Extreme pressure antiwear agent, method of making, and heavy duty vehicle gear oil

Abstract

The application provides an extreme pressure anti-wear agent, a preparation method thereof and heavy load vehicle gear oil, and belongs to the technical field of extreme pressure anti-wear additives. The application provides an extreme pressure anti-wear agent with a chemical structure shown in formula I or formula II. Through molecular design, the prepared extreme pressure anti-wear agent has excellent high-temperature oxidation resistance, can reduce the friction coefficient of the surface of a friction pair, and in the friction process, nitrogen elements and boron elements in the borate ester diffuse from the friction surface to the matrix to form a permeation layer, improve the wear resistance of the surface of the material, play an extreme pressure anti-wear role, make the heavy load vehicle gear oil have better load-carrying capacity and extreme pressure resistance, and thus play an energy-saving and consumption-reducing role.

Description

Technical Field

[0001] This invention belongs to the field of extreme pressure anti-wear additive technology, specifically relating to an extreme pressure anti-wear agent, its preparation method, and heavy-duty vehicle gear oil. Background Technology

[0002] Heavy-duty vehicle gear oil is a lubricant specifically designed for high-load mechanical transmission systems. It forms a stable oil film under extreme pressure and high temperature conditions, effectively reducing direct friction between gears. Heavy-duty vehicle gear oils have high requirements for extreme pressure anti-wear properties, as well as for copper strip corrosion (national standard requires no higher than level 3) and oxidation stability. The sulfur and phosphorus extreme pressure anti-wear agents typically added can easily increase the oil's acid value at high temperatures, accelerating oxidation and deterioration. Therefore, improving the high-temperature oxidation resistance of extreme pressure anti-wear agents has become a pressing technical problem in this field. Summary of the Invention

[0003] The purpose of this invention is to provide an extreme pressure anti-wear agent, its preparation method, and a heavy-duty vehicle gear oil. The heavy-duty vehicle gear oil prepared from the extreme pressure anti-wear agent provided by this invention possesses excellent high-temperature oxidation resistance, high load-carrying capacity, and is energy-saving and environmentally friendly.

[0004] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides an extreme pressure anti-wear agent having the chemical structure shown in Formula I or Formula II: Formula I; Formula II; In Formula I, R1 is an alkyl group; In Formula II, R2 is an alkyl or olefin.

[0005] Preferably, R1 is a C2-C16 alkyl group; and R2 is a C1-C20 alkyl group.

[0006] This invention also provides a method for preparing the extreme pressure anti-wear agent described in the above technical solution, comprising the following steps: (1) Boric acid and ethanolamine are mixed and subjected to esterification to obtain borate ester; (2) The borate ester obtained in step (1) is mixed with an alkylating agent and subjected to an alkylation reaction to obtain the extreme pressure anti-wear agent of formula I; the alkylating agent is an alcohol or a haloalkane.

[0007] Preferably, the temperature of the esterification reaction in step (1) and the alkylation reaction in step (2) are independently 100~130℃ and the time is independently 3~6h.

[0008] This invention also provides a method for preparing the extreme pressure anti-wear agent described in the above technical solution, comprising the following steps: 1) A carboxylic acid and diethanolamine are mixed and subjected to an amide reaction to obtain a first intermediate; the chemical structure of the first intermediate is shown in Formula III: Formula III; 2) The first intermediate obtained in step 1), diethanolamine, and a base are mixed and hydrolyzed to obtain a second intermediate; the chemical structure of the second intermediate is shown in Formula IV: Formula IV; 3) Mix the second intermediate obtained in step 2), boric acid, ethanolamine and solvent, and carry out esterification reaction to obtain the extreme pressure anti-wear agent of formula II.

[0009] Preferably, the temperature of the amide reaction in step 1) is 130~150℃, and the reaction time is 5~7h.

[0010] Preferably, in step 2), the hydrolysis temperature is 70~90℃, the hydrolysis time is 4~7h, and the hydrolysis pH value is 11~14.

[0011] Preferably, the temperature of the esterification reaction in step 3) is 100~135℃, and the time of the esterification reaction is 3~8h.

[0012] The present invention also provides a heavy-duty vehicle gear oil comprising the following components by mass percentage: Base oil 70-80% Viscosity index improver 10-24% Extreme pressure anti-wear agent 3~6% Antioxidant 1.5~3% Alkaline neutralizing agent 0.3~0.9% Antifoaming agent 0.02~0.06% Detergent dispersant 0.5~2% Metal deactivator 0.1~0.3%; The extreme pressure anti-wear agent is the extreme pressure anti-wear agent described in the above technical solution or the extreme pressure anti-wear agent prepared by the preparation method described in the above technical solution.

[0013] Preferably, the viscosity index improver is a star-shaped polymethacrylate.

[0014] This invention provides an extreme pressure anti-wear agent with a chemical structure as shown in Formula I or Formula II. Through molecular design, the ethanolamine and diethanolamine segments of this invention impart a weak alkalinity to the extreme pressure anti-wear agent, while also giving it a high thermal decomposition temperature. Furthermore, the borate ester groups can coordinate with ions on the metal surface to form chemical bonds. The ethanolamine segments can spread on the metal surface, forming a dense, continuous, and strongly adhesive protective film that effectively isolates corrosive media such as oxygen and moisture, thereby preventing metal oxidation. This results in an extreme pressure anti-wear agent with excellent high-temperature oxidation resistance, reducing the friction coefficient of the friction pair surface. During friction, nitrogen and boron elements in the borate ester diffuse from the friction surface to the matrix, forming a penetrating layer that improves the wear resistance of the material surface, thus playing an extreme pressure anti-wear role. This gives heavy-duty vehicle gear oil better load-bearing capacity and extreme pressure resistance, thereby achieving energy saving and consumption reduction. The results of the examples show that the high-temperature oxidation initiation temperature of the heavy-duty vehicle gear oil prepared using the extreme pressure anti-wear agent provided by the present invention is 235~242℃, the pitting / stripping rating is ≥9.4, and it passes the copper strip corrosion test. Attached Figure Description

[0015] Figure 1 The 1H NMR spectrum of the extreme pressure anti-wear agent prepared in Example 1; Figure 2 The carbon NMR spectrum of the extreme pressure anti-wear agent prepared in Example 1; Figure 3 The 1H NMR spectrum of the extreme pressure anti-wear agent prepared in Example 3; Figure 4 The carbon NMR spectrum of the extreme pressure anti-wear agent prepared in Example 3; Figure 5 The 1H NMR spectrum of the extreme pressure anti-wear agent prepared in Example 5; Figure 6 The carbon NMR spectrum of the extreme pressure anti-wear agent prepared in Example 5; Figure 7 The 1H NMR spectrum of the extreme pressure anti-wear agent prepared in Example 7; Figure 8 The carbon NMR spectrum of the extreme pressure anti-wear agent prepared in Example 7; Figure 9 Thermogravimetric analysis (TGA) diagram of the extreme pressure anti-wear agent prepared in Example 1; Figure 10 Thermogravimetric analysis (TGA) diagram of isobutylene sulfide in Comparative Example 1; Figure 11 The initial oxidation temperature of the heavy-duty vehicle gear oil prepared in Example 2; Figure 12 The image shows the copper corrosion of the heavy-duty vehicle gear oil prepared in Example 2. Figure 13The image shows the copper corrosion of the heavy-duty vehicle gear oil prepared in Comparative Example 1. Detailed Implementation

[0016] This invention provides an extreme pressure anti-wear agent having the chemical structure shown in Formula I or Formula II: Formula I; Formula II; In Formula I, R1 is an alkyl group; In Formula II, R2 is an alkyl or olefin.

[0017] In this invention, R1 is an alkyl group, preferably a C2-C16 alkyl group, more preferably a C4, C8, C12 or C16 alkyl group. As one embodiment, R1 can be octane or dodecane.

[0018] In this invention, R2 is an alkyl or olefin; the alkyl group is preferably a C1-C20 alkyl group. As one embodiment, R2 can be pentane or heptane.

[0019] This invention enables the preparation of extreme pressure anti-wear agents through molecular design, which can have excellent high-temperature oxidation resistance and reduce the friction coefficient of the friction pair surface. During the friction process, nitrogen and boron elements in the borate ester diffuse from the friction surface to the matrix to form a penetration layer, which improves the wear resistance of the material surface and plays an extreme pressure anti-wear role. This gives the gear oil of heavy-duty vehicles better load-bearing capacity and extreme pressure resistance, thereby playing a role in energy saving and consumption reduction.

[0020] This invention also provides a method for preparing the extreme pressure anti-wear agent described in the above technical solution, comprising the following steps: (1) Boric acid and ethanolamine are mixed and subjected to esterification to obtain borate ester; (2) The borate ester obtained in step (1) is mixed with an alkylating agent and subjected to an alkylation reaction to obtain the extreme pressure anti-wear agent of formula I; the alkylating agent is an alcohol or a haloalkane.

[0021] The present invention does not have any special limitations on the source of the raw materials, and commercially available products known to those skilled in the art can be used.

[0022] This invention involves mixing boric acid and ethanolamine and performing an esterification reaction to obtain a borate ester.

[0023] In this invention, the equation for the esterification reaction of boric acid and ethanolamine is as follows: .

[0024] In this invention, the molar ratio of boric acid to ethanolamine is preferably 1:(2~3), more preferably 1:3.

[0025] The present invention does not have any special limitations on the operation of mixing boric acid and ethanolamine, and any technical solution for preparing the mixture well known to those skilled in the art can be used.

[0026] In this invention, the preferred temperature for the esterification reaction is 100-130°C; the preferred time for the esterification reaction is 3-6 hours. As one embodiment, the temperature for the esterification reaction can be 115°C, 120°C, or 125°C; the preferred time for the esterification reaction can be 4 hours or 5 hours. Limiting the temperature and time of the esterification reaction to the above ranges in this invention further enhances the degree of esterification.

[0027] After the esterification reaction is completed, the present invention preferably performs post-processing on the product obtained from the esterification reaction to obtain a borate ester.

[0028] In this invention, the post-treatment preferably includes sequential standing / centrifugation, separation, extraction, and distillation. The present invention utilizes standing or separation to remove incompletely reacted boric acid.

[0029] The present invention does not have any special limitations on the standing operation, and the operation known to those skilled in the art can be carried out by standing at room temperature.

[0030] In this invention, the centrifugation temperature is preferably room temperature; the centrifugation speed is preferably 6000~8000 r / min.

[0031] The present invention does not impose any special limitations on the separation operation; any operation known to those skilled in the art can be used.

[0032] The present invention does not impose any particular limitation on the extraction operation; any operation well known to those skilled in the art can be used. As one embodiment, the extractant used in the extraction can be ethanol.

[0033] The present invention does not impose any special limitations on the distillation operation; any operation known to those skilled in the art can be used to remove the solvent.

[0034] In this invention, the chemical structure of the borate ester is preferably as shown in Formula V: Formula V.

[0035] After obtaining the borate ester, the present invention mixes the borate ester with an alkylating agent and performs an alkylation reaction to obtain the extreme pressure anti-wear agent of Formula I.

[0036] In this invention, the reaction equation for the borate ester and the alkylating agent is as follows: .

[0037] In this invention, the alkylating agent is an alcohol or a haloalkane; the alcohol is preferably butanol, octanol, dodecyl alcohol, hexadecyl alcohol, or octadecyl alcohol; the haloalkane is preferably one or more of halobutane, halooctane, halododecane, and halooctadecane. In this invention, the alkylating agent contains an R1 group, and the alkylating agent is selected according to the desired Formula I structure.

[0038] In one embodiment, the haloalkane may be bromooctane.

[0039] In this invention, the molar ratio of the borate ester to the alkylating agent is preferably 1:(5~6), more preferably 1:6.

[0040] The present invention does not have any special limitations on the operation of mixing the borate ester and the alkylating agent; any technical solution for preparing the mixture well known to those skilled in the art can be used.

[0041] In this invention, the preferred temperature for the alkylation reaction is 100-130°C; the preferred time for the alkylation reaction is 3-6 hours. As one embodiment, the temperature for the alkylation reaction can be 105°C, 110°C, 115°C, 120°C, or 125°C; the preferred time for the alkylation reaction can be 4 hours or 5 hours. Limiting the temperature and time of the alkylation reaction to the above ranges in this invention further enhances the degree of alkylation.

[0042] After the alkylation reaction is completed, the present invention preferably performs post-processing on the product obtained by the alkylation reaction to obtain the extreme pressure anti-wear agent of Formula I.

[0043] In this invention, the post-treatment is preferably extraction; the extractant used for extraction is preferably petroleum ether at 60-90°C; and the extraction temperature is preferably room temperature. This invention uses extraction to remove unreacted alkylating agents, obtaining a relatively pure extreme pressure anti-wear agent.

[0044] This invention also provides a method for preparing the extreme pressure anti-wear agent described in the above technical solution, comprising the following steps: 1) A carboxylic acid and diethanolamine are mixed and subjected to an amide reaction to obtain a first intermediate; the chemical structure of the first intermediate is shown in Formula III: Formula III; 2) The first intermediate obtained in step 1), diethanolamine, and a base are mixed and hydrolyzed to obtain a second intermediate; the chemical structure of the second intermediate is shown in Formula IV: Formula IV; 3) Mix the second intermediate obtained in step 2), boric acid, ethanolamine and solvent, and carry out esterification reaction to obtain the extreme pressure anti-wear agent of formula II.

[0045] The present invention does not have any special limitations on the source of the raw materials, and commercially available products known to those skilled in the art can be used.

[0046] In this invention, carboxylic acid and diethanolamine are mixed and subjected to an amide reaction to obtain a first intermediate.

[0047] In this invention, the equation for the amide reaction between carboxylic acid and diethanolamine is as follows: .

[0048] In this invention, the carboxylic acid is preferably one or more selected from acetic acid, propionic acid, butyric acid, hexanoic acid, octanoic acid, quinic acid, palmitic acid, oleic acid, and stearic acid. In this invention, the carboxylic acid contains an R2 group, and the desired carboxylic acid can be selected according to the chemical structure of Formula II.

[0049] In this invention, the molar ratio of the carboxylic acid and diethanolamine is preferably 1:1.

[0050] The present invention does not have any special limitations on the operation of mixing the carboxylic acid and diethanolamine, and any technical solution for preparing the mixture well known to those skilled in the art can be used.

[0051] In this invention, the preferred temperature for the amide reaction is 130-150°C; the preferred reaction time is 5-7 hours. As one embodiment, the temperature for the amide reaction can be 135°C, 140°C, or 145°C; the reaction time can be 6 hours. In this invention, the carboxylic acid and diethanolamine undergo an amide reaction at 130-150°C for 5-7 hours.

[0052] After the amide reaction is completed, the present invention preferably performs post-processing on the product obtained by the amide reaction to obtain a first intermediate.

[0053] In this invention, the post-treatment is preferably a combination of washing and drying performed sequentially.

[0054] The present invention does not have any special limitations on the water washing operation; water washing is sufficient to remove impurities.

[0055] The present invention does not impose any special limitations on the drying operation; drying to a constant weight is sufficient.

[0056] In this invention, the chemical structure of the first intermediate is as shown in Formula III: Formula III.

[0057] After obtaining the first intermediate, the present invention mixes the first intermediate, diethanolamine and alkali, and hydrolyzes them to obtain the second intermediate.

[0058] In this invention, the hydrolysis equation is as follows: .

[0059] In this invention, the molar ratio of the first intermediate to diethanolamine is preferably (1~2):(1~2), more preferably 1:1.

[0060] In this invention, the alkali is preferably potassium hydroxide (KOH). There is no particular limitation on the amount of alkali used, as long as the pH value during hydrolysis is maintained within the range of 11-14.

[0061] The present invention does not have any special limitations on the operation of mixing the first intermediate, diethanolamine and alkali, and any technical solution for preparing the mixture well known to those skilled in the art can be used.

[0062] In this invention, the hydrolysis temperature is preferably 70-90°C; the hydrolysis time is preferably 4-7 hours; and the hydrolysis pH is preferably 11-14. As one embodiment, the hydrolysis temperature can be 75°C, 80°C, or 85°C; the hydrolysis time can be 5 hours or 6 hours; and the hydrolysis pH can be 12 or 13. By limiting the hydrolysis temperature, time, and pH within the above ranges, this invention can further improve the degree of hydrolysis.

[0063] After hydrolysis, the present invention preferably performs post-processing on the product obtained by hydrolysis to obtain a second intermediate.

[0064] In this invention, the post-treatment is preferably a combination of washing and drying performed sequentially.

[0065] The present invention does not have any special limitations on the water washing operation; water washing is sufficient to remove impurities.

[0066] The present invention does not impose any special limitations on the drying operation; drying to a constant weight is sufficient.

[0067] In this invention, the chemical structure of the second intermediate is shown in Formula IV: Formula IV.

[0068] After obtaining the second intermediate, the present invention mixes the second intermediate, boric acid, ethanolamine and solvent, and carries out an esterification reaction to obtain the extreme pressure anti-wear agent of Formula II.

[0069] In this invention, the equation for the esterification reaction is as follows: .

[0070] In this invention, the molar ratio of the second intermediate, boric acid and ethanolamine is preferably (1~2):(1~2):(1~2), more preferably 1:1:1.

[0071] In this invention, the solvent is preferably at least one of toluene and dichloromethane, more preferably toluene. This invention does not have a particular limitation on the amount of solvent used, as long as all raw materials are completely dissolved.

[0072] The present invention does not have any special limitations on the operation of mixing the second intermediate, boric acid, ethanolamine and solvent, and any technical solution for preparing the mixture well known to those skilled in the art can be used.

[0073] In this invention, the preferred temperature for the esterification reaction is 100-135°C; the preferred reaction time is 3-8 hours. As one embodiment, the esterification reaction temperature can be 105°C, 110°C, 115°C, 120°C, or 125°C; the reaction time can be 4 hours, 5 hours, 6 hours, or 7 hours. Limiting the temperature and time of the esterification reaction to the above ranges further enhances the degree of esterification.

[0074] After the esterification reaction is completed, the present invention preferably performs post-processing on the product obtained by the esterification reaction to obtain an extreme pressure anti-wear agent.

[0075] In this invention, the post-treatment preferably includes sequential standing / centrifugation, separation, extraction, and distillation. The present invention utilizes standing or separation to remove incompletely reacted boric acid.

[0076] The present invention does not have any special limitations on the standing operation, and the operation known to those skilled in the art can be carried out by standing at room temperature.

[0077] In this invention, the centrifugation temperature is preferably room temperature; the centrifugation speed is preferably 6000~8000 r / min.

[0078] The present invention does not impose any special limitations on the separation operation; any operation known to those skilled in the art can be used.

[0079] The present invention does not impose any particular limitation on the extraction operation; any operation well known to those skilled in the art can be used. As one embodiment, the extractant used in the extraction can be ethanol. The present invention uses ethanol to remove unreacted ethanolamine.

[0080] The present invention does not impose any special limitations on the distillation operation; any operation known to those skilled in the art can be used to remove the solvent.

[0081] The present invention also provides a heavy-duty vehicle gear oil comprising the following components by mass percentage: Base oil 70-80% Viscosity index improver 10-24% Extreme pressure anti-wear agent 3~6% Antioxidant 1.5~3% Alkaline neutralizing agent 0.3~0.9% Antifoaming agent 0.02~0.06% Detergent dispersant 0.5~2% Metal deactivator 0.1~0.3%; The extreme pressure anti-wear agent is the extreme pressure anti-wear agent described in the above technical solution or the extreme pressure anti-wear agent prepared by the preparation method described in the above technical solution.

[0082] In one embodiment, the mass percentage of the base oil can be 71%, 72%, 73%, 74%, 75%, 76%, 76.98%, 77%, 77.98%, 78%, 79%, or 79.98%. In this invention, the base oil is preferably one or more of Group II hydrotreated base oils, paraffinic base oils, synthetic oils, and naphthenic oils with a viscosity index of 95-120.

[0083] In one embodiment, the base oil may be MVI 500, PAO 10, PAO 20 or industrial white oil 100#.

[0084] In one embodiment, the base oil may be MVI 500 and PAO 10 in a mass ratio of 62.98:15, MVI 500 and PAO 20 in a mass ratio of 63.98:16, industrial white oil 100# and PAO 10 in a mass ratio of 56.98:20, or MVI 500 and PAO 10 in a mass ratio of 4:1.

[0085] In one embodiment, the mass percentage of the viscosity index improver can be 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, or 23%. In this invention, the viscosity index improver is preferably a star-shaped polymethyl methacrylate, more preferably a star-shaped polymethyl methacrylate.

[0086] In one implementation, the extreme pressure anti-wear agent may be 3.5%, 4%, or 5% by mass.

[0087] In one embodiment, the antioxidant may be 2% or 2.5% by mass. In this invention, the antioxidant is preferably one or more of phenols, amines, and metal alkylating agents.

[0088] In one embodiment, the phenol may be 2,4-di-tert-butylphenol; the amine may be L57.

[0089] In this invention, when the antioxidant is a phenol and an amine, the mass ratio of the phenol to the amine is preferably 1:3.

[0090] In one embodiment, the mass percentage of the alkaline neutralizing agent can be 0.4%, 0.5%, 0.6%, 0.7%, or 0.8%. In this invention, the alkalinity of the alkaline neutralizing agent is preferably 380~420 mgKOH / g; the alkaline neutralizing agent is preferably one or more of sulfonates, alkylphenol calcium, and alkyl salicylates.

[0091] In one embodiment, the antifoaming agent may be present in a mass percentage of 0.03%, 0.04%, or 0.05%. In this invention, the antifoaming agent is preferably one or more of organosilicon, polyvinyl alcohol, and polyether.

[0092] In one embodiment, the mass percentage of the detergent-dispersant can be 1.0% or 1.5%. In this invention, the detergent-dispersant is preferably one or more of the following: sulfonate with an alkalinity of 300-330 mg KOH / g, alkylphenol calcium with an alkalinity of 120-160 mg KOH / g, and alkyl salicylate with an alkalinity of 120-150 mg KOH / g.

[0093] In one embodiment, the metal deactivator may be 0.2% by mass. In this invention, the metal deactivator is preferably a derivative of benzotriazole or thiadiazole. In one embodiment, the metal deactivator may be T551 or T561.

[0094] In this invention, the preferred method for preparing the heavy-duty vehicle gear oil is as follows: The base oil and viscosity index improver are mixed, and then extreme pressure anti-wear agent, antioxidant, detergent dispersant, metal deactivator, alkaline neutralizer and antifoaming agent are added to obtain heavy-duty vehicle gear oil.

[0095] In this invention, the mixing temperature of the base oil and viscosity index improver is preferably 50-60°C. There is no particular limitation on the mixing time, as long as the mixture is homogeneous. In this invention, the viscosity grades of the products obtained by mixing the base oil and viscosity index improver are primarily 85W-140 and 85W-90.

[0096] The present invention does not have any special limitations on the operation of adding extreme pressure anti-wear agent, antioxidant, detergent dispersant, metal deactivator and alkaline neutralizer, as long as they are mixed evenly.

[0097] In this invention, the antifoaming agent is preferably added using a spray device. This invention utilizes a spray device to uniformly spray the antifoaming agent, which can significantly improve production efficiency and reduce costs.

[0098] This invention, through molecular design and process improvement, enables the prepared borate ester-based extreme pressure anti-wear agent to possess higher load-carrying capacity, high-temperature oxidation resistance, and energy-saving and environmentally friendly properties. The addition of antifoaming agents via a spray device ensures uniform dispersion of the antifoaming agent in the oil, and the synergistic effect of the antifoaming agent combined with other additives is more pronounced. Secondly, due to the high high-temperature oxidation resistance of borate esters, the increase in the acid value of the oil is smaller, resulting in less corrosion of copper sheets and less sludge formation. Finally, the star-shaped polymethyl methacrylate, with its high molecular weight, significantly improves the viscosity and viscosity index of the base oil due to its star-shaped structure, thereby also improving the high-temperature resistance and lubrication of the lubricating oil.

[0099] The beneficial effects of this invention are as follows: The borate ester-based extreme pressure anti-wear agent provided by this invention can reduce the coefficient of friction of the friction pair surface. During the friction process, nitrogen and boron elements in the borate ester diffuse from the friction surface to the matrix to form a penetrating layer, improving the wear resistance of the material surface and playing an extreme pressure anti-wear role. This gives the vehicle gear oil better load-bearing capacity and extreme pressure resistance, thereby achieving energy saving and consumption reduction. The extreme pressure anti-wear agent provided by this invention does not corrode gears, avoiding the corrosive problems associated with traditional sulfur- and phosphorus-containing extreme pressure anti-wear agents. Simultaneously, other components in the vehicle gear oil, such as rust inhibitors, also endow the gear oil with rust-preventive and corrosion-preventive properties, protecting gears from corrosion and rust. The raw materials used in this invention include extreme pressure anti-wear agents that are colorless and odorless, posing little harm to the environment and animals and plants. Some borate esters are biodegradable. Adding specific viscosity index improvers, such as star-shaped polymethyl methacrylate, to vehicle gear oil can improve the low-temperature performance of the gear oil, ensure its low-temperature fluidity, and make the gear oil suitable for low-temperature environments.

[0100] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0101] Example 1 Extreme pressure anti-wear agent has the chemical structure shown in Formula I, where R1 is octane; The preparation method of the extreme pressure anti-wear agent is as follows: (1) Boric acid and ethanolamine were mixed in a molar ratio of 1:3 and esterified at 125°C for 5 hours. After the esterification reaction was completed, the mixture was centrifuged at 6000 r / min at room temperature, separated, extracted with ethanol, and finally distilled to obtain borate ester. (2) The borate ester and bromooctane obtained in step (1) are mixed in a molar ratio of 1:6 and alkylated at 125°C for 4 hours. Then, the mixture is extracted at room temperature with petroleum ether at 60~90°C to obtain an extreme pressure anti-wear agent.

[0102] Example 2 Heavy-duty vehicle gear oils consist of the following components by weight percentage: Base oil 77.98% Viscosity index improver 15% Extreme pressure anti-wear agent 3.5% Antioxidant 2% Alkaline neutralizer 0.4% Antifoaming agent 0.02% 1% detergent dispersant Metal deactivator 0.1%; The base oils are MVI 500 and PAO 10 in a mass ratio of 62.98:15; The viscosity index improver is Dow's ACULYN 88 star-shaped polymethyl methacrylate; The extreme pressure anti-wear agent is the extreme pressure anti-wear agent of Example 1; The antioxidant is 2,4-di-tert-butylphenol and L57 in a mass ratio of 1:3; The alkaline neutralizing agent is a high-alkalinity sulfonate, Xinxiang Ruifeng New Materials Co., Ltd., T106D; The antifoaming agent is an organosilicone antifoaming agent, Dow Corning's XIAMETERAFE-400; The cleaning and dispersing agent is a low-to-medium alkalinity sulfonate, specifically T104 from Xinxiang Ruifeng New Materials Co., Ltd. The metal deactivator is T 561; The preparation method of the heavy-duty vehicle gear oil is as follows: add base oil and viscosity index improver to a mixing tank, stir evenly at 55°C to obtain a mixed base oil; then add extreme pressure anti-wear agent, antioxidant, detergent dispersant and metal deactivator in sequence, stir at 55°C for 1 hour, then add alkali neutralization reagent, and finally add antifoaming agent using a spray device to obtain heavy-duty vehicle gear oil.

[0103] Example 3 Extreme pressure anti-wear agent has the chemical structure shown in Formula II, where R2 is pentane; The preparation method of the extreme pressure anti-wear agent is as follows: 1) Hexanoic acid and diethanolamine were mixed in a molar ratio of 1:1 and subjected to an amide reaction at 135°C for 6 hours. The mixture was then washed with water and dried to obtain the first intermediate. 2) The first intermediate obtained in step 1) and diethanolamine are mixed in a molar ratio of 1:1, KOH is added to adjust the pH to 12, and hydrolysis is carried out at 75°C for 5 hours. Then, the mixture is washed with water and dried to obtain the second intermediate. 3) The second intermediate obtained in step 2), boric acid, ethanolamine and toluene are mixed and esterified at 135°C for 6 hours. Then, the mixture is centrifuged at 6000 r / min at room temperature, separated, extracted with ethanol, and finally distilled to obtain the extreme pressure anti-wear agent. The molar ratio of the second intermediate, boric acid and ethanolamine is 1:1:1.

[0104] Example 4 Heavy-duty vehicle gear oils consist of the following components by weight percentage: Base oil 79.98% Viscosity index improver 13% Extreme pressure anti-wear agent 3.5% Antioxidant 2% Alkaline neutralizer 0.4% Antifoaming agent 0.02% 1% detergent dispersant Metal deactivator 0.1%; The base oils are MVI 500 and PAO 20 in a mass ratio of 63.98:16; The viscosity index improver is Dow's ACULYN 88 star-shaped polymethyl methacrylate; The extreme pressure anti-wear agent is the extreme pressure anti-wear agent of Example 3; The antioxidant is 2,4-di-tert-butylphenol and L57 in a mass ratio of 1:3; The alkaline neutralizing agent is a high-alkalinity sulfonate, Xinxiang Ruifeng New Materials Co., Ltd., T106D; The antifoaming agent is an organosilicone antifoaming agent, Dow Corning's XIAMETERAFE-400; The cleaning and dispersing agent is a low-to-medium alkalinity sulfonate, specifically T104 from Xinxiang Ruifeng New Materials Co., Ltd. The metal deactivator is T 551; The preparation method of the heavy-duty vehicle gear oil is as follows: add base oil and viscosity index improver to a mixing tank, stir evenly at 55°C to obtain a mixed base oil; then add extreme pressure anti-wear agent, antioxidant, detergent dispersant and metal deactivator in sequence, stir at 55°C for 1 hour, then add alkali neutralization reagent, and finally add antifoaming agent using a spray device to obtain heavy-duty vehicle gear oil.

[0105] Example 5 Extreme pressure anti-wear agents have the chemical structure shown in Formula I, where R1 is dodecane; The preparation method of the extreme pressure anti-wear agent is as follows: (1) Boric acid and ethanolamine were mixed in a molar ratio of 1:3 and esterified at 125°C for 5 hours. After the esterification reaction was completed, the mixture was centrifuged at 6000 r / min at room temperature, separated, extracted with ethanol, and finally distilled to obtain borate ester. (2) The borate ester and bromododecane obtained in step (1) are mixed in a molar ratio of 1:6, and alkylation reaction is carried out at 125°C for 4 hours. Then, the mixture is extracted at room temperature with petroleum ether at 60~90°C to obtain an extreme pressure anti-wear agent.

[0106] Example 6 Heavy-duty vehicle gear oils consist of the following components by weight percentage: Base oil 76.98% Viscosity index improver 16% Extreme pressure anti-wear agent 3.5% Antioxidant 2% Alkaline neutralizer 0.4% Antifoaming agent 0.02% 1% detergent dispersant Metal deactivator 0.1%; The base oil is industrial white oil 100# and PAO 10 in a mass ratio of 56.98:20; The viscosity index improver is Dow's ACULYN 88 star-shaped polymethyl methacrylate; The extreme pressure anti-wear agent is the extreme pressure anti-wear agent of Example 5; The antioxidant is 2,4-di-tert-butylphenol and L57 in a mass ratio of 1:3; The alkaline neutralizing agent is a high-alkalinity salicylate, Xinxiang Ruifeng New Materials Co., Ltd., T109; The antifoaming agent is an organosilicone antifoaming agent, Dow Corning's XIAMETERAFE-400; The cleaning and dispersing agent is a low-to-medium alkalinity sulfonate, specifically T104 from Xinxiang Ruifeng New Materials Co., Ltd. The metal deactivator is T 561; The preparation method of the heavy-duty vehicle gear oil is as follows: add base oil and viscosity index improver to a mixing tank, stir evenly at 55°C to obtain a mixed base oil; then add extreme pressure anti-wear agent, antioxidant, detergent dispersant and metal deactivator in sequence, stir at 55°C for 1 hour, then add alkali neutralization reagent, and finally add antifoaming agent using a spray device to obtain heavy-duty vehicle gear oil.

[0107] Example 7 Extreme pressure anti-wear agent has the chemical structure shown in Formula II, where R2 is heptane; The preparation method of the extreme pressure anti-wear agent is as follows: 1) Octanoic acid and diethanolamine were mixed in a molar ratio of 1:1 and subjected to an amide reaction at 135°C for 6 hours. The mixture was then washed with water and dried to obtain the first intermediate. 2) The first intermediate obtained in step 1) and diethanolamine are mixed in a molar ratio of 1:1, KOH is added to adjust the pH to 12, and hydrolysis is carried out at 75°C for 5 hours. Then, the mixture is washed with water and dried to obtain the second intermediate. 3) The second intermediate obtained in step 2), boric acid, ethanolamine and toluene are mixed and esterified at 135°C for 6 hours. Then, the mixture is centrifuged at 6000 r / min at room temperature, separated, extracted with ethanol, and finally distilled to obtain the extreme pressure anti-wear agent. The molar ratio of the second intermediate, boric acid and ethanolamine is 1:1:1.

[0108] Example 8 Heavy-duty vehicle gear oils consist of the following components by weight percentage: Base oil 77.98% Viscosity index improver 15% Extreme pressure anti-wear agent 3.5% Antioxidant 2% Alkaline neutralizer 0.4% Antifoaming agent 0.02% 1% detergent dispersant Metal deactivator 0.1%; The base oils are MVI 500 and PAO 10 in a mass ratio of 4:1; The viscosity index improver is Dow's ACULYN 88 star-shaped polymethyl methacrylate; The extreme pressure anti-wear agent is the extreme pressure anti-wear agent of Example 7; The antioxidant is 2,4-di-tert-butylphenol and L57 in a mass ratio of 1:3; The alkaline neutralizing agent is a high-alkalinity sulfonate, Xinxiang Ruifeng New Materials Co., Ltd., T106D; The antifoaming agent is an organosilicone antifoaming agent, Dow Corning's XIAMETERAFE-400; The cleaning and dispersing agent is a low-to-medium alkalinity sulfonate, specifically T104 from Xinxiang Ruifeng New Materials Co., Ltd. The metal deactivator is T 561; The preparation method of the heavy-duty vehicle gear oil is as follows: add base oil and viscosity index improver to a mixing tank, stir evenly at 55°C to obtain a mixed base oil; then add extreme pressure anti-wear agent, antioxidant, detergent dispersant and metal deactivator in sequence, stir at 55°C for 1 hour, then add alkali neutralization reagent, and finally add antifoaming agent using a spray device to obtain heavy-duty vehicle gear oil.

[0109] Example 9 Heavy-duty vehicle gear oils consist of the following components by weight percentage: Base oil 76.98% Viscosity index improver 16% Extreme pressure anti-wear agent 3.5% Antioxidant 2% Alkaline neutralizer 0.4% Antifoaming agent 0.02% 1% detergent dispersant Metal deactivator 0.1%; The base oil is industrial white oil 100# and PAO 10 in a mass ratio of 56.98:20; The viscosity index improver is Dow's ACULYN 88 star-shaped polymethyl methacrylate; The extreme pressure anti-wear agent is the extreme pressure anti-wear agent of Example 3; The antioxidant is 2,4-di-tert-butylphenol and L57 in a mass ratio of 1:3; The alkaline neutralizing agent is a high-alkalinity salicylate, Xinxiang Ruifeng New Materials Co., Ltd., T109; The antifoaming agent is an organosilicone antifoaming agent, Dow Corning's XIAMETERAFE-400; The cleaning and dispersing agent is a low-to-medium alkalinity sulfonate, specifically T104 from Xinxiang Ruifeng New Materials Co., Ltd. The metal deactivator is T 561; The preparation method of the heavy-duty vehicle gear oil is as follows: add base oil and viscosity index improver to a mixing tank, stir evenly at 55°C to obtain a mixed base oil; then add extreme pressure anti-wear agent, antioxidant, detergent dispersant and metal deactivator in sequence, stir at 55°C for 1 hour, then add alkali neutralization reagent, and finally add antifoaming agent using a spray device to obtain heavy-duty vehicle gear oil.

[0110] Comparative Example 1 Based on Example 2, sulfurized isobutylene was used to replace the extreme pressure anti-wear agent in Example 1, while other conditions remained unchanged.

[0111] Comparative Example 2 Based on Example 2, linear polymethacrylate was used as a viscosity index improver, while other conditions remained unchanged.

[0112] The 1H NMR spectrum of the extreme pressure anti-wear agent prepared in Example 1 is as follows: Figure 1 As shown; the carbon NMR spectrum of the extreme pressure anti-wear agent prepared in Example 1 is as follows. Figure 2 As shown.

[0113] from Figure 1 It can be seen that the extreme pressure anti-wear agent mainly contains methylene hydrogen, with a chemical shift of 1.1~1.2 ppm, and the peak of methylene hydrogen connected to O, with a chemical shift of 3.4~4.3 ppm.

[0114] from Figure 2 It can be seen that the extreme pressure anti-wear agent mainly consists of carbon in the methylene group, with a chemical shift of 18~34 ppm, and the peak of the methylene carbon bonded to O, with a chemical shift of 51~72 ppm.

[0115] The 1H NMR spectrum of the extreme pressure anti-wear agent prepared in Example 3 is as follows: Figure 3 As shown; the carbon NMR spectrum of the extreme pressure anti-wear agent prepared in Example 3 is as follows. Figure 4 As shown.

[0116] from Figure 3 It can be seen that the extreme pressure anti-wear agent mainly contains methylene hydrogen, with a chemical shift of 1.1~1.2 ppm, as well as the peak of methylene hydrogen connected to O, with a chemical shift of 3.4~4.3 ppm, and methylene hydrogen connected to C=O bond.

[0117] from Figure 4 It can be seen that the extreme pressure anti-wear agent mainly contains carbon in the methylene group, with a chemical shift of 18~34 ppm, and the peak of the methylene carbon connected to O, with a chemical shift of 51~72 ppm, of which the chemical shift of the carbon in C=O is at 160~175 ppm.

[0118] The 1H NMR spectrum of the extreme pressure anti-wear agent prepared in Example 5 is as follows: Figure 5As shown; the carbon NMR spectrum of the extreme pressure anti-wear agent prepared in Example 5 is as follows. Figure 6 As shown; the 1H NMR spectrum of the extreme pressure anti-wear agent prepared in Example 7 is as follows. Figure 7 As shown; the carbon NMR spectrum of the extreme pressure anti-wear agent prepared in Example 7 is as follows. Figure 8 As shown.

[0119] from Figures 5-8 It can be seen that the extreme pressure anti-wear agents in Examples 5 and 7 have similar structures to those in Examples 1 and 3, except that the carbon atoms in the R1 and R2 groups are slightly different.

[0120] The overall 1H and 1C NMR spectra show that the extreme pressure anti-wear agent contains a mixture of monoesters and diesters, which is unavoidable. From the perspective of industrial application, it is not necessary to purify it completely.

[0121] The kinematic viscosity and viscosity index of the base oils blended in Examples 2, 4, 6, 8 and 9, as well as Comparative Examples 1 and 2, were tested using a kinematic viscometer. The results are shown in Table 1.

[0122] The performance of Examples 2, 4, 6, 8 and 10, as well as Comparative Examples 1 to 2, were tested using a four-ball tribometer (GB / T 3142), a PDSC (dynamic oxidation test, heating rate of 10℃ / min), a copper strip corrosion tester (GB / T 5096), and a storage stability tester (GB / T 11143). The results are shown in Table 1.

[0123] Table 1 Evaluation of kinematic viscosity, viscosity index, and antioxidant properties

[0124] Note: In Table 1, "pass" in copper sheet corrosion refers to a level below 3.

[0125] Figure 9 Thermogravimetric analysis (TGA) diagram of the extreme pressure anti-wear agent prepared in Example 1; Figure 10 Thermogravimetric analysis (TGA) diagram of isobutylene sulfide in Comparative Example 1; Figure 11 The initial oxidation temperature of the heavy-duty vehicle gear oil prepared in Example 2; Figure 12 The image shows the copper corrosion of the heavy-duty vehicle gear oil prepared in Example 2. Figure 13 The image shows the copper corrosion of the heavy-duty vehicle gear oil prepared in Comparative Example 1.

[0126] From Table 1 and Figures 9-13It can be seen that the heavy-duty vehicle gear oil provided by this invention has excellent extreme pressure and anti-wear properties, as well as resistance to copper corrosion and high-temperature oxidation. The extreme pressure anti-wear agent of this invention significantly improves the oxidation and copper corrosion resistance of the oil compared to commonly used extreme pressure anti-wear agents. The star-shaped polymethyl methacrylate used in this invention improves the viscosity index of the oil much better than the linear polymethyl methacrylate viscosity index improver. The heavy-duty vehicle gear oil provided by this invention does not show significant changes in acid value and produces less sludge even after long-term high-temperature use. This indicates that the heavy-duty vehicle gear oil with the extreme pressure anti-wear agent of this invention can meet the application requirements of heavy-duty trucks, dump trucks, tractors, and special transport vehicles under heavy load and high-temperature conditions, solving problems such as lubricant oxidation, decomposition, and corrosion caused by increased acid value under high-temperature conditions.

[0127] As can be seen from the examples, the heavy-duty vehicle gear oil prepared by the extreme pressure anti-wear agent provided by the present invention has excellent high-temperature oxidation resistance, high load-bearing capacity, and is energy-saving and environmentally friendly.

[0128] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. An extreme pressure anti-wear agent having the chemical structure shown in Formula I or Formula II: Equation I; Formula II; In Formula I, R1 is an alkyl group; In Formula II, R2 is an alkyl or olefin.

2. The extreme pressure anti-wear agent according to claim 1, characterized in that, R1 is a C2-C16 alkyl group; R2 is a C1-C20 alkyl group.

3. A method for preparing the extreme pressure anti-wear agent according to claim 1 or 2, comprising the following steps: (1) Boric acid and ethanolamine are mixed and subjected to esterification to obtain borate ester; (2) The borate ester obtained in step (1) is mixed with an alkylating agent and subjected to an alkylation reaction to obtain the extreme pressure anti-wear agent of formula I; the alkylating agent is an alcohol or a haloalkane.

4. The preparation method according to claim 3, characterized in that, The temperature of the esterification reaction in step (1) and the alkylation reaction in step (2) are independently 100~130℃, and the time is independently 3~6h.

5. A method for preparing the extreme pressure anti-wear agent according to claim 1 or 2, comprising the following steps: 1) A carboxylic acid and diethanolamine are mixed and subjected to an amide reaction to obtain a first intermediate; the chemical structure of the first intermediate is shown in Formula III: Formula III; 2) The first intermediate obtained in step 1), diethanolamine, and a base are mixed and hydrolyzed to obtain a second intermediate; the chemical structure of the second intermediate is shown in Formula IV: Formula IV; 3) Mix the second intermediate obtained in step 2), boric acid, ethanolamine and solvent, and carry out esterification reaction to obtain the extreme pressure anti-wear agent of formula II.

6. The preparation method according to claim 5, characterized in that, In step 1), the temperature of the amide reaction is 130~150℃, and the reaction time is 5~7h.

7. The preparation method according to claim 5, characterized in that, In step 2), the hydrolysis temperature is 70~90℃, the hydrolysis time is 4~7h, and the hydrolysis pH value is 11~14.

8. The preparation method according to claim 5, characterized in that, In step 3), the esterification reaction temperature is 100~135℃ and the esterification reaction time is 3~8h.

9. A heavy-duty vehicle gear oil, characterized in that, The components include the following percentages by mass: Base oil 70-80% Viscosity index improver 10-24% Extreme pressure anti-wear agent 3~6% Antioxidant 1.5~3% Alkaline neutralizing agent 0.3~0.9% Antifoaming agent 0.02~0.06% Detergent dispersant 0.5~2% Metal deactivator 0.1~0.3%; The extreme pressure anti-wear agent is the extreme pressure anti-wear agent according to claim 1 or 2, or the extreme pressure anti-wear agent prepared by the preparation method according to any one of claims 3 to 8.

10. The heavy-duty vehicle gear oil according to claim 9, characterized in that, The viscosity index improver is a star-shaped polymethyl methacrylate.

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