Calixarene molecule composite friction material and preparation method and application thereof

Abstract

The invention discloses a calixarene molecule composite friction material and a preparation method and application thereof, the calixarene molecule composite friction material is used as an additive in lubricating oil, the lubricating oil is used as base oil, the lubricating oil and the calixarene molecule composite friction material are mixed, a compounding agent is added, and after uniform ultrasonic treatment, the composite lubricating oil is obtained. According to the preparation method, an organic chemical synthesis method is adopted, calixarene molecules and oleic acid molecules are added into base oil, and molecular dynamic deformation can be achieved through the host-guest chemical effect, so that a continuous oil film is constructed on a friction interface, and the tribological performance of the lubricating oil is synergistically improved. According to the preparation method, the tribological performance of the calixarene molecule composite friction material on the base oil is enhanced, and the application of the calixarene molecule composite friction material in lubricating oil is expanded.

Description

Technical Field

[0001] The present invention belongs to the technical field of lubricating oils, and particularly relates to a calixarene molecular composite friction material, a preparation method thereof, and an application thereof. Background Art

[0002] In recent years, driven by the rapid development of advanced manufacturing, the performance of traditional lubricating materials has gradually approached its physical limit. Conventional lubricating oil base oils and additive systems are prone to oil film rupture under complex conditions such as high temperature and high pressure, alternating loads, etc., resulting in increased wear on the surface of friction pairs and even mechanical failure. This has made high-performance lubricating materials with special functional characteristics an important research direction in the field of mechanical lubrication.

[0003] Since the 21st century, molecular composite friction materials, as new lubricating additives, have continuously received attention due to their remarkable friction reduction, anti-wear, and extreme pressure characteristics shown in lubricating oil systems, and especially their synergistic lubrication function. Summary of the Invention

[0004] To solve the above problems, the present invention provides a calixarene molecular composite friction material, a preparation method thereof, and an application thereof. The method is convenient and high-yield. Applying the calixarene molecular composite friction material to lubricating oil realizes the enhancement of the friction performance of the calixarene molecular composite friction material on the base lubricating oil and expands its application in lubricating oil.

[0005] The present invention is achieved through the following technical solutions: The present invention provides an application of a calixarene molecular composite friction material in lubricating oil.

[0006] Further, the calixarene molecular composite friction material is used as an additive in lubricating oil, and the lubricating oil is used as the base oil. After mixing the lubricating oil with the calixarene molecular composite friction material and adding a compounding agent, and ultrasonicating uniformly, a composite lubricating oil is obtained.

[0007] Further, the lubricating oil is one of PEG200, PEG400, PAO6, and trioctyl trimellitate.

[0008] Further, the compounding agent is oleic acid.

[0009] Further, the mass ratio of the base oil, the additive, and the compounding agent is 1000 : (1 - 6) : 20.

[0010] The present invention also provides a preparation method of a calixarene molecular composite friction material, which includes the following steps: S1. Add p-tert-butylphenol, paraformaldehyde, KOH, and xylene into a container, heat and reflux in an N 2 atmosphere. After heating for a period of time, white precipitates are generated; After the reaction mixture refluxes for a period of time, filter off the filtrate with a funnel. The solid product is successively washed with toluene, ether, acetone, and water, and dried to obtain the calixarene molecular composite friction material.

[0011] Furthermore, in S1, the content of p-tert-butylphenol is above 98%, the content of paraformaldehyde is above 95%, KOH is of analytical purity with a content above 85%, and the content of xylene is above 98%.

[0012] Furthermore, in S2, toluene, ether, and acetone are all of analytical purity with contents above 99.5%.

[0013] On the other hand, the present invention also provides the calixarene molecular composite friction material prepared by the above preparation method.

[0014] The beneficial effects of the present invention are as follows: (1) The present invention applies the calixarene molecular composite friction material as an additive in the base lubricating oil. With its excellent properties, the calixarene molecular composite friction material can be efficiently dispersed in various lubricating base oils to form a dynamic lubrication regulation system. (2) The present invention adds calixarene molecules and oleic acid molecules to the base oil. When the mechanical transmission system enters the lubrication demand stage, through external field stimuli such as thermal field excitation, electric field drive, stress triggering, or magnetic field induction, molecular dynamic deformation and synergistic effects based on host-guest chemistry such as hydroxyl groups, ether groups, and carboxyl groups are realized, so as to construct a continuous oil film at the friction interface, synergistically improve the tribological properties of the lubricating oil, and thus achieve the goal of precise lubrication regulation. In summary, the preparation method of the composite lubricating oil realizes the enhancement of the tribological properties of the base oil by the calixarene molecular composite friction material and expands its application in lubricating oils. Description of the Drawings

[0015] Figure 1 is a top view of the calixarene molecule. Figure 2 is a top view of the host-guest interaction between the calixarene molecular composite friction material and the oleic acid molecule. Figure 3 is a side view of the host-guest interaction between the calixarene molecular composite friction material and the oleic acid molecule. Figure 4 is the Fourier transform infrared spectrum of the calixarene molecule. Figure 5 is the nuclear magnetic resonance spectrum of the calixarene molecule. Figure 6 is a graph showing the change of the friction coefficient of 0.2% calixarene in different base oils over time. Figure 7 is a graph showing the change of the friction coefficient with time when using different concentrations of additives in PEG200. Figure 8 Figures (a), (b), (c), (d), and (e) are the diagrams of the wear diameters on the surfaces of steel balls after testing with different concentrations of additives in PEG200. Detailed implementation

[0016] A calixarene molecular composite friction material is added as an additive to lubricating oil to prepare a composite lubricating oil, which specifically includes the following steps: (1) Prepare the calixarene molecular composite friction material. Specifically: Add 27.8 g (0.18 mol) of p-tert-butylphenol, 9.0 g (0.30 mol) of paraformaldehyde, 0.4 mL (0.004 mol) of 10N KOH, and 150 mL of xylene into a 500 mL three-necked flask, and reflux at 130 °C for 4 h in an N 2 atmosphere. During the reaction process, after heating for 30 minutes, all solids dissolve into the solution and white precipitates start to form. After the reaction mixture refluxes for 4 hours, filter off the filtrate with a sintered glass funnel. The solid product is successively washed with 100 mL of toluene, ether, acetone, and water, and then dried in a vacuum drying oven at 80 °C for 18 h to obtain the calixarene molecular composite friction material; The p-tert-butylphenol used in the synthesis has a content of more than 98%, the paraformaldehyde has a content of more than 95%, the potassium hydroxide is of analytical grade with a content of more than 85%, the xylene has a content of more than 98%, and the toluene, ether, and acetone are all of analytical grade with a content of more than 99.5%; (2) After adding the calixarene molecular composite friction material as an additive to the lubricating oil and mixing, add a small amount of oleic acid as a compounding agent to uniformly disperse the calixarene molecules in the lubricating oil, and ultrasonicate for 5 min to make it uniformly dispersed to obtain a homogeneous composite lubricating oil; Among them, the lubricating oil is one of PEG200, PEG400, PAO6, and trioctyl trimellitate; the mass ratio of the base oil, additive, and dispersant is 1000 : (1 - 6) : 20, that is, the addition amount of the calixarene molecular composite friction material is 0.1% - 0.6% of the mass of the base oil; (3) Test the obtained composite lubricating oil on a friction machine in a four-ball friction mode.

[0017] The present invention will be further described below in conjunction with the accompanying drawings and specific preferred embodiments, but the protection scope of the present invention is not limited thereby.

[0018] In the following examples, unless otherwise specified, the raw materials used are ordinary commercially available products that can be directly purchased. For example, p-tert-butylphenol was purchased from Anhui Zesheng Technology Co., Ltd., paraformaldehyde was purchased from Tianjin Damao Chemical Reagent Factory, potassium hydroxide was purchased from Tianjin De'en Chemical Reagent Co., Ltd.; xylene was purchased from Tianjin Damao Chemical Reagent Factory. Toluene, ether, and acetone were all purchased from Tianjin Damao Chemical Reagent, and polyethylene glycol 200 was purchased from Tianjin Damao Chemical Reagent Factory.

[0019] The steel balls used in the experiment were composed of GCr 15 bearing steel (hardness: 64 - 66 Rockwell hardness C (HRC), diameter: 12.7 mm). The balls were cleaned with acetone by ultrasonic waves before and after use and then dried. Three repeated friction and wear tests were carried out under preset conditions to minimize the dispersion of data. At the end of each test, the wear scar diameter (WSD) of the three lower fixed balls was measured using the image acquisition system (±0.01 mm) of the four-ball tribometer.

[0020] Example 1 For the application of a calixarene molecular composite friction material in lubricating oil, the specific steps are as follows: (1) Preparation of the calixarene molecular composite friction material: Specifically, 27.8 g (0.18 mol) of p-tert-butylphenol, 9.0 g (0.30 mol) of paraformaldehyde, 0.4 mL (0.004 mol) of 10N KOH, and 150 mL of xylene were added to a 500 mL three-necked flask and refluxed at 130 °C for 4 h in an N 2 atmosphere. During the reaction, after heating for 30 minutes, all the solids dissolved in the solution and white precipitates began to form. After the reaction mixture was refluxed for 4 hours, the filtrate was filtered off with a sintered glass funnel. The solid product was successively washed with 100 mL of toluene, ether, acetone, and water, and then dried in a vacuum drying oven at 80 °C for 18 h to obtain the calixarene molecular composite friction material; (2) Weigh 10 g of PEG200, 0.02 g of calixarene molecules, and 200 μL of oleic acid into a 200 ml beaker. Ultrasonic the liquid in the beaker for 5 min until it is evenly mixed to obtain a homogeneous composite lubricating oil solution; (3) Carry out friction tests on the prepared composite lubricating oil solution. Through the four-ball mode, test it at 392 N for 30 min.

[0021] Example 2 For the application of a calixarene molecular composite friction material in lubricating oil, the specific steps are as follows: (1) Prepare a calixarene molecular composite friction material, specifically: Add 27.8 g (0.18 mol) of p-tert-butylphenol, 9.0 g (0.30 mol) of paraformaldehyde, 0.4 mL (0.004 mol) of 10N KOH, and 150 mL of xylene into a 500 mL three-necked flask, and reflux at 130 °C for 4 h in an N 2 atmosphere. During the reaction, after heating for 30 minutes, all solids dissolve into the solution, and white precipitates begin to form. After the reaction mixture refluxes for 4 hours, filter off the filtrate with a sintered glass funnel. The solid product is successively washed with 100 mL of toluene, ether, acetone, and water, and then dried in a vacuum drying oven at 80 °C for 18 h to obtain calixarene molecules; (2) Weigh 10 g of PEG400, 0.02 g of calixarene molecules, and 200 μL of oleic acid into a 200 ml beaker, and ultrasonicate the liquid in the beaker for 5 min until it is evenly mixed to obtain a homogeneous composite lubricating oil solution; (3) Conduct a friction test on the prepared composite lubricating oil solution. Through the four-ball mode, test it at 392 N for 30 min.

[0022] Example 3 In the application of a calixarene molecular composite friction material in lubricating oil, it specifically includes the following steps: (1) Prepare a calixarene molecular composite friction material, specifically: Add 27.8 g (0.18 mol) of p-tert-butylphenol, 9.0 g (0.30 mol) of paraformaldehyde, 0.4 mL (0.004 mol) of 10N KOH, and 150 mL of xylene into a 500 mL three-necked flask, and reflux at 130 °C for 4 h in an N 2 atmosphere. During the reaction, after heating for 30 minutes, all solids dissolve into the solution, and white precipitates begin to form. After the reaction mixture refluxes for 4 hours, filter off the filtrate with a sintered glass funnel. The solid product is successively washed with 100 mL of toluene, ether, acetone, and water, and then dried in a vacuum drying oven at 80 °C for 18 h to obtain calixarene molecules; (2) Weigh 10 g of PAO6, 0.02 g of calixarene molecules, and 200 μL of oleic acid into a 200 ml beaker, and ultrasonicate the liquid in the beaker for 5 min until it is evenly mixed to obtain a homogeneous composite lubricating oil solution; (3) Conduct a friction test on the prepared composite lubricating oil solution. Through the four-ball mode, test it at 392 N for 30 min.

[0023] Example 4 In the application of a calixarene molecular composite friction material as a friction material in lubricating oil, it specifically includes the following steps: (1) Prepare calixarene molecular composite friction materials, specifically: Add 27.8 g (0.18 mol) of p-tert-butylphenol, 9.0 g (0.30 mol) of paraformaldehyde, 0.4 mL (0.004 mol) of 10N KOH, and 150 mL of xylene into a 500 mL three-necked flask, and reflux at 130 °C for 4 h in an N 2 atmosphere. During the reaction, after heating for 30 minutes, all solids dissolve into the solution and white precipitates start to form. After the reaction mixture refluxes for 4 hours, filter off the filtrate with a fritted funnel. The solid product is successively washed with 100 mL of toluene, ether, acetone, and water, and then dried in a vacuum drying oven at 80 °C for 18 h to obtain calixarene molecules; (2) Weigh 10 g of trioctyl trimellitate, 0.02 g of calixarene molecules, and 200 μL of oleic acid into a 200 ml beaker, and ultrasonicate the liquid in the beaker for 5 min until it is evenly mixed to obtain a homogeneous composite lubricating oil solution; (3) Conduct a friction test on the prepared composite lubricating oil solution. Through the four-ball mode, test it at 392 N for 30 min.

[0024] Example 5 Weigh 10 g of the base oil PEG200, which is a homogeneous lubricating oil; Conduct a friction test on the homogeneous lubricating oil on a friction machine. Test it in the four-ball mode at 50 N for 30 min.

[0025] Example 6 A calixarene molecular composite friction material is added as a friction material to lubricating oil, and the specific steps are as follows: (1) Prepare calixarene molecular composite friction materials, specifically: Add 27.8 g (0.18 mol) of p-tert-butylphenol, 9.0 g (0.30 mol) of paraformaldehyde, 0.4 mL (0.004 mol) of 10N KOH, and 150 mL of xylene into a 500 mL three-necked flask, and reflux at 130 °C for 4 h in an N 2 atmosphere. During the reaction, after heating for 30 minutes, all solids dissolve into the solution and white precipitates start to form. After the reaction mixture refluxes for 4 hours, filter off the filtrate with a fritted funnel. The solid product is successively washed with 100 mL of toluene, ether, acetone, and water, and then dried in a vacuum drying oven at 80 °C for 18 h to obtain calixarene molecules; (2) Weigh 10 g of PEG200, 0.01 g of calixarene molecules, and 200 μL of oleic acid into a 200 ml beaker, and ultrasonicate the liquid in the beaker for 5 min until it is evenly mixed to obtain a composite lubricating oil solution; (3) Perform a friction test on the composite lubricating oil solution. Through the four-ball mode, test it at 50 N for 30 min.

[0026] Example 7 A calixarene molecular composite friction material is added to the lubricating oil as a friction material. The specific steps are as follows: (1) Prepare the calixarene molecular composite friction material. Specifically: Add 27.8 g (0.18 mol) of p-tert-butylphenol, 9.0 g (0.30 mol) of paraformaldehyde, 0.4 mL (0.004 mol) of 10N KOH, and 150 mL of xylene into a 500 mL three-necked flask, and reflux at 130 °C for 4 h in an N 2 atmosphere. During the reaction, after heating for 30 minutes, all the solids dissolve into the solution and white precipitates start to form. After the reaction mixture refluxes for 4 hours, filter off the filtrate with a sintered glass funnel. The solid product is successively washed with 100 mL of toluene, ether, acetone, and water, and then dried in a vacuum drying oven at 80 °C for 18 h to obtain calixarene molecules; (2) Weigh 10 g of PEG200, 0.02 g of calixarene molecules, and 200 μL of oleic acid into a 200 ml beaker. Ultrasonic the liquid in the beaker for 5 min until it is evenly mixed to obtain a homogeneous composite lubricating oil solution; (3) Perform a friction test on the prepared composite lubricating oil solution. Through the four-ball mode, test it at 50 N for 30 min.

[0027] Example 8 A calixarene molecular composite friction material is added to the lubricating oil as a friction material. The specific steps are as follows: (1) Prepare the calixarene molecular composite friction material. Specifically: Add 27.8 g (0.18 mol) of p-tert-butylphenol, 9.0 g (0.30 mol) of paraformaldehyde, 0.4 mL (0.004 mol) of 10N KOH, and 150 mL of xylene into a 500 mL three-necked flask, and reflux at 130 °C for 4 h in an N 2 atmosphere. During the reaction, after heating for 30 minutes, all the solids dissolve into the solution and white precipitates start to form. After the reaction mixture refluxes for 4 hours, filter off the filtrate with a sintered glass funnel. The solid product is successively washed with 100 mL of toluene, ether, acetone, and water, and then dried in a vacuum drying oven at 80 °C for 18 h to obtain calixarene molecules; (2) Weigh 10 g of PEG200, 0.04 g of calixarene molecules, and 200 μL of oleic acid into a 200 ml beaker. Ultrasonic the liquid in the beaker for 5 min until it is evenly mixed to obtain a homogeneous composite lubricating oil solution; (3) Perform a friction test on the composite lubricating oil solution. Through the four-ball mode, test it at 50 N for 30 min.

[0028] Example 9 A calixarene molecular composite friction material is added to the lubricating oil as a friction material. The specific steps are as follows: (1) Prepare the calixarene molecular composite friction material. Specifically, add 27.8 g (0.18 mol) of p-tert-butylphenol, 9.0 g (0.30 mol) of paraformaldehyde, 0.4 mL (0.004 mol) of 10N KOH, and 150 mL of xylene into a 500 mL three-necked flask, and reflux at 130 °C for 4 h in an N 2 atmosphere. During the reaction process, after heating for 30 minutes, all solids dissolve into the solution, and white precipitates start to form. After the reaction mixture refluxes for 4 hours, filter off the filtrate with a sintered glass funnel. The solid product is successively washed with 100 mL of toluene, ether, acetone, and water, and then dried in a vacuum drying oven at 80 °C for 18 h to obtain calixarene molecules; (2) Weigh 10 g of PEG200, 0.06 g of calixarene molecules, and 200 μL of oleic acid into a 200 ml beaker, and ultrasonicate the liquid in the beaker for 5 min until it is uniformly mixed to obtain a homogeneous composite lubricating oil solution; (3) Perform a friction test on the composite lubricating oil solution. Through the four-ball mode, test it at 50 N for 30 min.

[0029] Summarize the friction test data of the composite lubricating oil solutions prepared in Examples 1 to 4. From Figure 6 it can be seen that after adding calixarene molecules with the same mass fraction, the friction coefficient of PAO6 lubricating oil is the largest, and the friction coefficient of PEG200 is the smallest, indicating that calixarene molecules can cooperate well with oleic acid to improve the tribological properties of PEG200; Summarize the friction test data of the composite lubricating oil solutions prepared in Examples 5 to 9. From Figure 7 it can be seen that after adding different contents of calixarene molecules to PEG200, the friction coefficient decreases significantly. Among them, when the addition amount is 0.4%, the friction coefficient decreases by 85%; From Figure 8 it can be seen that the wear diameter of pure PEG200 is the largest. After adding the calixarene molecular composite friction material, the wear diameter decreases significantly. Among them, when the addition amount of calixarene molecules is 0.4%, the wear diameter is the smallest, which is 56% lower than that of pure PEG200.

[0030] It should be noted that although the present invention has been described through the above embodiments, the present invention can also have many other embodiments. Without departing from the spirit and scope of the present invention, those skilled in the art can obviously make various corresponding changes and deformations to the present invention, but these changes and deformations should all fall within the scope protected by the appended claims of the present invention and their equivalents.

Claims

1. Application of a calixarene molecular composite friction material in lubricating oil.

2. The use of a calixarene molecular composite friction material in lubricating oil according to claim 1, characterized in that: The calixarene molecular composite friction material is used as an additive in lubricating oil, and the lubricating oil is used as a base oil. The lubricating oil and the calixarene molecular composite friction material are mixed, a compounding agent is added, and the composite lubricating oil is obtained after ultrasonic homogenization.

3. The use of a calixarene molecular composite friction material in lubricating oil according to claim 2, characterized in that: The lubricating oil is one of PEG200, PEG400, PAO6 and trioctyl trimellitate.

4. The use of a calixarene molecular composite friction material in lubricating oil according to claim 2, characterized in that: The compounding agent is oleic acid.

5. The use of a calixarene molecular composite friction material in lubricating oil according to claim 2, characterized in that: The mass ratio of base oil, additive and compounding agent is 1000: (1-6):

20.

6. The method for preparing a calixarene molecular composite friction material according to any one of claims 1 to 5, characterized in that: The following steps are involved: S1. Add p-tert-butylphenol, paraformaldehyde, KOH and xylene into a container, heat and reflux in a N2 atmosphere, and generate a white precipitate after heating for a period of time; S2. After the reaction mixture refluxes for a period of time, the filtrate is filtered out with a funnel, and the solid product is washed successively with toluene, ether, acetone and water in sequence, and dried to obtain a calixarene molecular composite friction material.

7. The method for preparing a calixarene molecular composite friction material according to claim 6, characterized in that: The content of p-tert-butylphenol in S1 is more than 98%, the content of paraformaldehyde is more than 95%, KOH is analytically pure and its content is more than 85%, and the content of xylene is more than 98%.

8. The method for preparing a calixarene molecular composite friction material according to claim 6, characterized in that: Toluene, ether and acetone in S2 are all analytically pure, and the contents are all above 99.5%.

9. The calixarene molecular composite friction material obtained by the preparation method according to any one of claims 6 to 8.

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