A high lubricity diesel anti-wear agent and a preparation method thereof

Abstract

The application discloses a high-lubricity diesel anti-wear agent and a preparation method thereof, and belongs to the technical field of anti-wear agent processing. The application is used for solving the technical problem that the lubricating performance and high-temperature stability of the diesel anti-wear agent in the prior art need to be further improved. The high-lubricity diesel anti-wear agent and the preparation method thereof comprise the following steps: a high-lubricity diesel anti-wear agent comprises the following raw material components in parts by weight: modified organic lubricant 80-100 parts, modified inorganic lubricant 5-10 parts, corrosion inhibitor 1-5 parts, antioxidant 1-5 parts and viscosity index improver 1-5 parts. The modified phosphate ester is polymerized and cross-linked with fatty amine, and then the fatty amine is amidated to obtain amidated fatty amine, the modified organic lubricant is obtained through esterification, and the modified inorganic lubricant and the auxiliary materials are combined, so that the lubricating performance and high-temperature resistance of the anti-wear agent are improved.

Description

Technical Field

[0001] This invention relates to the field of diesel anti-wear agent processing technology, specifically to a high-lubricity diesel anti-wear agent and its preparation method. Background Technology

[0002] Diesel oil anti-wear additives are additives used in diesel engine lubricating oils. Their main function is to reduce friction and wear between metal surfaces, thereby extending engine life and improving performance stability. The primary function of diesel oil anti-wear additives is to form a protective film during engine operation, reducing the coefficient of friction between metal surfaces, thus reducing wear and heat loss. They also improve the strength and stability of the oil film, ensuring effective protection of engine operation under various working conditions. Diesel oil anti-wear additives play a crucial role in modern diesel engine technology, improving engine reliability, efficiency, and lifespan by reducing friction and wear, which is essential for the operational safety and economy of automobiles, ships, and industrial equipment.

[0003] Existing technology CN102277212A discloses a diesel anti-wear agent comprising a mixture of the following components: (A) tar oil fatty acid; (B) oleic acid amide; (C) naphthenic acid imidazoline; characterized in that the weight ratio of components A, B and C is 100:5-100:5-50. This invention obtains a diesel anti-wear agent through a simple physical mixing method, which is easy to implement and convenient to use. However, it overlooks the negative impact of tar oil fatty acid, oleic acid amide, and naphthenic acid imidazoline on diesel combustion. Furthermore, under high-temperature conditions, tar oil fatty acid, oleic acid amide, and naphthenic acid imidazoline decompose to produce smoke and residues, resulting in extremely unstable lubrication performance and a significant decrease in the performance of the anti-wear agent. In summary, the lubrication performance and high-temperature stability of existing diesel anti-wear agents require further improvement.

[0004] To address this technical deficiency, a solution is proposed. Summary of the Invention

[0005] The purpose of this invention is to provide a high-lubricity diesel anti-wear agent and its preparation method, which solves the technical problem that the lubrication performance and high-temperature stability of diesel anti-wear agents in the prior art need to be further improved.

[0006] The objective of this invention can be achieved through the following technical solutions:

[0007] A high-lubricating diesel anti-wear agent comprises the following raw material components in parts by weight: 80-100 parts of modified organic lubricant, 5-10 parts of modified inorganic lubricant, 1-5 parts of corrosion inhibitor, 1-5 parts of antioxidant, and 1-5 parts of viscosity index improver.

[0008] The modified organic lubricant is prepared as follows: Weigh 3-5 parts by weight of N-hydroxysuccinimide, 1-2 parts by weight of N,N-dicyclohexylcarboimide, 0.3-0.5 parts by weight of triethylamine and 30-40 parts by weight of N,N-dimethylformamide and add them to a reaction vessel. After reacting at room temperature for 0.5-1 h, add 20-30 parts by weight of amidated fatty amine to the reaction vessel. Raise the temperature of the reaction vessel to 40-50℃ and keep it at that temperature for 2-4 h. The modified organic lubricant is then obtained after post-treatment.

[0009] The reaction equation for preparing the modified organic lubricant is as follows:

[0010]

[0011] In the formula:

[0012] The reaction principle for preparing modified organic lubricants is as follows: This reaction process involves a special esterification reaction, in which the active intermediate N,N-dicyclohexylcarboimide converts carboxylic acids into their corresponding esters. In the reaction, N-hydroxysuccinimide and N,N-dicyclohexylcarboimide are first mixed to form an imine salt at room temperature. Then, an amidated aliphatic amine with a carboxyl group is added. At this point, the imine salt is attacked by hydroxide ions and loses the N,N-dicyclohexylcarboimide ions, thus generating the modified organic lubricant.

[0013] Further post-processing includes: after the reactor is cooled to room temperature, the reaction solution is added to a rotary evaporator with a water bath temperature of 80-100℃, and distilled under reduced pressure until no liquid is collected, to obtain the modified organic lubricant.

[0014] Furthermore, the preparation method of amidated fatty amine is as follows: weigh 20-30 parts by weight of cross-linked fatty amine, 5-10 parts by weight of pyromellitic dianhydride, 75-100 parts by weight of N,N-dimethylformamide and 1-3 parts by weight of triethylamine and add them to the reaction vessel, stir at room temperature for 2-4 hours, and then perform post-treatment to obtain amidated fatty amine.

[0015] The reaction equation for preparing amidated polyurethane is as follows:

[0016]

[0017] In the formula:

[0018] The principle of preparing amidated polyurethane is as follows: a cross-linked fatty amine nucleophile with a secondary amino group attacks the carbonyl carbon atom in the pyromellitic dianhydride molecule. The nitrogen atom of the secondary amino group has a lone pair of electrons, which can form a new covalent bond with the carbonyl carbon atom to form an amide acid polymer, and finally prepare the amidated fatty amine.

[0019] Further post-processing includes: after the reaction vessel is cooled to room temperature, the reaction solution is added to a rotary evaporator with a water bath temperature of 80-100℃, and distilled under reduced pressure until no liquid is collected, to obtain amidated fatty amines.

[0020] Furthermore, the preparation method of cross-linked fatty amine is as follows: weigh 5-8 parts of modified phosphate ester, 3-5 parts of dimethyl biphenyl diisocyanate, 4-6 parts of tetraethylene glycol and 40-50 parts of N,N-dimethylformamide by weight and add them to the reaction vessel. Raise the temperature of the reaction vessel to 70-90℃, keep it warm and stir for 2-4 hours, and then perform post-treatment to obtain cross-linked fatty amine.

[0021] The reaction equation for the preparation of cross-linked fatty amines is as follows:

[0022]

[0023] In the formula:

[0024] The principle of preparing cross-linked fatty amines is as follows: the isocyanate group (-NCO) undergoes a nucleophilic addition reaction with the hydroxyl group (-OH) to form a polymer linked by urethane. In this process, the hydroxyl oxygen atom acts as a nucleophile to attack the carbon atom of the isocyanate, generating urethane. The isocyanate group reacts with the hydroxyl groups in tetraethylene glycol and modified phosphate ester to form a long-chain structure, and finally, the cross-linked fatty amine is obtained.

[0025] Further post-processing includes: after the reactor is cooled to room temperature, the reaction solution is added to a rotary evaporator with a water bath temperature of 80-100℃, and distilled under reduced pressure until no liquid is collected, to obtain cross-linked fatty amines.

[0026] Furthermore, the modified phosphate ester is prepared as follows: 5-8 parts by weight of naphthol phosphate ester, 3-5 parts by weight of 3H,8H-2a,8a:3a,7a diepoxyanthracene [2,3-b]epoxyene, octahydro-(9CI), 0.5-0.8 parts by weight of triethylamine and 30-40 parts by weight of N,N-dimethylformamide are added to a reaction vessel. The temperature of the reaction vessel is raised to 60-80℃ and the reaction is maintained for 1-3 hours. The modified phosphate ester is then obtained after post-treatment.

[0027] The reaction equation for preparing the modified phosphate ester is as follows:

[0028]

[0029] In the formula:

[0030] The principle of preparing modified phosphate ester is as follows: Under weakly alkaline conditions, the hydroxyl group (-OH) of binaphthol phosphate and the epoxy group of 3H,8H-2a,8a:3a,7a diepoxyanthracene [2,3-b]epoxyene,octahydro-(9CI) undergo a ring-opening reaction. Binaphthol phosphate and 3H,8H-2a,8a:3a,7a diepoxyanthracene [2,3-b]epoxyene,octahydro-(9CI) are polymerized by ether bonding to obtain modified phosphate ester.

[0031] Further post-processing includes: after the reactor is cooled to room temperature, the reaction solution is added to a rotary evaporator with a water bath temperature of 80-100℃, and distilled under reduced pressure until no liquid is collected to obtain modified phosphate ester.

[0032] Furthermore, the preparation method of the modified inorganic lubricant is as follows: 10-20 parts by weight of α-MnO2@CTS, 1-2 parts by weight of bis(2-ethylhexyl)dithiophosphate, 40-50 parts by weight of N,N-dimethylformamide and 0.5-0.8 parts by weight of triethylamine are added to a reaction vessel, the temperature of the reaction vessel is raised to 40-60℃, and the reaction is maintained for 2-4 hours. The modified inorganic lubricant is then obtained after post-treatment.

[0033] The reaction equation for preparing the modified inorganic lubricant is as follows:

[0034]

[0035] The reaction principle for preparing modified inorganic lubricants is as follows: under alkaline conditions, thiol and carboxyl groups undergo a substitution reaction to generate thioesters.

[0036] Further post-processing includes: after the reactor is cooled to room temperature, the filter cake is collected by vacuum filtration, and the filter cake is placed in a drying oven at 80°C and vacuum dried until the filter cake reaches a constant weight to obtain the modified inorganic lubricant.

[0037] Furthermore, the preparation method of α-MnO2@CTS is as follows: 20-30 parts by weight of α-MnO2, 50-60 parts by weight of carboxysuccinic acid powder and 800-1000 parts by weight of anhydrous ethanol are added to an ultrasonic instrument, and the mixture is ultrasonicated at room temperature while being stirred for 8-12 hours. The ultrasonic frequency is 20-40KHz and the stirring rate is 120-180rpm. The α-MnO2@CTS is then obtained after post-treatment.

[0038] The principle of preparing α-MnO2@CTS is as follows: using the mechanical action of ultrasound and the help of stirring, α-MnO2 and carboxysuccinic acid powder are fully mixed and reacted in ethanol medium. Some of the carboxyl groups in carboxysuccinic acid can react with the active sites on the surface of manganese dioxide to form coordinate bonds. Carboxysuccinic acid is then attached to the surface of MnO2 by chemical grafting to obtain α-MnO2@CTS.

[0039] Further post-processing includes: after the reactor is cooled to room temperature, the filter cake is collected by vacuum filtration, and the filter cake is placed in a drying oven at 80°C and vacuum dried until the filter cake reaches constant weight to obtain α-MnO2@CTS.

[0040] Furthermore, the preparation method of α-MnO2 is as follows: Weigh 10-20 parts by weight of potassium permanganate powder, 2-4 parts by weight of potassium chloride powder, 0.5-0.8 parts by weight of polyvinylpyrrolidone with a molecular weight of 1,200,000-1,300,000, and 40-50 parts by weight of deionized water and add them to the reaction vessel and stir. After the solid is completely dissolved, raise the temperature of the reaction vessel to 150-160℃ and keep it at this temperature for 12 hours. After post-processing, α-MnO2 is obtained.

[0041] Furthermore, the stirring rate is 120-160 rpm, and the post-treatment includes: after the reactor is cooled to room temperature, the filter cake is collected by vacuum filtration, the filter cake is washed with deionized water 3-5 times, and the filter cake is placed in a drying oven at 80℃ and vacuum dried for 24 hours to obtain the dried product. The dried product is placed in a tube furnace, protected by nitrogen, and the tube furnace is heated to 400±10℃ at a rate of 10℃ / min. After holding at this temperature for 6-8 hours, it is naturally cooled to room temperature to obtain α-MnO2.

[0042] Furthermore, the corrosion inhibitor is one or more of ferrous phosphate, benzothiadiazolindiphenol and mercaptodiethylamine, the antioxidant is one or more of di-tert-butyl-p-cresol, dibutylhydroquinone and diphenyl disulfide phosphate, and the viscosity index improver is polyisobutylene.

[0043] A method for preparing a high-lubricating diesel anti-wear agent is as follows: a modified organic lubricant, a modified inorganic lubricant, an antioxidant, and a viscosity index improver are added to a reaction vessel, mixed evenly, and passed through a 100-mesh sieve to obtain the diesel anti-wear agent.

[0044] The present invention has the following beneficial effects:

[0045] 1. In the preparation of a high-lubricity diesel anti-wear agent, this invention first synthesizes a modified organic lubricant. This modified organic lubricant has a large number of functional groups, which, while possessing lubricating properties, also clean diesel combustion products. Furthermore, the functional groups also give the modified organic lubricant a partial dispersant function, keeping the prepared modified inorganic lubricant dispersed in diesel fuel to prevent the formation of deposits in critical engine parts and promoting the discharge of the modified inorganic lubricant. Simultaneously, manganese dioxide acts as a catalyst for the combustion reaction, improving the combustion performance of diesel fuel and reducing environmental pollution. Further, in the preparation of the modified inorganic lubricant, the surface of nano-metal oxide particles is modified to give them certain lubricating properties and promote diesel combustion, reducing the impact of the diesel anti-wear agent on diesel combustion, making diesel combustion more complete, and reducing environmental pollution. Finally, by mixing and sieving the modified organic lubricant, modified inorganic lubricant, and excipients, a high-lubricity and high-temperature resistant diesel anti-wear agent is obtained.

[0046] 2. In the preparation of a modified organic lubricant, this invention first utilizes the ring-opening reaction of epoxy groups between reacting monomers to prepare a modified phosphate ester with a complex spatial structure. This complex spatial structure facilitates stronger interactions between molecules, thereby enhancing the adhesion and stability of the lubricant on the contact surface and maintaining the integrity of the lubricating film. Furthermore, the generated active hydroxyl groups provide a foundation for subsequent reactions. Further, a cross-linked aliphatic amine with numerous ether bonds and phosphate groups is prepared using the modified phosphate ester and polymer monomers. This is then reacted with pyromellitic dianhydride to generate an amidated aliphatic amine. The phosphate groups can chemically react with the metal surface to form phosphorus compounds or phosphate films. These films can form a protective lubricating film on the metal surface, reducing the coefficient of friction and minimizing direct contact and wear. The amide groups also form a protective film on the metal surface, reducing the coefficient of friction and improving lubrication. Simultaneously, under high-temperature conditions, the numerous benzene ring structures and amide groups in the structure can improve the thermal stability and heat resistance of the lubricant, maintaining lubrication... The effect does not decrease with increasing temperature. The presence of amide groups enhances the extreme pressure performance of the lubricant, improves its working ability under high load and high pressure, and prevents contact wear on metal surfaces due to excessive pressure. The synergistic effect of these three factors significantly improves the lubrication performance of the organic chain segments. At the same time, phosphate groups and a large number of ether bonds can improve the thermal and oxidative stability of the lubricant, making it effective under high temperature conditions, thus maintaining its long-term stability and lubrication effect. Under high pressure, phosphate groups can form metal phosphates, forming stronger chemical bonds with metal surfaces, thereby enhancing the extreme pressure performance of the lubricant and preventing contact and damage to metal surfaces under extreme loads. Finally, N-hydroxysuccinimide is reacted with amidated aliphatic amines under the catalysis of N,N-dicyclohexylcarboimide to introduce thioethers and succinimide. The succinimide groups give the modified organic lubricant a certain cleaning ability and the ability to disperse insoluble substances in diesel fuel, while improving the lubrication performance of the modified organic lubricant. Finally, a modified organic lubricant with high lubricity and high temperature resistance is obtained.

[0047] 3. In the process of preparing the modified inorganic lubricant, this invention first prepares a spherical α-MnO2. The spherical spatial structure improves its lubrication performance and increases its contact area with the modified material. α-MnO2@CTS is prepared through surface modification. The surface modification of α-MnO2 with carboxysuccinic acid enhances its dispersion ability and introduces the active carboxyl group. Furthermore, bis(2-ethylhexyl) dithiophosphate reacts with the carboxyl group on its surface to form a thioester. At high temperature, the sulfur and phosphorus elements in bis(2-ethylhexyl) dithiophosphate form a tribochemical reaction film during friction. The synergistic effect of this chemical reaction film and the "ball bearing" effect of nanoparticles effectively reduces the friction and wear of the friction pair surface. At the same time, MnO2 can lower the activation energy of the combustion reaction, allowing the fuel to burn at a lower temperature, thereby improving combustion efficiency, promoting diesel combustion, and reducing the impact of diesel additives on diesel combustion performance. Finally, a highly lubricating modified inorganic lubricant is obtained. Attached Figure Description

[0048] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0049] Figure 1 This is a SEM image of α-MnO2. Detailed Implementation

[0050] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0051] Example 1

[0052] This embodiment provides a method for preparing a highly lubricating diesel anti-wear agent, comprising the following steps:

[0053] S1. Preparation of modified organic lubricant

[0054] 47.4 g of naphthol phosphate, 31.6 g of 3H,8H-2a,8a:3a,7a diepoxyanthracene [2,3-b]epoxyene, octahydro-(9Cl), 4.6 g of triethylamine and 279.6 g of N,N-dimethylformamide were weighed and added to a reaction vessel. The temperature of the reaction vessel was raised to 60 °C and the reaction was maintained at this temperature for 1 h. After the reaction vessel was cooled to room temperature, the reaction solution was added to a rotary evaporator with a water bath temperature of 100 °C and distilled under reduced pressure until no liquid was collected, yielding 79.0 g of modified phosphate.

[0055] 58.2g of modified phosphate ester, 26.2g of dimethyl biphenyl diisocyanate, 19.4g of tetraethylene glycol and 299.6g of N,N-dimethylformamide were weighed and added to a reaction vessel. The temperature of the reaction vessel was raised to 70℃ and stirred for 2 hours. After the reaction vessel was cooled to room temperature, the reaction solution was added to a rotary evaporator with a water bath temperature of 80℃ and distilled under reduced pressure until no liquid was collected, yielding 102.3g of cross-linked aliphatic amine.

[0056] Weigh 88.3g of cross-linked fatty amine, 22.1g of pyromellitic dianhydride, 335.3g of N,N-dimethylformamide and 5.3g of triethylamine and add them to a reaction vessel. Stir at room temperature for 2 hours. After the reaction vessel is cooled to room temperature, add the reaction solution to a rotary evaporator with a water bath temperature of 80℃ and distill under reduced pressure until no liquid is collected, to obtain 108.4g of amidated fatty amine.

[0057] 16.3g of N-hydroxysuccinimide, 6.7g of N,N-dicyclohexylcarboimide, 1.6g of triethylamine and 168.3g of N,N-dimethylformamide were weighed and added to a reaction vessel. After reacting at room temperature for 0.5h, 101.3g of amidated aliphatic amine was added to the reaction vessel. The temperature of the reaction vessel was raised to 40℃ and kept at this temperature for 2h. After the reaction vessel was cooled to room temperature, the reaction solution was added to a rotary evaporator with a water bath temperature of 80℃ and distilled under reduced pressure until no liquid was collected, yielding 113.2g of modified organic lubricant.

[0058] S2. Preparation of modified inorganic lubricants

[0059] Weigh 6.4g of potassium permanganate powder, 0.9g of potassium chloride powder, 0.28g of polyvinylpyrrolidone with a molecular weight of 1213512.3, and 17.6g of deionized water and add them to a reaction vessel. Stir until the solids are completely dissolved. Raise the temperature of the reaction vessel to 150℃ and keep it at that temperature for 12 hours. After the reaction vessel is cooled to room temperature, filter the cake by suction filtration. Wash the cake three times with deionized water and place it in a drying oven at 80℃ for vacuum drying for 24 hours to obtain the dried product. Place the dried product in a tube furnace and purge it with nitrogen. Raise the temperature of the tube furnace to 390℃ at a rate of 10℃ / min and keep it at that temperature for 6 hours. Then, let it cool naturally to room temperature to obtain 5.6g of α-MnO2.

[0060] Weigh 4.2g α-MnO2, 9.7g carboxysuccinic acid powder, and 140.4g anhydrous ethanol and add them to an ultrasonic instrument. Sonicate at room temperature while stirring for 8 hours. The ultrasonic frequency is 20KHz and the stirring rate is 120rpm. After the reaction vessel is cooled to room temperature, filter cake is collected by vacuum filtration. Place the filter cake in a drying oven at 80℃ and vacuum dry until the filter cake reaches constant weight to obtain 12.8g α-MnO2@CTS.

[0061] 10.2g of α-MnO2@CTS, 1.8g of bis(2-ethylhexyl)dithiophosphate, 42.3g of N,N-dimethylformamide and 0.6g of triethylamine were weighed and added to a reaction vessel. The temperature of the reaction vessel was raised to 40℃ and the reaction was maintained at this temperature for 2 hours. After the reaction vessel was cooled to room temperature, the filter cake was collected by vacuum filtration and placed in a drying oven at 80℃ for vacuum drying until the filter cake reached a constant weight, yielding 11.3g of modified inorganic lubricant.

[0062] S3, Preparation of diesel anti-wear agent

[0063] Weigh 94.0g of modified organic lubricant, 6.0g of modified inorganic lubricant, 2.0g of benzothiadiazolinodiphenol, 2.0g of di-tert-butyl-p-cresol and 2.0g of polyisobutylene and add them to the reaction vessel. Mix them evenly and pass them through a 100-mesh sieve to obtain 105.3g of diesel anti-wear agent.

[0064] Example 2

[0065] This embodiment provides a method for preparing a highly lubricating diesel anti-wear agent, comprising the following steps:

[0066] S1. Preparation of modified organic lubricant

[0067] 48.6 g of naphthol phosphate, 27.4 g of 3H,8H-2a,8a:3a,7a diepoxyanthracene [2,3-b]epoxyene, octahydro-(9Cl), 5.4 g of triethylamine and 273.6 g of N,N-dimethylformamide were weighed and added to a reaction vessel. The temperature of the reaction vessel was raised to 80℃ and the reaction was maintained at this temperature for 3 h. After the reaction vessel was cooled to room temperature, the reaction solution was added to a rotary evaporator with a water bath temperature of 100℃ and distilled under reduced pressure until no liquid was collected, yielding 71.2 g of modified phosphate.

[0068] Weigh 58.2g of modified phosphate ester, 26.4g of dimethyl biphenyl diisocyanate, 19.4g of tetraethylene glycol trioxide, and 258.9g of N,N-dimethylformamide and add them to a reaction vessel. Raise the temperature of the reaction vessel to 90℃ and stir for 4 hours. After the reaction vessel is cooled to room temperature, add the reaction solution to a rotary evaporator with a water bath temperature of 100℃ and distill under reduced pressure until no liquid is collected, to obtain 101.3g of cross-linked aliphatic amine.

[0069] Weigh 79.1g of cross-linked fatty amine, 17.4g of pyromellitic dianhydride, 270.0g of N,N-dimethylformamide and 7.1g of triethylamine and add them to a reaction vessel. Stir at room temperature for 4 hours. After the reaction vessel is cooled to room temperature, add the reaction solution to a rotary evaporator with a water bath temperature of 100℃ and distill under reduced pressure until no liquid is collected, to obtain 93.5g of amidated fatty amine;

[0070] 19.5g of N-hydroxysuccinimide, 5.7g of N,N-dicyclohexylcarboimide, 1.4g of triethylamine and 125.3g of N,N-dimethylformamide were weighed and added to a reaction vessel. After reacting at room temperature for 1 hour, 89.1g of amidated aliphatic amine was added to the reaction vessel. The temperature of the reaction vessel was raised to 50℃ and kept at this temperature for 4 hours. After the reaction vessel was cooled to room temperature, the reaction solution was added to a rotary evaporator with a water bath temperature of 100℃ and distilled under reduced pressure until no liquid was collected, yielding 102.3g of modified organic lubricant.

[0071] S2. Preparation of modified inorganic lubricants

[0072] Weigh 8.4g of potassium permanganate powder, 1.5g of potassium chloride powder, 0.4g of polyvinylpyrrolidone with a molecular weight of 1284325.5, and 28.8g of deionized water and add them to a reaction vessel. Stir until the solid is completely dissolved. Raise the temperature of the reaction vessel to 160℃ and keep it at that temperature for 12h. After the reaction vessel is cooled to room temperature, filter the cake by suction filtration. Wash the cake five times with deionized water and place it in a drying oven at 80℃ for vacuum drying for 24h to obtain the dried product. Place the dried product in a tube furnace and purge it with nitrogen. Raise the temperature of the tube furnace to 410℃ at a rate of 10℃ / min and keep it at that temperature for 8h. Then, let it cool naturally to room temperature to obtain 6.0g of α-MnO2.

[0073] 4.8g of α-MnO2, 11.2g of carboxysuccinic acid powder and 179.2g of anhydrous ethanol were weighed and added to an ultrasonic instrument. The mixture was ultrasonicated at room temperature while being stirred for 12 hours. The ultrasonic frequency was 40KHz and the stirring rate was 180rpm. After the reaction vessel was cooled to room temperature, the filter cake was collected by vacuum filtration and placed in a drying oven at 80℃ for vacuum drying until the filter cake reached a constant weight, yielding 14.4g of α-MnO2@CTS.

[0074] 12.6g of α-MnO2@CTS, 1.8g of bis(2-ethylhexyl)dithiophosphate, 43.2g of N,N-dimethylformamide and 0.6g of triethylamine were weighed and added to a reaction vessel. The temperature of the reaction vessel was raised to 60℃ and the reaction was maintained at this temperature for 4h. After the reaction vessel was cooled to room temperature, the filter cake was collected by vacuum filtration and placed in a drying oven at 80℃ for vacuum drying until the filter cake reached a constant weight, yielding 12.4g of modified inorganic lubricant.

[0075] S3, Preparation of diesel anti-wear agent

[0076] Weigh out 92.4g of modified organic lubricant, 7.6g of modified inorganic lubricant, 2.1g of benzothiadiazolinodiphenol, 2.0g of di-tert-butyl-p-cresol and 2.1g of polyisobutylene and add them to the reaction vessel. Mix them evenly and pass them through a 100-mesh sieve to obtain 105.6g of diesel anti-wear agent.

[0077] Example 3

[0078] This embodiment provides a method for preparing a highly lubricating diesel anti-wear agent, comprising the following steps:

[0079] S1. Preparation of modified organic lubricant

[0080] 56.8 g of naphthol phosphate, 33.4 g of 3H,8H-2a,8a:3a,7a diepoxyanthracene [2,3-b]epoxyene, octahydro-(9Cl), 5.4 g of triethylamine and 315.7 g of N,N-dimethylformamide were weighed and added to a reaction vessel. The temperature of the reaction vessel was raised to 70 °C and the reaction was maintained at this temperature for 2 h. After the reaction vessel was cooled to room temperature, the reaction solution was added to a rotary evaporator with a water bath temperature of 90 °C and distilled under reduced pressure until no liquid was collected, yielding 86.4 g of modified phosphate.

[0081] 58.2g of modified phosphate ester, 26.4g of dimethyl biphenyl diisocyanate, 19.4g of tetraethylene glycol and 270.9g of N,N-dimethylformamide were weighed and added to a reaction vessel. The temperature of the reaction vessel was raised to 80℃ and stirred for 3 hours. After the reaction vessel was cooled to room temperature, the reaction solution was added to a rotary evaporator with a water bath temperature of 90℃ and distilled under reduced pressure until no liquid was collected, yielding 102.3g of cross-linked fatty amine.

[0082] Weigh 75.5g of cross-linked fatty amine, 23.0g of pyromellitic dianhydride, 255.8g of N,N-dimethylformamide and 7.9g of triethylamine and add them to a reaction vessel. Stir at room temperature for 3 hours. After the reaction vessel is cooled to room temperature, add the reaction solution to a rotary evaporator with a water bath temperature of 90℃ and distill under reduced pressure until no liquid is collected, to obtain 98.4g of amidated fatty amine;

[0083] 15.5g of N-hydroxysuccinimide, 4.7g of N,N-dicyclohexylcarboimide, 1.55g of triethylamine and 135.8g of N,N-dimethylformamide were weighed and added to a reaction vessel. After reacting at room temperature for 0.75h, 93.1g of amidated aliphatic amine was added to the reaction vessel. The temperature of the reaction vessel was raised to 45℃ and kept at this temperature for 3h. After the reaction vessel was cooled to room temperature, the reaction solution was added to a rotary evaporator with a water bath temperature of 90℃ and distilled under reduced pressure until no liquid was collected, yielding 105.3g of modified organic lubricant.

[0084] S2. Preparation of modified inorganic lubricants

[0085] Weigh 8.0g of potassium permanganate powder, 1.2g of potassium chloride powder, 0.3g of polyvinylpyrrolidone with a molecular weight of 1261432.5 and 24.5g of deionized water and add them to the reaction vessel. Stir until the solid is completely dissolved. Raise the temperature of the reaction vessel to 155℃ and keep it at that temperature for 12h. After the reaction vessel is cooled to room temperature, filter the cake by suction filtration. Wash the cake with deionized water 4 times and place it in a drying oven at 80℃ for vacuum drying for 24h to obtain the dried product. Place the dried product in a tube furnace and purge it with nitrogen. Raise the temperature of the tube furnace to 400℃ at a rate of 10℃ / min and keep it at that temperature for 7h. Then, let it cool naturally to room temperature to obtain 6.4g of α-MnO2.

[0086] Weigh 5.2g α-MnO2, 11.4g carboxysuccinic acid powder and 177.5g anhydrous ethanol and add them to an ultrasonic instrument. Sonicate at room temperature while stirring for 10h. The ultrasonic frequency is 30KHz and the stirring rate is 150rpm. After the reaction vessel is cooled to room temperature, filter cake is collected by vacuum filtration. Place the filter cake in a drying oven at 80℃ and vacuum dry until the filter cake reaches constant weight to obtain 15.6g α-MnO2@CTS.

[0087] 13.2g of α-MnO2@CTS, 1.2g of bis(2-ethylhexyl)dithiophosphate, 43.5g of N,N-dimethylformamide and 0.6g of triethylamine were weighed and added to a reaction vessel. The temperature of the reaction vessel was raised to 50℃ and the reaction was maintained at this temperature for 3 hours. After the reaction vessel was cooled to room temperature, the filter cake was collected by vacuum filtration and placed in a drying oven at 80℃ for vacuum drying until the filter cake reached a constant weight, yielding 12.3g of modified inorganic lubricant.

[0088] S3, Preparation of diesel anti-wear agent

[0089] Weigh 92.3g of modified organic lubricant, 7.7g of modified inorganic lubricant, 2.3g of benzothiadiazolinodiphenol, 2.1g of di-tert-butyl-p-cresol and 2.0g of polyisobutylene and add them to the reaction vessel. Mix them evenly and pass them through a 100-mesh sieve to obtain 105.5g of diesel anti-wear agent.

[0090] Comparative Example 1

[0091] The difference between this comparative example and Example 3 is that step S1 is omitted, and in step S3, dithiodiphenol phosphate is used to replace the modified organic lubricant in an equal amount.

[0092] Comparative Example 2

[0093] The difference between this comparative example and Example 3 is that step S2 is omitted, and the modified inorganic lubricant is omitted in step S3.

[0094] Comparative Example 3

[0095] The difference between this comparative example and Example 3 is that steps S1 and S2 are omitted, and in step S3, dithiodiphenol phosphate is used to replace the modified organic lubricant in an equal amount, while the modified inorganic lubricant is omitted.

[0096] Performance testing:

[0097] The acid value, anti-wear properties, and combustion properties of the diesel anti-wear agents prepared in Examples 1-3 and Comparative Examples 1-3 were tested:

[0098] The acid value and anti-wear performance were determined in accordance with the standard NB / SH / T 6074-2023 "Diesel Anti-wear Agents" and the average wear scar diameter was measured.

[0099] Combustion performance was tested according to standard GB 36886-2018 "Limits and Measurement Methods for Exhaust Smoke from Non-Road Mobile Diesel Machinery". The results are shown in Table 1.

[0100] High-temperature wear resistance tests were conducted on the oils in Examples 1-3 and Comparative Examples 1-3 using a high-frequency reciprocating friction testing machine. The test conditions were: load 1000g, frequency 20Hz, temperature 100℃, and test time 60min. The wear scar diameter and friction coefficient of the samples were recorded. The cleaning performance of Examples 1-3 and Comparative Examples 1-3 was tested using an engine crankcase coking simulation test. 300mL of test sample was added to a coking plate simulator and heated to 150℃. Oil was continuously splashed onto an aluminum plate at 310℃. After 6 hours, the amount of coke generated on the aluminum plate was weighed and expressed as deposit mass to simulate deposits on the piston. The test results are shown in Table 2.

[0101] Table 1 - Performance Test Data of Samples

[0102]

[0103] Table 2 - Performance Simulation Test Data of Samples

[0104]

[0105] Data Analysis:

[0106] Comparative analysis of the data in Tables 1 and 2 shows that the acid value (calculated as KOH) of the diesel anti-wear agent prepared in this invention is 0.5 mg·g. -1 The average wear scar diameter is 228 μm, and the opacity (P) by the opacity method is... Max＜ 19) is 1.68m -1The Ringelmann blackness base number is 1, the amount of deposited material in the scorch test is 13.6 mg, the wear scar diameter obtained by the high-frequency reciprocating friction test is 235 μm, and the friction coefficient is 0.092. All the performance test data are better than the comparative example, indicating that the diesel anti-wear agent prepared by the present invention has achieved the expected effect.

[0107] By comparing the data from Example 3, Comparative Example 1, and Comparative Example 3, it can be found that, compared to the diesel anti-wear agent prepared using dithiodiphenol phosphate in Comparative Example 1, the diesel anti-wear agent prepared using modified organic lubricant in Example 3 shows significant improvement in all properties. Comparison of anti-wear performance and high-frequency reciprocating test data reveals that the modified organic lubricant prepared in this invention exhibits excellent lubrication performance. Furthermore, data comparing the amount of deposits in the char spot test shows that the modified organic lubricant prepared in this invention significantly improves the dispersion and discharge of the modified inorganic lubricant prepared in this invention. It has a very strong promoting effect, which greatly improves the performance of the modified inorganic lubricant. By comparing the data of Example 3, Comparative Example 2 and Comparative Example 3, it can be found that the addition of the prepared modified inorganic lubricant greatly improves the lubrication performance of the diesel anti-wear agent. Moreover, by comparing the data of the amount of deposits in the char spot test, it can be found that the modified inorganic lubricant promotes more complete combustion of diesel and greatly reduces the amount of deposits. By comparing the data of Example 3 and Comparative Example 3, it can be found that the diesel anti-wear agent prepared in Example 3 has better performance in all aspects than the diesel anti-wear agent directly used in Comparative Example 3.

[0108] In summary, this invention prepares a cross-linked fatty amine by polymerizing the prepared modified phosphate ester, and then amidates it to further introduce imide groups to obtain a modified organic lubricant. Finally, the modified organic lubricant is mixed and sieved with a modified inorganic lubricant obtained by surface modification of α-MnO2 using carboxysuccinic acid and bis(2-ethylhexyl) dithiophosphate, and excipients to obtain a diesel anti-wear agent with high lubricity and high temperature resistance.

[0109] The above description is merely an example and illustration of the structure of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the structure of the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

[0110] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0111] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A high-lubricating diesel anti-wear agent, characterized in that, It is composed of the following raw material components in parts by weight: 80-100 parts modified organic lubricant, 5-10 parts modified inorganic lubricant, 1-5 parts corrosion inhibitor, 1-5 parts antioxidant and 1-5 parts viscosity index improver; The modified organic lubricant is prepared as follows: 3-5 parts by weight of N-hydroxysuccinimide, 1-2 parts by weight of N,N'-dicyclohexylcarboimide, 0.3-0.5 parts by weight of triethylamine and 30-40 parts by weight of N,N-dimethylformamide are added to a reaction vessel. After reacting at room temperature for 0.5-1 h, 20-30 parts by weight of amidated fatty amine are added to the reaction vessel. The temperature of the reaction vessel is raised to 40-50℃ and kept at this temperature for 2-4 h. The modified organic lubricant is then obtained after post-treatment. The preparation method of amidated fatty amine is as follows: weigh 20-30 parts by weight of cross-linked fatty amine, 5-10 parts by weight of pyromellitic dianhydride, 75-100 parts by weight of N,N-dimethylformamide and 1-3 parts by weight of triethylamine and add them to the reaction vessel. Stir at room temperature for 2-4 hours and then process to obtain amidated fatty amine. The preparation method of cross-linked fatty amine is as follows: weigh 5-8 parts of modified phosphate ester, 3-5 parts of dimethyl biphenyl diisocyanate, 4-6 parts of tetraethylene glycol and 40-50 parts of N,N-dimethylformamide by weight and add them to the reaction vessel. Raise the temperature of the reaction vessel to 70-90℃, keep it warm and stir for 2-4 hours, and then perform post-treatment to obtain cross-linked fatty amine. The modified phosphate ester is prepared by weighing 5-8 parts by weight of naphthol phosphate ester, 3-5 parts by weight of 3H,8H-2a,8a:3a,7a diepoxyanthracene [2,3-b]epoxyene, octahydro-(9CI), 0.5-0.8 parts by weight of triethylamine and 30-40 parts by weight of N,N-dimethylformamide and adding them to a reaction vessel. The temperature of the reaction vessel is raised to 60-80℃ and the reaction is maintained for 1-3 hours. The modified phosphate ester is then obtained after post-treatment. The modified inorganic lubricant is prepared as follows: 10-20 parts by weight of α-MnO2@CTS, 1-2 parts by weight of O,O-di(2-ethylhexyl)dithiophosphate, 40-50 parts by weight of N,N-dimethylformamide and 0.5-0.8 parts by weight of triethylamine are added to a reaction vessel. The temperature of the reaction vessel is raised to 40-60℃ and the reaction is maintained for 2-4 hours. The modified inorganic lubricant is then obtained after post-treatment. The preparation method of α-MnO2@CTS is as follows: Weigh 20-30 parts by weight of α-MnO2, 50-60 parts by weight of carboxysuccinic acid powder and 800-1000 parts by weight of anhydrous ethanol and add them to an ultrasonic instrument. While ultrasonicating at room temperature, stir for 8-12 hours. The ultrasonic frequency is 20-40KHz and the stirring rate is 120-180rpm. After post-processing, α-MnO2@CTS is obtained.

2. The high-lubricity diesel anti-wear agent according to claim 1, characterized in that, The preparation method of α-MnO2 is as follows: Weigh 10-20 parts by weight of potassium permanganate powder, 2-4 parts by weight of potassium chloride powder, 0.5-0.8 parts by weight of polyvinylpyrrolidone with a molecular weight of 1,200,000-1,300,000 and 40-50 parts by weight of deionized water and add them to the reaction vessel and stir. After the solid is completely dissolved, raise the temperature of the reaction vessel to 150-160℃ and keep it at this temperature for 8-12 hours. After post-treatment, α-MnO2 is obtained.

3. The high-lubricity diesel anti-wear agent according to claim 1, characterized in that, The corrosion inhibitor is one or more of ferrous phosphate, benzothiadiazolindiphenol and mercaptodiethylamine, the antioxidant is one or more of di-tert-butyl-p-cresol, dibutylhydroquinone and diphenyl disulfide phosphate, and the viscosity index improver is polyisobutylene.

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