CN115404115A - Nano-copper lubricating oil additive and preparation method thereof - Google Patents
Nano-copper lubricating oil additive and preparation method thereof Download PDFInfo
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M163/00—Lubricating compositions characterised by the additive being a mixture of a compound of unknown or incompletely defined constitution and a non-macromolecular compound, each of these compounds being essential
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
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- C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
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- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
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- C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
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- C10M2207/10—Carboxylix acids; Neutral salts thereof
- C10M2207/16—Naphthenic acids
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
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- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
- C10M2215/04—Amines, e.g. polyalkylene polyamines; Quaternary amines having amino groups bound to acyclic or cycloaliphatic carbon atoms
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/044—Sulfonic acids, Derivatives thereof, e.g. neutral salts
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/04—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
- C10M2219/046—Overbasedsulfonic acid salts
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/06—Thio-acids; Thiocyanates; Derivatives thereof
- C10M2219/062—Thio-acids; Thiocyanates; Derivatives thereof having carbon-to-sulfur double bonds
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- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
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Abstract
The invention belongs to the technical field of nano material preparation, and particularly relates to a nano copper lubricating oil additive and a preparation method thereof. The preparation method adopts a copper precursor without heteroatoms to prepare the nano-copper lubricating oil additive in a lubricating oil medium by one step by utilizing an in-situ surface modification technology. The preparation method realizes the in-situ one-step preparation of the nano-copper lubricating oil additive, has the characteristics of high yield and environmental protection, simplifies the application steps of nano-copper and improves the application universality.
Description
Technical Field
The invention belongs to the technical field of nano material preparation, and particularly relates to a nano copper lubricating oil additive and a preparation method thereof.
Background
In recent years, with the rapid development of advanced manufacturing industry, conventional lubricating materials have approached the limit of their service performance, and high-performance nano lubricating materials with unique properties have become one of the research hotspots in the field of mechanical lubrication. Since the last 90 years, nano-copper as a lubricating oil additive shows excellent performances of friction reduction, wear resistance, extreme pressure and wear self-repair, and has received extensive attention of scientists in various countries. However, pure copper nanoparticles cannot be used because of poor dispersibility and stability in lubricating oils. It is generally necessary to modify the surface of the material during the preparation process to improve its dispersion stability.
Generally, the preparation and surface modification of nano-copper are completed in a water-organic two-phase or water-phase medium to obtain the oil-soluble nano-copper with oleophylic surface. Chinese patent No. CN101200667B discloses a preparation method of surface-modified oil-soluble nano-copper, and the invention prepares the oil-soluble nano-copper in a water-organic two-phase system. The surface organic modification of the nano-copper in the forming process is completed at the interface of a water phase and an organic phase, the reaction process is transferred from the water phase to the organic phase, a product stays in the organic phase, and the oil-soluble nano-copper is obtained by separating the organic phase and carrying out reduced pressure distillation; the method has simple process and is suitable for large-scale production, but the reaction process uses a large amount of organic solvent, so the danger is high, and the addition of acid and alkali causes a large amount of soluble salt in the water phase, thereby being not beneficial to energy conservation and environmental protection. Chinese patent No. CN110744068B discloses oil-soluble nano-copper and a preparation method thereof, and the oil-soluble nano-copper is prepared by adopting a precursor without heteroatoms in a water-phase system. The method has high process yield, high safety and environmental protection, and solves the problems of interfacial reaction, process safety and the like in the synthesis process of the oil-soluble nano copper; however, when the oil-soluble nano-copper is used as a lubricating oil additive in a compounding manner, the dispersion state of the lubricating oil and the oil-soluble nano-copper in the lubricating oil can be influenced by the polarity difference of the lubricating oil and the oil-soluble nano-copper, so that a partial coagulation phenomenon is generated, and the functions of lubricating parts are further influenced. Therefore, other additives such as viscosity index improver and dispersant are additionally added to maintain the stable dispersion of the oil-soluble nano-copper in the lubricating oil in the actual use process.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a nano-copper lubricating oil additive and a preparation method thereof. The preparation method is convenient and pollution-free, realizes in-situ and one-step preparation of the nano-copper lubricating oil additive, has the characteristics of high yield and environmental protection, simplifies the application steps of nano-copper and improves the application universality of the nano-copper.
In order to realize the purpose, the technical scheme of the invention is as follows:
a preparation method of a nano-copper lubricating oil additive comprises the following steps:
1) Stirring the lubricating oil and the copper modifier at 25-85 ℃ for 10-60min until uniformly mixing to obtain a composite reaction solvent;
2) Stirring and reacting the copper precursor and the composite reaction solvent at 25-85 ℃ for 0.5-5h to obtain a copper suspension mixed solution;
3) Adjusting the pH value of the copper suspension mixed solution in the step 2) to 7-9, adding a reducing agent at the temperature of 25-85 ℃ for reduction reaction for 0.5-24h to obtain nano-copper lubricating oil emulsion;
4) And (3) carrying out reduced pressure distillation on the nano-copper lubricating oil emulsion in the step 3), cooling to below 40 ℃, adding a small amount of antioxidant, and uniformly stirring to obtain the nano-copper lubricating oil additive.
Specifically, the lubricating oil in the step 1) is one of synthetic oil, mineral oil, compound oil and the like; the mass ratio of the copper modifier to the lubricating oil is 1 (0.1-5).
More preferably, the synthetic oil is one of poly-alpha-olefin, dioctyl sebacate, diisooctyl cyclohexanedicarboxylate and the like; the mineral oil is liquid paraffin; the compound oil consists of base oil, a dispersant and a detergent according to the mass ratio of (2-8) to (1-4).
Further, the dispersant in the compound oil is one of mono-alkenyl succinimide, di-alkenyl succinimide, multi-alkenyl succinimide, polyisobutylene succinimide and the like; the detergent is sulfonate detergent, such as one of high, medium and low base number synthetic calcium sulfonate, petroleum calcium sulfonate and the like; the base oil is one of liquid paraffin, poly-alpha-olefin, dioctyl sebacate, diisooctyl cyclohexanedicarboxylate and the like.
In the invention, the synthetic calcium sulfonate with high, medium and low base numbers and the petroleum calcium sulfonate are all from the market, and the base number range of the product is as follows: low base number: 20-35mgKOH/g, medium base value: greater than or equal to 145mgKOH/g, high base number: more than or equal to 295 mgKOH/g.
Specifically, in the step 1), the copper modifier is one or more of aliphatic carboxylic acid, alkyl primary amine, alkyl secondary amine, alkyl tertiary amine, dialkyl dithiophosphoric acid, N-dialkyl dithiocarbamic acid, naphthenic acid, alkyl phosphoric acid and the like, and the carbon number of the alkyl is 4-18. For example, dioctyl dithiophosphoric acid, diisooctyl dithiophosphoric acid, N-diisobutyl dithiocarbamate, di (2-ethyl-hexyl) phosphoric acid (also known as P204, a widely used industrial extractant), oleic acid, oleyl amine, di-N-butyl amine, trioctyl decyl tertiary amine, and the like may be mentioned.
Further, the copper precursor in the step 2) is one or more of cupric oxide, cuprous oxide, cupric hydroxide, basic cupric carbonate and the like; the concentration of the copper precursor in the copper suspension mixed solution is 1-4mol/L.
Specifically, the reducing agent in step 3) is one or more of hydrazine hydrate, formaldehyde, ethylene glycol, formic acid and the like. In the step 3), one of ammonia water, short-carbon-chain organic primary amine and secondary amine (C1-4), glacial acetic acid and the like can be adopted to adjust the pH value of the copper-suspended mixed solution to 7-9, the mass concentration of the ammonia water is 25-28%, and the content of the short-carbon-chain organic primary amine, the short-carbon-chain organic secondary amine and the glacial acetic acid is 99% or more.
Further preferably, the mass ratio of the copper precursor, the reducing agent and the copper modifier is 1 (0.5-5) to (0.3-3).
Specifically, the antioxidant in the step 4) is one of zinc alkyl phenol dithiophosphate, butyl octyl zinc dithiophosphate, dioctyl alkaline zinc dithiophosphate, dialkyl zinc dithiophosphate, di-tert-butyl-p-cresol, di-tert-butyl mixed phenol and the like; the mass ratio of the antioxidant to the nano-copper lubricating oil additive is (0.01-0.05): 1.. The ditertiary butyl mixed phenol is 2,6-ditertiary butyl mixed phenol, has the industrial code of T502A in the lubricating oil industry, and is a mixed shielding phenol antioxidant.
The invention also provides a nano-copper lubricating oil additive prepared by the method.
The invention adopts a copper precursor without heteroatom, and directly prepares the nano-copper lubricating oil additive in a lubricating oil medium by one step by utilizing an in-situ surface modification technology under the condition of no added solvent. The invention is a convenient and pollution-free in-situ preparation method. The invention utilizes the lubricating oil of a target application system as a reaction medium and a dispersion medium, and the prepared nano-copper lubricating additive is uniform and stable, is similar to a homogeneous system, has the same or similar inherent properties with the lubricating oil for actual working conditions during application, and can be directly added into the lubricating oil without other adjustment on the working conditions. From the aspects of economy, environmental friendliness, convenience in application and the like, the method and the product disclosed by the invention have important practical value and significance in research and development. Compared with the prior art, the invention has the following beneficial effects:
1) The invention has no external solvent, only contains a small amount of water generated by synthesis reaction in the reaction system, and directly concentrates to obtain the product after the preparation is finished, thereby greatly improving the yield of the product;
2) The invention takes the lubricating oil as a reaction medium and a dispersion phase, and the copper nanoparticles in the target product are uniformly dispersed in the lubricating oil;
3) The properties such as viscosity and the like of the nano-copper lubricating oil additive prepared by the invention can be adjusted through the proportion change among the components of the compound oil, so that the properties are basically consistent with the inherent properties of the lubricating oil used in the target application lubricating working condition, and the application universality is enlarged;
4) The invention has no three wastes generated in the reaction process, has no conventional organic solvent as a reaction medium, has simple production process, is safe and environment-friendly, and is suitable for large-scale industrial production.
Drawings
FIG. 1 is a TEM photograph of nano-copper contained in the nano-copper lubricant additive prepared in example 1 after washing with acetone; as can be seen from the figure, the size of the copper nanoparticles is 5-10nm, the average particle size is 8nm, and the monodispersity of the particles is good;
fig. 2 is an optical photograph of the nano-copper lubricant additive prepared in example 1 dispersed in an organic solvent, wherein the oil-soluble nano-copper is added in an amount of 1wt% and 2wt%, and the solvent is sequentially from left to right: petroleum ether, xylene; as can be seen from the figure, the nano-copper lubricating additive has good dispersion stability in various organic solvents;
FIG. 3 shows the four-ball friction wear test results of the nano-copper lubricating oil additive prepared in example 1 applied to Compton gasoline engine oil (10W-40), a finished product oil; KPD is Compton gasoline engine oil, DNCu-0.5wt% is Compton gasoline engine oil added with 0.5wt% of the nano-copper lubricating oil additive prepared in the embodiment; in the graph, the a test temperature is 120 ℃, where WSD represents the wear-mark diameter and COF represents the coefficient of friction; the test temperatures of B and C are 75 ℃ and 120 ℃ respectively;
FIG. 4 is an optical photograph of the color change during the reduction reaction of the nano-copper lubricant additive prepared in example 2 and the state of the product before and after distillation;
FIG. 5 is a TEM photograph of the nano-copper contained in the nano-copper lubricant additive prepared in example 3 after washing with acetone.
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited thereto.
In the following examples, all the raw materials were general commercial products which can be directly purchased, unless otherwise specified. For example, detergents such as high-base-number calcium petroleum sulfonate and medium-base-number synthetic calcium sulfonate, dispersants such as mono-alkenyl succinimide, and antioxidants such as dialkyl zinc dithiophosphate are purchased from new materials of Xinxiangruifeng, inc.; copper modifiers such as N, N-diisobutyldithiocarbamate were purchased from Hao New materials group, inc. of Heliowa. Diisooctyl dithiophosphoric acid and N, N-diisobutyl dithiocarbamic acid are synthetic intermediates of corresponding zinc salts and can be directly purchased.
Example 1
A preparation method of a nano-copper lubricating oil additive specifically comprises the following steps:
1) Weighing 27g (0.076 mol) of copper modifier dioctyl dithiophosphate and 27g of lubricating oil dioctyl sebacate in a 250mL three-necked bottle, and stirring at constant temperature of 50 ℃ for 30min until the components are uniformly mixed to obtain light yellow green liquid (namely a composite reaction solvent);
2) Adding 7.84g (0.08 mol) of copper hydroxide into the composite reaction solvent, keeping the temperature at 50 ℃, stirring and reacting for 60min, wherein the solution is changed from light yellow green to yellow green turbid liquid (namely a copper suspension mixed liquid, the concentration of a copper precursor is about 1.48 mol/L), and the pH value of the turbid liquid is 9 without adjusting the pH value;
3) Weighing 5.06g of hydrazine hydrate (the mass concentration is 80 percent, and the mol is 0.08 mol), slowly adding the hydrazine hydrate into a three-neck flask under stirring, carrying out reduction reaction at 50 ℃ for 2h, and then heating to 80 ℃ for reaction for 1h to obtain orange brown reaction liquid (namely nano-copper lubricating oil emulsion);
4) And (3) reducing the pressure of the reaction liquid, distilling the reaction liquid, cooling to 40 ℃, adding 0.6g of di-tert-butyl mixed phenol antioxidant, and uniformly stirring to obtain the nano-copper lubricating oil additive.
The total volume of the reaction system was about 75mL, the yield of the nano-copper lubricant additive was 59g (about 62 mL), and the product volume was about 82% of the total volume of the reaction. The grain diameter of the contained nano-copper particles is 5-10nm, a transmission electron micrograph is shown in figure 1, and a dispersity photograph of the obtained nano-copper lubricating oil additive in an organic solvent is shown in figure 2 (the organic solvent comprises petroleum ether and dimethylbenzene from left to right in sequence, and the addition amounts of the oil-soluble nano-copper are respectively 1wt% and 2 wt%). As can be seen from FIGS. 1-2: the obtained oil-soluble nano-copper has small and uniform particle size and better dispersion stability.
FIG. 3 shows the four-ball friction wear test results of the nano-copper lubricating oil additive prepared in example 1 applied to Compton gasoline engine oil (10W-40), a finished product. As can be seen from the figure: the addition of the nano-copper lubricating oil additive enables the friction coefficient and the wear-scar diameter of the Compton gasoline engine oil to be reduced at different service temperatures, namely the lubricating performance of the Compton gasoline engine oil is improved, wherein the addition amount of 0.5wt% of the nano-copper lubricating oil additive has excellent antifriction and wear resistance.
Example 2
A preparation method of a nano-copper lubricating oil additive specifically comprises the following steps:
1) Weighing 12.5g of polyisobutylene succinimide, 12.5g of high-base number calcium petroleum sulfonate and 25g of dioctyl sebacate in a 250mL three-necked bottle, and stirring at the constant temperature of 60 ℃ for 10min to obtain dark red brown compound oil; adding 28.3g (0.08 mol) of diisooctyl dithiophosphoric acid into the compound oil, and stirring for 30min at 60 ℃ until the mixture is uniformly mixed to obtain a composite reaction solvent;
2) Adding 7.84g (0.08 mol) of copper hydroxide into the composite reaction solvent, and stirring and reacting for 2h at 60 ℃ to form a dark green near-black suspension (namely a copper suspension mixed solution, wherein the concentration of a copper precursor is about 1.02 mol/L);
3) After adjusting the pH value to 8 by glacial acetic acid, slowly adding 5.06g of hydrazine hydrate (the mass concentration is 80%,0.08 mol) into a three-neck flask under stirring, reacting at 60 ℃ for 1h, heating to 70 ℃ for 1h, and then heating to 80 ℃ for 2h to obtain a brown orange reaction solution (namely nano-copper lubricating oil emulsion);
4) And (3) carrying out reduced pressure distillation on the reaction liquid, cooling to 40 ℃, adding 0.85g of di-tert-butyl-p-cresol antioxidant, and uniformly stirring to obtain the nano-copper lubricating oil additive. The total volume of the reaction system was about 95mL, the nano-copper lube additive yield was 83.4g (about 90 mL), and the product volume was about 94% of the total reaction volume.
In the embodiment, the color change of the reduction reaction process is shown in fig. 4, and the color of the dark green near-black suspension containing the copper precursor is changed from near-black, brown, yellow and brown oranges in sequence after reduction; the dark red brown nano copper lubricating oil additive is obtained after distillation, and the volume change of the product before and after distillation is small, which indicates that the yield of the product is high.
Example 3
A preparation method of a nano-copper lubricating oil additive specifically comprises the following steps:
1) Weighing 20g of liquid paraffin and 36.7mL (32.8 g) of N, N-diisobutyl dithiocarbamate (0.16 mol) in a 250mL three-necked bottle, and stirring for 10min at 25 ℃ to uniformly mix to obtain a composite reaction solvent;
2) Weighing 8.0g (0.1 mol) of copper oxide, adding the copper oxide into the composite reaction solvent, and stirring for 3h at 25 ℃ to obtain a brown-green oil turbid liquid (namely a copper suspension mixed liquid, wherein the concentration of a copper precursor is about 1.78 mol/L);
3) Keeping the temperature at 25 ℃, adding ammonia water to adjust the pH value to 8 under stirring, dropwise adding 11.68g of hydrazine hydrate (the mass concentration is 30 percent and 0.07 mol), stirring for reacting for 3 hours, and then heating to 80 ℃ for reacting for 1 hour to obtain dark reddish brown reaction liquid (namely nano-copper lubricating oil emulsion);
4) And (3) reducing the pressure of the reaction liquid, distilling the reaction liquid, cooling to 40 ℃, adding 1.3g of di-tert-butyl mixed phenol antioxidant, and stirring and mixing uniformly to obtain the nano-copper lubricating oil additive. The total volume of the reaction system was about 75mL, the yield of the nano-copper lubricant additive was 59g (about 60 mL), and the product volume was about 80%.
FIG. 5 shows a TEM photograph of the nano-copper contained in the nano-copper lubricant additive prepared in example 3 after washing with acetone; as seen from the figure, the copper nanoparticles have a size of 8 to 20nm, an average particle diameter of 15nm, and good dispersibility.
Example 4
A preparation method of a nano-copper lubricating oil additive specifically comprises the following steps:
1) Weighing 15g of poly-alpha-olefin (PAO 6) and 33.5mL (29.8 g) of di (2-ethyl-hexyl) phosphoric acid (0.1 mol) in a 250mL three-necked bottle, and stirring for 30min at 40 ℃ to uniformly mix to obtain a composite reaction solvent;
2) Weighing 4.0g (0.05 mol) of copper oxide and 7.2g (0.05 mol) of cuprous oxide, adding into the composite reaction solvent, keeping at 40 ℃, stirring for 30min, heating to 60 ℃, stirring for 30min to obtain a copper suspension mixed solution, wherein the concentration of a copper precursor is about 2.08 mol/L;
3) Keeping the temperature at 60 ℃, adding ethylamine while stirring to adjust the pH value of the reaction liquid to 8, dropwise adding 12.5g of hydrazine hydrate (the mass concentration is 80%, and the mass concentration is 0.2 mol), and stirring to react for 5 hours to obtain dark reddish brown reaction liquid (namely nano copper lubricating oil emulsion);
4) And (3) carrying out reduced pressure distillation on the reaction liquid, cooling to 40 ℃, adding 0.56g of zinc dithiophosphate dicaprylyl (T203) antioxidant, and stirring and mixing uniformly to obtain the nano-copper lubricating oil additive. The total volume of the reaction system was about 75mL, the nano-copper lube additive yield was 51g (about 52 mL), and the product volume was about 69%.
Example 5
A preparation method of a nano-copper lubricating oil additive specifically comprises the following steps:
1) Weighing 30g of dioctyl sebacate, 35.4g (0.1 mol) of diisooctyl dithiophosphoric acid and 14.1g (0.05 mol) of oleic acid in a 250mL three-neck flask, and stirring for 50min at 50 ℃ to uniformly mix to obtain a composite reaction solvent;
2) Weighing 8.84g (0.04 mol) of basic copper carbonate and 8.46g (0.06 mol) of cuprous oxide, adding into a composite reaction solvent, and stirring for 1h at 50 ℃ to form a green viscous liquid (namely a copper suspension mixed solution, wherein the concentration of a copper precursor is about 1.25 mol/L);
3) Keeping the temperature at 50 ℃, adding diethylamine under stirring to adjust the pH value of the reaction solution to 9, dropwise adding 18.77g of hydrazine hydrate (the mass concentration is 80 percent, 0.3 mol) under stirring, stirring for 1h, heating to 80 ℃ and reacting for 5h to obtain a reddish brown reaction solution (namely nano-copper lubricating oil emulsion);
4) And (3) reducing the pressure of the reaction liquid, distilling the reaction liquid, cooling to 40 ℃, adding 2.5g of di-tert-butyl mixed phenol antioxidant, and uniformly stirring to obtain the nano-copper lubricating oil additive. The total volume of the reaction system was about 147mL, the yield of the nano-copper lubricant additive was 105g (about 110 mL), and the product volume was about 75%.
Example 6
A preparation method of a nano-copper lubricating oil additive specifically comprises the following steps: 1) Weighing 10g of diene succinimide, 20g of medium-base-value synthetic calcium sulfonate and 30g of cyclohexane dicarboxylic acid diisooctyl ester in a 250mL three-necked bottle, and stirring at the constant temperature of 65 ℃ for 1h to obtain brown compound oil; adding 14.1g (0.05 mol) of oleic acid and 13.4g (0.05 mol) of oleylamine into the compound oil, and stirring for 30min at 65 ℃ until the mixture is uniformly mixed to obtain a compound reaction solvent;
2) Adding 14.7g (0.15 mol) of copper hydroxide into the composite reaction solvent, and stirring and reacting for 1h at 65 ℃ to form green suspension (namely copper suspension mixed liquor);
3) Adjusting the pH value of the reaction system to 8 by using ethylamine under a stirring state, and then heating to 80 ℃. Adding 37.5g of hydrazine hydrate (with the mass concentration of 60 percent and the mol of 0.45) slowly into the three-port furnace while stirring, and keeping the temperature at 80 ℃ for reacting for 3h to obtain dark orange reaction liquid (namely nano-copper lubricating oil emulsion);
4) And (3) carrying out reduced pressure distillation on the reaction liquid, cooling to 40 ℃, adding 3.5g of di-tert-butyl-p-cresol antioxidant, and uniformly stirring to obtain the nano-copper lubricating oil additive. The total volume of the reaction system is about 145mL, the yield of the nano-copper lubricating oil additive is 97g (95 mL), and the volume of the product accounts for 65%.
Example 7
A preparation method of a nano-copper lubricating oil additive specifically comprises the following steps:
1) Weighing 10g of base oil dioctyl sebacate, 7.4g (0.02 mol) of copper modifier trioctyl decyl tertiary amine, 5.4g (0.03 mol) of naphthenic acid and 35.3g (0.1 mol) of diisooctyl dithiophosphoric acid in a 250mL three-necked bottle, and stirring for 1h at 65 ℃ until the materials are uniformly mixed to obtain a composite reaction solvent;
2) Adding 9.8g (0.1 mol) of copper hydroxide into the composite reaction solvent, and stirring and reacting for 1h at 65 ℃ to form dark green suspension (namely copper suspension mixed solution);
3) Adjusting the pH value of a reaction system to 9 by adopting ammonia water under a stirring state, slowly adding 6.33g of hydrazine hydrate (with the mass concentration of 80 percent and 0.1 mol) into a three-necked bottle under stirring, keeping the temperature at 60 ℃ for reaction for 2h, and then heating to 80 ℃ for reaction for 2h to obtain brown reaction liquid (namely nano-copper lubricating oil emulsion);
4) And (3) carrying out reduced pressure distillation on the reaction liquid, cooling to 40 ℃, adding 1.3g of sulfur-phosphorus dialkyl zinc salt antioxidant, and uniformly stirring to obtain the nano-copper lubricating oil additive. The total volume of the reaction system is about 85mL, the yield of the nano-copper lubricating oil additive is 64.5g (65 mL), and the volume of the product accounts for 76%.
Claims (10)
1. The preparation method of the nano-copper lubricating oil additive is characterized by comprising the following steps of:
1) Uniformly stirring and mixing the lubricating oil and the copper modifier at 25-85 ℃ to obtain a composite reaction solvent;
2) Stirring and reacting the copper precursor and the composite reaction solvent at 25-85 ℃ for 0.5-5h to obtain a copper suspension mixed solution;
3) Adjusting the pH value of the copper suspension mixed solution in the step 2) to 7-9, adding a reducing agent at the temperature of 25-85 ℃ for reduction reaction for 0.5-24h to obtain nano-copper lubricating oil emulsion;
4) And (3) carrying out reduced pressure distillation on the nano-copper lubricating oil emulsion in the step 3), cooling to below 40 ℃, adding an antioxidant, and uniformly stirring to obtain the nano-copper lubricating oil additive.
2. The method for preparing the nano-copper lubricating oil additive according to claim 1, wherein the lubricating oil in the step 1) is one of synthetic oil, mineral oil and compound oil; the mass ratio of the copper modifier to the lubricating oil is 1 (0.1-5).
3. The method for preparing nano-copper lubricant additive according to claim 2, wherein the synthetic oil is one of poly-alpha-olefin, dioctyl sebacate, and diisooctyl cyclohexanedicarboxylate; the mineral oil is liquid paraffin; the compound oil consists of base oil, a dispersant and a detergent according to the mass ratio of (2-8) to (1-4).
4. The method of claim 3, wherein the dispersant in the compounded oil is one of mono alkenyl succinimide, di alkenyl succinimide, poly alkenyl succinimide, and polyisobutylene succinimide; the cleaning agent is a sulfonate cleaning agent; the base oil is one of liquid paraffin, poly-alpha-olefin, dioctyl sebacate and cyclohexane dicarboxylic acid diisooctyl ester.
5. The method for preparing the nano-copper lubricating additive as claimed in claim 1, wherein the copper modifier in step 1) is one or more of aliphatic carboxylic acid, alkyl primary amine, alkyl secondary amine, alkyl tertiary amine, dialkyl dithiophosphoric acid, N-dialkyl dithiocarbamic acid, naphthenic acid and alkyl phosphoric acid, and the number of carbon atoms of the alkyl group is 4-18.
6. The method for preparing the nano-copper lubricant additive according to claim 1, wherein the copper precursor in the step 2) is one or more of copper oxide, cuprous oxide, cupric hydroxide and basic cupric carbonate; the concentration of the copper precursor in the copper suspension mixed solution is 1-4mol/L.
7. The method for preparing the nano-copper lubricating oil additive according to claim 1, wherein the reducing agent in the step 3) is one or more of hydrazine hydrate, formaldehyde, ethylene glycol and formic acid.
8. The method for preparing the nano-copper lubricating oil additive as claimed in claim 7, wherein the ratio of the amount of the copper precursor, the amount of the reducing agent and the amount of the copper modifier is 1 (0.5-5) to 0.3-3).
9. The method for preparing nano-copper lubricating oil additive according to claim 1, wherein the antioxidant in step 4) is one of zinc alkyl thiophosphate, zinc butyl octyl thiophosphate, basic zinc dioctyl thiophosphate, dialkyl zinc thiophosphate, di-tert-butyl-p-cresol and di-tert-butyl mixed phenol; the mass ratio of the antioxidant to the nano-copper lubricating oil additive is (0.01-0.05): 1..
10. A nano-copper lubricating oil additive prepared by the method of any one of claims 1 to 9.
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