An anti-rust agent composition with a high-activity sulfur content system for lubricating oil and its application

Abstract

The present invention relates to the field of lubricating oil technology, and in particular to a rust inhibitor composition with a high active sulfur content system for lubricating oil and its application. The rust inhibitor composition for lubricating oil comprises a rust inhibitor and an extreme pressure anti-wear agent; the acid value of the rust inhibitor is positively correlated with the active sulfur content of the extreme pressure anti-wear agent; when the active sulfur content of the extreme pressure anti-wear agent is between 5 and 10 wt%, the acid value of the rust inhibitor is between 50 and 150 mg KOH / g; when the active sulfur content of the extreme pressure anti-wear agent is between 10 and 15 wt%, the acid value of the rust inhibitor is between 150 and 250 mg KOH / g. The rust inhibitor composition of the present invention can be used in industrial gear oils with a high active sulfur content formula system, so that the gear oil has excellent resistance to moisture and heat, rust prevention, and extreme pressure anti-wear properties, as well as good resistance to oxidation and copper corrosion.

Description

Technical Field

[0001] The present invention relates to the technical field of lubricating oils, in particular to a rust inhibitor composition with a high active sulfur content system for lubricating oils and application thereof. Background Art

[0002] Rust inhibitors are commonly used components in lubricants. Appropriate dosages can improve a lubricant's corrosion resistance. Rust inhibitors are mostly polar substances, with a two-part molecular structure: a strongly polar group with hydrophilic properties at one end and a non-polar group with hydrophobic properties at the other. When a rust inhibitor comes into contact with a metal surface, its polar group adsorbs onto the metal, isolating it from the corrosive medium and preventing rust. Rust inhibitors also solubilize water and some corrosive substances, encapsulating them in micelles and dispersing or deactivating them, thereby reducing their ability to corrode the metal.

[0003] Mechanical transmission systems in industry, especially industrial gearboxes, are usually in an environment with high temperature, large impact load, high vibration intensity, high dust and high water content. Compared with other fields, they have the characteristics of heavy load, poor working environment, long working time and high temperature. In addition, the lubricating oil used in the mechanical transmission system will inevitably come into contact with water, which makes the gear surface prone to sintering caused by pressure, friction wear or rust caused by moisture and high temperature. Therefore, higher requirements are placed on the lubricating oil used in the mechanical transmission system in terms of rust prevention performance and extreme pressure and anti-wear performance. In industrial production, a large amount of energy loss and metal scrap are generated every year due to friction wear or rust, resulting in a large amount of resource waste. At the same time, when the above-mentioned mechanical transmission system is applied to coastal or offshore equipment, in addition to requiring the lubricating oil to have conventional rust prevention performance, it must also be resistant to high salt spray and high humidity environments. Therefore, it is often necessary to increase the amount of rust inhibitor to further improve the comprehensive performance of the oil product so that it meets the above-mentioned application conditions. Summary of the Invention

[0004] In order to achieve both rust prevention and extreme pressure and anti-wear performance, existing technologies currently adopt the method of adding rust inhibitors and extreme pressure and anti-wear agents simultaneously. However, since the action mechanisms of these two additives are relatively similar and both work after adsorption on the metal surface, there is competitive adsorption between the two, which affects the effects of the two additives and prevents them from fully exerting their respective properties. The above-mentioned impact is only reflected in extreme pressure and anti-wear agents with relatively low active sulfur content. This impact can be improved to a certain extent by increasing the amount of rust inhibitor used.

[0005] However, when the extreme pressure anti-wear agent is a substance with a high active sulfur content (active sulfur content is 5-15wt%, especially 10-15wt%), it is more strongly adsorbed on the metal surface, and may even cause conventional rust inhibitors that compete with the extreme pressure anti-wear agent for adsorption to be unable to function, resulting in poor anti-rust performance of the oil.

[0006] Currently, CN114426898A discloses a grease composition that combines an organic base-intercalated zirconium phosphate compound with an extreme pressure agent as the primary components of the grease additive composition. The grease exhibits excellent composite synergistic properties, particularly in terms of extreme pressure performance and stable anti-wear performance. However, this composition is applicable only to greases. Due to the differences in base oil systems and performance requirements between lubricating oils and greases, the additive ratios of the two cannot be directly transferred in actual applications. The additive formulation must also consider the stability of the lubricating grease. Direct transfer can lead to additive precipitation, thereby affecting the performance of the lubricating oil or grease.

[0007] After extensive research and development and practice, the present invention unexpectedly discovered that, with respect to the competitive adsorption of extreme pressure anti-wear agents with high active sulfur content, the acid value of the rust inhibitor has a certain correlation with the active sulfur content of the extreme pressure anti-wear agent. After verification and matching, the polarity of the rust inhibitor is slightly different from that of the extreme pressure anti-wear agent, and the competitive adsorption between the rust inhibitor and the extreme pressure anti-wear agent can be significantly reduced without introducing additional additives, thereby balancing the use of the two.

[0008] Specifically, the technical solutions of the present invention are as follows:

[0009] The present invention provides a rust inhibitor composition for lubricating oil, comprising a rust inhibitor and an extreme pressure anti-wear agent; the acid value of the rust inhibitor is positively correlated with the active sulfur content of the extreme pressure anti-wear agent;

[0010] When the active sulfur content of the extreme pressure anti-wear agent is 5-10 wt%, the acid value of the rust inhibitor is 50-150 mgKOH / g; when the active sulfur content of the extreme pressure anti-wear agent is 10-15 wt%, the acid value of the rust inhibitor is 150-250 mgKOH / g.

[0011] Preferably, in the rust inhibitor composition, the extreme pressure antiwear agent is selected from one or more of isobutylene sulfide, antimony alkylthiocarbamate, dibenzyl disulfide and thiadiazole dimer; wherein the active sulfur content of the isobutylene sulfide is 7-15wt%, the active sulfur content of the antimony alkylthiocarbamate is 5-9wt%, the active sulfur content of the dibenzyl disulfide is 5-8wt%, the active sulfur content of the thiocarbamate is 7-12wt%, and the active sulfur content of the thiadiazole dimer is 11-15wt%.

[0012] The rust preventive agent is one or more of calcium petroleum sulfonate, dodecenylsuccinic acid, dodecenylsuccinic acid half ester and liquid N-oleyl sarcosine; wherein the acid value of the calcium petroleum sulfonate is 30-55 mg KOH / g, the acid value of dodecenylsuccinic acid is 200-300 mg KOH / g, the acid value of dodecenylsuccinic acid half ester is 130-200 mg KOH / g, and the acid value of the liquid N-oleyl sarcosine is 120-180 mg KOH / g.

[0013] In the present invention, when the extreme pressure anti-wear agent has a sulfur-sulfur bond and is matched with the above-mentioned rust inhibitor, the rust inhibitor composition has moderate chemical activity, is less corrosive to copper, and has good copper component protection performance.

[0014] Preferably, in the rust inhibitor composition, the extreme pressure antiwear agent is selected from any two or more of isobutylene sulfide, antimony alkylthiocarbamate, dibenzyl disulfide and thiadiazole dimer;

[0015] The rust preventive agent is selected from any two or more of petroleum calcium sulfonate, dodecenylsuccinic acid, dodecenylsuccinic acid half ester and liquid N-oleyl sarcosine.

[0016] The present invention has found that when two or more extreme pressure anti-wear agents and rust inhibitors are used in the rust inhibitor composition, the effect is better than that of a single extreme pressure anti-wear agent and a single rust inhibitor.

[0017] As a preferred embodiment of the present invention, in the rust inhibitor composition, the extreme pressure antiwear agent is any two or three of sulfided isobutylene, thiocarbamate and thiadiazole dimer, and the rust inhibitor is dodecenylsuccinic acid and dodecenylsuccinic acid half ester;

[0018] As a preferred embodiment of the present invention, the extreme pressure anti-wear agent is antimony alkylthiocarbamate and thiocarbamate, and the rust inhibitor is calcium petroleum sulfonate and liquid N-oleyl sarcosine;

[0019] As a preferred embodiment of the present invention, the extreme pressure anti-wear agent is isobutylene sulfide and dibenzyl disulfide, and the rust inhibitor is calcium petroleum sulfonate, dodecenylsuccinic acid and dodecenylsuccinic acid half ester;

[0020] As a preferred embodiment of the present invention, the extreme pressure anti-wear agent is any two or three of antimony alkylthiocarbamate, dibenzyl disulfide and thiadiazole dimer, and the rust inhibitor is dodecenylsuccinate half ester and liquid N-oleyl sarcosine.

[0021] The present invention has found that the above-mentioned rust inhibitor composition combination can further improve the rust prevention performance of oil products in high humidity and heat environments, while achieving outstanding humidity and heat resistance, rust prevention performance and extreme pressure and anti-wear performance.

[0022] Preferably, in the rust inhibitor composition, the weight ratio of the rust inhibitor to the extreme pressure and anti-wear agent is 20:80 to 90:10; more preferably 30:70 to 70:30; further preferably 40:60 to 60:40.

[0023] The present invention further provides a method for preparing the above-mentioned rust inhibitor composition, comprising: mixing the extreme pressure anti-wear agent and the rust inhibitor at 40-55°C.

[0024] When an extreme pressure anti-wear agent has a high active sulfur content (5-15wt%, especially 10-15wt%), it is often more susceptible to oxidation than one with a lower active sulfur content. The present inventors unexpectedly discovered in subsequent research that by balancing the rust inhibitor with the sulfur-based extreme pressure anti-wear agent, the relative activity of the high-active sulfur extreme pressure anti-wear agent under high-temperature conditions can be suppressed, thereby slowing oil oxidation and imparting excellent antioxidant properties to the lubricant. This rust inhibitor composition can also function as an antioxidant, allowing its use in lubricating oils to achieve excellent oxidative stability while omitting the antioxidant.

[0025] In this regard, the present invention further provides the use of the rust inhibitor composition in anti-oxidation.

[0026] The present invention also provides a lubricating oil containing the above-mentioned rust inhibitor composition.

[0027] Preferably, the lubricating oil does not contain antioxidants.

[0028] Preferably, in the lubricating oil, the amount of the rust inhibitor composition is 0.1 to 1 wt%.

[0029] In the present invention, when the rust inhibitor composition is applied to lubricating oil, other components in the lubricating oil will not affect the normal performance of its effect. Therefore, those skilled in the art can select the selection and dosage of other additives such as base oil, thickener, pour point depressant and viscosity index improver conventional in the art as needed.

[0030] Preferably, the base oil in the lubricating oil is a refined mineral oil and / or a synthetic base oil; wherein the refined mineral oil is preferably a Class I and / or Class II hydrorefined mineral oil having a viscosity index greater than 90; and the synthetic base oil is preferably any one or a mixture of polyalphaolefin synthetic oil, polyol ester synthetic oil, and polyalkylene glycol synthetic oil.

[0031] More preferably, the base oil is a mixture of HVI 1b 400 and HVI 120BS or HVI 150BS.

[0032] Preferably, in some preferred embodiments of the present invention, the lubricating oil further contains 0 to 15 wt % of a viscosity index improver.

[0033] Preferably, in some preferred embodiments of the present invention, the lubricating oil further contains 0.1 to 1 wt % of a pour point depressant.

[0034] The present invention further provides use of the lubricating oil as a lubricating oil for a mechanical transmission system.

[0035] Preferably, the lubricating oil for the mechanical transmission system is industrial gearbox lubricating oil.

[0036] Based on the above technical solution, the beneficial effects of the present invention are:

[0037] The present invention optimizes the rust inhibitor and the extreme pressure antiwear agent by optimizing and matching the acid value of the rust inhibitor and the active sulfur content of the extreme pressure antiwear agent, which can effectively balance the competitive adsorption of the rust inhibitor and the extreme pressure antiwear agent in a high active sulfur content formulation system, and give full play to the rust prevention and extreme pressure antiwear properties. DETAILED DESCRIPTION

[0038] To make the objectives, technical solutions, and advantages of the present invention more clear, the technical solutions of the present invention are described clearly and completely below. Obviously, the embodiments described are only some of the embodiments of the present invention, not all of them. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0039] Example 1

[0040] This embodiment provides a moisture-heat resistant rust inhibitor composition suitable for a high-activity sulfur formulation system. The rust inhibitor composition is composed of the following components in percentage by weight:

[0041]

[0042] The acid value of dodecenylsuccinic acid is 250 mg KOH / g, and the acid value of dodecenylsuccinic acid half ester is 150 mg KOH / g. The active sulfur content of isobutylene sulfide is 13%, the active sulfur content of thiocarbamate is 10%, and the active sulfur content of thiadiazole dimer is 15%. The preparation process is as follows:

[0043] Mix the above substances according to the mass ratio, stir evenly at 40-55°C to obtain the product.

[0044] Example 2

[0045] This embodiment provides a moisture-heat resistant rust inhibitor composition suitable for a high-activity sulfur formulation system. The rust inhibitor composition is composed of the following components in percentage by weight:

[0046]

[0047] The acid value of the petroleum calcium sulfonate is 50 mg KOH / g, and the acid value of the liquid N-oleyl sarcosine is 140 mg KOH / g. The active sulfur content of the antimony alkylthiocarbamate is 6%, and the active sulfur content of the thiocarbamate is 10%. The preparation process is the same as in Example 1.

[0048] Example 3

[0049] This embodiment provides a moisture-heat resistant rust inhibitor composition suitable for a high-activity sulfur formulation system. The rust inhibitor composition is composed of the following components in percentage by weight:

[0050]

[0051] The acid value of calcium petroleum sulfonate is 50 mg KOH / g, the acid value of dodecenylsuccinic acid is 250 mg KOH / g, and the acid value of dodecenylsuccinic acid half ester is 150 mg KOH / g. The active sulfur content of isobutylene sulfide is 13%, and the active sulfur content of dibenzyl disulfide is 8%.

[0052] The preparation process is the same as that of Example 1.

[0053] Example 4

[0054] This embodiment provides a moisture-heat resistant rust inhibitor composition suitable for a high-activity sulfur formulation system. The rust inhibitor composition is composed of the following components in percentage by weight:

[0055]

[0056] The acid value of dodecenylsuccinic acid half ester is 150 mg KOH / g, the acid value of liquid N-oleylsarcosine is 140 mg KOH / g, the active sulfur content of thiadiazole dimer is 15%, the active sulfur content of antimony alkylthiocarbamate is 6%, and the active sulfur content of dibenzyl disulfide is 8%.

[0057] The preparation process is the same as that of Example 1.

[0058] Comparative Example 1

[0059] This comparative example provides a rust inhibitor composition, which is composed of the following components in percentage by mass:

[0060] Dodecenylsuccinic acid 50%

[0061] Sulfurized isobutylene 50%

[0062] The active sulfur content of the sulfided isobutylene is 7.5%, and the acid value of the dodecenylsuccinic acid is 250 mg KOH / g.

[0063] Comparative Example 2

[0064] This comparative example provides a rust inhibitor composition, which is composed of the following components in percentage by mass:

[0065]

[0066] The acid value of dodecenylsuccinic acid is 250 mg KOH / g, and the acid value of dodecenylsuccinic acid half ester is 150 mg KOH / g. The total sulfur content of the thiophosphate complex amine salt is 11%, and the active sulfur content is 2%. The total sulfur content of triphenyl thiophosphate is 9.45%, and the active sulfur content is 1.5%.

[0067] The preparation method is the same as that of Example 1.

[0068] Comparative Example 3

[0069] This comparative example provides a rust inhibitor composition, which is composed of the following components in percentage by mass:

[0070] Basic dinonylnaphthalenesulfonic acid 50%

[0071] Antimony alkylthiocarbamate 25%

[0072] Thiocarbamate 25%

[0073] The base value of the basic dinonylnaphthalenesulfonic acid was 45 mg KOH / g, the active sulfur content of the antimony alkylthiocarbamate was 6%, and the active sulfur content of the thiocarbamate was 10%.

[0074] The preparation method is the same as that of Example 1.

[0075] Test example

[0076] The rust inhibitor compositions and reference products of the Examples and Comparative Examples were added to a base oil mixture (containing base oil HVI 150BS, a viscosity index improver, and a pour point depressant) at a concentration of 0.5% by mass. The compositions were then tested for their wet heat resistance, rust prevention, extreme pressure and anti-wear properties, low-temperature performance, viscosity-temperature performance, oxidation stability, and corrosion resistance. The test results for the Examples, Reference Products, and Comparative Examples are shown in Tables 2 and 4, respectively.

[0077] The damp heat resistance assessment method follows GB / T 2361, the rust-inhibiting grease damp heat test method. The specific procedure is as follows: Pour 500mL of the shaken sample into a beaker, remove any surface bubbles, and adjust the temperature to 23±3°C. Use a hook to vertically immerse the specimen in the sample for 1 minute. Then, lift it at a speed of approximately 100mm / min and hang it on a rack. The specimen is then allowed to dry for 24 hours in a clean, dry area with a relative humidity below 70%, a temperature of 23±3°C, and no direct sunlight or ventilation. The damp heat test chamber is then started. Once the test conditions are met, the coated specimen is hung from the specimen rack using a hook. Stainless steel sheets should be hung in the hook slots not used for specimens. The test is then run continuously for the specified test duration. The damp heat test chamber is opened for inspection every 24 hours. The specimens are removed as specified and replaced with an equal number of stainless steel sheets. The removed specimens are rinsed with water and blown dry with hot air. The oil film is then cleaned with solvent oil for the rubber industry and finally blown dry with hot air. Use the side of the test piece facing the rotation direction of the test piece holder as the evaluation surface and evaluate according to the degree of rust.

[0078] Table 1

[0079]

[0080] Table 2

[0081]

[0082] The results in Table 2 demonstrate that lubricating oils incorporating the compositions of Examples 1-4 exhibit excellent resistance to moisture and heat, rust and corrosion, extreme pressure and anti-wear properties, and excellent oxidation stability. When used in industrial gearbox lubricants formulated with high-active sulfur, these lubricants effectively protect gear surfaces, reducing sintering, frictional wear, and corrosion.

[0083] Table 3

[0084]

[0085]

[0086] Table 4

[0087]

[0088]

[0089] The results in Table 4 show that if the rust inhibitor and extreme pressure anti-wear agent are not properly selected, the prepared gear oil cannot have good rust prevention and extreme pressure anti-wear properties at the same time, and cannot meet the working conditions of industrial gear oil.

[0090] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit it. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that they can still modify the technical solutions described in the aforementioned embodiments, or make equivalent replacements for some of the technical features therein. However, these modifications or replacements do not deviate the essence of the corresponding technical solutions from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. Application of a rust inhibitor composition for lubricating oil in anti-oxidation, characterized in that: The rust inhibitor composition for lubricating oil comprises a rust inhibitor and an extreme pressure anti-wear agent; wherein the acid value of the rust inhibitor is positively correlated with the active sulfur content of the extreme pressure anti-wear agent; When the active sulfur content of the extreme pressure anti-wear agent is 5-10wt%, the acid value of the rust inhibitor is 50-150 mg KOH / g; when the active sulfur content of the extreme pressure anti-wear agent is 10-15wt%, the acid value of the rust inhibitor is 150-250 mg KOH / g.

2. The use of the rust inhibitor composition for lubricating oil in anti-oxidation according to claim 1, characterized in that: The extreme pressure anti-wear agent is selected from one or more of thiocarbamate, isobutylene sulfide, antimony alkylthiocarbamate, dibenzyl disulfide and thiadiazole dimer; The active sulfur content of the isobutylene sulfide is 7-15 wt %, the active sulfur content of the antimony alkylthiocarbamate is 5-9 wt %, the active sulfur content of the dibenzyl disulfide is 5-8 wt %, the active sulfur content of the thiocarbamate is 7-12 wt %, and the active sulfur content of the thiadiazole dimer is 11-15 wt %. The rust inhibitor is selected from one or more of petroleum calcium sulfonate, dodecenylsuccinic acid, dodecenylsuccinic acid half ester and liquid N-oleyl sarcosine; The acid value of the calcium petroleum sulfonate is 30-55 mg KOH / g, the acid value of dodecenylsuccinic acid is 200-300 mg KOH / g, the acid value of dodecenylsuccinic acid half ester is 130-200 mg KOH / g, and the acid value of liquid N-oleylsarcosine is 120-180 mg KOH / g.

3. The use of the rust inhibitor composition for lubricating oil in anti-oxidation according to claim 2, characterized in that: In the rust inhibitor composition, the extreme pressure antiwear agent is selected from any two or more of thiocarbamate, isobutylene sulfide, antimony alkylthiocarbamate, dibenzyl disulfide and thiadiazole dimer; The rust preventive agent is selected from any two or more of petroleum calcium sulfonate, dodecenylsuccinic acid, dodecenylsuccinic acid half ester and liquid N-oleyl sarcosine.

4. Use of the rust inhibitor composition for lubricating oil according to any one of claims 1 to 3 in anti-oxidation, characterized in that: In the rust inhibitor composition, the extreme pressure anti-wear agent is any two or three of sulfided isobutylene, thiocarbamate and thiadiazole dimer, and the rust inhibitor is dodecenylsuccinic acid and dodecenylsuccinic acid half ester; Alternatively, the extreme pressure anti-wear agent is antimony alkylthiocarbamate and thiocarbamate, and the rust inhibitor is calcium petroleum sulfonate and liquid N-oleyl sarcosine; Alternatively, the extreme pressure anti-wear agent is isobutylene sulfide and dibenzyl disulfide, and the rust inhibitor is calcium petroleum sulfonate, dodecenylsuccinic acid, and dodecenylsuccinic acid half ester; Alternatively, the extreme pressure anti-wear agent is any two or three of antimony alkylthiocarbamate, dibenzyl disulfide and thiadiazole dimer, and the rust inhibitor is dodecenylsuccinate half ester and liquid N-oleyl sarcosine.

5. Use of the rust inhibitor composition for lubricating oil according to any one of claims 1 to 3 in anti-oxidation, characterized in that: In the rust inhibitor composition, the weight ratio of the rust inhibitor to the extreme pressure antiwear agent is 20:80 to 90:

10.

6. Use of the rust inhibitor composition for lubricating oil in anti-oxidation according to claim 5, characterized in that: In the rust inhibitor composition, the weight ratio of the rust inhibitor to the extreme pressure anti-wear agent is 30:70 to 70:

30.

7. Use of the rust inhibitor composition for lubricating oil according to any one of claims 1 to 3 in anti-oxidation, characterized in that: The amount of the rust inhibitor composition in the lubricating oil is 0.1-1 wt %.

8. Use of the rust inhibitor composition for lubricating oil according to any one of claims 1 to 3 in anti-oxidation, characterized in that: In the lubricating oil, the base oil is refined mineral oil and / or synthetic base oil.

9. Use of the rust inhibitor composition for lubricating oil in anti-oxidation according to claim 8, characterized in that: The refined mineral oil is a Class I and / or Class II hydrorefined mineral oil with a viscosity index greater than 90; the synthetic base oil is any one of polyalphaolefin synthetic oil, polyol ester synthetic oil, and polyalkylene glycol synthetic oil, or a mixture of several of them.

10. Use of the rust inhibitor composition for lubricating oil in anti-oxidation according to claim 8, wherein the base oil is a mixture of HVI 1b 400 and HVI 120BS or HVI 150BS.

Images