Two-dimensional covalent organic polymer composite lubricating oil additive, preparation method and application thereof

Abstract

The application discloses a two-dimensional covalent organic polymer composite lubricating oil additive, a preparation method and application thereof, and provides a two-dimensional covalent organic polymer composite lubricating oil additive which can simultaneously have nitrogen-containing, sulfur-free and phosphorus-free, environmental protection, energy saving, excellent wear resistance, and can reduce corrosion of metal parts and prolong service life. The additive prepared by the application has relatively stable physical and chemical properties, can prolong the service life of lubricating oil, improves the dispersibility of traditional two-dimensional covalent organic polymers in lubricating oil, and simultaneously widens the application range of the two-dimensional covalent organic polymers.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of lubricating oil, and particularly relates to a two-dimensional covalent organic polymer composite lubricating oil additive, a preparation method and application thereof. BACKGROUND

[0002] Lubricating oil plays an indispensable role in energy-intensive sectors such as industry, transportation, power generation and manufacturing by improving production efficiency and reliability of engineering systems. Functional additives are important components in lubricating oil with anti-friction wear, anti-corrosion and anti-oxidation properties. Among these petroleum additives, nanomaterials are widely used due to their unique physicochemical properties and excellent mechanical properties. Traditional inorganic nanomaterials, such as metals (such as Cu and Fe) and metal oxides (such as Al2O3, ZnO and TiO2), exhibit anti-wear properties due to the formation of protective friction films and the effect of ball bearings, polishing and repair. However, these materials have poor compatibility with base oil, resulting in poor dispersibility, which cannot meet the requirements of lubricants. A typical strategy to improve the dispersibility and stability of inorganic nanomaterials in lubricating oil is to introduce organic materials on the inorganic-organic interface.

[0003] Two-dimensional covalent organic framework material is a covalent porous material with regular two-dimensional sheet structure with atomic precision, which is combined by structural units through covalent bonds. It has attracted widespread attention due to its high porosity, high surface area, adjustable structure, rich active sites, high crystallinity and other advantages. Two-dimensional covalent organic framework materials are widely used in molecular storage and separation, electrochemical energy storage, catalysis, sensing, optoelectronic engineering, drug delivery and release, etc. However, there are only a few reports on the application of two-dimensional covalent organic framework materials in the field of lubrication. Document CN113105644B discloses a functionalized two-dimensional covalent organic framework material additive synthesized from 2,4,6-triaminophenyl-1,3,5-triazine and 2,4-divinyl terephthaldehyde modified by DDP. Document CN114874406A discloses a polydopamine modified (4-aminophenyl) amine and 3,6-bis(5-formylthiophene-2-yl)-2,5-bis(2-ethylhexyl) pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione two-dimensional covalent organic framework material additive.

[0004] In summary, the two-dimensional covalent organic framework material additives disclosed so far have improved the friction and wear resistance problem to some extent under certain working conditions, but they are all materials obtained by modifying the external material, and the anti-wear effect still needs to be further improved. Therefore, the invention of a nitrogen-containing, sulfur-free and phosphorus-free, green and environmentally friendly, high-efficiency anti-wear lubricating oil additive has a positive impact on the field of lubricating oil additive technology. SUMMARY

[0005] This section is intended to introduce some aspects of one or more embodiments of the present application, which are described below. This section is not intended to limit the scope or content of the application in any way. The concepts described herein can apply equally to any embodiment of the application.

[0006] The present application is proposed in view of the above and / or problems in the prior art.

[0007] Therefore, the purpose of the present application is to overcome the deficiencies in the prior art, and provide a preparation method of two-dimensional covalent organic polymer composite lubricating oil additive.

[0008] To solve the above technical problems, the present application provides the following technical scheme: a preparation method of two-dimensional covalent organic polymer composite lubricating oil additive, comprising,

[0009] Vitamin C is ultrasonically dispersed into an ethanol solvent, pre-reacted by refluxing for 10 hours, and then hexadecylamine is added for continuous refluxing reaction. After rotary evaporation, washing, centrifugation and drying, the product carbon quantum dots CDs are obtained.

[0010] The CDs are dispersed in a solvent by stirring, and then cyanuric chloride and melamine are added and dissolved by stirring. Triethylamine is added, and after stirring, the mixture is placed in a hydrothermal kettle for reaction. After centrifugation, washing and drying, the two-dimensional covalent organic polymer composite lubricating oil additive is obtained.

[0011] As a preferred scheme of the preparation method, the concentration of vitamin C in the ethanol solution is 0.5-2 mg / L, and the mass ratio of vitamin C to hexadecylamine is 1:1.5-3.0.

[0012] As a preferred scheme of the preparation method, the continuous refluxing reaction is performed for 1-8 hours.

[0013] As a preferred scheme of the preparation method, the molar ratio of cyanuric chloride to melamine is 1:1.

[0014] As a preferred scheme of the preparation method, the mass ratio of triethylamine to the total mass of cyanuric chloride and melamine is 1.0-1.5:1.

[0015] As a preferred scheme of the preparation method, the mass ratio of CDs to the total mass of cyanuric chloride and melamine is 1:10-50.

[0016] As a preferred scheme of the preparation method, the washing solvent is one or more of methanol, ethanol, acetone, tetrahydrofuran, toluene and dimethylformamide.

[0017] As a preferred scheme of the preparation method, the solvent is one or more of deionized water, methanol, anhydrous ethanol or dimethylformamide.

[0018] Another object of the present application is to overcome the deficiencies in the prior art and provide a two-dimensional covalent organic polymer composite lubricating oil additive and its application in the preparation of lubricating oil.

[0019] As a preferred scheme of the preparation method, the application comprises,

[0020] The two-dimensional covalent organic polymer composite lubricating oil is prepared by uniformly mixing the functionalized two-dimensional covalent organic framework material additive with lubricating oil.

[0021] As a preferred scheme of the application, the mass ratio of the total mass of the lubricating oil and the two-dimensional covalent organic polymer composite lubricating oil additive to the mass of the two-dimensional covalent organic polymer composite lubricating oil additive is 100:0.01-1.5.

[0022] As a preferred scheme of the application, the lubricating oil is one of polyalphaolefin base oil PAO, synthetic ester ether-based lubricating oil POE, polyether synthetic oil PEG and mineral oil base oil.

[0023] The present application has the following advantages:

[0024] The present application provides a two-dimensional covalent organic polymer composite lubricating oil additive, its preparation method and its application in the preparation of lubricating oil.

[0025] The additive prepared by the present application can simultaneously have nitrogen-containing, sulfur-free and phosphorus-free, environmental protection, energy saving, excellent wear resistance, and can reduce metal part corrosion and prolong service life.

[0026] The additive prepared by the present application improves the dispersibility of traditional two-dimensional covalent organic polymers in lubricating oil, and also widens the application range of two-dimensional covalent organic polymers. BRIEF DESCRIPTION OF DRAWINGS

[0027] In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the embodiments will be briefly introduced as follows. Obviously, the drawings in the following description only constitute some embodiments of the present application, and other drawings can be obtained by those skilled in the art without any creative effort based on these drawings. Among them:

[0028] Figure 1 The morphological diagram of the two-dimensional covalent organic polymer composite material.

[0029] Figure 2 The wear scar diameter diagram of the steel ball of PAO6 and examples 1-3, comparative examples 1-3.

[0030] Figure 3 The friction coefficient diagram of the oil product of PAO6 and examples 1-3, comparative examples 1-3. DETAILED DESCRIPTION

[0031] In order to make the above objectives, characteristics and advantages of the present application more apparent and easy to understand, the specific embodiments of the present application will be described in detail below with the description of the embodiments.

[0032] In the following description, a lot of specific details are set forth in order to provide a thorough understanding of the present application, but the present application can also be implemented in other ways different from those described herein, and those skilled in the art can make similar generalizations without departing from the connotation of the present application, therefore the present application is not limited to the specific embodiments disclosed below.

[0033] Secondly, the "one embodiment" or "embodiment" referred to herein means that the specific features, structures or characteristics can be included in at least one implementation of the present application. "In one embodiment" appearing in different places in the specification does not mean the same embodiment, nor is it an independent or alternative embodiment mutually exclusive with other embodiments.

[0034] Unless otherwise specified, the raw materials used in the embodiments are commercially purchased.

[0035] Performance test:

[0036] Friction performance test: the MS-10A four-ball friction tester produced by Xiamen Tianji Factory was used to test the friction performance, and the test conditions were as follows: room temperature 25℃, load 392N, running time 30min, and rotation speed 1450rpm. The optical microscope was used to measure the wear scar diameter of the steel ball.

[0037] Example 1

[0038] The preparation method of the two-dimensional covalent organic polymer composite material lubricating oil comprises the following steps:

[0039] (1) Preparation of carbon quantum dots: 0.1 g of vitamin C was ultrasonically dispersed in 1000 mL of ethanol solvent, pre-reacted by refluxing for 10 hours, 0.2 g of hexadecylamine was added, and the reflux reaction was continued for 6 hours. After rotary evaporation, ethanol washing, centrifugation, and freeze-drying drying, the product oil-soluble carbon quantum dots CDs were obtained.

[0040] (2) Preparation of two-dimensional covalent organic polymer composite lubricating oil additive: 0.1 g of CDs was dispersed in dimethylformamide by stirring, 1.18 g of cyanuric chloride and 0.82 g of melamine were added, stirring for 30 min, 2.1 g of triethylamine was added, stirring for 20 min, and then put into a hydrothermal kettle, 110℃ reaction for 24 hours. After the reaction was completed, centrifugation, ethanol washing, and vacuum drying, the two-dimensional covalent organic polymer composite lubricating oil additive CDs@TriCF was obtained.

[0041] (3) Preparation of two-dimensional covalent organic polymer composite lubricating oil: 0.03 mg of CDs@TriCF was added to 999.7 mg of PAO6 oil, and ultrasonic dispersion was uniform to obtain PAO6+0.03 mg of CDs@TriCF.

[0042] The morphology of the two-dimensional covalent organic polymer composite material is shown in Figure 1 The synthesized two-dimensional covalent organic polymer composite material is a two-dimensional sheet structure.

[0043] Example 2

[0044] The preparation method of the two-dimensional covalent organic polymer composite material lubricating oil comprises the following steps:

[0045] (1) Preparation of carbon quantum dots: 0.1 g of vitamin C was ultrasonically dispersed in 1000 mL of ethanol solvent, pre-reacted by refluxing for 10 hours, 0.2 g of hexadecylamine was added, and the reflux reaction was continued for 6 hours. After rotary evaporation, ethanol washing, centrifugation, and freeze-drying drying, the product oil-soluble carbon quantum dots CDs were obtained.

[0046] (2) Preparation of two-dimensional covalent organic polymer composite lubricating oil additive: 0.1 g of CDs was dispersed in dimethylformamide by stirring, 1.18 g of cyanuric chloride and 0.82 g of melamine were added, stirring for 30 min, 2.1 g of triethylamine was added, stirring for 20 min, and then put into a hydrothermal kettle, 110℃ reaction for 24 hours. After the reaction was completed, centrifugation, ethanol washing, and vacuum drying, the two-dimensional covalent organic polymer composite lubricating oil additive CDs@TriCF was obtained.

[0047] (3) Preparation of two-dimensional covalent organic polymer composite lubricating oil: 0.03 mg CDs@TriCF was added to 999.7 mg PAO6 oil, and ultrasonic dispersion was performed to obtain PAO6+0.03 mg CDs@TriCF.

[0048] Example 3

[0049] The preparation method of the two-dimensional covalent organic polymer composite lubricating oil comprises the following steps:

[0050] (1) Preparation of carbon quantum dots: 0.1 g of vitamin C was ultrasonically dispersed in 1000 mL of ethanol solvent, pre-reacted by refluxing for 10 hours, 0.15 g of hexadecylamine was added, and the reaction was continued by refluxing for 4 hours. After rotary evaporation, tetrahydrofuran and ethanol were used for washing, centrifugation was performed, and vacuum drying was carried out at 60°C to obtain the product oil-soluble carbon quantum dots CDs.

[0051] (2) Preparation of two-dimensional covalent organic polymer composite lubricating oil additive: 0.05 g of CDs was dispersed in dimethylformamide by stirring, 1.18 g of cyanuric chloride and 0.82 g of melamine were added, stirring was performed for 30 min, 2.1 g of triethylamine was added, stirring was performed for 20 min, and then it was placed in a hydrothermal kettle, and the reaction was carried out at 110°C for 24 hours. After the reaction was completed, centrifugation was performed, ethanol and dimethylformamide were used for washing, and freeze-drying was carried out to obtain the two-dimensional covalent organic polymer composite lubricating oil additive CDs@TriCF.

[0052] (3) Preparation of two-dimensional covalent organic polymer composite lubricating oil: 0.03 mg CDs@TriCF was added to 999.7 mg PAO6 oil, and ultrasonic dispersion was performed to obtain PAO6+0.03 mg CDs@TriCF.

[0053] Comparative Example 1

[0054] The preparation method of the two-dimensional covalent organic polymer lubricating oil comprises the following steps:

[0055] (1) Preparation of two-dimensional covalent organic polymer composite lubricating oil additive: 1.18 g of cyanuric chloride and 0.82 g of melamine were dispersed in dimethylformamide by stirring, 2.1 g of triethylamine was added, stirring was performed for 20 min, and then it was placed in a hydrothermal kettle, and the reaction was carried out at 110°C for 24 hours. After the reaction was completed, centrifugation was performed, dimethylformamide was used for washing, and freeze-drying was carried out to obtain the two-dimensional covalent organic polymer material additive TriCF.

[0056] (2) Preparation of two-dimensional covalent organic polymer lubricating oil: 0.03 mg TriCF was added to 999.7 mg PAO6 oil, and ultrasonic dispersion was performed to obtain PAO6+0.03 mg TriCF.

[0057] Comparative Example 2

[0058] The preparation method of carbon quantum dot lubricating oil includes the following steps:

[0059] (1) Preparation of carbon quantum dots: 0.1g of vitamin C was ultrasonically dispersed in 1000mL of ethanol solvent and refluxed for 10 hours for pre-reaction. 0.2g of hexadecylamine was added and the reaction was continued to reflux for 6 hours. After rotary evaporation, washing with ethanol, centrifugation, and freeze-drying, oil-soluble carbon quantum dots (CDs) were obtained.

[0060] (2) Preparation of carbon quantum dot lubricating oil: 0.03 mg CDs were added to 999.7 mg PAO6 oil and ultrasonically dispersed evenly to obtain PAO6 + 0.03 mg CDs.

[0061] Comparative Example 3

[0062] A method for preparing a two-dimensional covalent organic polymer-co-carbon quantum dot lubricating oil includes the following steps:

[0063] (1) Preparation of carbon quantum dots: 0.1g of vitamin C was ultrasonically dispersed in 1000mL of ethanol solvent and refluxed for 10 hours for pre-reaction. 0.2g of hexadecylamine was added and the reaction was continued to reflux for 6 hours. After rotary evaporation, washing with ethanol, centrifugation, and freeze-drying, oil-soluble carbon quantum dots (CDs) were obtained.

[0064] (2) Preparation of two-dimensional covalent organic polymer additive: 1.18 g of melamine chloride and 0.82 g of melamine were stirred and dispersed in dimethylformamide, 2.1 g of triethylamine was added, and the mixture was stirred for 20 min. Then it was placed in a hydrothermal reactor and reacted at 110 °C for 24 hours. After the reaction was completed, the mixture was centrifuged, washed with ethanol, and dried under vacuum to obtain the two-dimensional covalent organic polymer material additive TriCF.

[0065] (3) Preparation method of two-dimensional covalent organic polymer synergistic carbon quantum dot lubricating oil: 0.01mg CDs and 0.02mg TriCF were added to 999.7mg PAO6 oil and ultrasonically dispersed evenly to obtain PAO6+0.01mg CDs+0.02mg TriCF.

[0066] The frictional properties of the lubricating oils prepared from base oil PAO6 in Examples 1-3 and Comparative Examples 1-3 were tested, and the results are as follows: Figure 2 and Figure 3 As shown. Figure 2 The variation in wear scar diameter was demonstrated. Compared with pure PAO6 base oil, oil obtained in Comparative Example 1, oil obtained in Comparative Example 2, and oil obtained in Comparative Example 3, the oil obtained in Example 1 had the smallest wear scar diameter. Figure 3The change of friction coefficient is shown, the oil product of example 1 has the lowest friction coefficient compared with the pure PAO6 base oil, the oil product of comparative example 1, the oil product of comparative example 2 and the oil product of comparative example 3, and the comprehensive performance of the oil products of examples 1-3 is better than that of the oil products of comparative examples 1-3, therefore, the two-dimensional covalent organic polymer composite material has excellent friction-reducing and anti-wear performance in the PAO6 lubricating oil and can be used as an additive of the lubricating oil.

[0067] It should be noted that the above examples are only used to illustrate the technical solutions of the present application but not limit the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced equivalently without departing from the spirit and scope of the present application, and all of them should be covered in the scope of the present application.

Claims

1. A method for the preparation of a two-dimensional covalent organic polymer composite lubricating oil additive, characterized by: The preparation method comprises the following steps: The vitamin C is ultrasonically dispersed into an ethanol solvent, pre-reaction is carried out by refluxing for 10 hours, the cetylamine is added, and the reaction is continuously carried out by refluxing; the product carbon quantum dots CDs are obtained by rotary evaporation, washing, centrifugation and drying. The CDs are dispersed in a solvent by stirring, the cyanuric chloride and the melamine are added, stirring and dissolving are carried out, the triethylamine is added, and the reaction is carried out in a hydrothermal kettle after stirring; the two-dimensional covalent organic polymer composite lubricating oil additive is obtained by centrifugation, washing and drying after the reaction is completed.

2. The method for preparing a two-dimensional covalent organic polymer composite lubricating oil additive according to claim 1, characterized in that: The concentration of the vitamin C in the ethanol solution is 0.5-2 mg / L; and the mass ratio of the vitamin C to the cetylamine is 1:1.5-3.

0.

3. The method for preparing a two-dimensional covalent organic polymer composite lubricating oil additive according to claim 1, characterized in that: The reaction time of the continuous refluxing is 1-8 hours.

4. The method for preparing a two-dimensional covalent organic polymer composite lubricating oil additive according to claim 1, characterized by: The molar ratio of the cyanuric chloride to the melamine is 1:

1.

5. The method for preparing the two-dimensional covalent organic polymer composite lubricant additive as described in claim 1, characterized in that: The mass ratio of the triethylamine to the total mass of the cyanuric chloride and the melamine is 1.0-1.5:1; and the mass ratio of the CDs to the total mass of the cyanuric chloride and the melamine is 1:10-50.

6. The method for preparing the two-dimensional covalent organic polymer composite lubricant additive as described in claim 1, characterized in that: The solvent for the rotary evaporation and the washing is one or more of methanol, ethanol, acetone, tetrahydrofuran, toluene and dimethylformamide; and the solvent for the centrifugation and the washing is one or more of methanol, ethanol, acetone, tetrahydrofuran, toluene and dimethylformamide.

7. The method for preparing the two-dimensional covalent organic polymer composite lubricant additive as described in claim 1, characterized in that: The solvent is one or more of deionized water, methanol, anhydrous ethanol and dimethylformamide.

8. The two-dimensional covalent organic polymer composite lubricating oil additive prepared by the preparation method in any one of claims 1-7.

9. The application of the two-dimensional covalent organic polymer composite lubricating oil additive in claim 8 in the preparation of a two-dimensional covalent organic polymer composite lubricating oil.

10. The use according to claim 9, characterized in that: The two-dimensional covalent organic polymer composite lubricating oil is prepared by uniformly mixing the two-dimensional covalent organic polymer composite lubricating oil additive with lubricating oil; The mass ratio of the total mass of the lubricating oil and the two-dimensional covalent organic polymer composite lubricating oil additive to the mass of the two-dimensional covalent organic polymer composite lubricating oil additive is 100:0.01-1.

5. The lubricating oil is one of poly-alpha olefin base oil PAO, synthetic ester ether-based lubricating oil POE, polyether synthetic oil PEG and mineral oil base oil.

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