore, it becomes necessary to research and develop a lubricant for improving the tribological properties of titanium alloys.
Research shows that because titanium is active in nature, a dense oxide film is easily formed on the surface of a titanium alloy material in the air, so that a stable lubricating film is hardly formed on the surface of the titanium alloy by a plurality of liquid lubricants, particularly the untreated alloy surface. For example, mineral oil, polyalphaolefin and the like, which are traditional lubricants, have difficulty in achieving a good lubricating effect on titanium alloys. Therefore, attempts have been made to apply ionic liquids to titaniumIn alloys, it is desirable to improve the poor tribological properties of titanium alloys. Jimenez et al reported the use of imidazole-based ionic liquids as lubricants for steel/titanium friction pairs and showed that: compared with traditional mineral oil, with Cl - 、BF 4 - Or PF 6 - 、TFSI - Imidazole-based ionic liquids, which are anions, are effective in reducing the frictional wear of titanium alloys (TribolLett,2009,33(2): 111-. Li et al reported the effect of different fluorine-containing ionic liquid lubricants such as tetrafluoroborate and perfluorosulfonate on the tribological properties of TC21 titanium alloys, and the results showed that: the perfluorosulfonate ionic liquid is an excellent lubricant of TC21 titanium/Si 3N4 friction pair (J.alloys Compd.2018,743: 576-585).
However, the above ionic liquid lubricants are all halogen-containing compounds, and their use is difficult to meet the current environmental requirements. With the increasing awareness of environmental protection, the development of halogen-free environmentally friendly ionic liquid lubricants for improving the tribological properties of titanium alloys has become one of the important contents of current research in the lubrication field.
Disclosure of Invention
In view of the defects of the prior art, the first object of the present invention is to provide a halogen-free heterocyclic sulfonic acid ionic liquid, which has excellent friction reducing and wear resisting properties as a lubricant of a titanium alloy friction pair, and can significantly reduce the friction coefficient of a titanium alloy friction member and reduce the wear volume of the titanium alloy friction member in the friction process.
In order to achieve the above technical objects, the present inventors have conducted extensive experimental studies and diligent research, and finally obtained the following technical solutions: a 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 4 Each independently selected from alkyl groups having 1 to 16 carbon atoms.
Further excellenceOptionally, the halogen-free heterocyclic sulfonic acid ionic liquid is as described above, wherein X is P element or N element, R 1 、R 2 、R 3 And R 4 The alkyl groups have the same structure and are all selected from alkyl groups with 4-8 carbon atoms.
Still further preferably, the halogen-free heterocyclic sulfonic acid ionic liquid as described above, wherein X is P element or N element, R is 1 、R 2 、R 3 And R 4 The alkyl groups have the same structure and are all selected from alkyl groups with 4 or 8 carbon atoms.
In the most preferred embodiment of the present invention, the halogen-free heterocyclic sulfonic acid ionic liquid is as described above, wherein when X is P element, R is 1 、R 2 、R 3 And R 4 Are all straight-chain butyl groups; when X is an N element, R 1 、R 2 、R 3 And R 4 All are 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 by using dichloromethane after the reaction is finished, washing an extraction layer for 1-5 times by using deionized water, dissolving and filtering by using acetonitrile after evaporating the solvent under reduced pressure, evaporating the solvent under reduced pressure again, and drying to obtain a target product.
Further preferably, the halogen-free heterocyclic sulfonic acid ionic liquid is prepared by the method, wherein the molar ratio of the tetraalkyl phosphonium bromide or the tetraalkyl amine bromide to the sodium 3- (benzothiazole-2-mercapto) propane sulfonate is 1: 2-1: 3.
Further preferably, the halogen-free heterocyclic sulfonic acid ionic liquid is prepared by a method as described above, wherein the reaction solvent is one or more selected from the following: methanol, water and acetone.
Finally, the ionic liquid has excellent friction reducing and wear resisting performance as a lubricant of the titanium alloy friction pair, so that the friction coefficient of the titanium alloy friction piece can be obviously reduced, and the wear volume of the titanium alloy friction piece in the friction process is reduced. Therefore, the third purpose of the invention is to provide a new application of the halogen-free heterocyclic sulfonic acid ionic liquid as a lubricant for titanium alloy.
Compared with the commercial lubricant PAO10, the halogen-free heterocyclic sulfonic acid ionic liquid provided by the invention has the following advantages and remarkable progress:
(1) the thermal stability is ideal, the decomposition temperature of the ionic liquid with the cation of tetraalkyl phosphonium reaches 359.0 ℃, the decomposition temperature is improved by 17.1 percent compared with the thermal decomposition temperature 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 firm and ordered physical adsorption protective film and a chemical reaction protective film on the surface of a titanium alloy friction pair, thereby showing excellent antifriction and wear resistance properties.
Drawings
FIG. 1 shows two lubricants of PAO10 and the halogen-free heterocyclic sulfonic acid ionic liquid lubricant provided by the invention, namely tetra-n-butylphosphonium 3- (benzothiazole-2-mercapto) propane sodium sulfonate ionic liquid (P) 4444 ZPS) and sodium tetra-N-octylamine 3- (benzothiazole-2-mercapto) propane sulfonate ionic liquid (N) 8888 ZPS) versus temperature.
FIG. 2 shows two lubricants of PAO10 and the halogen-free heterocyclic sulfonic acid ionic liquid lubricant provided by the invention, namely tetra-n-butylphosphonium 3- (benzothiazole-2-mercapto) propane sodium sulfonate ionic liquid (P) 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, a graph of the experimentally measured friction coefficient as a function of time.
FIG. 3 shows two lubricants of PAO10 and the halogen-free heterocyclic sulfonic acid ionic liquid lubricant provided by the invention, namely tetra-n-butylphosphonium 3- (benzothiazole-2-mercapto) propane sodium sulfonate ionic liquid (P) 4444 ZPS) and sodium tetra-N-octylamine 3- (benzothiazole-2-mercapto) propane sulfonate ionic liquid (N) 8888 ZPS) wear volume as experimentally measured when used as a lubricant for a titanium alloy friction pair.
Detailed Description
In order that those skilled in the art may better understand the technical solutions of the present invention and can practice the same, the present invention will be further described with reference to the following specific examples, which should not be construed as limiting 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 tetrabutyl phosphonium bromide, taking methanol as a solvent, stirring and reacting for 24-48 hours at 60 ℃, extracting a reaction solution 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, carrying out reduced pressure distillation 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 tetraoctyl ammonium bromide, stirring and reacting for 24-48 hours in methanol at 60 ℃, extracting reaction liquid by using dichloromethane after the reaction is finished, washing an extraction layer by using water, evaporating the solvent under reduced pressure, repeating for 3 times, dissolving and filtering by using 50-100g of acetonitrile, carrying out reduced pressure distillation 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 using nuclear magnetic resonance spectroscopy (N) 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 Lubricant
To evaluate the thermal stability of the ionic liquid lubricant, the present inventors measured its thermal stability using a (DSC/DTA-TG) STA449F3 synchronous thermal analyzer.
Fig. 1 is a graph of the thermogravimetric loss of PAO10 and the 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 4444 The decomposition temperature of the ZPS is as high as more than 350 ℃, is improved by 17.1 percent compared with the thermal decomposition temperature of PAO10, and has excellent thermal stability.
Example 4: research on antifriction and wear resistance of ionic liquid lubricant
And 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-disk point contact, and the testing conditions are as follows: the load is 50N, the temperature is 25 ℃, the frequency is 25Hz, the amplitude is 1mm, and the experimental time is 30 min; in the test, the upper test ball is an AISI52100 steel ball with the diameter of phi 10 mm; the lower sample is Ti6Al4V titanium alloy with phi of 24mm and thickness of 7.9mm, and the hardness is 32-35 HRC; 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 lubricant as a titanium alloy friction pair under the conditions of 50N and 25 ℃ are respectively as follows: 0.512 and 76.564 x 10 -2 mm 3 (Table 1, FIG. 3), the change curve of the friction coefficient with time is shown in FIG. 2. As can be seen from the data in Table 1 and FIG. 3, PAO10 is used as a lubricant for titanium alloy friction pair, and is compatible with P synthesized by us 4444 ZPS、N 8888 Compared with ZPS ionic liquid lubricant, the lubricating effect is poorer.
Ionic liquid (P) 4444 ZPS) the average friction coefficient and the wear volume of the titanium alloy friction pair lubricant under the conditions of 50N and 25 ℃ are respectively as follows: 0.092 and 1.008 x 10 -2 mm 3 (Table 1, FIG. 3), the change curve of the friction coefficient with time is shown in FIG. 2. As can be seen from the data in Table 1 and FIGS. 2 and 3, the ionic liquid (P) 4444 ZPS) has obvious friction reducing and wear resisting effects when used as a lubricant of a titanium alloy friction pair, and compared with a reference PAO10, the friction coefficient is reduced by 82.0 percent, and the wear volume is reduced by 98.7 percent.
Ionic liquid (N) 8888 ZPS) as a titanium alloy friction pair lubricant under the conditions of 50N and 25 ℃, the average friction coefficient and the wear volume are respectively as follows: 0.085 and 0.712 x 10 -2 mm 3 (Table 1, FIG. 3), the change curve of the friction coefficient with time is shown in FIG. 2. As can be seen from the data in Table 1 and FIGS. 2 and 3, the ionic liquid (N) 8888 ZPS) has excellent friction reducing and wear resisting effects as a lubricant of a titanium alloy friction pair, and compared with a reference PAO10, the friction coefficient is reduced by 83.4 percent, and the wear volume is reduced by 99.1 percent.
Table 1: the PAO10 and the ionic liquid provided by the invention have the tribological performance as the titanium alloy lubricant
Lubricant agent | Average coefficient of friction | Average wear volume/10 -2 mm 3 |
Reference sample (PAO10) | 0.512 | 76.564 |
Ionic liquid (P) 4444 ZPS) | 0.092 | 1.008 |
Ionic liquid (N) 8888 ZPS) | 0.085 | 0.712 |
As can be seen from Table 1, FIG. 2 and FIG. 3, the halogen-free heterocyclic sulfonic acid ionic liquid provided by the present invention, especially sodium tetra-N-octylamine 3- (benzothiazole-2-mercapto) propane sulfonate ionic liquid (N) 8888 ZPS) is used as a lubricant of a titanium alloy friction pair, and has excellent antifriction and antiwear properties.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of protection is not limited thereto. The equivalents and modifications of the present invention which may occur to those skilled in the art are within the scope of the present invention as defined by the appended claims.
Claims (8)
2. The halogen-free heterocyclic sulfonic acid ionic liquid of claim 1, wherein R is 1 、R 2 、R 3 And R 4 The alkyl groups have the same structure and are all selected from alkyl groups with 4-8 carbon atoms.
3. According toThe halogen-free heterocyclic sulfonic acid ionic liquid of claim 2 wherein R is 1 、R 2 、R 3 And R 4 The alkyl groups have the same structure and are all selected from alkyl groups with 4 or 8 carbon atoms.
4. The halogen-free heterocyclic sulfonic acid ionic liquid of claim 3, wherein R is 1 、R 2 、R 3 And R 4 Both are linear butyl or linear octyl.
5. A process for the preparation of the halogen-free heterocyclic sulfonic acid ionic liquid of any of claims 1 to 4, characterized in that the process comprises the steps of: 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 a reaction solution with dichloromethane after the reaction is finished, washing an extraction layer with deionized water, repeating for 1-5 times after evaporating the solvent under reduced pressure, dissolving and filtering with acetonitrile, evaporating the solvent under reduced pressure again, and drying to obtain a target product.
6. The method for preparing the halogen-free heterocyclic sulfonic acid ionic liquid of claim 5, wherein the molar ratio of the tetraalkyl phosphonium bromide or the tetraalkyl amine bromide to the sodium 3- (benzothiazole-2-mercapto) propane sulfonate is 1: (2-3).
7. The method for preparing the halogen-free heterocyclic sulfonic acid ionic liquid of claim 5, wherein the reaction solvent is one or more selected from the group consisting of: methanol, water and acetone.
8. Use of the halogen-free heterocyclic sulfonic acid ionic liquid as defined in any of claims 1 to 4 as a lubricant for titanium alloys.
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