KR100686640B1 - Anti-wear additve - Google Patents

Abstract

A noble lubricating property improving additive which has a superior lubricating property improving effect and contains no nitrogen is provided. A lubricating property improving additive comprises: (a) at least one glycol ether compound; and (b) at least one compound selected from the group consisting of fatty acid, unsaturated fatty acid dimer, unsaturated fatty acid trimer, fatty acid ester and dicarboxylic acid ester. The glycol ether compound is at least one compound selected from the group consisting of compounds represented by a formula 1, wherein R^1 is hydrogen or a straight chained, branched or cyclic alkyl group, alkenyl group or aryl group with 1 to 12 carbon atoms, R^2 is hydrogen or a methyl group, R^3 is hydrogen or a straight chained, branched or cyclic alkyl group, alkenyl group or aryl group with 1 to 12 carbon atoms, and n is from 2 to 4.

Description

Lubricity Enhancement Additives {anti-wear additve}

1 is a photograph showing the rust prevention function of an embodiment of the present invention.

The present invention relates to fuel additives, and more particularly to "anti-wear additives".

"Lubricating property of fuel" means lubrication of fuel itself, which can suppress wear of moving parts of various devices related to the fuel supply system of various fuel combustion systems such as engines and boilers. It refers to the ability to competence.

For example, in the case of diesel engines using diesel as fuel, the fuel pump and injector included in the fuel supply system have perturbation parts that function to on-and-off the flow of fuel. have. Wear of friction surfaces exposed to the flow of fuel in such perturbation parts should be prevented by the lubrication of the fuel itself. Therefore, "fuel lubricity" is one of the most important factors to ensure the smooth operation of the fuel supply system.

However, it has been found that "low sulfur sulphation" of fuels to meet the emission regulations that are tightened for the protection of the atmospheric environment degrades the lubricity of the fuel. It is known that certain sulfur-containing compounds, aromatic compounds, polar compounds which affect the lubricity of the fuel, for example in the desulfurization process for producing low sulfur fuels such as low sulfur gasoline, low sulfur kerosene and low sulfur diesel. Since etc. are removed, the lubricity of the low sulfur fuel is falling.

Thus, the need for "anti-wear additives" to improve the lubricity of fuels is increasing. As conventional lubricity enhancing additives, various compounds or compositions have been proposed that do not contain sulfur.

For example, US Pat. No. 4,185,594 is a lubricity enhancing additive for compressed ignition fuels for diesel engines containing monohydroxy alkanols having 1 to 5 carbon atoms and ignition accelerators, which are dimerized unsaturated fatty acids. Started.

USP 4,204,481 is a lubrication enhancing additive for compressed ignition fuels for diesel engines comprising monohydric alkanols having 1 to 5 carbon atoms and optionally ignition accelerators such as organic nitrates. Fatty acid amides, fatty acid esters of diethanolamine, or mixtures thereof are disclosed.

USP 4,208,190 discloses straight-chain aliphatic primary amines having alkyl or alkenyl radicals having 8 to 50 carbon atoms as lubrication enhancing additives for diesel fuel.

US Pat. No. 4,375,360 is an aliphatic alcohol represented by ROH (R is 6 to 30 carbon atoms), RO (CH ₂ CH ₂ O) _x H (R is 6 to 30 carbon atoms, x is 1 to 1) as a lubricant improving additive for methanol fuel. Alcohol ethoxylates represented by 20), fatty acids represented by RCOOH (R is 6 to 30 carbon atoms), RCOO (CH ₂ CH ₂ O) _x H (R is 6 to 30 carbon atoms, x is 1 to 1) Fatty acid ethoxylates represented by 20), dialkylbenzenes, each alkyl group having 1 to 20 carbon atoms, the sum of carbon atoms of two alkyl groups is 8 to 36), and R ¹ COOR ² (R ¹ and R ² are Monoesters represented by 1 to 30 carbon atoms, R ¹ and R ² is 10 to 40), R ¹ OOCR ² COOR ³ (R ¹ , R ² and R ³ are each 1 to 30, The sum of the carbon number of R ¹ , R ² and R ³ is 10 to 50) diesters, R ¹ (CH ₂ OCOOR ² ) _x (R ¹ and R ² are each 1 to 30, x is Within 2 4, carbon atoms, the sum of the R ¹ and R ² is from 10 to 40), polyol esters ^{(polyol esters), R 1 O} (CH 2 (CR 2) represented by HO) _x R ³ (R ^1, R ² and R ³ Is hydrogen, or a linear or branched alkyl group, x is 1 to 100 poly (alkyleneglycols), R ¹ O (O = P = O) OR ³ (R ¹ , R The sum of the carbon number of ² and R ³ is 6-40, phosphate esters, olefin-carboxylic acid copolymers, vinyl alcohol polymers and copolymers. ), Or a combination thereof.

USP 4,609,376 discloses esters of monohydric or polyhydric carboxylic acids and polyhydric alcohols, but having at least two free hydroxyl groups, as lubrication enhancing additives for alkanol fuels.

USP 2,252,889 discloses fatty acid esters as a lubricity improving additive.

EP 635,558 and EP 605,857 are lubricating oil additives for diesel fuels, such as vegetable oils such as rapseed, lineseed, soya, canola oil and sunflower seed oil. Or esters of vegetable oils.

WO 95/33805 discloses a nitrogenous additive having at least one> N-R group as a lubricity enhancing additive for diesel fuels.

Lubricity enhancing additives for diesel fuel disclosed in US Pat. No. 6,592,639 include at least one saturated or unsaturated aliphatic hydrocarbon monovalent carboxylic acid and at least one polycyclic hydrocarbon compound. Herein, the aliphatic radical of the carboxylic acid is linear and has 12 to 24 carbon atoms, and each ring of the polycyclic hydrocarbon compound has at least one heteroatom such as N and O, and each ring is a carboxyl group or an aminecarboxylate group. It may have a substituent such as an ester group, a nitrile group. The use amount of the lubricity improving additive of USP 6,592,639 is at least 20 ppm, and at least 60 ppm when the lubricity improving additive is tall oil.

Korean Patent Laid-Open Publication No. 10-2005-0052460 discloses a fatty acid composition having a specific distribution of fatty acids having different chain lengths and a specific amount of saturated fatty acids and unsaturated fatty acids as a lubricant improving additive having low temperature properties.

Korean Patent Laid-Open Publication No. 10-2005-0048619 discloses a composition comprising, as a lubricity improving additive, (a) an additive having a detergent action with a hydrophobic hydrocarbon radical and a polar terminal, and (b) a partially or fully neutralized fatty acid. Doing.

Korean Patent Laid-Open Publication No. 10-2004-0091520 discloses an alkoxylated amine or ether amine salt of saturated carboxylic acid as a lubricant improving additive of gasoline.

Korean Patent Laid-Open Publication No. 10-1999-0043777 discloses a refined fatty acid, an ester compound obtained by reacting a fatty acid with an alcohol compound, or a mixture thereof as a lubricant improving additive.

Korean Patent Laid-Open Publication No. 10-2002-0086956 discloses, as an additive for improving lubricity and low temperature properties, (a) a compound having at least one aromatic ring having at least one hydroxy group and at least one ester group, and (b) defined in the compound (a). Disclosed are compositions comprising aromatic condensates and / or ethylene polymers different from those mentioned above.

Korean Patent Laid-Open Publication No. 10-2002-0051935 discloses a fatty acid salt of an alkoxylated oligoamine as a lubricity improving additive.

However, amine or amide based compounds which are nitrogen compounds are known to cause side effects of increasing the NOx content in the exhaust gas. In addition, compounds such as fatty acids, fatty acid esters, fatty acid dimers, aliphatic amines, carboxylic acids, carboxylic acid esters, vegetable oils, and esters derived from vegetable oils should be used in high amounts of additives in order to obtain effective lubricity improvement. Therefore, it is known to cause high cost and other side effects.

Therefore, there is still a need for an improved lubricity improving additive that does not cause side effects and can exert an effective lubricity improving effect even with a low amount of addition.

The present invention provides a novel lubricity improving additive composition which exhibits an excellent lubricity improving effect and does not contain nitrogen.

The lubricity improving additive provided by the present invention includes (a) at least one glycol ether compound and (b) at least one compound selected from the group consisting of fatty acids, unsaturated fatty acid dimers, unsaturated fatty acid trimers, fatty acid esters and dicarboxylic acid esters. do.

The inventors of the present invention, when a glycol ether compound is added to kerosene and light oil together with a compound selected from fatty acids, unsaturated fatty acid dimers, unsaturated fatty acid trimers, fatty acid esters and dicarboxylic acid esters, the lubricity of kerosene and light oil is very improved. Revealed that it is elevated. Based on this phenomenon, the present invention provides a lubricity enhancing additive comprising (a) a glycol ether compound and (b) at least one compound selected from the group consisting of fatty acids, fatty acid esters and dicarboxylic acid esters.

In addition, the lubricity improving additive of the present invention exhibits an excellent rust preventing function that can prevent corrosion of metal parts of the fuel supply system by kerosene and diesel. In addition, since the lubricity improving additive of the present invention does not contain nitrogen, it is not a factor for increasing the NOx content of the exhaust gas. Moreover, since the lubricity improvement additive of this invention contains the component excellent in biodegradability, it is environmentally friendly. In addition, the lubricity improving additive of the present invention exhibits an excellent lubricity improving effect over a wide temperature range. In addition, the lubricity improving additive of the present invention exhibits excellent thermodynamic stability that does not phase separate from kerosene and light oil over a wide temperature range. Moreover, since the lubricity improvement additive of this invention contains the component which is harmless to a human body, it exhibits the outstanding safety also at the time of human contact. In addition, the lubricity improving additive of the present invention has an excellent cleaning effect to prevent adhesion of oxidized products resulting from the deterioration of fuel or various fuel additives and soot generated from incomplete combustion of fuel to the metal surface of the fuel supply system. Can be.

Below, the lubricity improving additive of this invention is demonstrated in more detail.

The lubricity improving additive provided by the present invention includes (a) at least one glycol ether compound and (b) at least one compound selected from the group consisting of fatty acids, unsaturated fatty acid dimers, unsaturated fatty acid trimers, fatty acid esters and dicarboxylic acid esters. It is a composition.

The glycol ethers refer to ether compounds derived from glycol (an organic compound in which two hydroxyl groups (OH) are bonded to different carbon atoms). In the glycol ether, the hydrogen atom of at least one hydroxy group of the glycol is substituted by another hydrocarbon radical.

Glycol ether compounds have been mainly used for applications such as cleaning agents for semiconductor strippers, automotive antifreezes, brake fluids, and the like, but their use as fuel additives, in particular, as lubricant improving additives, is not known. However, as found in the present invention, the glycol ether compound not only enhances the lubricity improvement effect, but also the soot generated from the incomplete combustion of the fuel and the oxidation product resulting from the deterioration of the fuel or various fuel additives, and the like. It is possible to exert an excellent cleaning action to prevent adhesion to the surface. In addition, glycol ether compounds are excellent in biodegradability and are also environmentally advantageous.

Specific and non-limiting examples of the glycol ether compound include a compound represented by the formula (1).

In Formula 1, R ¹ may be hydrogen or a linear, branched or cyclic alkyl group, alkenyl group, or aryl group having 1 to 12 carbon atoms, R ² may be hydrogen or methyl group, and R ³ may be hydrogen or 1 to C carbon. It may be a straight, branched or cyclic alkyl, alkenyl group or aryl group of 12, n may be 2 to 4.

More specific and non-limiting examples of the glycol ether compound represented by the formula (1) include diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether Diethylene glycol monopropyl ether, diethylene glycol methyl propyl ether, diethylene glycol ethyl propyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl butyl ether, diethylene glycol ethyl butyl ether, Diethylene glycol propyl butyl ether, diethylene glycol monopentyl ether, diethylene glycol dipentyl ether, diethylene glycol methyl pentyl ether, diethylene glycol ethyl pentyl ether, diethylene glycol propyl pentyl ether, diethylene glycol butyl pentyl ether, these Tree with substituents similar to Tylene glycol ether compounds, tetraethylene glycol ether compounds having substituents similar to these, dipropylene glycol ether compounds having substituents similar to these, tripropylene glycol ether compounds having substituents similar to these, tetrapropylene glycol having substituents similar to these Ether compounds, and combinations thereof.

The content of the glycol ether compound in the lubricity improving additive of the present invention is not particularly limited, but if it is too small, the degree of increase of the lubricity improvement effect may be insignificant, and even if too large, the degree of increase of the lubricity improvement effect may be saturated. For example, the content of the glycol ether compound in the lubricity improving additive of the present invention may be about 0.01 to about 30% by weight, preferably about 5 to about 25% by weight, more preferably, About 10 to about 20 weight percent.

The compound (b) is at least one compound selected from the group consisting of fatty acids, unsaturated fatty acid dimers, unsaturated fatty acid trimers, fatty acid esters and dicarboxylic acid esters. The compound (b) can exert an improvement in lubricity, is excellent in biodegradability, and is harmless to humans.

The fatty acid is mainly derived from lipids of plants, animals or microorganisms, and means a straight-chain, branched or cyclic hydrocarbon compound having a carboxyl group (-COOH) at one end and having an even number of carbon atoms. . The fatty acids include saturated fatty acids and unsaturated fatty acids. The carbon number of the fatty acid used in the present invention may typically be about 8 to about 22.

Specific examples of the fatty acid include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, ricinoleic acid, arachidonic acid , Erucic acid, and combinations thereof. Unsaturated fatty acids are more advantageous for improving lubricity and have the advantage of maintaining fluidity at room temperature and exhibiting relatively low viscosity even if the carbon number is increased. Thus, the fatty acid is more preferably unsaturated fatty acid such as, for example, oleic acid, linoleic acid, linolenic acid.

The unsaturated fatty acid dimer means a compound produced by condensation of two unsaturated fatty acids. Specific and non-limiting examples of such unsaturated fatty acid dimers include dimers resulting from condensation of oleic acid, linoleic acid, linolenic acid, or combinations thereof.

The unsaturated fatty acid trimer means a compound produced by condensation of three unsaturated fatty acids. Specific and non-limiting examples of such unsaturated fatty acid trimers are trimers resulting from condensation of oleic acid, linoleic acid, linolenic acid, or combinations thereof.

The fatty acid ester means an ester compound derived from the fatty acid. As a specific example of the said fatty acid ester, the ester compound produced | generated from the esterification reaction of an alcohol compound and a fatty acid is mentioned, for example. More specific and non-limiting examples of the fatty acid esters include glycerol fatty acid ester, pentaerythritol fatty acid ester, sorbitan fatty acid ester, polyoxyalkylene fatty acid ester, polyoxyalkylene glycerol fatty acid ester, polyoxyalkylene sorbitan fatty acid Esters, polyoxyalkylene pentaerythritol fatty acid esters, polypropylene glycerol fatty acid esters, polypropylene sorbitan fatty acid esters, polypropylene pentaerythritol fatty acid esters, and combinations thereof.

The dicarboxylic acid ester compound means an ester compound derived from an organic compound having two carboxyl groups, for example, maleic acid, adipic acid and succinic acid. Specific and non-limiting examples of such dicarboxylic acid ester compounds include dioctyl malate, dioctyl adipate, dioctyl succinate and combinations thereof.

The content of the compound (b) in the lubricity improving additive of the present invention is not particularly limited, but may be, for example, about 70 to about 99.99% by weight, and preferably about 75 to about 95% by weight. And, more preferably, about 80 to about 90% by weight.

Lubricity enhancing additives of the present invention can be prepared by conventional mixing methods that are well known. Therefore, the manufacturing method of the lubricity improving additive of this invention is not demonstrated in detail.

The lubricity enhancing additives of the present invention can be used to improve lubricity of fuels such as gasoline, kerosene, diesel and alkanol fuels. In particular, the lubricity improving additive of the present invention is more useful for improving lubricity of low sulfur diesel oil having a sulfur content of 500 ppm or less.

The lubricity improving additive of the present invention can exert an excellent lubricity improving effect even at a small dosage of, for example, about 10 to about 500 ppm.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the scope of the present invention is not limited to the following examples.

<Example>

Lubrication Evaluation

In the present invention, the lubricity improving effect of the lubricity improving additives of Examples and Comparative Examples was measured by the high frequency reciprocating rig (HFRR) test method according to ASTM D 6078. This test is one of the most suitable methods for measuring the lubricity of fuels in modern diesel engine structures.

In the HFRR test method, 200 g of steel balls were placed on a flat surface, followed by injection of fuel (with low sulfur diesel gas of GS Caltex) with the lubrication enhancing additives of Examples and Comparative Examples, followed by 1 mm of steel balls for 75 minutes. It was quickly reciprocated in width. Then, the size of the spots formed on the surface of the steel sphere was measured using a microscope (100x). The smaller the HFRR index (size of scratch trace, unit: µm), the better the lubricity of the fuel.

Cloud point evaluation

The cloud point is an indicator of the low temperature fluidity of kerosene and diesel. Cloud point measurements were performed to determine if the low temperature fluidity of the fuel would be degraded due to the addition of a lubricant improving additive. The cloud point was determined by measuring the temperature at which white crystals began to precipitate while gradually lowering the temperature of the fuel to which the lubricity improving additives of Examples and Comparative Examples were added (low sulfur diesel gas of GS Caltex). If the cloud point is -18 ° C or lower, it can be determined that the lubricity improving additive does not affect the low temperature fluidity of the fuel. If the cloud point is -18 deg. C or less, it is determined as "good"; if it is more than -18 deg.

Phase stability evaluation

If the lubricity improving additive is phase separated from the fuel or if a precipitate occurs in the fuel to which the lubricity improving additive is added, the lubricity improving additive cannot be used. The evaluation of phase safety was carried out by storing low-sulfur diesel oil containing 2000 ppm of the lubricant improving additives of Examples and Comparative Examples for 7 days in an incubator at 10 ° C., 45 ° C. and 60 ° C., and then confirming whether phase separation or sediment formation occurred. Was performed. It is good if there is no phase separation and precipitate generation, and it is bad if there is phase separation or precipitation generation.

Antirust evaluation

In order to evaluate the rust resistance of the lubricity improving additive of the present invention, a corrosion test was performed. Corrosion tests included: i) a stock solution of lubricity additive additive, ii) a blank low sulfur diesel sample (low sulfur diesel sample without lubrication enhancing additive), and iii) a low sulfur diesel sample with 300 ppm lubricity improving additive. After immersing the metal iron in g for 7 days, the appearance of the metal iron was observed to compare the degree of corrosion of the metal iron in each sample.

Lubricant Impact Assessment

Lubricants used inside engines, such as engine oil, can sometimes deteriorate by interacting with fuel additives in the fuel. As such, the tendency of the fuel additive to interact with the lubricant is referred to as lubricant influence. First, a mixture of 5 g of lubricating oil enhancing additive and 5 g of lubricating oil was heated at 90 ° C. for 72 hours. Then, the mixture was cooled to room temperature and then its appearance was observed. Then, to the cooled mixture, 205 ml of ultra low sulfur diesel oil with 30 ppm of foam inhibitor was added thereto to prepare a diluted sample. Next, the time for which the whole diluted sample passed through the 0.8 μm filter was measured. If the filter passage time was less than 300 seconds, it was determined that there was no lubricating oil influence of the lubricity improving additive. Lubricants used in the lubricant impact assessment are i) "DELO V-1 (GS Caltex, Korea)", ii) "ZIC 5000 POWER (SK, Korea)" and iii) "DRAGON TURBO BEST (Soil Oil, Korea) ) " In lubricating oil impact evaluation, the same experiment was performed on 10 g of lubricating oil to which the lubrication enhancing additive was not added as a control group.

Example

Examples 1-6 of the lubricity improvement additive of this invention were prepared. The compositions of Examples 1-3 are summarized in Table 1. The compositions of Examples 4-6 are summarized in Table 2.

Lubricating evaluation for Examples 1 to 6 was carried out using low sulfur diesel oil of GS Caltex Co., Ltd. having a sulfur content of 30 ppm or less and the content of lubricity improving additives of 100 ppm and 70 ppm. The lubricity improvement evaluation results of Examples 1-3 are summarized in Table 1. The lubricity improvement evaluation results of Examples 4 to 6 are summarized in Table 2.

Using low sulfur diesel oil of GS Caltex Co., Ltd. of sulfur content of 30 ppm or less, cloud point evaluation and phase stability evaluation of Examples 1-6 were performed. The results of Examples 1-3 are summarized in Table 1. The results of Examples 4-6 are summarized in Table 2.

Using low sulfur diesel oil of GS Caltex Co., Ltd. of sulfur content of 30 ppm or less, the antirust property evaluation and the lubricating oil influence evaluation of Example 6 were performed. The antirust evaluation result of Example 6 is shown in FIG. The lubricating oil impact evaluation results of Example 6 are summarized in Table 3.

Comparative example

The fatty acid, fatty acid ester, and dicarboxylic acid ester were used to prepare the lubricity improving additives of Comparative Examples 1-6. The composition of Comparative Examples 1-2 is summarized in Table 1. The composition of Comparative Examples 3-6 is summarized in Table 2. In Comparative Example 1, no lubricity improving additive was used.

Lubricating evaluation for Comparative Examples 1 to 6 was carried out using low sulfur diesel oil of GS Caltex Co., Ltd. having a sulfur content of 30 ppm or less, and the content of lubricity improving additives as 100 ppm and 70 ppm. The lubricity improvement evaluation results of Comparative Examples 1 and 2 are summarized in Table 1. The lubricity improvement evaluation results of Comparative Examples 3 to 6 are summarized in Table 2.

Using low sulfur diesel gas of GS Caltex Co., Ltd. of sulfur content of 30 ppm or less, cloud point evaluation and phase stability evaluation of Comparative Examples 1-6 were performed. The results of Comparative Examples 1 and 2 are summarized in Table 1. The results of Comparative Examples 3 to 6 are summarized in Table 2.

Composition (% by weight) Comparative Example 1 Comparative Example 2 Example 1 Example 2 Example 3 Diethylene dimethyl ether - - - - One Diethylenediethyl ether - - - 5 - Diethylene monobutyl ether - - 10 - - Palmitic acid - 1.5 1.5 1.5 1.5 Stearic acid - 4 4 4 4 Oleic acid - 55 50 55 55 Linoleic acid - 36 31 31 35 Linolenic acid - 3 3 3 3 Arachidic acid - 0.5 0.5 0.5 0.5 Glycerol Oleic Acid Ester - - - - - Sorbitan Oleic Acid Ester - - - - - Polyoxyalkylene sorbitan oleic acid ester - - - - - Dioctylmaleate - - - - - Dioctyl adipate - - - - - Sum - 100 100 100 100 Lubrication Evaluation (HFRR Index) Blank 824 - - - - 100 ppm - 382 339 334 350 70 ppm - 432 351 334 378 Cloud point evaluation Good Good Good Good Good Phase stability evaluation 10 ℃ - Good Good Good Good 45 ℃ - Good Good Good Good 60 ℃ - Good Good Good Good

Composition (% by weight) Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Example 4 Example 5 Example 6 Diethylene dimethyl ether - - - - - 5 - Diethylenediethyl ether - - - - - - 10 Diethylene monobutyl ether - - - - 5 - - Palmitic acid - - - - - - - Stearic acid - - - - - - 4 Oleic acid 45 45 35 45 35 35 33.5 Linoleic acid 35 35 35 35 35 35 30 Linolenic acid 10 10 10 10 10 10 2.5 Arachidic acid - - - - - - - Glycerol Oleic Acid Ester - - 20 - - 10 Sorbitan Oleic Acid Ester - - - - 10 - - Polyoxyalkylene sorbitan oleic acid ester - - - 10 - 10 - Dioctylmaleate 10 - - - 5 - 10 Dioctyl adipate - 10 - - - 5 - Sum 100 100 100 100 100 100 100 Lubrication Evaluation (HFRR Index) Blank - - - - - - - 100 ppm 321 321 319 332 311 309 317 70 ppm 357 357 339 363 325 329 329 Cloud point evaluation Good Good Good Good Good Good Good Phase stability evaluation 10 ℃ Good Good Good Good Good Good Good 45 ℃ Good Good Good Good Good Good Good 60 ℃ Good Good Good Good Good Good Good

As shown in Tables 1 and 2, it was found that the HFRR index of Examples 1 to 6 using the lubricity enhancing additive including a glycol ether compound was significantly reduced compared to the HFRR index of Comparative Example 1 without using the lubricant improving additive. Can be.

In Table 1, the HFRR index for the lubricity improving additive of Comparative Example 2 consisting of saturated and unsaturated fatty acids such as palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, and arachidic acid is 100 ppm to 382 and 70 ppm 432 was. On the other hand, the HFRR indexes for the lubricity enhancing additives of Examples 1 to 3 containing a glycol ether compound together with the saturated and unsaturated fatty acids were 339, 334 and 350 at 100 ppm, respectively, and 351, respectively at 70 ppm. 334, 378. That is, it can be seen that the HFRR indexes of Examples 1 to 3 are significantly reduced compared to Comparative Example 2 when compared at the same amount of addition. It is further surprising that the HFRR index of Examples 1-3 at an addition amount of 70 ppm is smaller than the HFRR index of Comparative Example 2 at an addition amount of 100 ppm. That is, even if a smaller addition amount is applied, the lubricity improving additives of Examples 1 to 3 exhibit better lubricity improving effects than the lubricity improving additives of Comparative Example 2. From these results, it turns out that the lubricity improvement additive of this invention containing a glycol ether compound exhibits the outstanding lubricity improvement effect compared with the conventional fatty acid compound. In other words, it can also be seen that the glycol ether compound greatly increases the lubricity improving effect of the conventional fatty acid compound.

Table 2 shows the HFRR index measurement results for the lubricity improving additives of Comparative Examples 3 to 6, which are mainly composed of unsaturated fatty acids and ester compounds or dicarboxylic acid compounds such as oleic acid, linoleic acid and linolenic acid. Compared with the HFRR index of Comparative Example 2 shown in Table 1, the HFRR index of Comparative Examples 3 to 6 is greatly reduced. From this, it turns out that the lubricity improvement additive which has an unsaturated fatty acid, an ester compound, or a dicarboxylic acid compound as a main component demonstrates more lubricity improvement effect than the lubricity improvement additive containing saturated fatty acid. However, it is further surprising that the HFRR index of the lubricity improving additives of Examples 4 to 6, which further contains not only unsaturated fatty acids, ester compounds and dicarboxylic acid compounds, but also glycol ether compounds, does not contain glycol ether compounds. Is less than the HFRR index of the lubricity enhancing additives of Examples 3-6. That is, at 100 ppm of addition amount, the HFRR indexes of Comparative Examples 3 to 6 were 321, 321, 319, and 332, respectively, while the HFRR indexes of Examples 4 to 6 were 311, 309, and 317, respectively. This lubricity improving effect of the lubricity improving additive of the present invention is more pronounced at a small addition amount. That is, at the addition amount of 70 ppm, the HFRR indexes of Comparative Examples 3 to 6 were 357, 357, 339 and 363, respectively, while the HFRR indexes of Examples 4 to 6 were 325, 329 and 329, respectively. From this, it turns out that the lubricity improvement additive of this invention containing a glycol ether compound exhibits more excellent lubricity improvement effect compared with the conventional lubricity improvement additive which does not contain a glycol ether compound. In addition, even with a smaller amount of addition, it can be expected that the same or better lubricity improvement effect than the conventional lubricity improvement additive can be obtained.

In addition, as shown in Table 1 and Table 2, because the cloud point evaluation results of Examples 1 to 6, all of the phase stability evaluation results are excellent, the lubricity improving additive of the present invention is a fuel additive, in particular a fuel additive for low sulfur diesel As can be seen, it can be usefully used.

Lubricant Class DELO V-1 ZIC 5000 POWER DRAGON TURBO BEST Contrast Example 5 Contrast Example 5 Contrast Example 5 Appearance evaluation No change No change No change No change No change No change Evaluation results Pass Pass Pass Pass Pass Pass Filter Pass Time (sec) 44.48 59.65 41.47 42.39 41.47 42.39 Evaluation results Pass Pass Pass Pass Pass Pass

Table 3 shows the results of the evaluation of the lubricant influence on the lubricity improving additive of Example 6. As shown in Table 3, the filter passing time of Example 6 was increased by 1 to 15 seconds than the control group, but all were less than 300 seconds. In addition, when the lubricity improving additive of Example 6 was added, there was no change in appearance. From this, it can be seen that the lubricity improving additive of the present invention can be used as a useful fuel additive because it does not affect the lubricant.

BRIEF DESCRIPTION OF THE DRAWINGS It is a photograph which shows the evaluation result of antirust property about the lubricity improvement additive of Example 6. In Fig. 1, photograph (1) is metal iron before the corrosive test, photograph (2) is metal iron immersed in the lubricity improving additive of Example 6, and photograph (3) is metal immersed in a low sulfur diesel diesel sample. It is iron, and the photograph (4) is the metal iron which was immersed in the low sulfur diesel oil sample to which the lubricity improvement additive of Example 6 was added 300 ppm. As shown in the photograph (2), the lubricity improving additive itself of the present invention is not corrosive. From this, it can be seen that the lubricity enhancing additive of the present invention can be used as a useful fuel additive. It should be noted that, as shown in the photographs (3) and (4), compared to the metal iron immersed in the low sulfur diesel fuel sample, the low sulfur diesel fuel sample containing 300 ppm of the lubricity enhancing additive of Example 6 was added. The corrosion of metal iron is much less. From this, it can be seen that the lubricating oil improving additive of the present invention has a rust preventing function capable of suppressing corrosion of metal by fuel. Therefore, when the lubricating oil improving additive of this invention is used, not only a lubricity improvement effect but also a rust prevention effect can be obtained at once.

The lubricity improving additive of the present invention is very excellent in improving the lubricity of kerosene and light oil, and can also exhibit a rust preventing function. In addition, since the lubricity improving additive of the present invention does not contain nitrogen, it is not a factor for increasing the NOx content of the exhaust gas. Moreover, since the lubricity improvement additive of this invention contains the component excellent in biodegradability, it is environmentally friendly. In addition, the lubricity improving additive of the present invention exhibits excellent thermodynamic stability that does not phase separate from kerosene and light oil over a wide temperature range. Moreover, since the lubricity improvement additive of this invention contains the component harmless to a human body, it can exhibit the outstanding safety also at the time of human contact. In addition, the lubricity improving additive of the present invention has an excellent cleaning effect to prevent adhesion of oxidized products resulting from the deterioration of fuel or various fuel additives and soot generated from incomplete combustion of fuel to the metal surface of the fuel supply system. Can be.

Claims (13)

(a) at least one glycol ether compound and (b) a lubricity enhancing additive comprising at least one compound selected from the group consisting of fatty acids, unsaturated fatty acid dimers, unsaturated fatty acid trimers, fatty acid esters and dicarboxylic acid esters. The additive for improving lubricity according to claim 1, wherein the glycol ether compound is at least one compound selected from the group consisting of compounds represented by the general formula (1). <Formula 1>

In Formula 1, R ¹ may be hydrogen or a linear, branched or cyclic alkyl group, alkenyl group, or aryl group having 1 to 12 carbon atoms, R ² may be hydrogen or methyl group, and R ³ may be hydrogen or 1 to C carbon. It may be a straight, branched or cyclic alkyl, alkenyl or aryl group of 12, n may be 2 to 4. The method of claim 1, wherein the glycol ether compound is diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol mono Propyl ether, diethylene glycol methyl propyl ether, diethylene glycol ethyl propyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol methyl butyl ether, diethylene glycol ethyl butyl ether, diethylene glycol propyl butyl Ether, diethylene glycol monopentyl ether, diethylene glycol dipentyl ether, diethylene glycol methyl pentyl ether, diethylene glycol ethyl pentyl ether, diethylene glycol propyl pentyl ether, diethylene glycol butyl pentyl ether, having substituents similar to these Triethylene glycol ether compounds, these Tetraethyleneglycol ether compounds having similar substituents, dipropyleneglycol ether compounds having similar substituents, tripropyleneglycol ether compounds having similar substituents thereto, tetrapropyleneglycol ether compounds having similar substituents, or combinations thereof Lubricity improvement additive characterized by the above-mentioned. The lubricity improving additive according to claim 1, wherein the content of the glycol ether compound in the lubricity improving additive is 0.01 to 30% by weight. The fatty acid of claim 1, wherein the fatty acid is caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, oleic acid, linoleic acid, linolenic acid, eleostearic acid, ricinol Lubrication enhancing additive, characterized in that the resin, arachidonic acid, erucic acid, or a combination thereof. The lubricity improving additive according to claim 1, wherein the fatty acid is an unsaturated fatty acid. 7. The lubricant improving additive according to claim 6, wherein the unsaturated fatty acid is oleic acid, linoleic acid, linolenic acid, or a combination thereof. The additive for improving lubricity according to claim 1, wherein the unsaturated fatty acid dimer is a dimer produced from condensation of oleic acid, linoleic acid, linolenic acid, or a combination thereof. The additive for improving lubricity according to claim 1, wherein the unsaturated fatty acid trimmer is a trimmer produced from condensation of oleic acid, linoleic acid, linolenic acid, or a combination thereof. The lubricant improving additive according to claim 1, wherein the fatty acid ester is an ester compound produced from an esterification reaction between an alcohol compound and a fatty acid. The fatty acid ester according to claim 10, wherein the fatty acid ester is glycerol fatty acid ester, pentaerythritol fatty acid ester, sorbitan fatty acid ester, polyoxyalkylene fatty acid ester, polyoxyalkylene glycerol fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, poly A lubricating property enhancing additive, which is an oxyalkylene pentaerythritol fatty acid ester, polypropylene glycerol fatty acid ester, polypropylene sorbitan fatty acid ester, polypropylene pentaerythritol fatty acid ester, or a combination thereof. The lubricity improving additive according to claim 1, wherein the dicarboxylic acid ester is an ester compound derived from an organic compound having two carboxyl groups. 13. The lubricity improving additive according to claim 12, wherein the dicarboxylic acid ester is dioctyl malate, dioctyl adipate, dioctyl succinate or a combination thereof.

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