KR101114829B1 - Lubricant additive composition having excellent wear resistance and method of the composition - Google Patents

Abstract

PURPOSE: A lubricant additive having excellent abrasion resistance, and a producing method thereof are provided to offer the chemically and physically stable additive to lubricant oil. CONSTITUTION: A lubricant additive having excellent abrasion resistance contains the following: 20-40wt% of fatty acid amide compound containing an alkyl group with 1-30 carbons; 20-40wt% of glycerol monostearate; 0.001-5wt% of molybdenium oxide or ammonium molybdate; 0.1-10wt% of catalyst containing a sulfonic acid group; and the balance of solvent oil.

Description

Lubricant additive composition having excellent wear resistance and method of the composition

The present invention relates to a wear resistant lubricant additive using a catalyst and a method of manufacturing the same. More particularly, the present invention relates to the active surfaces (particularly friction surfaces) of mechanical devices such as gear oils of various pumps, engine oils and mission oils of automobiles, etc. The present invention relates to a lubricating oil additive having excellent abrasion resistance that maximizes its function by adding to lubricating oil used to prevent material damage, abrasion, and heat generation, and a method of manufacturing the same.

Typically, various methods have been tried to reduce the fuel consumption of automobiles. Korean Unexamined Patent Publication No. 10-2008-0010505 discloses a technology related to a fuel efficiency improvement system and method using an automotive torque converter. This technology puts an electronic external oil pump on the vehicle to start lubrication of each gear element before starting the vehicle, and connects the lock-up clutch directly to the torque converter cover connected to the engine at a half-clutch level to suppress excessive engine speed increase. Improves. Korean Patent Laid-Open Publication No. 10-2008-0093848 relates to a vehicle fuel efficiency improving apparatus and method using an engine number calculating device for calculating the engine speed of a vehicle, and displays the current engine status to a driver for economical driving through fuel economy. A technique for providing conditions is disclosed. These techniques have been attempted in terms of changing mechanical devices.

Another approach to improving fuel economy is to reduce the internal friction to reduce engine energy consumption. Friction is a very important factor in internal combustion engines and other devices. This is because a significant loss of theoretical mileage or device run time is due to friction.

Friction increases the force required for movement and thus increases the consumption of fuel, electricity and other energy. Therefore, minimizing friction is the main purpose of lubrication. In general, lubrication means applying friction or other materials including solid lubricants to the friction surface to reduce friction and abrasion damage and to prevent the friction surfaces from sticking together (fusion). Lubricant oil is the oil causing the lubrication action, in more detail, by reducing the friction between the two solid motion in contact with each other to prevent heat generation, damage, wear of the active surface and improve the mechanical efficiency as well as mechanical noise due to friction A substance used to minimize its occurrence.

The most commonly used lubricating oils include animal and vegetable oils, mineral oils and synthetic lubricating oils, which form a thin oil film between the two solids to support the loads, and at the same time, the friction surfaces are partially or completely separated from each other according to the loads. Decreases.

Such lubricating oils require appropriate viscosity, physical and chemical stability, oxidative stability, etc. in addition to wear resistance, load resistance, and friction resistance, and suitable additives may be mixed to improve physical properties. Particularly when organic molybdenum compounds are used as additives for lubricants, they show excellent results of load and wear resistance at extreme pressures.

U.S. Patent 4,889,647 discloses molybdenum complexes prepared by reacting fatty acids, diethanolamines, and molybdenum. However, in the case of molybdenum compounds, precipitation occurs due to agglomeration between particles in the oil during long-term storage, and as a result, homogeneous molybdenum components may not be distributed, and thus, wear resistance may not be improved unlike the original intention.

Molybdenum sulfide is widely used as an additive, but foreign additives are much more expensive than conventional products, can be thermally decomposed and oxidized at high temperatures, and inexpensive molybdenum sulfide is too large to disperse in the base oil. It has a disadvantage.

In order to solve the problems of the prior art as described above, the present invention utilizes a catalyst to combine the organic material and molybdenum oxide nanoparticles of the organic molybdenum oxide compound, which is chemically and physically stable and wear resistance that can be dispersed in oil It is an object to provide good lubricant additives.

Another object of the present invention is to provide a method for preparing a lubricant additive having excellent wear resistance, which is chemically and physically stable and can be dispersed in oil by nanoparticles of an organic molybdenum oxide compound by combining an organic material and molybdenum oxide using a catalyst. .

In order to achieve the above object, the present invention

i) 20 to 40% by weight of a fatty acid amide compound comprising an alkyl group having 1 to 30 carbon atoms;

ii) 20 to 40% by weight of glycerol monostearate;

iii) 0.001 to 5.0 weight percent molybdenum oxide or ammonium molybdate;

iv) 0.1 to 10.0 wt% of a catalyst comprising a sulfonic acid group; And

v) A lubricant additive having excellent abrasion resistance using a catalyst, comprising a residual amount of a lubricant oil.

In order to achieve the above another object, the present invention

i) 20 to 40% by weight of a fatty acid amide compound comprising an alkyl group having 1 to 30 carbon atoms; ii) 20 to 40% by weight of glycerol monostearate; iii) 0.001 to 5.0 weight percent molybdenum oxide or ammonium molybdate; iv) 0.1 to 10.0 wt% of a catalyst comprising a sulfonic acid group; And v) a residual amount of lubricating oil is mixed and reacted at 130 to 200 ° C. for 2 to 4 hours, thereby providing a method for preparing a lubricant additive having excellent wear resistance using a catalyst.

According to the present invention, an organic molybdenum oxide compound having a particle size of about 1 to 100 nm can be prepared in molybdenum oxide or ammonium molybdate by an action of a catalyst, and surrounded by an organic compound bonded with an amide. Due to the dispersing characteristics of the particles and the combination of the organic material, it is possible to disperse homogeneously in the oil component and to prepare a lubricant additive having excellent wear resistance.

1 is an FT-IR spectrum of the compound prepared by Example 1 and Comparative Example 1.
2 is a TEM photograph of the organic molybdenum oxide compound prepared in Example 1. FIG.
3 is a photograph of a commercial ATF oil and 1 wt% of an organic molybdenum oxide compound prepared according to Example 1 to an ATF oil.
4 is a photograph taken from the side surface of the sample prepared by Example 1 and the sample prepared by Comparative Example 1 after one month.
5 is a photograph taken from the lower surface of the sample prepared by Example 1 and the sample prepared by Comparative Example 1 upside down after one month.

The present invention is described in more detail below.

I) 20 to 40% by weight of a fatty acid amide compound comprising an alkyl group having 1 to 30 carbon atoms; ii) 20 to 40% by weight of the substituted or unsubstituted ester compound; iii) 0.001 to 5.0 weight percent molybdenum oxide or ammonium molybdate; iv) 0.1 to 10.0 wt% of a catalyst comprising a sulfonic acid group; And v) a residual amount of lubricating oil, which provides a lubricant additive having excellent abrasion resistance using a catalyst.

In the present invention, the 'additive' means a composition comprising the fatty acid amide compound, the ester compound, molybdenum oxide or ammonium molybdate, the catalyst and the solvent oil. Such additives are added to the lubricant to improve the wear resistance of the lubricant itself.

The fatty acid amide compound includes a hydrophobic C12 to C24 alkyl group in addition to the amide group in the compound structure, and may include up to three double bonds. Specifically, for example, stearamide (stearamide), erucamide (erucamide), oleamide (oleamide), behenamide (behenamide) or a combination thereof may be mentioned, but is not limited thereto. According to one embodiment of the invention, the amide may be used AkosNobel's Armoslip CP (Oleamide). The structural formula is as follows.

The amide used in the present invention is preferably 20 to 40% by weight of the additive content. If the content is less than 20% by weight, the content may be low and the synthesis reaction may not be performed smoothly. If the content is more than 40% by weight, more than necessary amides may be contained, which may increase the price and increase the viscosity, thereby preventing control of the synthesis. Therefore, it is not preferable.

Substituted or unsubstituted ester compounds may be added to enhance reactivity. At this time, the ester compound may be a glycerin ester containing a hydroxyl group, is known as oil of cereals, meat. The kind may be coconut, corn, cotton seed, sunflower seed, rapeseed seed, soybean oil, suet oil and the like. Since the functional group is alive, it may contribute to increased reactivity.

Specifically, glycerol monostearate, isopropyl myristic acid, cetyl octanoate, octylate acid decylate, palmitic acid isopropyl, butyl stearate, hexyl laurate, myristin myristyl, decyl oleate, hexyl dimethyl octanoate Decyl, cetyl lactate, myristyl lactate, octyldodecyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearic acid, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester , N-alkylglycol monoisostearic acid, neopentyl glycol dicapric acid, diisostearyl malic acid, glycerin di-2-heptyl undecanoate, trimethylolpropane tri-2-ethylhexanoic acid trimethylolpropane, triisostearic acid propane 2-ethylhexanoic acid pentaerythritol, tri-2-ethylhexanoic acid glyceryl, tri (carfilcapricin myristin stearic acid) Riseide, triisostearic acid trimethylolpropane, cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, trimyristin glycerine, tri-2-heptyl undecanoic acid glycerides, castor oil fatty acid methyl ester, oleic acid oleyl , Acetoglycerides, 2-heptyl undecyl palmitic acid, diisobutyl adipic acid, (adipic acid-2-ethylhexane-stearic acid) glycerin oligo ester, (2-hexyldecanoic acid-sebacic acid) diglyceryl oligo ester), N-lauroyl-L-glutamic acid-2-octyldodecyl ester, adipic acid di-2-heptyl undecyl, ethyl aurate, sebacic acid di-2-ethylhexyl, myristic acid 2-hexyldecyl, palmitic acid 2 -Hexyldecyl, adipic acid 2-hexyldecyl, sebacic acid diisopropyl, succinic acid 2-ethylhexyl, ethyl acetate, butyl acetate, triethyl citrate, etc. can be mentioned.

The content of the substituted or unsubstituted ester compound is preferably about 20 to 40% by weight of the lubricant additive. If the amount is less than 20% by weight, the reaction may not proceed smoothly. If the amount is more than 40% by weight, the reaction may be solidified due to an increase in viscosity, which may be difficult to synthesize.

In the catalyst including a sulfonic acid group according to the present invention, more molybdenum reacts to decrease the -OH peak intensity, thereby improving reactivity and conversely, more surface of molybdenum oxide is ester-bonded. The result is the synthesis of nanoparticles.

In the present invention, the catalyst is preferably alkyl sulfonic acid. Sulfonic acid salts (Na ₂ SO 4, MgSO _4, etc.), aromatic sulfonic acid (aromatic sulfonic acid), alkyl sulfonic acid (alkyl sulfonic acid), alkyl aromatic acid (alkyl aromatic acid). It may be sodium sulfonate or sulfonic acid.

Examples of the catalyst containing a sulfonic acid group include p-Xylene-2-sulfonic acid, methylene sulfonic acid dihydrate, benzene sulfonic acid, and p-toluenesulfonic acid. P-Toluene sulfonic acid monohydrate, Dodecylbenzene sulfonic acid, 1-methyl-2-propynyl p-toluene sulfonate, 2- 2-amino-1-naphthalene sulfonic acid, and the like.

The content of the catalyst including a sulfonic acid group is preferably 0.01 to 10.0% by weight. If the content of the catalyst is less than 0.01% by weight, it is not preferable because the content of the catalyst is too small, which makes it difficult to form nanoparticles. If the content of the catalyst is more than 10.0% by weight, it affects the pH of the entire system and affects the balance of the synthesis reaction. Is not preferred. It is also undesirable to exceed 10.0% by weight because precipitation occurs in the product in the form of a salt without melting beyond the saturated solubility of the catalyst. Initially, it melts due to the reaction temperature, but precipitates as it cools down after completion of synthesis.

Molybdenum oxide (MoOn, n = 0.1 ~ 100) or ammonium molybdate is added to the synthesis of the organic molybdenum oxide compound. The content of molybdenum in the lubricant additive is 0.1 to 10% by weight, preferably 0.5 to 5% by weight. If the content of molybdenum in the lubricating oil additive is less than 0.5% by weight, the content of molybdenum is too low, which may cause unnecessary dilution. If the content is more than 10% by weight, unreacted raw materials may remain. Can not do it.

As in the present invention, when manufacturing an organic molybdenum oxide compound surrounded by an organic compound bonded to the amide and molybdenum oxide, not only the price is competitive with existing expensive products, but also as a catalyst to the organic molybdenum oxide compound It is made of nanoparticle size of about 1 to 100 nm, preferably about 20 to 40 nm, and has excellent dispersibility, so that it is easy to apply to conventional commercial oils, and when added, the friction resistance is much superior to that of a single oil. Characteristic

You may mix | blend another type of antiwear agent in the range which does not impair the objective of this invention. As the antiwear agent, zinc dithiophosphate, zinc phosphate, zinc dithiocarbamate, dithiocarbamate molybdenum, molybdenum dithiophosphate, disulfide, sulfide olefins, sulfide fats and oils, sulfide esters, thiocarbonates and thio Sulfur-containing compounds such as carbamates and polysulfides; Phosphorus-containing compounds such as phosphite esters, phosphate esters, phosphonic acid esters, and amine salts and metal salts thereof; Sulfur and phosphorus containing antiwear agents, such as thiophosphoric acid ester, thiophosphoric acid ester, thiophosphonic acid ester, and these amine salt or a metal salt, may be further included.

According to another embodiment of the present invention, i) 20 to 40% by weight of a fatty acid amide compound containing an alkyl group having 1 to 30 carbon atoms; ii) 20 to 40% by weight of the substituted or unsubstituted ester compound; iii) 0.001 to 5.0 weight percent molybdenum oxide or ammonium molybdate; iv) 0.1 to 10.0 wt% of a catalyst comprising a sulfonic acid group; And v) a residual amount of lubricating oil is mixed and reacted at 130 to 200 ° C. for 2 to 4 hours, thereby providing a method for preparing a lubricant additive having excellent wear resistance using a catalyst.

In the process of preparing the lubricating oil additive of the present invention, i) to v) may be mixed at the same time to form a mixture and then reacted at 130 to 200 ° C. for 2 to 4 hours, on the other hand, i) the fatty acid amide compound, ii) ester compound and iii) molybdenum oxide or ammonium molybdate may be mixed first, followed by iv) catalyst and v) solvent oil. In the process of preparing the lubricant additive, in the case of i) to iii) of the components, the mixing order may be arbitrarily selected to form a mixture in advance, and then a catalyst including a sulfonic acid group is added to proceed with the synthesis. For the synthesis of molybdenum-bonded amides, the synthesis is carried out at 70 to 200 ° C. If the reaction temperature is higher than 200 ° C, carbonization and gelation may occur due to high heat, which is not preferable.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples.

Example

Example  One

100 g of Armoslip CP purchased from AkzoNobel, 100 g of glycerol monostearate (from Samjung Chemical), 20 g of ammonium molybdate ((NH ₄ ) ₆ Mo ₇ O ₂₄ ) (Gwangyang alloy), 0.5 g of catalyst (Samjung Chemical) , 200 g of Castol oil (Malaysia imported, Everchem) was added as a solvent and reacted at 140 ° C. for 3 hours. As a catalyst, p-toluenesulfonic acid monohydrate was used. About 4% by weight of molybdenum raw material was included, and the particle diameter was about 25 nm, and the color was dark brown.

Example 2

100 g of Armoslip CP from AkzoNobel, 100 g of glycerol monostearate (purchased from Samjung Chemical), 20 g of ammonium molybdate ((NH ₄ ) ₆ Mo ₇ O ₂₄ ) (photocatalyst iron), catalyst (purchased from Samjung Chemical), 200 g of Castol oil (Malaysia imported, Everchem) was added as a solvent and reacted at 140 ° C. for 3 hours. As a catalyst, dodecylbenzenesulfonic acid was used. About 4% by weight of molybdenum raw material was included, and the particle diameter was about 25 nm, and the color was dark brown.

Example 3

100 g of Armoslip CP from AkzoNobel, 100 g of glycerol monostearate (purchased from Samjung Chemical), 20 g of ammonium molybdate ((NH ₄ ) ₆ Mo ₇ O ₂₄ ) (photocatalyst iron), catalyst (purchased from Samjung Chemical), 200 g of Castol oil (Malaysia imported, Everchem) was added as a solvent and reacted at 140 ° C. for 3 hours. The catalyst used was 1-methyl-2-propynyl p-toluenesulfonate. About 4% by weight of molybdenum raw material was included, and the particle diameter was about 25 nm, and the color was dark brown.

Comparative example  One

No catalyst was added and the rest was performed in the same manner as in Example 1.

Evaluation and Results

Abrasion Resistance Test

A 4 ball abrasion resistance test was performed by adding 1 wt% of a lubricant additive including the nanoparticle organic molybdenum oxide prepared in Examples 1 to 3 and Comparative Example 1 to a commercial automation (ATF) oil. The condition was to rotate the upper ball (rotator) for 60 minutes at a speed of 1200 rpm at a temperature of 75 ℃, 40 Kg load was measured the average diameter of the wear scar of the fixture. Each measurement resulted in an average diameter of six measurements, which showed improvement in wear resistance of 71%, 68%, 67% and 2.5%, respectively, compared to ATF oil without the nanoparticle organic molybdenum oxide compound. The results of Examples and Comparative Examples are shown in Table 1 below.

sample Wear Mark Average Diameter (mm) % Wear ATF oil 1.871 100 Organic Molybdenum Compounds Prepared in Example 1
1 wt% added ATF oil 0.543 29 Organic Molybdenum Compounds Prepared in Example 2
1 wt% added ATF oil 0.627 32 Organic Molybdenum Compounds Prepared in Example 3
1 wt% added ATF oil 0.610 33 Organic Molybdenum Prepared in Comparative Example 1
ATF oil with 1% by weight of compound 1.825 97.5

Referring to Table 1, in the case of the ATF oil to which the organic molybdenum compounds prepared in Examples 1 to 3 were added, the average diameter of the wear scars was small, and the amount of the wear was less than 29 to 33%. On the other hand, in the case of the ATF oil added with 1% by weight of the organic molybdenum compound prepared in Comparative Example 1, the wear trace average diameter was larger than those of Examples 1 to 3, and the amount of wear was also very large. Therefore, it can be seen that the composition according to the present invention has very improved wear resistance.

1 is an FT-IR spectrum of the compound prepared by Example 1 and Comparative Example 1. Referring to FIG. 1, since both the carbonyl band of the ester in the vicinity of 1740 cm ⁻¹ and the carbonyl band of the amide in the vicinity of 1620 cm ⁻¹ can be identified, it can be seen that the ester and amide bond states after the reaction with molybdenum. Therefore, it can be seen that when the catalyst is not used, the synthesis is unstable and the OH peak is large. In the case of using a catalyst, the synthesis is stable and the OH peak becomes small. However, even in the case of using a catalyst, it is assumed that the OH peak contained in glycerol monostearate due to the small amount of glycerol monostearate added.

2 is a TEM photograph of the organic molybdenum oxide compound prepared in Example 1. FIG. Referring to Figure 2, it can be seen that not only the size of the particles but also uniform particle distribution.

Figure 3 shows a photograph of the commercial ATF oil and 1% by weight of the organic molybdenum compound prepared according to Example 1 to the ATF oil. Referring to Figure 3 it can be seen that very well dispersed very transparent.

Figure 4 is a photograph taken from the side after leaving the sample prepared by Example 1 and the sample prepared by Comparative Example 1 for one month. The use of a catalyst can confirm a stable synthesis state, but when the catalyst is not used it can be seen that the particles gradually increase due to collision between particles, precipitation occurs.

According to the result of the embodiment, an organic molybdenum oxide compound surrounded by an organic compound bonded with an amide to molybdenum oxide can be produced by the action of a catalyst including a sulfonic acid group, and the oil component is dispersed in the solvent due to the dispersing property of the ultrafine nanoparticles and organic matter. It can be seen that homogeneous dispersion is possible in, and that an additive including the organic molybdenum oxide compound is added to obtain a lubricant having improved wear resistance.

The present invention is not limited to the above embodiments and can be manufactured in various forms, and those skilled in the art to which the present invention pertains can carry out in other specific forms without changing the technical spirit or essential features of the present invention. I can understand that it can be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (6)

i) 20 to 40% by weight of a fatty acid amide compound comprising an alkyl group having 1 to 30 carbon atoms;
ii) 20 to 40% by weight of glycerol monostearate;
iii) 0.001 to 5.0 weight percent molybdenum oxide or ammonium molybdate;
iv) 0.1 to 10.0 wt% of a catalyst comprising a sulfonic acid group; And
v) A lubricant additive excellent in wear resistance using a catalyst, comprising a residual amount of solvent oil.
The method of claim 1,
The amide compound is at least one selected from the group consisting of stearamide, erucamide, oleamide, behenamide, and a combination thereof, wear resistance using a catalyst Excellent lubricant additive.
delete The method of claim 1,
The additive,
An organic molybdenum oxide compound in which the fatty acid amide compound and glycerol monostearate and molybdenum oxide or ammonium molybdate are bonded by the action of the catalyst,
The particle size of the organic molybdenum oxide compound is characterized in that 1 ~ 100 nm, lubricant additive excellent in wear resistance using a catalyst.
The method of claim 1,
The catalyst is p-xylene-2-sulfonic acid (p-Xylene-2-sulfonic acid), methylene sulfonic acid dihydrate (benzene sulfonic acid), benzene sulfonic acid (benzene sulfonic acid), p-toluenesulfonic acid monohydrate (p-toluene sulfonic acid monohydrate, dodecylbenzene sulfonic acid, 1-methyl-2-propynyl p-toluene sulfonate, and 2-amino-1-naphthalene A lubricant having excellent wear resistance using a catalyst, characterized in that it comprises at least one selected from the group consisting of sulfonic acid (2-amino-1-naphthalene sulfonic acid).
i) 20 to 40% by weight of an amide compound having 1 to 30 carbon atoms; ii) 20 to 40% by weight of glycerol monostearate; iii) 0.001 to 5.0 weight percent molybdenum oxide or ammonium molybdate; iv) 0.1 to 10.0 wt% of a catalyst comprising a sulfonic acid group; And v) mixing residual amount of lubricating oil and reacting at 130 to 200 ° C. for 2 to 4 hours to produce a lubricant additive having excellent wear resistance using a catalyst.

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