Iron oleate lubricating oil additive composition and application thereof in anti-wear lubrication

Abstract

The invention discloses an iron oleate lubricating oil additive composition and an application of the iron oleate lubricating oil additive composition in anti-wear lubrication. The composition comprises 5-30 parts of iron oleate; 60 to 100 parts of fatty acid ester; 1-10 parts of a dispersant; 1-3 parts of an antioxidant; the ferric oleate forms a chemical adsorption protective film on the metal surface through a polar group of the ferric oleate, so that the wear resistance is remarkably improved, and the dispersing agent is fatty acid polyamide; the antioxidant is an amine antioxidant; the composition disclosed by the invention is completely free of harmful elements such as zinc, phosphorus and sulfur, and has excellent environmental protection property and wear resistance; the additive disclosed by the invention shows good dispersion stability and thermal oxidation stability in lubricating oil, and is free from precipitation after long-term storage; the diameter of four-ball test wear scars can be reduced by 30-50% by adding 5% of lubricating oil of the composition; the lubricating oil can be widely applied to the industrial lubrication fields of engine oil, gear oil, hydraulic oil and the like, is particularly suitable for a new energy automobile ash-free lubrication system, and has remarkable economic benefits and environmental protection values.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of lubricating oil additives, in particular to a ferric oleate lubricating oil additive composition and its application in anti-wear lubrication. BACKGROUND

[0002] In the field of lubricating oil additives, anti-wear and extreme pressure performance are the key to ensuring the long-term stable operation of mechanical equipment. For a long time, zinc dialkyldithiophosphate (ZDDP) has been the most widely used anti-wear additive due to its excellent anti-wear, antioxidant and corrosion inhibition performance, and has dominated the engine oil, gear oil and hydraulic oil market. However, with the increasing strictness of environmental regulations and the development of new energy power systems, the shortcomings of traditional ZDDP additive systems have become increasingly prominent, mainly including the following aspects: ZDDP contains elements such as phosphorus, sulfur and zinc, which can cause serious harm to the environment during combustion or emission: phosphorus can cause poisoning of the automobile three-way catalytic converter (TWC), reducing the efficiency of exhaust treatment and affecting emission compliance; sulfur generates SOx after combustion, which not only pollutes the atmosphere but also accelerates the corrosion of engine parts; zinc may form ash deposits at high temperatures, affecting the service life of the particulate filter (GPF / DPF).

[0003] Due to the above problems, major emission regulations around the world have gradually restricted the use of ZDDP, especially in passenger car engine oil, where the phosphorus content is strictly controlled. Insufficient high-temperature stability, ZDDP is prone to decomposition at high temperatures (> 120℃), leading to failure of the anti-wear film and a decrease in boundary lubrication performance; oxidation products (such as sulfates and phosphates) accelerate the formation of sludge, affecting the cleanliness of lubricating oil. And ZDDP is a high-ash additive (Sulfated Ash, ≤1.0wt%), which can form deposits inside the engine after high-temperature combustion, affecting the long-term reliability of modern high-power density engines (such as turbocharged and direct injection engine types). There are also problems with compatibility with new energy lubrication systems: with the popularity of pure electric (BEV) and hybrid (HEV / PHEV) vehicles, traditional ZDDP systems face new challenges: electric motor bearings and reduction gears require low electrical conductivity and ash-free lubrication solutions, while the electrical conductivity and ash residue of ZDDP can affect the safety of electrical systems. The working temperature range of new energy vehicle lubrication systems is wider (-40℃~150℃), and ZDDP cannot simultaneously ensure solubility at low temperatures and stability at high temperatures. Currently, the technologies that attempt to replace ZDDP on the market mainly include: organic molybdenum compounds (such as molybdenum dithiocarbamate): although they have friction-reducing effects, they contain sulfur and are expensive; borate esters: high-temperature anti-wear performance is insufficient and they are prone to hydrolysis; ashless anti-wear agents (such as phosphates): still contain phosphorus and cannot completely solve the problem of catalyst poisoning.

[0004] Therefore, aiming at the above problems, the application provides an iron oleate lubricating oil additive composition and application thereof in anti-wear lubrication, which can replace traditional phosphorus-containing zinc anti-wear additives, has good metal surface protection ability, shear stability and thermal oxidation stability under the premise of ensuring lubrication performance, and is suitable for engine oil, hydraulic oil, gear oil and the like. SUMMARY

[0005] The application aims to provide an iron oleate lubricating oil additive composition and application thereof in anti-wear lubrication, so as to replace traditional phosphorus-containing zinc anti-wear additives and have good metal surface protection ability, shear stability and thermal oxidation stability under the premise of ensuring lubrication performance.

[0006] The application achieves the above-mentioned purpose by the following technical scheme.

[0007] An iron oleate lubricating oil additive composition comprises the following components in parts by mass:

[0008] Iron oleate 5-30 parts;

[0009] Fatty acid ester 60-100 parts;

[0010] Dispersant 1-10 parts;

[0011] Antioxidant 1-3 parts.

[0012] Preferably, the fatty acid ester is at least one selected from monobasic fatty acid ester, dibasic fatty acid ester or polyhydric alcohol fatty acid ester, the monobasic fatty acid ester is at least one selected from methyl nonanoate, ethyl nonanoate and isopropyl decanoate, the dibasic fatty acid ester is at least one selected from diethyl sebacate, diisooctyl sebacate and dibutyl adipate, and the polyhydric alcohol fatty acid ester is at least one selected from trimethylolpropane oleate, pentaerythritol oleate and pentaerythritol tetranonanoate.

[0013] Preferably, the dispersant is a fatty acid polyamide dispersant with a molecular weight of 1000-5000 g / mol, and the fatty acid polyamide dispersant is one or more selected from oleic acid tetraethylene pentaamine polyamide, tall oil acid triethylene tetramine polyamide and stearic acid pentaethylene hexamine polyamide.

[0014] Preferably, the antioxidant is an amine antioxidant, the amine antioxidant is alkylated diphenylamine or a phenyl-alpha-naphthylamine compound, the alkylated diphenylamine is one or more selected from diisooctyl diphenylamine, nonyl diphenylamine and p,p'-diisopropylphenyl diphenylamine, and the phenyl-alpha-naphthylamine is one or more selected from N-phenyl-1-naphthylamine and N-phenyl-2-naphthylamine.

[0015] Preferably, the iron content of the iron oleate is 5-8%, which forms a stable colloidal dispersion system in the composition without precipitation for 6 months at room temperature.

[0016] The application also claims a lubricating oil comprising a base oil and the above-mentioned iron oleate lubricating oil additive composition, wherein the additive amount of the iron oleate lubricating oil additive composition is 1-10% of the total mass of the lubricating oil, and the base oil is at least one of PAO, mineral oil or synthetic ester.

[0017] The application also claims the application of the above-mentioned iron oleate lubricating oil additive composition in anti-wear lubrication, which is used in engine oil, gear oil, hydraulic oil or lubricating grease, and a dense protective film is formed by the chemical adsorption of iron oleate on the metal surface under boundary lubrication conditions, so that the friction coefficient is reduced by 20-40% and the wear scar diameter is reduced by 30-50%.

[0018] Preferably, the additive composition is particularly suitable for ash-free lubrication system of new energy automobile drive motor bearing and reducer gear, and still maintains stable anti-wear performance under high temperature (150℃) and high load (≥3.5GPa) conditions.

[0019] The application also claims a preparation method of the above-mentioned iron oleate lubricating oil additive composition, comprising the following steps:

[0020] (1) adding iron oleate into fatty acid ester at 50-70℃, and mechanically stirring for 30-60 minutes until completely dissolved;

[0021] (2) adding dispersant and antioxidant, and continuing to stir for 1-2 hours to form a uniform brown-red transparent liquid;

[0022] (3) filtering through a 0.5-1.0μm filter, and storing for observation for 1 month without delamination or precipitation, so that the iron oleate lubricating oil additive composition is obtained.

[0023] Preferably, in step (1), ultrasonic auxiliary dispersion treatment is adopted, the ultrasonic power is 200-500W, and the treatment time is 10-30 minutes, so that the particle size of iron oleate is controlled in the range of 100-500nm.

[0024] The working mechanism of the application is that iron oleate is used as the main anti-wear functional component, an adsorption film is formed on the metal surface through the polar group, and the wear is significantly reduced under high load and boundary lubrication conditions. The additive system is constructed by supplementing ester base oil and functional dispersant, which can improve the stability and dispersibility of iron oleate in lubricating oil, and meet the comprehensive requirements of cleanliness, environmental protection and lubricity of industrial lubricating oil.

[0025] Due to the use of the above technical scheme, the application has the following beneficial effects compared with the prior art:

[0026] 1、The present application has excellent environmental performance, the additive system of the present application is completely free of restricted elements such as zinc, phosphorus, sulfur in traditional ZDDP, which fundamentally solves the problem of poisoning of existing anti-wear additives to automobile exhaust aftertreatment system; its ash-free characteristic makes it fully comply with the current most stringent environmental regulations, especially suitable for use in areas and application scenarios with strict environmental requirements;

[0027] 2、The present application has excellent anti-wear performance, through the unique polar molecular structure of iron oleate, a dense and stable chemical adsorption protective film can be formed on the metal friction surface; this protective film performs well under boundary lubrication conditions, can effectively reduce the friction coefficient, significantly reduce the wear scar diameter, and its anti-wear performance can be comparable to or even surpass that of traditional ZDDP system;

[0028] 3、The present application has excellent storage stability and thermal stability, the use of specific structure of ester base oil combined with high-efficiency dispersant ensures that iron oleate remains uniformly dispersed in lubricating oil for a long time, and still maintains stable anti-wear performance under high temperature conditions of 150℃;

[0029] 4、The present application has wide applicability, the additive system has excellent compatibility and can be applied to traditional internal combustion engine lubricating oil (engine oil, transmission oil, etc.); industrial lubricating system (hydraulic oil, gear oil, compressor oil, etc.); special lubricants (lubricating grease, metal working fluid, etc.); its performance indicators fully meet the requirements of various lubrication scenarios for high temperature stability, shear stability and long-term performance;

[0030] 5、The present application has future-oriented technical advantages, the present application perfectly meets the development needs of new energy vehicles: ash-free characteristic avoids damage to motor insulation materials; excellent electrical insulation performance ensures the safety of electrical systems; wide temperature range performance adapts to extreme working conditions of electric vehicles; good compatibility with new materials (such as light alloys and composite materials);

[0031] 6、The present application is easy to obtain compared with traditional additive raw materials, the production cost is controllable, the service life of lubricating oil is prolonged, the oil change frequency is reduced; equipment wear is reduced, the service life of parts is prolonged; completely biodegradable, in line with the requirements of circular economy and sustainable development. BRIEF DESCRIPTION OF DRAWINGS

[0032] In order to more clearly illustrate the specific embodiments of the present application or the technical solutions in the prior art, the following will briefly introduce the drawings needed to be used in the specific embodiments or prior art description. Obviously, some of the drawings described below are some embodiments of the present application, and those skilled in the art can also obtain other drawings according to these drawings without creative labor.

[0033] Figure 1 is a high temperature viscosity / shear thinning curve of the inventive Example 1, Comparative Example 1, Comparative Example 2;

[0034] Figure 2 is a SEM friction surface film formation photo of the inventive Example 1 iron oleate additive lubricating oil;

[0035] Figure 3 is a SEM friction surface film formation photo of the inventive Comparative Example 1 lubricating oil;

[0036] Figure 4 is a SEM friction surface film formation photo of the inventive Comparative Example 2 lubricating oil. DETAILED DESCRIPTION

[0037] In order to have a clearer understanding of the technical features, objectives and effects of the present application, the specific embodiments will be described in detail.

[0038] The present application will be further described below in conjunction with the embodiments, but the present application is not limited to the following embodiments. The implementation conditions used in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions indicated are the conventional conditions in the industry. The technical features involved in each embodiment of the present application can be combined with each other as long as there is no conflict.

[0039] Example 1

[0040] Referring to the accompanying Figure 1 and the accompanying Figure 2 ,the present embodiment provides an iron oleate lubricating oil additive composition, comprising the following components by mass fraction:

[0041] 20 parts of iron oleate;

[0042] 100 parts of methyl nonanoate;

[0043] 5 parts of tetraethylene pentaamine polyamide dispersant;

[0044] 2 parts of diisooctyl diphenylamine antioxidant;

[0045] The iron content of the iron oleate is 6%, which forms a stable colloidal dispersion system in the composition, and no precipitate is precipitated after 6 months of storage at room temperature.

[0046] The present embodiment also provides a lubricating oil comprising a base oil and the above-mentioned iron oleate lubricating oil additive composition, wherein the addition amount of the iron oleate lubricating oil additive composition is 5% of the total mass of the lubricating oil, and the base oil is PAO-6.

[0047] The preparation method of the above-mentioned iron oleate lubricating oil additive composition comprises the following steps:

[0048] (1) Iron oleate was added into the fatty acid ester at 60°C, and mechanically stirred for 50 minutes until completely dissolved; and ultrasonic assisted dispersion treatment was used, with an ultrasonic power of 300 W and a treatment time of 20 minutes, so that the particle size of the iron oleate was controlled in the range of 100-500 nm;

[0049] (2) A dispersant and an antioxidant were added, and stirring was continued for 1-2 hours to form a uniform brown-red transparent liquid;

[0050] (3) The liquid was filtered through a 0.5 μm filter, and stored for observation for 1 month without stratification or precipitation, so that the iron oleate lubricating oil additive composition was obtained.

[0051] Comparative Example 1

[0052] Referring to the accompanying Figure 3 , this comparative example is a lubricating oil system composed of a base oil and 5% of a traditional ZDDP.

[0053] Comparative Example 2

[0054] Referring to the accompanying Figure 4 , this comparative example is a lubricating oil of a blank base oil.

[0055] The lubricating oils of the above examples and comparative examples were subjected to comparative tests on a four-ball friction tester, and the test results are shown in Table 1.

[0056] Table 1

[0057] Test item Grinding ball diameter (mm) Extreme pressure load (kg) Example 1 0.49 240 Comparative Example 1 0.52 210 Comparative Example 2 0.78 140

[0058] As can be seen from Table 1, the anti-wear performance of the lubricating oil of Example 1 after adding the iron oleate composition of the present application is superior to that of the traditional ZDDP system; in order to evaluate the film forming effect of different lubricating additives on the metal friction surface, the surface of the metal sample after the four-ball friction test was subjected to scanning electron microscope (SEM) analysis with a magnification of 10,000x, and the results are as follows:

[0059] Figure 2 Example 1: The iron oleate additive of the present application: the surface is covered with a dense, uniform and fine lubricating film structure, and there is almost no obvious wear or cracking trace, indicating that the iron oleate can chemically adsorb on the metal surface during friction to form a stable and effective protective film, and has excellent anti-wear and friction-reducing performance;

[0060] Figure 3 Comparative Example 1: The traditional ZDDP additive: the surface is covered with a relatively continuous granular layer, and there are some sintering traces, indicating that it can generate certain phosphate friction film under high temperature and high pressure, which can play a certain wear-reducing role, but the uniformity of the film layer is poor;

[0061] Figure 4: Comparative Example 2 blank base oil: rough surface, obvious cracks and particle peeling traces, indicating that the metal contact surface is severely worn without additives, and it is difficult to form an effective protective film.

[0062] In summary, the present application has excellent environmental performance, the additive system of the present application does not contain limited elements such as zinc, phosphorus and sulfur in the traditional ZDDP, which fundamentally solves the problem of poisoning of existing anti-wear additives to the automobile exhaust aftertreatment system; its ash-free characteristic completely meets the requirements of the current most stringent environmental protection regulations, and is especially suitable for use in areas and application scenarios with strict environmental protection requirements; the present application has excellent anti-wear protection performance, through the unique polar molecular structure of iron oleate, a dense and stable chemisorption protective film can be formed on the metal friction surface; such protective film performs well under boundary lubrication conditions, can effectively reduce the friction coefficient and significantly reduce the wear scar diameter, and its anti-wear performance can be comparable or even superior to that of the traditional ZDDP system; the present application has excellent storage stability and thermal stability, the use of ester base oil with a specific structure and high-efficiency dispersant ensures that iron oleate remains uniformly dispersed in the lubricating oil for a long time, and still maintains stable anti-wear performance under high temperature conditions of 150 DEG C; the present application has wide applicability, the additive system has excellent compatibility and can be applied to traditional internal combustion engine lubricating oil (engine oil, transmission oil, etc.); industrial lubrication system (hydraulic oil, gear oil, compressor oil, etc.); special lubricants (lubricating grease, metal working fluid, etc.); its performance indicators completely meet the requirements of various lubrication scenarios for high-temperature stability, shear stability and long-term performance; the present application has future-oriented technical advantages, the present application technology perfectly meets the development needs of new energy vehicles: the ash-free characteristic avoids damage to the motor insulation material; excellent electrical insulation performance ensures the safety of the electrical system; wide temperature range performance adapts to the extreme working conditions of electric vehicles; good compatibility with new materials (such as light alloys and composite materials); the raw materials of the present application are easy to obtain compared with traditional additives, the production cost is controllable, the service life of the lubricating oil is prolonged, the oil change frequency is reduced; reduce equipment wear and prolong the service life of parts; completely biodegradable, in line with the requirements of circular economy and sustainable development.

[0063] The above-described embodiments only express one embodiment of the present application, which is described in more detail and in more detail, but it should not be understood as limiting the scope of the patent

[0064] application. It should be noted

[0065] that those skilled in the art can make several modifications and improvements without departing from the concept of the present application

[0066] under the premise of , the protection scope of the present application patent should be subject to the appended claims.

Claims

1. An iron oleate lubricating oil additive composition, characterized in that: Calculated by mass, it includes the following components: 5-30 parts of iron oleate; 60-100 parts of fatty acid ester; 1 to 10 parts of dispersant; 1 to 3 parts of antioxidant.

2. The iron oleate lubricant additive composition according to claim 1, characterized in that: The fatty acid ester is selected from at least one of monobasic fatty acid esters, dibasic fatty acid esters or polyol fatty acid esters, the monobasic fatty acid ester is selected from at least one of methyl nonanoate, ethyl nonanoate and isopropyl caprate; the dibasic fatty acid ester is selected from at least one of diethyl sebacate, diisooctyl sebacate and dibutyl adipate; the polyol fatty acid ester is selected from at least one of trimethylolpropane oleate, pentaerythritol oleate and pentaerythritol tetrapelargonate.

3. The iron oleate lubricating oil additive composition according to claim 1, characterized in that: The dispersant is a fatty acid polyamide dispersant with a molecular weight of 1000 to 5000 g / mol. The fatty acid polyamide dispersant is selected from one or more of oleic acid tetraethylene pentamine polyamide, tall oil acid triethylene tetraamine polyamide or stearic acid pentaethylene hexamine polyamide.

4. The iron oleate lubricant additive composition according to claim 1, characterized in that: The antioxidant is an amine antioxidant; the amine antioxidant is an alkylated diphenylamine or phenyl-α-naphthylamine compound; the alkylated diphenylamine is selected from one or more of diisooctyldiphenylamine, nonyldiphenylamine or p,p'-diisopropylphenyldiphenylamine; the phenyl-α-naphthylamine is selected from one or more of N-phenyl-1-naphthylamine or N-phenyl-2-naphthylamine.

5. The iron oleate lubricating oil additive composition according to any one of claims 1 to 4, characterized in that: The iron content of the ferric oleate is 5-8%, and the ferric oleate forms a stable colloidal dispersion system in the composition. No precipitation occurs when the ferric oleate is stored at room temperature for 6 months.

6. A lubricating oil, characterized in that: The invention comprises a base oil and the iron oleate lubricant additive composition according to any one of claims 1 to 5, wherein the addition amount of the iron oleate lubricant additive composition is 1 to 10% of the total mass of the lubricant, and the base oil is at least one of PAO, mineral oil or synthetic ester.

7. Application of an iron oleate lubricant additive composition in anti-wear lubrication, characterized in that: Used in engine oil, gear oil, hydraulic oil or grease, it forms a dense protective film through the chemical adsorption of iron oleate on the metal surface under boundary lubrication conditions.

8. A method for preparing an iron oleate lubricating oil additive composition, characterized in that: The steps include: (1) Add ferric oleate to fatty acid ester at 50-70°C and mechanically stir for 30-60 minutes until completely dissolved; (2) Add dispersant and antioxidant and continue stirring for 1 to 2 hours to form a uniform brown-red transparent liquid; (3) Fine filtration is performed through a 0.5-1.0 μm filter, and storage is observed for 1 month without stratification or precipitation, thereby obtaining the iron oleate lubricating oil additive composition.

9. The method for preparing the iron oleate lubricating oil additive composition according to claim 8, characterized in that: In step (1), ultrasonic-assisted dispersion treatment is adopted, with an ultrasonic power of 200 to 500 W and a treatment time of 10 to 30 minutes, so that the particle size of the iron oleate particles is controlled within the range of 100 to 500 nm.

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