CN111039948A - Triethylene diamine diionic liquid, preparation method and application thereof - Google Patents
Triethylene diamine diionic liquid, preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
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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
- 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
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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
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
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Abstract
The invention discloses a triethylene diamine diionic liquid, and a preparation method and application thereof. The triethylene diamine diionic liquid contains an alkyl triethylene diamine structure, and the structural formula is as follows:
wherein X includes hydroxyl, carboxyl or amino, Y‑Including a dimonomandelic acid borate anion, a dioxalate borate anion, a dipropionic acid borate anion, a disalicylic acid borate anion, a hexafluorophosphoric acid anion, a bis (trifluoromethanesulfonyl) anion, a trifluoromethanesulfonic acid anion, an ethylsulfonic acid anion, a tetrafluoroboric acid anion, a bisulfate anionA bis (2-ethylhexyl) phosphate anion, a bromide anion, a chloride anion, and the like, and n is an integer of 1 to 10. The triethylene diamine diionic liquid has excellent wear-resistant and friction-reducing performances as a wear-resistant and friction-reducing agent, can regulate and control the solubility, the thermal stability, the wear-resistant and friction-reducing performances and the like by regulating the structures of anions and cations, and has the advantages of few synthesis steps and simple separation and purification.
Description
Technical Field
The invention relates to a triethylene diamine diionic liquid, in particular to a triethylene diamine diionic liquid, a preparation method thereof and application of the triethylene diamine diionic liquid in preparation of an anti-wear and anti-friction agent and lubricating oil, belonging to the technical field of anti-wear and anti-friction agents.
Background
With the development of modern industrial production, mechanical equipment is more and more widely used, and the harm brought by frictional wear is more and more obvious. Lubricating oils and/or greases are widely used in order to reduce the energy consumption associated with frictional wear, to extend the useful life of the machine, and to reduce the economic losses associated therewith. At present, the development trend of lubricating oil is to prolong the oil change period and improve the economy, and the main way of improving the economy is to reduce the viscosity of oil products and reduce the friction loss between machine parts, which requires that the lubricating oil has excellent friction-reducing and wear-resisting properties, and the common solution is to add a small amount of additives into the lubricating oil to improve the friction-reducing and wear-resisting effects of the lubricating oil. At present, the traditional lubricating oil additives such as organic metal antiwear agents, halogen antiwear agents and the like cannot meet the industrial technical requirements of high-speed development, and the materials have certain selectivity and corrosivity on the surfaces of friction pairs, so that the development of novel antiwear and antifriction agents is always a hot spot and a difficult point concerned by the industry.
The ionic liquid is used as a novel anti-wear and anti-friction agent, is widely researched, and has the advantages of low volatility, high thermal stability, wide solubility and the like. Meanwhile, the physical and chemical properties of the ionic liquid are highly adjustable due to the designability of the ionic liquid. Solubility, thermal stability and chemical stability can be adjusted by changing the types, structures, hydrophobicity and the like of anions and cations; functionalization of ionic liquids can also be achieved by introducing specific functional groups. Currently, common ionic liquids are classified into imidazoles, pyridines, quaternary ammonium salts, quaternary phosphonium salts and the like according to the cationic species, but research on ionic liquids based on triethylene diamine is very little, and research on the use of triethylene diamine ionic liquids as lubricating oil additives is basically blank. In addition, the conventional diionic liquid anti-wear and anti-friction additive for the lubricating oil additive also has the defects of lacking of varieties, multiple synthesis steps, complicated separation and purification, lower yield and the like.
Disclosure of Invention
The invention mainly aims to provide a novel triethylene diamine diionic liquid, and a preparation method and application thereof, so as to 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 a triethylene diamine diionic liquid which contains an alkyl triethylene diamine structure and has the following structural formula:
wherein X includes hydroxyl, carboxyl or amino, Y-The anion-exchange resin comprises any one or a combination of more than two of dimmandelic acid borate anion, oxalic acid borate anion, dipropionic acid borate anion, disalicylic acid borate anion, hexafluorophosphoric acid anion, bis (trifluoromethanesulfonyl) anion, trifluoromethanesulfonic acid anion, ethylsulfonic acid anion, tetrafluoroboric acid anion, bisulfate anion, di (2-ethylhexyl) phosphate anion, bromine anion and chlorine anion, and n is an integer of 1-10.
The embodiment of the invention also provides a preparation method of the triethylene diamine diionic liquid, which comprises the following steps: heating a uniformly mixed reaction system containing triethylene diamine, halogenated alkane and a solvent at the temperature of 60-100 ℃ and carrying out reflux reaction for 48-108 hours to obtain the triethylene diamine diionic liquid.
The embodiment of the invention also provides the triethylene diamine diionic liquid prepared by the method.
The embodiment of the invention also provides application of the triethylene diamine diionic liquid as an anti-wear and anti-friction agent.
The embodiment of the invention also provides a triethylene diamine diionic liquid anti-wear and anti-friction agent which comprises the triethylene diamine diionic liquid.
For example, in some embodiments, the present invention also provides a lubricating oil composition comprising the foregoing trivinyldiamine-based diionic liquid antiwear and friction reducing agent.
Compared with the prior art, the invention has the advantages that:
1) the triethylene diamine diionic liquid anti-wear and anti-friction agent has a unique and novel diionic structure;
2) compared with the traditional wear-resistant friction reducer, the triethylene diamine diionic liquid wear-resistant friction reducer has the advantages of few synthesis steps, simplicity in operation, easiness in separation and purification and high synthesis yield;
3) the triethylene diamine diionic liquid has excellent wear-resistant and friction-reducing performances as an additive, and the solubility, thermal stability, wear-resistant and friction-reducing performances and the like of the triethylene diamine diionic liquid can be regulated and controlled by regulating the structures of anions and cations of the triethylene diamine diionic liquid.
Drawings
FIG. 1 is a schematic diagram showing the friction coefficient and the volume of the wear marks of the trivinyldiamine-based diionic liquid obtained in example 1 of the present invention at different addition amounts.
FIG. 2 is a schematic diagram showing the friction coefficient and the volume of the stains of the triethylene diamine type diionic liquid obtained in example 1 of the present invention with the same amount of the anionic ligand.
Detailed Description
In view of the technical problems of the prior art that the conventional diionic liquid used as the lubricating oil additive is lack of types of anti-wear and anti-friction additives, multiple synthesis steps, complicated separation and purification, low yield and the like, the inventor of the present invention can provide the technical scheme of the present invention through long-term research and a great deal of practice. The technical solution, its implementation and principles, etc. will be further explained as follows.
The inventor considers that the centers of two nitrogen atoms in the trivinyldiamine structure can be quaternized in a chemical synthesis mode under specific conditions, so that infinite possibilities are provided for alkylation and functionalization of the ionic liquid, and meanwhile, the quaternization of the two nitrogen atoms in the trivinyldiamine structure also realizes formation of dication centers, which is also the key for synthesizing the dication liquid.
One aspect of the embodiment of the present invention provides a triethylenediamine diionic liquid, which contains an alkyl triethylenediamine structure, and has a structural formula as follows:
wherein X includes, but is not limited to, hydroxyl (-OH), carboxyl (-COOH), or amino (-NH)2)，Y-Including but not limited to the boron dimalonate anion (BMB)-) Boron bis (oxalato) anion (BOB)-) Boron dipropionate anion (BMLB)-) Bis-salicylic acid boron anion (BScB)-) Hexafluorophosphate anion (PF)6 -) Bis (trifluoromethanesulfonyl) anion (NTf)2 -) Trifluoromethanesulfonic acid anion (CF)3SO3 -) Ethyl sulfonic acid anion (C)2H5SO3 -) Tetrafluoroborate anion (BF)4 -) Hydrogen sulfate anion (HSO)4 -) Bis (2-ethylhexyl) phosphate anion (DEHP)-) Bromine anion (Br)-) And chloride anion (Cl)-) Any one or a combination of two or more of them, and n is an integer of 1 to 10.
In another aspect of the embodiments of the present invention, a preparation method of a triethylene diamine diionic liquid is provided, which includes: heating a uniformly mixed reaction system containing triethylene diamine, halogenated alkane and a solvent at the temperature of 60-100 ℃ and carrying out reflux reaction for 48-108 hours to obtain the triethylene diamine diionic liquid.
In some embodiments, the method of making further comprises: and after the reflux reaction is finished, carrying out anion exchange reaction on the obtained triethylene diamine diionic liquid and ionic salt to obtain the triethylene diamine diionic liquid with anions.
Further, the temperature of the anion exchange reaction is 20-60 ℃, and the time is 10 min-5 h.
In some embodiments, the method of making further comprises: after the reflux reaction or anion exchange reaction is completed, the obtained crude product is subjected to post-treatment.
Further, the post-processing comprises: and (3) carrying out recrystallization treatment or extraction filtration treatment on the crude product, and then drying at room temperature to 100 ℃ for 6-24 h under a reduced pressure condition.
In some preferred embodiments, the preparation method specifically comprises: fully and uniformly mixing triethylene diamine and halogenated alkane under the condition of a solvent, and then heating in an oil bath at the temperature of 60-100 ℃ and carrying out reflux reaction for 48-108 hours. In order to remove possible residual unreacted substances, adding the crude product into an organic solvent for recrystallization, and finally drying the product at the constant temperature of room temperature to 100 ℃ under the reduced pressure condition for 6-24 hours to obtain the triethylene diamine diionic liquid.
In some more preferred embodiments, the preparation method may comprise: triethylene diamine and terminal hydroxyl-OH, carboxyl-COOH and amino-NH2Alkyl halides with equivalent functional groups in solvent, N2Fully and uniformly mixing under protection, then heating in an oil bath at the temperature of 60-100 ℃, reacting for 48-108 hours under the reflux condition, removing possible residual unreacted substances, adding an organic solvent for recrystallization, and finally drying the product at the constant temperature of room temperature-100 ℃ under the reduced pressure condition for 6-24 hours to obtain the triethylene diamine double-ion productA sub-liquid.
As a more preferred embodiment of the present invention, the triethylene diamine-based diionic liquid can be further ion-exchanged with other ionic salts under specific conditions, the crude product is extracted and filtered by a solvent, and finally, the product is dried under reduced pressure at room temperature to 100 ℃ for 6 to 24 hours, such that the target product can be obtained. And obtaining a target product triethylene diamine diionic liquid with different anions through post-treatment.
Further, the ionic salt contains anions including, but not limited to, the boron dimaleate anion (BMB)-) Boron bis (oxalato) anion (BOB)-) Boron dipropionate anion (BMLB)-) Bis-salicylic acid boron anion (BScB)-) Hexafluorophosphate anion (PF)6 -) Bis (trifluoromethanesulfonyl) anion (NTf)2 -) Trifluoromethanesulfonic acid anion (CF)3SO3 -) Ethyl sulfonic acid anion (C)2H5SO3 -) Tetrafluoroborate anion (BF)4 -) Hydrogen sulfate anion (HSO)4 -) Bis (2-ethylhexyl) phosphate anion (DEHP)-) Bromine anion (Br)-) Chloride anion (Cl)-) And the like, but are not limited thereto.
In some embodiments, the haloalkane comprises C3-C12Linear or branched alkanes.
Further, the halogenated alkane may be selected from, but not limited to, hydroxyl-OH, carboxyl-COOH, amino-NH at the terminal2And isofunctional haloalkanes.
Further, the solvent may be, but is not limited to, any one or a combination of two or more of water, methanol, ethanol, acetone, ethyl acetate, chloroform, and the like, but is not limited thereto.
Further, the molar ratio of the triethylene diamine to the halogenated alkane is 1: 2-1: 12, preferably 1: 2-1: 10.
further, the molar ratio of the triethylene diamine ionic liquid to the ionic salt is 1: 2-1: 6.
in the preparation method of the present invention, after the completion of the reaction, unreacted raw materials are removed, and general methods include, but are not limited to: filtration, centrifugation, decantation, etc. separate unreacted solid materials and impurities from the desired product phase and a filter aid such as diatomaceous earth (Celite) may be used to improve the separation efficiency.
Further, the post-treatment comprises removing water and solvent from the obtained reaction product, typically by atmospheric distillation or vacuum distillation.
In another aspect of the embodiments of the present invention, there is also provided a triethylene diamine diionic liquid prepared by the foregoing method.
In another aspect of the embodiment of the invention, the application of the triethylene diamine diionic liquid as an anti-wear and anti-friction agent is also provided.
Correspondingly, the embodiment of the invention also provides a triethylene diamine diionic liquid anti-wear and anti-friction agent, which comprises the triethylene diamine diionic liquid.
Preferably, the triethylene diamine diionic liquid anti-wear friction reducer provided by the invention has good solubility.
Furthermore, the triethylene diamine diionic liquid anti-wear and anti-friction agent can be stored in polar lubricating oil base oil at room temperature for more than half a year, no precipitate is separated out, and the dispersion stability is good.
For example, in some embodiments, the present invention also provides a lubricating oil composition comprising the foregoing trivinyldiamine-based diionic liquid antiwear and friction reducing agent.
In conclusion, the triethylene diamine diionic liquid has a unique and novel diionic structure, has excellent wear-resistant and anti-friction properties when used as an additive, and can regulate and control the dissolution property, the thermal stability, the wear-resistant and anti-friction properties and the like by adjusting the anion and cation structures; and has the advantages of few synthesis steps, simple operation, easy separation and purification and high synthesis yield.
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.
Although the following examples relate to the preparation of certain triethylene diamine ionic liquids, the various reaction participants and process conditions used therein are typical examples, it is verified by a lot of experiments by the inventors that other types of reaction participants and other process conditions listed above are suitable and can achieve the claimed technical effects. In addition, "%" in the following examples is "wt%" unless otherwise specified.
Example 1
6.0g (0.053mol) of triethylene diamine was weighed and directly charged into a 250ml three-necked flask, and 44.0g (0.320mol) of bromobutane and 50ml of methanol solvent were added to the flask. Heating in oil bath, raising the temperature to 60 ℃, and carrying out reflux reaction for 48 hours. After the reaction is finished, ethyl acetate is used for recrystallization, an organic layer is removed, and a certain amount of white solid is obtained by filtration. Drying the obtained product under reduced pressure at constant temperature of 60 deg.C for 6 hr to obtain white solid [ C ]4DABCOC4][Br]2。
Product [ C ] obtained in this example4DABCOC4][Br]2The nuclear magnetic characterization data of (A) is:
nuclear magnetic hydrogen spectrum: (1H NMR):δ4.09(s,12H,N-(C2H4)3-N),3.68–3.60(m,4H,N-CH2),1.90–1.79(m,4H,CH2),1.52–1.40(m,4H,CH2),1.04(t,J＝7.4Hz,6H,CH3)ppm；
Nuclear magnetic carbon spectrum (13C NMR):δ64.64,51.00,23.74,19.13,12.48ppm；
Mass spectrum (MS (ESI)) m/z calcd for [ C ]14H30N2]2+:113.1,found:113.1；calcd for[Br]-:78.9,found:78.9.
Example 2
Triethylene diamine 5.0g (0.045mol) is weighed and directly added into a 250ml three-necked bottleThen, 21.1g (0.223mol) of 3-chloro-1-propanol and 50ml of a methanol solvent were added to the flask. Heating in oil bath to 60 deg.C, N2And (5) refluxing the reaction for 108h under protection. After the reaction is finished, ethyl acetate is used for recrystallization, an organic layer is removed, and a certain amount of white solid is obtained by filtration. Drying the obtained product under reduced pressure at constant temperature of 60 deg.C for 10 hr to obtain white solid [ C ]3BHDABCOC3][Cl]2。
Product [ C ] obtained in this example3BHDABCOC3][Cl]2The nuclear magnetic characterization data of (A) is:
nuclear magnetic hydrogen spectrum (1H NMR):δ4.06(s,12H,N-(C2H4)3-N),3.70(dd,J＝13.9,8.2Hz,8H,N-CH2,CH2-OH),2.11–1.98(m,4H,CH2)ppm；
Nuclear magnetic carbon spectrum (13C NMR):δ62.89,57.77,51.11,24.52ppm；
Mass spectrum (MS (ESI)) m/z calcd for [ C ]12H26N2O2]2+:115.1,found:115.1；calcd for[Cl]-:35.0,found:35.0.
Example 3
Weighing [ C ]4DABCOC4][Br]21.0g (0.0025mol) was directly charged into a 250ml three-necked flask, and further LiBScB1.58g (0.0054mol) was added and dissolved in 15ml of deionized water, respectively. At normal temperature, [ C ] is reacted4DABCOC4][Br]2The solution was added dropwise to the libsccb solution with constant stirring. After the reaction, the reaction mixture was filtered and washed with water to remove unreacted materials. Drying the obtained product under reduced pressure at constant temperature of 60 deg.C for 4 hr to obtain white solid [ C ]4DABCOC4][BScB]2。
Product [ C ] obtained in this example4DABCOC4][BScB]2The nuclear magnetic characterization data of (A) is:
nuclear magnetic hydrogen spectrum (1H NMR):δ7.84(dd,J＝7.8,1.4Hz,4H,C6H4),7.49–7.42(m,4H,C6H4),6.95–6.86(m,8H,C6H4),3.95(s,12H,N-(C2H4)3-N),3.53–3.45(m,4H,N-CH2),1.76–1.66(m,4H,CH2),1.33(dq,J＝15.1,7.5Hz,4H,CH2),0.93(t,J＝7.4Hz,6H,CH3)ppm；
Nuclear magnetic carbon spectrum (13C NMR):δ164.17,159.49,135.09,129.69,119.24,118.49,115.84,63.80,50.92,23.72,19.46,13.84ppm；
Nuclear magnetic boron spectrum (11B NMR):δ4.27ppm；
Mass spectrum (MS (ESI)) m/z calcd for [ C ]14H30N2]2+:113.1,found:113.1；calcd for[C14H8O6B]-:283.0,found:283.1.
Example 4
Weighing [ C ]4DABCOC4][Br]21.0g (0.0025mol) is directly added into a 250ml three-neck bottle, and KPF is added61.049g (0.0055mol), respectively, were dissolved in 15ml of deionized water. At normal temperature, [ C ] is reacted4DABCOC4][Br]2The solution was added dropwise to KPF6In the solution, stirring is continuously carried out. After the reaction, the reaction mixture was filtered and washed with water to remove unreacted materials. Drying the obtained product under reduced pressure at constant temperature of 60 deg.C for 6 hr to obtain white solid [ C ]4DABCOC4][PF6]2。
Product [ C ] obtained in this example4DABCOC4][PF6]2The nuclear magnetic characterization data of (A) is:
nuclear magnetic hydrogen spectrum (1H NMR):δ3.93(s,12H,N-(C2H4)3-N),3.57–3.48(m,4H,N-CH2),1.79(dt,J＝16.1,8.0Hz,4H,CH2),1.44(dq,J＝14.7,7.4Hz,4H,CH2),1.03(t,J＝7.3Hz,6H,CH3)ppm；
Nuclear magnetic carbon spectrum (13C NMR):δ64.86,51.41,23.75,19.16,12.84ppm；
Nuclear magnetic phosphorus spectrum (31P NMR):δ-145.14ppm；
Nuclear magnetic fluorine spectrum (19F NMR):δ-72.07ppm；
Mass spectrum (MS (ESI)) m/z calcd for [ C ]14H30N2]2+:113.1,found:113.1；calcd for[PF6]-:145.0,found:145.0.
Example 5
Weighing [ C ]4DABCOC4][Br]21.0g (0.0025mol) was added directly to a 250ml three-necked flask, and LiNTf was added thereto21.56g (0.0054mol) of the polymer was dissolved in 15ml of deionized water. At normal temperature, [ C ] is reacted4DABCOC4][Br]2The solution was added dropwise to LiNTf2In the solution, stirring is continuously carried out. After the reaction, the reaction mixture was filtered and washed with water to remove unreacted materials. Drying the obtained product under reduced pressure at constant temperature of 100 deg.C for 24 hr to obtain white solid [ C ]4DABCOC4][NTf2]2。
Product [ C ] obtained in this example4DABCOC4][NTf2]2The nuclear magnetic characterization data of (A) is:
nuclear magnetic hydrogen spectrum (1H NMR):δ3.94(s,12H,N-(C2H4)3-N),3.58–3.49(m,4H,N-CH2),1.85–1.74(m,4H,CH2),1.50–1.38(m,4H,CH2),1.03(t,J＝7.4Hz,6H,CH3)ppm；
Nuclear magnetic carbon spectrum (13C NMR):δ121.37,64.72,50.96,23.58,19.03,12.35ppm；
Nuclear magnetic fluorine spectrum (19F NMR):δ-80.61ppm；
Mass spectrum (MS (ESI)) m/z calcd for [ C ]14H30N2]2+:113.1,found:113.1；calcd for[C2NO4F6S2]-:279.9,found:280.0.
Example 6
0.05mol of triethylene diamine is weighed and directly added into a 250ml three-neck flask, and then 0.1mol of bromobutane and 50ml of aqueous solvent are added into the flask. Heating in oil bath, raising the temperature to 100 ℃, and carrying out reflux reaction for 100 h. After the reaction is finished, ethyl acetate is used for recrystallization, an organic layer is removed, and a certain amount of white solid is obtained by filtration. The obtained product is subjected to reduced pressureDrying at room temperature for 24 hr to obtain white solid4DABCOC4][Br]2。
Example 7
0.01mol of triethylene diamine is weighed and directly added into a 250ml three-neck flask, 0.12mol of bromobutane is added, and 50ml of ethanol solvent is added into the flask. Heating in oil bath, raising the temperature to 70 ℃, and carrying out reflux reaction for 80 h. After the reaction is finished, ethyl acetate is used for recrystallization, an organic layer is removed, and a certain amount of white solid is obtained by filtration. Drying the obtained product under reduced pressure at constant temperature of 100 deg.C for 6 hr to obtain white solid [ C ]4DABCOC4][Br]2。
Example 8
0.01mol of triethylene diamine is weighed and directly added into a 250ml three-neck flask, 0.1mol of 3-chloro-1-propanol and 50ml of chloroform solvent are added into the flask. Heating in oil bath to 65 deg.C, N2And (5) refluxing the reaction for 108h under protection. After the reaction is finished, ethyl acetate is used for recrystallization, an organic layer is removed, and a certain amount of white solid is obtained by filtration. Drying the obtained product under reduced pressure at 80 deg.C for 20 hr to obtain white solid [ C ]3BHDABCOC3][Cl]2。
Example 9
This embodiment is substantially the same as embodiment 3 except that: the ionic salt adopted is LiBMB, [ C4DABCOC4][Br]2Molar ratio to LiBMB 1: 2, the temperature of the ion exchange reaction is 20 ℃, and the time is 5 hours.
Example 10
This embodiment is substantially the same as embodiment 4 except that: the ionic salt adopted is LiBOB, [ C4DABCOC4][Br]2The molar ratio to LiBOB is 1: 4, the temperature of the ion exchange reaction is 50 ℃, and the time is 2 hours.
Example 11
This embodiment is substantially the same as embodiment 5 except that: the ionic salt adopted is KC2H5SO3，[C4DABCOC4][Br]2And KC2H5SO3In a molar ratio of 1: 6, the temperature of the ion exchange reaction is 60 ℃, and the time is 10 min.
The inventors also tested the performance of the triethylenediamine diionic liquid obtained in example 1, wherein the experimental oil sample adopted was an oil sample prepared by dissolving a certain mass of an additive sample in the base oil PEG 200. The test results are shown in fig. 1 and 2.
Anti-wear and anti-friction test (four-ball friction tester): performed according to SH/T0189-92 (rotation speed 1200rpm +/-60 rpm, temperature 75 +/-2 ℃, time 60min +/-1 min)
FIG. 1 is a graph showing the results of the friction coefficient and the volume of the wear marks of the trivinyldiamine-based diionic liquid obtained in example 1 in different addition amounts. As can be seen from FIG. 1, the triethylenediamine diionic liquid of the present embodiment has significant anti-wear and anti-friction effects in lubricating oil. When the addition amount is 2%, the friction coefficient is 0.093, and compared with PEG200, the friction coefficient can be reduced by 17.70%, and the grinding volume is 1.68 × 10-3mm3The reduction in the volume of the wear scar was 85.30% compared to PEG200 lube base oil.
FIG. 2 is a graph showing the results of the friction coefficient and the volume of the abraded spots of the trivinyldiamine-based diionic liquid obtained in example 1 with the same addition amount and different anionic ligands. As can be seen from FIG. 2, the triethylene diamine diionic liquids with different anions show adjustable anti-wear and anti-friction performances to different degrees, and are all significantly better than PEG200 lubricating oil base oil. Therefore, the invention can effectively improve the wear resistance of the lubricating oil when used in the lubricating oil, and is beneficial to improving the overall fuel economy.
Similarly, the triethylene diamine type diionic liquid obtained in the other examples of the present invention has similar performance to that of example 1.
In conclusion, the triethylene diamine diionic liquid obtained by the technical scheme of the invention has a unique and novel diionic structure, has excellent wear-resistant and anti-friction properties when used as an additive, and can regulate and control the solubility, thermal stability, wear-resistant and anti-friction properties and the like by adjusting the anion and cation structures; and has the advantages of few synthesis steps, simple operation, easy separation and purification and high synthesis yield.
In addition, the inventor also refers to the modes of examples 1 to 11, and tests are carried out by using other raw materials, conditions and the like listed in the specification, and a triethylene diamine diionic liquid with excellent wear-resistant and friction-reducing performances and a wear-resistant and friction-reducing agent capable of reducing 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 triethylene diamine diionic liquid is characterized in that the triethylene diamine diionic liquid contains an alkyl triethylene diamine structure, and the structural formula is as follows:
wherein X includes hydroxyl, carboxyl or amino, Y-The anion-exchange resin comprises any one or a combination of more than two of dimmandelic acid borate anion, oxalic acid borate anion, dipropionic acid borate anion, disalicylic acid borate anion, hexafluorophosphoric acid anion, bis (trifluoromethanesulfonyl) anion, trifluoromethanesulfonic acid anion, ethylsulfonic acid anion, tetrafluoroboric acid anion, bisulfate anion, di (2-ethylhexyl) phosphate anion, bromine anion and chlorine anion, and n is an integer of 1-10.
2. A preparation method of a triethylene diamine diionic liquid is characterized by comprising the following steps: heating a uniformly mixed reaction system containing triethylene diamine, halogenated alkane and a solvent at the temperature of 60-100 ℃ and carrying out reflux reaction for 48-108 hours to obtain the triethylene diamine diionic liquid.
3. The method of claim 3, further comprising: after the reflux reaction is finished, carrying out anion exchange reaction on the obtained triethylene diamine diionic liquid and ionic salt to obtain triethylene diamine diionic liquid with anions; preferably, the temperature of the anion exchange reaction is 20-60 ℃, and the time is 10 min-5 h.
4. The method of claim 2, wherein: the halogenated alkane comprises C3-C12Linear or branched alkanes of (a); preferably, the halogenated alkane includes a halogenated alkane having a hydroxyl group, a carboxyl group or an amino group at a terminal.
5. The production method according to claim 3, characterized in that: the anion contained in the ionic salt comprises any one or the combination of more than two of a dimmandelic acid borate anion, a oxalic acid borate anion, a dipropionic acid borate anion, a disalicylic acid borate anion, a hexafluorophosphate anion, a bis (trifluoromethanesulfonyl) anion, a trifluoromethanesulfonic acid anion, an ethylsulfonic acid anion, a tetrafluoroborate anion, a bisulfate anion, a bis (2-ethylhexyl) phosphate anion, a bromine anion and a chlorine anion;
and/or the solvent comprises any one or the combination of more than two of water, methanol, ethanol, acetone, ethyl acetate and chloroform.
6. The production method according to claim 3, characterized in that: the molar ratio of the triethylene diamine to the halogenated alkane is 1: 2-1: 12, preferably 1: 2-1: 10; and/or the molar ratio of the triethylene diamine ionic liquid to the ionic salt is 1: 2-1: 6;
and/or, the preparation method further comprises the following steps: after the reflux reaction or the anion exchange reaction is finished, carrying out post-treatment on the obtained crude product; preferably, the post-treatment comprises: and (3) carrying out recrystallization treatment or extraction filtration treatment on the crude product, and then drying at room temperature to 100 ℃ for 6-24 h under a reduced pressure condition.
7. A triethylenediamine diionic liquid prepared by the process of any one of claims 2-6.
8. The use of the trivinyldiamine-based diionic liquid according to any one of claims 1 and 7 as an anti-wear and anti-friction agent.
9. A triethylene diamine diionic liquid anti-wear and anti-friction agent, which is characterized by comprising the triethylene diamine diionic liquid as claimed in any one of claims 1 and 7.
10. A lubricating oil composition characterized by comprising the triethylenediamine diionic liquid anti-wear friction agent according to claim 9.
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| CN114560863A (en) * | 2022-01-27 | 2022-05-31 | 青岛科技大学 | Triethylene diamine quaternary ammonium salt, preparation method of triethylene diamine quaternary ammonium base and application |
| CN115557943A (en) * | 2022-09-22 | 2023-01-03 | 中国辐射防护研究院 | Functionalized amine ionic liquid for adsorbing radioactive iodine and preparation method thereof |
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| CN114560863A (en) * | 2022-01-27 | 2022-05-31 | 青岛科技大学 | Triethylene diamine quaternary ammonium salt, preparation method of triethylene diamine quaternary ammonium base and application |
| CN115557943A (en) * | 2022-09-22 | 2023-01-03 | 中国辐射防护研究院 | Functionalized amine ionic liquid for adsorbing radioactive iodine and preparation method thereof |
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