WO2015162137A1

WO2015162137A1 - Use of a lubricant composition for reducing knocking

Info

Publication number: WO2015162137A1
Application number: PCT/EP2015/058615
Authority: WO
Inventors: Nicolas Obrecht; Steve FAURE
Original assignee: Total Marketing Services
Priority date: 2014-04-25
Filing date: 2015-04-21
Publication date: 2015-10-29
Also published as: JP2017513995A; MX2016014018A; KR102392304B1; CN106459804A; US20170051226A1; EP3134495A1; KR20160147911A; FR3020377A1; EP3134495B1; FR3020377B1

Abstract

The invention relates to a lubricant composition comprising at least one base oil and at least one organic compound. The lubricant composition according to the invention thereby enables the reduction, and even elimination, of knocking in vehicle engines, preferably motor vehicle engines.

Description

USE OF A LUBRICATING COMPOSITION TO DECREASE CLICKS

Technical area

The present invention is applicable to the field of lubricants, more particularly to the field of engine lubricants. More particularly, the present invention relates to the use of a lubricating composition for decreasing rattling in a vehicle engine, said lubricating composition comprising at least one base oil and at least one organic anti-rattling compound. The lubricant composition according to the invention thus makes it possible to reduce or even eliminate rattling in an engine of vehicles, preferably motor vehicles, while retaining good lubricating properties.

The present invention also relates to a lubrication process using this composition.

The present invention also relates to a method for reducing or even suppressing rattling in an engine of vehicles, preferably motor vehicles, implementing this lubricant composition.

The present invention also relates to the use of an organic compound in a lubricant composition for reducing or even suppressing rattling in an engine of vehicles, preferably motor vehicles.

The present invention also relates to the use of a concentrated composition of additives comprising at least one organic compound for reducing or even suppressing rattling in an engine of vehicles, preferably motor vehicles, using said organic compound. Technological background

Knocking is a phenomenon that occurs in a spark ignition engine of vehicles, and more particularly in a spark ignition engine of motor vehicles and is due to the self-ignition of the fuel upstream of the flame front in the chamber of combustion.

This auto-ignition propagates at a very high speed in the combustion chamber and causes vibrations at high frequencies of the gaseous mass and thermal overload of the engine, which can lead to serious mechanical incidents.

Solutions commonly used by engine manufacturers to avoid this phenomenon, such as reduced ignition timing, significantly reduce the efficiency of spark ignition engines. In addition, following the establishment of the Kyoto Protocol, new environmental protection standards require the automotive sector to build vehicles with reduced pollutant emissions.

However, there is a trend today in vehicles to reduce the size of engines that must however operate at high power levels to maximize the gain in fuel economy.

However, this gain can be very easily altered by the rattling phenomenon.

The combustion phenomenon is a compromise between the propagation speed of the flame front from the spark plug and the self-ignition time of the fuel. When the latter is too short, the rattling occurs in the remote areas of the spark plug and most often near the piston and the cylinder.

A lubricant, and more particularly a motor lubricant, is used in the cylinders to reduce friction and wear. The proximity of the engine lubricant to the zones of occurrence of rattling opens the possibility of interaction between it and combustion.

Thus, it has been sought lubricants to reduce or even reduce the rattling in an engine. Documents US2763613, US2898359 have notably described the use of anti-knock compounds selected from organometallic compounds, and more particularly ferrocene compounds in a lubricating composition.

Furthermore, the document WO2004 / 101717 describes the use of organometallic compounds based on manganese in a lubricant composition to reduce the phenomenon of rattling in an engine.

However, the use of such organometallic compounds promotes deposits in the combustion chamber and can thus cause abnormal combustion such as hot-spot ignition which can cause significant mechanical failure. In addition, they may pose a risk to human health.

WO2004 / 104717 also describes various organic compounds of alcohol, ester or ether type that can be used in a lubricant composition to reduce the knocking phenomenon in an engine. Furthermore, US 8129320 discloses oils selected from esters of trimellitic acid or alkyl naphthalene type compounds, as well as their use in a lubricant composition to reduce rattling in an engine.

However, the content by weight of these oils in the lubricant is at least 50% which can greatly reduce the friction reduction or oxidation resistance performance of the lubricant composition.

Thus, there remains the need for organic compounds to reduce or even eliminate the phenomenon of rattling in an engine and can be easily formulated in a lubricant composition. An object of the present invention is therefore to provide organic compounds and a lubricating composition comprising these organic compounds which overcome all or part of the aforementioned drawbacks.

Another object of the present invention is to provide a composition for reducing or even suppressing rattling in an engine and whose formulation is easy to implement.

Another objective of the present invention is to provide a lubricant composition that makes it possible to reduce or even eliminate rattling in an engine while avoiding the appearance of deposits in the combustion chamber.

Another object of the present invention is to provide a lubrication method for reducing or even suppressing the rattling in an engine. Summary of the invention

The invention thus relates to the use of a lubricant composition for reducing rattling in an engine of vehicles, preferably motor vehicles, said lubricant composition comprising:

at least one base oil,

at least one compound of formula (I):

(I)

in which :

R1 represents a hydrogen atom, a linear or branched, saturated or unsaturated, substituted or unsubstituted alkyl group comprising from 1 to 10 carbon atoms, a group -OR7, a group -NR8R9;

R2 represents a hydrogen atom, a linear or branched, saturated or unsaturated, substituted or unsubstituted alkyl group comprising from 1 to 10 carbon atoms, a group -OR10, a group - NR1 1 R12;

R3 represents a hydrogen atom, a linear or branched, saturated or unsaturated, substituted or unsubstituted alkyl group comprising from 1 to 10 carbon atoms, a group -OR13, a group -NR14R15;

R4 represents a hydrogen atom, a linear or branched, saturated or unsaturated, substituted or unsubstituted alkyl group comprising from 1 to 10 carbon atoms, a group -OR16, a group - NR17R18;

• R5 represents a hydrogen atom, a linear or branched, saturated or unsaturated, substituted or unsubstituted alkyl group comprising from 1 to 10 carbon atoms, a group -OR19, a group - NR20R21;

R6 represents a hydrogen atom, a linear or branched, saturated or unsaturated, substituted or unsubstituted alkyl group comprising from 1 to 10 carbon atoms, a group -OR22, a group - NR23R24;

R7, R10, R13, R16, R19 and R22, which may be identical or different, independently represent a linear or branched, saturated or unsaturated, substituted or unsubstituted alkyl group comprising from 1 to 10 carbon atoms;

R8, R9, R1, R12, R14, R15, R17, R18, R20, R21, R23 and R24, which may be identical or different, independently represent a hydrogen atom or a saturated or unsaturated, substituted or unsubstituted alkyl group having 1 to 3 carbon atoms;

At least one of the groups R1, R2, R3, R4, R5 and R6 is different from a hydrogen atom.

Surprisingly, the Applicant has found that the presence of a compound of formula (I) as defined above in a lubricant composition allows the lubricating composition, once implemented in an engine, to reduce or even eliminate the phenomenon of rattling in the engine.

Thus, the present invention makes it possible to formulate lubricating compositions having both good stability and good properties of reducing or even suppressing the knocking phenomenon once implemented in an engine.

Advantageously, the lubricant compositions according to the invention have good properties of reducing or even suppressing the pinging phenomenon once implemented in an engine without the need to add a high content of anticliquid compound in the lubricating composition.

Advantageously, the lubricant compositions according to the invention have good properties for reducing or even suppressing the pinging phenomenon once implemented in an engine without the need to add other anti-knock additives, and in particular not anti-knock additives selected from organometallic compounds.

Advantageously, the lubricant compositions according to the invention have good properties of reducing or even suppressing the knocking phenomenon once implemented in an engine and whose formulation is easy to implement.

Advantageously, the lubricant compositions according to the invention have good properties of reducing or even eliminating the knocking phenomenon once implemented in an engine while reducing or even eliminating the risk of deposits in the combustion chamber.

In one embodiment of the invention, the lubricant composition consists essentially of:

at least one base oil,

at least one compound of formula (I):

(I)

in which :

The invention also relates to an engine oil comprising a lubricant composition as defined above.

The invention also relates to the use of a lubricant composition as defined above for the lubrication of vehicle engines, preferably motor vehicles.

The invention also relates to the use of a lubricant composition as defined above to reduce or even eliminate rattling in engines, preferably motor vehicles.

The invention also relates to a method for lubricating a motor vehicle, preferably motor vehicles, said method comprising at least one step of contacting a mechanical part of the engine with a lubricant composition as defined above .

The invention also relates to a method for reducing or even suppressing rattling in a motor vehicle, preferably motor vehicles, comprising at least one step of contacting a mechanical part of the vehicle engine with a lubricant composition as defined herein. -above.

The invention also relates to the use of a compound of formula (I) as defined above in a lubricant composition for reducing or even suppressing rattling in engines, preferably motor vehicles.

The invention also relates to the use of a composition of the additive concentrate type in a lubricant composition comprising at least one base oil for reducing or even suppressing rattling in engines, preferably motor vehicles, said composition of concentrated type. additives comprising:

at least one compound of formula (I):

(I)

in which :

R1 represents a hydrogen atom, a linear or branched, saturated or unsaturated, substituted or unsubstituted alkyl group comprising from 1 to

10 carbon atoms, a group -OR7, a group -NR8R9;

R4 represents a hydrogen atom, a linear or branched, saturated or unsaturated, substituted or unsubstituted alkyl group comprising from 1 to 10 carbon atoms, a group -OR16, a group -NR17R18;

R5 represents a hydrogen atom, a linear or branched, saturated or unsaturated, substituted or unsubstituted alkyl group comprising from 1 to

10 carbon atoms, a group -OR19, a group - NR20R21;

R6 represents a hydrogen atom, a saturated or unsaturated, substituted or unsubstituted, linear or branched alkyl group comprising from 1 to 10 carbon atoms, a group -OR22, a group -

NR23R24;

at least one additive chosen from detergents, friction modifiers, anti-wear additives, dispersants, extreme pressure additives, antioxidants, viscosity index improving polymers, pour point improvers, defoamers, thickeners and mixtures thereof.

Detailed description of the invention

The percentages given below correspond to percentages by mass of active ingredient.

The lubricating composition comprises at least one compound of formula (I):

in which :

R 3 represents a hydrogen atom, a linear or branched, saturated or unsaturated, substituted or unsubstituted alkyl group comprising from 1 to 10 carbon atoms, a group -OR 13, a group - NR 14 R 15;

R 4 represents a hydrogen atom, a linear or branched, saturated or unsaturated, substituted or unsubstituted alkyl group comprising from 1 to

10 carbon atoms, a group -OR16, a group - NR17R18; • R5 represents a hydrogen atom, a linear or branched, saturated or unsaturated, substituted or unsubstituted alkyl group comprising from 1 to 10 carbon atoms, a group -OR19, a group - NR20R21;

R8, R9, R1, R12, R14, R15, R17, R18, R20, R21, R23 and R24, which may be identical or different, independently represent a hydrogen atom or a saturated or unsaturated, substituted or unsubstituted alkyl group comprising from 1 to 3 carbon atoms;

At least one of the groups R1, R2, R3, R4, R5 and R6 is different from a hydrogen atom. Thus, the compound of formula (I) as defined above does not comprise metal or any metal derivative.

The compound of formula (I) as defined above is not an organometallic compound. The compound of formula (I) as defined above comprises at least one group R 1 to R 6 other than a hydrogen atom.

Thus, the compound of formula (I) as defined above is different from benzene.

In one embodiment of the invention, the lubricating composition comprises at least one compound of formula (I) as defined above in which R 1 represents a hydrogen atom.

In a preferred embodiment of the invention, the lubricating composition comprises at least one compound of formula (I) as defined above in which:

R1 represents a hydrogen atom, R2 represents a hydrogen atom, a linear or branched, saturated or unsaturated, substituted or unsubstituted alkyl group comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, advantageously from 1 to 3 carbon atoms; carbon,

R3 represents a hydrogen atom, a linear or branched, saturated or unsaturated, substituted or unsubstituted alkyl group comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, advantageously from 1 to 3 carbon atoms; carbon,

R 4 represents a hydrogen atom, a linear or branched, saturated or unsaturated, substituted or unsubstituted alkyl group comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, advantageously from 1 to 3 carbon atoms; carbon, R5 represents a hydrogen atom, a linear or branched, saturated or unsaturated, substituted or unsubstituted alkyl group comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, advantageously from 1 to 3 carbon atoms; carbon atoms,

R 6 represents a hydrogen atom, a linear or branched, saturated or unsaturated, substituted or unsubstituted alkyl group comprising from 1 to 10 carbon atoms, preferably from 1 to 5 carbon atoms, advantageously from 1 to 3 carbon atoms, carbon,

at most one of the groups R2 to R6 represents a hydrogen atom.

Examples of the compound of formula (I) used according to the invention include 1,2,4,5-tetramethylbenzene.

In another embodiment of the invention, the lubricating composition comprises at least one compound of formula (I) as defined above in which R 1 represents a linear or branched, saturated or unsaturated, substituted or unsubstituted alkyl group comprising from 1 to 10 carbon atoms, a group -OR7, a group - NR8R9, R7, R8 and R9 being as defined above.

R 1 represents a linear or branched saturated alkyl group comprising from 1 to 5 carbon atoms, preferably from 1 to 3 carbon atoms, advantageously a methyl or ethyl group,

R2 represents a hydrogen atom or a linear or branched saturated alkyl group comprising from 1 to 5 carbon atoms, preferably from 1 to 3 carbon atoms, advantageously a methyl or ethyl group,

R 3 represents a hydrogen atom or a linear or branched saturated alkyl group comprising from 1 to 5 carbon atoms, preferably from 1 to 3 carbon atoms, advantageously a methyl or ethyl group, R 4 represents a hydrogen atom or a linear or branched saturated alkyl group comprising from 1 to 5 carbon atoms, preferably from 1 to 3 carbon atoms, advantageously a methyl or ethyl group,

R 5 represents a hydrogen atom or a linear or branched saturated alkyl group comprising from 1 to 5 carbon atoms, preferably from 1 to 3 carbon atoms, advantageously a methyl or ethyl group,

R 6 represents a hydrogen atom or a linear or branched saturated alkyl group comprising from 1 to 5 carbon atoms, preferably from 1 to 3 carbon atoms, advantageously a methyl or ethyl group,

only two of the groups R2 to R6 represent a linear or branched saturated alkyl group comprising from 1 to 5 carbon atoms, preferably from 1 to 3 carbon atoms, advantageously a methyl or ethyl group.

Thus, as examples of compound of formula (I) used according to the invention, mention may be made of 1,3,5-trimethylbenzene (or mesitylene).

In a preferred embodiment of the invention, the lubricating composition comprises at least one compound of formula (I) as defined above in which R5 represents a hydrogen atom.

In another preferred embodiment of the invention, the lubricating composition comprises at least one compound of formula (I) as defined above in which R 6 represents a hydrogen atom. In a preferred embodiment of the invention, the lubricating composition comprises a compound of formula (I) as defined above in which R1 represents:

A linear or branched saturated alkyl group comprising from 1 to 5 carbon atoms, preferably from 1 to 3 carbon atoms;

A group -OR7 in which R7 represents a linear or branched saturated alkyl group comprising from 1 to 5 carbon atoms, preferably from 1 to 3 carbon atoms;

A group -NR8R9 in which:

R8 represents a hydrogen atom or a saturated alkyl group comprising from 1 to 3 carbon atoms;

R 9 represents a hydrogen atom or a saturated alkyl group comprising from 1 to 3 carbon atoms. In another preferred embodiment of the invention, the lubricating composition comprises a compound of formula (I) as defined above wherein R2 represents:

• a hydrogen atom;

A group -NR1 1 R12 in which:

R 1 represents a hydrogen atom or a saturated alkyl group comprising from 1 to 3 carbon atoms;

R12 represents a hydrogen atom or a saturated alkyl group comprising from 1 to 3 carbon atoms.

In another preferred embodiment of the invention, the lubricating composition comprises a compound of formula (I) as defined above in which R 3 represents:

• a hydrogen atom;

A group -NR14R15 in which:

R14 represents a hydrogen atom or a saturated alkyl group comprising from 1 to 3 carbon atoms;

R15 represents a hydrogen atom or a saturated alkyl group comprising from 1 to 3 carbon atoms.

In another preferred embodiment of the invention, the lubricating composition comprises a compound of formula (I) as defined above in which R4 represents:

• a hydrogen atom;

A group -NR17R18 in which:

R17 represents a hydrogen atom or a saturated alkyl group comprising from 1 to 3 carbon atoms;

R 18 represents a hydrogen atom or a saturated alkyl group comprising from 1 to 3 carbon atoms. In another preferred embodiment of the invention, the lubricating composition comprises at least one compound of formula (I) in which:

R1 represents:

A group -NR8R9 in which:

- R8 represents a hydrogen atom or a saturated alkyl group comprising from 1 to 3 carbon atoms;

R9 represents a hydrogen atom or a saturated alkyl group comprising from 1 to 3 carbon atoms,

and R2 represents:

· A hydrogen atom;

A group -NR1 1 R12 in which:

R12 represents a hydrogen atom or a saturated alkyl group comprising from 1 to 3 carbon atoms,

and R3 represents:

• a hydrogen atom;

A group -NR14R15 in which:

R 15 represents a hydrogen atom or a saturated alkyl group comprising from 1 to 3 carbon atoms,

and R4 represents:

• a hydrogen atom;

A group -NR17R18 in which: R17 represents a hydrogen atom or a saturated alkyl group comprising from 1 to 3 carbon atoms;

R 18 represents a hydrogen atom or a saturated alkyl group comprising from 1 to 3 carbon atoms,

and R5 and R6 both represent a hydrogen atom.

In another embodiment of the invention, the lubricating composition comprises at least one

in L

R1 represents a linear or branched saturated alkyl group comprising from 1 to 10 carbon atoms, a group -OR7, a group - NR8R9;

R2 represents a hydrogen atom, a linear or branched saturated alkyl group comprising from 1 to 10 carbon atoms, a group - OR10, a group -NR1 1 R12; R3 represents a hydrogen atom, a linear or branched saturated alkyl group comprising from 1 to 10 carbon atoms, a group -OR13, a group -NR14R15;

R4 represents a hydrogen atom, a linear or branched saturated alkyl group comprising from 1 to 10 carbon atoms, a group - OR16, a group --NR17R18;

R7, R10, R13 and R16, which are identical or different, independently represent a linear or branched saturated alkyl group comprising from 1 to 10 carbon atoms;

R8, R9, R1, R12, R14, R15, R17 and R18, which may be identical or different, independently represent a hydrogen atom or a saturated alkyl group comprising from 1 to 3 carbon atoms.

In a preferred embodiment of the invention, the lubricating composition comprises at least one compound of formulas (la) to (Ic):

in which :

R1 represents:

A group -NR8R9 in which: R8 represents a hydrogen atom or a saturated alkyl group comprising from 1 to 3 carbon atoms;

and R2 represents:

• a hydrogen atom;

A group -NR1 1 R12 in which:

and R3 represents:

· A hydrogen atom;

A group -NR14R15 in which:

R15 represents a hydrogen atom or a saturated alkyl group comprising from 1 to 3 carbon atoms,

and R4 represents:

• a hydrogen atom;

A group -NR17R18 in which:

R 18 represents a hydrogen atom or a saturated alkyl group comprising from 1 to 3 carbon atoms.

In a more preferred embodiment of the invention, the lubricating composition comprises at least one compound of formulas (la) to (Ic):

in which :

R1 represents a group -OR7 group in which R7 represents a saturated alkyl group comprising from 1 to 3 carbon atoms;

R2 represents a hydrogen atom or a saturated alkyl group comprising from 1 to 3 carbon atoms;

R3 represents a hydrogen atom or a saturated alkyl group comprising from 1 to 3 carbon atoms;

R4 represents a hydrogen atom or a saturated alkyl group comprising from 1 to 3 carbon atoms.

Advantageously, the lubricating composition comprises at least one compound of formulas (la) to (Ic) as defined above in which:

R1 represents a group -OCH ₃ or -OC ₂ H _5, preferably -OC ₂ H ₅ ;

As an example of a compound of formula (I) used according to the invention, mention may be made of methoxybenzene or ethoxybenzene. In another more preferred embodiment of the invention, the lubricating composition comprises at least one compound of formulas (la) to (Ic):

in which :

R1 represents a group -NR8R9 in which:

R9 represents a hydrogen atom or a saturated alkyl group comprising from 1 to 3 carbon atoms;

R2 represents a hydrogen atom, a saturated alkyl group comprising from 1 to 3 carbon atoms or a group -NR1 1 R12;

R3 represents a hydrogen atom, a saturated alkyl group comprising from 1 to 3 carbon atoms or a group -NR14R15;

R4 represents a hydrogen atom, a saturated alkyl group comprising from 1 to 3 carbon atoms or a group -NR17R18;

• R1 1, R12, R14, R15, R17 and R18, identical or different, independently represent a hydrogen atom or a saturated alkyl group comprising from 1 to 3 carbon atoms.

In another even more preferred embodiment of the invention, the lubricating composition comprises at least one compound of formulas (la) to (Ic):

in which :

R1 represents a group -NR8R9 in which:

R 9 represents a hydrogen atom or a saturated alkyl group comprising from 1 to 3 carbon atoms;

R2 represents a hydrogen atom, a saturated alkyl group comprising from 1 to 3 carbon atoms or a group -NH ₂ ;

R3 represents a hydrogen atom, a saturated alkyl group comprising from 1 to 3 carbon atoms or a group -NH ₂ ;

R 4 represents a hydrogen atom, a saturated alkyl group comprising from 1 to 3 carbon atoms or an -NH ₂ group.

Advantageously, the lubricating composition comprises at least one compound of formulas (la) to (le):

(la) (lb)

(the)

in which :

Examples of the compound (I) used according to the invention are aniline, orthophenylenediamine, meta-phenylenediamine, para-phenylenediamine, ortho-toluidine, meta-toluidine or para-phenylenediamine. toluidine.

in which :

R1 represents a group -NR8R9 in which:

R8 represents a saturated alkyl group comprising from 1 to 3 carbon atoms;

R9 represents a saturated alkyl group comprising from 1 to 3 carbon atoms;

Examples of compounds of formula (I) used according to the invention include dimethylaniline.

In another more preferred embodiment of the invention, the lubricating composition comprises at least one compound of formulas (la) to (Ic):

in which :

R1 represents a linear or branched saturated alkyl group comprising from 1 to 5 carbon atoms;

R2 represents a hydrogen atom or linear or branched saturated alkyl comprising from 1 to 5 carbon atoms;

R3 represents a hydrogen atom or a linear or branched saturated alkyl group comprising from 1 to 5 carbon atoms;

R4 represents a hydrogen atom or a linear or branched saturated alkyl group comprising from 1 to 5 carbon atoms.

Advantageously, the lubricant composition used according to the invention comprises at least one compound of formulas (la) to (Ic) as defined above in which:

R1 represents a linear or branched saturated alkyl group comprising from 1 to 5 carbon atoms, preferably comprising from 1 to 3 carbon atoms;

R4 represents a hydrogen atom or a saturated alkyl group comprising from 1 to 3 carbon atoms. As examples of compounds of formula (I) used according to the invention, mention may be made of toluene, ortho-xylene, meta-xylene, para-xylene, ortho-cymene, meta-cymene or para-xylene. -cymène. In one embodiment of the invention, the content by weight of compound of formula (I) ranges from 0.5 to 25%, preferably from 1 to 20%, advantageously from 5 to 15% relative to the total weight of the lubricating composition.

In one embodiment of the invention, the compound of formula (I) may be in pure form.

By pure form according to the invention is meant that the compound of formula (I) is monocomponent and does not comprise any other component other than the compound of formula (I) or is not associated with another compound. In another embodiment of the invention, the compound of formula (I) may be encapsulated.

Thus, the compound of formula (I) may be present in the form of a capsule or a microcapsule comprising a minimum content of compound of formula (I), this minimum content being chosen so that the content by weight of compound of formula (I) ranges from 0.5 to 25%, preferably from 1 to 20%, advantageously from 5 to 15% relative to the total weight of the lubricating composition.

The capsules or microcapsules comprising the compound of formula (I) may be chosen from any type of capsule or microcapsule known to those skilled in the art. The capsules or microcapsules may especially consist of a polymeric envelope chosen from polyurethanes, polyureas, polystyrenes, polyesters, polyamides or copolymers thereof, polyacrylonitriles, vinyl resins, formaldehyde resins or aminoplast resins. In a preferred embodiment of the invention, the compound (I) will be salted out of the capsules or microcapsules when the capsules or microcapsules are subjected to physico-chemical constraints, and more particularly when the capsules or microcapsules are subjected to high temperatures, for example temperatures above 150 ° C as may be encountered in areas near the piston, or when the capsules or microcapsules are subjected to high shear stresses, which is generally the case in a motor, corresponding for example to values of 10 to 100 million seconds reciprocals (s ^"1 ), or when the capsules or microcapsules are subjected to variations in the acidity or basicity of the surrounding medium, and more particularly to variations in acidity as may occur in the piston zone Examples of capsules or microcapsules that can be used in the present invention are described in particular in WO2010 / 134044, US20130146009 or WO2014 / 046876.

In another embodiment of the invention, the compound (I) can be released by volatilization.

Volatilization of the compound of formula (I) can in particular be implemented by adjusting the distillation curve of the lubricant composition. As an example, mention may be made of the use of a compound of formula (I) which is more volatile than the rest of the lubricating composition and which makes it possible to extract the compound of formula (I) in the zones subjected to temperatures above the point boiling of the compound of formula (I) but lower than the boiling point of the lighter components of the rest of the lubricating composition.

In another embodiment of the invention, the compound of formula (I) can be synthesized in situ in the lubricating composition Base oil

The lubricant compositions used according to the invention may contain any type of mineral lubricating base oil, synthetic or natural, animal or plant adapted to their use.

The base oil (s) used in the lubricant compositions used 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 (or their equivalents according to the ATI EL classification) such as as summarized below, alone or as a mixture.

Table I

The mineral base oils used 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, desalting, solvent dewaxing, hydrotreatment, hydrocracking and hydroisomerization. , hydrofinishing.

The base oils of the lubricant compositions used according to the invention may also be synthetic oils, such as certain carboxylic acid esters of alcohols or polyalphaolefins. The polyalphaolefins used as base oils are, for example, obtained from monomers having from 4 to 32 carbon atoms (for example octene, decene), and a viscosity at 100 ° C. of between 1.5 and 15 cSt according to the standard. ASTM D445. Their weight average molecular weight is typically between 250 and 3000 according to ASTM D5296. Mixtures of synthetic and mineral oils can also be used.

There is no limitation as to the use of such or such lubricating base for producing the lubricating compositions used according to the invention, except that they must have properties, in particular viscosity, viscosity index, sulfur, oxidation resistance, suitable for use in a gearbox, particularly in a gearbox of motor vehicles, particularly in a manual gearbox.

In one embodiment of the invention, the lubricating bases represent at least 50% by weight, with respect to the total mass of the lubricating composition, preferably at least 60%, or at least 70%. Typically, they represent between 75 and 99.9% by weight, relative to the total mass of the lubricant compositions used according to the invention.

In a preferred embodiment of the invention, the lubricating compositions comprise Group I and / or III mineral bases, or Group IV synthetic bases according to the API classification.

In another preferred embodiment of the invention, the lubricating compositions have a kinematic viscosity at 100 ° C. measured according to ASTM D445 ranging from 3 to 25 cSt, preferably from 5 to 22 cSt, advantageously from 5 to 13 cSt. .

In another preferred embodiment of the invention, the lubricating compositions have a viscosity index (VI) greater than or equal to 130, preferably greater than or equal to 140, advantageously greater than or equal to 150 measured according to the ISO 2909 standard.

Other additives

The lubricant compositions used according to the invention may also contain at least one additive chosen from detergents, anti-wear additives, extreme pressure additives, dispersants, pour point improvers, defoamers, thickeners, viscosity index improvers and mixtures thereof.

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 used in lubricating compositions, especially for motor oil, is that of phosphosulfur additives such as metal alkylthiophosphates, in particular zinc alkylthiophosphates, and more specifically dialkyldithiophosphates. zinc or ZnDTP. Amine phosphates are also anti-wear additives that can be used in the lubricant compositions used according to the invention. However, the phosphorus provided by these additives acts as poison catalytic systems of automobiles because these additives are ash generators. These effects can be minimized by partially substituting amine phosphates with non-phosphorus additives, such as, for example, polysulfides, especially sulfur-containing olefins.

In one embodiment, in particular for a motor application, the anti-wear and extreme-pressure additives may be present in the lubricating composition at contents ranging from 0.01 to 6% by weight, preferably from 0.05 to 4%, preferentially from 0.1% to 2% relative to the total mass of the lubricating composition. The friction modifying additive can be a compound providing metallic elements or a compound without ash. Among the compounds providing metal elements, mention may be made of transition metal complexes such as Mo, Sb, Sn, Fe, Cu, Zn, W, the ligands of which may be hydrocarbon compounds containing oxygen, nitrogen or sulfur atoms. or phosphorus, and especially molybdenum dithiocarbamates. The ashless friction modifiers are of organic origin and may be selected from monoesters of fatty acids and polyols, alkoxylated amines, fatty alkoxylated amines, fatty epoxides, borate fatty epoxides; fatty amines or fatty acid glycerol esters. For the purposes of the present invention, the term "fatty" or "fatty (s)" is intended to mean a hydrocarbon group comprising from 10 to 24 carbon atoms.

In one embodiment, the friction modifying additive may be present at levels ranging from 0.01 to 5% by weight, preferably from 0.1 to 2% relative to the total weight of the lubricating composition.

The antioxidant additives retard the degradation of the lubricating compositions in service, in particular engine oils in service, which degradation can notably result in the formation of deposits, the presence of sludge, or an increase in the viscosity of the lubricant composition, especially the engine oil. Antioxidant additives act in particular as radical inhibitors or destroyers of hydroperoxides. Among the antioxidants commonly used, mention may be made of antioxidants of phenolic or amine type, phosphosulfur antioxidants. Some of these antioxidants, for example phosphosulfides, can be ash generators. Phenolic antioxidants may be ashless, or may be in the form of neutral or basic metal salts.

The antioxidant agents may especially be chosen from sterically hindered phenols, sterically hindered phenol esters and sterically hindered phenols comprising a thioether bridge, diphenylamines, diphenylamines substituted with at least one C 1 -C 12 alkyl group, and the Ν, Ν dialkyl aryl diamines and combinations thereof. For the purposes of the present invention, sterically hindered phenol means a compound comprising a phenol group in which at least one vicinal carbon of the carbon carrying the alcohol function is substituted by at least one C 1 -C 10 alkyl group, preferably an alkyl group containing C1-C6, preferably a C4 alkyl group, preferably by the ter-butyl group. Amino compounds are another class of antioxidants that can be used, optionally in combination with phenolic antioxidants. Examples Typical aromatic amines of formula R25R26R27N, wherein R25 is an optionally substituted aliphatic or aromatic group, R26 is an optionally substituted aromatic group, R27 is a hydrogen atom, an alkyl group, an aryl group or a group of the formula R28S (O) _Z R29, wherein R28 represents an alkylene group or an alkenylene group, R29 represents an alkyl group, an alkenyl group or an aryl group and z represents an integer equal to 0, 1 or 2. Alkylphenols sulfurized or their alkali and alkaline earth metal salts can also be used as antioxidants. Another class of antioxidants is copper compounds, for example copper thio- or dithiophosphates, copper and carboxylic acid salts, dithiocarbamates, sulphonates, phenates, copper acetylacetonates. Copper salts I and II, succinic acid or anhydride may also be used.

The lubricant composition used according to the invention may contain any type of antioxidant additives known to those skilled in the art. Advantageously, the ashless antioxidants are used.

In one embodiment, the lubricant composition used according to the invention may comprise from 0.5 to 2% of at least one antioxidant additive by weight relative to the total weight of the lubricant composition.

The detergent additives reduce in particular the formation of deposits on the surface of the metal parts by dissolving the secondary products of oxidation and combustion. The detergents that can be used in the lubricant composition used according to the invention are well known to those skilled in the art. The detergents commonly used in the formulation of lubricating compositions may be anionic compounds having a long lipophilic hydrocarbon chain and a hydrophilic head. The associated cation is typically a metal cation of an alkali or alkaline earth metal. The detergents are preferably chosen from the alkali metal or alkaline earth metal salts of carboxylic acids, sulphonates, salicylates and naphthenates, as well as the salts of phenates. The alkali 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 excess of the stoichiometric amount). In the latter case, these detergents are called overbased detergents. The excess metal, bringing the overbased character to the detergent, is in the form of metal salts insoluble in the oil, for example carbonate, hydroxide, oxalate, acetate, glutamate, preferably carbonate. In one embodiment, the lubricant composition used according to the invention may comprise from 0.5 to 4% by weight of detergent, relative to the total mass of the lubricating composition.

The pour point depressant additives notably improve the cold behavior of the lubricating compositions, by slowing down the formation of paraffin crystals. As examples of pour point depressant additives, mention may be made of alkyl polymethacrylates, polyacrylates, polyarylamides, polyalkylphenols, polyalkylnaphthalenes and alkylated polystyrenes. In one embodiment, the lubricant composition used according to the invention may comprise, in addition, at least one dispersant. The dispersants may be chosen from groups formed by Mannich bases or bases, succinimides and their derivatives, in particular borated succinimides.

In one embodiment, the lubricating composition used according to the invention may comprise from 0.2 to 10% by weight of dispersants relative to the total mass of the lubricant composition.

The viscosity index improver polymers may be chosen from among polymeric esters, ethylene-based copolymers, especially ethylene / propylene copolymers and ethylene / α-olefin copolymers, homopolymers or copolymers of styrene, butadiene or isoprene, hydrogenated or not, polymethacrylates (PMA).

In one embodiment, the lubricant composition used according to the invention may comprise from 1 to 15% by weight of viscosity index improving polymers with respect to the total weight of the lubricating composition.

The anti-foam additives can be chosen from polyacrylates or silicone compounds and their derivatives, and in particular polysiloxanes. In one embodiment of the invention, the lubricant composition comprises:

from 75 to 99.5% of at least one base oil,

from 0.5 to 25% of at least one compound of formula (I).

In another embodiment of the invention, the lubricating composition comprises: from 75 to 99% of at least one base oil;

from 0.5 to 25% of at least one compound of formula (I), - from 0.5 to 5% of at least one other additive.

In another embodiment of the invention, the lubricant composition consists essentially of:

- 75 to 99.5% of at least one base oil,

- 0.5 to 25% of at least one compound of formula (I).

75 to 99% of at least one base oil,

0.5 to 25% of at least one compound of formula (I),

- 0.5 to 5% of at least one other additive.

All the characteristics and preferences presented above for the base oil, the compound of formula (I) and the additional additive also apply to the above lubricating compositions.

In one embodiment of the invention, the lubricating composition is not an emulsion. In another embodiment of the invention, the lubricant composition is anhydrous.

The invention also relates to an engine oil comprising a lubricant composition used according to the invention.

All the characteristics and preferences presented for the lubricant composition also apply to the engine oil used according to the invention.

In one embodiment of the invention, the engine oil may be grade OW-16, 0W-20 and 5W-30 according to the classification SAEJ300, characterized by a kinematic viscosity at 100 ° C (KV100) ranging from 5, 6 to 12.5 cSt measured according to ASTM D445 international standard.

In another embodiment of the invention, the engine oil may be characterized by a viscosity index, calculated according to the international standard ISO 2909, greater than or equal to 130, preferably greater than or equal to 150. To formulate an oil motor can advantageously use base oils having a sulfur content of less than 0.3%, for example mineral oils of group III, and synthetic bases free of sulfur, preferably of group IV, or mixtures thereof.

The subject of the invention is also the use of a lubricant composition as defined above for the lubrication of vehicle engines, preferably of motor vehicles, advantageously engines of spark-ignition motor vehicles.

The subject of the invention is also the use of a lubricant composition as defined above for reducing or even suppressing rattling in engines, preferably motor vehicles, advantageously engines of spark-ignition motor vehicles.

The invention also relates to the use of a lubricant composition as defined above for reducing the fuel consumption of vehicles, particularly motor vehicles.

All of the features and preferences presented for the lubricant composition above also apply to the above uses.

The subject of the invention is also a method of lubricating a motor of vehicles, preferably of motor vehicles, advantageously of a spark ignition motor vehicle, said method comprising at least one step of contacting a motor vehicle. mechanical part of the engine with a lubricating composition as defined above.

The subject of the invention is also a method for reducing or even suppressing rattling in an engine of vehicles, preferably of motor vehicles, advantageously of spark ignition automotive vehicles comprising at least one step of bringing into contact a mechanical part of the engine of the engine. vehicle with a lubricating composition as defined above.

The reduction or even the suppression of rattling in an engine can be evaluated by any method known to those skilled in the art.

The reduction or even the suppression of knock in an engine by the use of a lubricating composition can in particular be evaluated by measuring the evolution of the motor power and by measuring the evolution of the ignition timing parameter in the presence of the lubricating composition.

A method is more particularly described below. The invention also relates to a method for reducing the fuel consumption of a vehicle, in particular of a motor vehicle comprising at least one step of contacting a mechanical part of the engine of the vehicle with a lubricant composition such as as defined above.

All the characteristics and preferences presented above for the lubricating composition also apply to the above processes.

The vehicles may include a two or four stroke internal combustion engine and spark ignition engine.

Engines may be gasoline engines for use with gasoline or natural gas. For the purposes of the present invention, the term "conventional gasoline" is understood to mean engines that are powered by a fuel obtained after refining an oil of mineral origin (such as oil for example). The engines may also be petrol engines modified to be fueled by a fuel based on oils derived from renewable materials such as alcohol-based fuels.

The vehicles may be light vehicles such as automobiles and motorcycles. The vehicles can also be heavy goods vehicles.

The subject of the invention is also the use of a compound of formula (I) as defined above in a lubricant composition for reducing or even suppressing rattling in engines, preferably motor vehicles, advantageously motor vehicle engines. spark ignition.

The set of characteristics and preferences presented above for the compound of formula (I) also applies to the use above. The subject of the invention is also a composition of concentrated additive type comprising:

at least one compound of formula (I):

(I)

in which :

at least one additive chosen from detergents, friction modifiers, anti-wear additives, dispersants, extreme pressure additives, antioxidants, viscosity index improving polymers, pour point improvers, defoamers, thickeners and mixtures thereof. The set of characteristics and preferences presented above for the compound of formula (I) and for the additional additive also applies to the composition of the additive concentrate type above.

In one embodiment of the invention, to the additive concentrate type composition used according to the invention can be added at least one base oil to obtain a lubricant composition used according to the invention.

The various objects of the present invention and their implementations will be better understood on reading the examples which follow. These examples are given for information only, and are not limiting in nature.

Examples:

A lubricant composition No. 1 was prepared from the following compounds:

- base oil 1: PAO grade 4,

- base oil 2: PAO grade 6,

base oil 3: trimethylolpropane ester having a kinematic viscosity at 100 ° C., measured according to ASTM D445 equal to 4.5 mm ² / s,

polymer: hydrogenated styrene / isoprene copolymer dispersed at 10.7% w / w in a Group I oil,

additive package: a mixture comprising a calcium salicylate as a detergent, a zinc dithiophosphate as an anti-wear, a borated succinimide dispersant, a phenolic antioxidant, an aminated antioxidant (alkylated diphenylamine), a polysiloxane derivative as an anti-foam, a molybdenum dithiocarbamate as a friction modifier and a polymethacrylate as a pour point improver. The lubricating composition No. 1 is described in Table II: the percentages indicated are percentages by weight.

Table II

To the lubricant composition No. 1 was added a compound of formula (I) used according to the invention to obtain the lubricating compositions No. 2 and No. 3, the compound of formula (I) being:

meta-toluidine (marketed by Sigma-Aldrich) of formula:

or ethoxybenzene (marketed by Sigma-Aldrich) of the formula

Lubricating compositions Nos. 2 and 3 are described in Table III: the percentages indicated are percentages by weight. Table III

The impact of lubricant compositions No. 1 to No. 3 was evaluated according to the method described below.

A 1.6 liter turbocharged engine with a spark ignition was fitted near each cylinder of accelerometers to detect the occurrence of knock. The motor control analyzes this information and reduces the ignition advance parameter in the event of knocking. In the opposite case, if the combustion takes place without the occurrence of knocking, the engine calculation increases the ignition advance in order to improve the engine efficiency and to increase the power measured at the output of the engine.

The engine was installed in a test cell where engine speed and engine output power were measured using an electromagnetic brake. Control parameters such as engine speed, amount of fuel injected, ignition advance and engine power were recorded during the test.

The engine coolant temperature was maintained at 94 ° C at the engine inlet and the oil temperature was maintained at 99 ° C at the engine inlet. The tests were carried out under full load and the swept engine speed was extended from 3000 to 8500 rpm.

The lubricant composition No. 1 was used as a reference oil to check the stability of the engine behavior.

The impact of Lubricant compositions No. 2 and No. 3 on the knock phenomenon was observed by measuring the evolution of the engine power and measuring the evolution of the ignition advance parameter. comparing each of these two lubricating compositions with the lubricating composition No. 1.

The engine power is expressed in horse or horses (cv).

The ignition advance is expressed in degree crankshaft (° V). A difference of at least one CV with respect to the power and a difference of at least 0.4 ° V is considered significant and thus makes it possible to validate the benefit of the lubricating composition in reducing the knocking phenomenon.

The lubricant composition No. 2 is tested on the test described above box before and after by the lubricant composition No. 1. The power gain and ignition advance is determined with respect to the average of the results obtained on the lubricant composition No. 1 before and after the test with the lubricant composition No. 2.

The lubricant composition No. 3 is tested on the test described above before and after by the lubricant composition No. 1. The power gain and ignition advance is determined with respect to the average of the results obtained on the lubricant composition No. 1 before and after the test with the lubricant composition No. 3.

The results for No. 2 and No. 3 lubricating compositions at 6500 rpm and 7500 rpm are presented in Tables IV and V (the results of the lubricating composition No. 1 are not indicated since the lubricant composition No. 1 is the reference to which the lubricant compositions No. 2 and No. 3 were compared).

Table IV

Composition N ° 2 N ° 3

Delta +3.0 + 1, 3

power (cv)

at 6500 rpm

Delta advance +1, 2 +0.4

on ignition

(° V) to 6500

rpm Table V

Composition N ° 2 N ° 3

Delta + 1, 6 + 1, 0

power (cv)

at 7500 rpm

Delta Advance + 1, 6 + 1, 0

on ignition

(° V) to 7500

rev / min The results show that the presence of a compound of formula (I) used according to the invention in a lubricant composition (lubricant compositions No. 2 and No. 3) significantly reduces the phenomenon of rattling in an engine.

It should be noted that this reduction is present over a wide range of engine speed, and even at high engine speeds, such as 7500 rpm.

It should also be noted that the use of lubricant compositions according to the invention (lubricant compositions No. 2 and No. 3) did not lead to any abnormal deposition in the combustion chamber of the engine.

The lubricant compositions used according to the invention (lubricant compositions No. 2 and No. 3) also retain good lubricating properties.

Claims

Use of a lubricant composition to reduce rattling in a vehicle engine, said lubricant composition comprising:

at least one base oil,

at least one compound of formula (I):

(I)

in which :

2. Use of the composition according to claim 1 wherein R1 represents:

a linear or branched, saturated or unsaturated, substituted or unsubstituted alkyl group comprising from 1 to 10 carbon atoms;

a group -OR7 in which R7 represents a linear or branched, saturated or unsaturated, substituted or unsubstituted alkyl group comprising from 1 to 10 carbon atoms;

a group -NR8R9 in which R8 and R9, which may be identical or different, independently represent a hydrogen atom or a saturated or unsaturated, substituted or unsubstituted alkyl group comprising from 1 to 3 carbon atoms.

3. Use of the composition according to claim 1 or 2 wherein R5 represents a hydrogen atom.

4. Use of the composition according to any one of the preceding claims wherein R6 represents a hydrogen atom.

5. Use of the lubricant composition according to any preceding claim wherein R1 represents:

A saturated linear or branched alkyl group comprising from 1 to 5 carbon atoms;

A group -OR7 in which R7 represents a linear or branched saturated alkyl group comprising from 1 to 5 carbon atoms, preferably from 1 to 3 carbon atoms; A group -NR8R9 in which:

R9 represents a hydrogen atom or a saturated alkyl group comprising from 1 to 3 carbon atoms.

6. Use of the lubricating composition according to any one of the preceding claims wherein R2 represents:

• a hydrogen atom;

A saturated linear or branched alkyl group comprising from 1 to 5 carbon atoms;

A group -NR1 1 R12 in which:

7. Use of the lubricant composition according to any preceding claim wherein R3 represents:

• a hydrogen atom;

A saturated linear or branched alkyl group comprising from 1 to 5 carbon atoms;

A group -NR14R15 in which:

8. Use of the lubricant composition according to any one of the preceding claims wherein R4 represents:

• a hydrogen atom;

A saturated linear or branched alkyl group comprising from 1 to 5 carbon atoms;

A group -NR17R18 in which:

R17 represents a hydrogen atom or a saturated alkyl group comprising from 1 to 3 carbon atoms; R 18 represents a hydrogen atom or a saturated alkyl group comprising from 1 to 3 carbon atoms.

9. Use of the lubricant composition according to any one of the claims

R2 represents a hydrogen atom, a linear or branched saturated alkyl group comprising from 1 to 10 carbon atoms, a group - OR10, a group -NR1 1 R12;

R3 represents a hydrogen atom, a linear or branched saturated alkyl group comprising from 1 to 10 carbon atoms, a group -OR13, a group -NR14R15; R4 represents a hydrogen atom, a linear or branched saturated alkyl group comprising from 1 to 10 carbon atoms, a group - OR16, a group --NR17R18;

Use of the lubricant composition according to the preceding claim comprising a compound of formulas (la) to (Ic) in which:

R1 represents a group -OR7 in which R7 represents a saturated alkyl group comprising from 1 to 3 carbon atoms;

Use of the lubricating composition according to claim 9 comprising a compound of formulas (la) to (Ic) in which:

R1 represents a group -NR8R9 in which:

12. Use of the lubricant composition according to claim 9 comprising a compound of formulas (la) to (Ic) in which:

R2 represents a hydrogen atom or a linear or branched saturated alkyl group comprising from 1 to 5 carbon atoms;

13. Use of the lubricant composition according to any one of the preceding claims wherein the weight content of compound of formula (I) ranges from 0.5 to 25%, preferably from 1 to 20%, advantageously from 5 to 15% by weight. % relative to the total weight of the lubricating composition.

14. Use of the lubricant composition according to any one of the preceding claims further comprising at least one additive selected from detergents, friction modifiers, dispersants, anti-wear additives, extreme pressure additives, antioxidants, viscosity index improvers, pour point improvers, defoamers, thickeners and mixtures thereof.

Use of a concentrate additive composition in a lubricating composition comprising at least one base oil for reducing rattling in a vehicle engine, said additive concentrate composition comprising:

at least one compound of formula (I):

(I)

in which :

R1 represents a hydrogen atom, a linear or branched, saturated or unsaturated, substituted or unsubstituted alkyl group comprising from 1 to 10 carbon atoms, a group -OR7, a group -NR8R9; R2 represents a hydrogen atom, a linear or branched, saturated or unsaturated, substituted or unsubstituted alkyl group comprising from 1 to 10 carbon atoms, a group -OR10, a group - NR1 1 R12;

at least one additive chosen from detergents, friction modifiers, anti-wear additives, dispersants, extreme pressure additives, antioxidants, viscosity index improving polymers, pour point improvers, antifoams, thickeners and mixtures thereof.