Composite additive for lubricating oil and preparation method thereof

Abstract

The invention relates to the technical field of lubricating materials, in particular to a composite additive for lubricating oil and a preparation method thereof. The composite additive for the lubricating oil consists of the following components in parts by weight: 4-10 parts of base oil, 3-6 parts of copper dialkyl dithiophosphate, 1-2 parts of intercalation modified bentonite, 1-2 parts of a composite three-dimensional copper-based solid-liquid additive, 4-8 parts of a high-temperature antioxidant, 8-10 parts of nano borate, 12-18 parts of an antirust agent and 1-5 parts of trimethylolpropane ester. By adding a small amount of the composite three-dimensional copper-based solid-liquid additive and intercalation modified bentonite, the lubricating property of the lubricating oil is synergistically improved, and the lubricating oil has a good application prospect.

Description

Technical Field

[0001] The invention belongs to the technical field of lubricating materials, and in particular relates to a composite additive for lubricating oil and a preparation method thereof. Background Art

[0002] The regulation of friction and wear is crucial to industrial development, as friction causes energy loss, material waste, and reduced machine life. Lubricants, lubricating additives, coatings, solid-liquid composites, etc. are considered to be the most effective lubrication methods. Lubricants can take away the heat generated during the friction process and further reduce destructive contact and corrosive chemicals. This is achieved by forming a low shear strength tribofilm on the sliding asperities. More importantly, the self-assembly behavior of lubricating materials and the formation of tribofilms at the sliding interface become the key to effectively regulating friction. The morphology and composition of the tribofilms formed by various lubricating materials during the friction process are also different.

[0003] According to statistics, about 30% of energy consumption is caused by friction, and 80% of damaged parts are scrapped due to wear. Therefore, a new type of lubricant compound additive is needed that can improve lubrication effect, reduce use loss, and add less amount. Summary of the invention

[0004] The object of the present invention is to provide a composite additive for lubricating oil and a preparation method thereof, so as to solve the technical problem that the amount of additive added is too large and the lubricating effect is poor in the prior art.

[0005] In order to achieve the above object, the present invention adopts the following technical solutions:

[0006] The technical solution provided by the present invention is as follows:

[0007] In a first aspect, the present invention provides a composite additive for lubricating oil, wherein the composite additive for lubricating oil specifically comprises the following components in parts by weight:

[0008] 4-10 parts of base oil, 3-6 parts of dialkyl copper dithiophosphate, 1-2 parts of intercalated modified bentonite, 1-2 parts of composite three-dimensional copper-based solid-liquid additives, 4-8 parts of high-temperature antioxidant, 8-10 parts of nano borate, 12-18 parts of rust inhibitor, and 1-5 parts of trimethylolpropane ester.

[0009] The base oil includes at least one of a synthetic base oil or a vegetable oil base oil.

[0010] The high temperature antioxidant is 2,6-dibutyl mixed phenol or 3,5-di-tert-butyl-4-hydroxyphenyl acrylate.

[0011] The rust inhibitor is one of barium sulfonate, alkylbenzene sulfonate and zinc epoxyate.

[0012] Preferably, the method for preparing the composite three-dimensional copper-based solid-liquid additive comprises the following steps:

[0013] A1: Add 400-800mL, 0.12mol / L CuSO 4 Add 2-4L of 0.2mol / L Na 2 HPO 4 The solution was washed with water for 3-5 times, then washed with ethanol for 1-2 times, and dried at 55-65°C to constant weight to obtain a three-dimensional precipitate;

[0014] A2: 5-10 g of three-dimensional precipitate is mixed with 40-60 mL of modified ionic liquid, the mixing process is repeated 3-5 times, then washed with water 2-3 times, and vacuum dried to constant weight to obtain a composite three-dimensional copper-based solid-liquid additive.

[0015] Preferably, the method for preparing the modified ionic liquid comprises the following steps:

[0016] S1: 74-148 g of trioctylphosphine and 44.6-89.2 g of dodecane bromide were added to 80-160 mL of acetonitrile, stirred for 30-50 min, and then refluxed at 80-90° C. for 20-28 h, cooled to room temperature, added 80-160 mL of petroleum ether, and then added anhydrous sodium sulfate overnight, after removing the acetonitrile under reduced pressure, the product was extracted with petroleum ether, and then the petroleum ether was removed under reduced pressure to obtain intermediate A;

[0017] S2: Add 59.4-120g of the intermediate and 32.2-64.4g of di(2-ethylhexyl) phosphate to 0.5-1L of ethanol containing 5-10g of NaOH, reflux at 80-90°C for 68-76h, remove the ethanol by rotary evaporation, add 100-200mL of petroleum ether, wash with water 3-5 times, add anhydrous sodium sulfate and dry overnight, remove the petroleum ether by rotary evaporation to obtain a modified ionic liquid.

[0018] The structural formula of the modified ionic liquid is as follows:

[0019]

[0020] Among them, the modified ionic liquid was subjected to mass spectrometry analysis, HRMS (ESI) m / z: 321.22 (100.0%), 322.22 (17.5%), 323.23 (1.5%).

[0021] Preferably, the method for preparing the intercalated modified bentonite comprises the following steps:

[0022] Add 35-70 g of bentonite to 0.88-1.76 L of water, stir and treat at 55-65° C. for 20-28 h, then add 46-92 g of 1-butyl-3-methylimidazolium hexafluorophosphate, ultrasonically treat for 5-7 h, continue stirring for 20-28 h, filter, wash the filter residue with water for 4-6 times to a pH of 7-8, and dry at 70-80° C. to constant weight to obtain intercalated modified bentonite.

[0023] In a second aspect, the present invention further provides a method for preparing a composite additive for lubricating oil, comprising the following steps:

[0024] Step (1) adding 3-6 parts of dialkyl copper dithiophosphate, 1-2 parts of intercalated modified bentonite, 1-2 parts of composite three-dimensional copper-based solid-liquid additives and 8-10 parts of nano borate to 4-10 parts of base oil, heating to 50-60° C. and maintaining the temperature, and uniformly dispersing in a high-speed disperser to obtain a mixed oil;

[0025] Step (2) adding 4-8 parts of high temperature antioxidant, 12-18 parts of rust inhibitor and 1-5 parts of trimethylolpropane ester to the mixed oil in sequence, stirring evenly, and cooling to room temperature to obtain a composite additive for lubricating oil.

[0026] In summary, due to the adoption of the above technical solution, the beneficial effects of the present invention are:

[0027] 1. In the present invention, 1-butyl-3-methylimidazolium hexafluorophosphate is intercalated into bentonite to obtain an intercalated modified bentonite having an ultra-thin layered structure with a smooth surface. At the same time, the lipophilicity of the alkyl chain improves the dispersion stability of the intercalated modified bentonite in the base oil. The silicon oxide octahedron and aluminum oxide hexahedron of the bentonite block material form an Al-containing 2 O 3 and SiO 2 The interfacial protective film, together with the stronger interlayer slip generated by the increased interlayer spacing of the intercalated modified bentonite, significantly improves the lubrication performance; the active elements in the molecular structure of 1-butyl-3-methylimidazolium hexafluorophosphate can provide excellent load-bearing performance and tribochemical reactions at the sliding interface. The polar groups in 1-butyl-3-methylimidazolium hexafluorophosphate will cause interfacial tribochemical reactions, thereby forming a tribochemical friction film with enhanced load-bearing performance; the intercalated modified bentonite can fill grooves and cracks, thereby making the substrate surface smoother, reducing wear during friction, and shortening the running-in period.

[0028] 2. The modified ionic liquid in the present invention is used as a liquid phase lubricant and a three-dimensional precipitation (Cu 3 (PO 4 ) 2 ·3H 2O) as a wear-resistant phase, the friction of the composite three-dimensional copper-based solid-liquid additive loaded with ionic liquid can be greatly reduced, and the wear resistance is enhanced; the prepared three-dimensional precipitation (Cu 3 (PO 4 ) 2 ·3H 2 O) molecules, there are polar water molecules, which generate Coulomb repulsion with non-polar base oil molecules, reducing friction; the three-dimensional precipitation has a large number of macroporous nano-flower-like structures and thus has a strong capillary effect, absorbing the modified ionic liquid, and the ionic liquid is released under load pressure as a liquid lubricant, and the anions of the modified ionic liquid and the cations of the matrix show chemical adsorption ability, inducing a tribochemical reaction between the friction interface, thereby producing effective lubrication; and the strong capillary effect of the three-dimensional precipitation makes the base oil dispersed in the multi-microporous structure of the three-dimensional precipitation, improving the dispersion stability in the lubricating oil, and the synergistic lubrication of the three-dimensional precipitation and the modified ionic liquid provides excellent friction reduction and wear resistance.

[0029] 3. The modified ionic liquid added in the present invention, due to the high reactivity of the phosphorus (P) component, the ionic liquid quickly adheres to the metal surface through intermolecular forces and Coulomb interactions during the friction process, and the slender alkyl chains of the modified ionic liquid molecules interact with each other to eventually form a comprehensive lubricating film on the metal surface. At the same time, the modified ionic liquid has a significant affinity for the intercalated modified bentonite, and the intercalated modified bentonite will be adsorbed to the top of the lubricating film formed on the metal surface; the attraction of the ionic liquid to the intercalated modified bentonite also increases the interlayer spacing of the bentonite, making it easier to peel off and firmly adsorbed on the surface of the lubricating film; at the same time, the interlayer lubrication provided by the intercalated modified bentonite not only has a good lubricating effect, but also can prevent the ionic liquid from tearing or degrading under high temperature and high pressure conditions. The double-layer lubrication generated by the synergistic effect of the modified ionic liquid and the intercalated modified bentonite effectively improves the tribological properties of the base oil and improves the friction characteristics. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0031] Figure 1 It is a process flow chart of the preparation of the composite additive for lubricating oil of the present invention;

[0032] Figure 2 This is a histogram of the friction performance of the composite additive for lubricating oil of the present invention. ; DETAILED DESCRIPTION

[0033] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0034] Example 1

[0035] This embodiment discloses a method for preparing a modified ionic liquid, comprising the following steps:

[0036] S1: 111 g of trioctylphosphine and 66.9 g of dodecane bromide were added to 120 mL of acetonitrile, stirred for 40 min, and then refluxed at 85° C. for 24 h, cooled to room temperature, added with 120 mL of petroleum ether, and then added with anhydrous sodium sulfate overnight, the acetonitrile was removed under reduced pressure, the product was extracted with petroleum ether, and then the petroleum ether was removed under reduced pressure to obtain intermediate A;

[0037] S2: 90 g of the intermediate and 48.6 g of di(2-ethylhexyl) phosphate were added to 0.75 L of ethanol containing 7.5 g of NaOH, and the mixture was refluxed at 85 ° C for 72 h. After removing the ethanol by rotary evaporation, 150 mL of petroleum ether was added, and the mixture was washed with water four times, anhydrous sodium sulfate was added and dried overnight, and the petroleum ether was removed by rotary evaporation to obtain a modified ionic liquid.

[0038] Example 2

[0039] This embodiment discloses a method for preparing a composite three-dimensional copper-based solid-liquid additive, comprising the following steps:

[0040] A1: 600mL, 0.12mol / L CuSO 4 Add 3L of 0.2mol / L Na 2 HPO 4 The solution was washed with water 4 times, then washed with ethanol 2 times, and dried at 60 °C to constant weight to obtain a three-dimensional precipitate;

[0041] A2: 7.5 g of the three-dimensional precipitate was mixed with 50 mL of the modified ionic liquid prepared in Example 1, the mixing process was repeated 4 times, and then washed with water 3 times, and vacuum dried to constant weight to obtain a composite three-dimensional copper-based solid-liquid additive.

[0042] Example 3

[0043] This embodiment discloses a method for preparing intercalated modified bentonite, comprising the following steps:

[0044] 52.5 g of bentonite was added to 1.32 L of water, stirred at 60 ° C for 24 h, and then 69 g of 1-butyl-3-methylimidazolium hexafluorophosphate was added. After ultrasonic treatment for 6 h, stirring was continued for 24 h, and the filter was filtered. The filter residue was washed with water for 5 times to a pH of 7.5, and dried at 75 ° C to constant weight to obtain intercalated modified bentonite.

[0045] Example 4

[0046] See also Figure 1 As shown, this embodiment discloses a method for preparing a composite additive for lubricating oil, comprising the following steps:

[0047] Step (1) adding 4.5 g of dialkyl copper dithiophosphate, 1.5 g of intercalated modified bentonite, 1.5 g of composite three-dimensional copper-based solid-liquid additive and 9 g of nano borate to 6 g of synthetic base oil, heating to 55° C. and maintaining the temperature, and uniformly dispersing in a high-speed disperser to obtain a mixed oil;

[0048] Step (2) 6 g of 2,6-dibutyl mixed phenol, 15 g of barium sulfonate and 3 g of trimethylolpropane ester were added to the mixed oil in sequence, stirred evenly, and cooled to room temperature to obtain a composite additive for lubricating oil.

[0049] Example 5

[0050] See also Figure 1 As shown, this embodiment discloses a method for preparing a composite additive for lubricating oil, comprising the following steps:

[0051] Step (1) adding 3 g of dialkyl copper dithiophosphate, 2 g of intercalated modified bentonite, 1 g of a composite three-dimensional copper-based solid-liquid additive and 10 g of nano borate to 4 g of a vegetable oil base oil, heating the oil to 60° C. and maintaining the temperature, and uniformly dispersing the mixture in a high-speed disperser to obtain a mixed oil;

[0052] Step (2) Add 4 g of 3,5-di-tert-butyl-4-hydroxyphenyl acrylate, 18 g of alkylbenzene sulfonate, and 1 g of trimethylolpropane ester to the mixed oil in sequence, stir evenly, and cool to room temperature to obtain a composite additive for lubricating oil.

[0053] Example 6

[0054] See also Figure 1 As shown, this embodiment discloses a method for preparing a composite additive for lubricating oil, comprising the following steps:

[0055] Step (1) adding 6 g of dialkyl copper dithiophosphate, 1 g of intercalated modified bentonite, 2 g of composite three-dimensional copper-based solid-liquid additive and 8 g of nano borate to 10 g of synthetic base oil, heating to 50° C. and maintaining the temperature, and uniformly dispersing in a high-speed disperser to obtain a mixed oil;

[0056] Step (2) 8 g of 2,6-dibutyl mixed phenol, 12 g of zinc epoxyate and 5 g of trimethylolpropane ester were added to the mixed oil in sequence, the mixture was stirred evenly and then cooled to room temperature to obtain a composite additive for lubricating oil.

[0057] Example 7

[0058] See also Figure 1 As shown, this embodiment discloses a method for preparing a composite additive for lubricating oil, comprising the following steps:

[0059] Step (1) adding 4 g of dialkyl copper dithiophosphate, 1.8 g of intercalated modified bentonite, 1.2 g of composite three-dimensional copper-based solid-liquid additive and 9 g of nano borate to 5 g of vegetable oil base oil, heating to 55° C. and maintaining the temperature, and uniformly dispersing in a high-speed disperser to obtain a mixed oil;

[0060] Step (2) Add 5 g of 3,5-di-tert-butyl-4-hydroxyphenyl acrylate, 17 g of barium sulfonate and 2 g of trimethylolpropane ester to the mixed oil in sequence, stir evenly and cool to room temperature to obtain a composite additive for lubricating oil.

[0061] Example 8

[0062] See also Figure 1 As shown, this embodiment discloses a method for preparing a composite additive for lubricating oil, comprising the following steps:

[0063] Step (1) adding 5 g of dialkyl copper dithiophosphate, 1.2 g of intercalated modified bentonite, 1.8 g of composite three-dimensional copper-based solid-liquid additive and 9 g of nano borate to 9 g of base oil, heating to 55° C. and maintaining the temperature, and uniformly dispersing in a high-speed disperser to obtain a mixed oil;

[0064] Step (2) 7 g of high temperature antioxidant, 13 g of rust inhibitor and 4 g of trimethylolpropane ester are added to the mixed oil in sequence, stirred evenly and cooled to room temperature to obtain a composite additive for lubricating oil.

[0065] Comparative Example 1

[0066] Comparative Example 1 Compared with Example 4, in the process of preparing the composite additive for lubricating oil in Comparative Example 1, no intercalated modified bentonite was added, and other conditions remained unchanged.

[0067] Comparative Example 2

[0068] Comparative Example 2 Compared with Example 4, in the process of preparing the composite additive for lubricating oil in Comparative Example 2, no composite three-dimensional copper-based solid-liquid additive was added, and other conditions remained unchanged.

[0069] Experimental example

[0070] The performance of the composite additives for lubricating oil prepared in Examples 4-8 and Comparative Examples 1-2 was tested. Three parts of the composite additives for lubricating oil were added to 200 parts of lubricating base oil without additives, and the effect was tested. The results of the effect test are shown in Table 1:

[0071] Table 1

[0072]

[0073]

[0074] It can be seen from Table 1 that the composite additives for lubricating oil prepared in Examples 4-8 can significantly improve the lubricating effect of the lubricating oil; from the comparison between Comparative Example 1 and Example 4, it can be seen that in the process of preparing the composite additive for lubricating oil, the present invention adds intercalated modified bentonite, which can significantly improve the lubricating effect of the lubricating oil; from the comparison between Comparative Example 2 and Example 4, it can be seen that in the process of preparing the composite additive for lubricating oil, the present invention adds a composite three-dimensional copper-based solid-liquid additive, which can significantly improve the lubricating effect of the lubricating oil.

[0075] The lubricating oil composite additive obtained in Example 4 was mixed with a lubricating base oil without additives in different proportions, and the effect was tested. The effect test results are shown in Table 2:

[0076] Table 2

[0077]

[0078] It can be seen from Table 2 that when 3 parts of the lubricating oil composite additive of Example 4 is added without 200 parts of the lubricating base lubricating oil, the lubricating effect of the lubricating oil can be significantly improved.

[0079] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

[0080] The preferred embodiments of the present invention disclosed above are only used to help explain the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to only specific implementation methods. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. A composite additive for lubricating oil, characterized in that: The composite additive for lubricating oil is composed of the following components in parts by weight: 4-10 parts of base oil, 3-6 parts of dialkyl copper dithiophosphate, 1-2 parts of intercalation modified bentonite, 1-2 parts of composite three-dimensional copper-based solid-liquid additive, 4-8 parts of high-temperature antioxidant, 8-10 parts of nano borate, 12-18 parts of rust inhibitor and 1-5 parts of trimethylolpropane ester.

2. The lubricating oil additive package according to claim 1, characterized in that: The base oil includes at least one of a synthetic base oil or a vegetable oil base oil.

3. The lubricating oil additive package according to claim 1, characterized in that: The high temperature antioxidant is 2,6-dibutyl mixed phenol or 3,5-di-tert-butyl-4-hydroxyphenyl acrylate.

4. The lubricating oil additive package according to claim 1, characterized in that: The rust inhibitor is one of barium sulfonate, alkylbenzene sulfonate and zinc epoxyate.

5. The lubricating oil additive package according to claim 1, characterized in that: The preparation method of the composite three-dimensional copper-based solid-liquid additive comprises the following steps: A1: Add 400-800 mL of 0.12 mol / L CuSO4 solution to 2-4 L of 0.2 mol / L Na2HPO4 solution, wash with water 3-5 times, then wash with ethanol 1-2 times, and dry at 55-65°C to constant weight to obtain a three-dimensional precipitate; A2: 5-10 g of three-dimensional precipitate is mixed with 40-60 mL of modified ionic liquid, the mixing process is repeated 3-5 times, then washed with water 2-3 times, and vacuum dried to constant weight to obtain a composite three-dimensional copper-based solid-liquid additive.

6. The lubricating oil additive package according to claim 5, characterized in that: The preparation method of the modified ionic liquid comprises the following steps: S1: 74-148 g of trioctylphosphine and 44.6-89.2 g of dodecane bromide were added to 80-160 mL of acetonitrile, stirred for 30-50 min, and then refluxed at 80-90° C. for 20-28 h, cooled to room temperature, added 80-160 mL of petroleum ether, and then added anhydrous sodium sulfate overnight, after removing the acetonitrile under reduced pressure, the product was extracted with petroleum ether, and then the petroleum ether was removed under reduced pressure to obtain intermediate A; S2: Add 59.4-120g of the intermediate and 32.2-64.4g of di(2-ethylhexyl) phosphate to 0.5-1L of ethanol containing 5-10g of NaOH, reflux at 80-90°C for 68-76h, remove the ethanol by rotary evaporation, add 100-200mL of petroleum ether, wash with water 3-5 times, add anhydrous sodium sulfate and dry overnight, remove the petroleum ether by rotary evaporation to obtain a modified ionic liquid.

7. The lubricating oil additive package according to claim 1, characterized in that: The preparation method of the intercalated modified bentonite comprises the following steps: Add 35-70g of bentonite to 0.88-1.76L of water, stir and treat at 55-65°C for 20-28h, then add 46-92g of 1-butyl-3-methylimidazolium hexafluorophosphate, ultrasonically treat for 5-7h, continue stirring for 20-28h, filter, wash the filter residue with water 4-6 times to a pH of 7-8, and dry at 70-80°C to constant weight to obtain intercalated modified bentonite.

8. A method for preparing the composite additive for lubricating oil according to any one of claims 1 to 7, characterized in that: The steps include: Step (1) adding 3-6 parts of dialkyl copper dithiophosphate, 1-2 parts of intercalated modified bentonite, 1-2 parts of composite three-dimensional copper-based solid-liquid additives and 8-10 parts of nano borate to 4-10 parts of base oil, heating and maintaining the temperature, and dispersing uniformly to obtain a mixed oil; Step (2) adds 4-8 parts of high temperature antioxidant, 12-18 parts of rust inhibitor and 1-5 parts of trimethylolpropane ester to the mixed oil in sequence, stirs evenly and cools to room temperature to obtain a composite additive for lubricating oil.

9. The method for preparing the composite additive for lubricating oil according to claim 8, characterized in that: In the step (1), the heating temperature is 50-60°C.

10. The method for preparing the composite additive for lubricating oil according to claim 8, characterized in that: In the step (1), the method for uniform dispersion is to disperse in a high-speed disperser.

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