A high-temperature resistant extreme pressure lubricating oil and its preparation method

Abstract

The present invention discloses a high-temperature resistant extreme pressure lubricating oil and a preparation method thereof, which relates to the technical field of lubricating materials. First, the present invention uses 1,1,3,3-tetrachloro-1,3-diphenyldisiloxane and methyltrifluoropropylcyclotrisiloxane as raw materials to prepare fluorosilicone oil, which contains multiple benzene rings and chlorine atoms, can improve the high-temperature resistance and stability of the fluorosilicone oil, and at the same time helps to form a more stable lubricating film on the friction surface, improving the extreme pressure resistance of the fluorosilicone oil; then, bentonite and tungsten diselenide precursor solution are mixed, and tungsten diselenide is directly prepared on the surface of bentonite by ultrasonic pyrolysis. The ultrasonic wave enables tungsten diselenide to better combine with the active sites on the surface of bentonite, increasing the loading amount of tungsten diselenide, reducing the aggregation and loss of tungsten diselenide additive during use, prolonging the service life of the tungsten diselenide additive, and further improving the high-temperature resistance and extreme pressure resistance of the system. The lubricating oil prepared by the present invention has the effects of high-temperature resistance and extreme pressure resistance.

Description

Technical Field

[0001] The present invention relates to the technical field of lubricating materials, and particularly to a high-temperature extreme-pressure lubricating oil and a preparation method thereof. Background Art

[0002] Lubricating oil generally consists of two parts: base oil and additives. The base oil is the main component of lubricating oil, determining the basic properties of lubricating oil. Additives can make up for and improve the deficiencies in the performance of the base oil, endowing some new properties, and are an important part of lubricating oil. Lubricating oil base oils are mainly divided into three categories: mineral base oils, synthetic base oils, and biological base oils.

[0003] With the progress of technology, new materials and new processes have emerged continuously, putting forward higher requirements for the performance of lubricating oil. In high-temperature, high-pressure, and heavy-load working environments, ordinary lubricating oil may fail quickly, leading to increased equipment wear and even failures. Especially in key industries such as steel, chemical engineering, and electric power, the continuous and stable operation of equipment is crucial for production. For the lubricating oils in the prior art, under high-temperature extreme-pressure conditions, the adhesion ability of the lubricating oil is greatly reduced, and oil dripping is very likely to occur, and a large amount of oily coke is generated, which needs to be cleaned regularly. Moreover, under high-temperature extreme-pressure conditions, the lubricating oil volatilizes excessively, generating toxic fumes and irritating odor gases, with a large oil consumption and environmental pollution. In the prior art, all raw materials are often put into the lubricating oil production equipment at the same time, and through stirring and heating, the materials are fully mixed and then homogenized and sieved, etc. to prepare lubricating oil, but there are still problems with poor high-temperature and extreme-pressure resistance performance. Summary of the Invention

[0004] The purpose of the present invention is to provide a high-temperature extreme-pressure lubricating oil and a preparation method thereof to solve the problems existing in the prior art.

[0005] To solve the above technical problems, the present invention provides the following technical solution: A high-temperature extreme-pressure lubricating oil, which is prepared by using 1,1,3,3-tetrachloro-1,3-diphenyldisiloxane, methyltrifluoropropylcyclotrisiloxane, and a catalyst to prepare fluorosilicone oil, and then adding tungsten diselenide modified by bentonite.

[0006] Further, the catalyst is one of strongly acidic cation exchange resin or tetramethylammonium hydroxide.

[0007] Further, the strongly acidic cation exchange resin is sulfonated coal or sulfonated styrene-based cation exchange resin.

[0008] Further, the tungsten diselenide modified by bentonite is prepared by mixing bentonite and a tungsten diselenide precursor solution, and directly preparing tungsten diselenide on the surface of bentonite by ultrasonic pyrolysis.

[0009] Further, a preparation method of a high-temperature resistant extreme pressure lubricating oil comprises the following preparation steps:

[0010] (1) Mix methyltrifluoropropylcyclotrisiloxane and 1,1,3,3-tetrachloro-1,3-diphenyldisiloxane at a molar ratio of 1:1.0 - 1.5, stir at 200 - 300 r / min for 20 - 30 min, add a catalyst with a molar ratio of 0.11 - 0.16 times that of methyltrifluoropropylcyclotrisiloxane, stir at 100 - 150 r / min for 20 - 30 min, heat up to 115 - 120 °C, react for 7 - 8 h, filter to obtain a filtrate, and distill at 1 - 2 mmHg and 70 - 80 °C to obtain fluorosilicone oil;

[0011] (2) Dissolve selenium dioxide and sodium tungstate in deionized water to ensure that the concentrations of tungsten ions and selenious acid ions are both 0.2 - 0.4 mol / dm 3 , add hydrazine hydrate with a mass 8 - 9 times that of sodium tungstate and bentonite with a mass 1.1 - 1.5 times that of sodium tungstate, and stir at 300 - 400 r / min for 30 - 40 min to obtain a tungsten diselenide precursor;

[0012] (3) Place the tungsten diselenide precursor solution in an ultrasonic nebulizer, and transport it to a reactor through nitrogen, and react for 2 - 3 h to obtain bentonite-modified tungsten diselenide;

[0013] (4) Grind the bentonite-modified tungsten diselenide in a ball mill, and add it to the fluorosilicone oil to obtain a high-temperature resistant extreme pressure lubricating oil.

[0014] Further, the bentonite in step (3) is prepared by calcining at 450 - 470 °C for 1 - 1.5 h.

[0015] Further, the frequency of the ultrasonic nebulizer in step (3) is 1.7 - 2.0 MHz.

[0016] Further, the flow rate of nitrogen in step (3) is 1.5 - 2.0 dm 3 / min.

[0017] Further, the temperature of the reactor in step (3) is 600 - 700 °C.

[0018] Further, the particle size of the bentonite-modified tungsten diselenide after grinding in step (4) is 30 - 40 nm..

[0019] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0020] The present invention uses 1,1,3,3-tetrachloro-1,3-diphenyldisiloxane and methyltrifluoropropylcyclotrisiloxane as raw materials to prepare fluorosilicone oil, and then adds a tungsten diselenide additive modified by bentonite to obtain a lubricating oil, so as to achieve the effects of high temperature resistance and extreme pressure resistance.

[0021] First, 1,1,3,3-tetrachloro-1,3-diphenyldisiloxane and methyltrifluoropropylcyclotrisiloxane are used as raw materials to prepare fluorosilicone oil. Containing multiple benzene rings and chlorine atoms, it can make the fluorosilicone oil maintain stable performance at higher temperatures and greatly improve the antioxidant ability of the fluorosilicone oil, enhance the high temperature resistance and stability of the fluorosilicone oil. At the same time, it helps to form a more stable lubricating film on the friction surface, reduce the friction coefficient, thereby reducing the wear between the friction pairs and improving the extreme pressure resistance of the fluorosilicone oil.

[0022] Secondly, bentonite and a tungsten diselenide precursor solution are mixed, and tungsten diselenide is directly prepared on the surface of bentonite by ultrasonic pyrolysis. Ultrasonic waves can modify the structure of bentonite, making the structure of bentonite looser and the specific surface area larger, so that more active sites are exposed. Ultrasonic waves also make the tungsten diselenide precursor solution more evenly distributed on the surface of bentonite, enabling tungsten diselenide to better combine with the active sites on the surface of bentonite, increasing the loading amount of tungsten diselenide. Ultrasonic waves can also form a stronger interaction force between tungsten diselenide and bentonite, reducing the aggregation and loss of the tungsten diselenide additive during use, extending the service life of the tungsten diselenide additive, and further improving the high temperature resistance and extreme pressure resistance of the system. Specific embodiments

[0023] The following will combine 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 a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative work belong to the scope of protection of the present invention.

[0024] In order to more clearly illustrate the method provided by the present invention, the following embodiments are used for detailed description. The test methods for each index of the high temperature resistant extreme pressure lubricating oil prepared in the following embodiments are as follows:

[0025] Thermal stability: The high temperature resistant extreme pressure lubricating oils prepared in the examples and comparative examples with the same mass are tested for their thermal stability at 400 °C according to SH / T0680-1999 "Determination Method for Thermal Stability of Heat Transfer Fluids".

[0026] Oxidation stability: The high temperature resistant extreme pressure lubricating oils prepared in the examples and comparative examples with the same mass are tested for their oxidation stability according to SH / T0193-2008 "Determination of Oxidation Stability of Lubricating Oils - Rotating Bomb Method".

[0027] Extreme pressure resistance: The high-temperature resistant extreme pressure lubricating oils prepared from the examples and comparative examples with the same mass were tested for the extreme pressure and anti-wear characteristics of the lubricating oil using the SRV4 friction and wear performance in accordance with SH / T 0882-2014 "Determination of Extreme Pressure Performance of Lubricating Oils - SRV Test Machine Method".

[0028] Example 1

[0029] A preparation method of a high-temperature resistant extreme pressure lubricating oil, comprising the following preparation steps:

[0030] (1) Mix methyltrifluoropropylcyclotrisiloxane and 1,1,3,3-tetrachloro-1,3-diphenyldisiloxane at a molar ratio of 1:1.0, stir at 200 r / min for 20 min, add a sulfonated styrene-based cation exchange resin with a molar ratio of 0.11 times that of methyltrifluoropropylcyclotrisiloxane, stir at 100 r / min for 20 min, heat up to 115 °C, react for 7 h, filter to obtain a filtrate, and distill at a reduced pressure of 1 mmHg and 70 °C to obtain fluorosilicone oil;

[0031] (2) Calcinate bentonite at 450 °C for 1 h to obtain activated bentonite. Dissolve selenium dioxide and sodium tungstate in deionized water to ensure that the concentrations of tungsten ions and selenious acid ions are both 0.2 mol / dm 3 , add hydrazine hydrate 8 times the mass of sodium tungstate and activated bentonite 1.1 times the mass of sodium tungstate, and stir at 300 r / min for 30 min to obtain a tungsten diselenide precursor;

[0032] (3) Place the tungsten diselenide precursor solution in an ultrasonic nebulizer with a frequency of 1.7 MHz, and transport it to the reactor through nitrogen with a flow rate of 1.5 dm 3 / min, heat up to 600 °C and react for 2 h to obtain bentonite-modified tungsten diselenide;

[0033] (4) Grind the bentonite-modified tungsten diselenide in a ball mill. After grinding to a particle size of 30 nm of the bentonite-modified tungsten diselenide, add it to the fluorosilicone oil to obtain a high-temperature resistant extreme pressure lubricating oil.

[0034] Example 2

[0035] A preparation method of a high-temperature resistant extreme pressure lubricating oil, comprising the following preparation steps:

[0036] (1) Mix methyltrifluoropropylcyclotrisiloxane and 1,1,3,3-tetrachloro-1,3-diphenyldisiloxane at a molar ratio of 1:1.3, stir at 250 r / min for 25 min, add a sulfonated styrene-based cation exchange resin with a molar ratio of 0.13 times that of methyltrifluoropropylcyclotrisiloxane, stir at 130 r / min for 25 min, heat up to 118 °C, react for 7 h, filter to obtain a filtrate, and distill at a reduced pressure of 2 mmHg and 75 °C to obtain fluorosilicone oil;

[0037] (2) The bentonite is calcined at 460 °C for 1 h to obtain activated bentonite. Selenium dioxide and sodium tungstate are dissolved in deionized water to ensure that the concentrations of tungsten ions and selenious acid ions are both 0.3 mol / dm 3 , add hydrazine hydrate 8 times the mass of sodium tungstate and activated bentonite 1.3 times the mass of sodium tungstate, and stir at 350 r / min for 35 min to obtain a tungsten diselenide precursor;

[0038] (3) Place the tungsten diselenide precursor solution in an ultrasonic nebulizer with a frequency of 1.8 MHz, and transport it to the reactor through nitrogen with a flow rate of 1.8 dm 3 / min, heat up to 650 °C and react for 3 h to obtain bentonite-modified tungsten diselenide;

[0039] (4) Grind the bentonite-modified tungsten diselenide in a ball mill. After grinding to a particle size of 35 nm of the bentonite-modified tungsten diselenide, add it to fluorosilicone oil to obtain a high-temperature resistant extreme pressure lubricating oil.

[0040] Example 3

[0041] A preparation method of a high-temperature resistant extreme pressure lubricating oil, comprising the following preparation steps:

[0042] (1) Mix methyltrifluoropropylcyclotrisiloxane and 1,1,3,3-tetrachloro-1,3-diphenyldisiloxane at a molar ratio of 1:1.5, stir at 300 r / min for 20 - 30 min, add a sulfonated styrene-based cation exchange resin 0.16 times the molar ratio of methyltrifluoropropylcyclotrisiloxane, stir at 150 r / min for 30 min, heat up to 120 °C, react for 8 h, filter to obtain a filtrate, and distill under reduced pressure to 2 mmHg and 80 °C to obtain fluorosilicone oil;

[0043] (2) The bentonite is calcined at 470 °C for 1.5 h to obtain activated bentonite. Selenium dioxide and sodium tungstate are dissolved in deionized water to ensure that the concentrations of tungsten ions and selenious acid ions are both 0.4 mol / dm 3 , add hydrazine hydrate 9 times the mass of sodium tungstate and activated bentonite 1.5 times the mass of sodium tungstate, and stir at 400 r / min for 40 min to obtain a tungsten diselenide precursor;

[0044] (3) Place the tungsten diselenide precursor solution in an ultrasonic nebulizer with a frequency of 2.0 MHz, and transport it to the reactor through nitrogen with a flow rate of 2.0 dm 3 / min, heat up to 700 °C and react for 3 h to obtain bentonite-modified tungsten diselenide;

[0045] (4) Grind the bentonite-modified tungsten diselenide in a ball mill. After grinding to a particle size of 40 nm of the bentonite-modified tungsten diselenide, add it to fluorosilicone oil to obtain a high-temperature resistant extreme pressure lubricating oil.

[0046] Comparative Example 1

[0047] The difference between Comparative Example 1 and Example 2 lies in the difference in step (1). Step (1) is changed to: Mix methyltrifluoropropylcyclotrisiloxane and octamethylcyclotetrasiloxane at a molar ratio of 1:1.3, stir at 250 r / min for 25 min, add a sulfonated styrene-based cation exchange resin with a molar ratio of 0.13 times that of methyltrifluoropropylcyclotrisiloxane, stir at 130 r / min for 25 min, heat up to 118 °C, react for 7 h, filter to obtain a filtrate, and distill at a reduced pressure of 2 mmHg and 75 °C to obtain fluorosilicone oil; the remaining steps are the same as those in Example 2.

[0048] Comparative Example 2

[0049] The difference between Comparative Example 2 and Example 2 lies in the difference in step (2). Step (2) is changed to: Dissolve selenium dioxide and sodium tungstate in deionized water to ensure that the concentrations of tungsten ions and selenious acid ions are both 0.3 mol / dm3, add hydrazine hydrate 8 times the mass of sodium tungstate, and stir at 350 r / min for 35 min to obtain a tungsten diselenide precursor; step (3) is changed to: (3) Place the tungsten diselenide precursor solution in an ultrasonic nebulizer with a frequency of 1.8 MHz, and transport it to the reactor through nitrogen with a flow rate of 1.8 dm3 / min, heat up to 650 °C and react for 3 h to obtain tungsten diselenide; the remaining steps are the same as those in Example 2.

[0050] Comparative Example 3

[0051] The difference between Comparative Example 3 and Example 2 is that step (3) is absent. Step (2) is changed to: Roast bentonite at 460 °C for 1 h to obtain activated bentonite; step (4) is changed to: Place bentonite in a ball mill and grind it until the particle size of bentonite is 35 nm, then add it to fluorosilicone oil to obtain a high-temperature resistant extreme pressure lubricating oil; the remaining steps are the same as those in Example 2.

[0052] Comparative Example 4

[0053] The difference between Comparative Example 4 and Example 2 is that step (3) is absent. Step (3) is changed to: Heat the tungsten diselenide precursor to 200 °C, react for 48 h, naturally cool to room temperature, centrifuge and wash 5 times, wash with 25 wt% NaOH solution, filter to obtain a filtrate, and wash with deionized water until neutral to obtain bentonite-modified tungsten diselenide; the remaining steps are the same as those in Example 2.

[0054] Effect Example

[0055] The following Table 1 gives the performance analysis results of the high-temperature resistant extreme pressure lubricating oils using Examples 1 to 3 and Comparative Examples 1 to 4 of the present invention.

[0056]

[0057] From the comparison of the experimental data between Example 2 and Comparative Example 1, it can be found that by using 1,1,3,3-tetrachloro-1,3-diphenyldisiloxane and methyltrifluoropropylcyclotrisiloxane as raw materials to prepare fluorosilicone oil, the fluorosilicone oil contains multiple benzene rings and chlorine atoms, which can make the fluorosilicone oil maintain stable performance at higher temperatures and greatly improve the antioxidant ability of the fluorosilicone oil, enhance the high-temperature resistance and stability of the fluorosilicone oil. At the same time, it helps to form a more stable lubricating film on the friction surface, reduce the friction coefficient, thereby reducing the wear between friction pairs and improving the extreme pressure resistance of the fluorosilicone oil. From the comparison of the experimental data between Example 2 and Comparative Example 2, it can be found that by adding bentonite, the dispersibility of tungsten diselenide additive in the lubricating oil is improved, the aggregation and loss of tungsten diselenide during use are reduced, the service life of the tungsten diselenide additive is prolonged, and the high-temperature resistance and extreme pressure resistance of the system are improved. From the comparison of the experimental data between Example 2 and Comparative Example 3, it can be found that by adding tungsten diselenide, the high-temperature resistance and extreme pressure resistance of the system are improved, a protective film can be formed on the metal surface to prevent direct contact and wear of the metal surface, and it has a certain antioxidant effect, which can slow down the oxidation process of the lubricating oil at high temperatures. From the comparison of the experimental data between Example 2 and Comparative Example 4, it can be found that tungsten diselenide is directly prepared on the surface of bentonite by ultrasonic pyrolysis. Ultrasonic waves can modify the structure of bentonite, making the structure of bentonite looser and the specific surface area larger, so that more active sites are exposed. Ultrasonic waves also make the tungsten diselenide precursor solution distribute more evenly on the surface of bentonite, enabling tungsten diselenide to better combine with the active sites on the surface of bentonite, increasing the loading amount of tungsten diselenide. Ultrasonic waves can also form a stronger interaction force between tungsten diselenide and bentonite, reduce the aggregation and loss of tungsten diselenide additive during use, prolong the service life of the tungsten diselenide additive, and further improve the high-temperature resistance and extreme pressure resistance of the system.

[0058] For those skilled in the art, it is obvious that the present invention is not limited to the details of the above exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the spirit or basic characteristics of the present invention. Therefore, from any point of view, the embodiments should be regarded as exemplary and non-limiting. The scope of the present invention is defined by the appended claims rather than the above description. Therefore, all changes falling within the meaning and scope of the equivalent elements of the claims are intended to be included in the present invention. Any reference signs in the claims should not be regarded as limiting the claimed claim.

Claims

1. A high-temperature and extreme-pressure lubricating oil, characterized in that, The high-temperature extreme pressure lubricating oil is prepared by using 1,1,3,3-tetrachloro-1,3-diphenyldisiloxane, methyltrifluoropropylcyclotrisiloxane and a catalyst to prepare fluorosilicone oil, and then adding tungsten diselenide modified by bentonite; The tungsten diselenide modified by bentonite is prepared by mixing bentonite and a tungsten diselenide precursor solution and directly preparing tungsten diselenide on the surface of bentonite by ultrasonic pyrolysis.

2. An extreme pressure lubricating oil resistant to high temperatures according to claim 1, characterized in that, The catalyst is one of strongly acidic cation exchange resin or tetramethylammonium hydroxide.

3. The high-temperature extreme-pressure lubricating oil according to claim 2, characterized in that, The strongly acidic cation exchange resin is sulfonated coal or sulfonated styrene-based cation exchange resin.

4. A preparation method of a high-temperature resistant extreme pressure lubricating oil, characterized in that, It includes the following preparation steps: (1) Mix methyltrifluoropropylcyclotrisiloxane and 1,1,3,3-tetrachloro-1,3-diphenyldisiloxane at a molar ratio of 1:1.0 - 1.5, stir at 200 - 300 r / min for 20 - 30 min, add a catalyst with a molar ratio of 0.11 - 0.16 times that of methyltrifluoropropylcyclotrisiloxane, stir at 100 - 150 r / min for 20 - 30 min, heat up to 115 - 120 °C, react for 7 - 8 h, filter to obtain a filtrate, and distill at a reduced pressure of 1 - 2 mmHg and 70 - 80 °C to obtain fluorosilicone oil; (2) Dissolve selenium dioxide and sodium tungstate in deionized water to ensure that the concentrations of tungsten ions and selenious acid ions are both 0.2 - 0.4 mol / dm 3 , add hydrazine hydrate which is 8 - 9 times the mass of sodium tungstate and bentonite which is 1.1 - 1.5 times the mass of sodium tungstate, stir at 300 - 400 r / min for 30 - 40 min to obtain a tungsten diselenide precursor; (3) Place the tungsten diselenide precursor solution in an ultrasonic nebulizer, transport it to the reactor through nitrogen, and react for 2 - 3 h to obtain tungsten diselenide modified by bentonite; (4) Place the tungsten diselenide modified by bentonite in a ball mill for grinding, and add it to the fluorosilicone oil after grinding to obtain the high-temperature extreme pressure lubricating oil.

5. The preparation method of a high-temperature extreme pressure lubricating oil according to claim 4, characterized in that, In the step (3), the bentonite is obtained by calcining at 450 - 470 °C for 1 - 1.5 h.

6. The preparation method of a high-temperature extreme pressure lubricating oil according to claim 4, wherein, In the step (3), the frequency of the ultrasonic nebulizer is 1.7 - 2.0 MHz.

7. The preparation method of a high-temperature extreme pressure lubricating oil according to claim 4, characterized in that, The flow rate of nitrogen in step (3) is 1.5~2.0dm 3 / min.

8. The preparation method of a high-temperature extreme pressure lubricating oil according to claim 4, characterized in that, In the step (3), the temperature of the reactor is 600 - 700 °C.

9. The preparation method of a high-temperature extreme pressure lubricating oil according to claim 4, characterized in that In the step (4), the particle size of the tungsten diselenide modified by bentonite after grinding is 30 - 40 nm.

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