CN111116480A - Bilateral asymmetric alkyl imidazole ionic liquid, and preparation method and application thereof - Google Patents
Bilateral asymmetric alkyl imidazole ionic liquid, and preparation method and application thereof Download PDFInfo
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- CN111116480A CN111116480A CN201811294420.XA CN201811294420A CN111116480A CN 111116480 A CN111116480 A CN 111116480A CN 201811294420 A CN201811294420 A CN 201811294420A CN 111116480 A CN111116480 A CN 111116480A
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- ionic liquid
- alkyl imidazole
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title claims abstract description 225
- -1 alkyl imidazole Chemical compound 0.000 title claims abstract description 90
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 77
- 230000002146 bilateral effect Effects 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 150000001450 anions Chemical group 0.000 claims abstract description 15
- 125000000858 thiocyanato group Chemical group *SC#N 0.000 claims abstract description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-M Trifluoroacetate Chemical compound [O-]C(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-M 0.000 claims abstract description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 238000001035 drying Methods 0.000 claims description 21
- 238000005342 ion exchange Methods 0.000 claims description 16
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 claims description 14
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 claims description 14
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- 150000001449 anionic compounds Chemical class 0.000 claims description 9
- 239000002199 base oil Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 8
- 239000010687 lubricating oil Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 7
- 239000003638 chemical reducing agent Substances 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 125000000129 anionic group Chemical group 0.000 claims description 2
- 239000003831 antifriction material Substances 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- 238000000605 extraction Methods 0.000 claims description 2
- 238000005292 vacuum distillation Methods 0.000 claims description 2
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims 1
- 238000005119 centrifugation Methods 0.000 claims 1
- 229960001701 chloroform Drugs 0.000 claims 1
- 238000010908 decantation Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- 239000000654 additive Substances 0.000 abstract description 12
- 230000001050 lubricating effect Effects 0.000 abstract description 12
- 230000000996 additive effect Effects 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 230000008859 change Effects 0.000 abstract description 5
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- 239000000178 monomer Substances 0.000 abstract description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 54
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 37
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 36
- 239000002904 solvent Substances 0.000 description 31
- 239000012071 phase Substances 0.000 description 29
- 239000008367 deionised water Substances 0.000 description 20
- 229910021641 deionized water Inorganic materials 0.000 description 20
- 239000012074 organic phase Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 14
- 238000005406 washing Methods 0.000 description 12
- 239000000460 chlorine Substances 0.000 description 11
- 239000012300 argon atmosphere Substances 0.000 description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 230000007935 neutral effect Effects 0.000 description 6
- 238000005299 abrasion Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 229910001961 silver nitrate Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000004803 Di-2ethylhexylphthalate Substances 0.000 description 4
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 125000002883 imidazolyl group Chemical group 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000003879 lubricant additive Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 239000005909 Kieselgur Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000002783 friction material Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000003003 phosphines Chemical group 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- UYCAUPASBSROMS-AWQJXPNKSA-M sodium;2,2,2-trifluoroacetate Chemical compound [Na+].[O-][13C](=O)[13C](F)(F)F UYCAUPASBSROMS-AWQJXPNKSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
-
- 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
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/38—Heterocyclic nitrogen compounds
- C10M133/44—Five-membered ring containing nitrogen and carbon only
- C10M133/46—Imidazoles
-
- 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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/1033—Polyethers, i.e. containing di- or higher polyoxyalkylene groups 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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
- C10M2215/224—Imidazoles
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- 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 bilateral asymmetric alkyl imidazole ionic liquid, and a preparation method and application thereof. The bilateral asymmetric alkyl imidazole ionic liquid has the following structural formula:
wherein, X‑Including bis (2-ethylhexyl) phosphate anions, bis (trifluoromethanesulfonimide) anions, hexafluorophosphate, thiocyanato, trifluoroacetate or dicyanamide. The invention synthesizes a series of bilateral asymmetric alkyl imidazole ionic liquids with novel structures from imidazole monomers, and enriches the types of the imidazole ionic liquids; at the same time, the user can select the desired position,the bilateral asymmetric alkyl imidazole ionic liquid has obvious antifriction and antiwear effects as a lubricating additive, can regulate and control the physical state change, solubility, thermal stability, antifriction and antiwear performances and the like by regulating the anion structure, and has wide application prospect.
Description
Technical Field
The invention relates to an imidazole ionic liquid, in particular to a bilateral asymmetric alkyl imidazole ionic liquid, a preparation method thereof and application of the bilateral asymmetric alkyl imidazole ionic liquid in preparation of an anti-wear friction reducer and lubricating oil, belonging to the technical field of preparation of lubricating materials.
Background
According to incomplete statistics, energy loss of about 1/3 worldwide is caused by friction and abrasion, and about 60% of failures of mechanical parts are caused by abrasion, wherein the loss of developed countries caused by friction and abrasion accounts for 5% -7% of GDP, and even China causes the loss of GDP to be as high as about 10% -20%. Therefore, it is highly desirable to improve the friction-reducing and wear-resisting properties of friction materials. The addition of lubricating oil during the operation of a machine is one of the most common and effective methods to slow wear, reduce friction, and increase the life of the machine parts. In order to improve the friction-reducing and anti-wear properties of lubricating oil, a proper amount of lubricating additive is usually required to be added. However, the conventional additives generally contain metal ions of zinc and molybdenum and active elements of chlorine, sulfur or phosphorus, and are harmful to the environment, and the application of the conventional additives is increasingly limited. There is therefore a need to develop new highly effective lubricant additives.
An ionic liquid is an organic liquid substance consisting of anions and cations and being liquid at or near room temperature. The lubricating oil has the characteristics of low melting point, high thermal stability, non-volatility, non-flammability, non-explosion and the like, and is used as a lubricating agent or a friction-reducing antiwear agent in recent years. When the lubricating additive is used as a lubricating additive, the lubricating additive has negative charges, and can be easily combined with positive charge points generated on a friction pair in the lubricating process to form a stable and ordered transition state, and the transition state can keep a certain thickness, thereby playing a plurality of roles of resisting wear, reducing friction and the like.
The ionic liquid has various types, different combinations of cations and anions are changed, different ionic liquids can be designed and synthesized, and the structure adjustability is realized. The existing ionic liquids mainly comprise imidazoles, pyridines and quaternary phosphines, wherein imidazole cations are widely researched due to good thermal stability. However, the existing imidazole ionic liquid also has the defects of lacking in species, multiple synthesis steps, complex separation and purification, low yield and the like. For example, the 1-methyl-3 alkyl imidazole disalicylic acid prepared by Zhang et al (advanced chemical science, 2017,38(04): 598) 605.) chelates boron ionic liquids, but has poor anti-wear performance.
Disclosure of Invention
The invention mainly aims to provide a novel bilateral asymmetric alkyl imidazole ionic liquid, a preparation method and application thereof, so as to improve the friction performance of the imidazole ionic liquid and overcome the defects of the prior art.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides bilateral asymmetric alkyl imidazole ionic liquid, which has the following structural formula:
wherein, X-Including bis (2-ethylhexyl) phosphate anions, bis (trifluoromethanesulfonimide) anions, hexafluorophosphate, thiocyanato, trifluoroacetate or dicyanamide.
The embodiment of the invention also provides a preparation method of the bilateral asymmetric alkyl imidazole ionic liquid, which comprises the following steps:
uniformly mixing imidazole and 1-bromooctane, and carrying out a first reaction at 20-40 ℃ for more than 6h to obtain a C8 alkyl imidazole precursor;
uniformly mixing the C8 alkyl imidazole precursor and bromohexane, and carrying out a second reaction at a temperature of more than 60 ℃ for more than 30h to obtain imidazole cations;
and carrying out ion exchange reaction on the imidazole cation and an anionic compound to obtain the bilateral asymmetric alkyl imidazole ionic liquid.
The embodiment of the invention also provides the bilateral asymmetric alkyl imidazole ionic liquid prepared by the method.
The embodiment of the invention also provides the application of the bilateral asymmetric alkyl imidazole ionic liquid as an anti-wear and anti-friction agent.
The embodiment of the invention also provides a bilateral asymmetric alkyl imidazole ionic liquid anti-wear friction reducer, which comprises the bilateral asymmetric alkyl imidazole ionic liquid.
For example, in some embodiments, the present invention also provides a lubricating oil composition comprising the foregoing bilaterally asymmetric alkyl imidazole ionic liquid and a base oil.
Compared with the prior art, the invention has the advantages that:
1) the invention synthesizes a series of bilateral asymmetric alkyl imidazole ionic liquids with novel structures from imidazole monomers, and enriches the types of the imidazole ionic liquids;
2) the bilateral asymmetric alkyl imidazole ionic liquid has obvious antifriction and antiwear effects as a lubricating additive, can regulate and control the physical state change, solubility, thermal stability, antifriction and antiwear performances and the like by regulating the anion structure, and has wide application prospect;
3) the bilateral asymmetric alkyl imidazole ionic liquid as a lubricating additive has better wear resistance than 1-methyl-3 alkyl imidazole disalicylic acid chelating boron ionic liquid.
Drawings
FIG. 1 is a graph showing the test results of the wear-reducing wear-resisting agent of bilateral asymmetric alkyl imidazole ionic liquid obtained in examples 1-3 at a concentration of 1% and the average friction coefficient.
Detailed Description
As described above, in view of the defects in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide a technical solution of the present invention, which mainly utilizes the designability of the ionic liquid structure to prepare a series of novel imidazole ionic liquids with different anions, so as to adjust the tribological properties of the ionic liquids as lubricant additives. The technical solution, its implementation and principles, etc. will be further explained as follows.
One aspect of an embodiment of the present invention provides a bilateral asymmetric alkyl imidazole ionic liquid, in which one side of an imidazole ring of the ionic liquid is connected with a linear alkane with a carbon chain length of 6, and the other side of the imidazole ring of the ionic liquid is connected with a linear alkane with a carbon chain length of 8.
The carbon chain length of the alkyl imidazole cation has an influence on the friction performance of the ionic liquid, and researches show that the long carbon chain is degraded in the friction process and participates in the formation of a lubricating film, and the long alkyl chain is beneficial to improving the friction performance of the ionic liquid. And the bilateral asymmetric alkyl long-chain imidazole cation, namely one side of the imidazole ring is connected with straight-chain alkane with the carbon chain length of 6, and the other side of the imidazole ring is connected with straight-chain alkane with the carbon chain length of 8, has a novel structure, has a proper long chain and has friction lubrication potential. In order to enable the ionic liquid to have better friction effect, anions containing active friction elements such as S, P, N are selectively introduced. The bilateral asymmetric alkyl imidazole ionic liquid prepared by the invention has better antiwear performance (the abrasion spot diameter is reduced to be > 13 percent) with less addition amount.
Specifically, the bilateral asymmetric alkyl imidazole ionic liquid has the following structural formula:
wherein, X-Including but not limited to the bis (2-ethylhexyl) phosphate anion ([ DEHP)]-) Bis (trifluoromethanesulfonylimide) anion ([ NTf)2]-) Hexafluorophosphate ([ PF ]6]-) Thiocyanato ([ SCN ]]-) Trifluoroacetic acid ([ CF ]3CO2]-) Or dicyanamide ([ N (CN))2]-)。
The bilateral asymmetric alkyl imidazole ionic liquid provided by the invention is liquid or solid at room temperature, and can be well dissolved in polar base oil.
Furthermore, the bilateral asymmetric alkyl imidazole ionic liquid oil sample can be stored at room temperature for more than half a year without precipitation.
In another aspect of the embodiments of the present invention, a preparation method of a bilateral asymmetric alkylimidazole ionic liquid is provided, which includes:
uniformly mixing imidazole and 1-bromooctane, and carrying out a first reaction at 20-40 ℃ for more than 6h to obtain a C8 alkyl imidazole precursor;
uniformly mixing the C8 alkyl imidazole precursor and bromohexane, and carrying out a second reaction at a temperature of more than 60 ℃ for more than 30h to obtain imidazole cations;
and carrying out ion exchange reaction on the imidazole cation and an anionic compound to obtain the bilateral asymmetric alkyl imidazole ionic liquid.
In some embodiments, the preparation method specifically comprises: starting from an imidazole monomer, mixing imidazole and 1-bromooctane for a first-stage reaction, then removing possible residual unreacted substances and impurities, adding bromohexane for a second-stage reaction, obtaining target imidazole cations through treatment, finally performing ion exchange reaction with anionic compounds, and performing post-treatment with an organic extractant and the like to obtain the bilateral asymmetric alkyl imidazole ionic liquid.
In some preferred embodiments, the preparation method may comprise: reacting imidazole and 1-bromooctane at 20-40 ℃ for 6-14 h, performing post-treatment to obtain a C8 alkyl imidazole precursor, adding bromohexane, performing condensation reflux at 60-80 ℃ for 30-50 h, performing treatment to obtain target imidazole cation, performing ion exchange reaction with an anionic compound, and performing post-treatment by using an organic extractant, vacuum drying and the like to obtain a target crude product. And finally, drying the crude product at a constant temperature of 20-80 ℃ for 6-12 hours under a reduced pressure condition, thus obtaining the target product bilateral asymmetric alkyl imidazole ionic liquid.
For example, a more typical embodiment of the present invention is a synthetic route for a bilaterally asymmetric alkyl imidazole ionic liquid according to the following formula:
for example, in a more typical embodiment, the preparation method may include: and stirring and reacting metered imidazole and 1-bromooctane for more than 6 hours at the temperature of 20-40 ℃, and performing post-treatment to obtain a C8 alkyl imidazole precursor. And (3) condensing and refluxing metered precursors and bromohexane at the temperature of more than 60 ℃ for more than 30h, and treating to obtain the target imidazole cation. And finally, adding a metered anionic compound into the imidazole cation solution, performing ion exchange in a deionized water solution at room temperature, and performing post-treatment by using an organic extractant and the like to obtain a target crude product. And finally, drying the crude product at a constant temperature of 20-80 ℃ for 6-12 hours under a reduced pressure condition, thus obtaining the target product.
Further, the molar ratio of the imidazole to the 1-bromooctane is 1: 0.9-1: 1.1.
further, the molar ratio of the C8 alkyl imidazole precursor to bromohexane is 1: 0.9-1: 1.1.
further, the temperature of the ion exchange reaction is 20-40 ℃, and the time is 2-4 hours.
In some embodiments, the anionic compound comprises an anionic salt, and more preferably, the anionic compound is an anion with bis (2-ethylhexyl) phosphate ([ DEHP)]-) Bis (trifluoromethanesulfonylimide) anion ([ NTf)2]-) Hexafluorophosphate ([ PF ]6]-) Thiocyanato ([ SCN ]]-) Trifluoroacetic acid ([ CF ]3CO2]-) Or dicyanamide ([ N (CN))2]-) Salt compounds, but are not limited thereto.
In some embodiments, after the ion exchange reaction is complete, the resulting reaction system is worked up to obtain a crude product.
Further, the post-treatment comprises an extraction treatment with an organic extractant.
Preferably, the organic extractant is any one or a combination of two or more of ethyl acetate, dichloromethane, chloroform, n-hexane, heptane, toluene and acetone, but is not limited thereto.
In the preparation method of the present invention, after the reaction in each stage is completed, unreacted raw materials are removed, and general methods include, but are not limited to: filtering, centrifuging, decanting, etc. to separate unreacted solid material and impurities from the desired product phase.
Further, the filtration may use a filter aid such as diatomaceous earth to improve separation efficiency.
Further, the post-treatment comprises removing water and solvent from the obtained reaction product, typically by atmospheric distillation and/or vacuum distillation.
In another aspect of the embodiments of the present invention, there is also provided a bilateral asymmetric alkyl imidazole ionic liquid prepared by the foregoing method.
In another aspect of the embodiment of the invention, the application of the bilateral asymmetric alkyl imidazole ionic liquid as an anti-wear friction reducer is also provided.
Correspondingly, the embodiment of the invention also provides a bilateral asymmetric alkyl imidazole ionic liquid antiwear friction reducer, which comprises the bilateral asymmetric alkyl imidazole ionic liquid.
For example, the bilateral asymmetric alkyl imidazole ionic liquid friction reducing antiwear agent is added to polar base oil.
For example, in some embodiments, the present invention also provides a lubricating oil composition comprising the foregoing bilateral asymmetric alkyl imidazole ionic liquid friction reducing antiwear agent and a base oil.
For example, in some embodiments, the bilateral asymmetric alkyl imidazole ionic liquid friction reducing antiwear agent may be dissolved in a polyethylene glycol (PEG) base oil.
In conclusion, a series of bilateral asymmetric alkyl imidazole ionic liquids with novel structures are synthesized from imidazole monomers, so that the types of the imidazole ionic liquids are enriched; meanwhile, the bilateral asymmetric alkyl imidazole ionic liquid obtained by the invention has obvious antifriction and antiwear effects as a lubricating additive, and the physical state change, solubility, thermal stability, antifriction and antiwear performances and the like of the ionic liquid can be regulated and controlled by regulating the anion structure of the ionic liquid.
The technical scheme of the invention is further explained in detail by a plurality of embodiments and the accompanying drawings. However, the examples are chosen only for the purpose of illustrating the invention and are not to be construed as limiting the scope of the invention.
The following examples relate to the preparation of bilateral asymmetric alkyl imidazole ionic liquid friction reducing antiwear agents, wherein the various reaction participants and process conditions are typical examples, but through a great deal of experimental verification by the inventor, other types of reaction participants and other process conditions listed above are applicable and can achieve the technical effects claimed by the invention. In addition, "%" in the following examples is "wt%" unless otherwise specified.
Example 1
The first stage is as follows: 2.72g (IM, 0.04mol) of imidazole and 4.49g (KOH, 0.08mol) of potassium hydroxide were weighed into a 250ml three-necked flask, 50ml of acetonitrile was added thereto, and the mixture was stirred under argon atmosphere at 40 ℃ for 2 hours, and then 7.92g (0.041mol) of weighed 1-bromooctane was slowly added thereto and reacted for 6 hours. After the reaction is finished, the reaction product is filtered and CH is used2Cl2The filtrate was washed to remove most of the solvent using a rotary evaporator. The resulting yellow liquid was then further dissolved in CH2Cl2Washing solvent with deionized water in separating funnel, discarding water phase (removing alkaline substances), repeating for several times until water phase is neutral, adding anhydrous sodium sulfate into organic phase for dewatering, filtering, removing solvent with rotary evaporator, and drying in vacuum oven at 60 deg.C for 6 hr to obtain C8IM。
And a second stage: weighing C8IM 5.40g (0.03mol) and bromohexane 5.12g (0.031mol) in a 250ml three-necked flask, adding 50ml acetonitrile, refluxing at 80 deg.C under argon atmosphere for 30h, removing acetonitrile solvent with a rotary evaporator, adding ethyl acetate, stirring for 30min, standing, separating phases,discarding ethyl acetate phase (except raw material), repeating the above steps for several times, removing ethyl acetate with rotary evaporator, and drying in vacuum oven at 60 deg.C for 3 hr to obtain C8IMC6-Br。
Ion exchange stage: 7.09g (HDEHP, 0.022mol) of bis (2-ethylhexyl) phosphate was weighed into a round-bottomed flask, and 1.60g (NaOH, 0.04mol) of sodium hydroxide dissolved in deionized water was added thereto, and the mixture was stirred at 40 ℃ for reaction for 0.5 hour, followed by addition of C8IMC6Stirring 6.90g (0.02mol) of-Br in deionized water, reacting for 2h, extracting with n-heptane, washing with deionized water for multiple times, taking the organic phase, removing the solvent with a rotary evaporator, and drying in a vacuum oven at 80 ℃ for 6h to obtain C8IMC6-DEHP。
Example 2
The first stage is as follows: 2.72g (IM, 0.04mol) of imidazole and 4.49g (KOH, 0.08mol) of potassium hydroxide were weighed into a 250ml three-necked flask, 50ml of acetonitrile was added thereto, and the mixture was stirred under argon atmosphere at 40 ℃ for 2 hours, and then 7.92g (0.041mol) of weighed 1-bromooctane was slowly added thereto and reacted for 6 hours. After the reaction is finished, the reaction product is filtered and CH is used2Cl2The filtrate was washed to remove most of the solvent using a rotary evaporator. The resulting yellow liquid was then further dissolved in CH2Cl2Washing solvent with deionized water in separating funnel, discarding water phase (removing alkaline substances), repeating for several times until water phase is neutral, adding anhydrous sodium sulfate into organic phase for dewatering, filtering, removing solvent with rotary evaporator, and drying in vacuum oven at 60 deg.C for 6 hr to obtain C8IM。
And a second stage: weighing C8IM 5.40g (0.03mol) and bromohexane 5.12g (0.031mol) in 250ml three-necked flask, adding 50ml acetonitrile, reflux condensing at 80 deg.C under argon atmosphere for 30h, removing acetonitrile solvent with rotary evaporator, adding ethyl acetate, stirring for 30min, standing, separating phases, discarding ethyl acetate phase (except raw material), repeating the above steps for multiple times, removing ethyl acetate with rotary evaporator, and drying in 60 deg.C vacuum oven for 3h to obtain C8IMC6-Br。
Ion exchange stage: potassium hexafluorophosphate 4.05g (KPF) was weighed60.022mol) and C8IMC66.90g (0.02mol) of-Br, respectively dissolved in 30ml of deionized water, and then mixed and stirred at 30 ℃ for reaction for 3 hours, and then 40ml of CH is added2Cl2Stirring for 30min to extract product, standing, collecting organic phase, washing with deionized water for several times until no precipitate is formed by adding silver nitrate solution into water phase, removing solvent from organic phase with rotary evaporator, and drying in vacuum oven at 20 deg.C for 12 hr to obtain C8IMC6-PF6。
Example 3
The first stage is as follows: 2.72g (IM, 0.04mol) of imidazole and 4.49g (KOH, 0.08mol) of potassium hydroxide were weighed into a 250ml three-necked flask, 50ml of acetonitrile was added thereto, and the mixture was stirred under argon atmosphere at 40 ℃ for 2 hours, and then 7.92g (0.041mol) of weighed 1-bromooctane was slowly added thereto and reacted for 6 hours. After the reaction is finished, the reaction product is filtered and CH is used2Cl2The filtrate was washed to remove most of the solvent using a rotary evaporator. The resulting yellow liquid was then further dissolved in CH2Cl2Washing solvent with deionized water in separating funnel, discarding water phase (removing alkaline substances), repeating for several times until water phase is neutral, adding anhydrous sodium sulfate into organic phase for dewatering, filtering, removing solvent with rotary evaporator, and drying in vacuum oven at 60 deg.C for 6 hr to obtain C8IM。
And a second stage: weighing C8IM 5.40g (0.03mol) and bromohexane 5.12g (0.031mol) in 250ml three-necked flask, adding 50ml acetonitrile, reflux condensing at 80 deg.C under argon atmosphere for 30h, removing acetonitrile solvent with rotary evaporator, adding ethyl acetate, stirring for 30min, standing, separating phases, discarding ethyl acetate phase (except raw material), repeating the above steps for multiple times, removing ethyl acetate with rotary evaporator, and drying in 60 deg.C vacuum oven for 3h to obtain C8IMC6-Br。
Ion exchange stage: 6.32g (Li NTf) of lithium bistrifluoromethanesulfonylimide was weighed20.022mol) and C8IMC66.90g (0.02mol) of-Br, respectively dissolved in 20ml of deionized water, and then mixed and stirred at 20 ℃ for reaction for 4 hours, and then 40ml of CH is added2Cl2Stirring for 1 hr to extract product, standing, collecting organic phase, washing with deionized water for several times until the organic phase is completely dissolvedAdding silver nitrate solution into water phase to prevent precipitate formation, removing solvent from organic phase with rotary evaporator, and drying in vacuum oven at 60 deg.C for 8 hr to obtain C8IMC6-NTf2。
Example 4
The first stage is as follows: 2.72g (IM, 0.04mol) of imidazole and 4.49g (KOH, 0.08mol) of potassium hydroxide were weighed into a 250ml three-necked flask, 50ml of acetonitrile was added thereto, and the mixture was stirred at 30 ℃ under argon atmosphere for 2 hours, followed by slowly adding 8.50g (0.044mol) of weighed 1-bromooctane and reacting for 8 hours. After the reaction is finished, the reaction product is filtered and CH is used2Cl2The filtrate was washed to remove most of the solvent using a rotary evaporator. The resulting yellow liquid was then further dissolved in CH2Cl2Washing solvent with deionized water in separating funnel, discarding water phase (removing alkaline substances), repeating for several times until water phase is neutral, adding anhydrous sodium sulfate into organic phase for dewatering, filtering, removing solvent with rotary evaporator, and drying in vacuum oven at 60 deg.C for 6 hr to obtain C8IM。
And a second stage: weighing C8IM 5.40g (0.03mol) and bromohexane 5.12g (0.033mol) in a 250ml three-necked flask, adding 50ml acetonitrile, reflux condensing at 70 deg.C under argon atmosphere for 40h, removing acetonitrile solvent with rotary evaporator, adding ethyl acetate, stirring for 30min, standing, separating phases, discarding ethyl acetate phase (except raw material), repeating the above steps for several times, removing ethyl acetate with rotary evaporator, and drying in a vacuum oven at 60 deg.C for 3h to obtain C8IMC6-Br。
Ion exchange stage: sodium thiocyanate 1.78g (NaSCN, 0.022mol) and C were weighed8IMC66.90g (0.02mol) of-Br, respectively dissolving with 30ml of deionized water, then mixing and stirring at 30 ℃ for reaction for 3h, adding 40ml of acetone, stirring for 30min to extract a product, standing, taking an organic phase, washing with deionized water for multiple times until no precipitate is generated by adding a silver nitrate solution into an aqueous phase, taking the organic phase, removing the solvent by using a rotary evaporator, and drying in a vacuum oven at 60 ℃ for 10h to obtain C8IMC6-SCN。
Example 5
The first stage is as follows: weighing imidazole 2.72g (IM, 0.04mol) and 4.49g (KOH, 0.08mol) of potassium hydroxide were put in a 250ml three-necked flask, 50ml of acetonitrile was added thereto, and the mixture was stirred at 20 ℃ under argon atmosphere for 2 hours, and then 6.95g (0.036mol) of weighed 1-bromooctane was slowly added thereto to conduct reaction for 14 hours. After the reaction is finished, the reaction product is filtered and CH is used2Cl2The filtrate was washed to remove most of the solvent using a rotary evaporator. The resulting yellow liquid was then further dissolved in CH2Cl2Washing solvent with deionized water in separating funnel, discarding water phase (removing alkaline substances), repeating for several times until water phase is neutral, adding anhydrous sodium sulfate into organic phase for dewatering, filtering, removing solvent with rotary evaporator, and drying in vacuum oven at 60 deg.C for 6 hr to obtain C8IM。
And a second stage: weighing C8IM 5.40g (0.03mol) and bromohexane 4.46g (0.027mol) in a 250ml three-necked flask, adding 50ml acetonitrile, reflux condensing at 60 deg.C under argon for 50h, removing acetonitrile solvent with a rotary evaporator, adding ethyl acetate, stirring for 30min, standing, separating phases, discarding ethyl acetate phase (except raw material), repeating the above steps for several times, removing ethyl acetate with a rotary evaporator, and drying in a vacuum oven at 60 deg.C for 3h to obtain C8IMC6-Br。
Ion exchange stage: sodium dicyandiamide (1.96 g) was weighed (Na N (CN)20.022mol) and C8IMC66.90g (0.02mol) of-Br, respectively dissolved in 30ml of deionized water, and then mixed and stirred at 30 ℃ for reaction for 3 hours, and then 40ml of CH is added2Cl2Stirring for 30min to extract product, standing, collecting organic phase, washing with deionized water for several times until no precipitate is formed by adding silver nitrate solution into water phase, removing solvent from organic phase with rotary evaporator, and drying in vacuum oven at 60 deg.C for 10 hr to obtain C8IMC6-N(CN)2。
Example 6
The first stage is as follows: 2.72g (IM, 0.04mol) of imidazole and 4.49g (KOH, 0.08mol) of potassium hydroxide were weighed into a 250ml three-necked flask, 50ml of acetonitrile was added thereto, and the mixture was stirred at 25 ℃ under argon atmosphere for 2 hours, followed by slowly adding 8.50g (0.044mol) of weighed 1-bromooctane and reacting for 9 hours. After the reaction is finished, the reaction product is filtered and CH is used2Cl2The filtrate was washed to remove most of the solvent using a rotary evaporator. The resulting yellow liquid was then further dissolved in CH2Cl2Washing solvent with deionized water in separating funnel, discarding water phase (removing alkaline substances), repeating for several times until water phase is neutral, adding anhydrous sodium sulfate into organic phase for dewatering, filtering, removing solvent with rotary evaporator, and drying in vacuum oven at 60 deg.C for 6 hr to obtain C8IM。
And a second stage: weighing C8IM 5.40g (0.03mol) and bromohexane 4.46g (0.027mol) in a 250ml three-necked flask, adding 50ml acetonitrile, reflux condensing at 75 deg.C under argon for 42h, removing acetonitrile solvent with rotary evaporator, adding ethyl acetate, stirring for 30min, standing, separating phases, discarding ethyl acetate phase (except raw material), repeating the above steps for several times, removing ethyl acetate with rotary evaporator, and drying in a vacuum oven at 60 deg.C for 3h to obtain C8IMC6-Br。
Ion exchange stage: sodium trifluoroacetate 2.99g (NaCF) is weighed out3CO20.022mol) and C8IMC66.90g (0.02mol) of-Br, respectively dissolved in 30ml of deionized water, and then mixed and stirred at 30 ℃ for reaction for 3 hours, and then 40ml of CH is added2Cl2Stirring for 30min to extract product, standing, collecting organic phase, washing with deionized water for several times until no precipitate is formed by adding silver nitrate solution into water phase, removing solvent from organic phase with rotary evaporator, and drying in vacuum oven at 60 deg.C for 10 hr to obtain C8IMC6-CF3CO2。
The inventor also tests the performances of the bilateral asymmetric alkyl imidazole ionic liquid antifriction antiwear agent obtained in the embodiments 1, 2 and 3, wherein the adopted experimental oil sample is an oil sample prepared by dissolving an additive sample with a certain mass in base oil PEG.
Anti-wear and anti-friction test (four-ball friction tester): the test results are shown in FIG. 1, which is performed according to SH/T0189-92 (rotation speed 1200 rpm. + -. 60rpm, temperature 75 ℃ C.. + -. 2 ℃ C., time 60 min. + -. 1 min).
In conclusion, the bilateral asymmetric alkyl imidazole ionic liquid antifriction antiwear agent disclosed by the invention is 1% by mass is added into PEG200 base oil, the abrasion spot diameter and the average friction coefficient are reduced, wherein C8IMC6The respective reductions in DEHP were 29.8% and 45.5%, C8IMC6-PF6Respective reduction rates of 14.7% and 14.0%, C8IMC6-NTf2The reduction rates were 26.1% and 25.6%, respectively. Therefore, the present invention can increase the friction-reducing and wear-resisting performance of lubricating oil, and the friction performance changes with the change of anions.
In conclusion, the bilateral asymmetric alkyl imidazole ionic liquid obtained by the technical scheme of the invention has obvious antifriction and antiwear effects when being used as a lubricating additive, and the physical state change, the solubility, the thermal stability, the antifriction and antiwear performances and the like of the bilateral asymmetric alkyl imidazole ionic liquid can be regulated and controlled by adjusting the anion structure of the bilateral asymmetric alkyl imidazole ionic liquid.
In addition, the inventor also refers to the modes of examples 1-6, and tests are carried out by using other raw materials and conditions listed in the specification, and the bilateral asymmetric alkyl imidazole ionic liquid with excellent wear-resistant and friction-reducing performances and the wear-resistant and friction-reducing agent capable of reducing the friction coefficient, wear resistance and energy consumption are also prepared.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, and are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A bilateral asymmetric alkyl imidazole ionic liquid is characterized by having the following structural formula:
wherein, X-Including bis (2-ethylhexyl) phosphate anions, bis (trifluoromethanesulphonimide) anions, hexafluorophosphate, thiocyanato, trifluoroacetate or dicyanamide。
2. A preparation method of bilateral asymmetric alkyl imidazole ionic liquid is characterized by comprising the following steps:
uniformly mixing imidazole and 1-bromooctane, and carrying out a first reaction at 20-40 ℃ for more than 6h to obtain a C8 alkyl imidazole precursor;
uniformly mixing the C8 alkyl imidazole precursor and bromohexane, and carrying out a second reaction at a temperature of more than 60 ℃ for more than 30h to obtain imidazole cations;
and carrying out ion exchange reaction on the imidazole cation and an anionic compound to obtain the bilateral asymmetric alkyl imidazole ionic liquid.
3. The method of claim 2, wherein: the first reaction time is 6-14 h; and/or the molar ratio of the imidazole to the 1-bromooctane is 1: 0.9-1: 1.1.
4. the method of claim 2, wherein: the temperature of the second reaction is 60-80 ℃, and the time is 30-50 h; and/or, the molar ratio of the C8 alkyl imidazole precursor to bromohexane is 1: 0.9-1: 1.1.
5. the method of claim 2, wherein: the temperature of the ion exchange reaction is 20-40 ℃, and the time is 2-4 h;
and/or, the anionic compound comprises an anionic salt; preferably, the anion contained in the anion salt includes any one or a combination of two or more of bis (2-ethylhexyl) phosphate anion, bis (trifluoromethanesulfonylimide) anion, hexafluorophosphate, thiocyanato, trifluoroacetate and dicyanamide.
6. The method of claim 2, wherein: after the ion exchange reaction is finished, carrying out post-treatment on the obtained reaction system to obtain a crude product; preferably, the post-treatment comprises an extraction treatment with an organic extractant; particularly preferably, the organic extractant comprises any one or a combination of more than two of ethyl acetate, dichloromethane, trichloromethane, n-hexane, heptane, toluene and acetone;
preferably, the preparation method further comprises: carrying out atmospheric distillation and/or vacuum distillation treatment on the crude product;
preferably, the preparation method further comprises: drying the crude product at a constant temperature of 20-80 ℃ for 6-12 h under a reduced pressure condition;
and/or, the preparation method further comprises the following steps: separating unreacted starting material from product after completion of the first and/or second reaction; preferably, the means of separation comprises filtration, centrifugation or decantation; it is particularly preferred to add a filter aid during the filtration.
7. A bilateral asymmetric alkylimidazolium ionic liquid prepared by the method of any one of claims 2-6.
8. Use of the bilateral asymmetric alkyl imidazole ionic liquids of any one of claims 1, 7 as antiwear and antifriction agents.
9. A bilateral asymmetric alkyl imidazole ionic liquid antiwear friction reducer, characterized by comprising the bilateral asymmetric alkyl imidazole ionic liquid of any one of claims 1 and 7.
10. A lubricating oil composition characterized by comprising the bilateral asymmetric alkylimidazolium ionic liquid antiwear and friction reducing agent according to claim 9 and a base oil; preferably, the base oil comprises polyethylene glycol.
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Application publication date: 20200508 |