Extreme pressure anti-wear agent, extreme pressure anti-wear agent preparation method and cross-axle universal joint grease containing the agent

Abstract

The invention relates to the technical field of extreme pressure anti-wear agents, in particular to an extreme pressure anti-wear agent, a method for preparing the extreme pressure anti-wear agent and a cross-axle universal joint grease containing the agent. The invention uses a phosphite ester and cyanuric acid and its derivatives under weak base catalysis to carry out an ester exchange reaction to generate a partially monosubstituted or partially disubstituted phosphite extreme pressure and anti-wear additive, which is prepared in a cross-axle universal joint grease. Since a nitrogen-containing aromatic structure is introduced into the molecule, the adsorption and film-forming ability of the phosphite ester is enhanced, thereby improving the extreme pressure and anti-wear properties of the grease. At the same time, a longer atomic group is introduced into the molecule, so that the acidity of the phosphite ester is reduced, thereby improving the problem of severe corrosion.

Description

Technical Field

[0001] The invention relates to the technical field of extreme pressure anti-wear agents, and in particular to an extreme pressure anti-wear agent, a method for preparing the extreme pressure anti-wear agent, and a cross-axle universal joint grease containing the agent. Background Art

[0002] With the implementation of the country's "dual carbon" policy, the requirements for lubricants are getting higher and higher. Grease products need to make efforts in product research and development, application, service and other fields, actively fulfill corporate social responsibility, and provide more efficient, more environmentally friendly, and longer-life lubricant products and solutions in traditional fields, reduce material consumption and energy consumption, and reduce emissions.

[0003] The cross-shaft universal joint bearing gear device of the automobile is subjected to large torque and alternating load during operation. Its damage forms are mainly wear of the cross-shaft journal and needle bearing, indentation and peeling of the cross-shaft journal and the working surface of the needle bearing bowl. At present, the cross-shaft universal joint bearing gear of the automobile has been running for a long time under heavy load, the oil film is gradually lost, the gear is seriously worn, and the grease deteriorates and evaporates to form a hard soap, which does not provide lubrication itself and also hinders the rolling of the needle roller.

[0004] At present, the extreme pressure and anti-wear agents added to the cross-axle universal joint grease of vehicles are mainly sulfur-containing additives (sulfurized olefins, polysulfides), nano-extreme pressure anti-wear agents, and phosphorus-containing additives. The types of phosphorus-containing additives mainly include phosphites, phosphates, phosphite ammonium salts, phosphate ammonium salts, thiophosphates, and thiophosphate ammonium salts. Due to the differences in their respective properties, their formulations and applications are also very different. Phosphites have good extreme pressure and anti-wear properties, but they are highly acidic and have a strong corrosive effect on friction pairs. They achieve higher extreme pressure and anti-wear properties by self-sacrifice and corrosive chemical reactions with the friction pair surface to form a chemical reaction film. Through amination and sulfurization, the extreme pressure and anti-wear properties of phosphites or phosphates will be more or less reduced.

[0005] At present, many domestic companies are also researching phosphorus-containing agents, and there are also some patent reports: Chinese invention patent, publication number CN111057107A reports a phosphonothioate compound and a preparation method thereof, the method is to epoxidize phosphonothioate phenol ester with an epoxy compound, and during the reaction, the catalyst used is a strongly acidic inorganic acid, which has high requirements on equipment.

[0006] Chinese invention patent, publication number CN115109090A reports a sulfur-phosphorus-nitrogen type extreme pressure anti-wear agent and its preparation method and application. The method uses dialkyl dithiophosphoric acid and cyanuric chloride as raw materials, and the acid binding agent selected is mainly a strong base, such as sodium hydroxide and potassium carbonate, which has relatively high requirements for reaction equipment and post-treatment; there are also some sulfur-phosphorus-nitrogen type additives, which are mainly prepared by introducing elements such as sulfur and nitrogen to improve their anti-wear performance and multifunctionality. Summary of the invention

[0007] In view of the serious corrosion problem of phosphites as extreme pressure anti-wear agents and the urgent need for high-temperature, long-life and high-load-bearing capacity additives in the rapid development of the automobile industry, the present invention provides an extreme pressure anti-wear agent, a method for preparing the extreme pressure anti-wear agent and a cross-axis universal joint grease containing the agent. The present invention mainly introduces aromatic heterocycles into phosphites to reduce their acidity, and adds them as extreme pressure anti-wear agents to cross-axis universal joint grease, thereby improving the serious corrosion problem of existing greases; at the same time, the aromatic heterocycles have a strong adsorption effect and can effectively improve the extreme pressure and anti-wear properties of phosphites; at the same time, they are applied to cross-axis universal joints to improve their extreme pressure and anti-wear properties, thereby reducing environmental pollution and harm to humans.

[0008] In a first aspect, the present invention provides an extreme pressure anti-wear agent, wherein the general structural formula of the extreme pressure anti-wear agent is as shown in (I) and (II):

[0009]

[0010] Wherein, in the general formula (I), the group R1 is selected from C1-C 12 An alkyl group, preferably C1, C2, C4, C8;

[0011] R2 and R3 can be the same or different, and R2 and R3 are selected from C0-C 22 An alkyl or unsaturated olefin group;

[0012] The extreme pressure anti-wear agent is produced by the reaction of two reactant raw materials, including a first reactant raw material and a second reactant raw material, wherein the general structural formula of the first reactant raw material is shown in (III):

[0013]

[0014] The general structural formula of the second reactant raw material is shown in (IV):

[0015]

[0016] In a second aspect, the present invention provides a method for preparing an extreme pressure anti-wear agent, using the first reactant raw material and the second reactant raw material as reactants to carry out an ester exchange reaction to obtain a first product, and the general reaction formula is:

[0017]

[0018] Wherein, the catalyst is an alkaline catalyst, the reaction temperature of the transesterification reaction is 110-140° C., and the reaction time is 1-6 hours.

[0019] Preferably, the first reactant raw material is one or more of dimethyl phosphite, diethyl phosphite, di-n-butyl phosphite, diisobutyl phosphite, di-n-octyl phosphite and diisooctyl phosphite.

[0020] Further, R2 and R3 are the same, and the second reactant raw material is one or more of cyanuric acid, diallyl cyanurate, cyanuric acid dioleate, cyanuric acid distearate, cyanuric acid dipalmitate, and cyanuric acid diacetate;

[0021] Further, R2 and R3 are different, and the second reactant raw material is one or more of cyanuric acid monoacetate, cyanuric acid monooleate, cyanuric acid monostearate, cyanuric acid monopalmitate, cyanuric acid acetic oleate, cyanuric acid acetic stearate, and cyanuric acid acetic palmitate.

[0022] Furthermore, the catalyst is an alkaline catalyst, the reaction temperature of the transesterification reaction is 110-140° C., and the reaction time is 1-6 h.

[0023] Preferably, the alkaline catalyst is one or more of high base sulfonate, alkaline alkylphenol, NaHCO3, ethanolamine, sodium acetate, thiadiazole and its derivatives, benzotriazole and its derivatives.

[0024] Preferably, the reaction temperature of the transesterification reaction is 120°C.

[0025] Preferably, the reaction time of the transesterification reaction is 3-4 h.

[0026] Furthermore, after the ester exchange reaction is completed, the first product is subjected to reduced pressure distillation and extraction to obtain an extreme pressure anti-wear agent, wherein the reduced pressure distillation conditions are: temperature 110-120°C, vacuum degree 0.01-0.09 mmHg; the extraction solvent is methanol, ethanol, dichloromethane, benzene, toluene, petroleum ether, N,N-dimethylformamide.

[0027] A cross-axis universal joint grease, measured by weight percentage, comprising

[0028]

[0029] The base oil is a type II hydrogenated base oil;

[0030] The extreme pressure anti-wear agent is the extreme pressure anti-wear agent mentioned above or is prepared based on the preparation method of the extreme pressure anti-wear agent mentioned above;

[0031] The corrosion inhibitors are low-base sulfonates, salicylates, benzotriazoles and thiadiazoles.

[0032] The beneficial effects of the present invention are:

[0033] 1. The extreme pressure anti-wear agent provided by the present invention is an extreme pressure anti-wear agent of a new structure. Compared with the existing commonly used extreme pressure anti-wear agents, it has less corrosiveness, high load-bearing capacity, good extreme pressure and anti-wear performance, and as an extreme pressure anti-wear additive used in grease, the required addition amount is relatively low, which is 0.1%-1%. Applying it in cross-axis universal joint grease can greatly improve its extreme pressure and anti-wear performance, and at the same time, it makes it possible to improve the extreme pressure and anti-wear performance of the cross-axis universal joint grease without adding extreme pressure anti-wear additives that cause serious environmental pollution, thereby reducing environmental pollution and harm to people.

[0034] 2. The extreme pressure and anti-wear agent preparation method provided by the present invention utilizes phosphite and cyanuric acid and its derivatives to prepare phosphorus-containing heterocyclic compounds through ester exchange reaction. The compound has a novel structure and excellent extreme pressure and anti-wear properties. By adding a small dose of the additive, the effect of ordinary commercially available phosphorus-containing agents can be achieved. The method mainly reduces the acidity of phosphite by introducing aromatic heterocycles into the phosphite. At the same time, since the aromatic heterocycles have a strong adsorption effect, the extreme pressure and anti-wear properties of the phosphite can be effectively improved. Compared with the existing extreme pressure and anti-wear agent preparation method, the extreme pressure and anti-wear agent preparation method of the present invention is simple and has low equipment requirements.

[0035] 3. The cross-axle universal joint grease provided by the present invention and containing the extreme pressure anti-wear agent of the present invention has good extreme pressure and anti-wear properties, can still maintain the structural state of phosphorus at high temperatures, and can maintain the structure of the phosphorus-containing agent for a long time, so that the phosphorus release cycle is long and has durability; and because the nitrogen-containing aromatic structure is introduced into the extreme pressure anti-wear agent molecule, its adsorption and film-forming ability is enhanced, thereby improving the extreme pressure and anti-wear properties of the grease. At the same time, longer atomic groups are introduced into its molecules, so that the acidity of the phosphite is reduced, thereby improving the serious corrosion problem of the grease. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 This is the nuclear magnetic resonance phosphorus spectrum of the extreme pressure antiwear agent prepared in Example 1 of the present invention;

[0037] Figure 2 This is the nuclear magnetic resonance phosphorus spectrum of the extreme pressure antiwear agent prepared in Example 2 of the present invention;

[0038] Figure 3 This is the nuclear magnetic resonance phosphorus spectrum of the extreme pressure antiwear agent prepared in Example 3 of the present invention;

[0039] Figure 4 This is the nuclear magnetic resonance phosphorus spectrum of the extreme pressure antiwear agent prepared in Example 4 of the present invention;

[0040] Figure 5 This is the nuclear magnetic resonance phosphorus spectrum of the extreme pressure antiwear agent prepared in Example 5 of the present invention;

[0041] Figure 6 It is the nuclear magnetic resonance phosphorus spectrum of the existing extreme pressure anti-wear agent di-n-butyl phosphite;

[0042] Figure 7 This is a graph of extreme pressure and friction coefficient measured by using a fretting friction and wear tester (SRV) for the existing extreme pressure anti-wear agent di-n-butyl phosphite;

[0043] Figure 8 This is a graph of extreme pressure and friction coefficient of the extreme pressure antiwear agent prepared in Example 1 of the present invention measured by a fretting friction and wear tester (SRV); DETAILED DESCRIPTION

[0044] In order to deepen the understanding of the present invention, the present invention will be further described in detail below in conjunction with examples. The examples are only used to explain the present invention and do not constitute a limitation on the protection scope of the present invention.

[0045] Example 1

[0046] S1. In a reactor equipped with stirring, condensing and water separation devices, 19.4 g of di-n-butyl phosphite, 0.39 g of high base calcium sulfonate, and 12.91 g of cyanuric acid were added, and the temperature was raised to 120 ° C and refluxed for 3 h for transesterification reaction to obtain a first product;

[0047] S2. The first product is subjected to reduced pressure distillation to remove the n-butanol produced by the reaction; 100 ml of methanol is added to dissolve the solid product obtained by the reaction, the insoluble matter is filtered out, and the methanol is removed to obtain an extreme pressure anti-wear agent.

[0048] S3. The extreme pressure anti-wear agent prepared above was added to the prepared cross-shaft universal joint grease at a dosage of 0.3% for performance analysis; the extreme pressure anti-wear agent sample prepared in Example 1 was subjected to nuclear magnetic resonance analysis to obtain Figure 1 .

[0049] Example 2

[0050] S1. In a reactor equipped with stirring, condensing and water separation devices, 13.81 g of diethyl phosphite, 0.39 g of calcium alkylphenol, 21.02 g of diallyl cyanurate were added, and the temperature was raised to 120 ° C and refluxed for 3 h for transesterification to obtain a first product;

[0051] S2. The first product is subjected to reduced pressure distillation to remove the ethanol produced by the reaction; 100 ml of ethanol is added to dissolve the solid product obtained by the reaction, the insoluble matter is filtered out, and the methanol is removed to obtain an extreme pressure anti-wear agent.

[0052] S3. The extreme pressure anti-wear agent prepared above was added to the cross-shaft universal joint grease prepared at a dosage of 0.3% for performance analysis; the extreme pressure anti-wear agent sample prepared in Example 2 was subjected to nuclear magnetic resonance analysis to obtain Figure 2 .

[0053] Example 3

[0054] S1. In a reactor equipped with stirring, condensing and water separation devices, 30.54 g of diisooctyl phosphite, 0.39 g of calcium alkylphenol, 25.22 g of cyanuric acid monoacetate were added, and the temperature was raised to 120 ° C and refluxed for 3 h for transesterification reaction to obtain a first product;

[0055] S2. The first product is subjected to reduced pressure distillation to remove isooctyl alcohol produced by the reaction; 100 ml of ethanol is added to dissolve the solid product obtained by the reaction, the insoluble matter is filtered out, and the ethanol is removed to obtain an extreme pressure anti-wear agent.

[0056] S3. The extreme pressure anti-wear agent prepared above was added to the prepared cross-shaft universal joint grease at a dosage of 0.3% for performance analysis; the extreme pressure anti-wear agent sample prepared in Example 3 was subjected to nuclear magnetic resonance analysis to obtain Figure 3 .

[0057] Example 4

[0058] S1. In a reactor equipped with stirring, condensing and water separation devices, 19.4 g of di-n-butyl phosphite, 0.39 g of NaHCO3 and 12.91 g of cyanuric acid were added, and the temperature was raised to 120 ° C and refluxed for 3 h for transesterification to obtain a first product;

[0059] S2. The first product is subjected to reduced pressure distillation to remove the n-butanol produced by the reaction; 100 ml of methanol is added to dissolve the solid product obtained by the reaction, the insoluble matter is filtered out, and the methanol is removed to obtain an extreme pressure anti-wear agent.

[0060] S3. The extreme pressure anti-wear agent prepared above was added to the cross-shaft universal joint grease prepared at a dosage of 0.3% for performance analysis; the extreme pressure anti-wear agent sample prepared in Example 4 was subjected to nuclear magnetic resonance analysis to obtain Figure 4 .

[0061] Example 5

[0062] S1. In a reactor equipped with stirring, condensing and water separation devices, 13.81 g of diethyl phosphite, 0.39 g of alkylphenol calcium, 93.59 g of cyanuric acid dioleate were added, and the temperature was raised to 120 ° C and refluxed for 3 h for transesterification to obtain a first product;

[0063] S2. The first product is subjected to vacuum distillation to remove the ethanol produced by the reaction; 100 ml of toluene is added to dissolve the solid product obtained by the reaction, the insoluble matter is filtered, and the toluene is removed to obtain an extreme pressure anti-wear agent.

[0064] S3. The extreme pressure anti-wear agent prepared above was added to the cross-shaft universal joint grease prepared at a dosage of 0.3% for performance analysis; the extreme pressure anti-wear agent sample prepared in Example 5 was subjected to nuclear magnetic resonance analysis to obtain Figure 5 .

[0065] Comparative Example 1

[0066] The performance of the prepared cross-axle universal joint grease was analyzed by adding di-n-butyl phosphite at a dosage of 2%. The di-n-butyl phosphite sample was analyzed by nuclear magnetic resonance to obtain Figure 6 .

[0067] Comparative Example 2

[0068] Diethyl phosphite was added into the prepared cross-axle universal joint grease at a dosage of 2% for performance analysis.

[0069] The copper sheet corrosion of the above extreme pressure anti-wear agent and the extreme pressure and anti-wear performance test of the above cross shaft universal joint grease (extreme pressure performance: four-ball test (GB / T3142); anti-wear performance: anti-wear performance (SH / T 0204)), the results are shown in Table 1:

[0070]

[0071] Table 1 Analysis of copper sheet corrosion, extreme pressure and anti-wear performance

[0072] From the analysis of Table 1, it can be seen that the cross-axle universal joint grease containing the extreme pressure anti-wear agent of the present invention has excellent extreme pressure and anti-wear properties; the extreme pressure anti-wear agent of the present invention has greatly improved corrosion resistance compared with the existing commonly used di-n-butyl phosphite extreme pressure and anti-wear agent; the extreme pressure anti-wear agent prepared in Example 5 of the present invention has the smallest wear spot diameter and the best anti-wear property. It can be seen that the introduction of long-chain carboxylic acid in the preparation of the extreme pressure anti-wear agent of the present invention can make its anti-wear property more obvious; in addition, from the analysis of Tables 1, Figure 1-Figure 6It can be seen that the extreme pressure anti-wear agent prepared by the present invention is used in the cross-axis universal joint for a long time at high temperature, and the structural state of phosphorus is maintained for a longer time than that of di-n-butyl phosphite; the extreme pressure and friction coefficient of the existing extreme pressure anti-wear agent di-n-butyl phosphite are measured using a fretting friction and wear tester (SRV), and the results are as follows: Figure 7 ; Figure 7 It can be seen that when the existing extreme pressure anti-wear agent di-n-butyl phosphite is used to measure the extreme pressure and friction coefficient using a fretting friction and wear tester (SRV), the load applied when cold welding occurs on the friction pair does not exceed 1000N; the extreme pressure anti-wear agent prepared in Example 1 of the present invention is used to measure the extreme pressure and friction coefficient using a fretting friction and wear tester (SRV), and the results are as follows: Figure 8 , Figure 7 It can be seen that when the extreme pressure and friction coefficient are measured by the fretting friction and wear tester (SRV) in Example 1 of the present invention, cold welding still does not occur when the load applied to the friction pair is 2000N; Figure 7 , Figure 8 It can be seen that the extreme pressure and anti-wear properties of the extreme pressure anti-wear agent prepared in Example 1 of the present invention are far superior to those of the existing extreme pressure anti-wear agent di-n-butyl phosphite.

[0073] The above shows and describes the basic principles, main features and advantages of the present invention. It should be understood by those skilled in the art that the present invention is not limited to the above embodiments. The above embodiments and descriptions are only for explaining the principles of the present invention. Without departing from the spirit and scope of the present invention, the present invention may have various changes and improvements, which fall within the scope of the present invention. The scope of protection of the present invention is defined by the attached claims and their equivalents.

Claims

1. An extreme pressure anti-wear agent, characterized in that: The extreme pressure anti-wear agent is composed of compounds with the general structural formulas (I) and (II): The extreme pressure anti-wear agent is produced by reacting two reactant raw materials, including a first reactant raw material and a second reactant raw material. Raw materials, the general structural formula of the first reactant raw material is shown as (III): The general structural formula of the second reactant raw material is shown in (IV): Wherein, in the general formula (I), (II), (III) and (IV), the group R1 is selected from C1-C 12 R2 and R3 may be the same or different, and R2 and R3 are selected from C0-C 22 Alkyl groups or C0-C 22 An unsaturated olefin group of C0, and is not an alkyl group of C0 or an unsaturated olefin group of C0.

2. The extreme pressure anti-wear agent according to claim 1, characterized in that: The first reactant raw material is one or more of dimethyl phosphite, diethyl phosphite, di-n-butyl phosphite, diisobutyl phosphite, di-n-octyl phosphite and diisooctyl phosphite.

3. An extreme pressure anti-wear agent, characterized in that: The extreme pressure anti-wear agent is composed of compounds with the general structural formulas (I) and (II): The extreme pressure anti-wear agent is produced by reacting two reactant raw materials, including a first reactant raw material and a second reactant raw material. Raw materials, the general structural formula of the first reactant raw material is shown as (III): The general structural formula of the second reactant raw material is shown in (IV): Wherein, in the general formula (I), (II), (III) and (IV), the group R1 is selected from C1-C 12 R2, R3 are consistent with the second reactant raw material structure, and the second reactant raw material is one or more of cyanuric acid and diallyl cyanurate.

4. A method for preparing an extreme pressure anti-wear agent, characterized in that: The first reactant raw material and the second reactant raw material according to claim 1 are used as reactants to carry out an ester exchange reaction to obtain a first product, and the general reaction formula is: Wherein, the catalyst is an alkaline catalyst, the reaction temperature of the transesterification reaction is 110-140° C., and the reaction time is 1-6 hours.

5. The preparation method according to claim 4, characterized in that: The alkaline catalyst is one or more of high base sulfonate, alkaline alkylphenol, NaHCO3, ethanolamine, sodium acetate, thiadiazole, and benzotriazole.

6. The preparation method according to claim 4, characterized in that: The reaction temperature of the transesterification reaction is 120°C.

7. The preparation method according to claim 4, characterized in that: The reaction time of the transesterification reaction is 3-4h.

8. The preparation method according to claim 4, characterized in that: After the ester exchange reaction is completed, the first product is subjected to reduced pressure distillation and extraction to obtain an extreme pressure anti-wear agent, wherein the reduced pressure distillation conditions are: temperature 110-120°C, vacuum degree 0.01-0.09 mmHg; the extraction solvent is one or more of methanol, ethanol, dichloromethane, benzene, toluene, petroleum ether, N, N-dimethylformamide.

9. A cross-axis universal joint grease, characterized in that: In terms of weight percentage, including The base oil is a type II hydrogenated base oil; The extreme pressure anti-wear agent is any one of the extreme pressure anti-wear agents in claims 1-3 or is prepared by the preparation method of any one of the extreme pressure anti-wear agents in claims 4-8; the corrosion inhibitor is low-base sulfonates, salicylates, benzotriazoles and thiadiazoles.

Images