Non-aqueous lubricant and fuel compositions comprising fatty acid esters of hydroxy- carboxylic acids, and uses thereof

[0001] The invention relates to anti-wear additives and friction modifiers and their use in lubricant compositions and fuel compositions.

[0002] It is known to use anti-wear additives and / or friction modifiers in lubricating compositions. It is also known to use anti-wear additives and / or friction modifiers in fuel compositions for internal combustion engines.

[0003] The penetration of fuel and fuel additives into the crankcase lubricant of an internal combustion engine is known, for example, from paragraph 2 of the SAE summary of the actu- ate 2001-01-1962 by CY Thiel et al. "The Fuel Additive / lubricant Interactions: ...".

[0004] Zinc dihydrogen phosphate dendrocarbons (ZDDP) have been used as anti-wear additives in lubricating compositions for many years. The disadvantage of these additives is that when used to lubricate the internal system / composition of the engines, they cause the formation of ash, which contributes to the presence of dust in the exhaust of internal combustion engines. It is therefore desirable to reduce the amount of ash-forming additives used for the lubrication of internal combustion engines. It is also desirable to limit the amount of zinc and / or phosphorus and / or sulfur in the exhaust of internal combustion engines. Attempts have been made to provide anti-wear additives and / or friction modifiers that do not contain either zinc or phosphorus or sulfur, or at least contain them in limited quantities.

The publication of British patent application GB-2097813-A relates to economically advantageous fuel lubricating oil compositions which contain an oil with lubricating viscosity and, as an economically advantageous fuel additive, from 0.05 to 0.2 mass percent of glycerol C16-C18 partial ester. fatty acids. The composition is illustrated by glycerol monooleate and glycerol dioleate.

[0006] The publication of international patent application WO 2008/147704 relates to a lubricating composition comprising an oil with a lubricating viscosity, an oil soluble molybdenum compound and an ashless anti-wear compound with a particular formula (I). According to WO 2008/147704, (recital [0042]), in one embodiment, the ashless anti-wear agent comprises a compound that is a hydroxycarboxylic acid derivative. It has been found (paragraph [0048]) that in one embodiment the ashless agent contains imide, diesters, diimides, ester-amide tartaric acid derivatives. It was also found (recital [0049]) that examples of the corresponding (their) citric acid derivative (s) include trialkyl citrate or boronated trialkyl citrates. It was found (para

[0049]) that a more detailed description of suitable citrates is disclosed in WO 2005/087904 and US 5,338,470.

[0007] The publication of international patent application WO 2005/087904 related to US 2005/0198894 relates to lubricating and fuel compositions comprising a hydroxycarboxylic acid and hydroxypolycarboxylic acid esters represented by the general formula:

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wherein R3 is selected from the group consisting of a linear or branched C1-C18 alkyl, linear or branched C1-C18 alkenyl, alkoxyalkyl, hydroxyalkyl, aryl and benzyl; and X is selected from a wide range of structures defined herein. It is believed that the preferred esters include citrates, tartrates, malts, lactates, almonds, glycolates, hydroxypropionates, hydroxyglutarates, salicylates and the like. It is believed that trialkyl citrates and borated trialkyl citrates are particularly preferred, especially triethyl citrate and borated triethyl citrate. An especially preferred class of additives is believed to be those where R3 is a linear or branched alkyl chain with 1 to 5 carbon atoms, e.g. methyl, ethyl, propyl, butyl, pentyl, isomers of the above, and mixtures thereof.

[0008] US patent 5,338,470 relates to alkylated citric acid adducts as anti-wear and friction-modifying additives to fuel and lubricant compositions. It is believed that alkylated citric acid adducts are formed by the reaction of citric acid with alkyl alcohols and amines. The reaction is described by nXRy, where R is a C1-200 hydrocarbon or a hydrocarbon (a divalent hydrocarbon radical), or a mixture thereof, and may optionally include an oxygen, nitrogen or sulfur atom. "X" is an amine, alcohol, thiol or metal amide, alcoholate or thiolate. It is believed that the metal is preferably sodium, potassium or calcium, and "n" is a number from 0.2 to 5.0. Such additives are shown only when reacting with citric acid and oleyl alcohol.

[0009] According to WO 2008/147704 [composition] additionally contains a friction modifier (paragraph [0089]). According to paragraph [0093]: "In one embodiment, the friction modifier is a long chain fatty acid ester (previously described above as an ashless anti-wear agent.) In another embodiment, the long chain fatty acid ester is a mono-ester, and in another embodiment a long-chain fatty acid ester there is (tri) glyceride. "

The publication of international patent application WO 2009/101276 relates to a lubricating composition for a low-ash four-stroke engine that contains, in addition to other components, at least one hydroxylated ester of formula R (OH) m, (COOR '(OH)) p) n, wherein m is an integer from 0 to 8, preferably from 1 to 4, n is an integer from 1 to 8, preferably from 1 to 4, and p is an integer from 0

-3 to 8, preferably from 1 to 4, wherein the sum of p + m is absolutely greater than zero, R and R 'are independently a linear or branched, saturated or unsaturated hydrocarbon group, optionally substituted with one or more aromatic groups, and containing from 1 up to 30 carbon atoms, or their borated derivatives. It is believed that the hydroxylated esters can be selected from monoesters or diesters derived from glycerol, such as glycerol monooleate, stearate or glycerol isostearate and their borated derivatives. It is also believed that the hydroxylated esters may be selected from citrates, tartrates, malates, lactates, mandelates, glycolates, hydroxypropionates, hydroxyglutarates or their borated derivatives. The composition is illustrated only with triethyl citrate and glycerol monostearate.

[0011] WO 2010/093519 and US 2010/0210487 relate to friction modifiers based on sorbitan fatty acids that are solid or semi-solid. According to these documents, the sorbitan fatty acid ester compositions may contain tartrates and / or citrates which may be substituted with an alkyl, aryl, acyloalkoxy and / or alkoxy group. A particularly preferred embodiment uses the alkyl tartrate in combination with a sorbitan fatty acid ester. Preferred additional additives are those including C12-C14 acetal tartrate, diethyl tartrate, diisopropyl tartrate and mixtures thereof. The laboratory experimental products HXL 7121 and HXL 7353 from Chemtura Corporation are the alkyl tartrate of preferred embodiments.

[0012] There is still a need for alternative compositions exhibiting anti-wear and / or friction modifiers, for example for use in non-aqueous lubricating compositions and / or for use in fuel compositions for an internal combustion engine.

[0013] Thus, according to the invention, a non-aqueous lubricant composition comprising a significant amount of lubricating oil and a smaller amount of at least one long chain fatty acid ester of a hydroxycarboxylic acid is provided, wherein the long chain fatty acid has from 8 to 22 carbon atoms, and the ester is soluble in mono- or poly-hydroxycarboxylic acid ester oil having 1 to 4 groups, which are independently carboxylic acid groups or its lower hydrocarbon esters, the lower hydrocarbon esters having hydrocarbon moieties which independently have 1 to 6 carbon atoms, and wherein the hydroxycarboxylic acid is a mono-hydroxycarboxylic acid, the ester has a long-chain fatty acid ester moiety with a hydroxyl group of the hydroxycarboxylic acid,and when the hydroxycarboxylic acid is a polyhydroxycarboxylic acid, the ester has, independently, esters of long-chain fatty acids with one or two hydroxyl groups of the poly-hydroxycarboxylic acid.

[0014] Accordingly, the lubricity composition can be used to lubricate an internal combustion engine, for example for lubricating the crankcase of an internal combustion engine.

and when the hydroxycarboxylic acid is a polyhydroxycarboxylic acid, the ester has, independently, esters of long-chain fatty acids with one or two hydroxyl groups of the poly-hydroxycarboxylic acid. Accordingly, the internal combustion engine is lubricated with a lubricant composition according to the invention, e.g. a lubricant for the crankcase. Additionally or alternatively, the ester may be provided in the liquid fuel composition used for operating / operating the internal combustion engine, and when the engine is running, at least a portion of the ester passes into the lubricating composition containing the lubricating oil, while the lubricant composition is used for lubrication engine, for example as a lubricant for the crankcase. the ester has, independently, esters of long-chain fatty acids with one or two hydroxyl groups of poly-hydroxycarboxylic acid. Accordingly, the internal combustion engine is lubricated with a lubricant composition according to the invention, e.g. a lubricant for the crankcase. Additionally or alternatively, the ester may be provided in the liquid fuel composition used for operating / operating the internal combustion engine, and when the engine is running, at least a portion of the ester passes into the lubricating composition containing the lubricating oil, while the lubricant composition is used for lubrication engine, for example as a lubricant for the crankcase. the ester has, independently, esters of long-chain fatty acids with one or two hydroxyl groups of poly-hydroxycarboxylic acid. Accordingly, the internal combustion engine is lubricated with a lubricant composition according to the invention, e.g. a lubricant for the crankcase. Additionally or alternatively, the ester may be provided in the liquid fuel composition used for operating / operating the internal combustion engine, and when the engine is running, at least a portion of the ester passes into the lubricating composition containing the lubricating oil, while the lubricant composition is used for lubrication engine, for example as a lubricant for the crankcase. Accordingly, the internal combustion engine is lubricated with a lubricant composition according to the invention, e.g. a lubricant for the crankcase. Additionally or alternatively, the ester may be provided in the liquid fuel composition used for operating / operating the internal combustion engine, and when the engine is running, at least a portion of the ester passes into the lubricating composition containing the lubricating oil, while the lubricant composition is used for lubrication engine, for example as a lubricant for the crankcase. Accordingly, the internal combustion engine is lubricated with a lubricant composition according to the invention, e.g. a lubricant for the crankcase. Additionally or alternatively, the ester may be provided in the liquid fuel composition used for operating / operating the internal combustion engine, and when the engine is running, at least a portion of the ester passes into the lubricating composition containing the lubricating oil, while the lubricant composition is used for lubrication engine, for example as a lubricant for the crankcase.

Also, according to the invention, a method for improving the anti-wear and / or friction properties of a lubricating oil is provided, which method comprises mixing said oil with an effective amount of at least one long chain fatty acid ester of a hydroxycarboxylic acid, wherein the long chain fatty acid is from 8 to 22 carbon atoms, and the ester is an oil-soluble mono- or poly-hydroxycarboxylic acid ester having 1 to 4 groups, which are independently carboxylic acid groups or their lower hydrocarbon esters, the lower carbohydrate esters having hydrocarbon moieties that independently have 1 to 6 carbon atoms, and wherein when the hydroxycarboxylic acid is a mono-hydroxycarboxylic acid,the ester has a long chain fatty acid ester moiety with a hydroxy group of a hydroxycarboxylic acid, and when the hydroxycarboxylic acid is a polyhydroxy carboxylic acid, the ester has, independently, esters of long-chain fatty acids with one or two hydroxyl groups of the polyhydroxycarboxylic acid.

[0017] Also, according to the invention, there is provided a process for the preparation of a non-aqueous lubricating composition, which method comprises mixing an oil with a lubricating viscosity with an effective amount of at least one long chain fatty acid ester of a hydroxycarboxylic acid, wherein the long chain fatty acid has from 8 to 22 carbon atoms. , and the ester is an oil-soluble mono- or polyhydroxycarboxylic acid ester having 1 to 4 groups, which are independently acid groups

-Carboxylic esters or their lower hydrocarbon esters, wherein the lower hydrocarbon esters have hydrocarbon moieties that independently have 1 to 6 carbon atoms, and wherein when the hydroxycarboxylic acid is a monohydroxycarboxylic acid, the ester has a long-chain fatty acid ester moiety with a hydroxy hydroxycarboxylic acid group, and when the hydroxycarboxylic acid is a polyhydroxycarboxylic acid, the ester has, independently, esters of long-chain fatty acids with one or two hydroxyl groups of the poly-hydroxycarboxylic acid.

the ester has independent long-chain fatty acid ester moieties with one or two hydroxyl groups of poly-hydroxycarboxylic acid and (ii) at least one other lubricating additive. The additive concentrate can be used in a method for improving the anti-wear and / or friction properties of an oil with a lubricating viscosity according to the invention. The additive concentrate may be used in a method for preparing a lubricant composition according to the invention.

[0019] According to a further embodiment of the invention, there is provided a fuel composition for an internal combustion engine, which composition comprises a larger amount of liquid fuel and a small amount of at least one long chain fatty acid ester of a hydroxycarboxylic acid, wherein the long chain fatty acid is from 8 to 22 carbon atoms, and the ester is an oil-soluble mono- or poly-hydroxycarboxylic acid ester having 1 to 4 groups, which are independently carboxylic acid groups or their lower hydrocarbon esters, the lower hydrocarbon esters having hydrocarbon moieties that independently have 1 to 6 carbon atoms, and wherein when the hydroxycarboxylic acid is a monohydroxycarboxylic acid,the ester has a long chain fatty acid ester moiety with a hydroxy group of the hydroxycarboxylic acid, and when the hydroxycarboxylic acid is a polyhydroxycarboxylic acid, the ester has, independently, the esters of long-chain fatty acids with one or two hydroxyl groups of the poly-hydroxycarboxylic acid.

[0020] Also, according to the invention, there is provided a method of improving anti-wear and / or friction properties of a liquid fuel, which method comprises mixing

- a liquid fuel with an effective amount of at least one long chain fatty acid ester of a hydroxycarboxylic acid, wherein the long chain fatty acid has from 8 to 22 carbon atoms, and the ester is an oil-soluble mono- or poly-hydroxycarboxylic acid ester having 1 to 4 groups, which are independently carboxylic acid groups or their lower hydrocarbon esters, wherein the lower hydrocarbon esters have hydrocarbon moieties which independently have 1 to 6 carbon atoms, and wherein when the hydroxycarboxylic acid is a mono-hydroxycarboxylic acid, the ester has a long-chain fatty acid ester moiety. with a hydroxy group of a hydroxycarboxylic acid, and when the hydroxycarboxylic acid is a polyhydroxycarboxylic acid,the ester has, independently, esters of long-chain fatty acids with one or two hydroxyl groups of poly-hydroxycarboxylic acid.

[0021] Also, according to the invention, a method of making a fuel composition for an internal combustion engine is provided, which method comprises mixing a liquid fuel with an effective amount of at least one long chain fatty acid ester of a hydroxycarboxylic acid, wherein the long chain fatty acid is from 8 to 22. carbon atoms, and the ester is an oil-soluble mono- or poly-hydroxycarboxylic acid ester having 1 to 4 groups, which are independently carboxylic acid groups or their lower hydrocarbon esters, the lower hydrocarbon esters having hydrocarbon moieties that independently have 1 to 6 carbon atoms, and wherein when the hydroxycarboxylic acid is a monohydroxycarboxylic acid,the ester has a long chain fatty acid ester moiety with a hydroxy group of the hydroxycarboxylic acid, and when the hydroxycarboxylic acid is a polyhydroxycarboxylic acid, the ester has, independently, the esters of long-chain fatty acids with one or two hydroxyl groups of the poly-hydroxycarboxylic acid.

and when the hydroxycarboxylic acid is a polyhydroxy carboxylic acid, the ester has, independently, esters of long-chain fatty acids with one or two hydroxyl groups of the polyhydroxycarboxylic acid and (ii) at least one other lubricating additive. The additive concentrate can be used in a method for improving anti-wear and / or friction properties

- solid fuel according to the invention. The additive concentrate may be used in the method for producing the fuel composition of the invention.

According to a further aspect of the invention there is provided a method of operating an internal combustion engine, which method comprises providing a liquid fuel oil, lubricity viscosity oil and at least one long chain fatty acid ester of a hydroxycarboxylic acid, wherein the long chain fatty acid is from 8 to 22 carbon atoms, and the ester is an oil-soluble mono- or polyhydroxy carboxylic acid ester having 1 to 4 groups, which are independently carboxylic acid groups or their lower hydrocarbon esters, wherein the lower hydrocarbon esters have hydrocarbon moieties that independently have 1 to 6 atoms carbon, and wherein when the hydroxycarboxylic acid is a monohydroxycarboxylic acid,the ester has a long chain fatty acid ester moiety with a hydroxy hydroxycarboxylic acid group, and when the hydroxycarboxylic acid is a polyhydroxycarboxylic acid, the ester has independently long-chain fatty acid ester moieties with one or two hydroxyl groups of poly-hydroxycarboxylic acid, the long-chain fatty acid ester is provided in a mixture with liquid fuel and / or oil with lubricating viscosity.

[0024] It has been found that the ester, as defined herein, has the effect of a friction modifier. It has been found that the ester, as defined herein, has an anti-wear effect. It has been found that, in particular, the ester as defined herein has both a friction modifier effect and an anti-wear action. Accordingly, the invention provides in particular for the use of an ester as defined herein as a friction modifier. The invention provides the use of an ester as defined herein as an anti-wear additive. The invention also provides the use of an ester as defined herein as a friction modifier and anti-wear additive.

and when the hydroxycarboxylic acid is a polyhydroxycarboxylic acid, the ester has, independently, esters of long-chain fatty acids with one or two hydroxyl groups of the poly-hydroxycarboxylic acid. The use can be in any of the embodiments of the invention including: non-aqueous lubricating composition, method

- lubricating the internal combustion engine, a method for improving the anti-wear and / or friction properties of a lubricating oil, a non-aqueous lubricating composition, an additive concentrate for a non-aqueous lubricant composition, a fuel composition (e.g. for an internal combustion engine), a method for improving anti-wear and anti-wear properties and / or friction of liquid fuel, a method of producing a fuel composition for an internal combustion engine, a concentrate of an additive for a fuel composition for an internal combustion engine and an internal combustion engine operating method.

In a particular aspect, the invention provides use as an anti-wear additive and / or friction modifier in a non-aqueous lubricant composition and / or in a fuel composition of at least one long-chain fatty acid ester of a hydroxycarboxylic acid, wherein the long-chain fatty acid has from 8 to 22 carbon atoms. , and the ester is an oil-soluble mono- or polyhydroxycarboxylic acid ester having 1 to 4 groups, which are independently carboxylic acid groups or their lower hydrocarbon esters, the lower hydrocarbon esters having hydrocarbon moieties that independently have 1 to 6 carbon atoms, and wherein, when the hydroxycarboxylic acid is a monohydroxycarboxylic acid, the ester has a long chain fatty acid ester moiety with a hydroxyl group of a hydroxycarboxylic acid,and when the hydroxycarboxylic acid is a polyhydroxycarboxylic acid, the ester has, independently, esters of long-chain fatty acids with one or two hydroxyl groups of the poly-hydroxycarboxylic acid.

[0027] Preferably, the oil-soluble ester comprises at least one long-chain fatty acid ester moiety in the alpha position relative to the carboxylic acid or lower hydrocarbon ester group.

[0028] The oil-soluble ester of the invention may desirably contain from 16 to 80 carbon atoms. The number of carbon atoms in the ester may affect its solubility in oil with lubricating viscosity and / or liquid fuel.

[0029] By oil-soluble it is understood that the ester is dissolved in an oil with a lubricating viscosity and / or a liquid fuel, respectively in an amount improving the friction and / or anti-wear properties, for example in a mass amount of at least 200 ppm at oil with a lubricating viscosity and / or a mass amount of at least 10 ppm in liquid fuel. The solubility can be determined at ambient temperature, e.g. at 20 ° C. The solubility can be determined at atmospheric pressure.

[0030] Suitable mono-hydroxycarboxylic acids include:

o glycolic acid (sometimes also referred to as 2-hydroxyethanic acid or hydroxyacetic acid);

o citric acid (sometimes also referred to as 3-carboxy-3-hydroxypentanedioic acid; 2-hydroxypropane-1,2,3-tricarboxylic acid or 3-hydroxypentanedioic acid-3-carboxylic acid);

- lactic acid (sometimes also referred to as 2-hydroxypropanoic acid);

o malic acid (sometimes also called hydroxybutanedioic acid);

o monohydric trimesic acid; and hydrogenated monohydric trimesic acid (sometimes also called 1,3,5 tricarboxy, 2-hydroxy cyclohexane).

[0031] A preferred mono-hydroxycarboxylic acid is citric acid.

[0032] Suitable poly-hydroxycarboxylic acids include:

o tartaric acid (sometimes also called 2,3-dihydroxybutanedioic acid, or 2,3-dihydroxysuccinic acid).

[0033] A preferred poly-hydroxycarboxylic acid is tartaric acid.

[0034] The long-chain fatty acid ester has from 8 to 22 carbon atoms. The long-chain fatty acid may be saturated, mono-unsaturated or polyunsaturated. Suitable long-chain fatty acids which are saturated carboxylic acids include, for example, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid and arachidic acid. Suitable long-chain fatty acids, which are mono-unsaturated acids or polyunsaturated acids, include, for example, oleic acid, linoleic acid, linolenic acid, oleomininic acid, palmitoleic acid, sapienic acid, erucic acid and brasidic acid. The long chain fatty acid may be branched or linear. The long-chain fatty acid may be a monocarboxylic or a polycarboxylic acid. The long chain fatty acid may have 8 to 22 carbon atoms, more suitably 8 to 18 carbon atoms or 14 to 22 carbon atoms, e.g. 8, 14, 16 or 18 carbon atoms, particularly 8, 14 or 18 carbon atoms, more particularly 14 atoms coal. Suitable saturated C8 monocarboxylic acids include octanoic acid. Suitable saturated C14 monocarboxylic acids include myristic acid. Suitable saturated C 16 monocarboxylic acids include palmitic acid. Suitable saturated C18 monocarboxylic acids include stearic acid. Suitable unsaturated C18 monocarboxylic acids include oleic acid and linoleic acid. more particularly 14 carbon atoms. Suitable saturated C8 monocarboxylic acids include octanoic acid. Suitable saturated C14 monocarboxylic acids include myristic acid. Suitable saturated C 16 monocarboxylic acids include palmitic acid. Suitable saturated C18 monocarboxylic acids include stearic acid. Suitable unsaturated C18 monocarboxylic acids include oleic acid and linoleic acid. more particularly 14 carbon atoms. Suitable saturated C8 monocarboxylic acids include octanoic acid. Suitable saturated C14 monocarboxylic acids include myristic acid. Suitable saturated C 16 monocarboxylic acids include palmitic acid. Suitable saturated C18 monocarboxylic acids include stearic acid. Suitable unsaturated C18 monocarboxylic acids include oleic acid and linoleic acid.

[0035] Each carboxylic acid group of a mono- or polyhydroxy carboxylic acid can be independently substituted or substituted as a lower hydrocarbon ester. The lower hydrocarbon esters have hydrocarbon moieties that can have independently 1 to 6 carbon atoms. The lower hydrocarbon moieties can be independently straight or branched alkyl moieties. The lower hydrocarbon moieties of the lower hydrocarbon esters can be independently C1 to C6 alkyl moieties respectively C1 to C3 alkyl moieties, more suitably ethyl moieties.

[0036] Suitably, the ester is triethyl citrate oleate (sometimes also referred to as oleyl triethyl citrate). It is believed that triethyl citrate oleate is

-New relationship. Suitably, the ester is triethyl citrate octaate or triethyl citrate myristate, especially triethyl citrate myristate.

[0037] Suitably, the ester is diethyl diolate (sometimes also called diethyl dioleate tartrate or dioleyl diethyl tartrate).

[0038] Long-chain fatty acid esters as defined in accordance with the invention have the advantage that they do not contain zinc or molybdenum, i.e. they are free of molybdenum and zinc. They also have the advantage that they are free of sulfur and phosphorus. Generally, esters as defined herein have low volatility.

[0039] Long chain fatty acid esters as defined according to the invention may be prepared by methods known in the art, for example by reaction of a suitable long-chain fatty acid with a suitable mono- or poly-hydroxycarboxylic acid or its corresponding lower hydrocarbon esters. Another suitable method is to react the acyl halide with a suitable long-chain fatty acid with the corresponding mono- or poly-hydroxycarboxylic acid or its corresponding lower hydrocarbon ester. For example, triethyl citrate oleate can be prepared by reacting triethyl citrate with oleyl chloride, e.g. in the presence of sodium hydride and a tetrahydrofuran solvent. Esters can be made in the Yamaguchi reaction.

[0040] Esters can also be prepared using enzymes as catalysts for biological esterification. Lubricant compositions and additive concentrates for lubricating compositions.

[0041] The amount of the at least one long-chain fatty acid ester in the lubricant composition may be in the range of 0.02% to 5% by weight, preferably in the range of 0.1 to 2.5% by mass.

[0042] The concentration of the at least one long chain fatty acid ester in the additive concentrate may be in an amount sufficient to produce the required concentration used in the lubricant composition. The additive concentrate may be used in the lubricant composition in an amount of 0.5 to 20% by weight. Accordingly, the amount of long-chain fatty acid ester and other additives in the lubricant concentrate may be more concentrated than in the lubricant composition, e.g. by a factor of from 1: 0.005 to 1: 0.20.

[0043] The lubricious composition contains a significant amount of lubricating oil and a small amount of at least one long chain fatty acid ester. The main quantity means more than 50%, and the smaller amount means less than 50% by mass.

[0044] The lubricant composition and lubricity viscosity oil may comprise a base oil. The base oil contains at least one base solution. The lubricating oil may contain one or more additives other than at least one long chain fatty acid ester. Suitably, a lubricant composition and / or a viscous oil

The lubricant contains a base oil in an amount from above 50% to about 99.5% by weight, e.g. from about 85% to about 95% by weight.

[0045] Base solutions can be defined as groups I, II, III, IV and V of the base solutions according to the API standard 1509, "ENGINE OIL LICENSING AND CERTIFICATION SYSTEM", April 2007, version 16 edition, Annex E, as specified in Table 1 .

Base solutions of Group I, Group II and Group III can be obtained from stock solutions of Group I mineral oils, which are usually prepared using known processes including solvent extraction and solvent dewaxing, or solvent extraction and catalytic dewaxing. Group II and Group III stock solutions are usually prepared by known processes including catalytic hydrogenation and / or catalytic hydrocracking, and catalytic hydroisomerization. The appropriate Group I stock solution is AP / E core 150, available from ExxonMobil. Suitable Group II stock solutions are EHC 50 and EHC 110, available from ExxonMobil. Suitable Group III stock solutions include Yubase 4 and Yubase 6 available from, for example, SK Lubricants. Suitable Group V base solutions are ester base solutions, for example, Priolube 3970, available from Croda International plc. Suitable Group IV stock solutions include hydrogenated oligomers of alphaolefins. Accordingly, the oligomers may be prepared by free radical processes, in a Zeigler catalyst or a Friedel-Crafts cation catalyst. The polyalphaolefin base solutions can be derived from C8, C10, C12, C14 olefins and mixtures of one or more of them.

Table 1

<td>Group</td><td>Content of saturated hydrocarbons (in% by mass) ASTM D2007</td><td></td><td>Sulfur content (in% mass) ASTM D2622 or D4294 or D4927 or D3120</td><td></td><td>ASTM D2270 viscosity index</td>

<td>AND</td><td>&lt;90</td><td>and / or</td><td>&gt; 0.03</td><td>and</td><td>&gt; 80 and &lt;120</td>

<td>II</td><td>&gt; 90</td><td>and</td><td>&lt;0.03</td><td>and</td><td>&gt; 80 and &lt;120</td>

<td>III</td><td>&gt; 90</td><td>and</td><td>&lt;0.03</td><td>and</td><td>&gt; 120</td>

<td>IV</td><td colspan="5">polyalphaolefins</td>

<td>V</td><td colspan="5">All stock solutions not in groups I, II, III or IV</td>

[0047] The lubricity composition and lubricating viscosity oil may comprise one or more base oils and / or stock solutions which are / are natural oils, mineral oils (sometimes called crude oil oils or petroleum mineral oils), non-mineral oils and mixtures thereof. Natural oils include animal oils, fish oils, and vegetable oils. Mineral oils include paraffin oils, oils

-Tenaphtenes and naphthenic paraffinic oils. Mineral oils may also contain oils derived from coal or slate.

[0048] Suitable base oils and oils of the stock solutions can be obtained from processes such as the chemical combination of simpler or smaller molecules into larger or more complex molecules (eg, polymerization, oligomerization, condensation, alkylation, acylation).

[0049] Suitable base solutions and base oils can be obtained from liquid materials from gases, liquid carbon materials, liquid biomass materials, and combinations thereof.

[0050] Liquid materials from gases (sometimes also referred to as GTL materials) can be obtained in one or more steps of the synthesis, combination, transformation, rearrangement, degradation and combination of two or more of them used for gaseous carbon-containing compounds. Base solutions and base oils derived from GTL can be obtained by the Fischer-Tropsch synthesis process, where a synthesis gas containing a mixture of hydrogen and carbon monoxide is catalytically converted to hydrocarbons, usually waxy hydrocarbons, which are generally converted to lower boiling point materials. by means of hydroisomerization and / or removal of the wax (see, for example, WO 2008/124191).

[0051] Liquid materials from biomass (sometimes also referred to as BTL materials) can be produced from compounds of plant origin, for example by hydrogenation of carboxylic acids or triglycerides to form linear paraffins, followed by hydroisomerization to form branched paraffins (see, for example, WO -2007068799-A).

[0052] Liquid carbon materials can be produced by gasification of coal to produce synthesis gas, which is then converted to hydrocarbons.

The base oil and / or the oil with a lubricating viscosity may have a kinematic viscosity at 100 ° C in the range of from 2 to 100 cSt, in the range of 3 to 50 cSt, and more suitably in the range of 3.5 to 25 cSt.

[0054] The lubricant composition according to the invention may be a composition of a multi-grade oil composition with a lubricating viscosity according to API xW-y, where x is 0, 5, 10, 15 or 20, and y is 20, 30, 40, 50 or 60, as determined according to SAE standard J300 2004, eg 5W-20, 5W-30, 0W-20. The lubricant composition may have an HTHS viscosity at 150 ° C of at least 2.6cP, for example measured according to ASTM D4683, CEC L-36-A-90 or ASTM D5481.

[0055] The lubricious composition may have an HTHS viscosity at 150 ° C, according to ASTM D4683 from 1 to &lt;2.6cp, e.g. 1.8cP.

[0056] The lubricious composition can be prepared by mixing an oil with a lubricating viscosity with an effective amount of at least one long-chain fatty acid ester, together with optionally at least one other lubricating additive.

[0057] The method of preparing the lubricant composition and the method for improving the anti-wear and / or friction properties of an oil with a lubricating viscosity include mixing an oil with a lubricating viscosity with an effective amount of at least one long-chain fatty acid ester.

[0058] The oil with a lubricating viscosity can be mixed with at least one long-chain fatty acid ester in one or more steps by methods known in the art. The at least one long-chain fatty acid ester may be admixed as one or more additive concentrates or a portion of the additive concentrate package, optionally containing a solvent or diluent. Lubricating oil can be prepared by mixing at one or more stages by methods known in the art, one or more base oils and / or stock solutions, optionally with one or more additives and / or part of the additive concentrate package. Long chain fatty acid esters,

Other anti-wear additives [0059] The lubricious composition and the additive to the lubricant concentrate composition may further comprise at least one anti-wear additive other than at least one long-chain fatty acid ester. Such other anti-wear additives may be ash-producing additives or ash-free additives. Examples of such other anti-wear additives that do not contain phosphorus include, for example, sulphated olefins. Examples of such other anti-wear additives also include anti-wear additives containing phosphorus. Examples of suitable phosphorus-containing phosphorus-containing additives are triaryllyl phosphite and triphenylphosphorothionate and those disclosed in paragraph [0036] US2005 / 0198894. Examples of suitable ash-producing anti-wear additives containing phosphorus include dihydrogen phosphorodithioate metal salts. Examples of suitable metals for the dihydrogen phosphorodithium metal salts include alkali and alkaline earth metals, aluminum, lead, tin, molybdenum, manganese, nickel, copper and zinc. Particularly suitable divinylhydromysulfophosphate metal salts are zinc dihydrofluorophosphates (ZDDP). The ZDDP may contain hydrocarbon groups having independently 1 to 18 carbon atoms, 2 to 13 carbon atoms, or 3 to 18 carbon atoms, more suitably 2 to 12 carbon atoms, or 3 to 13 carbon atoms, e.g. 3 to 8 carbon atoms, respectively. . Examples of suitable hydrocarbon groups include alkyl, cycloalkyl and alkylaryl groups which may contain ether or ester linkages, and which may contain substituent groups, for example, halogen or nitro groups. The hydrocarbon groups may be alkyl groups that are linear and / or branched and may have from 3 to 8 carbon atoms, respectively. The ZDDP having a hydrocarbon group which is a mixture of secondary alkyl groups and primary alkyl groups, e.g., 90 mol, is particularly suitable. % secondary alkyl groups and 10 mol. % primary alkyl groups. % secondary alkyl groups and 10 mol. % primary alkyl groups. % secondary alkyl groups and 10 mol. % primary alkyl groups.

[0060] The at least one long-chain fatty acid of the invention can reduce the amount of phosphorus and / or zinc containing anti-wear additives that may be required to achieve the desired amount of anti-wear properties in the lubricant composition.

[0061] Phosphorous-containing anti-wear additives may be present in the lubricating oil composition at a concentration of 10 to 6000 ppm by mass of phosphorus, suitably 10 to 1000 ppm by mass of phosphorus, e.g. 200 to 1400 ppm by mass of phosphorus, or 200 to 800 ppm by mass of phosphorus or from 200 to 600 ppm by mass phosphorus.

[0062] It has been found that the presence in the lubricant composition of at least one long-chain fatty acid ester, defined according to the invention, can participate in the performance of anti-wear additives, e.g. additions of zinc divinylglycium phosphate. This may have the advantage of reducing the amount of metals, e.g. zinc, or other ash-forming elements present in the lubricant composition.

[0063] It may also have the advantage of reducing the amount of anti-wear additives containing phosphorus in the lubricant composition, which in turn may reduce the amount of phosphorus in the exhaust when the lubricant is used to lubricate the internal combustion engine. Reducing the amount of phosphorus in the exhaust can have benefits for any exhaust gas treatment system.

[0064] It may also have the advantage of reducing the amount of sulfur-containing anti-wear additives in the lubricant composition, which in turn may reduce the amount of sulfur in the exhaust when the lubricant is used to lubricate the internal combustion engine. Reducing the amount of sulfur in the exhaust can have benefits for any exhaust gas cleaning system.

Other friction modifiers.

[0065] The lubricious composition and additive concentrate for the lubricant composition may further comprise at least one friction modifier other than at least one long chain fatty acid ester. Such other friction modifiers may be ash producing additives or ashless additives. Examples of such other friction modifiers include fatty acid derivatives, including, for example, other fatty acid esters, amides, amines, and ethoxylated amines. Examples of suitable ester friction modifiers include glycerol esters, for example mono-, di- and tri-oleinates, mono-palmitates and mono-myristinates. A particularly suitable friction modifier of the fatty acid ester is glycerol monooleate. Examples of such other friction modifiers may also include molybdenum compounds, e.g. organic molybdenum compounds, molybdenum dialkyldithiocarbamates, molybdenum dialkylthiophosphates, molybdenum disulphide, cluster molybdenum tri-dialkilithiocarbamates, non-sulfur molybdenum compounds and the like. Suitable molybdenum containing compounds are described, for example, in EP-1533362-A1, e.g. in the paragraphs [0101] to [0117].

[0066] Friction modifiers other than the long-chain fatty acid esters of the invention may also comprise a combination of alkoxylated hydrocarbon amines and

A partial polyol of a saturated or unsaturated fatty acid ester or a mixture of such esters, e.g. as described in WO 93/21288.

[0067] The long chain fatty acid esters of the invention may be used as an alternative to other friction modifiers or may reduce the amount of such other friction modifiers that may be required to achieve the desired frictional property of the lubricant composition. This may have the advantage of reducing the amount of metals, e.g. molybdenum, present in the lubricant composition.

[0068] Friction modifiers other than the long chain fatty acid esters of the invention, which are other derivatives of fatty acid friction modifiers, may be present in the lubricating oil composition at a concentration of 0.01 to 5% by weight of active compounds, more suitably in the range of 0 , 01 to 1.5% by mass of active substances.

[0069] Molybdenum containing friction modifiers may be present in the lubricious oil composition at a concentration of 10 to 1000 ppm by mass molybdenum, more suitably in the range of 400 to 600 ppm by mass.

Other additions.

[0070] The lubricity composition and concentrate of the additive to the lubricant composition may also contain other additives. Examples of such other additives include dispersants (metallic and non-metallic), dispersion viscosity modifiers, detergents (metallic and non-metallic), viscosity index improving, viscosity modifiers, freezing point depressants, rust inhibitors, corrosion inhibitors, antioxidants (sometimes called also oxidation inhibitors), antifoaming agents (sometimes also referred to as antifoaming agents), swelling agents (sometimes also known as sealing compatibility measures), extreme pressure additives (metallic, non-metallic, phosphorus-free, phosphorus-free, sulfur-containing) and sulfur-free), surfactants, demulsifiers,

Dispersants [0071] Dispersants (also called dispersant additives) help to maintain a solid and liquid impurity, for example due to oxidation during use of a lubricant composition, in a slurry and thus reduce sludge flocculation, precipitation and / or deposition e.g. on a lubricant coated surface. In general, they contain long-chain hydrocarbons to promote solubility of the oil and a polar head capable of associating with the material to be dispersed. Examples of suitable dispersants, including oil-soluble polymer hydrocarbon backbones, each of which has one or more functional groups that are capable of association with molecules to be dispersed. The functional groups may be amine, alcohol, amino-alcohol, amide or ester groups. The functional groups can be attached to the hydrocarbon backbone via bridging groups. More than one dispersing agent may be present in the additive concentrate and / or the lubricant composition.

[0072] Examples of suitable ashless dispersing agents include oil-soluble salts, esters, amino esters, amides, imides and oxazolines of long-chain hydrocarbons with substituted mono- and poly-carboxylic acids and their anhydrides; thiocarboxylate derivatives of long-chain hydrocarbons; long-chain aliphatic hydrocarbons having polyamine moieties attached directly to it; Mannich condensation products formed by the condensation of long-chain substituted phenol with formaldehyde and polyalkylene polyamine; reaction products Kocha and the like. Examples of suitable dispersing agents include derivatives of long-chain hydrocarbyl-substituted carboxylic acids, for example when the hydrocarbon group has a number-average molecular weight of up to 20,000, e.g. 300 to 20,000, 500 to 10000, 700 to 5000 or less than 15,000. Examples of suitable dispersing agents include hydrocarbon-substituted succinic acid compounds, e.g. succinimide, succinate esters or succinate ester amides, and especially polyisobutenyl succinimide dispersible. The dispersing agents can be borated or not borated. A suitable dispersant is ADX 222.

Dispersing viscosity modifiers.

[0073] Additionally or alternatively, the dispersibility can be provided by polymeric compounds that can provide a viscosity index that improves properties and dispersion. Such compounds are generally known as the dispersing viscosity of the improving or multifunctional additives that increase the viscosity. Examples of suitable dispersion viscosity modifiers may be prepared by chemical attachment of functional moieties (e.g., amines, alcohols and amides) to polymers that typically have number average molecular weights of at least 15,000, for example in the range of 20,000 to 600,000 (for example, gel permeation chromatography) -permission or light scattering methods). Examples of suitable viscosity modifying dispersants and processes for their preparation are described in WO 99/21902, WO2003 / 099890 and WO2006 / 099250.

Detergents [0074] Detergents (also called detergent additives) can contribute to reducing the formation of high temperature deposits, for example on pistons in internal combustion engines, including, for example, high temperature deposits of varnish and varnish, helping to keep the solids suspended in the slurry in lubricating composition. The detergents may also have acid neutralizing properties. Ashless (that is, no metal detergent) may be present. The metal-containing detergent contains at least one metal salt of at least one organic acid, which is called a soap or a surfactant. The detergents may be alkaline in which the detergent contains an excess of metal relative to the stoichiometric amount required to neutralize the organic acid. The excess metal is usually in the form of a colloidal dispersion of carbonate and / or metal hydroxide. Examples of suitable

-17 metals include Group I and Group 2 metals, more preferably calcium, magnesium and their combinations, especially calcium. More than one metal may be present.

[0075] Examples of suitable organic acids are sulphonic acids, phenols (sulphurized or preferably sulphurised, including, for example, phenols with more than one hydroxyl group, phenols from condensed aromatic rings, phenols that have been modified, for example phenols linked by alkylene and condensed phenols according to the Mannich principle and saligenin phenols, for example produced by reacting a phenol with an aldehyde under basic conditions) and sulphated derivatives thereof, as well as carboxylic acids, including, for example, aromatic carboxylic acids (e.g. hydrocarbyl-substituted salicylic acids and theirs); sulphurised derivatives, e.g. a hydrocarbon substituted salicylic acid and its derivatives). More than one type of organic acid may be present.

[0076] Additionally or alternatively, non-metallic detergents may be present. Suitable non-metallic detergents are described, for example, in US7622431.

[0077] More than one detergent may be present in the lubricant composition and / or the additive concentrate.

Viscosity Index Improvers / Viscosity Modifiers [0078] Viscosity index improvers (also called viscosity modifiers, viscosity improvers or VI enhancers) provide high and low temperature lubricity composition functionality and its simplification requires shear stability at elevated temperatures, while also exhibiting an acceptable viscosity and fluidity at low temperatures.

[0079] Examples of suitable viscosity modifiers include high molecular weight hydrocarbon polymers (e.g. polyisobutylene, ethylene and propylene copolymers and higher alpha-olefins); polyesters (e.g. polymethacrylates); hydrogenated poly (styrene-co-butadiene or isoprene) polymers and polymer modifications (e.g., star-shaped polymers); and esterified poly (styrene-co-maleic anhydride) polymers. The oil-soluble viscosity-modifying polymers generally have a number average molecular weight of at least 15,000 to 1,000,000, preferably 20,000 to 600,000, as determined by gel permeation chromatography or light scattering methods.

[0080] Viscosity modifiers may have additional functions as multifunctional viscosity modifiers. More than one viscosity index improver may be present.

Clot Point Depressants [0081] Clotting point depressants (also called lubricating oil improvers or lubricity oil flow improvers) lower the minimum temperature at which the lubricant will flow and can be poured. Examples of suitable freezing point depressants include C8 to C18 dialkyl fumarate / vinyl acetate copolymers, methacrylates, polyacrylates, polyarylamides, polymethacrylates, polyalkyl polyacrylates, vinyl fumarates, styrene esters, wax condensation products

-18haloparafinowych and aromatic compounds, vinyl carboxylate polymers, terpolymers of dialkylfumaranes, vinyl esters of fatty acids and allyl vinyl ethers, naphthalene wax and the like.

[0082] More than one freezing point depressant may be present.

Rust inhibitors [0083] Rust inhibitors generally protect lubricated metal surfaces against chemical attack by water or other contaminants. Examples of suitable rust inhibitors include nonionic polyoxyalkylene polyols and their esters, polyoxyalkylene phenols, polyoxyalkylene polyols, anionic alkylsulfonic acids, zinc dithiophosphates, metal phenolates, basic metal sulfonates, fatty acids and amines.

[0084] More than one rust inhibitor may be present.

Corrosion inhibitors [0085] Corrosion inhibitors (also called anti-corrosion agents) reduce the degradation of metal parts treated with a lubricating composition. Examples of corrosion inhibitors include phosphated hydrocarbons and products obtained by reacting a phosphored sulfuric hydrocarbon with an alkaline earth metal oxide or hydroxide, nonionic polyoxyalkylene polyols and their esters, polyoxyalkylene phenols, thiadiazoles, triazoles and anionic alkyl sulfonic acids. Examples of suitable corrosion inhibitors of epoxidized esters are described in US2006 / 0090393.

[0086] More than one corrosion inhibitor may be present.

Antioxidants [0087] Antioxidants (also called oxidation inhibitors) reduce the tendency of the oil to perish during use. Proof of this deterioration may be, for example, the production of varnish-type deposits on metal surfaces, the formation of deposits and the increase in viscosity. ZDDP have some antioxidant properties.

[0088] Examples of suitable anti-oxidants other than ZDDP include alkylated diphenylamines, N-alkylated phenylene diamines, phenyl-α-naphthylamines, alkylated phenyl-α-naphthylamines, dimethyl quinolines, trimethyl dihydroquinolines and oligomeric compositions derived therefrom, related phenolic compounds (in including ashless (metal-free) phenolic and neutral compounds and basic metal salts of certain phenolic compounds), aromatic amines (including alkylated and non-alkylated aromatic amines), sulphated alkyl phenols and alkali metal and alkaline earth metal salts, alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylidene bisphenols, thiopropionates, metal dithiocarbamates, 1,3,4-dimercaptothiadiazole and derivatives, oil-soluble copper compounds (e.g. dihydrocarbyl thio or thio-phosphate copper),salts of synthetic copper or natural carboxylic acid, e.g. C8 to C18 fatty acid, unsaturated acid or branched carboxylic acid, e.g. basic, neutral or acidic Cu salts^AND and / or Cu^II obtained from alkenylsuccinic acids or anhydrides), alkaline earth metal salts

-19-alkylpropano-esters, preferably having C5 to C12 alkyl side chains, nonylphenol calcium sulfide, t-octylphenyl sulphide, dioctylphenylamine, phosphorusulfurized or sulphurised hydrocarbons, oil-soluble phenolates, oil soluble sulphated phenolates, dodecylphenol calcium sulphide, phosphated hydrocarbons, sulphurated hydrocarbons, phosphoric esters, low sulfur decomposition agents and the like.

[0089] There may be more than one antioxidant. More than one type of antioxidant may be present.

Skimmers [0090] Defoamers (sometimes also referred to as defoaming agents) delay the formation of stable foams. Examples of suitable anti-foaming agents include silicones, organic polymers, siloxanes (including poly and (poly) dimethyl siloxanes, phenylmethyl siloxanes), acrylates and the like.

[0091] More than one skimmer may be present.

Swellable sealants [0092] Swellable sealants (sometimes also referred to as compatible sealants or elastomer compatibility additives) help swell elastomeric seals for example by causing a liquid reaction or a physical change in the elastomer. Examples of suitable swellable sealing agents are long-chain organic acids, organic phosphates, aromatic esters, aromatic hydrocarbons, esters (e.g. butylbenzyl phthalate) and polybutyl succinic anhydride.

[0093] More than one swellable sealing means may be present.

Other additives Examples of other additives that may be present in the composition of lubricating compositions and / or additive concentrates include additives for extreme pressures (including metallic, non-metallic, phosphorus-containing, phosphorus-free, sulfur-containing and sulfur-free additives for extreme pressures), surfactants, demulsifiers, anticonvulsants, wax-modifying agents, lubricants, anti-staining agents, chromophore agents and metal deactivators.

[0095] Some supplements may have more than one function.

[0096] The amount of the demulsifier, if present, can be higher than in conventional lubricants to compensate for each emulsification of at least one long-chain fatty acid ester.

Solvent [0097] The additive concentrate for the lubricant composition may include a solvent. Examples of suitable solvents include high aromatic solvents with low viscosity of base stocks, e.g. 100 N, 60 N and 100SP base stocks.

[0098] A representative corresponding and more suitable independent amount of additives (if present) in the lubricant composition are given in table 2. The concentrations in Table 2 are given in mass terms by active compound additions, regardless of any solvent or diluent.

[0099] More than one additive of each type may be present . For each type of additive, more than one class of this type of additive may be present. More than one additive of each additive class may be present. Additives may be conveniently provided by manufacturers and suppliers of solvents or diluents.

Table 2

<td></td><td colspan="2">Smooth composition</td>

<td>TYPE OF ADDITION</td><td>Right amount (active substances), if there (By weight)</td><td>More the right amount (substance active) if there (By weight)</td>

<td>The ester of a long-chain fatty acid hydroxycarboxylic acid, where the long-chain fatty acid is 8 to 22 carbon atoms and ester is an oil-soluble mono- or polyhydroxycarboxylic acid ester having 1 to 4 groups, which are independently acid groups % carboxylic acid or a lower hydrocarbon ester thereof, and wherein when the hydroxycarboxylic acid is a monohydroxycarboxylic acid, the ester has a long chain fatty acid ester moiety with an acid hydroxyl group hydroxycarboxylic acid, and when the acid Hydroxycarboxylic acid is a polyhydroxycarboxylic acid, the ester has, independently, esters of long-chain fatty acids with one or two hydroxyl groups of polyhydroxycarboxylic acid</td><td>0.02 to 5%</td><td>0.1 to 2.5%</td>

<td>Anti-wear additives containing phosphorus</td><td>corresponding to 10 to 6000 ppm P</td><td>corresponding to 10 to 1000 ppm P</td>

<td>Anti-wear additives containing molybdenum</td><td>corresponding to 10 up to 1000 ppm Mo</td><td>corresponding to 40 to 600 ppm Mo</td>

<td>Anti-wear additives containing boron</td><td>corresponding to 10 to 250 ppm B</td><td>corresponding to 50 to 100 ppm B</td>

<td>Friction modifiers other than esters of long-chain fatty acids</td><td>0.01 to 5%</td><td>0.01 to 1.5%</td>

<td>Friction modifiers containing molybdenum</td><td>corresponding to 10 to 1000 ppm Mo</td><td>corresponding to 400 to 600 ppm Mo</td>

<td>Dispersing agents</td><td>0.1 to 20%</td><td>0.1 to 8%</td>

<td>detergents</td><td>0.01 to 6%</td><td>0.01 to 4%</td>

<td>Additives improving viscosity index</td><td>0.01 to 20%</td><td>0.01 to 15%</td>

<td>Freezing point depressants</td><td>0.01 to 5%</td><td>0.01 to 1.5%</td>

<td>Corrosion and / or rust inhibitors</td><td>0.01 to 5%</td><td>0.01 to 1.5%</td>

<td>Antioxidants</td><td>0.1 to 10%</td><td>0.5 to 5%</td>

<td>Silicone-containing antifoams</td><td>corresponding to 1 to 20 ppm Si</td><td>corresponding to 1 to 10 ppm Si</td>

Lubricant applications.

[0100] Long chain fatty acid esters as defined according to the invention can be used as an anti-wear additive and / or friction modifier in a non-aqueous lubricant composition and / or in a fuel composition.

[0101] Long-chain fatty acid esters as defined according to the invention can be used as an over-loading additive and / or friction modifier in a lubricating composition that is a functional liquid, e.g. a metalworking fluid, which can be used to lubricate metals during machining, rolling and the like. Accordingly, the lubricant composition is a lubricious composition according to the invention.

[0102] Esters of long-chain fatty acids as defined according to the invention can be used as an over-loading additive and / or friction modifier in a lubricating composition that is a drive fluid, e.g. useful as an automatic transmission fluid, clutch fluid (e.g. a double clutch) , wetting agent, or other automotive applications and the like. Accordingly, the lubricant composition is a lubricious composition according to the invention. The additive and lubricant compositions may suitably be used in aviation lubricant applications [aircraft equipment].

[0103] Long-chain fatty acid esters as defined according to the invention can be used as an over-load additive and / or friction modifier in a lubricating composition suitable for use in turbine lubrication.

Long-chain fatty acid esters as defined according to the invention can be used as an over-loading additive and / or a friction modifier in a non-aqueous lubricating composition and / or fuel composition used for the lubrication of a solid surface, including for example metallic and non-metallic surfaces. Suitable metallic surfaces include surfaces of iron-based materials, e.g. cast iron and steel; surfaces of aluminum-based solids, e.g. aluminum-silicon alloys; surfaces of composites with a metallic matrix; surfaces of copper and copper alloys; surfaces of lead and lead alloys; surfaces of zinc and zinc alloys; and surfaces made of chromium-plated materials. Suitable non-metallic surfaces include surfaces of ceramic materials; surfaces of polymeric materials; surfaces made of carbon materials; and glass surfaces. Other surfaces that may be lubricated include surfaces of coated materials, e.g. surfaces of hybrid materials, e.g. metallic materials coated with non-metallic materials and non-metallic materials coated with metallic materials; surfaces of diamond-coated materials as well as SUMEBore ™ materials, for example as described in Sultzer technical overview 4/2009 on pages 1113.

[0105] Long chain fatty acid esters, as defined in accordance with the invention, can be used in non-aqueous lubricating compositions and / or fuel lubricants for surface spreading at any conventional temperature that can occur under lubricating conditions, e.g. at a temperature such as occur in an internal combustion engine, e.g. at a temperature ranging from ambient temperature to 250 ° C, e.g. 90 to 120 ° C. A typical ambient temperature may be 20 ° C, but may be less than 20 ° C, e.g. 0 ° C.

Lubrication of the internal combustion engine.

[0106] Long-chain fatty acid esters, as defined in accordance with the present invention, can be used as an anti-wear additive and / or friction modifier in a lubricating composition that can be used to lubricate an internal combustion engine, e.g. as a lubricant in the crankcase. The engine may be a spark-ignition engine, an internal combustion engine, or a compression-ignition internal combustion engine. The internal combustion engine can be a spark-ignition internal combustion engine used in the automotive and aerospace industries. The internal combustion engine can be a two-stroke diesel engine and the fatty acid ester with at least one long chain can be used as an anti-wear additive and / or friction modifier in the lubricating oil composition system and / or lubricator oil composition used for engine lubrication. The two-stroke diesel engine can be used in marine applications.

[0107] In the method of lubricating an internal combustion engine according to the invention, the fatty acid ester with at least one long chain may be present in the lubricating composition used for the lubrication of the engine, e.g. for the lubrication of the engine crankcase. Accordingly, such a lubricious composition is a lubricating composition according to the invention.

[0108] A fatty acid ester of at least one long chain can be added to the lubricant composition used to lubricate the engine by slow release of the additive to the lubricant - e.g. by contacting the lubricant composition with the additive-containing gel, e.g. as described in US6843916 and publication international patent application PCT - WO 2008/008864 and / or controlled release of an additive, e.g. when the back pressure of the lubricant passing through the filter exceeds a predetermined backpressure, e.g. as described in PCT Patent Application Publication WO2007 / 148047.

[0109] Additionally, or alternatively, a fatty acid ester with at least one long chain may be present in the fuel for the internal combustion engine. In use, a fatty acid ester with at least one long chain may pass with or without fuel to the lubricant composition used for lubricating the engine, e.g. as a lubricant for the crankcase, and thus provides the engine with favorable anti-wear and / or friction modifying properties.

[0110] According to a further aspect of the invention, there is provided a fuel composition for an internal combustion engine, wherein the composition comprises a larger amount of liquid fuel and a small amount of at least one ester of a long-chain fatty acid hydroxycarboxylic acid, which is an oil-soluble mono-ester of an acid. or a polyhydroxycarboxylic acid having from 1 to 4 groups, which are independently carboxylic acid groups or its lower hydrocarbon esters, wherein when the hydroxycarboxylic acid is mono-hydroxy carboxylic acid, the ester has a long chain fatty acid ester group hydroxyl hydroxylic acid group, and when the acid is Hydroxycarboxylic is a poly-hydroxycarboxylic acid,the ester has, independently, two long-chain fatty acid ester moieties from two hydroxyl groups of the poly-hydroxycarboxylic acid.

[0111] The engine may be a spark-ignition engine, an internal combustion engine, or a compression-ignition internal combustion engine. The engine may be a high-pressure internal combustion engine with a homogeneous charge. The internal combustion engine can be a spark-ignition internal combustion engine used in the automotive or aerospace industry. The internal combustion engine can be a two-cycle diesel internal combustion engine. The two-stroke diesel engine can be used in marine applications.

[0112] A fatty acid ester with at least one long chain may be present in the fuel at a concentration of up to 500 ppm by mass, for example from 20 to 200 ppm by mass or 50 to 100 ppm by mass.

[0113] Typically, the rate of fuel entering the crankcase lubricant is higher for spark-ignition internal combustion engines than for diesel engines. However, the rate at which fuel penetrates into the lubricant of the crankcase for diesel engines may depend and may increase depending on the strategy employed after the injection for engine operation.

[0114] At least one long-chain fatty acid ester as defined according to the invention when present in the fuel composition can reduce the fuel consumption in the engine fuel system, e.g. a fuel pump.

Fuels [0115] Suitable liquid fuels, in particular for internal combustion engines, include hydrocarbon fuels, oxygen fuels and combinations thereof. Hydrocarbon fuels may come from mineral sources and / or from renewable sources, such as biomass (e.g. biomass to a liquid source) and / or gas to a source liquid and / or from coal to a liquid source. Suitable biomass sources include sugar (e.g. sugar for diesel fuel) and algae. Suitable oxygen fuels include alcohols, for example, straight and / or branched alkyl alcohol chains containing from 1 to 6 carbon atoms, esters, e.g., fatty acid alkyl esters and ethers, e.g. methyl tert-butyl ether. Suitable fuels may also include LPG Diesel fuels (LPG is a liquid fuel gas). The fuel composition may be an emulsion. However,

[0116] Suitable fatty acid alkyl esters include methyl, ethyl, propyl, butyl and hexyl esters. Typically, a fatty acid alkyl ester is a fatty acid methyl ester. The fatty acid alkyl ester can have from 8 to 25 carbon atoms, suitably from 12 to 25 carbon atoms, for example from 16 to 18 carbon atoms. The fatty acid may be saturated or unsaturated. Typically, the fatty acid alkyl ester is acyclic. The fatty acid alkyl esters can be produced by esterifying one or more fatty acids and / or transesterifying one or more fatty acid triglycerides. Triglycerides can be obtained from vegetable oils, for example, castor oil, soybean oil, cottonseed oil, sunflower oil, rapeseed oil (which is sometimes called canola oil), Jatropha oil or palm oil, or obtained from sebum (for example, sheep and / or tallow of ox), fish oil or cooking oil. Suitable fatty acid alkyl esters include rapeseed oil methyl ester (RME), soybean methyl ester or combinations thereof.

[0117] The fuel composition according to the invention may be produced by mixing one or more hydrocarbon fuel stage, an oxygen fuel or combination thereof with an effective amount of at least one long chain fatty acid ester as defined in accordance with the invention and optionally at least one other fuel additive.

[0118] The method of producing a fuel composition and a method for improving anti-wear and / or frictional properties of a liquid fuel may include mixing in one or more steps of said liquid fuel (it may be, for example, hydrocarbon fuel, oxygen fuel or a combination thereof) with an effective amount of at least one ester of a long-chain fatty acid hydroxycarboxylic acid which is an oil-soluble ester of a mono- or poly-hydroxy carboxylic acid having from 1 to 4 groups which are independently carboxylic acid groups or their lower hydrocarbon esters in which when the hydroxycarboxylic acid is monohydroxy- carboxylic ester, the ester has a long chain fatty acid ester group of the carboxylic acid hydroxyl group, and when the hydroxycarboxylic acid is polyhydroxy carboxylic acid,the ester has independently two long-chain fatty acid ester groups from two hydroxyl groups of the carboxylic acid and optionally at least one other fuel additive.

[0119] The fuel may be mixed with at least one additive in one or more steps using methods known in the art. The additives can be mixed as one or more additive concentrates or a part of a set of additive concentrates, optionally containing a solvent or a diluent. The hydrocarbon fuel, oxygen fuel or a combination thereof may be prepared by mixing at one or more stages using methods known in the art, one or more base fuels and their components, optionally with one or more additives and / or part of the additive concentrate package. Additives, additive concentrates and / or a part of a set of additive concentrates may be mixed with fuel or their components in one or more of the stages using methods known in the art.

Fuels and concentrates for diesel engines.

[0120] The fuel composition of the invention may be suitable for use in an internal combustion engine in which a diesel internal combustion engine, respectively a direct injection diesel engine, e.g. a rotary pump, a straight pump, a generator pump, an electronic injector assembly, or a common type of railway, or in a diesel engine with indirect injection. The fuel composition can suitably be used in heavy and / or light light loads of diesel engines.

[0121] The fuel composition for compression-ignition internal combustion engines may have a sulfur content up to 500 ppm by mass, for example, up to 15 ppm by mass or up to 10 ppm by mass. The fuel composition for compression-ignition internal combustion engines can meet the requirements of EN 590, for example as defined in BS EN 590: 2009.

[0122] Suitable oxygenator components in the fuel composition for high pressure internal combustion engines include fatty acid alkyl esters, e.g. fatty acid methyl esters. The fuel may contain one or more fatty acid methyl esters, according to EN 14214, in a concentration of up to 7% by volume. Stability-enhancing agents for oxidation may be present in

A fuel composition comprising one or more alkyl or methyl fatty acid esters, e.g. at a concentration providing activity similar to that obtained with 1000 mg / kg of 3,5-di-tert-butyl-4-hydroxy-toluene (also referred to as butylated hydroxyl-toluene) or BHT). Dyes and / or markers may be present in the fuel composition for diesel internal combustion engines.

[0123] The fuel composition for compression-ignition internal combustion engines may have one or more of the following, for example as defined according to BS EN 590: 2009: - minimum cetane number 51.0, minimum cetane ratio 46.0, density at temperature 15 ° C from 820.0 to 845.0 kg / m³, maximum polycyclic aromatics content from 8.0% by mass, flashpoint above 55 ° C, maximum carbon residue (10%, distillation) from 0.30% by mass, maximum water content 200 mg / kg, maximum impurity 24 mg / kg , Class 1 Copper Corrugated Tape (3 h at 50 ° C) determines the minimum oxidation stability limit for 20 hours in accordance with EN 15751 and upper limit of oxidation stability 25 g / m³, in accordance with EN ISO 12205, the maximum limit for the wear scar diameter adjusted for lubricity at 60 ° C 460 μm, the minimum viscosity at 40 ° C is 2.00 mm²/ si maximum viscosity at 40 ° C, 4.50 mm²/ s, &lt;65% by volume recovery distillation at 250 ° C, minimum recovery distillation at 350 ° C 85% by volume, and maximum 95% volume recovery at 360 ° C.

[0124] The fuel composition, and the concentrate of additives to the fuel composition suitable for use in an internal diesel engine may further comprise at least one friction modifier other than a long chain fatty acid ester as defined in accordance with the invention. Such other friction modifiers include those described herein as friction modifiers for lubricant compositions and concentrates of additives for lubricant compositions.

[0125] The fuel composition and concentrate of additives for fuel compositions suitable for use in an internal diesel engine may further comprise at least one lubricity additive. Suitable lubricating additives include tall oil fatty acids, mono- and di-basic acids and esters.

[0126] The fuel composition and concentrate of additives for a fuel composition suitable for use in an internal diesel engine may further comprise independently one or more cetane imprints, one or more detergents, one or more antioxidants, one or more anti-foaming agents, one or more a demulsifier, one or more cold flow improver, one or more coagulation temperature depressants, one or more biocides, one or more fragrances, one or more coloring agent (sometimes called dyes), one or more markers, one or more rescue ignition and / or combinations of one or more of them. Other suitable additives that may be present include thermal stabilizers, metal deactivators, corrosion inhibitors, anti-static additives, drag agents, reducers,

Anti-recession nozzle valves, surfactants and combustion aids, e.g. as described in EP-2107102-A.

[0127] The additive concentrate for fuel compositions for a diesel internal combustion engine may include a solvent. Suitable solvents include carrier oils (e.g. mineral oils), polyethers (which may be closed or endless), non-polar solvents (e.g., toluene, xylene, white spirit and products sold by Shell under the trademark "SHELLSOL"), and polar solvents (for example, esters and alcohols, e.g. hexanol, 2-ethylhexanol, decanol, mixtures of isotridecanol and alcohol, for example those sold by Shell under the trade name "LINEVOL", e.g. LINEVOL 79 alcohol, which is a C7-9 mixture of primary alcohols, or C12-14 alcohol mixture that is commercially available.

[0128] Suitable cetane-improving agents include 2-ethyl hexyl nitrate, cyclohexyl nitrate and di-tert-butyl peroxide. Suitable defoamers include siloxanes. Suitable detergents include polyolefin substituted succinimides and polyamine succinamides, e.g. polyisobutene succinimides, polyisobutylene succinimide succinimides, aliphatic amines, Mannich bases and amines and polyolefins (e.g., polyisobutylene) maleic anhydrides. Suitable antioxidants include phenolic antioxidants (e.g. 2,6-di-tert-butylphenol) and amine antioxidants (e.g., N, N'-di-sec-butyl-p-phenylenediamine). Suitable defoamers include polyether-modified polysiloxanes.

[0129] A representative corresponding and more suitable independent amount of additives (if present) in the diesel fuel composition is given in Table 3. The concentrations expressed in Table 3 are by mass given for the active additive compounds, i.e. independently of any solvent or diluent.

[0130] Additives in the fuel composition suitable for use in high pressure internal combustion engines are suitably present in a total amount in the range of 100 to 1500 ppm by mass. Accordingly, the concentrations of the individual additives in the additive concentrates will be respectively higher than in the fuel composition, for example in a ratio of 1: 0.0002 to 0.0015. Additives can be used as partial packages, for example a part of additives (sometimes called refinery additions) added to a refinery for the production of a replacement fuel and some of the additives (called final or market additives) are added at the terminal or distribution point. At least one long chain fatty acid ester as defined according to the invention may be suitably added or used as an additive to a refinery or a turnover,

Table 3

<td></td><td colspan="2">Fuel composition for the combustion engine internal diesel</td>

<td>TYPE OF ADDITION</td><td>Right amount</td><td>More</td>

<td></td><td>(active substances), if present (ppm by mass)</td><td>the right amount (active substances), if any (ppm by mass)</td>

<td>A long chain fatty acid ester of the hydroxycarboxylic acid wherein the long chain fatty acid has 8 to 22 carbon atoms and the ester is an oil-soluble mono- or polyhydroxycarboxylic acid ester having 1 to 4 groups which are independently carboxyl groups or their lower hydrocarbon esters and wherein when the hydroxycarboxylic acid is a monohydroxycarboxylic acid, the ester has esters of long-chain fatty acids with an hydroxyl group of the acid hydroxycarboxylic acid, and when the acid Hydroxycarboxylic acid is a polyhydroxycarboxylic acid, the ester has, independently, esters of long-chain fatty acids with one or two hydroxyl groups of polyhydroxycarboxylic acid</td><td>20 to 500</td><td>20 to 200</td>

<td>Lubricating additives</td><td>1 to 200</td><td>50 to 200</td>

<td>Cetane enhancers</td><td>50 to 2000</td><td>100 to 1200</td>

<td>detergents</td><td>20 to 300</td><td>50 to 200</td>

<td>Antioxidants</td><td>1 to 100</td><td>2 to 50</td>

<td>Defoamers</td><td>1 to 50</td><td>5 to 20</td>

<td>Emulsifiers</td><td>1 to 50</td><td>5 to 25</td>

<td>Means that improve fluidity in low-caliber</td><td>10 to 500</td><td>50 to 100</td>

Fuels and concentrates for spark-ignition engines.

[0131] The fuel composition of the invention may be suitable for use in an internal combustion engine that is a spark-ignition internal combustion engine.

[0132] The fuel composition for spark-ignition internal combustion engines may have a sulfur content up to 50.0 ppm by mass, e.g. up to 10.0 ppm by mass.

[0133] The fuel composition for spark-ignition internal combustion engines may be lead-free or lead-free.

[0134] The fuel composition for spark-ignition internal combustion engines may meet the requirements of the EN 228 standard, for example defined in BS EN 228: 2008. The fuel composition for spark-ignition internal combustion engines may meet the requirements of ASTM D4814-09b.

[0135] The fuel composition for spark-ignition internal combustion engines may have one or more of the following, as defined in accordance with BS EN 228: 2008: - minimum octane number 95.0, minimum engine octane rating 85.0 maximum lead content 5.0 mg / l, density from 720.0 to 775.0 kg / m³, stability to oxidation of at least 360 minutes, maximum content of rubber (solvent washed) 5 mg / 100 ml, grade 1 of copper tape for corrosion (3 h at 50 ° C), clear and bright appearance, maximum olefin content 18.0% by mass , a maximum content of 35.0% by weight aromatic compounds, and a maximum benzene content of 1.00% by volume.

[0136] Suitable oxygenator components in the internal combustion fuel composition of the spark-ignition internal combustion include straight and / or branched chains of alkyl alcohols containing from 1 to 6 carbon atoms, e.g. methanol, ethanol, n-propanol, n-butanol, isobutanol, tert. butanol. Suitable oxygen components in the fuel composition for internal spark-ignition engines include ethers, for example having 5 or more carbon atoms. The fuel composition may have a maximum oxygen content of 2.7% by mass. The fuel composition may have a maximum amount of oxygenates as stated in EN 228, e.g. methanol: 3.0% by volume, ethanol: 5.0% by volume, iso-propanol: 10.0% by volume, iso-butyl alcohol 10.0% by volume, tert-butyl alcohol: 7.0% by volume, ethers (C5 or higher): 10% by volume and other oxygenates (subject to the respective final boiling point): 10.0% by volume. The fuel composition may contain ethanol in accordance with EN 15376, at a concentration of up to 5.0% by volume.

[0137] The fuel composition and concentrate of the additive to the fuel composition suitable for use in a spark-ignition engine may further comprise at least one friction modifier other than at least one long-chain fatty acid ester. Such other friction modifiers include compounds described herein as friction modifiers for lubricating compositions and concentrates of additives for lubricant compositions.

[0138] The fuel composition and concentrate of the additive to the fuel composition suitable for use in the spark ignition engine may further comprise independently one or more detergents, one or more octane improvers, one or more friction modifiers, one or more antioxidants, one or more valve seat recession additives, one or more corrosion inhibitor, one or more anti-static agent,

- one or more fragrances, one or more coloring agents, one or more markers and / or combinations of one or more of them.

[0139] The fuel additive additive composition for a spark-ignition internal combustion engine may contain a solvent. Suitable solvents include aromatic polyethers and / or aliphatic polyethers, e.g. naphtha, e.g. Solvesso (trade mark), xylenes and kerosene.

[0140] Suitable detergents include polyisobutylene amines (PIB amines) and polyether amines.

[0141] Suitable octane enhancers include N-methylanilines, tricarbonyl methyl cyclopentadienyl manganese (MMT) (for example at concentrations up to 120 ppm by mass), ferrocene (e.g. up to 16 ppm by mass) and lead tetraethyl (e.g. up to 0.7 g / l, e.g. up to 0.15 g / l).

[0142] Suitable antioxidants include phenolic antioxidants (e.g., 2,4-di-tert-butylphenol and 3,5-di-tert-butyl-4-hydroxyphenyl propionic acid) and amine antioxidants (e.g., para-phenylenediamine, dicyclohexylamine and its derivatives).

[0143] Suitable corrosion inhibitors include the ammonium salts of organic carboxylic acids, amines and heterocyclic aromatic compounds, for example, alkylamines, imidazolines and tolyl triazoles.

[0144] Additives for a valve-nest recession can be present in concentrations up to 15000 ppm by mass, e.g. up to 7,500 ppm by mass.

[0145] A representative suitable and more suitable independent amount of additives (if present) in the fuel composition suitable for a spark-ignition engine are shown in Table 4. The concentrations in Table 4 are expressed by mass according to active additive compounds that are independent of any solvent or diluent.

[0146] Additives in the fuel composition suitable for use in spark-ignition engines are suitably present in a total amount ranging from 20 to 25000 ppm by mass. Accordingly, the concentrations of the individual additives in the additive concentrate will be respectively higher than in the fuel composition, for example in a ratio of 1: 0.00002 to 0.025. Additives can be used as partial packages, for example a part of additives (sometimes called refinery additions) are added to the refinery for the production of replacement fuel, and some additives (sometimes called final or market additives) are added at the terminal at the distribution point. At least one long-chain fatty acid ester may be suitably added or used as an additive to the refinery or turnover, preferably as a marketing additive,

Table 4

<td></td><td colspan="2">Fuel composition for a spark-ignition internal combustion engine</td>

<td>Type of additive</td><td>Appropriate amount (active substances), if any (ppm by mass)</td><td>More the right amount (active substances), if any (ppm by mass)</td>

<td>The ester of a long-chain fatty acid hydroxycarboxylic acid, where the long chain fatty acid has 8 to 22 carbon atoms and the ester is an oil-soluble mono- or polyhydroxycarboxylic acid ester having 1 to 4 groups, which are independently carboxyl groups or their lower hydrocarbon esters and wherein, when the hydroxycarboxylic acid is a monohydroxycarboxylic acid, the ester has ester groups of long-chain fatty acids with the hydroxyl group of the acid hydroxycarboxylic acid when the acid Hydroxycarboxylic acid is a polyhydroxycarboxylic acid, the ester has, independently, esters of long-chain fatty acids with one or two hydroxyl groups of polyhydroxycarboxylic acid</td><td>20 to 500</td><td>20 to 200</td>

<td>Friction modifiers other than the above esters of long-chain fatty acids</td><td>10 to 500</td><td>25 to 150</td>

<td>detergents</td><td>10 to 2000</td><td>50 to 300</td>

<td>Octane enhancers</td><td>50 to 20,000</td><td></td>

<td>Antioxidants</td><td>1 to 100</td><td>10 to 50</td>

<td>Antistatic agents</td><td>0.1 to 5</td><td>0.5 to 2</td>

[0147] The invention will now be described by way of example only with reference to the following experiments and examples, wherein examples according to the invention are designated

Numerically as Example 1, Example 2, etc. and experiments not according to the invention are marked alphabetically as Experiment A, Experiment B, etc.

Preparation of triethyl citrate oleate.

A solution of triethyl citrate (0.87 g, 1 equivalent) in tetrahydrofuran (THF) was added to a solution of sodium hydride (0.2 g, 1.5 eq) in THF at 0 ° C and stirred at 0 ° C. for 1 hour. Then, oleoyl chloride (0.87 g, 1 equivalent) was added and stirred for 1 hour at 0 ° C under nitrogen. The mixture was stirred at 25-30 ° C for 8 hours. Thin layer chromatography analysis indicated that the reaction was complete. The mixture was quenched with cold water and extracted with ethyl acetate. The ethyl acetate layer was washed with sodium bicarbonate solution (10%), followed by water and then with brine solution. The resulting mixture was dried over sodium sulfate and concentrated to give the crude product. The purified product was obtained from the crude product by column chromatography, using 10% petroleum ether in ethyl acetate as the eluent. The product yield was 0.6 g. Preparation of lubricating compositions.

[0149] The 5W-30 lubricity composition (lubricant A) was prepared for a typical lubricant composition model suitable for passenger cars with a compression ignition or spark ignition internal combustion engine, but with a lower ZDDP content than a typical lubricant. The lubricant composition was made by mixing additives, such as in a commercially available set of additives containing a dispersant, detergent, antioxidant, anti-foam agent and ZDDP (but with a reduced amount of ZDDP) with Group III base oil, clotting point depressant, viscosity modifier and dispersing modifier viscosity.

[0150] The lubricity composition (lubricant) of the invention was obtained in the same manner as lubricant A, but from 2% by weight triethyl citrate oleate was prepared as described above. 2% by weight triethyl citrate oleate is a concentration comparable in molarity to 1% by mass of triethyl citrate, because the molecular weights of these compounds are 540.73 and 276.28, respectively.

[0151] Numerous other lubricant compositions (lubricants B to D) were prepared as lubricant 1, but with friction modifiers / anti-wear additives other than triethyl citrate oleate, as indicated below. Thus, glycerol monooleate (HiTEC® 7133) was used in lubricant B, triethyl citrate was used in lubricant C and Sakura-lube 165, the active ingredient that is molybdenum dithiocarbamate (MoDTC), was used in lubricant D.

[0152] Lubricants A to D are not, according to the invention, because the lubricant compositions do not contain any ester of a long-chain fatty acid with a hydroxycarboxylic acid, where the long acid chain has from 8 to 22 carbon atoms, the ester is an oil-soluble mono- or acid-ester; polyhydroxycarboxylic acid having 1 to 4 groups, which are independently carboxylic acid groups or their lower hydrocarbon esters, when the acid

-33-hydroxycarboxylic acid is a mono-hydroxy-carboxylic acid, the ester has a long-chain fatty acid ester group of the hydroxy hydroxycarboxylic acid group, and when the hydroxycarboxylic acid is polyhydroxycarboxylic, the ester contains independently long-chain fatty acid ester moieties with one or two hydroxyl groups of the polyhydroxycarboxylic acid. Lubricant 1 is according to the invention.

[0153] All lubricating compositions with a ZDDP content correspond to 0.0285 mass% of phosphorus.

1. Wear testing for lubricating compositions.

[0154] The thin-film wear test (TLA) was performed for lubricants A to D and lubricant 1.

[0155] The TLA wear test is a radio abrasion test for nucleotides used to simulate cam follower wear in the engine. The wear elements were radioactive and the rate at which the radioactive metal was consumed and accumulated in the oil was measured to assess wear in nm / h. The results for these tests carried out at 40 ° C are shown in Table 5. Experiments A to D are not, according to the invention, because the lubricant compositions do not contain at least one long-chain fatty acid ester. Example 1 is according to the invention.

[0156] The results in Table 5 show that the ester of a long-chain fatty acid hydroxycarboxylic acid, wherein the long-chain fatty acid has 8 to 22 carbon atoms and the ester is an oil-soluble mono- or polyhydroxycarboxylic acid ester having 1 to 4 groups, which are independently groups The hydroxyl carboxylic acid is a mono-hydroxycarboxylic acid, the ester has a long-chain fatty acid ester moiety with a hydroxy carboxylic acid group, and when the hydroxycarboxylic acid is a polyhydroxycarboxylic acid, the ester has, independently, the esters of long-chain fatty acids with one another. or two hydroxyl groups of a polyhydroxycarboxylic acid, in particular a long-chain fatty acid ester (e.g.oleic acid) of a hydroxycarboxylic acid having esters of lower hydrocarbons (e.g., ethyl) with 3 carboxylic acid groups (e.g., triethylcitric acid), e.g. triethyl citrate oleate, when used in the lubricant composition has good anti-wear properties, e.g. when used in combination with a low concentration of zinc dihydrogen dithiophosphates (ZDDP), for example corresponding to 285 ppm phosphorus.for example, corresponding to 285 ppm phosphorus.for example, corresponding to 285 ppm phosphorus.

Table 5.

<td></td><td>Center lubricant</td><td>Addition</td><td>The dose of the supplement antiwear (% by mass)</td><td>Speed consumption (Nm / h)</td><td>Reduction in wear compared to the Experience AND</td>

<td>Experience AND</td><td>AND</td><td>-</td><td>-</td><td>98.9</td><td>-</td>

<td>Example 1</td><td>1</td><td>oleate citrate triethyl</td><td>2%</td><td>45.1</td><td>54.4%</td>

<td>Experience B</td><td>B</td><td>monooleate glycerol (GMO)</td><td>0.5%</td><td>39.6</td><td>60.0%</td>

<td>Experience C</td><td>C</td><td>citrate triethyl</td><td>1%</td><td>37.1</td><td>62.5%</td>

<td>Experience D</td><td>D</td><td>Sakura-lube 165</td><td>1% (450 ppm Mo)</td><td>28.7</td><td>71%</td>

2. Wear tests of Cameron Plint.

[0157] Cameron Plint wear tests were performed on lubricants with the same compositions as those used in the previously described tests.

[0158] The Cameron Plint wear test was used to simulate boundary piston friction and produce wear at higher temperatures (100 ° C). The device was set in a configuration in the pin on the board. The bolt was moved in a reciprocating motion along the plate, at a frequency of 25 Hz, a stroke length of 2.3 mm, and using a pressure of 150N. The oil was introduced into the contact area at 3 ml / hour. In these tests a standard flat plate B01 made of steel and EN31 components were used. Plint roller. The results of the 21-hour tests are shown in Table 6. Experiments E to H are not according to the invention, because the lubricant compositions do not contain any ester of a long-chain fatty acid hydroxycarboxylic acid, wherein the long-chain fatty acid has 8 to 22 carbon atoms and the ester is an oil-soluble mono- or poly-hydroxycarboxylic acid ester having 1 to 4 groups, which are independently carboxyl groups or their lower hydrocarbon esters, and wherein the hydroxycarboxylic acid is monoacid. -hydroxycarboxylic acid, the ester has long chain fatty acid ester moieties with a hydroxy carboxylic acid group, and when the hydroxycarboxylic acid is a polyhydroxy carboxylic acid, the ester has, independently, the esters of long-chain fatty acids with one or two hydroxyl groups of the polyhydroxycarboxylic acid. Example 2 is according to the invention. which are independently carboxylic groups or their lower hydrocarbon esters and wherein when the hydroxycarboxylic acid is a mono-hydroxycarboxylic acid, the ester has long-chain fatty acid ester moieties with hydroxylic acid, and when the hydroxycarboxylic acid is a polyhydroxycarboxylic acid, the ester has independently long-ester esters fatty acids with one or two hydroxyl groups of polyhydroxycarboxylic acid. Example 2 is according to the invention. which are independently carboxylic groups or their lower hydrocarbon esters and wherein when the hydroxycarboxylic acid is a mono-hydroxycarboxylic acid, the ester has long-chain fatty acid ester moieties with hydroxylic acid, and when the hydroxycarboxylic acid is a polyhydroxycarboxylic acid, the ester has independently long-ester esters fatty acids with one or two hydroxyl groups of polyhydroxycarboxylic acid. Example 2 is according to the invention. the ester has, independently, esters of long-chain fatty acids with one or two hydroxyl groups of the polyhydroxycarboxylic acid. Example 2 is according to the invention. the ester has, independently, esters of long-chain fatty acids with one or two hydroxyl groups of the polyhydroxycarboxylic acid. Example 2 is according to the invention.

-35 Table 6

<td></td><td>Center lubricant</td><td>Addition</td><td>The dose of the supplement anti-wear (% by mass)</td><td>Volume consumption (m³/ Nm)</td><td>Redkucja consumption in compared to Experiment E</td>

<td>Experience E</td><td>AND</td><td>-</td><td>-</td><td>5,71x10^-17</td><td>-</td>

<td>Example 2</td><td>1</td><td>oleate citrate triethyl</td><td>2%</td><td>2,48x10^-18</td><td>95.7%</td>

<td>Experience F</td><td>B</td><td>monooleate glycerol (GMO)</td><td>0.5%</td><td>6,11615x10^-18</td><td>89.3%</td>

<td>Experience G</td><td>C</td><td>citrate triethyl</td><td>1%</td><td>2,96357x10^-18</td><td>94.8%</td>

<td>Experience H</td><td>D</td><td>Sakura-lube 165</td><td>1% (450 ppm Mo)</td><td>2,5002x10^-18</td><td>95.6%</td>

[0159] The results in Table 6 show that the long chain fatty acid ester of a hydroxycarboxylic acid, wherein the long chain fatty acid has 8 to 22 carbon atoms and the ester is an oil-soluble mono- or polyhydroxy carboxylic acid ester having 1 to 4 groups that are independently carboxylic groups or a lower hydrocarbon ester thereof, wherein when the hydroxycarboxylic acid is a mono-hydroxycarboxylic acid, the ester has long chain fatty acid ester moieties with a hydroxy carboxylic acid group, and when the hydroxycarboxylic acid is a polyhydroxycarboxylic acid, the ester has, independently, the long chain fatty acid ester moieties with one or more two hydroxyl groups of a polyhydroxycarboxylic acid, in particular a long-chain fatty acid ester (e.g.oleic acid) of a hydroxycarboxylic acid having esters of lower hydrocarbons (e.g., ethyl) with 3 carboxylic acid groups (e.g., triethylcitric acid), e.g. triethyl citrate oleate, when used in a lubricant composition exhibiting good anti-wear properties, e.g. when used in combination with a low concentration of zinc dihydrogen dithiophosphates (ZDDP), for example corresponding to 285 ppm phosphorus.for example, corresponding to 285 ppm phosphorus.for example, corresponding to 285 ppm phosphorus.

3. Four-ball wear tests.

[0160] Four-ball type tests in accordance with ASTM D 4172, but modified for a mild test / test, hence the discriminating / discriminating conditions 30 kg and 60 minutes for lubricants with the same compositions as those used in the previously described tests. In a wear test using 4 balls, one ball bearing was rotated above the other three base in the presence of a lubricant. The results are shown in Table 7. Experiments I to L are not according to the invention because the lubricant compositions do not contain any ester of long-chain fatty acids hydroxycarboxylic acid, where the long-chain fatty acid has 8 to 22 carbon atoms and the ester is an oil-soluble mono- or polyhydroxycarboxylic acid ester having 1 to 4 groups, which are independently carboxylic groups or their lower hydrocarbon esters and wherein when the hydroxycarboxylic acid is a mono-hydroxycarboxylic acid, the ester has long-chain fatty acid ester moieties with hydroxylic acid, and when the hydroxycarboxylic acid is a polyhydroxycarboxylic acid, the ester has independently long-ester esters fatty acids with one or two hydroxyl groups of polyhydroxycarboxylic acid. Example 3 is according to the invention. the ester has, independently, esters of long-chain fatty acids with one or two hydroxyl groups of the polyhydroxycarboxylic acid. Example 3 is according to the invention. the ester has, independently, esters of long-chain fatty acids with one or two hydroxyl groups of the polyhydroxycarboxylic acid. Example 3 is according to the invention.

Table 7.

<td></td><td>Artwork a lubricant</td><td>Addition</td><td>The dose of the supplement anti-wear by (% by mass)</td><td>Average sentinel k consumption (Ang. wear scar diameter ) ^(Mm)</td><td>Reduction of consumption in compared to Experience m</td>

<td>Experienced e</td><td>AND</td><td>-</td><td>-</td><td>.447</td><td>-</td>

<td>Example 3</td><td>1</td><td>oleate citrate triethyl</td><td>2%</td><td>0.414</td><td>7.4%</td>

<td>Experienced e J</td><td>B</td><td>glyceryl monoolein (GMO)</td><td>0.5%</td><td>0.302</td><td>32.4%</td>

<td>Experienced e</td><td>C</td><td>citrate triethyl</td><td>1%</td><td>0.346</td><td>22.6%</td>

<td></td><td>Lubricant composition</td><td>Addition</td><td>The dose of the supplement anti-wear by (% by mass)</td><td>Average sentinel k consumption (Ang. wear scar diameter ) ^(Mm)</td><td>Reduction of consumption in compared to Experience m</td>

<td>Experienced e L</td><td>D</td><td>Sakura-lube 165</td><td>1% (450 ppm Mo)</td><td>0.387</td><td>13.4%</td>

[0161] The results in Table 7 show that the ester of a long-chain fatty acid hydroxycarboxylic acid, wherein the long-chain fatty acid has 8 to 22 carbon atoms and the ester is an oil-soluble mono- or polyhydroxycarboxylic acid ester having 1 to 4 groups that are independently carboxylic groups or a lower hydrocarbon ester thereof, wherein when the hydroxycarboxylic acid is a mono-hydroxycarboxylic acid, the ester has long chain fatty acid ester moieties with a hydroxy carboxylic acid group, and when the hydroxycarboxylic acid is a polyhydroxycarboxylic acid, the ester has, independently, the long chain fatty acid ester moieties with one or more two hydroxyl groups of a polyhydroxycarboxylic acid, in particular a long-chain fatty acid ester (e.g.oleic acid) of a hydroxycarboxylic acid having esters of lower hydrocarbons (e.g., ethyl) with 3 carboxylic acid groups (e.g., triethylcitric acid), e.g. triethyl citrate oleate, when used in the lubricant composition has good anti-wear properties, e.g. when used in combination with a low concentration of zinc dihydrogen dithiophosphates (ZDDP), for example corresponding to 285 ppm phosphorus.for example, corresponding to 285 ppm phosphorus.for example, corresponding to 285 ppm phosphorus.

4. HFRR friction tests.

[0162] A friction test in a high frequency reciprocating rig was performed for lubricants with the same composition as those used in the previously described tests.

[0163] The HFRR test is usually used to assess the lubricity of diesel fuels (according to ASTM D6079-97). It can also be used to assess the friction coefficients between sliding solid surfaces in the presence of lubricating compositions with various friction modifiers over a wide temperature range, so the test can be used to evaluate the properties of friction modifiers.

[0164] The results are shown in Table 8. The M to P experiments are not according to the invention because the lubricating compositions do not contain any long-chain acid ester

Fatty hydroxykarboxylic acid, wherein the long chain fatty acid has 8 to 22 carbon atoms and the ester is an oil-soluble mono- or polyhydroxycarboxylic acid ester having 1 to 4 groups, which are independently carboxyl groups or their lower hydrocarbon esters and wherein, when the hydroxycarboxylic acid is a mono-hydroxycarboxylic acid, the ester has long-chain fatty acid ester moieties with hydroxylic acid, and when the hydroxycarboxylic acid is a polyhydroxycarboxylic acid, the ester has independent esters of long-chain fatty acids with one or two hydroxyl groups of the polyhydroxy-carboxylic acid. Example 4 is according to the invention.

Table 8

<td></td><td>Composition lubricating</td><td>Addition</td><td>FC 40 ° C</td><td>FC 140 ° C</td><td>Average FC</td><td>Average FC reduction</td>

<td>Experience M</td><td>AND</td><td>-</td><td>0.138</td><td>0.159</td><td>0.145</td><td>-</td>

<td>Example 4</td><td>1</td><td>triethyl citrate oleate</td><td>0.124</td><td>0,117</td><td>0.128</td><td>11.7%</td>

<td>Experience N</td><td>B</td><td>glycerol monooleate (GMO)</td><td>0.129</td><td>0.118</td><td>0.124</td><td>14.5%</td>

<td>Experience ABOUT</td><td>C</td><td>triethyl citrate</td><td>0.134</td><td>0.15</td><td>0.143</td><td>1.4%</td>

<td>Experience P</td><td>D</td><td>Sakura-lube 165</td><td>0,137</td><td>0.113</td><td>0.121</td><td>16.6%</td>

<td colspan="7">Note: FC = coefficient of friction</td>

[0165] The results in Table 8 show that the ester of a long-chain fatty acid hydroxycarboxylic acid, wherein the long-chain fatty acid has 8 to 22 carbon atoms and the ester is an oil-soluble mono- or polyhydroxycarboxylic acid ester having 1 to 4 groups that are independently carboxylic groups or a lower hydrocarbon ester thereof, wherein when the hydroxycarboxylic acid is a mono-hydroxycarboxylic acid, the ester has long chain fatty acid ester moieties with a hydroxy carboxylic acid group, and when the hydroxycarboxylic acid is a polyhydroxycarboxylic acid, the ester has, independently, the long chain fatty acid ester moieties with one or more two hydroxyl groups of a polyhydroxycarboxylic acid, in particular a long-chain fatty acid ester (e.g.oleic acid) of a hydroxycarboxylic acid having esters of lower hydrocarbons (e.g.

-39ethyl) with 3 carboxylic acid groups (e.g., triethylcitric acid), e.g. triethyl citrate oleate, when it is used in the lubricant composition has good friction modifier properties, e.g. when used in combination with low concentration of zinc dihydrogen dibrarboro phosphate (ZDDP), for example, corresponding to 285 ppm phosphorus. The yield of friction modifier triethyl citrate oleate was much better than the yield of triethyl citrate used in comparable molar concentrations.

[0166] The results in Table 8 also indicate that a long chain fatty acid ester of a hydroxycarboxylic acid, wherein the long chain fatty acid has 8 to 22 carbon atoms and the ester is an oil-soluble mono- or polyhydroxycarboxylic acid ester having 1 to 4 groups, which are independently groups The hydroxyl carboxylic acid is a mono-hydroxycarboxylic acid, the ester has a long-chain fatty acid ester moiety with a hydroxy carboxylic acid group, and when the hydroxycarboxylic acid is a polyhydroxycarboxylic acid, the ester has, independently, the esters of long-chain fatty acids with one another. or two hydroxyl groups of a polyhydroxycarboxylic acid, in particular a long-chain fatty acid ester (e.g.oleic acid) of a hydroxycarboxylic acid having esters of lower hydrocarbons (e.g., ethyl) with 3 carboxylic acid groups (e.g., triethylcitric acid), e.g. triethyl citrate oleate, can be used as a friction modifier in a non-aqueous lubricating oil composition, e.g. a lubricating oil composition for a gearbox a crank motor with internal combustion and / or a fuel composition for an internal combustion engine, e.g. a fuel composition for a compression ignition engine.for example a lubricating oil composition for an engine crankcase with internal combustion and / or in a fuel composition for an internal combustion engine, e.g. a diesel fuel composition.for example a lubricating oil composition for an engine crankcase with internal combustion and / or in a fuel composition for an internal combustion engine, e.g. a diesel fuel composition.

Additional experiences and examples

Preparation of triethyl citrate butyrate.

[0167] To a solution of sodium hydride (0.651 g, 1.5 eq.) In THF at 0 ° C, triethyl citrate (5 g, 1 eq.) In THF (50 mL) was added dropwise and stirred for 1 h. at 0 ° C. Then, Butaryl chloride (2.12 g, 1.1 eq.) Was added dropwise and stirred for 1 h. at 0 ° C under a nitrogen atmosphere. Stirring was continued for a further 12 hours. at 25-30 ° C.

The reaction was monitored by means of liquid-thin-layer chromatography. The reaction mixture was quenched with cold water and extracted with ethyl acetate. The ethyl acetate layer was washed with sodium hydrogen carbonate solution (10%), followed by water and brine solution. The organic layer was dried over sodium sulfate and concentrated to give the crude product.

The crude product was purified by column chromatography using 6% ethyl acetate in petroleum ether as eluent. The product was characterized by means of NMR. 3g was obtained; 48.6%.

Preparation of triethyl citrate octaate.

[0168] The same procedure as in the preparation of triethyl citrate butante, but octyl chloride was used.

-40 Generation of triethyl citrate myristate.

[0169] The same procedure as for the preparation of triethyl citrate butyrate, but myristyl chloride was used.

Preparation of diethyl tartrate butyrate [0170] To a solution of sodium hydride (0.8712 g, 1.5 eq.) In THF at 0 ° C, diethyl tartrate (5 g, 1 eq.) In THF (50 mL) was added dropwise and stirred by stirring. 1 hour at 0 ° C. Then, butaryl chloride (7.735 g, 3 eq.) Was added dropwise and the mixture was stirred for 1 hour. at 0 ° C under a nitrogen atmosphere. Stirring was continued for a further 12 hours. at 25-30 ° C. The reaction was monitored by thin layer chromatography. The reaction mixture was quenched with cold water and extracted with ethyl acetate. The ethyl acetate layer was washed with sodium hydrogen carbonate solution (10%), followed by water and brine solution. The organic layer was dried over sodium sulfate and concentrated to give the crude product. The crude product was purified by column chromatography using 7% ethyl acetate in petroleum ether as eluent. The product was characterized by means of NMR. 3.2 g was obtained; 38.5%.

Manufacture of lubricating compositions.

[0171] The esters prepared above were formulated into compositions in combination with a packet of lubricity additives (10.21% by mass) which contained a conventional uncon manned dispersant dihydrate, calcium sulfonate and phenolate detergents, phenolic and amine antioxidants, defoamers and Group III base oil. The lubricating compositions also contained ZDDP at a dose corresponding to 400 ppm of phosphorus, a viscosity modifier (4%) and a mixture of Yubase 4 and 6 base oils.

[0172] Lubricant compositions were prepared so as to have the same concentration of ester additive (when present) on a mole basis of 0.036 molL^-1.

Wear testing [0173] The lubricant compositions prepared as described above were tested in a Cameron Plint consuming test using the same procedure as described in item 2 above, except that the duration of the test was 21 hours. The results are shown in Table 9 below.

Testing the coefficient of friction.

[0174] The lubricant compositions prepared as described above were tested in the HFRR assay in the same manner as described in section 4 above, except that the results were given as mean measurements taken at the end of each of the 15-minute periods at each of the three test temperatures 60 , 90 and 120 ° C. The results are shown in Table 9 below.

[0175] The results in Table 9 show that the esters according to the invention show anti-wear properties.

[0176] The results in Table 9 also show that the esters of the invention exhibit friction modifying properties. Especially in the case of esters with triethyl citrate, the friction modifying properties appear to peak in yield as they grow

Length of a chain of a long-chain fatty acid with a peak at or around the length of the carbon chain of 14 carbon atoms.

[0177] The results in Table 9 also show that the diethyl diethyl modifier friction modifier properties are better compared to diethyl tartrate and diethyl tartrate diacetate.

Table 9

<td></td><td>Addition</td><td>Size / Capacity of wear (m³/ Nm)</td><td>Reduction in consumption in compared to Experience m Q (%)</td><td>Average coefficient of friction</td><td>Reduction of the average coefficient of friction in compared to Experience m Q (%)</td>

<td>Experienced e</td><td>none (400 ppm P)</td><td>1.59 x 10^-17</td><td>-</td><td>0.16</td><td>-</td>

<td>Experienced e R</td><td>triethyl citrate (1.00% by mass)</td><td>2.75x10^-18</td><td>82.68</td><td>0.15</td><td>4.13</td>

<td>Experienced e</td><td>acetate citrate triethyl (1.15% mass )</td><td>2.45x10^-18</td><td>84.57</td><td>0.15</td><td>4.25</td>

<td>Example 5</td><td>oleate citrate triethyl (1.96% mass )</td><td>2.53 x 10^-18</td><td>84.05</td><td>0.14</td><td>11.39</td>

<td>Example 6 *</td><td>butyrate citrate triethyl (1.25% mass )</td><td>2.48x10^-18</td><td>84.36</td><td>0.15</td><td>3.19</td>

<td></td><td>Addition</td><td>Size / Capacity of wear (m³/ Nm)</td><td>Reduction in consumption in compared to Experience m Q (%)</td><td>Average coefficient of friction</td><td>Reduction of the average coefficient of friction in compared to Experience m Q (%)</td>

<td>Example 7</td><td>octoate citrate triethyl (1.46% mass )</td><td>2.89 x 10^-18</td><td>81.80</td><td>0.14</td><td>12.97</td>

<td>Example 8</td><td>myristate n triethyl citrate (1.76% by mass)</td><td>2.90 x 10^-18</td><td>81.70</td><td>0.13</td><td>19.93</td>

<td>Experienced e T</td><td>Sakuralub e 165 @ 1%</td><td>2.53 x 10^-18</td><td>84.07</td><td>0.12</td><td>27.38</td>

<td>Experienced e</td><td>GMO @ 0.5%</td><td></td><td></td><td>0.13</td><td>21.58</td>

<td>Experienced e</td><td>diethyl tartrate (0.75% mass)</td><td>3.10 x 10^-18</td><td>80.46</td><td>0.15</td><td>5.42</td>

<td>Experience in</td><td>diacetate diethyl tartrate (1.05% mass)</td><td>3.40 x 10^-18</td><td>78.58</td><td>0.16</td><td>2.99</td>

<td></td><td>Addition</td><td>Size / This included wear (m³/ Nm)</td><td>Reduction size consumption in compared to Experience m Q (%)</td><td>The average friction coefficient</td><td>Reduction of the average coefficient of friction in compared to Experience m Q (%)</td>

<td>Example 9 *</td><td>dibutyltin tartrate diethyl (1.25% mass )</td><td>3.53 x 10^-18</td><td>77.78</td><td>0.15</td><td>8.85</td>

<td>experienced e X</td><td>battlements (285 ppm Q)</td><td>6.84 x 10^-18</td><td>59.16</td><td>0.16</td><td>2.66</td>

<td>Example 10</td><td>oleate citrate triethyl at 285 ppm P</td><td>2.24 x 10^-18</td><td>85.87</td><td>0.14</td><td>15,19</td>

<td colspan="6">* not according to reservations</td>

Piotr Godlewski Patent attorney