CN116535643A - Ionic liquid functionalized polydopamine nano lubricating oil additive and preparation method thereof - Google Patents
Ionic liquid functionalized polydopamine nano lubricating oil additive and preparation method thereof Download PDFInfo
- Publication number
- CN116535643A CN116535643A CN202310505598.9A CN202310505598A CN116535643A CN 116535643 A CN116535643 A CN 116535643A CN 202310505598 A CN202310505598 A CN 202310505598A CN 116535643 A CN116535643 A CN 116535643A
- Authority
- CN
- China
- Prior art keywords
- polydopamine
- particles
- water
- aminopropyl
- imidazole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229920001690 polydopamine Polymers 0.000 title claims abstract description 105
- 239000000654 additive Substances 0.000 title claims abstract description 34
- 230000000996 additive effect Effects 0.000 title claims abstract description 27
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 27
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002105 nanoparticle Substances 0.000 claims abstract description 93
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000003756 stirring Methods 0.000 claims abstract description 39
- KDHWOCLBMVSZPG-UHFFFAOYSA-N 3-imidazol-1-ylpropan-1-amine Chemical compound NCCCN1C=CN=C1 KDHWOCLBMVSZPG-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000003921 oil Substances 0.000 claims abstract description 36
- 239000002904 solvent Substances 0.000 claims abstract description 18
- -1 anion salt Chemical class 0.000 claims abstract description 13
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011737 fluorine Substances 0.000 claims abstract description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical group CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 39
- 238000005406 washing Methods 0.000 claims description 32
- 239000012071 phase Substances 0.000 claims description 28
- 239000000047 product Substances 0.000 claims description 26
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 25
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 20
- 239000007790 solid phase Substances 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 15
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000007795 chemical reaction product Substances 0.000 claims description 8
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- 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 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 1
- 230000001050 lubricating effect Effects 0.000 abstract description 16
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 238000005119 centrifugation Methods 0.000 description 15
- 239000002199 base oil Substances 0.000 description 13
- 239000002245 particle Substances 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 238000012986 modification Methods 0.000 description 7
- 230000004048 modification Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000009423 ventilation Methods 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- 238000005461 lubrication Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000005345 coagulation Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000005349 anion exchange Methods 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 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 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000002262 Schiff base Substances 0.000 description 1
- 150000004753 Schiff bases Chemical class 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000006701 autoxidation reaction Methods 0.000 description 1
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 238000000464 low-speed centrifugation Methods 0.000 description 1
- 239000003879 lubricant additive Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000004533 oil dispersion Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000012521 purified sample Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 231100000241 scar Toxicity 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0666—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0672—Polycondensates containing five-membered rings, condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring
-
- 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
- C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
- C10M149/12—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention provides an ionic liquid functionalized polydopamine nanometer lubricating oil additive and a preparation method thereof, and relates to the technical field of new materials. The preparation steps of the additive comprise: dispersing polydopamine nano particles in water, adding 1- (3-aminopropyl) imidazole, continuously stirring for reacting for 10-12 h, and separating and purifying the product to obtain the polydopamine nano particles; dispersing the product of the previous step into monohydric alcohol, adding methyl iodide, continuously stirring for 6-12 h at 60-80 ℃, and separating and purifying the product to obtain the product; dispersing the product of the last step into water, then adding an oil phase solvent, dripping an oil-added fluorine-containing anion salt water solution, stirring and reacting for 0.5-1 h, separating the oil phase after the reaction is finished, and removing the solvent in the oil phase. The additive provided by the invention has rich functional groups, so that a large number of adsorption sites can be provided when the additive is used as a lubricating additive, the formation of a friction film is accelerated, and the lubricating performance of nano particles is positively improved.
Description
Technical Field
The invention belongs to the technical field of new materials, and particularly relates to an ionic liquid functionalized polydopamine nanometer lubricating oil additive and a preparation method of the ionic liquid functionalized polydopamine nanometer lubricating oil additive.
Background
The lubricating oil additive has important significance for improving the tribological property of the base oil, in particular to the antifriction and antiwear properties. The addition of the lubricating additive can effectively make up the defects of insufficient bearing capacity, unstable lubricating performance and the like of the base oil in the use process. The organic polymer nano particles have uniform particle size, wide raw material sources, good interfacial adsorption performance and excellent tribological potential value. However, organic polymer nano lubricating oil additives that provide excellent synthetic oil dispersibility and interfacial activity present a number of challenges. As a derivative of the adhesive protein, dopamine can form polydopamine nano-particles with easily-modified surfaces in weak alkaline aqueous solution through autoxidation polymerization, and a potential approach is provided for breaking through the difficulties.
Ionic liquids have significant advantages of high thermal stability, flame retardancy, high ionic conductivity, and wide electrochemical window, and have been used directly or indirectly in the field of lubricating additives. The ionic liquid is grafted to the surface of the nano particles to form a composite material, so that the synergistic lubrication effect of the ionic liquid and the nano particles can be exerted, and the dispersion of the nano particles in various solvents can be effectively promoted. Unfortunately, in the conventional direct grafting method, the inherent polarity and chargeability of the ionic liquid make the ionic liquid easily cause nano-material coagulation in the modification process, so that the grafting efficiency can not be ensured while the dispersibility is affected. The design of a new grafting strategy has positive pushing effect on exploring the synergistic lubrication effect between the ionic liquid and the nano particles.
Although polydopamine nanoparticles have excellent tribological potential, their inherent property of poor oil dispersion stability limits their wide application as lubricating oil additives. Therefore, improving the oil dispersibility of polydopamine nanoparticles is an effective way to broaden the application of polydopamine nanoparticles in the field of oil-based lubrication additives.
Disclosure of Invention
In order to solve at least one of the problems, the additive is modified based on polydopamine, can provide more adsorption sites when being used as a lubricating additive, accelerates the formation of a friction film, and plays a positive role in improving the lubricating performance of nano particles.
The technical scheme of the invention is as follows: the preparation method of the ionic liquid functionalized polydopamine nanometer lubricating oil additive comprises the following steps:
s1, taking polydopamine nano-particles, dispersing the polydopamine nano-particles in water, adding 1- (3-aminopropyl) imidazole, continuously stirring and reacting for 10-12 hours, and separating and purifying the product to obtain 1- (3-aminopropyl) imidazole modified polydopamine nano-particles, wherein each 100-200 mg polydopamine nano-particles corresponds to 2-4 mL of 1- (3-aminopropyl) imidazole;
s2, dispersing the 1- (3-aminopropyl) imidazole modified polydopamine nano-particles into monohydric alcohol, adding methyl iodide, continuously stirring for 6-12 hours at the temperature of 60-80 ℃, and separating and purifying the product to obtain the 1- (3-aminopropyl) imidazole iodisalt modified polydopamine nano-particles, wherein each 100-200 mg polydopamine nano-particles corresponds to 10-15 mL methyl iodide;
s3, dispersing the polydopamine nano-particles modified by the 1- (3-aminopropyl) imidazole iodized salt into water, then adding an oil phase solvent, dripping an oil phase fluorine-containing anion salt water solution, stirring and reacting for 0.5-1 h, separating the oil phase after the reaction is finished, and removing the solvent in the oil phase, wherein the mass ratio of the oil phase fluorine-containing anion salt to the polydopamine nano-particles modified by the 1- (3-aminopropyl) imidazole iodized salt is 1-3:1.
In S2, since the boiling point of the monohydric alcohol and methyl iodide is not too high and the reaction temperature is relatively high, in order to avoid volatilization of the solvent during the reaction, a condensation reflux apparatus may be used for the reaction.
In S3, in order to avoid emulsification after mixing the oil phase solvent and the water phase, the addition amounts of the oil phase solvent and the water phase are not easy to differ too much, and the volume ratio of the oil phase solvent to the water phase is preferably 1:0.8-1.2.
One embodiment of the invention is that the polydopamine nanoparticle is prepared by the following method:
adding dopamine hydrochloride into water and dissolving to obtain a dopamine hydrochloride solution, then uniformly mixing water, ethanol and ammonia water in a volume ratio of 90:40:1.5-3 to obtain a mixed solution, mixing the dopamine hydrochloride solution and the mixed solution, continuously stirring and reacting for 6-24 hours under normal temperature and light-shielding conditions, and separating and purifying the reacted product to obtain polydopamine nano particles; wherein, for the dopamine hydrochloride solution, 0.3-0.8 g of dopamine hydrochloride is corresponding to every 10ml of water. Meanwhile, the addition volume ratio of the mixed solution to the dopamine hydrochloride solution is 6-14:1.
In theory, the polydopamine nanoparticles in the prior art have relatively rich functional groups, and therefore, can be applied to the invention as well. However, the cost of the existing polydopamine nanoparticles is high, and in order to reduce the cost, the inventor proposes a new preparation method of polydopamine nanoparticles.
In this method, the concentration of polydopamine hydrochloride in water should not be too high: too high can cause the polydopamine to sink and gather in the reaction process, so that nano-scale polydopamine is difficult to obtain; but should not be too low: too low results in separation of the reaction products after the reaction, which makes it difficult to obtain shaped polydopamine nanoparticles. The inventor finds that when 10ml of water contains 0.3-0.8 g of dopamine hydrochloride, the final performance is better. Also, the addition amount of ammonia water should not be too high for the mixed solution: when the particle size of the obtained polydopamine nano particles is too small, the subsequent separation and purification process is difficult, and the yield is low; but should not be too low: the particle size of the obtained polydopamine particles is too large to meet the actual use requirement due to too low, and a large number of experiments by the inventor show that the effects of water, ethanol and ammonia water with the volume ratio of 90:40:1.5-3 are good, and the preferable ratio of the water to the ethanol to the ammonia water is 90:40:2.5.
Further, the specific operation of separating and purifying the polydopamine nano-particles is as follows: centrifuging the reaction product for 20-30 min under 10000-12000 r/min, washing the solid phase with water, and repeating the above operation for several times.
In S1, the specific operation of separation and purification is as follows: centrifuging the reaction product for 20-30 min under 10000-12000 r/min, washing the solid phase with ethanol, and repeating the above operation for several times. In this process, the inventors found that if the 1- (3-aminopropyl) imidazole-modified polydopamine nanoparticles were washed with water, this would result in dissociation of the 1- (3-aminopropyl) imidazole grafted to the surfaces of the polydopamine nanoparticles, whereas when the washing was performed with ethanol, this could be avoided. At the same time, the other purpose of ethanol washing is to remove water in the product as much as possible, so as to avoid the influence of the water in the product on the subsequent reaction.
In one embodiment of the present invention, in S2, the monohydric alcohol is methanol or ethanol, and at the same time, ethanol is preferable in view of biotoxicity of both.
In S2, the specific operation of separation and purification is as follows: centrifuging the reaction product for 3-5 min at 8000-9000 r/min, washing the solid phase with ethanol, and repeating the above operation for several times. In the step, the reacted product can appear in a form of precipitation, and generally, the reaction product can be obtained by filtration, vacuum suction filtration and centrifugation or by spin evaporation by utilizing the characteristic of low boiling point of a reaction solvent, but the nano particles obtained by filtration and suction filtration are not beneficial to purification and collection of samples, the spin evaporation also faces the same problems, and the purified sample can be better collected by comprehensively considering the short-time low-speed centrifugation process, the centrifugation speed is 8000-9000 r/min, and the centrifugation time is 3-5 min.
In one embodiment of the present invention, in S3, the oil phase solvent is ethyl acetate, and the oily fluorine-containing anion salt is one of sodium tetrafluoroborate, lithium bistrifluoro methanesulfonimide, and potassium hexafluorophosphate. For oily fluoroanion salts, they can be used in the present invention as long as they have a corresponding affinity for the lubricating base oil and are capable of forming an ionic liquid by ion exchange; however, in consideration of actual acquisition difficulty and cost, sodium tetrafluoroborate, lithium bistrifluoromethylsulfonimide and potassium hexafluorophosphate which are relatively common are selected in the invention.
In particular, as the oil phase solvent, generally, any oil phase solvent which is not miscible with water, such as ethyl acetate, n-butanol, etc., can be used in the present invention, but from the practical production, n-butanol has a relatively high boiling point and is not easily removed in the subsequent process, and thus, an oil phase solvent having a lower boiling point, such as ethyl acetate, is preferably used.
In particular, in S3, since the boiling point of ethyl acetate is relatively low when separating the solvent in the oil phase, it is theoretically possible to remove the oil phase solvent in various manners such as rotary evaporation, distillation under reduced pressure, natural evaporation, and the like. However, from the viewpoint of the ease of collecting the final product, it is preferable to naturally volatilize the oil phase under ventilation, and the difficulty of collecting the final product is lower.
Meanwhile, the oily fluorine-containing anion salt can be dissolved in water in advance in the use process, so that the reaction speed is convenient to be accelerated.
The invention also aims to provide an ionic liquid functionalized polydopamine nanometer lubricating oil additive which is prepared by adopting any one of the methods, and can be used for antifriction and antiwear of a metal/metal friction pair when being added into lubricating oil.
The invention has the beneficial effects that:
according to the preparation method of the ionic liquid functionalized polydopamine nanometer lubricating oil additive, the 1- (3-aminopropyl) imidazole is firstly modified on the surfaces of polydopamine nanometer particles by utilizing the Michael addition reaction and the Schiff base reaction between the amino groups and the catechol groups, and then the imidazole groups are 'attacked' by methyl iodide, so that the 1- (3-aminopropyl) imidazole iodized polydopamine nanometer particles are gradually obtained, and the method successfully avoids the formation of coagulation of the nanometer particles due to the charge effect when the ionic liquid is directly grafted on the surfaces of the polydopamine nanometer particles. Meanwhile, through simple anion exchange, lipophilic anions are exchanged to the surfaces of the nano particles, so that the permanent and stable dispersion of the polydopamine nano particles in the oil is realized. The ionic liquid has rich functional groups, can provide more adsorption sites when being used as a lubricating additive, accelerates the formation of a friction film and plays a positive role in improving the lubricating performance of nano particles.
Drawings
FIG. 1 is SEM results of the product of the various steps of example 1;
FIG. 2 is an SEM result of polydopamine nanoparticles prepared according to the comparative example of the present invention;
FIG. 3 is XPS results before and after modification of polydopamine nanoparticles prepared according to example 1 of the present invention;
FIG. 4 is the dispersibility of polydopamine nanoparticles before and after modification in polyethylene glycol base oil prepared according to example 1 of the present invention;
FIG. 5 is a graph comparing friction coefficients of ionic liquid functionalized polydopamine nanolubricating oil additives according to examples 1, 2, 3 of the present invention as oil-based lubricating additives;
fig. 6 is a 3-dimensional profiler analysis of wear scar track in a friction test according to example 1 of the present invention.
Detailed Description
In order to make the technical scheme and technical advantages of the present invention more clear, the technical scheme in the implementation process of the present invention will be clearly and completely described below with reference to the embodiments and the accompanying drawings.
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Example 1
(1) Preparation of polydopamine nanoparticles: adding 0.5g of dopamine hydrochloride powder into 10ml of water, and performing ultrasonic treatment to obtain a dopamine hydrochloride solution; taking water, ethanol and ammonia water with the volume ratio of 90:40:2.5ml, and stirring for 30min at 30 ℃ to obtain a mixed solution; mixing the dopamine hydrochloride solution and the mixed solution, and continuously stirring for 12 hours at 30 ℃ in a dark condition; centrifuging the reacted product for 25min at the speed of 11500r/min, washing the solid phase with water, and repeating the centrifugation and washing operation for 4 times to obtain polydopamine nano particles;
(2) Dispersing 200mg of polydopamine nano particles into 40ml of water, stirring at 30 ℃ to form a stable dispersion liquid, adding 3ml of 1- (3-aminopropyl) imidazole, continuously stirring for 12 hours, centrifuging the reacted product for 25 minutes under the condition of 11500r/min, washing a solid phase with ethanol, and repeating the centrifugation and washing operation for 3 times to obtain 1- (3-aminopropyl) imidazole modified polydopamine nano particles;
(3) Dispersing the 1- (3-aminopropyl) imidazole modified polydopamine nano-particles obtained in the step (2) into 40ml of ethanol, adding 15ml of methyl iodide, stirring for 12 hours at 60 ℃, centrifuging the reacted product for 4 minutes under the condition of the speed of 8500r/min, washing a solid phase with ethanol, and repeating the centrifugation and washing operation for 3 times to obtain the 1- (3-aminopropyl) imidazole iodized salt modified polydopamine nano-particles;
(4) Dispersing the 1- (3-aminopropyl) imidazole iodized salt modified polydopamine nano-particles obtained in the step (3) into 20ml of water, then adding 20ml of ethyl acetate, dropwise adding 5ml of aqueous solution dissolved with 400mg of lithium bistrifluoromethylsulfonylimide into the mixture, and continuously stirring the mixture for 0.5h; separating out an oil phase, and removing ethyl acetate under the ventilation condition of 30 ℃ to obtain the ionic liquid functionalized polydopamine nanometer lubricating oil additive.
Example 2
(1) Adding 0.7g of dopamine hydrochloride powder into 10ml of water, and stirring to obtain a dopamine hydrochloride solution; taking water, ethanol and ammonia water with the volume ratio of 90:40:3.0ml, and stirring for 20min at 30 ℃ to obtain a mixed solution; mixing the dopamine hydrochloride solution and the mixed solution, and continuously stirring for 6 hours at 30 ℃ in the dark; centrifuging the reacted product for 30min at the speed of 11000r/min, washing the solid phase with water, and repeating the centrifugation and washing operation for 4 times to obtain polydopamine nano particles;
(2) Dispersing 200mg of polydopamine nano particles into 40ml of water, stirring at 30 ℃ to form a stable dispersion liquid, adding 4ml of 1- (3-aminopropyl) imidazole, continuously stirring for 10 hours, centrifuging the reacted product for 30 minutes under the condition of 11000r/min, washing a solid phase with ethanol, and repeating the centrifugation and washing operation for 3 times to obtain 1- (3-aminopropyl) imidazole modified polydopamine nano particles;
(3) Dispersing the 1- (3-aminopropyl) imidazole modified polydopamine nano-particles obtained in the step (2) into 40ml of anhydrous monohydric alcohol, adding 15ml of methyl iodide, stirring at 60 ℃ for 12h, centrifuging the reacted product for 3min under the condition of 9000r/min, washing a solid phase with ethanol, and repeating the centrifugation and washing operation for 3 times to obtain the 1- (3-aminopropyl) imidazole iodized salt modified polydopamine nano-particles;
(4) Dispersing the 1- (3-aminopropyl) imidazole iodized salt modified polydopamine nano-particles obtained in the step (3) into 30ml of water, then adding 30ml of ethyl acetate, dropwise adding 5ml of aqueous solution dissolved with 300mg of potassium hexafluorophosphate during stirring, and continuously stirring for 0.5h; separating out an oil phase, and removing ethyl acetate under the ventilation condition of 30 ℃ to obtain the ionic liquid functionalized polydopamine nanometer lubricating oil additive.
Example 3
(1) Adding 0.4g of dopamine hydrochloride powder into 10ml of water, and carrying out ultrasonic treatment or stirring to obtain a dopamine hydrochloride solution; taking water, ethanol and ammonia water with the volume ratio of 90:40:2.0ml, and stirring for 30min at 30 ℃ to obtain a mixed solution; mixing the dopamine hydrochloride solution and the mixed solution, and continuously stirring for 12 hours at 30 ℃ in a dark condition; centrifuging the reacted product for 20min at the speed of 12000r/min, washing the solid phase with water, and repeating the centrifugation and washing operation for 4 times to obtain polydopamine nano particles;
(2) Dispersing 100mg of polydopamine nano particles into 30ml of water, stirring at 35 ℃ to form a stable dispersion liquid, adding 2ml of 1- (3-aminopropyl) imidazole, continuously stirring for 10 hours, centrifuging the reacted product for 20 minutes under the condition of 12000r/min, washing a solid phase with ethanol, and repeating the centrifugation and washing operation for 3 times to obtain the 1- (3-aminopropyl) imidazole modified polydopamine nano particles;
(3) Dispersing the 1- (3-aminopropyl) imidazole modified polydopamine nano-particles obtained in the step (2) into 30ml of anhydrous monohydric alcohol, adding 10ml of methyl iodide, stirring for 6 hours at 80 ℃, centrifuging the reacted product for 4 minutes under the condition of the speed of 8500r/min, washing the solid phase with ethanol, and repeating the centrifugation and washing operation for 3 times to obtain the 1- (3-aminopropyl) imidazole iodized salt modified polydopamine nano-particles;
(4) Dispersing the 1- (3-aminopropyl) imidazole iodized salt modified polydopamine nano-particles obtained in the step (3) into 30ml of water, then adding 30ml of ethyl acetate, dropwise adding 5ml of aqueous solution dissolved with 100mg of sodium tetrafluoroborate into the mixture while stirring, and continuously stirring for 1h; separating out an oil phase, and removing ethyl acetate under the ventilation condition of 30 ℃ to obtain the ionic liquid functionalized polydopamine nanometer lubricating oil additive.
To further illustrate the effects of the present invention, the ionic liquid functionalized polydopamine nanolubricating oil additives of the above examples were specifically tested as follows.
Comparative example
(1) Preparation of polydopamine nanoparticles: adding 0.5g of dopamine hydrochloride powder into 10ml of water, and performing ultrasonic treatment to obtain a dopamine hydrochloride solution; taking water, ethanol and ammonia water with the volume ratio of 90:40:0.5ml, and stirring for 30min at 30 ℃ to obtain a mixed solution; mixing the dopamine hydrochloride solution and the mixed solution, and continuously stirring for 12 hours at 30 ℃ in a dark condition; centrifuging the reacted product for 25min at the speed of 11500r/min, washing the solid phase with water, and repeating the centrifugation and washing operation for 4 times to obtain polydopamine nano particles;
(2) Dispersing 200mg of polydopamine nano particles into 40ml of water, stirring at 30 ℃ to form a stable dispersion liquid, adding 3ml of 1- (3-aminopropyl) imidazole, continuously stirring for 12 hours, centrifuging the reacted product for 25 minutes under the condition of 11500r/min, washing a solid phase with ethanol, and repeating the centrifugation and washing operation for 3 times to obtain 1- (3-aminopropyl) imidazole modified polydopamine nano particles;
(3) Dispersing the 1- (3-aminopropyl) imidazole modified polydopamine nano-particles obtained in the step (2) into 40ml of ethanol, adding 15ml of methyl iodide, stirring for 12 hours at 60 ℃, centrifuging the reacted product for 4 minutes under the condition of the speed of 8500r/min, washing a solid phase with ethanol, and repeating the centrifugation and washing operation for 3 times to obtain the 1- (3-aminopropyl) imidazole iodized salt modified polydopamine nano-particles;
(4) Dispersing the 1- (3-aminopropyl) imidazole iodized salt modified polydopamine nano-particles obtained in the step (3) into 20ml of water, then adding 20ml of ethyl acetate, dropwise adding 5ml of aqueous solution dissolved with 400mg of lithium bistrifluoromethylsulfonylimide into the mixture, and continuously stirring the mixture for 0.5h; separating out an oil phase, and removing ethyl acetate under the ventilation condition of 30 ℃ to obtain the ionic liquid functionalized polydopamine nanometer lubricating oil additive.
Sem analysis
SEM results of the product of example 1 are given in fig. 1. Wherein fig. 1a is an SEM result of the unmodified polydopamine nanoparticle, fig. 1b is an SEM result of the 1- (3-aminopropyl) imidazole-modified polydopamine nanoparticle, fig. 1c is an SEM result of the 1- (3-aminopropyl) imidazole-iodisalt-modified polydopamine nanoparticle, and fig. 1d shows an SEM result of the oil-soluble 1- (3-aminopropyl) imidazole-iodisalt-modified polydopamine nanoparticle. From the SEM results, the nanoparticles before and after modification were spherical, and their average particle diameters were slightly increased as the reaction proceeded, 92.71nm, 93.45nm, 94.09nm and 96.36nm, respectively. Meanwhile, referring to fig. 2, SEM results of polydopamine nanoparticles obtained under the comparative example condition, namely under an alkaline environment regulated by 0.5ml of ammonia water, are provided, wherein the particle size distribution is uneven, the average particle size is 299.81nm, the particle size is large, the polydopamine nanoparticles are not beneficial to entering a friction interface, and when the polydopamine nanoparticles are used as a lubricating additive, good antifriction and antiwear effects may not be achieved.
XPS analysis
The XPS results of the product of example 1 are given in FIG. 3. From the graph, the unmodified polydopamine nano-particles mainly detect C, N and O elements, after imidazole groups containing more N elements are grafted to the surfaces of the polydopamine nano-particles, the detected signals of the N elements become stronger, then the I element is detected by adding methyl iodide, meanwhile, the content of the C element is obviously improved due to the introduction of methyl, after anion exchange, the signals of the I element disappear, and F and S elements belonging to the bistrifluoro methanesulfonimide are correspondingly detected. The above results indicate that the synthesis of the examples of the present invention was successful.
3. Dispersion stability test
The ability of a lubricant additive to disperse stably in a base oil is an important indicator for evaluating its performance. The nanoparticles obtained in example 1 before and after modification were sonicated into a base oil under the same conditions, the mass fraction was 1.2wt%, and the dispersion stability was compared by standing for a period of time. As shown in fig. 4, the pure polydopamine nanoparticles just after the end of ultrasound show obvious coagulation, a large amount of precipitation exists at the bottom, obvious precipitation occurs on day 2 due to the action of gravity, and the dispersibility is poor; the polydopamine nano particles modified by the ionic liquid form clear dispersion liquid in oil, and after standing for 30 days, the polydopamine nano particles still have no precipitation and have better dispersion stability.
4. Antifriction and antiwear performance test
The products of examples 1, 2, 3 and comparative example were uniformly dispersed in a base oil, and then subjected to a steel/steel friction pair lubricating property test, and the friction coefficient comparison results thereof are shown in fig. 5 a. The modified polydopamine nanoparticles of the three oil-soluble ionic liquids have obvious improvement effects on the lubricating performance of the base oil, and the modified polydopamine nanoparticles obtained by the comparative example have poor improvement effects on the lubricating performance of the base oil. Fig. 5b shows the results of the friction performance test of the product of example 1 in base oil at different additive concentrations, demonstrating that at a concentration of 1.2 wt.%, the additive enhances the lubricating properties of the base oil most significantly. Meanwhile, referring to fig. 6, it can be seen from the width and depth of the trace of the grinding mark, the width and depth of the grinding mark of the base oil after the additive is added are reduced from 483.2 μm and 10.2 μm under the lubrication of the pure base oil to 353.5 μm and 4.7 μm respectively, and the abrasion resistance is obviously improved.
The present invention is not limited to the above-mentioned embodiments, but is intended to be limited to the following embodiments, and any modifications, equivalents and modifications can be made to the above-mentioned embodiments without departing from the scope of the invention.
Claims (8)
1. The preparation method of the ionic liquid functionalized polydopamine nanometer lubricating oil additive is characterized by comprising the following steps of:
s1, taking polydopamine nano-particles, dispersing the polydopamine nano-particles in water, adding 1- (3-aminopropyl) imidazole, continuously stirring and reacting for 10-12 hours, and separating and purifying the product to obtain 1- (3-aminopropyl) imidazole modified polydopamine nano-particles, wherein each 100-200 mg polydopamine nano-particles corresponds to 2-4 mL of 1- (3-aminopropyl) imidazole;
s2, dispersing the 1- (3-aminopropyl) imidazole modified polydopamine nano-particles into monohydric alcohol, adding methyl iodide, continuously stirring for 6-12 hours at the temperature of 60-80 ℃, and separating and purifying the product to obtain the 1- (3-aminopropyl) imidazole iodisalt modified polydopamine nano-particles, wherein each 100-200 mg polydopamine nano-particles corresponds to 10-15 mL methyl iodide;
s3, dispersing the polydopamine nano-particles modified by the 1- (3-aminopropyl) imidazole iodized salt into water, then adding an oil phase solvent, dripping an oil phase fluorine-containing anion salt water solution, stirring and reacting for 0.5-1 h, separating the oil phase after the reaction is finished, and removing the solvent in the oil phase, wherein the mass ratio of the oil phase fluorine-containing anion salt to the polydopamine nano-particles modified by the 1- (3-aminopropyl) imidazole iodized salt is 1-3:1.
2. The method of claim 1, wherein the polydopamine nanoparticle is prepared by the following method:
adding dopamine hydrochloride into water and dissolving to obtain a dopamine hydrochloride solution, then uniformly mixing water, ethanol and ammonia water in a volume ratio of 90:40:1.5-3 to obtain a mixed solution, mixing the dopamine hydrochloride solution and the mixed solution, continuously stirring and reacting for 6-24 hours under normal temperature and light-shielding conditions, and separating and purifying the reacted product to obtain polydopamine nano particles; wherein, for the dopamine hydrochloride solution, each 10ml of water corresponds to 0.3 to 0.8g of dopamine hydrochloride; the addition volume ratio of the mixed solution to the dopamine hydrochloride solution is 6-14:1.
3. The method according to claim 2, wherein the specific operations of separating and purifying the polydopamine nanoparticles are as follows: centrifuging the reaction product for 20-30 min under 10000-12000 r/min, washing the solid phase with water, and repeating the above operation for several times.
4. The method according to claim 1, wherein in S1, the specific operations of separation and purification are: centrifuging the reaction product for 20-30 min under 10000-12000 r/min, washing the solid phase with ethanol, and repeating the above operation for several times.
5. The method of claim 1, wherein in S2, the monohydric alcohol is methanol or ethanol.
6. The method according to claim 1, wherein in S2, the specific operations of separation and purification are: centrifuging the reaction product for 3-5 min at 8000-9000 r/min, washing the solid phase with ethanol, and repeating the above operation for several times.
7. The method of claim 1, wherein in S3, the oil phase solvent is ethyl acetate and the oily fluoride-containing anion salt is one of sodium tetrafluoroborate, lithium bistrifluoromethylsulfonimide and potassium hexafluorophosphate.
8. An ionic liquid functionalized polydopamine nanometer lubricating oil additive prepared by the method of any one of claims 1-7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310505598.9A CN116535643A (en) | 2023-05-08 | 2023-05-08 | Ionic liquid functionalized polydopamine nano lubricating oil additive and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310505598.9A CN116535643A (en) | 2023-05-08 | 2023-05-08 | Ionic liquid functionalized polydopamine nano lubricating oil additive and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116535643A true CN116535643A (en) | 2023-08-04 |
Family
ID=87448348
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310505598.9A Pending CN116535643A (en) | 2023-05-08 | 2023-05-08 | Ionic liquid functionalized polydopamine nano lubricating oil additive and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116535643A (en) |
-
2023
- 2023-05-08 CN CN202310505598.9A patent/CN116535643A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Mchedlov-Petrossyan | Fullerenes in liquid media: an unsettling intrusion into the solution chemistry | |
| Tombácz et al. | The role of reactive surface sites and complexation by humic acids in the interaction of clay mineral and iron oxide particles | |
| US20040115345A1 (en) | Nanoparticle fractionation and size determination | |
| Huang et al. | Efficient and sustainable regeneration of bifunctional ionic liquid for rare earth separation | |
| Zeinali et al. | Fabrication of a selective and sensitive electrochemical sensor modified with magnetic molecularly imprinted polymer for amoxicillin | |
| CN1709617A (en) | Method for preparing nano copper particle | |
| CN101433726A (en) | Magnetic resonance contrast agent based on carbon nano-tube and preparation method | |
| Hunter et al. | Colloid stability and aggregation in estuaries: 1. Aggregation kinetics of riverine dissolved iron after mixing with seawater | |
| CN116535643A (en) | Ionic liquid functionalized polydopamine nano lubricating oil additive and preparation method thereof | |
| Gan et al. | Coagulation of bitumen with kaolinite in aqueous solutions containing Ca2+, Mg2+ and Fe3+: Effect of citric acid | |
| JP4275976B2 (en) | Concentration method of fine particle-containing dispersion and fine particle recovery method | |
| EP3538679B1 (en) | Ionic liquid-acid aqueous two-phase system | |
| CN112247158B (en) | Method for enriching gold nanoclusters in aqueous phase | |
| CN102431994A (en) | Method using salt free zwitterion vesicle aqueous solution for extracting purified fullerene C60 | |
| Yu et al. | Effects of particle wettability and water moisture on separation efficiency and drop size distribution of particle-laden droplets in oil | |
| JP4904572B2 (en) | Extraction method and use of metal fine particles | |
| Obiora-Okafo | Performance of polymer coagulants for colour removal from dye simulated medium: Polymer adsorption studies | |
| EP0099804B1 (en) | Separation processes of metals contained in hyper acid mediums by way of ionic flotation | |
| CN100345608C (en) | Organic substance extraction in water with ionic liquid as extractant | |
| CN113209938A (en) | Preparation of gold nanoparticle @ phosphorus and sulfur co-doped graphene quantum nanocomposite with core-shell structure, product and application | |
| Es’haghi et al. | Surface Modified Nanomagnetite-Assisted Hollow Fiber Solid/Liquid Phase Microextraction for Pre-concentration and Determination of Palladium in Water Samples by Differential Pulse Voltammetry | |
| AU2016238725A1 (en) | Treatment of degraded oxime metal extractants in process organic solutions | |
| CN116574547B (en) | Oil-dispersible hyperbranched polyionic liquid functionalized carbon dot and preparation method and application thereof | |
| CN116239771A (en) | Oil-dispersible polydopamine nano lubricating additive and preparation method and application thereof | |
| WO2021078574A1 (en) | Method for separating polymers in an aqueous fluid by means of magnetisable particles and a zirconium salt |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |