EP2867350A1

EP2867350A1 - Lubricant composition

Info

Publication number: EP2867350A1
Application number: EP13732185.7A
Authority: EP
Inventors: Raphaele IOVINE; Carine PIZARD; Philippe Marechal
Original assignee: Total Marketing Services SA
Current assignee: TotalEnergies Marketing Services SA
Priority date: 2012-06-29
Filing date: 2013-06-28
Publication date: 2015-05-06
Also published as: WO2014001521A1; JP2015521685A; FR2992655A1; IN2015DN00357A; US20150203778A1; US9914894B2; CN104508096A; JP6370293B2; FR2992655B1; KR20150040813A

Abstract

The present invention concerns a lubricant composition comprising: at least one base oil; and at least two glycerol esters E₁ and E₂, ester E₁ being an ester of glycerol and of a C₁₂- C₂₆ carboxylic acid and ester E₂ being an ester of glycerol and of a C₄-C₁₀ carboxylic acid. The lubricant composition has good friction properties, and the use thereof promotes fuel savings.

Description

LUBRICANT COMPOSITION

Field of the invention

The present invention relates to a lubricating composition comprising at least two esters of glycerol. This combination of two glycerol esters makes it possible to obtain a lubricating composition having a very low coefficient of friction. The use of this lubricant composition promotes fuel economy. It is particularly useful for lubricating the engines of light vehicles, trucks or ships.

Technological Background of the Invention

Due to environmental concerns, there is increasing interest in reducing pollutant emissions and fuel savings in vehicles. The nature of the engine lubricant has an influence on these two phenomena.

The lubricant's behavior in reducing friction has an impact on fuel consumption. It is mainly the quality of the base oils, alone or in combination with viscosity index (VI) improving polymers and friction modifying (MF) additives, that gives the lubricant its "Fuel Eco" (FE) properties. .

Among the friction modifiers conventionally used, mention may be made of molybdenum dialkyldithiocarbamate (or Mo-DTC) which is an inorganic friction modifier and glycerol monooleate (or GMO) which is an organic friction modifier. GMO, unlike Mo-DTC, is a friction modifier that has the advantages of not containing ash, phosphorus or sulfur and being produced from renewable raw materials. But its friction properties are worse than those of Mo-DTC for example.

It would therefore be desirable to be able to formulate lubricating compositions with friction modifiers obtained from compounds derived from raw materials of renewable origin, having no ash, having improved friction properties compared to lubricating compositions comprising GMO. .

It is known documents US2005 / 075254 and WO2005 / 030912 to use a mixture of esters to reduce friction in the engines. These esters are obtained from an esterification reaction between a polyol and a cyclic fatty acid comprising from 12 to 28 carbon atoms and / or a branched fatty acid comprising from 12 to 28 carbon atoms.

US2008 / 176778 discloses a lubricating composition in the form of an emulsion. This composition comprises in particular a lipophilic compound and an emulsifier. The lipophilic compound may be chosen in particular from caprylate or caprate triglycerides and the emulsifying compound may especially be glycerol monooleate.

US5064546 discloses a lubricating composition comprising a base oil and a friction modifier which may be a coconut oil.

JP2005082709 discloses a method for reducing friction in engines using a lubricating composition comprising at least one glycerol ester. These esters are obtained from carboxylic acids comprising from 10 to 18 carbon atoms.

US2005 / 070450 discloses lubricating compositions comprising a product obtained by transesterification reaction between a glycerol ester and a polyol ester other than glycerol.

The present invention therefore relates to lubricant compositions, in particular for engines comprising at least two glycerol esters of different chemical natures. The combination of these two glycerol esters of different chemical natures makes it possible to obtain good performance in terms of friction and in terms of fuel economy.

Summary of the invention.

The subject of the present invention is lubricating compositions, especially for an engine, comprising at least two friction-modifying additives that do not contain any sulphated ash, sulfur or phosphorus; these additives totally or partially replacing conventional additives used in this type of application, such as molybdenum dialkyldithiocarbamate or glycerol monooleate. In addition, these friction-modifying additives which do not provide any sulphated ash, in combination with each other, allow said lubricant compositions to retain optimum properties in terms of fuel economy (also known as Fuel Eco in English terminology). while having a low or very low rate of sulphated ash, sulfur, phosphorus. The compositions according to the invention are lubricant compositions, in particular for an engine, comprising:

a) at least one base oil,

b) at least one ester of glycerol and a carboxylic acid C ₁₂ to C ₂₆ , designated Ei,

c) at least one ester of glycerol and a C ₄ to C ₁₀ carboxylic acid, designated

E ₂ .

In one embodiment of the invention, the lubricating composition may comprise at least one base oil and at least two esters of glycerol E ₁ and E ₂ , the glycerol ester E ₁ being an ester of glycerol and a carboxylic acid at C ₁₂ to C ₂₆ , the glycerol ester E ₂ being an ester of glycerol and a C ₄ to C ₁₀ carboxylic acid, said ester Ei is a mixture of glycerol monoesters, glycerol diesters, glycerol triesters and free glycerol and said ester E ₂ is a mixture of glycerol monoesters, glycerol diesters, glycerol triesters and free glycerol.

Advantageously, the lubricant compositions of the invention make it possible to save fuel during the starting phase of the engine compared to lubricating compositions comprising Mo-DTC.

Thus, an object of the invention is a lubricating composition comprising at least one base oil and at least two esters of glycerol E ₁ and E ₂ , the glycerol ester E ₁ being an ester of glycerol and a carboxylic acid in C ₁₂ to C ₂₆ , the glycerol ester E ₂ being an ester of glycerol and a carboxylic acid C ₄ to C ₁₀ .

In one variant of the invention, the glycerol esters E ₁ and E ₂ are independently selected from monoesters, diesters, glycerol triesters and mixtures thereof.

In one variant of the invention, the carboxylic acids of the glycerol esters E ₁ and E ₂ are saturated or unsaturated carboxylic acids, linear or branched, optionally substituted with hydroxyl groups and / or epoxides.

In one variant of the invention, the lubricating composition may further comprise glycerol.

In a variant of the invention, the glycerol ester Ei is an ester of glycerol and a carboxylic acid C ₁₄ to C ₂₄ , preferably C ₁₆ to C ₂₂ , more preferably C ₁₈ to C ₂ o -

In one variant of the invention, the glycerol ester Ei is an ester of glycerol and a C ₁₂ to C ₂₆ carboxylic acid, the hydrocarbon chain of the carboxylic acid comprising at least two unsaturations.

In a variant of the invention, the glycerol ester E ₂ is an ester of glycerol and a carboxylic acid C ₅ to C ₉ , preferably C ₆ to C ₈ , more preferably C ₇ .

In one variant of the invention, the glycerol ester Ei is chosen from glycerol linoleates and their mixtures, and the ester of glycerol E ₂ is chosen from glycerol heptanoates and their mixtures.

In one variant of the invention, the sum of the masses of the glycerol esters E ₁ and E ₂ , and optionally glycerol, represents 0.1 to 5% by weight, relative to the total weight of the lubricating composition, preferably from 0.2 to 4%, more preferably 0.5 to 3%, even more preferably 1 to 2%. In one variant of the invention, the mass ratio between the ester (s) of glycerol Ei and the ester (s) of glycerol E ₂ is between 10: 1 and 1: 10, preferably between 5: 1 and 1: 5, more preferably between 2: 1 and 1: 2, even more preferably is 1: 1.

In one variant of the invention, the lubricating composition may have a sulfated ash content of less than or equal to 0.8%, measured according to ASTM D874, preferably less than or equal to 0.5%.

In one variant of the invention, the lubricating composition may have a phosphorus level of less than or equal to 900 ppm measured according to ASTM D5185, preferably less than or equal to 500 ppm.

In one variant of the invention, the lubricating composition may have a sulfur content of less than or equal to 0.32%> measured according to ASTM D5185, preferably less than or equal to 0.3%), more preferably less than or equal to at 0.2%>.

In a variant of the invention, the lubricating composition may have a kinematic viscosity at 100 ° C. measured according to ASTM D445 of between 3.8 and 41 cSt.

In an alternative embodiment of the invention, the lubricating composition may be free of molybdenum friction modifying additive such as Mo-DTC.

In one variant of the invention, the lubricant composition is an anhydrous composition.

In one variant of the invention, the lubricating composition is in the form of a homogeneous solution.

Another object of the present invention relates to a use of a lubricant composition as defined above to reduce the fuel consumption of light vehicles, trucks or ships.

Another subject of the invention relates to an engine oil comprising at least one lubricating composition as defined above.

In a variant of the invention, the engine oil may have a grade 5W-30 according to the classification SAEJ300.

In a variant of the invention, the motor oil may have a viscosity index greater than or equal to 130, preferably greater than or equal to 150, preferably greater than or equal to 160.

Another object of the present invention relates to a hydraulic oil, a transmission oil, a gear oil, a power steering fluid, a damping fluid, a brake fluid comprising at least one lubricating composition as defined above. Preferably, the transmission oil is a gearbox oil. Another subject of the present invention relates to the use of at least two glycerol esters E ₁ and E ₂ in a base oil, said ester E ₁ being an ester of glycerol and a C ₁₂ to C ₂₆ carboxylic acid. said ester E ₂ being an ester of glycerol and a C ₄ -C ₁₀ carboxylic acid to reduce the fuel consumption of light vehicles, trucks or ships.

Another object of the present invention is a method of lubricating at least one mechanical part of an engine, said method comprising a step in which said mechanical part is brought into contact with at least one lubricating composition as defined above. .

Another object of the invention is a method for reducing the fuel consumption of a vehicle, the method comprising a step of contacting a lubricant composition as defined above with at least one mechanical part of the engine of said vehicle.

In one embodiment, the vehicle is a light vehicle, a truck or a ship.

Detailed description.

Glycerol esters

Surprisingly, the applicant company has demonstrated that the use of at least two chemically different glycerol esters, one of the esters being obtained from a carboxylic acid of "long chain" and the other being obtained from a "short chain" carboxylic acid makes it possible to formulate lubricating compositions, in particular for engines having very good fuel economy performances.

The esters used are esters of glycerol. The first ester Ei is a glycerol ester and a carboxylic acid C ₁₂ to C ₂₆ , the second ester E ₂ is an ester of glycerol and a carboxylic acid C ₄ to C ₁₀ .

The first ester Ei is an ester of glycerol and a carboxylic acid C ₁₂ to C ₂₆ , preferably C ₁₄ to C ₂₄ , more preferably C ₁₆ to C ₂₂ , even more preferentially

Preferably, the glycerol ester Ei is an ester of glycerol and a carboxylic acid C ₁₂ to C ₂₆ , the hydrocarbon chain of the carboxylic acid comprising at least two unsaturations.

The first ester Ei is an ester of glycerol and a fatty acid C ₁₂ to C ₂₆ , preferably C ₁₄ to C ₂₄ , more preferably C ₁₆ to C ₂₂ , even more preferably Cis to C ₂₀ . For the purposes of the present invention, the term "fatty acid" is intended to mean a carboxylic acid comprising from 12 to 16 carbon atoms, preferably from 14 to 24 carbon atoms, more preferably from 16 to 22 carbon atoms, even more preferably from 18 to 20 carbon atoms.

The fatty acids used to prepare the glycerol ester Ei are saturated or unsaturated fatty acids, linear or branched, optionally substituted with hydroxyl groups and / or epoxides.

Advantageously, the glycerol ester Ei is obtained from raw materials of renewable origin.

For the purposes of the present invention, the term "raw materials of renewable origin" is intended to mean raw materials which contain carbon 14 denoted ¹⁴ C, unlike raw materials derived from fossil materials. The measurements carried out by the methods described in the international standard ASTM D6866-06, in particular by mass spectrometry or by liquid scintillation spectrometry, make it possible to distinguish the raw materials obtained from renewable materials from the raw materials of fossil origin. These measurements can be used as a test to identify the origin of raw materials.

The fatty acids that can be used to form the first glycerol ester Ei are, for example, the following fatty acids, taken alone or as a mixture: lauric acid, myristic acid, pentadecyl acid, palmitic acid, margaric acid, stearic acid, arachidic acid, behenic acid, acid lignoceric acid, cerotic acid, isopalmitic acid, isomargaric acid, ante-iso-margaric acid, isostearic acid, ante-isostearic acid, hypogeic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, petroselinic acid, gadoleic acid, gondoic acid, acid cetoleic acid, erucic acid, brassic acid, nervonic acid, linoleic acid, hiragonic acid, linolenic acid, γ-linolenic acid, eleostearic acid, parinaric acid, homo-γ-linolenic acid, arachidonic acid, clupanodonic acid, tariric acid, santalbic acid or acid xymenic, isanic acid, dihydroxy stearic acid, phellonic acid, c rébronique, ricinoleic acid, lesquerolic acid, hydroxynervonique acid, densipolic acid, kamlonénique acid, licanic acid, vernolic acid, coronarique acid.

These various fatty acids can be found in vegetable oils, fats of animal or vegetable origin, beeswax, almond oil, peanut oil, babassu oil, whalebottom, baobab oil , butter fat, china oil, cocoa butter, camelina oil, carnauba wax, safflower oil, chaulmoogra oil, horse fat, rapeseed oil, coconut oil, cottonseed oil, croton oil oil of herring, illipe butter, jojoba oil, shea butter, lanolin, lignite wax, linseed oil, corn germ oil, menhaden oil, cod liver oil, mustard oil, hazelnut oil, oil nuts, new rapeseed oil, kernel oil, flaxseed oil, goose fat, goose oil, olive oil, olive oil, evening primrose oil, bone fat, palm oil, palm kernel oil , Grape seed oil, Oxtail oil, Shark liver oil, Castor oil, Rice bran oil, Lard, Sardine oil, Sesame oil, Soybean oil, Spermaceati, Tallow, Sunflower oil , tall oil. ..

The preferred oils are palm, olive, peanut, rapeseed, sunflower, soybean, corn, safflower, camelina, flax or cotton oils. More preferably, the oils are peanut, rapeseed, sunflower, soybean, corn, safflower, camelina, flax or cotton oils. Even more preferentially, the oils are sunflower, soybean, corn, safflower or cotton oils. The preferred oils comprise a significant amount of linoleic acid, that is to say comprise from 25 to 85% by weight of linoleic acid relative to the total weight of fatty acids of the oils, preferably from 35 to 75%, preferably 45 to 65%>.

The glycerol esters Ei according to the invention are advantageously mixtures of glycerol monoesters, glycerol diesters, glycerol triesters and free glycerol.

Preferably, the glycerol esters Ei according to the invention comprise from 0.1 to 15% by weight of free glycerol, relative to the total weight of the glycerol esters, more preferably from 0.5 to 10%, and even more preferably from 1 to 5%.

Preferably, the glycerol esters Ei according to the invention comprise from 30 to 70% by weight of glycerol monoester, relative to the total weight of the glycerol esters, more preferably from 40 to 60%, even more preferably from 45 to 60% by weight. at 55%.

Preferably, the glycerol esters Ei according to the invention comprise from 20 to 60% by weight of glycerol diester, relative to the total weight of the glycerol esters, more preferably from 30 to 50%, even more preferentially from at 45%.

Preferably, the glycerol esters Ei according to the invention comprise from 1 to 20% by weight of glycerol triester, relative to the total weight of the glycerol esters, more preferably from 2 to 15%, even more preferably from 5 to 10%.

The glycerol esters Ei are obtained by esterification of glycerol and fatty acids or by transesterification. These chemical reactions, well known to those skilled in the art, can take place with or without a catalyst, with or without a solvent. The other glycerol ester designated E ₂ is an ester between glycerol and a carboxylic acid C ₄ to C ₁₀ , preferably C ₅ to C ₉ , more preferably C ₆ to C ₈ , more preferably C ₇ .

For the purposes of the present invention, the term "short-chain or short-chain carboxylic acid" means a carboxylic acid comprising from 4 to 10 carbon atoms, preferably from 5 to 9 carbon atoms, preferably from 6 to 8 carbon atoms. carbon, preferably 7 carbon atoms.

The carboxylic acids used to prepare the glycerol ester E ₂ are saturated or unsaturated carboxylic acids, linear or branched, optionally substituted by hydroxyl groups and / or epoxides.

In one embodiment, the glycerol ester E ₂ is obtained from raw materials of renewable origin.

The carboxylic acids that can be used to form the second glycerol ester E ₂ are, for example, carboxylic acids derived from vegetable oils, fatty substances, of animal or vegetable origin, such as butyric acid, valeric acid and caproic acid. , heptyl acid, caprylic acid, pelargonic acid, capric acid, crotonic acid, isocrotonic acid, sorbic acid, isovaleric acid, alone or as a mixture.

In another embodiment, the glycerol ester E ₂ is obtained from raw materials of fossil origin. We then speak of synthetic carboxylic acids.

It is also possible to use synthetic carboxylic acids such as butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid or decanoic acid, taken alone or as a mixture.

The glycerol esters E ₂ according to the invention are advantageously mixtures of glycerol monoesters, glycerol diesters, glycerol triesters and free glycerol.

Preferably, the glycerol esters E ₂ according to the invention comprise from 0.1 to 20% by weight of free glycerol, relative to the total weight of the glycerol esters, more preferably from 0.5 to 15%, and even more preferably from 1 to 10%.

Preferably, the glycerol esters E ₂ according to the invention comprise from 30 to 70% by weight of glycerol monoester, relative to the total weight of the glycerol esters, more preferably from 40 to 60%, even more preferably from 45 to 55%.

Preferably, the glycerol esters E ₂ according to the invention comprise from 20 to 60% by weight of glycerol diester, relative to the total weight of the glycerol esters, more preferably from 30 to 50%, even more preferably from 35 to 45%. Preferably, the glycerol esters E ₂ according to the invention comprise from 1 to 15% by weight of glycerol triester, relative to the total weight of the glycerol esters, more preferably from 2 to 10%, more preferably from 5 to 10% by weight. at 8%.

The glycerol esters E _{2 are} obtained by reacting the C ₄ to C ₁₀ carboxylic acids with glycerol. These chemical reactions, well known to those skilled in the art, can take place with or without a catalyst, with or without a solvent.

In the composition according to the invention, the sum of the mass of the glycerol ester E ₁ and the mass of the glycerol ester E ₂ , in their monoester, diester and triester forms, as well as any glycerol, represents from 0.1 to 5% by weight, relative to the total weight of the lubricating composition, preferably from 0.2 to 4%, more preferably from 0.5 to 3%, even more preferably from 1 to 2%; %>.

The mass ratio between the ester of glycerol Ei and the ester of glycerol E ₂ , in their monoester, diester and triester forms, as well as any glycerol present, is between 10: 1 and 1: 10, preferably between 5 : 1 and 1: 5, more preferably between 2: 1 and 1: 2, even more preferably is 1: 1.

Ash rate

Preferably, the lubricating composition according to the invention is a so-called low ash composition (LOW SAPS in English terminology).

By the term "low ash rate" (LOW SAPS) is meant lubricants specifically formulated in accordance with certain specifications. These specifications developed by the Association of European Automakers (ACEA) require the lubricating compositions of the limit contents in sulphated ash (generated by the presence of metals), sulfur and phosphorus, hence the name "Low SAPS" for "Sulfated Ashes, Phosphorus, Sulfur". In the remainder of the present application, the term "ash" or "sulphated ash" is used interchangeably.

Indeed, sulfur, phosphorus and sulphated ash can damage post-treatment systems installed on vehicles. Ashes are harmful to particulate filters and phosphorus acts as a poison for catalytic systems.

Preferably, the lubricant composition according to the invention has a sulfated ash content of less than or equal to 0.8% by weight, measured according to the international standard ASTM D874, more preferably less than or equal to 0.5% by weight. Preferably, the lubricant composition according to the invention has a phosphorus content of less than or equal to 900 ppm measured according to the international standard ASTM D5185, more preferably less than or equal to 500 ppm (ppm means parts per million by weight). Preferably, the lubricant composition according to the invention has a sulfur content of less than 0.32%, measured according to International Standard ASTM D5185, more preferably less than or equal to 0.3%, even more preferably less than or equal to 0.2. %>.

Basic oils

The lubricating compositions according to the present invention comprise one or more base oils, generally representing at least 50% by weight of the lubricating compositions, generally greater than 70% and up to 90% or more, relative to the total weight of the compositions. lubricating compositions.

The base oil (s) used in the lubricating compositions according to the present invention may be oils of mineral or synthetic origin of groups I to V according to the classes defined in the API classification (American Petroleum Institute (or their equivalents according to the ATIEL classification (Technical Association of the European Lubricants Industry) as summarized below, alone or as a mixture.

These oils can be oils of vegetable, animal or mineral origin. The mineral base oils according to the invention include all types of bases obtained by atmospheric and vacuum distillation of crude oil, followed by refining operations such as solvent extraction, deasphalting, solvent dewaxing, hydrotreatment, hydrocracking and hydroisomerization, hydrofinishing.

The base oils of the lubricating compositions according to the present invention may also be synthetic oils, such as certain esters of carboxylic acids and alcohols, or polyalphaolefins. The polyalphaolefins used as base oils, and which are distinguished from the heavy polyalphaolefins also present in the compositions according to the present invention, are for example obtained from monomers having from 4 to 32 atoms. of carbon (e.g. octene, decene), and a viscosity at 100 ° C of 1.5 to 15 cSt measured according to ASTM D445. Their weight average molecular weight is typically between 250 and 3000 g / mol measured according to the international standard ASTM D5296.

Mixtures of synthetic and mineral oils can also be used.

Preferably, the compositions according to the present invention have a kinematic viscosity at 100 ° C (KV100) of between 3.8 and 41 cSt measured according to the international standard ASTM D445, preferably between 3.8 and 32.5 cSt, even more preferably between 3.8 and 24 cSt.

Preferably, base oils having a sulfur content of less than 0.3% may be advantageously used, for example Group III mineral oils, and synthetic bases free of sulfur, preferably of Group IV, or their mixture.

Thus, the lubricating composition according to the present invention can contain at least 70% base oil, typically at least 60% by weight of one or more Group III base oils and at least 10% by weight of one or more several Group IV base oils, based on the total weight of the lubricating composition.

In a preferred embodiment, the composition according to the invention is a motor oil having a kinematic viscosity at 100 ° C. (KV100), measured according to the international standard ASTM D445, of between 3.8 cSt and 26.1 cSt, of preferably between 4.1 cSt and 21.9 cSt, preferably between 5.6 cSt and 16.3 cSt. The motor oils according to the invention are of grade 20, 30 and 40 according to classification SAEJ300, preferably of grade 30 or grade 40. According to a particularly preferred embodiment, the compositions according to the present invention are grade 5W-30. according to the classification SAEJ300 (SAE stands for Society of Automotive Engineers).

The engine oils according to the present invention preferably have a viscosity index

VI greater than or equal to 130, preferably greater than or equal to 150, preferably greater than or equal to 160.

In another embodiment, the lubricant composition according to the invention is a transmission oil, preferably a gearbox oil, having a kinematic viscosity at 100 ° C., measured according to ASTM D445, of between 4.1 cSt. and 41 cSt, preferably between 4.1 cSt and 32.5 cSt, preferably between 4.1 cSt and 24 cSt, more preferably between 4.1 cSt and 18.5 cSt. The transmission oils according to the invention are of grade 75W, 80W, 85W, 80, 85 and 90 according to classification SAEJ306. Other additives

The composition according to the invention may comprise, in addition, at least one additive or several additives such as described below. The additive (s) that is added is selected based on the use of the lubricant composition. These additives may be introduced in isolation and / or included in packages of additives used in the formulations of lubricating compositions, in particular for engines.

Thus, the lubricating compositions according to the invention may contain, in particular and without limitation, anti-wear and extreme pressure additives, antioxidants, detergents, overbased or non-detergents, polymers which improve the viscosity index, pour point improvers, dispersants, defoamers, thickeners ...

The anti-wear and extreme pressure additives protect the friction surfaces by forming a protective film adsorbed on these surfaces.

There is a wide variety of anti-wear additives, but the category most commonly used in lubricating compositions, in particular for engines, is that of phospho-sulfur-containing additives such as metal alkylthiophosphates, in particular zinc alkylthiophosphates, and more specifically zinc dialkyldithiophosphates. or ZnDTP. The preferred compounds have the formula Zn ((SP (S) (OR ₁ ) (OR ₂ )) 2, or R 1 and R ₂ are alkyl groups, preferably containing from 1 to 18 carbon atoms.

Amine phosphates are also commonly used anti-wear additives. However, the phosphorus provided by these additives acts as poison catalytic systems of automobiles, and they also bring ash. These effects can be minimized by partially substituting non-phosphorus additives, such as, for example, polysulfides, especially sulfur-containing olefins.

Lubricant compositions are also usually encountered with nitrogen and sulfur-containing anti-wear and extreme pressure additives, such as, for example, metal dithiocarbamates, in particular molybdenum dithiocarbamate, which are also ash generators.

The anti-wear and extreme-pressure additives are present in the lubricant compositions according to the invention at contents of between 0.01 and 6% by weight, preferably between 0.05 and 4%, more preferably between 0.1 and 2%. %, relative to the mass of the lubricating compositions.

Friction modifiers may optionally be added in lubricating compositions comprising at least two glycerol esters E ₁ and E ₂ . These friction modifiers optionally added in the lubricant compositions, in particular for four-stroke engines, may be compounds providing metallic elements or compounds without ash. Solid compounds such as molybdenum sulfide, graphite or polytetrafluoroethylene (PTFE) are also found.

The metal compounds are, for example, transition metal complexes such as Mo, Sb, Sn, Fe, Cu and Zn, the ligands of which may be hydrocarbon compounds containing oxygen, nitrogen, sulfur or phosphorus atoms. In particular, the molybdenum-containing compounds may be particularly effective, such as, for example, molybdenum dithiocarbamates or dithiophosphates.

The ashless friction modifiers can be, for example, fatty alcohols, fatty acids, esters, fatty amines.

These friction modifying additives, optionally added, are present at contents of between 0.01 and 5% by weight relative to the total mass of the lubricating composition, preferably 0.1 and 2%. The combination of two glycerol esters E ₁ and E ₂ make it possible to formulate lubricating compositions which advantageously have, during the engine starting phase, improved friction properties compared with lubricating compositions comprising Mo-DTC. These friction modifiers E ₁ and E ₂ have the advantage of being additives that do not provide sulphated ash, phosphorus and sulfur.

In one embodiment, the lubricating composition according to the invention may comprise in addition to glycerol esters E ₁ and E ₂ , other friction modifiers, but their quantity will be limited.

In one embodiment of the invention, the amount of friction modifiers other than the two glycerol esters E ₁ and E ₂ is less than or equal to 2% by weight, relative to the total weight of the lubricating composition, more preferably less than or equal to 1% by weight, more preferably less than or equal to 0.5% by weight, more preferably less than or equal to 0.1% by weight.

Preferably, the amount of ash-providing friction modifiers, such as molybdenum friction modifiers, such as MoDTC, is less than or equal to 2% by weight, based on the total weight of the lubricating composition, more preferably lower or equal to 1% by weight, still more preferably less than or equal to 0.5% by weight, even more preferably less than or equal to

0.1%) by mass. In another embodiment of the invention, the lubricant compositions according to the present invention are free of ash-providing friction modifiers, for example molybdenum friction modifiers, such as MoDTC.

Antioxidants delay the degradation of oils in service, which can result in the formation of deposits, the presence of sludge, or an increase in the viscosity of the oil. They act as free radical inhibitors or destroyers of hydroperoxides. Among the commonly used antioxidants are antioxidants of phenolic or amine type. Some of these additives, for example phosphosulfides, can be ash generators.

Phenolic antioxidants may be ashless, or may be in the form of neutral or basic metal salts. Typically, these are compounds containing a sterically hindered hydroxyl group, for example when two hydroxyl groups are in the ortho or para position relative to each other, or when the phenol is substituted by an alkyl group comprising at least 6 atoms. of carbon.

Amino compounds are another class of antioxidants that can be used, possibly in combination with phenolic antioxidants. Typical examples are aromatic amines, of formula R ₈ R ₉ R ₁₀ N, where R 5 is an aliphatic group, or an optionally substituted aromatic group, R ₉ is an optionally substituted aromatic group, Rio is hydrogen, or a group alkyl or aryl, or a group of formula RnS (0) _x R ₂ wherein Ru and / or R ₁₂ is an alkylene, alkenylene, or aralkylene, and x is an integer equal to 0, 1 or 2.

Sulfurized alkyl phenols or their alkali and alkaline earth metal salts are also used as antioxidants.

Another class of antioxidants is that of copper compounds soaked in oil, for example copper thio- or dithiophosphates, copper and carboxylic acid salts, dithiocarbamates, sulphonates, phenates, acetylacetonates, and the like. copper. The copper salts I and II, succinic acid or anhydride are used.

The antioxidants, alone or as a mixture, are typically present in the lubricating compositions according to the invention in amounts of between 0.1 and 5% by weight, relative to the total weight of the lubricating compositions.

The lubricant compositions according to the present invention may contain all types of antioxidant additives known to those skilled in the art. Ashless antioxidants will be preferred. Detergents reduce the formation of deposits on the surface of metal parts by dissolving secondary oxidation and combustion products. The detergents that can be used in the lubricant compositions according to the present invention are well known to those skilled in the art.

The detergents commonly used in the formulation of lubricating compositions are typically anionic compounds having a long lipophilic hydrocarbon chain and a hydrophilic head. The associated cation is typically a metal cation of an alkali metal or alkaline earth metal.

The detergents are preferably chosen from alkali metal or alkaline earth metal salts of carboxylic acids, sulphonates, salicylates and naphthenates, as well as the salts of phenates.

The alkaline and alkaline-earth metals are preferably calcium, magnesium, sodium or barium.

These metal salts may contain the metal in an approximately stoichiometric amount or in excess (in an amount greater than the stoichiometric amount). In the latter case, we are dealing with so-called overbased detergents.

The excess metal providing the overbased detergent character is in the form of oil insoluble metal salts, for example carbonate, hydroxide, oxalate, acetate, glutamate, preferably carbonate.

The polymers improving the viscosity index make it possible to guarantee a good cold behavior and a minimum viscosity at high temperature, in particular to formulate multi-grade oils. The introduction of these compounds into the lubricating compositions enables them to reach viscosity index (VI) values giving them good fuel economy properties or fuel savings.

Thus, preferably, the viscosity index (VI) of the lubricant compositions according to the invention, measured according to the international standard ASTM D2270, is greater than or equal to 130, preferably greater than or equal to 150, and preferably greater than or equal to 160.

Examples of these compounds include polymeric esters, copolymer olefins (OCP), homopolymers or copolymers of styrene, butadiene or isoprene, hydrogenated or not, polymethacrylates (PMA).

The lubricant compositions according to the present invention may contain from about 0.1 to 10% by weight of viscosity index improving polymers, relative to the total weight of the lubricating compositions, preferably from 0.5 to 5%. preferably 1 to 2%. Pour point depressant additives improve the cold behavior of oils by slowing the formation of paraffin crystals. They are, for example, alkyl polymethacrylates, polyacrylates, polyarylamides, polyalkylsphenols, polyalkylnaphthalenes, alkylated polystyrenes, etc.

Dispersants, such as, for example, succinimides, PIBs (polyisobutene) succinimides, Mannich bases, ensure the suspension and evacuation of insoluble solid contaminants constituted by the secondary oxidation products which are formed when a lubricating composition is in use.

Surfaces

The lubricant compositions according to the invention can be used to lubricate the surfaces of parts that are conventionally found in an engine such as the piston, segment, and jacket system. They can also be used to lubricate transmissions such as manual or automatic gearboxes. The lubricant compositions according to the invention can be used in light vehicles, trucks, but also in ships.

In one embodiment, the mechanical part is chosen from the group formed by the piston system, the segments, the folders.

In another embodiment, the mechanical part forms a mechanical member such as transmissions, preferably manual gearboxes or automatic gearboxes.

In one embodiment, the vehicle is a light vehicle, a truck or a ship.

Example 1

A control lubricant composition T which does not comprise friction modifiers is prepared from: a group III base oil having a kinematic viscosity at 100 ° C (KV100) equal to 6 cSt (measured according to the international standard ASTM D445),

a Group III base oil having a kinematic viscosity at 100 ° C (KV100) equal to 4 cSt (measured according to the international standard ASTM D445),

a light polyalphaolefin (PAO), Group IV base oil having a kinematic viscosity at 100 ° C (KV100) equal to 6 cSt (measured according to the international standard ASTM D445),

a linear ethylene / propylene copolymer (OCP) olefin comprising 50% by weight of ethylene, relative to the weight of the copolymer, having a weight average molecular weight Mw equal to 171,700 g / mol (measured according to the international standard ASTM D5296) and a number average molecular weight Mn equal to 91 120 g / mol (measured according to the international standard ASTM D5296),

a heavy PAO having a kinematic viscosity at 100 ° C. (KV100) equal to 1000 cSt (measured according to the international standard ASTM D445),

a pour point depressant (PPD) which is a polymethacrylate,

an additive package comprising weakly and strongly overbased detergents, phenolic and amine antioxidants, a succinimide dispersant, an anti-wear agent based on amine phosphate and zinc dialkyl dithiophosphate (ZnDTP),

The percentages by weight of the various constituents are given in Table I below, as well as the properties of this control lubricant composition.

measured according to the international standard ASTM D5185

measured according to ASTM D874

measured according to the international standard ASTM D2896

measured according to ASTM D445 international standard

(6) measured according to ASTM D445 international standard Table I

Various friction modifiers are added to this composition:

- Glycerol monooleate (GMO) marketed by Stéarinerie Dubois under the name of DUB OG.

- Glycerol linoleate comprising 45% by weight of monoester, relative to the total weight of glycerol linoleate, 40% by weight of diesters, 10% by weight of triesters, 5% by weight of free glycerol. This glycerol linoleate is obtained from a mixture of fatty acids whose linoleic acid represents 75 to 80% by mass of the total mass of fatty acids, the rest being constituted:

• myristic acid (less than 1% of the total mass of fatty acids),

• palmitic acid (5 to 8% of the total mass of fatty acids),

• stearic acid (2 to 3% of the total mass of fatty acids),

• oleic acid (11 to 15% of the total mass of fatty acids),

• linolenic acid (less than 2% of the total mass of fatty acids),

• arachidic acid (less than 1% of the total mass of fatty acids) and

• gadoleic acid (less than 1% of the total mass of fatty acids).

This ester is marketed by Stéarinerie Dubois under the name DUB LIG. - Glycerol heptanoate, comprising 47% by weight of monoester, relative to the total weight of glycerol heptanoate, 36% by weight of diesters, 6% by mass of triesters, 1 1% by weight of free glycerol. This ester is obtained from heptanoic acid.

a pentaerythritol ester, as described in patent application WO2010064220, having the following characteristics: Ni = 73.2%, n2 = 26.8%, KV100 = 4.657 cSt, KV40 = 18.50 cSt, viscosity number = 183.

molybdenum dithiocarbamate sold under the name Sakura-lube 525 by the company Adeka.

Composition C ₇ illustrates a composition comprising Mo-DTC, the treatment rate of which is usually in the commercially available lubricating compositions of 400 ppm by weight of Mo-DTC.

The mass percentages of the resulting compositions are given in Table II below.

Table II

The physicochemical characteristics of the resulting compositions are given in Table III below.

Table III

measured according to the international standard ASTM D5185

measured according to ASTM D874

measured according to ASTM D445 international standard

(6) measured according to ASTM D445 international standard

The coefficient of friction of the compositions is then measured by a Cameron Plint Frottement laboratory test using a Cameron-Plint TE-77 alternative tribometer. The test bench consists of a plane cylinder tribometer immersed in the oil to be tested. A variable normal force is applied to the heated plane and the resulting frictional force is measured. The conditions of temperature, charge and frequency are varied. The values of the coefficient of friction, taken at different temperatures, loads and frequencies are shown in Table IV as well as the overall average value of these six different phases.

Table IV

It is found that the addition of 1% GMO reduces the overall coefficient of friction (over all 6 phases) of the lubricant composition.

Similarly for the addition of 1% glycerol linoleate or 1% glycerol heptanoate. At 2% of active material, the composition C ₄ has the lowest coefficient of friction of the lubricating compositions T, Ci to C ₆ .

At 1% by weight of active material, the C ₅ lubricant composition based on the mixture of long chain / short chain glycerol esters has a lower overall coefficient of friction than the T, C 1 to C ₃ and C ₆ lubricating compositions based on on other compounds also at 1% by weight of active ingredient.

The compositions C ₄ and C ₅ make it possible to obtain a lower coefficient of friction than the compositions comprising Mo-DTC (composition C ₇ ) during the engine start-up phases (that is to say for temperatures of 100.degree. ° C).

Example 2

The objective of this example is to show the influence of the presence of unsaturations in the C ₁₂ to C ₂₆ carboxylic acid of the ester E 1 according to the invention on the friction properties of the lubricant composition.

For this, the compositions Cs and C9 are prepared by adding to the control composition of Example 1 the following friction modifiers:

- Glycerol monoisostearate marketed by Stéarinerie Dubois under the name DUB ISG and obtained from a carboxylic acid saturated Cl 8,

- Glycerol monooleate marketed by Stéarinerie Dubois under the name DUB OG and obtained from a Cl 8 unsaturated carboxylic acid comprising unsaturation. Glycerol monooleate comprises 32-52% by weight of monoester, relative to the total weight of glycerol monooleate, 30-50% by weight of diesters, 5-20% by mass of triesters, at most 6% by weight of glycerol monooleate. free glycerol mass.

glycerol linoleate obtained from a C 18 unsaturated carboxylic acid comprising two unsaturations, its composition is described in Example 1.

glycerol heptanoate: its composition is described in Example 1.

The mass percentages of the resulting compositions are given in Table V below. Table V

The coefficient of friction of the compositions is then measured by a Cameron Plint Frottement laboratory test using a Cameron-Plint TE-77 type alternating tribometer under the conditions described in example 1. The results obtained are presented in FIG. table VI

Table VI

The results show that the choice of an unsaturated C 12 to C 26 carboxylic acid comprising at least two unsaturations to form the ester E 1 according to the invention allows an even more significant reduction in the overall mean friction coefficient, relative to a carboxylic acid. saturated C 12 to C 26 or unsaturated C 12 to C 26 carboxylic acid comprising a single unsaturation.

Claims

claims

A lubricating composition comprising at least one base oil and at least two esters of glycerol E ₁ and E ₂ , the glycerol ester E ₁ being an ester of glycerol and a C ₁₂ to C ₂₆ carboxylic acid, the ester with glycerol E ₂ being an ester of glycerol and a C ₄ -C ₁₀ carboxylic acid, said ester Ei is a mixture of glycerol monoesters, glycerol diesters, glycerol triesters and free glycerol and said ester E ₂ is a mixture of glycerol monoesters, glycerol diesters, glycerol triesters and free glycerol.

2. Lubricating composition according to claim 1 wherein the carboxylic acids glycerol esters Ei and E ₂ are saturated or unsaturated carboxylic acids, linear or branched, optionally substituted by hydroxyl groups and / or epoxides.

3. Lubricating composition according to any one of claims 1 to 2 wherein the glycerol ester Ei is an ester of glycerol and a carboxylic acid C ₁₄ to C ₂₄ , preferably C ₁₆ to C ₂₂ , more preferentially in C ₁₈ to C ₂ o-

4. Lubricating composition according to any one of claims 1 to 3 wherein the glycerol ester E ₂ is an ester of glycerol and a carboxylic acid C ₅ to C ₉ , preferably C ₆ to C ₈ , plus preferentially in C ₇ .

5. Lubricating composition according to any one of claims 1 to 4 wherein the glycerol ester Ei is selected from glycerol linoleates and mixtures thereof, and the ester of glycerol E ₂ is selected from glycerol heptanoates and their mixtures.

6. Lubricating composition according to any one of claims 1 to 5, wherein the sum of the masses of glycerol esters Ei and E ₂ , represents 0.1 to 5% by weight, relative to the total weight of the lubricating composition. preferably from 0.2 to 4%, more preferably from 0.5 to 3%, even more preferably from 1 to 2%.

7. Lubricating composition according to any one of claims 1 to 6 wherein the weight ratio between the ester (s) of glycerol Ei and the ester (s) of glycerol E ₂ is between 10: 1 and 1 : 10, preferably between 5: 1 and 1: 5, more preferably between 2: 1 and 1: 2, even more preferably is 1: 1.

8. Lubricating composition according to any one of claims 1 to 7 having a sulphated ash content of less than or equal to 0.8% measured according to ASTM D874, preferably less than or equal to 0.5%.

9. Lubricating composition according to any one of claims 1 to 8 having a phosphorus level of less than or equal to 900 ppm measured according to ASTM D5185, preferably less than or equal to 500 ppm.

10. Lubricating composition according to any one of claims 1 to 9 having a sulfur content less than or equal to 0.32% measured according to ASTM D5185, preferably less than or equal to 0.3%>, more preferably lower or equal to 0.2%>.

A lubricating composition according to any one of claims 1 to 10 having a kinematic viscosity at 100 ° C measured according to ASTM D445 of between 3.8 and 41 cSt.

12. Lubricating composition according to any one of claims 1 to 1 1 free of molybdenum friction modifier additive such as Mo-DTC.

13. Use of a lubricant composition according to any one of claims 1 to 12 to reduce the fuel consumption of light vehicles, trucks or ships.

Motor oil comprising at least one lubricating composition according to any one of claims 1 to 12.

The engine oil of claim 13 having a grade of 5W-30 according to the SAEJ300 classification.

16. Motor oil according to claim 14 or 15 having a viscosity index greater than or equal to 130, preferably greater than or equal to 150, preferably greater than or equal to 160.

17. Hydraulic oil, transmission oil, gear oil, power steering fluid, damping fluid, brake fluid comprising at least one lubricant composition according to one of claims 1 to 12.

18. Use of at least two glycerol esters Ei and E ₂ in a base oil, said ester Ei being an ester of glycerol and a carboxylic acid C ₁₂ to C ₂₆ , said ester E ₂ being an ester glycerol and a C ₄ -C ₁₀ carboxylic acid to reduce the fuel consumption of light vehicles, trucks or ships, said ester Ei is a mixture of glycerol monoesters, glycerol diesters, triesters of glycerol and free glycerol and said ester E ₂ is a mixture of glycerol monoesters, glycerol diesters, glycerol triesters and free glycerol.