Nano-composite low-temperature wind power lubricating grease and preparation method thereof
By combining copper or silver nanoparticles with low-freezing-point ionic liquids to form a high-strength lubricating film, the problems of poor fluidity and decreased lubrication performance of low-temperature greases are solved, achieving efficient lubrication and improved equipment reliability in low-temperature environments.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-15
- Publication Date
- 2026-03-13
AI Technical Summary
Existing low-temperature greases have poor fluidity, high starting torque, and reduced lubrication performance in extreme low-temperature environments, making it difficult to meet the low-load starting requirements of equipment in cold regions. Furthermore, additives are prone to precipitation, leading to equipment wear.
By combining surface-modified copper or silver nanoparticles with low-pour-point ionic liquids, a dense lubricating film is formed on the surface of the friction pair through van der Waals forces. The combination of the ductility of copper/silver nanoparticles and the long alkyl chain structure of the ionic liquid provides excellent low-temperature fluidity and high-strength lubrication performance.
It significantly reduces starting and running torque, improves the low-temperature lubrication performance of grease and equipment reliability, and extends service life.
Smart Images
Figure CN121652872A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the technical field of lubricating greases, and particularly relates to a low-temperature lubricating grease. Background Technology
[0002] As global industrial equipment continues to expand into low-temperature environments such as polar exploration, high-altitude aerospace, and cold-region wind power, lubricating grease, as a lubrication and protection material for key moving parts, directly determines the starting characteristics, operational reliability, and service life of equipment due to its low-temperature performance. Lubricating grease typically consists of base oil, thickener, and additives, and is widely used in mechanical friction parts to reduce friction, wear, and provide sealing protection. Under low-temperature conditions (such as -40℃ and below), conventional lubricating grease often suffers from loss of fluidity, excessive viscosity, and decreased adhesion due to base oil solidification, excessive shrinkage of the thickener structure, and additive precipitation. This leads to a sharp increase in starting torque, difficulty in forming a lubricating film, accelerated equipment wear, and even seizing failures.
[0003] Currently, most low-temperature greases on the market are formulated with synthetic base oils (such as ester oils and polyalphaolefins) and thickeners with good low-temperature adaptability (such as complex lithium and polyurea), and incorporate pour point depressants and low-temperature anti-wear agents to improve low-temperature performance. However, existing products still have significant shortcomings in extreme low-temperature environments: firstly, the low-temperature starting torque is too high, making it difficult to meet the low-load starting requirements of equipment in cold regions; secondly, greases are prone to additive precipitation or base oil separation at sustained low temperatures, leading to a decrease in lubrication performance; and thirdly, the activity of ordinary anti-wear agents decreases at low temperatures, making it difficult to effectively inhibit wear. Especially in applications such as wind power pitch control systems, polar transportation equipment, and high-altitude unmanned aerial vehicles, these problems have become bottlenecks restricting the reliable operation of equipment and technological development. Therefore, developing a high-performance low-temperature grease with excellent low-temperature fluidity, low starting torque, good viscosity-temperature characteristics, and stable anti-wear properties is of great significance for improving the operational reliability and lifespan of equipment in cold regions. Summary of the Invention
[0004] To address the technical problems of rapidly increasing viscosity, weak adsorption and film-forming ability, and difficulty in forming high-strength lubricating films in greases under low-temperature conditions, this invention proposes a nanocomposite low-temperature wind power grease and its preparation method. By optimizing the base oil composition and introducing efficient low-temperature functional additives, a grease system suitable for extreme environments at -40℃ and below is constructed to meet the urgent needs of modern high-end equipment for low-temperature lubricating materials.
[0005] To achieve the above objectives, the technical solution of the present invention is implemented as follows: A nano-composite low-temperature wind power lubricating grease, by mass percentage, comprises the following components: 0.10-5% copper or silver nanoparticles, 0.10-3.00% ionic liquid, 5.00-15.00% thickener, 1.50-5.00% saponification agent, 0.10-0.50% antioxidant, 0.01-1.00% rust inhibitor, 0.10-0.50% demulsifier, with the balance being base oil, and the sum of the mass percentages of the above components being 100%.
[0006] The copper or silver nanoparticles are spherical or sheet-like structures; the diameter of the spherical nanoparticles is distributed in the range of 1-50 nm, the side length of the sheet-like nanoparticles is distributed in the range of 5-50 nm, and the ratio of radial width to thickness is 2-10.
[0007] The surface of the copper or silver nanoparticles is modified with a modifier, which is a carboxylic acid, alkenoic acid, amine, or thiol compound containing an alkyl group, wherein the alkyl group is a primary or secondary alkyl group with 4-22 carbon atoms; the content of the modifier in the copper or silver nanoparticles is 10-70 wt%.
[0008] The anion of the ionic liquid is [NTf2]. - [OTf] - [B(CN)4] - Or [N(CN)2] - The cation is an imidazolium, piperidinium, pyrrolidineium, or an asymmetric phosphonium cation with a long alkyl chain substitution, or an ammonium cation and its derivatives. In the imidazolium and piperidinium cations, the side chain has 4-12 carbon atoms, and in the phosphonium cation or ammonium cation, one of the four alkyl chains has 4-16 carbon atoms.
[0009] The base oil is one or a blend of two or more of PAO4, PAO10, PAO40 and PAO150.
[0010] The thickener is 12-hydroxystearic acid and organic bentonite in a mass ratio of (2-5):(0-1); the saponification agent is lithium hydroxide.
[0011] The antioxidant is an amine antioxidant and / or a phosphonic acid antioxidant; the amine antioxidant is one or more of phenylenediamine, diphenylamine, N,N-dimethylaniline and alkylphenthiazine antioxidants; the phosphonic acid antioxidant is one or more of triphenylphosphonate, trioctyl phosphate, tris(2,4-dimethylphenyl)phosphonate and tris(2-ethylhexyl)phosphonate.
[0012] The rust inhibitor is one or more of petroleum sulfonates, synthetic sulfonates, heavy alkylbenzene sulfonates, benzotriazole, and thiadiazole derivatives.
[0013] The demulsifier is an alkylphenol demulsifier; the alkylphenol demulsifier is one or more of alkylphenol, octylphenol, p-methylphenol and tetramethylphenol.
[0014] A method for preparing a nanocomposite low-temperature wind power lubricating grease includes the following steps: (1) Dissolve copper or silver nanoparticles and ionic liquid in chloroform and stir. Remove chloroform by rotary evaporation to obtain a viscous ionic liquid-coated nanoparticle composite additive for later use.
[0015] (2) The saponification reaction is carried out in a reaction vessel; (3) After the saponification reaction is completed, add the remaining base oil and the composite additives from step 1, as well as antioxidants, rust inhibitors and deemulsifiers, and mix them evenly.
[0016] Preferably, a method for preparing a nanocomposite low-temperature wind power lubricating grease includes the following steps: (1) Dissolve copper or silver nanoparticles and ionic liquid in chloroform, stir for 20 minutes, and then remove the chloroform by rotary evaporation to obtain a viscous ionic liquid-coated nanoparticle composite additive for later use.
[0017] (2) Add 30% of the total mass of base oil to the saponification reactor. When the oil temperature rises to about 85°C, add dodecyl stearic acid and bentonite and stir. After they are completely dissolved, the base oil becomes clear again and is ready for use.
[0018] (3) Add 1 / 2 of the pre-prepared lithium hydroxide aqueous solution, heat to about 100℃, and keep at a constant temperature for 1 h to carry out a saponification reaction.
[0019] (4) Add 20% of the total mass of base oil, heat to about 120℃, and react at a constant temperature for 30 min.
[0020] (5) After the saponification reaction is complete, raise the temperature to about 150°C and maintain it for 30 minutes. Open the vent and stir to drain the water.
[0021] (6) Add the remaining saponification reaction agent aqueous solution, heat to 135℃, react for 2 h, and carry out secondary saponification.
[0022] (7) After the saponification reaction is complete, raise the temperature to about 145°C and maintain it for 30 minutes. Open the vent and stir to drain the water.
[0023] (8) Raise the temperature to 170-180℃, add 20% of the total mass of base oil, and heat and stir for 30 min.
[0024] (9) Raise the temperature to 200-220°C and quickly add 20% of the total base oil as quenching oil (base oil, pre-cooled to 0°C).
[0025] (10) Mix the composite additive from step (1) with the remaining quench oil in advance and stir to make the mixture uniform.
[0026] (11) When the temperature drops to about 175°C, add all the quenching oil with the mixed oil additive into the reactor and continue stirring until it is completely cooled.
[0027] (12) Add antioxidants, rust inhibitors and deemulsifiers, homogenize twice with a homogenizer, and degas to obtain nano-composite low-temperature grease.
[0028] The beneficial effects of this invention are as follows: This invention utilizes copper / silver nanoparticles with long alkyl chains modified on their surfaces and low-pour-point ionic liquids with long side-chain structures to form ionic liquid-modified metal nanocomposite materials through van der Waals forces. The ionic liquid in the composite material exhibits strong adsorption on the metal surface, rapidly inducing the formation of a dense and robust organic-inorganic composite film on the friction pair surface. Copper / silver nanoparticles, as soft metals, possess excellent ductility and self-healing properties, enabling them to fill surface micro-defects through plastic deformation during friction. Furthermore, the addition of copper / silver nanoparticles reduces viscosity. The long alkyl chain structure of the ionic liquid simultaneously provides excellent low-temperature fluidity, forming a high-strength, high-toughness lubricating film under extreme low-temperature conditions (-40°C and below), significantly reducing starting and running torque, improving the low-temperature lubrication performance of the grease and equipment reliability, and extending service life. Attached Figure Description
[0029] To clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the drawings described below are merely some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without any creative effort.
[0030] Figure 1 Images of copper nanoparticles obtained by transmission electron microscopy (TEM) and selected area electron diffraction (SAED).
[0031] Figure 2 The curves show the (a) adsorption frequency shift and (b) adsorption mass change over time of the friction-reducing and wear-resistant components on the gold-plated wafers in Example 1 (copper nanoparticles + ionic liquid), Comparative Example 1 (copper nanoparticles only), and Comparative Example 2 (ionic liquid only).
[0032] Figure 3 A comparison of the apparent viscosity of the grease without copper nanoparticles and ionic liquids and the grease of Example 1 of this invention at -40 °C.
[0033] Figure 4The average friction coefficients of the grease prepared in Example 1, the non-ionic liquid grease prepared in Comparative Example 1, the copper-free nanoparticle grease prepared in Comparative Example 2, and the greases without copper nanoparticles and ionic liquids are compared at -30 ℃, -10 ℃, 10 ℃, and 30 ℃.
[0034] Figure 5 Comparison of wear scar diameters at -30 ℃, -10 ℃, 10 ℃, and 30 ℃ for the grease prepared in Example 1, the non-ionic liquid grease prepared in Comparative Example 1, the copper-free nanoparticle grease prepared in Comparative Example 2, and the greases without copper nanoparticles and ionic liquids. Detailed Implementation
[0035] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0036] The copper or silver nanoparticles described in this application have their surfaces modified with a modifier. The preparation method is conventional in the art, differing only in the modifier used. One example of a solvothermal method for preparing copper nanoparticles involves adding a copper salt, a modifier, and a reducing agent to a solvent for a solvothermal reaction.
[0037] The following is a specific method for preparing oleic acid-modified copper nanoparticles: 1.0 g of copper oleate was dissolved in 4 mL of oleylamine, and 0.06 g of anhydrous glucose was added. High-purity N2 protective gas was introduced to purge air. The mixture was stirred at 60°C for 20 min to form a uniform, deep blue-green viscous liquid. The mixture was then slowly heated to 200°C and stirred continuously at this temperature for 2 h. After the reaction was complete, the mixture was allowed to cool naturally to room temperature. The product was centrifuged, and the precipitate was washed three times each with ethanol and acetone. The precipitate was then vacuum dried at 50°C for 6 h to obtain reddish-brown powdered oleic acid-modified copper nanoparticles. The copper nanoparticles prepared by the above method were used in Example 1. Figure 1 Transmission electron microscopy (TEM) images of the synthesized copper nanoparticles are shown. As shown, the material consists of near-spherical nanoparticles with an average particle size of 10 ± 0.5 nm, exhibiting uniform particle size distribution and good dispersibility. The corresponding selected area electron diffraction (SAED) pattern reveals sharp polycrystalline diffraction rings, corresponding to the (111), (200), and (220) crystal planes of face-centered cubic (fcc) copper, indicating that the prepared copper nanoparticles possess good crystallinity.
[0038] Here are the steps for preparing silver nanoparticles using a liquid-phase extraction method: silver salt is added to water to prepare an aqueous solution; a modifier and surfactant are mixed and added to an organic solvent to prepare an organic phase; the two are then mixed and a reducing agent is added to react and the nanoparticles are obtained.
[0039] The following is a method for preparing oil-soluble silver nanoparticles modified with dodecyl mercaptan: AgNO3 was dissolved in 30 mL of ultrapure water to prepare an aqueous solution. In another 250 mL three-necked flask, 0.97 g of tetra-n-octylammonium bromide (TOAB) and 0.81 g of dodecyl mercaptan (DDT) were dissolved in 60 mL of toluene to prepare an organic phase. Under vigorous stirring, the aqueous solution was poured into the organic phase, and the solution gradually turned milky white. High-purity N2 protective gas was introduced and stirring was continued for 30 minutes. Subsequently, under ice-water bath and vigorous stirring, a freshly prepared solution of 0.38 g of sodium borohydride (NaBH4) dissolved in 10 mL of ice-cold ultrapure water was rapidly injected into the mixture, and the solution immediately turned brownish-black. The ice-water bath was removed, and the reaction was continued vigorously at room temperature for 12 hours. After the reaction was completed, the mixture was allowed to stand and separate into layers. The organic phase was then washed three times with ultrapure water to remove inorganic salts. Excess ethanol was added to the organic phase, and the mixture was centrifuged. The precipitate was washed three times each with ethanol and acetone, and then vacuum dried at 40 °C for 8 hours to obtain black powdered silver nanoparticles modified with dodecyl mercaptan. TEM characterization showed that the average particle size was 5 ± 1 nm.
[0040] Example 1 A nanocomposite low-temperature wind power lubricating grease has the following formula (by weight percentage): 83.7% PAO10:PAO40 (1:1) blended base oil, 7.5% 12-hydroxystearic acid, 3.5% organobentonite, 1.8% lithium hydroxide, 2.0% oleic acid-modified copper nanoparticles, 1.0% [C5MIm][B(CN)4] ionic liquid, 0.3% antioxidant diphenylamine, 0.05% rust inhibitor benzotriazole, and 0.15% demulsifier octylphenol.
[0041] The preparation method includes the following steps: (1) Preparation of composite additive: Oleic acid modified copper nanoparticles and [C5MIm][B(CN)4] ionic liquid were dissolved in chloroform and stirred for 20 minutes. Then, the chloroform was removed by rotary evaporation in a water bath at 50°C to obtain a uniform viscous composite additive for later use.
[0042] (2) In a saponification reactor equipped with a stirring and heating device, add blended oil accounting for 30% of the total mass of base oil, heat to 85°C, and slowly add 12-hydroxystearic acid and organic bentonite, maintaining a stirring speed of 300 r / min until the system is clear and transparent.
[0043] (3) Prepare a 50% aqueous solution of lithium hydroxide, take half of the total amount and slowly add it into the reactor, heat it to 100°C, and saponify it at this temperature for 1 hour while maintaining a stirring speed of 400r / min.
[0044] (4) Add blending oil accounting for 20% of the total mass of base oil, heat to 120°C, and react at a constant temperature for 30 minutes.
[0045] (5) Continue to heat to 150°C and maintain for 30 minutes. Open the exhaust port of the reactor and adjust the stirring speed to 200 r / min for stirring and dehydration.
[0046] (6) Add the remaining lithium hydroxide aqueous solution, heat to 135°C, and continue the saponification reaction for 2 hours.
[0047] (7) Heat to 145°C and maintain for 30 minutes. Open the exhaust port of the reactor again and stir to dehydrate until there is no obvious water vapor in the system.
[0048] (8) Raise the temperature to 175°C, add blending oil accounting for 20% of the total mass of base oil, and heat and stir for 30 minutes.
[0049] (9) Heat to 205°C and quickly add 20% of the total mass of the base oil 0°C quenching oil (blended oil, pre-cooled to 0°C).
[0050] (10) The composite additive prepared in step (1) is premixed with the remaining 10% of 0°C quench oil and dispersed for 5 minutes at 2000 r / min using a high-speed disperser to ensure uniform mixing.
[0051] (11) When the temperature inside the reactor drops to 175°C, add all the quenching oil mixed with additives into the reactor and continue stirring to cool to room temperature.
[0052] (12) Add antioxidants, rust inhibitors and demulsifiers, homogenize twice with a homogenizer, and degas to obtain high-performance low-temperature grease.
[0053] Comparative Example 1 The difference between this comparative example and Example 1 is that no ionic liquid is added; only copper nanoparticles are used. The preparation method includes the following steps: (1) Add blended oil accounting for 30% of the total mass of base oil to the saponification reactor. When the oil temperature rises to 85°C, slowly add 12-hydroxystearic acid and organic bentonite, and stir until completely dissolved.
[0054] (...subsequent saponification, dehydration, and quenching steps are the same as in Example 1...) (10) Add 2.0% of oleic acid-modified copper nanoparticles (without ionic liquid composite) to the remaining 10% of 0℃ quench oil and stir until homogeneous.
[0055] (11) When the temperature inside the vessel drops to 175°C, add all the quenching oil mixed with nanoparticles and continue stirring to cool to room temperature.
[0056] (12) Finally, add antioxidant, rust inhibitor and deemulsifier in the same amount as in Example 1, homogenize and degas to obtain the product.
[0057] Comparative Example 2 The difference between this comparative example and Example 1 is that copper nanoparticles are not added; only ionic liquids are used. The preparation method includes the following steps: (1) Add blended oil accounting for 30% of the total mass of base oil to the saponification reactor. When the oil temperature rises to 85°C, slowly add 12-hydroxystearic acid and organic bentonite, and stir until completely dissolved.
[0058] (...subsequent saponification, dehydration, and quenching steps are the same as in Example 1...) (10) Add 1.0% of the ionic liquid (without any nanoparticles) to the remaining 10% of the 0℃ quenching oil and stir until homogeneous.
[0059] (11) When the temperature inside the vessel drops to 175°C, add all the quenching oil mixed with ionic liquid and continue stirring to cool to room temperature.
[0060] (12) Finally, add antioxidant, rust inhibitor and deemulsifier in the same amount as in Example 1, homogenize and degas to obtain the product.
[0061] The greases in Example 1 and Comparative Examples 1 and 2 were tested. The friction reduction and anti-wear performance was evaluated using an SRV-5 friction and wear testing machine. Typical test conditions were: load: 300N, stroke: 2mm, frequency: 10Hz, and time: 3600s.
[0062] The adsorption performance of the core friction-reducing and anti-wear additive in the grease on the metal surface was evaluated using a QCM-D quartz microbalance. The specific test conditions were as follows: a gold target was used to simulate the surface of the metal friction pair, and different samples were diluted with dodecane to a concentration of 1.0 wt%. The samples were then pumped into the liquid chamber at a flow rate of 40 μL / min at a test temperature of 25 °C.
[0063] Figure 2The figures show the (a) adsorption frequency shift and (b) adsorption mass changes over time of the friction-reducing and anti-wear components on gold-plated wafers in Example 1 (copper nanoparticles + ionic liquid), Comparative Example 1 (copper nanoparticles only), and Comparative Example 2 (ionic liquid only). As shown, the copper nanoparticle and ionic liquid combination additive in Example 1 exhibits the fastest and largest frequency decrease (ΔF > -120Hz), indicating rapid and substantial adsorption of the composite additive on the metal surface. The adsorption amount and adsorption rate of Comparative Example 1 (copper nanoparticles only) and Comparative Example 2 (ionic liquid only) are significantly lower than those in Example 1. This result indicates that the ionic liquid and copper nanoparticles produce a synergistic adsorption effect, enabling the formation of a thicker composite film on the metal surface more effectively, resulting in excellent high and low temperature lubrication and anti-wear properties.
[0064] Figure 3 This is a comparison chart of the apparent viscosity of the grease without copper nanoparticles and ionic liquid and the grease of Example 1 of this invention at -40°C. It can be seen that compared to the grease without these additives, the apparent viscosity of the grease at -40°C decreases after adding copper nanoparticles and ionic liquid. This indicates that the composite additive effectively improves the low-temperature fluidity of the grease and enhances its low-temperature pumping performance.
[0065] Figure 4 The graph compares the average coefficients of friction of the grease of this invention, the grease containing only copper nanoparticles, the grease containing only ionic liquid, and the grease without copper nanoparticles and ionic liquid at -30°C, -10°C, 10°C, and 30°C. As can be seen from the graph, the grease of this invention exhibits the best friction-reducing performance under low-temperature conditions, with a significantly lower coefficient of friction than the grease without copper nanoparticles and ionic liquid. Compared with the greases of Comparative Example 1 and Comparative Example 2, the grease of this invention has an even lower coefficient of friction, indicating that the synergistic effect of copper nanoparticles and ionic liquid can effectively reduce the coefficient of friction and improve friction-reducing performance.
[0066] Figure 5 The figures show a comparison of wear scar diameters at -30°C, -10°C, 10°C, and 30°C for the grease of this invention, the grease containing only copper nanoparticles, the grease containing only ionic liquids, and the grease without copper nanoparticles and ionic liquids. As can be seen from the figures, the grease of this invention maintains excellent anti-wear performance throughout the temperature range of -30°C to 30°C, and its wear scar diameter is significantly smaller than that of the grease without copper nanoparticles and ionic liquids. Compared with the greases of Comparative Example 1 and Comparative Example 2, the grease of this invention has the smallest wear scar diameter, indicating that the synergistic effect of copper nanoparticles and ionic liquids significantly improves anti-wear capability.
[0067] Example 2 A nanocomposite low-temperature wind power lubricating grease has the following formulation (by weight percentage): 83.7% PAO10:PAO150 (4:1) blended base oil, 7.5% 12-hydroxystearic acid, 3.5% organobentonite, 1.8% lithium hydroxide, 1.0% dodecyl carboxylic acid-modified copper nanoparticles, 2.0% [C5MIm][B(CN)4] ionic liquid, 0.3% antioxidant diphenylamine, 0.05% rust inhibitor benzotriazole, and 0.15% demulsifier octylphenol.
[0068] The preparation method includes the following steps: (1) Preparation of composite additive: Copper nanoparticles and ionic liquid [C5MIm][B(CN)4] were dissolved in chloroform at a mass ratio of 1:2 (i.e. 0.5:1). After stirring for 20 minutes, the chloroform was removed by rotary evaporation to obtain the composite additive for later use.
[0069] (2) Add blended oil accounting for 30% of the total mass of base oil to the saponification reactor. When the oil temperature rises to 85°C, add 12-hydroxystearic acid and organic bentonite, and stir until completely dissolved.
[0070] (3) Add the pre-prepared 50% lithium hydroxide aqueous solution, heat to 100°C, and saponify at a constant temperature for 1 hour.
[0071] (4) Add blending oil accounting for 20% of the total mass of base oil, heat to 120°C, and react at a constant temperature for 30 minutes.
[0072] (5) Heat to 150°C and maintain for 30 minutes. Open the exhaust port of the reactor and stir to dehydrate.
[0073] (6) Add the remaining 50% lithium hydroxide aqueous solution, heat to 135°C, and continue the saponification reaction for 2 hours.
[0074] (7) Heat to 145°C and maintain for 30 minutes. Then open the exhaust port of the reactor again and stir to dehydrate.
[0075] (8) Heat to 175°C, add blending oil accounting for 20% of the total mass of base oil, and heat and stir for 30 minutes.
[0076] (9) Heat to 205°C and quickly add 20% of the total mass of the base oil 0°C quenching oil (blended oil, pre-cooled to 0°C).
[0077] (10) Add the composite additive prepared in step (1) to the remaining 10% of 0℃ quench oil and stir until homogeneous.
[0078] (11) When the temperature inside the vessel drops to 175°C, add all the quenching oil mixed with additives and continue stirring to cool to room temperature.
[0079] (12) Finally, add antioxidant, rust inhibitor and deemulsifier, homogenize twice with a homogenizer, and degas to obtain the product.
[0080] Example 3 A nanocomposite low-temperature wind power lubricating grease has the following formulation (by weight percentage): 82.7% PAO4:PAO40 (2:1) blended base oil, 7.5% 12-hydroxystearic acid, 3.5% organobentonite, 1.8% lithium hydroxide, 2.0% octylcarboxylic acid-modified copper nanoparticles, 2.0% [C5MIm][NTf2] ionic liquid, 0.3% antioxidant diphenylamine, 0.05% rust inhibitor benzotriazole, and 0.15% demulsifier octylphenol.
[0081] The preparation method includes the following steps: (1) Preparation of composite additive: Copper nanoparticles and [C5MIm][NTf2] ionic liquid were dissolved in chloroform at a mass ratio of 1:1. After stirring for 20 minutes, the chloroform was removed by rotary evaporation to obtain the composite additive for later use.
[0082] (2) Add blended oil accounting for 30% of the total mass of base oil to the saponification reactor. When the oil temperature rises to 85°C, add 12-hydroxystearic acid and organic bentonite, and stir until completely dissolved.
[0083] (3) Add the pre-prepared 50% lithium hydroxide aqueous solution, heat to 100°C, and saponify at a constant temperature for 1 hour.
[0084] (4) Add blending oil accounting for 20% of the total mass of base oil, heat to 120°C, and react at a constant temperature for 30 minutes.
[0085] (5) Heat to 150°C and maintain for 30 minutes. Open the exhaust port of the reactor and stir to dehydrate.
[0086] (6) Add the remaining 50% lithium hydroxide aqueous solution, heat to 135°C, and continue the reaction for 2 hours.
[0087] (7) Heat to 145°C and maintain for 30 minutes. Then open the exhaust port of the reactor again and stir to dehydrate.
[0088] (8) Heat to 175°C, add blending oil accounting for 20% of the total mass of base oil, and heat and stir for 30 minutes.
[0089] (9) Heat to 205°C and quickly add 20% of the total mass of the base oil 0°C quenching oil (blended oil, pre-cooled to 0°C).
[0090] (10) Add the composite additive prepared in step (1) to the remaining 10% of 0℃ quench oil and stir until homogeneous.
[0091] (11) When the temperature inside the vessel drops to 175°C, add all the quenching oil mixed with additives and continue stirring to cool to room temperature.
[0092] (12) Finally, add antioxidant, rust inhibitor and deemulsifier, homogenize twice with a homogenizer, and degas to obtain the product.
[0093] Example 4 A nanocomposite low-temperature wind power lubricating grease, its formulation (by weight percentage) is as follows: 83.2% PAO4:PAO150 (2:1) blended base oil, 7.0% 12-hydroxystearic acid, 3.0% organobentonite, 1.8% lithium hydroxide, 3.0% hexylcarboxylic acid-modified copper nanoparticles, [P 6,6,6,14 [NTf2] Ionic liquid 1.5%, antioxidant diphenylamine 0.3%, rust inhibitor benzotriazole 0.05%, demulsifier octylphenol 0.15%.
[0094] The preparation method includes the following steps: (1) Preparation of composite additives: copper nanoparticles are combined with [P 6,6,6,14 The [NTf2] ionic liquid was dissolved in chloroform at a mass ratio of 2:1. After stirring for 20 minutes, the chloroform was removed by rotary evaporation to obtain a composite additive for later use.
[0095] (2) Add blended oil accounting for 30% of the total mass of base oil to the saponification reactor. When the oil temperature rises to 85°C, add 12-hydroxystearic acid and organic bentonite, and stir until completely dissolved.
[0096] (3) Add the pre-prepared 50% lithium hydroxide aqueous solution, heat to 100°C, and saponify at a constant temperature for 1 hour.
[0097] (4) Add blending oil accounting for 20% of the total mass of base oil, heat to 120°C, and react at a constant temperature for 30 minutes.
[0098] (5) Heat to 150°C and maintain for 30 minutes. Open the exhaust port of the reactor and stir to dehydrate.
[0099] (6) Add the remaining 50% lithium hydroxide aqueous solution, heat to 135°C, and continue the reaction for 2 hours.
[0100] (7) Heat to 145°C and maintain for 30 minutes. Then open the exhaust port of the reactor again and stir to dehydrate.
[0101] (8) Heat to 175°C, add blending oil accounting for 20% of the total mass of base oil, and heat and stir for 30 minutes.
[0102] (9) Heat to 205°C and quickly add 20% of the total mass of the base oil 0°C quenching oil (blended oil, pre-cooled to 0°C).
[0103] (10) Add the composite additive prepared in step (1) to the remaining 10% of 0℃ quench oil and stir until homogeneous.
[0104] (11) When the temperature inside the vessel drops to 175°C, add all the quenching oil mixed with additives and continue stirring to cool to room temperature.
[0105] (12) Finally, add antioxidant, rust inhibitor and deemulsifier, homogenize twice using a homogenizer, and degas to obtain the final product. Example 5 A nanocomposite low-temperature wind power lubricating grease has the following formula (by weight percentage): 80.7% PAO10:PAO40 (1:2) blended base oil, 11.5% 12-hydroxystearic acid, 1.5% organobentonite, 1.8% lithium hydroxide, 3.0% octadecyl carboxylic acid-modified silver nanoparticles, 1.0% [C5MIm][OTf] ionic liquid, 0.3% antioxidant diphenylamine, 0.05% rust inhibitor benzotriazole, and 0.15% demulsifier octylphenol.
[0106] The preparation method includes the following steps: (1) Preparation of composite additive: Silver nanoparticles and [C5MIm][OTf] ionic liquid were dissolved in chloroform at a mass ratio of 3:1. After stirring for 20 minutes, the chloroform was removed by rotary evaporation to obtain the composite additive for later use.
[0107] (2) Add blended oil accounting for 30% of the total mass of base oil to the saponification reactor. When the oil temperature rises to 85°C, add 12-hydroxystearic acid and organic bentonite, and stir until completely dissolved.
[0108] (3) Add the pre-prepared 50% lithium hydroxide aqueous solution, heat to 100°C, and saponify at a constant temperature for 1 hour.
[0109] (4) Add blending oil accounting for 20% of the total mass of base oil, heat to 120°C, and react at a constant temperature for 30 minutes.
[0110] (5) Heat to 150°C and maintain for 30 minutes. Open the exhaust port of the reactor and stir to dehydrate.
[0111] (6) Add the remaining 50% lithium hydroxide aqueous solution, heat to 135°C, and continue the reaction for 2 hours.
[0112] (7) Heat to 145°C and maintain for 30 minutes. Then open the exhaust port of the reactor again and stir to dehydrate.
[0113] (8) Heat to 175°C, add blending oil accounting for 20% of the total mass of base oil, and heat and stir for 30 minutes.
[0114] (9) Heat to 205°C and quickly add 20% of the total mass of the base oil 0°C quenching oil (blended oil, pre-cooled to 0°C).
[0115] (10) Add the composite additive prepared in step (1) to the remaining 10% of 0℃ quench oil and stir until homogeneous.
[0116] (11) When the temperature inside the vessel drops to 175°C, add all the quenching oil mixed with additives and continue stirring to cool to room temperature.
[0117] (12) Finally, add antioxidant, rust inhibitor and deemulsifier, homogenize twice with a homogenizer, and degas to obtain the product.
[0118] Example 6 A nanocomposite low-temperature wind power lubricating grease, its formulation (by weight percentage) is as follows: 82.7% PAO10:PAO40 (1:1) blended base oil, 8.5% 12-hydroxystearic acid, 1.5% organobentonite, 1.8% lithium hydroxide, 4.0% dodecyl mercaptan-modified silver nanoparticles, [P 55514 [NTf2] Ionic liquid 1.0%, antioxidant diphenylamine 0.3%, rust inhibitor benzotriazole 0.05%, demulsifier octylphenol 0.15%.
[0119] The preparation method includes the following steps: (1) Preparation of composite additive: silver nanoparticles and [P 55514 The ionic liquid [NTf2] was dissolved in chloroform at a mass ratio of 4:1. After stirring for 20 minutes, the chloroform was removed by rotary evaporation to obtain the composite additive, which was then ready for use.
[0120] (2) Add blended oil accounting for 30% of the total mass of base oil to the saponification reactor. When the oil temperature rises to 85°C, add 12-hydroxystearic acid and organic bentonite, and stir until completely dissolved.
[0121] (3) Add the pre-prepared 50% lithium hydroxide aqueous solution, heat to 100°C, and saponify at a constant temperature for 1 hour.
[0122] (4) Add blending oil accounting for 20% of the total mass of base oil, heat to 120°C, and react at a constant temperature for 30 minutes.
[0123] (5) Heat to 150°C and maintain for 30 minutes. Open the exhaust port of the reactor and stir to dehydrate.
[0124] (6) Add the remaining 50% lithium hydroxide aqueous solution, heat to 135°C, and continue the reaction for 2 hours.
[0125] (7) Heat to 145°C and maintain for 30 minutes. Then open the exhaust port of the reactor again and stir to dehydrate.
[0126] (8) Heat to 175°C, add blending oil accounting for 20% of the total mass of base oil, and heat and stir for 30 minutes.
[0127] (9) Heat to 205°C and quickly add 20% of the total mass of the base oil 0°C quenching oil (blended oil, pre-cooled to 0°C).
[0128] (10) Add the composite additive prepared in step (1) to the remaining 10% of 0℃ quench oil and stir until homogeneous.
[0129] (11) When the temperature inside the vessel drops to 175°C, add all the quenching oil mixed with additives and continue stirring to cool to room temperature.
[0130] (12) Finally, add antioxidant, rust inhibitor and deemulsifier, homogenize twice at 70MPa using a homogenizer, and degas to obtain the product.
[0131] Example 7 A nanocomposite low-temperature wind power lubricating grease has the following formulation (by weight percentage): 71.39% PAO40 base oil, 10% 12-hydroxystearic acid, 5% organobentonite, 5% lithium hydroxide, 5.0% oleic acid-modified copper nanoparticles, 3.0% [C5MIm][B(CN)4] ionic liquid, 0.1% antioxidant triphenylphosphonate, 0.01% rust inhibitor heavy alkylbenzene sulfonate, and 0.5% demulsifier p-methylphenol.
[0132] The preparation method includes the following steps: (1) Preparation of composite additive: Oleic acid modified copper nanoparticles and [C5MIm][B(CN)4] ionic liquid were dissolved in chloroform at a mass ratio of 2:1. After stirring for 20 minutes, the chloroform was removed by rotary evaporation in a water bath at 50°C to obtain a uniform viscous composite additive for later use.
[0133] (2) In a saponification reactor equipped with a stirring and heating device, add base oil accounting for 30% of the total mass of base oil, heat to 85°C, slowly add 12-hydroxystearic acid and organic bentonite, keep stirring speed at 300 r / min until the thickener is completely dissolved and the system is clear and transparent.
[0134] (3) Prepare a 50% aqueous solution of lithium hydroxide, take half of the total amount and slowly add it into the reactor, heat it to 100°C, and saponify it at this temperature for 1 hour while maintaining a stirring speed of 400r / min.
[0135] (4) Add base oil accounting for 20% of the total mass of base oil, heat to 120°C, and react at a constant temperature for 30 minutes.
[0136] (5) Continue to heat to 150°C and maintain for 30 minutes. Open the exhaust port of the reactor and adjust the stirring speed to 200 r / min for stirring and dehydration.
[0137] (6) Add the remaining lithium hydroxide aqueous solution, heat to 135°C, and continue the saponification reaction for 2 hours.
[0138] (7) Heat to 145°C and maintain for 30 minutes. Open the exhaust port of the reactor again and stir to dehydrate until there is no obvious water vapor in the system.
[0139] (8) Raise the temperature to 175°C, add base oil accounting for 20% of the total mass of base oil, and heat and stir for 30 minutes.
[0140] (9) Heat to 205°C and quickly add 20% of the total mass of the base oil with 0°C quench oil (PAO10 base oil, pre-cooled to 0°C).
[0141] (10) The composite additive prepared in step (1) is premixed with the remaining 10% of 0°C quench oil and dispersed for 5 minutes at 2000 r / min using a high-speed disperser to ensure uniform mixing.
[0142] (11) When the temperature inside the reactor drops to 175°C, add all the quenching oil mixed with additives into the reactor and continue stirring to cool to room temperature.
[0143] (12) Add antioxidants, rust inhibitors and demulsifiers, homogenize twice with a homogenizer, and degas to obtain high-performance low-temperature grease.
[0144] Example 8 A nanocomposite low-temperature wind power lubricating grease has the following formulation (by weight percentage): 91.7% PAO10 base oil, 4% 12-hydroxystearic acid, 1% organobentonite, 1.5% lithium hydroxide, 0.1% oleic acid-modified copper nanoparticles, 0.1% [C5MIm][B(CN)4] ionic liquid, 0.5% antioxidant N,N-dimethylaniline, 1% rust inhibitor heavy alkylbenzene sulfonate, and 0.1% demulsifier alkylphenol.
[0145] The preparation method includes the following steps: (1) Preparation of composite additive: Oleic acid modified copper nanoparticles and [C5MIm][B(CN)4] ionic liquid were dissolved in chloroform at a mass ratio of 2:1. After stirring for 20 minutes, the chloroform was removed by rotary evaporation in a water bath at 50°C to obtain a uniform viscous composite additive for later use.
[0146] (2) In a saponification reactor equipped with a stirring and heating device, add base oil accounting for 30% of the total mass of base oil, heat to 85°C, slowly add 12-hydroxystearic acid and organic bentonite, keep stirring speed at 300 r / min until the thickener is completely dissolved and the system is clear and transparent.
[0147] (3) Prepare a 50% aqueous solution of lithium hydroxide, take half of the total amount and slowly add it into the reactor, heat it to 100°C, and saponify it at this temperature for 1 hour while maintaining a stirring speed of 400r / min.
[0148] (4) Add blending oil accounting for 20% of the total mass of base oil, heat to 120°C, and react at a constant temperature for 30 minutes.
[0149] (5) Continue to heat to 150°C and maintain for 30 minutes. Open the exhaust port of the reactor and adjust the stirring speed to 200 r / min for stirring and dehydration.
[0150] (6) Add the remaining lithium hydroxide aqueous solution, heat to 135°C, and continue the saponification reaction for 2 hours.
[0151] (7) Heat to 145°C and maintain for 30 minutes. Open the exhaust port of the reactor again and stir to dehydrate until there is no obvious water vapor in the system.
[0152] (8) Raise the temperature to 175°C, add base oil accounting for 20% of the total mass of base oil, and heat and stir for 30 minutes.
[0153] (9) Heat to 205°C and quickly add 20% of the total mass of the base oil with 0°C quench oil (PAO10 base oil, pre-cooled to 0°C).
[0154] (10) The composite additive prepared in step (1) is premixed with the remaining 10% of 0°C quench oil and dispersed for 5 minutes at 2000 r / min using a high-speed disperser to ensure uniform mixing.
[0155] (11) When the temperature inside the reactor drops to 175°C, add all the quenching oil mixed with additives into the reactor and continue stirring to cool to room temperature.
[0156] (12) Add antioxidants, rust inhibitors and demulsifiers, homogenize twice at 70MPa using a homogenizer, and degas to obtain high-performance low-temperature grease.
[0157] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.
Claims
1. A nano-composite low-temperature wind power lubricating grease, characterized in that, By mass percentage, it includes the following components: 0.10-5% copper or silver nanoparticles, 0.10-3.00% ionic liquid, 5.00-15.00% thickener, 1.50-5.00% saponification agent, 0.10-0.50% antioxidant, 0.01-1.00% rust inhibitor, 0.10-0.50% demulsifier, with the balance being base oil. The sum of the mass percentages of the above components is 100%.
2. The nanocomposite low-temperature wind power lubricating grease according to claim 1, characterized in that, The surface of the copper or silver nanoparticles is modified with a modifier, which is a carboxylic acid, alkanoic acid, amine or thiol compound containing an alkyl group, wherein the alkyl group is a primary or secondary alkyl group with 4-22 carbon atoms; the content of the modifier in the copper or silver nanoparticles is 10-70 wt%.
3. The nanocomposite low-temperature wind power lubricating grease according to claim 2, characterized in that, The copper or silver nanoparticles are spherical or sheet-like structures; the diameter of the spherical nanoparticles is distributed in the range of 1-50 nm, the side length of the sheet-like nanoparticles is distributed in the range of 5-50 nm, and the ratio of radial width to thickness is 2-10.
4. The nanocomposite low-temperature wind power lubricating grease according to any one of claims 1-3, characterized in that, The anion of the ionic liquid is [NTf2]. - [OTf] - [B(CN)4] - Or [N(CN)2] - The cation is an imidazolium, piperidinium, pyrrolidineium, or an asymmetric phosphonium cation with a long alkyl chain substitution, or an ammonium cation and its derivatives. In the imidazolium and piperidinium cations, the side chain has 4-12 carbon atoms, and in the phosphonium cation or ammonium cation, one of the four alkyl chains has 4-16 carbon atoms.
5. The nanocomposite low-temperature wind power lubricating grease according to claim 4, characterized in that, The base oil is one or more of PAO4, PAO10, PAO40 and PAO150.
6. The nanocomposite low-temperature wind power lubricating grease according to claim 5, characterized in that, The thickener is 12-hydroxystearic acid and organic bentonite in a mass ratio of (2-5):(0-1); the saponification agent is lithium hydroxide.
7. The nanocomposite low-temperature wind power lubricating grease according to claim 6, characterized in that, The antioxidant is an amine antioxidant and / or a phosphonic acid antioxidant; the amine antioxidant is one or more of phenylenediamine, diphenylamine, N,N-dimethylaniline and alkylphenthiazine antioxidants; the phosphonic acid antioxidant is one or more of triphenylphosphonate, trioctyl phosphate, tris(2,4-dimethylphenyl)phosphonate and tris(2-ethylhexyl)phosphonate.
8. The nanocomposite low-temperature wind power lubricating grease according to claim 7, characterized in that, The rust inhibitor is one or more of petroleum sulfonates, synthetic sulfonates, heavy alkylbenzene sulfonates, benzotriazole, and thiadiazole derivatives.
9. The nanocomposite low-temperature wind power lubricating grease according to claim 8, characterized in that, The demulsifier is an alkylphenol demulsifier; the alkylphenol demulsifier is one or more of alkylphenol, octylphenol, p-methylphenol and tetramethylphenol.
10. A method for preparing the nanocomposite low-temperature wind power lubricating grease according to any one of claims 1-9, characterized in that, Includes the following steps: (1) Add the thickener to part of the base oil, stir, and wait until it is completely dissolved. After the base oil becomes clear again, it is ready for use. (2) Then add the saponification agent to carry out the saponification reaction; (3) After the saponification reaction is completed, add the remaining base oil and copper or silver nanoparticles, ionic liquid, antioxidant, rust inhibitor and deemulsifier and mix evenly.