FR3054223A1 - COPOLYMER AND ITS USE AS DETERGENT ADDITIVE FOR FUEL - Google Patents

Abstract

The invention relates to a copolymer and its use as a detergent additive in a liquid fuel for an internal combustion engine. The copolymer is obtained by copolymerization of at least: - one apolar monomer (ma) corresponding to formula (I): and - one polar monomer (mb) chosen from monomers derived from styrene or from alpha-methylstyrene whose aromatic nucleus is substituted by at least one R group or by at least one C1 to C12 hydrocarbon chain, linear or branched, preferably acyclic, substituted by at least one R group, said R group being chosen from: - the hydroxyl group, - a group -OR', - a group -(OCyH2yO)fH, - a group -(OCyH2yO)f-R', - a group -O-(CO)-R', and - a group -(CO)-OR' , y is an integer ranging from 2 to 8, f is an integer ranging from 1 to 10 and R′ is chosen from C1 to C24 alkyl chains. The invention also relates to a method for maintaining cleanliness and/or cleaning at least one of the internal parts of an internal combustion engine.

Description

(57) The invention relates to a copolymer and its use as a detergent additive in a liquid fuel of an internal combustion engine.

The copolymer is obtained by copolymerization of at least:

- an apolar monomer (m _a ) corresponding to formula (I):

FR 3 054 223 - A1

U l) and

- A polar monomer (m _b ) chosen from monomers derived from styrene or alphamethylstyrene, the aromatic nucleus of which is substituted by at least one R group or by at least one C hydrocarbon chain! at

C- ^, linear or branched, preferably acyclic, substituted by at least one group R, said group R being chosen from:

- the hydroxyl group,

- a group -OR ',

- a group - (OC _y H _2y O) _f -H,

- a group - (OC; _f H _2y O) _f -R ',

- a group -O- (CO) -R ', and

- a group - (CO) -OR ', y is an integer ranging from 2 to 8, f is an integer ranging from 1 to 10 and R' is chosen from C alkyl chains! to C ₂₄ .

The invention also relates to a method for maintaining the cleanliness and / or cleaning of at least one of the internal parts of an internal combustion engine.

ICG70096 FR text deposit

COPOLYMER AND ITS USE AS A DETERGENT ADDITIVE FOR

FUEL

The present invention relates to a copolymer and its use as a detergent additive in a liquid fuel of an internal combustion engine.

The invention also relates to a method for maintaining the cleanliness and / or cleaning of at least one of the internal parts of an internal combustion engine.

PRIOR STATE OF THE ART

Liquid fuels for internal combustion engines contain components that can degrade during engine operation. The problem of deposits in the internal parts of combustion engines is well known to engine manufacturers. It has been shown that the formation of these deposits has consequences on engine performance and in particular has a negative impact on consumption and particle emissions. Advances in fuel additive technology have made it possible to deal with this problem. So-called detergent additives used in fuels have already been proposed to maintain engine cleanliness by limiting deposits (“Keep-clean” effect) or by reducing deposits already present in the internal parts of the combustion engine (“effect”). clean-up ”. By way of example, mention may be made of document US4171959 which describes a detergent additive for petrol fuel containing a quaternary ammonium salt. The document WO2006135881 describes a detergent additive containing a quaternary ammonium salt used to reduce or clean the deposits, in particular on the intake valves. However, engine technology is constantly evolving and fuel requirements must evolve to meet these technological advances in combustion engines. In particular, the new direct petrol or diesel injection systems expose the injectors to more severe pressure and temperature conditions, which favors the formation of deposits. In addition, these new injection systems have more complex geometries to optimize spraying, in particular, more numerous holes having smaller diameters but which, on the other hand, induce a greater sensitivity to deposits. The presence of deposits can affect combustion performance, in particular increasing polluting emissions and particulate emissions. Other consequences of excessive deposits have been reported in the literature, such as increased fuel consumption and handling problems.

ICG70096 FR text deposit

Preventing and reducing deposits in these new engines is essential for optimal operation of today's engines. There is therefore a need to provide detergent additives for fuel promoting optimal operation of combustion engines, in particular for new engine technologies.

There is also a need for a universal detergent additive capable of acting on deposits regardless of the technology of the engine and / or the nature of the fuel.

OBJECT OF THE INVENTION

The Applicant has discovered that the copolymers according to the invention have remarkable properties as a detergent additive in the liquid fuels of an internal combustion engine. The copolymers according to the invention used in these fuels make it possible to maintain the cleanliness of the engine, in particular, by limiting or avoiding the formation of deposits (Keep-clean effect) or by reducing the deposits already present in the internal parts of the combustion engine (clean-up effect).

The advantages associated with the use of such copolymers according to the invention are:

- optimal engine operation,

- a reduction in fuel consumption,

- better handling of the vehicle,

- reduced pollutant emissions, and

- savings due to less maintenance of the engine.

The subject of the present invention relates to a copolymer obtained by copolymerization of at least:

- an apolar monomer (m _a ) corresponding to the following formula (I)

(l)

With

ICG70096 FR deposit text u = 0 or 1, w = 0 or 1,

E = -O- or -NH (Z) -, or -O-CO-, or -NH-CO- or -CO-NH-, with Z represents H or a C1-C6 alkyl group, it being understood that when E = -O-CO- E is linked to the vinyl carbon by the oxygen atom,

G represents a group chosen from C1-C34 alkyl, an aromatic ring, an aralkyl comprising at least one aromatic ring and at least one C1-C34 alkyl group, and

a polar monomer (m _b ) chosen from monomers derived from styrene or from alphamethylstyrene, the aromatic nucleus of which is substituted by at least one group R or by at least one hydrocarbon chain C1 to C12, linear or branched, preferably acyclic, substituted by at least one R group, said R group being chosen from:

- the hydroxyl group,

- a group -OR ’,

- a group - (OC _y H _2y O) fH,

- a group - (OC _y H _2y O) _r R ',

- a group-O- (CO) -R ’, and

- a group- (CO) -OR ', y is an integer ranging from 2 to 8, f is an integer ranging from 1 to 10 and R' is chosen from C1 to C ₂₄ alkyl chains.

According to an advantageous embodiment, the group E of the apolar monomer (m _a ) is -O-.

According to another advantageous embodiment, the group E of the apolar monomer (m _a ) is -NH (Z) - with Z represents H or a C1-C6 alkyl group.

According to yet another advantageous embodiment, the group E of the apolar monomer (m _a ) is and -O-CO- where E is linked to the vinyl carbon by the oxygen atom.

Advantageously, the apolar monomer (m _a ) is such that w is equal to 0.

According to a first preferred variant, the group G of the apolar monomer (m _a ) is a C4-C30 alkyl.

According to another preferred variant, the group G of the apolar monomer (m _a ) is a

ICG70096 FR aralkyl deposition text comprising at least one aromatic ring and at least one C4-30 alkyl group.

According to a preferred embodiment, the copolymer is chosen from block copolymers and random copolymers.

According to a particularly preferred embodiment, the copolymer is a block copolymer.

In particular, the block copolymer comprises at least:

a block A consisting of a chain of structural units derived from one or more apolar monomers chosen from apolar monomers (m _a ) of formula (I) and,

- a block B consisting of a chain of structural units derived from one or more polar monomers chosen from polar monomers (m _b ).

Advantageously, the copolymer comprises at least one block sequence AB, ABA or BAB where said blocks A and B are linked without the presence of an intermediate block of different chemical nature.

According to a particular development, the block copolymer is obtained by block polymerization, optionally, followed by one or more post-functionalizations.

Advantageously, the group R of the polar monomer (m _b ) is chosen from:

- the hydroxyl group and,

- a group -O- (CO) -R ’, R’ being chosen from C 1 to C 24 hydrocarbon chains

According to a preferred embodiment, the polar monomer (m _b ) is chosen from monomers derived from styrene or from alpha-methylstyrene the aromatic nucleus of which is substituted by at least one group —O- (CO) -R ′, R 'being chosen from C1 to C24 alkyls

According to another preferred embodiment, the polar monomer (m _b ) is chosen from monomers derived from styrene or from alpha-methylstyrene, the aromatic nucleus of which is substituted by at least one hydroxyl group or by a C1 to C hydrocarbon chain. C12, linear or branched, preferably acyclic, substituted by at least one hydroxyl group.

ICG70096 FR text deposit

The object of the present invention also relates to a fuel concentrate which comprises one or more copolymers as defined above, in admixture with an organic liquid, said organic liquid being inert with respect to the copolymer (s) and miscible with said fuel, said fuel coming from one or more sources chosen from the group consisting of mineral, animal, plant and synthetic sources.

The subject of the present invention also relates to a fuel composition which comprises:

(1) a fuel from one or more sources chosen from the group consisting of mineral, animal, plant and synthetic sources, and (2) one or more copolymers as defined above.

Preferably, the fuel composition comprises at least 5 ppm of copolymer (s) as defined above.

According to one embodiment, the fuel composition comprises the copolymer (s) as defined above in the form of a concentrate.

The copolymer of the invention is preferably used as a detergent additive in a liquid fuel of an internal combustion engine.

Advantageously, the copolymer of the invention is used in a liquid fuel of an internal combustion engine, to maintain the cleanliness and / or clean at least one of the internal parts of the internal combustion engine.

The copolymer is preferably used in the liquid fuel of an internal combustion engine to limit or avoid the formation of deposits in at least one of the internal parts of the internal combustion engine and / or to reduce the deposits existing in at least one of the internal parts of said engine.

The copolymer is preferably used to reduce the fuel consumption of the internal combustion engine.

The copolymer is preferably used to reduce the emission of pollutants, in particular, the emission of particles from the internal combustion engine.

ICG70096 FR text deposit

According to a particular embodiment, the internal combustion engine is a spark-ignition engine.

According to another particular embodiment, the internal combustion engine is a diesel engine, preferably a diesel engine with direct injection. The copolymer can, in this case, be used to limit or avoid and / or reduce deposits of soap and / or varnish type.

In particular, the copolymer can, in this case, be used to reduce and / or avoid the loss of power due to the formation of deposits in the internal parts of a direct injection diesel engine, said loss of power being determined according to the CEC F-98-08 standardized engine test method.

The copolymer can also be used to reduce and / or avoid the restriction of the flow of fuel emitted by the injector of a direct injection diesel engine during its operation, said restriction of flow being determined according to the method of CEC F-23-1-01 standardized engine test.

The subject of the present invention also relates to a process for maintaining the cleanliness and / or cleaning of at least one of the internal parts of an internal combustion engine comprising at least the following steps:

- the preparation of a fuel composition by additivation of a fuel with one or more copolymers and,

- the combustion of said fuel composition in said internal combustion engine.

According to a particular embodiment, the internal combustion engine is a spark-ignition engine.

In particular, the internal part of the spark ignition engine kept clean and / or cleaned is chosen from the engine intake system, in particular the intake valves (IVD), the combustion chamber (CCD or TCD) and the fuel injection system, in particular the injectors of an indirect injection system (PFI) or the injectors of a direct injection system (DISI).

According to another particular embodiment, the internal combustion engine is a

ICG70096 EN text deposit Diesel engine, preferably a direct injection diesel engine.

In particular, the internal part of the diesel engine kept clean and / or cleaned is the diesel engine injection system.

DETAILED DESCRIPTION

Other advantages and characteristics will emerge more clearly from the description which follows. The particular embodiments of the invention are given by way of nonlimiting examples.

According to a particular embodiment, a copolymer is obtained by copolymerization of at least one apolar monomer (m _a ) and at least one polar monomer (m _b ).

According to one embodiment, the copolymer is chosen from block or random copolymers.

According to a particularly preferred embodiment, the copolymer is a block copolymer.

The apolar monomer (m _a ) corresponds to the following formula (I):

With u = 0 or 1 w = 0 or 1

Advantageously, the apolar monomer (m _a ) is such that w = 0.

The group E of the apolar monomer (m _a ) is chosen from - E = -O-,

ICG70096 FR text deposit

E = -NH (Z) - with Z represents H or a C1-C6 alkyl group, linear or branched, cyclic or acyclic, preferably acylic,

E = -O-CO- it being understood that E is then connected to the vinyl carbon by the oxygen atom,

- E = -NH-CO-, and

- E = -CO-NH-.

According to a variant, the apolar monomer (m _a ) is chosen from those verifying u = 0

According to a preferred variant, the apolar monomer (m _a ) is chosen from those satisfying: u = 1, and the group E is chosen from

- E = -O-,

E = -NH (Z) - with Z represents H or a C1-C6 alkyl group, preferably CH3, linear or branched, cyclic or acyclic, preferably acylic, and E = -O-CO- where E is connected to vinyl carbon by the oxygen atom.

According to a more preferred variant, the apolar monomer (m _a ) is chosen from those satisfying: u = 1 and the group E is chosen from

E = -O-, and

E = -O-CO- where E is linked to vinyl carbon by the oxygen atom.

The group (G) of the apolar monomer (m _a ) may be a C1-C34 alkyl, preferably a C4-C30 alkyl radical, even better in C6-C24, even more preferably in C8 to C18. The alkyl radical is a linear or branched radical, cyclic or acyclic, preferably acyclic. This alkyl radical can comprise a linear or branched part and a cyclic part. Mention may be made, without limitation, of alkyl groups such as octyl, decyl, dodecyl, ethyl-2-hexyl, isooctyl, isodecyl and isododecyl.

Among the vinyl ester alkyl monomers that may be mentioned, for example, vinyl octanoate, vinyl decanoate, vinyl dodecanoate, vinyl tetradecanoate, vinyl hexadecanoate, vinyl octodecanoate, docosanoate of vinyl, vinyl 2-ethylhexanoate.

ICG70096 FR text deposit

The group (G) of the apolar monomer (m _a ) can also be an aromatic nucleus. Among the aromatic groups, there may be mentioned, without limitation, the phenyl or naphthyl group, preferably the phenyl group.

According to another preferred variant, the group (G) of the apolar monomer (m _a ) may be an aralkyl comprising at least one aromatic ring and at least one C1-C34 alkyl group. Preferably, according to this variant, the group (G) is an aralkyl comprising at least one aromatic ring and one or more alkyl groups in C4C30, advantageously in C6-C24, even more preferably in C8 to C18.

The aromatic ring can be mono-substituted or be substituted on several of its carbon atoms. Preferably, the aromatic nucleus is monosubstituted.

The C1-C34 alkyl group can be in the ortho, meta or para position on the aromatic ring, preferably in para.

The alkyl radical is a linear or branched radical, cyclic or acyclic, preferably acyclic.

The alkyl radical is preferably an acyclic radical, linear or branched, preferably linear.

The aromatic nucleus can be directly linked to the group E or to vinyl carbon, but it can also be linked to it via an alkyl substituent.

Mention may be made, by way of example of group G, of a benzyl group substituted in para with a C4-C30 alkyl group.

Preferably, according to this variant, the group (G) of the apolar monomer (m _a ) is an aralkyl comprising at least one aromatic ring and at least one alkyl group in C4-C30, advantageously in C6-C24, even more preferably in C8 to C18.

The polar monomer (m _b ) is preferably chosen from the monomers derived from styrene or from alpha-methylstyrene, the aromatic nucleus of which is substituted by at least one R group or by at least one C1 to C12 hydrocarbon chain, preferably in Ci to C ₄ , linear or branched, preferably acyclic, advantageously -CH ₂ -, substituted by at least one group R.

The term “hydrocarbon chain” means a chain consisting exclusively of atoms of

ICG70096 FR text carbon and hydrogen deposition, said chain possibly being linear or branched, cyclic, polycyclic or acyclic, saturated or unsaturated, and optionally aromatic or polyaromatic. A hydrocarbon chain can comprise a linear or branched part and a cyclic part. It can include an aliphatic part and an aromatic part.

The substitution on the aromatic nucleus of the styrenic group is in ortho, meta or para, preferably in para.

Preferably, the aromatic nucleus of the styrenic group is substituted by a single substituent.

The group R is chosen from:

- the hydroxyl group,

the alkoxy groups: -OR ′, R ′ representing a C ₁ to C ₂ 4 alkyl,

- polyalkoxy groups: - (OC _y H _2y O) rH where y is an integer ranging from 2 to 8 and f is an integer ranging from 1 to 10,

- polyalkoxy groups: - (OC _y H _2y O) rR 'where y is an integer ranging from 2 to 8, and f is an integer ranging from 1 to 10, R' representing a _C₁-C2 4

- carboxylates or alkyl esters: - (CO) -OR ', R' representing an alkyl to C _24,

- Alkyl carboxylates or alkyl esters: -O- (CO) -R ', R' representing a C 1 to C ₂₄ alkyl.

The group R is preferably chosen from:

- the hydroxyl group,

- alkoxy groups: -OR ’, R’ representing a C1 to C12 alkyl,

the polyalkoxy groups: - (OC _y H _2y O) fH where y is an integer ranging from 2 to 4, more preferably from 2 to 3 and f is an integer ranging from 2 to 8, more preferably from 2 to 4,

- the polyalkoxy groups: - (OC _y H _2y O) rR 'where y is an integer ranging from 2 to 4, more preferably from 2 to 3 and f is an integer ranging from 2 to 8, more preferably from 2 to 4, R ′ representing a C1 to C12 alkyl,

- carboxylates or alkyl esters: - (CO) -OR ', where R' is alkyl to C _2.

- the alkyies carboxylates or alkyies esters: -O- (CO) -R ', wherein R' is alkyl to C _2.

Even more preferably, R is selected from carboxylates alkyies: -O- (CO) -R ', R' representing an alkyl to C _24, preferably Ci-Ci _2.

ICG70096 FR text deposit

According to a preferred embodiment, the group R is the acetoxy group.

According to another preferred variant, the group R is the hydroxyl group.

According to a preferred embodiment, the polar monomer (m _b ) is chosen from monomers derived from styrene or from alpha-methylstyrene, the aromatic nucleus of which is substituted by a group -CH ₂ -R.

According to this preferred embodiment, the group R is preferably chosen from:

- the hydroxyl group and,

- alkyl carboxylates: -O- (CO) -R ', R' representing an alkyl, _Ci-C2 preferably 4 -C 12, more preferably C, to C _8, more preferably C ₄ -C , for example the acetoxy group.

According to this preferred embodiment, the group R is preferably chosen from the hydroxyl group.

The polar monomer (m _b ) can, in particular, be chosen from monomers derived from styrene or alpha-methylstyrene, the aromatic nucleus of which is substituted by at least one alkyl carboxylate group -O- (CO) -R ', R 'is an alkyl to C ₂ 4, preferably Ci to Ci _2, most preferably C, to C _8, more preferably to C _4, for example the acetoxy group.

The alkyl carboxylate group -O- (CO) -R ’can be in the ortho, meta or para position on the aromatic ring, preferably in the para position.

According to a particular embodiment, the polar monomer (m _b ) is chosen from monomers derived from styrene or alpha-methylstyrene whose aromatic nucleus is substituted in ortho, meta or para position, by at least one hydroxyl group or by a C 1 to C ₂ , preferably C 1 to C ₄ hydrocarbon chain, linear or branched, preferably acyclic, substituted by at least one hydroxyl group.

According to a particular embodiment, the monomer derived from styrene (m _b ) is represented by the following formula (II):

ICG70096 FR text deposit

(II)

In which: t = 0 yes g = 0 or 1

X represents a C 1 to C 12 hydrocarbon chain, preferably a C 1 to C ₄ chain, more preferably the group -CH ₂ ,

R is as described above, in particular chosen from -OH, -OR ', -O- (CO) -R' and (CO) -OR 'with R' being chosen from C 1 to C ₂₄ hydrocarbon chains , preferably in Ci to Ci ₂ , more preferably in Ci to C ₈ , even more preferably in Ci to C ₄

Generally, the monomers derived from styrene (t = 0) are preferred over the monomers derived from alpha-methylstyrene (t = 1).

The monomer derived from styrene (m _b ) is, for example, chosen from vinyl phenols and (vinyl phenyl) methanols in the ortho, meta and para position, preferably para.

The monomer derived from styrene (m _b ) is, for example, chosen from acetoxystyrene in the ortho, meta and para position, preferably para.

The copolymer can be prepared according to any known method of polymerization. The various techniques and conditions of polymerization are widely described in the literature and fall within the general knowledge of those skilled in the art.

It is understood that one would not depart from the invention if the copolymer according to the invention were obtained from other monomers other than (m _a ) and (m _b ), insofar as the final copolymer corresponds to that of the invention, that is to say obtained from at least (m _a ) and (m _b ) ,. For example, one would not depart from the invention, if the copolymer were obtained by copolymerization of monomers other than (m _a ) and (m _b ), followed by post-functionalization.

ICG70096 FR text deposit

For example, the blocks deriving from an apolar monomer (m _a ) can be obtained from vinyl alcohol or acrylic acid, respectively by transesterification or amidation reaction.

For example, the poly (vinyl phenol) blocks can be obtained from poly (acetoxystyrene) blocks obtained by copolymerization of polar acetoxystyrene monomers m _b , followed by hydrolysis according to any known process.

For example, the poly (alkyl styrene ester) block can be obtained from a poly (vinyl phenol) fragment by an esterification reaction.

The copolymer can be a block copolymer, a random copolymer or any other form of copolymer.

According to a particular embodiment, the block copolymer comprises at least:

a block A consisting of a chain of structural units derived from one or more apolar monomers chosen from apolar monomers (m _a ) of formula (I) and a block B consisting of a chain of structural units derived from one or more polar monomers chosen from polar monomers (m _b ),

It being understood that block A is derived only from apolar monomers (m _a ) and that block B contains only polar blocks (m _b ).

According to a particular preferred embodiment, the block copolymer comprises at least: a block A consisting of a chain of structural units derived from an apolar monomer chosen from apolar monomers (m _a ) of formula (I) and, a block B consisting of a chain of structural units derived from a polar monomer chosen from polar monomers (m _b ).

The block copolymers can be obtained by block polymerization, preferably by block and controlled polymerization and, optionally followed by one or more post-functionalizations.

The controlled polymerizations can be radical controlled polymerizations or ionic controlled polymerizations.

The choice of the polymerization process is a matter for the general knowledge of those skilled in the art depending on the monomers chosen.

According to a particular embodiment, the block copolymer described above is obtained by block and controlled polymerization. The polymerization is, advantageously,

ICG70096 FR text deposit chosen from controlled radical polymerization; for example, by atomic transfer radical polymerization (ATRP in English "Atom Transfer Radical Polymerization"); radical polymerization with nitroxide (NMP in English "Nitroxidemediated polymerization"); degenerative transfer processes (in English "degenerative transfer processes") such as degenerative iodine transfer polymerization (in English "ITRP- iodine transfer radical polymerization") or radical polymerization by reversible chain transfer by addition-fragmentation ( RAFT in English “Reversible Addition-Fragmentation Chain Transfer); polymerizations derived from ATRP such as polymerizations using initiators for continuous regeneration of the activator (ICAR - Initiators for continuous activator regeneration) or using activators regenerated by electron transfer (ARGET in English "activators regenerated by electron transfer ”). Block copolymers can be synthesized by living cationic polymerization. Living cationic polymerization is characterized by a reduction in the reactivity of the cationic propagating species, which makes it possible to suppress the termination and transfer reactions while keeping sufficient reactivity for propagation.

By way of example, mention may be made of the publication "Macromolecular Engineering by atom transfer radical polymerization", JACS, 136, 6513-6533 (2014) which describes a sequenced and controlled polymerization process for forming block copolymers.

The sequenced and controlled polymerization is typically carried out in a solvent, under an inert atmosphere, at a reaction temperature generally ranging from 0 to 200 ° C, preferably from 50 ° C to 130 ° C. The solvent can be chosen from polar solvents, in particular ethers such as anisole (methoxybenzene), dioxane or tetrahydrofuran or non-polar solvents, in particular, paraffins, cycloparaffins, aromatics and alkylaromatics having from 1 to 19 carbon atoms, for example, benzene, toluene, cyclohexane, methylcyclohexane, n-butene, n-hexane, n-heptane and the like.

For radical polymerization by atom transfer (ATRP in English "Atom Transfer Radical Polymerization"), the reaction is generally carried out under vacuum in the presence of an initiator, a ligand and a catalyst. By way of example of a ligand, mention may be made of Ν, Ν, Ν ', Ν'',Ν''- Pentamethyldiethylenetriamine (PMDETA), 1,1,4,7,10,10hexamethyltriethylene tetramine (HMTETA), 2,2'-Bipyridine (BPY) and Tris (2pyridylmethyl) amine (TPMA). Examples of catalysts that may be mentioned include: CuX, CuX ₂ ,

ICG70096 FR text deposit with X = CI, Br and ruthenium-based complexes Ru ²⁺ / Ru ³⁺ .

The ATRP polymerization is preferably carried out in a solvent chosen from polar solvents.

According to the sequenced and controlled polymerization technique, it can also be envisaged to work under pressure.

The numbers of equivalents of apolar monomer (m _a ) of block A and of polar monomer (m _b ) of block B reacted during the polymerization reaction are identical or different.

The number of equivalents of apolar monomer (m _a ) of block A is preferably from 2 to 50, preferably from 5 to 50, more preferably from 10 to 50.

The number of equivalents of polar monomer (m _b ) of block B is preferably from 2 to 50, preferably from 2 to 40, more preferably from 2 to 20.

The number of equivalents of apolar monomer (m _a ) of block A is advantageously greater than or equal to that of the polar monomer (m _b ) of block B. In addition, the molar mass by weight M _w of block A or of block B is preferably less than or equal to 15,000 g.mol. ' ¹ , more preferably less than or equal to 10,000 g.mol. ' ¹ .

The block copolymer advantageously comprises at least one block sequence AB, ABA or BAB where said blocks A and B are linked without the presence of an intermediate block of different chemical nature.

Other blocks may possibly be present in the block copolymer described above insofar as these blocks do not fundamentally change the character of the block copolymer. However, block copolymers containing only blocks A and B will be preferred.

Between each block A and B, there may optionally be an intermediate part resulting from the random polymerization of the polar (m _b ) and nonpolar (m _a ) monomers, depending on the type of copolymerization chosen and / or the type of initiator or transfer.

ICG70096 FR text deposit

Advantageously, A and B represent at least 70% by mass, preferably at least 90% by mass, more preferably at least 95% by mass, even more preferably at least 99% by mass of the block copolymer.

According to a particular embodiment, the block copolymer is a sequenced copolymer (diblocks).

According to another particular embodiment, the block copolymer is a triblock copolymer (triblocks) with alternating blocks comprising two blocks A and a block B (ABA) or comprising two blocks B and a block A (BAB).

According to a particular embodiment, the block copolymer also comprises a terminal chain I consisting of a hydrocarbon chain, cyclic or acyclic, saturated or unsaturated, linear or branched, in Ci to C ₃₂ , preferably in C ₄ to C ₂ 4 , more preferably in Cw to C ₂₄ .

The term cyclic hydrocarbon chain is understood to mean a hydrocarbon chain of which at least part is cyclic, in particular aromatic. This definition does not exclude hydrocarbon chains comprising both an acyclic part and a cyclic part.

The terminal chain I can comprise an aromatic hydrocarbon chain, for example benzene and / or a hydrocarbon chain, saturated and acyclic, linear or branched, in particular an alkyl chain.

The terminal chain I is preferably chosen from alkyl chains, preferably linear, more preferably alkyl chains of at least 4 carbon atoms, even more preferably of at least 12 carbon atoms.

For ATRP polymerization, the terminal chain I is located in the terminal position of the block copolymer. It can be introduced into the block copolymer using the polymerization initiator. Thus, the terminal chain I can advantageously constitute at least part of the polymerization initiator and is positioned within the polymerization initiator so as to allow the introduction, during the first initiation step of the polymerization , the terminal chain I in the terminal position of the block copolymer.

The polymerization initiator is, for example, chosen from radical initiators

ICG70096 FR free text deposit implemented in the ATRP polymerization process. These free radical initiators well known to those skilled in the art are described in particular in the article "Atom Transfer Radical Polymerization: current status and future perspectives, Macromolecules, 45, 4015-4039, 2012".

The polymerization initiator is, for example, chosen from alkyl esters of carboxylic acid substituted with a halide, preferably a bromine in the alpha position, for example, ethyl 2-bromopropionate, α-bromoisobutyrate ethyl, benzyl choride or bromide, ethyl α-bromophenylacetate and chloroethylbenzene. Thus, for example, ethyl 2-bromopropionate may make it possible to introduce into the copolymer the terminal chain I in the form of a C ₂ alkyl chain and the benzyl bromide in the form of a benzyl group.

For RAFT polymerization, the transfer agent can conventionally be removed from the copolymer at the end of polymerization according to any known process.

According to a variant, the terminal chain I can also be obtained in the copolymer by RAFT polymerization according to the methods described in the article by Moad, G. and co., Australian Journal of Chemistry, 2012, 65, 985-1076. The terminal chain I can, for example, be introduced by aminolysis when a transfer agent is used, in particular, transfer agents of the thiocarbonylthio, dithiocarbonate, xanthate, dithiocarbamate and trithiocarbonate type, for example S, S-bis (a, a'-dimethyl-a ”-acetic acid) trithiocarbonate (BDMAT) or 2-cyano-2-propyl benzodithioate.

According to a particular embodiment, the block copolymer is a sequenced copolymer (also called diblocks). The block copolymer structure can be of the IAB or IBA type, advantageously IAB. The terminal chain I can be directly linked to block A or B according to the structure respectively IAB or IBA or, be linked via a linking group, for example, an ester, amide, amine or ether function. The linking group then forms a bridge between the terminal chain I and the block A or B.

According to a particular embodiment, the block copolymer can also be functionalized at the end of the chain according to any known process, in particular by hydrolysis, aminolysis and / or nucleophilic substitution.

By aminolysis is meant any chemical reaction in which a molecule is split

ICG70096 FR text deposit in two parts by reaction of an ammonia molecule or an amine. A general example of aminolysis consists in replacing a halogen of an alkyl group by reaction with an amine, with elimination of hydrogen halide. Aminolysis can be used, for example, for ATRP polymerization which produces a copolymer having a halide in the terminal position or for RAFT polymerization to remove the thio, dithio or trithio bond introduced into the copolymer by the RAFT transfer agent.

It is thus possible to introduce a terminal chain I ′ by post-functionalization of the block copolymer obtained by sequenced and controlled polymerization of the monomers (m _a ) and (m _b ) described above.

The terminal chain I ′ advantageously comprises a hydrocarbon chain, linear or branched, cyclic or acyclic, C 1 to C 32, preferably C ₁ to C ₂ 4, more preferably C 1 to C 10, even more preferably an alkyl group, optionally substituted by one or more groups containing at least one heteroatom chosen from N and O, preferably N.

For an ATRP polymerization using a metal halide as catalyst, this functionalization can, for example, be carried out by treating the IAB or IBA copolymer obtained by ATRP with a primary C1 to C ₃₂ alkylamine or a C1 to C ₃₂ alcohol under conditions soft so as not to modify the functions present on blocks A, B and I.

According to a particular preferred embodiment, the block copolymer is represented by one of the following formulas (III) and (IV):

in which m = 0 or 1, n is an integer ranging from 2 to 50, preferably from 5 to 50, more preferably from 10 to 50, p is an integer ranging from 2 to 50, preferably from 2 to 40, more preferably from 2 to 20,

R _o is chosen from hydrogen or the methyl group, preferably R _o is H,

R! is chosen from hydrocarbon chains, preferably alkyl, cyclic or acyclic groups, saturated or unsaturated, linear or branched, in C1 to C32, preferably in C ₄ to C ₂ 4, more preferably in Cw to C ₂ 4, and the groups derived from a radical polymerization transfer agent by reversible chain transfer by addition-fragmentation (RAFT in English "Reversible Addition-Fragmentation Chain Transfer), it being understood that if Ri is a group derived from a transfer agent then m = 0.

RAFT type transfer agents are well known to those skilled in the art. A wide variety of RAFT type transfer agents are available or quite easily synthesizable. By way of example, mention may be made of transfer agents of the thiocarbonylthio, dithiocarbonate, xanthate, dithiocarbamate and trithiocarbonate type, for example S, S-bis (a, a'-dimethyl-a ”-acetic acid) trithiocarbonate (BDMAT ) or 2-cyano-2-propyl benzodithioate.

R ₂ represents the group - (E) _u -G

The groups E, G, and the integer u, have the same definition as that given above in formula (I),

R ₃ is a substituent in the ortho, meta or para position on the aromatic ring, preferably in the para position, chosen from the group consisting of:

- a hydroxyl group or -CH ₂ OH,

the C ₁ to C ₂ 4 alkoxy groups, preferably the C ₁ to C ₁₂ alkoxy groups,

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- the polyalkoxy groups: - (OC _y H _2y O) rH where y is an integer ranging from 2 to 8 preferably from 2 to 4, more preferably from 2 to 3 and f is an integer ranging from 1 to 10, preferably from 2 to 8, more preferably from 2 to 4,

- polyalkoxy groups: - (OC _y H _2y O) _r where R8 is as described above, and R ₈ represents an alkyl ₂ -C 4, preferably C ₂ to C,

- the -OCORg -COORg and groups wherein Rg is selected from alkyl groups C ₂ -C 4, preferably C ₂ to C, more preferably to C _6, linear or branched, acyclic and preferably,

R ₄ is chosen from the group consisting of:

- hydrogen;

-OH

- halogens, preferably bromine; and,

- hydrocarbon chains, cyclic or acyclic, saturated or unsaturated, linear or branched, in Ci to C ₃₂ , preferably in Ci to C ₂ 4, more preferably in Ci to Cw, preferably alkyl groups, said chains being optionally substituted by one or more groups containing at least one heteroatom chosen from N and O,

R ₅ and R ₆ are identical or different and independently chosen from the group consisting of hydrogen and C1 to Cm, preferably C1 to C ₄ alkyl groups, linear or branched, more preferably acyclic, even more preferably the group methyl,

R ₇ is chosen from hydrogen or the methyl group, preferably R ₇ is H.

R! is preferably chosen from alkyl, cyclic or acyclic groups, saturated or unsaturated, linear or branched, in C 1 to C ₃₂ , preferably in C ₄ to C ₂ 4, more preferably in Cw to C ₂ 4.

R ₃ is preferably a substituent in the ortho, meta or para position on the aromatic nucleus, preferably in the para position, chosen from the —OCORg groups where Rg is as described above.

In formulas (III) and (IV), block A corresponds to the motif repeated n times and block B corresponds to the motif repeated p times. In addition, the group R! may consist of the terminal chain I as described above and / or the group R ₄ may consist of the terminal chain as described above.

The copolymer described above is particularly advantageous when it is used as

ICG70096 EN text deposit detergent additive in a liquid fuel of an internal combustion engine.

The term “detergent additive for liquid fuel” is understood to mean an additive which is incorporated in small quantity into the liquid fuel and has an effect on the cleanliness of said engine compared to said non-specially additive liquid fuel.

The liquid fuel advantageously comes from one or more sources chosen from the group consisting of mineral, animal, plant and synthetic sources. Preferably, petroleum will be chosen as the mineral source.

The liquid fuel is preferably chosen from hydrocarbon fuels and non-essentially hydrocarbon fuels, alone or as a mixture.

Hydrocarbon fuel is understood to mean a fuel consisting of one or more compounds consisting solely of carbon and hydrogen.

The term non-essentially hydrocarbon fuel means a fuel made up of one or more compounds made up not essentially of carbon and hydrogen, that is to say which also contain other atoms, in particular oxygen atoms.

Hydrocarbon fuels include in particular middle distillates with a boiling temperature ranging from 100 to 500 ° C or lighter distillates with a boiling temperature in the range of gasolines. These distillates can, for example, be chosen from distillates obtained by direct distillation of crude hydrocarbons, vacuum distillates, hydrotreated distillates, distillates from catalytic cracking and / or hydrocracking of vacuum distillates, distillates resulting from ARDS type conversion processes (in English "atmospheric residue desulfurization") and / or visbreaking, the distillates from the recovery of Fischer Tropsch cuts. Hydrocarbon fuels are typically petrol and diesel (also called diesel fuel).

The gasolines include, in particular, all fuel compositions for spark ignition engines commercially available. As a representative example, mention may be made of gasolines meeting the NF EN 228 standard. Gasolines generally have octane numbers high enough to avoid the knocking phenomenon. Typically, gasoline-type fuels sold in Europe, compliant with standard NF EN 228 have an engine octane number (MON in English "Motor

ICG70096 FR text deposit

Octane Number ") greater than 85 and a Research Octane Number (RON) of a minimum of 95. Gasoline fuels generally have an RON ranging from 90 to 100 and a MON ranging from 80 to 90, the RON and MON being measured according to standard ASTM D 2699-86 or D 2700-86.

Diesel oils (diesel fuels) include, in particular, all fuel compositions for diesel engines commercially available. Mention may be made, as a representative example, of diesel oils meeting the standard NF EN 590.

Fuels that are not essentially hydrocarbon-based include in particular oxygenates, for example distillates resulting from the BTL (in English "biomass to liquid") conversion of plant and / or animal biomass, taken alone or in combination; biofuels, for example oils and / or esters of vegetable and / or animal oils; biodiesels of animal and / or vegetable origin and bioethanols.

The mixtures of hydrocarbon fuel and non-essentially hydrocarbon fuel are typically gas oils of type B _x or gasolines of type E _x .

By diesel fuel type B _{x means} a diesel fuel, a diesel fuel that contains x% (v / v) of vegetable or animal oil esters (including used cooking oils) transformed by a chemical process called transesterification, obtained by reacting this oil with an alcohol in order to obtain fatty acid esters (EAG). With methanol and ethanol, methyl esters of fatty acids (EMAG) and ethyl esters of fatty acids (EEAG) are obtained, respectively. The letter B followed by a number indicates the percentage of EAG contained in diesel. Thus, a B99 contains 99% of EAG and 1% of middle distillates of fossil origin (mineral source), B20, 20% of EAG and 80% of middle distillates of fossil origin, etc. type B _o gas oils which do not contain oxygenated compounds, type Bx gas oils which contain x% (v / v) of vegetable oil esters or fatty acids, most often methyl esters (EMHV or EMAG) . When the EAG is used alone in engines, the fuel is designated by the term B100.

The term “E _x type petrol for positive ignition engine” is understood to mean a petrol fuel which contains x% (v / v) of oxygenates, generally ethanol, bioethanol and / or ethyl-tertio-butyl-ether (ETBE).

ICG70096 FR text deposit

The sulfur content of the liquid fuel is preferably less than or equal to 5000 ppm, preferably less than or equal to 500 ppm, and more preferably less than or equal to 50 ppm, or even even less than or equal to 10 ppm and advantageously without sulfur. .

The copolymer described above is used as a detergent additive in liquid fuel at a content, advantageously at least 10 ppm, preferably at least 50 ppm, more preferably at a content ranging from 10 to 5 OOOppm, even more preferably from 10 to 1 OOOppm.

According to a particular embodiment, the use of a copolymer as described above in the liquid fuel makes it possible to maintain the cleanliness of at least one of the internal parts of the internal combustion engine and / or to clean at least one of the parts internal combustion engine.

The use of the copolymer in the liquid fuel makes it possible, in particular, to limit or avoid the formation of deposits in at least one of the internal parts of said engine (“keep-clean” effect in English) and / or reduce the deposits existing in the minus one of the internal parts of said engine ("clean-up" effect in English).

Thus, the use of the copolymer in the liquid fuel makes it possible, compared with the liquid fuel not specially additive, to limit or avoid the formation of deposits in at least one of the internal parts of said engine or to reduce the deposits existing in at least one of the internal parts of said motor.

Advantageously, the use of the copolymer in the liquid fuel makes it possible to observe both the two effects, limitation (or prevention) and reduction of deposits (“keepclean” and “clean-up” effects).

A distinction is made between deposits depending on the type of internal combustion engine and the location of deposits in the internal parts of said engine.

According to a particular embodiment, the internal combustion engine is a spark-ignition engine, preferably with direct injection (DISI in English "Direct Injection Spark Ignition engine"). The targeted deposits are located in at least one of the internal parts of said positive-ignition engine. The internal part of the spark-ignition engine kept clean (keep-clean) and / or cleaned (clean-up) is, advantageously,

ICG70096 EN text deposit chosen from the engine intake system, in particular the intake valves (IVD in English “Intake Valve Deposit”), the combustion chamber (CCD in English “Combustion Chamber Deposit” or TCD in English “ Total Chamber Deposit ”) and the fuel injection system, in particular the injectors of an indirect injection system (PFI in English“ Port Fuel Injector ”) or the injectors of a direct injection system (DISI) .

According to another particular embodiment, the internal combustion engine is a diesel engine, preferably a diesel engine with direct injection, in particular a diesel engine with common-rail injection system (CRDI in English "Common Rail Direct Injection ”), The target depots are located in at least one of the internal parts of said Diesel engine.

Advantageously, the targeted deposits are located in the injection system of the diesel engine, preferably located on an external part of an injector of said injection system, for example the nose of the injector and / or on an internal part. an injector of said injection system (IDID in English "Internai Diesel Injector Deposits"), for example on the surface of an injector needle.

The deposits may consist of deposits linked to the phenomenon of coking (“coking” in English) and / or deposits of the soap and / or varnish type (in English “lacquering”).

The copolymer as described above can advantageously be used in liquid fuel to reduce and / or avoid the loss of power due to the formation of deposits in the internal parts of a direct injection diesel engine, said loss of power being determined according to CEC F-98-08 standardized engine test method.

The copolymer as described above can advantageously be used in liquid fuel to reduce and / or avoid the restriction of the flow of fuel emitted by the injector of a direct injection diesel engine during its operation, said restriction of flux being determined according to the CEC F-23-1-01 standardized engine test method.

Advantageously, the use of the copolymer as described above makes it possible, compared with the liquid fuel not specially additive, to limit or avoid the formation of deposits on at least one type of deposits described above and / or reduce the deposits existing on at least a type of deposits described above.

ICG70096 FR text deposit

According to a particular embodiment, the use of the copolymer described above also makes it possible to reduce the fuel consumption of the internal combustion engine.

According to another particular embodiment, the use of the copolymer described above also makes it possible to reduce the emissions of pollutants, in particular, the emissions of particles from the internal combustion engine.

Advantageously, the use of the copolymer makes it possible to reduce both the fuel consumption and the pollutant emissions.

The copolymer described above can be used alone, in the form of a mixture of at least two of said copolymers or in the form of a concentrate.

The copolymer can be added to the liquid fuel within a refinery and / or be incorporated downstream of the refinery and / or optionally, as a mixture with other additives in the form of an additive concentrate, also called according to the use "additive package".

The concentrate described above comprises an organic liquid inert with respect to the copolymer described above and miscible in the liquid fuel described above. The term “miscible” is understood to mean the fact that the copolymer and the organic liquid form a solution or a dispersion so as to facilitate the mixing of the copolymer in the liquid fuels according to the conventional methods of fuel additivation.

The organic liquid is advantageously chosen from aromatic hydrocarbon solvents such as the solvent sold under the name "SOLVESSO", alcohols, ethers and other oxygenated compounds and paraffinic solvents such as hexane, pentane or isoparaffins, alone or as a mixture.

The concentrate can advantageously comprise from 5 to 99% by mass, preferably from 10 to 80%, more preferably from 25 to 70% of copolymer as described above.

The concentrate can, typically, comprise from 1 to 95% by mass, preferably from 10 to 70%, more preferably from 25 to 60% of organic liquid, the remainder corresponding to the copolymer, it being understood that the concentrate can comprise one or more copolymers as described above.

ICG70096 FR text deposit

In general, the solubility of the copolymer in the organic liquids and the liquid fuels described above will depend in particular on the average molar masses by weight and in number, respectively M _w and M _n of the copolymer. The average molar masses M _w and M _n of the copolymer will be chosen so that the copolymer is soluble in the liquid fuel and / or the organic liquid of the concentrate for which it is intended.

The average molar masses M _w and M _n of the copolymer can also have an influence on the effectiveness of this copolymer as a detergent additive. The average molar masses M _w and M _n will therefore be chosen so as to optimize the effect of the copolymer, in particular the detergency effect (engine cleanliness) in the liquid fuels described above.

Optimization of the average molar masses M _w and M _n can be carried out by routine tests accessible to those skilled in the art.

According to a particular embodiment, the copolymer advantageously has a weight-average molar mass (M _w ) ranging from 500 to 30,000 g.mol ¹ , preferably from 1000 to 10,000 g.mol ' ¹ , more preferably lower or equal to 4000 g.mol ' ¹ , and / or a number-average molar mass (Mn) ranging from 500 to 15,000 g.mol ¹ , preferably from 1000 to 10,000 g.mol' ¹ , more preferably lower or equal to 4000 g.mol ¹ . The number and weight average molar masses are measured by size exclusion chromatography (SEC in English “Size Exclusion Chromatography). The operating conditions of the SEC, in particular, the choice of solvent will be chosen according to the chemical functions present within the copolymer.

According to a particular embodiment, the copolymer is used in the form of a concentrate of additives in combination with at least one other additive for internal combustion engine fuel different from the copolymer described above.

The additive concentrate can typically comprise one or more other additives chosen from detergent additives different from the copolymer described above, for example from anti-corrosion agents, dispersants, demulsifiers, anti-foaming agents, biocides, reodorants, procetane additives, friction modifiers, lubricant additives or oiliness additives, combustion aid agents (catalytic combustion and soot promoters), cloud point improving agents, point

ICG70096 EN flow deposit text, TLF ("Filterability limit temperature"), anti-sedimentation agents, anti-wear agents and agents modifying conductivity.

Among these additives, there may be mentioned in particular:

a) procetane additives, in particular (but not limited to) chosen from alkyl nitrates, preferably 2-ethyl hexyl nitrate, aryl peroxides, preferably benzyl peroxide, and alkyl peroxides, preferably ter-butyl peroxide;

b) anti-foam additives, in particular (but not limited to) chosen from polysiloxanes, oxyalkylated polysiloxanes, and fatty acid amides derived from vegetable or animal oils. Examples of such additives are given in EP861882, EP663000, EP736590;

c) Cold fluidizing additives (CFI in English "Cold Flow Improver") chosen from ethylene and unsaturated ester copolymers, such as ethylene / vinyl acetate (EVA), ethylene / vinyl propionate (TEU) copolymers , ethylene / vinyl ethanoate (EVE), ethylene / methyl methacrylate (EMMA), and ethylene / alkyl fumarate described, for example, in US3048479, US3627838, US3790359, US3961961 and EP261957.

d) lubricating additives or anti-wear agents, in particular (but not limited to) chosen from the group consisting of fatty acids and their ester or amide derivatives, in particular glycerol monooleate, and derivatives of mono- and carboxylic acids polycyclic. Examples of such additives are given in the following documents: EP680506, EP860494, WO98 / 04656, EP915944, FR2772783, FR2772784.

e) cloud point additives, in particular (but not limited to) chosen from the group consisting of long chain olefin / (meth) acrylic ester / maleimide terpolymers, and polymers of fumaric / maleic acid esters. Examples of such additives are given in FR2528051, FR2528051, FR2528423, EP112195, EP172758, EP271385, EP291367;

f) detergent additives in particular (but not limited to) chosen from the group consisting of succinimides, polyetheramines and quaternary ammonium salts; for example those described in documents US4171959 and WO2006135881.

g) the polyfunctional additives for cold operability selected from the group consisting of polymers based on olefin and alkenyl nitrate as described in EP573490.

These other additives are generally added in an amount ranging from 100 to 1000 ppm (each).

The molar and / or mass ratio between the polar monomer (m _b ) and the apolar monomer

ICG70096 EN text deposit (m _a ) and / or between block A and B in the block copolymer described above will be chosen so that the copolymer is soluble in the fuel and / or the organic liquid of the concentrate for which he is destined. Likewise, this ratio can be optimized as a function of the fuel and / or of the organic liquid so as to obtain the best effect on engine cleanliness.

Optimization of the molar and / or mass ratio can be carried out by routine tests accessible to a person skilled in the art.

According to a particular embodiment, the molar ratio between the apolar monomer (m _a ) and the polar monomer (m _b ), or between blocks A and B in molar percentage between the apolar monomer (m _a ) of block A and the polar monomer (m _b ) of block B is preferably from 95: 5 to 70:30, more preferably from 85: 15 to 75: 25.

According to a particular embodiment, a fuel composition is prepared according to any known method by adding the liquid fuel described above with at least one copolymer as described above.

The combustion of this fuel composition comprising such a copolymer in an internal combustion engine produces an effect on the cleanliness of the engine compared to the liquid fuel not specially additive and makes it possible, in particular, to prevent or reduce the fouling of the internal parts of said engine . The effect on the cleanliness of the engine is as described above in the context of the use of the copolymer.

According to a particular embodiment, the combustion of the fuel composition comprising such a copolymer in an internal combustion engine also makes it possible to reduce the fuel consumption and / or the pollutant emissions.

The copolymer is preferably incorporated in a small amount in the liquid fuel described above, the amount of copolymer being sufficient to produce a detergent effect as described above and thus improve the engine cleanliness.

The fuel composition advantageously comprises at least 10 ppm, preferably at least 50 ppm, advantageously from 10 to 5,000 ppm, more preferably from 10 to 1,000 ppm of the copolymer described above.

ICG70096 FR text deposit

In addition to the copolymer described above, the fuel composition can also comprise one or more other additives different from the copolymer according to the invention chosen from other known detergent additives, for example from anti-corrosion agents, dispersants, demulsifiers, anti-foaming agents, biocides, reodorants, procetane additives, friction modifiers, lubricant additives or oiliness additives, combustion aid agents (catalytic combustion and soot promoters), cloud point, pour point improving agents, TLF, anti-sedimentation agents, anti-wear agents and / or conductivity modifiers.

The different additives of the copolymer according to the invention are, for example, the fuel additives listed above.

According to a particular embodiment, the copolymer is a block copolymer as described above.

According to a particular embodiment, a method of maintaining cleanliness ("keepclean") and / or cleaning ("clean-up") of at least one of the internal parts of an internal combustion engine comprises at least the following steps :

the preparation of a fuel composition by additivation of a fuel with one or more copolymers as described above and,

- the combustion of said fuel composition in the internal combustion engine.

According to a particular embodiment, the internal combustion engine is a spark-ignition engine, preferably with direct injection (DISI).

The internal part kept clean and / or cleaned of the positive-ignition engine is preferably chosen from the intake system of the engine, in particular the intake valves (IVD), the combustion chamber (CCD or TCD) and the fuel injection system, in particular the injectors of an indirect injection system (PFI) or the injectors of a direct injection system (DISI).

According to another particular embodiment, the internal combustion engine is a diesel engine, preferably a diesel engine with direct injection, in particular a diesel engine with common-rail injection systems (CRDI).

ICG70096 FR text deposit

The internal part kept clean and / or cleaned of the diesel engine is, preferably the injection system of the diesel engine, preferably an external part of an injector of said injection system, for example the nose of the injector and / or one of the internal parts of an injector of said injection system, for example the surface of an injector needle.

The process of maintaining cleanliness and / or cleaning comprises the successive stages of:

a) determining the most suitable additive for the fuel, said additive corresponding to the selection of the copolymer (s) described above to be incorporated in combination, optionally, with other fuel additives as described above and the determination of the rate of treatment necessary to achieve a given specification relating to the detergency of the fuel composition.

b) incorporation into the fuel of the copolymer (s) selected at the rate determined in step a) and, optionally, of the other fuel additives.

The copolymer (s) can be incorporated into the fuel, alone or as a mixture, successively or simultaneously.

Alternatively, the copolymer (s) can be used in the form of a concentrate or a concentrate of additives as described above.

Step a) is carried out according to any known process and is part of current practice in the field of fuel additivation. This step involves defining at least one characteristic representative of the detergency properties of the fuel composition.

The characteristic characteristic of the detergency properties of the fuel will depend on the type of internal combustion engine, for example Diesel or by positive ignition, on the direct or indirect injection system and on the location in the engine of the deposits targeted for cleaning and / or maintaining cleanliness.

For diesel engines with direct injection, the characteristic representative of the detergency properties of the fuel may, for example, correspond to the loss of power due to the formation of deposits in the injectors or the restriction of the flow of fuel emitted by the injector at during the operation of said engine.

The characteristic characteristic of the detergency properties can also correspond

ICG70096 EN text deposit at the appearance of lacquering type deposits at the level of the injector needle (IDID).

Methods for evaluating the detergent properties of fuels have been widely described in the literature and fall within the general knowledge of a person skilled in the art. Mention will be made, by way of nonlimiting example, of the tests standardized or recognized by the profession or the methods described in the following literature:

For direct injection diesel engines:

- the DW10 method, CEC F-98-08 standardized engine test method, for measuring the power loss of direct injection diesel engines

- the XUD9 method, CEC standard engine test method F-23-1-01 Issue 5, to measure the fuel flow restriction emitted by the injector

- the method described by the applicant in application WO2014 / 029770 page 17 to

20, for the evaluation of lacquering deposits (IDID), this method being cited by way of example and / or incorporated by reference into the present application.

For indirect ignition engines:

- the Mercedes Benz M102E method, CEC F-05-A-93 standardized test method, and

- the Mercedes Benz M111 method, CEC F-20-A-98 standardized test method.

These methods measure deposits on the intake valves (IVD), the tests generally being carried out on a Eurosuper petrol complying with the EN228 standard.

For direct injection ignition engines:

- the method described by the applicant in the article "Evaluating Injector Fouling in

Direct Injection Spark Ignition Engines ”, Mathieu Arondel, Philippe China, Julien Gueit; Conventional and future energy for automobiles; 10th international colloquium; January 20-22, 2015, p.375-386 (Technische Akademie Esslingen by Techn. Akad. Esslingen, Ostfildern), for the evaluation of coking deposits on the injector, this method being cited as an example and / or incorporated by reference into the present application.

- The method described in document US20130104826, for the evaluation of deposits of the coking type on the injector, this method being cited by way of example and / or incorporated by reference into the present application.

The determination of the quantity of copolymer to be added to the fuel composition in order to reach the specification (step a) described above) will typically be carried out by

ICG70096 EN text deposit comparison with the fuel composition but without the copolymer according to the invention, the given specification relating to detergency can for example be a target value for power loss according to the DW10 method or a flow restriction value according to the method XUD9 mentioned above.

The amount of copolymer can also vary depending on the nature and origin of the fuel, in particular depending on the level of compounds containing n-alkyl, iso-alkyl or n-alkenyl substituents. Thus, the nature and origin of the fuel can also be a factor to take into account for step a).

The method of maintaining cleanliness and / or cleaning may also comprise an additional step after step b) of verifying the target reached and / or of adjusting the rate of additivation with the copolymer (s) as detergent additive.

ICG70096 FR text deposit

Claims (24)

Copolymer obtained by copolymerization of at least: - an apolar monomer (m _a ) corresponding to the following formula (I) h ₂ c H u (l) With u = 0 or 1, w = 0 or 1, E = -O- or -NH (Z) -, or -O-CO-, or -NH-CO- or -CO-NH-, with Z represents H or a C1-C6 alkyl group, it being understood that when E = -O-CO- E is linked to the vinyl carbon by the oxygen atom, G represents a group chosen from C1-C34 alkyl, an aromatic ring, an aralkyl comprising at least one aromatic ring and at least one C1-C34 alkyl group, and a polar monomer (m _b ) chosen from monomers derived from styrene or from alphamethylstyrene, the aromatic nucleus of which is substituted by at least one group R or by at least one hydrocarbon chain C1 to C12, linear or branched, preferably acyclic, substituted by at least one R group, said R group being chosen from: - the hydroxyl group, - a group -OR ’, - a group - (OC _y H _2y O) fH, - a group - (OC _y H _2y O) _r R ', - a group-O- (CO) -R ’, and - a group- (CO) -OR ', y is an integer ranging from 2 to 8, f is an integer ranging from 1 to 10 and R' is chosen from C1 to C alkyl chains ₂ 43054223 ICG70096 FR text deposit 2. Copolymer according to claim 1, in which the group E of the apolar monomer (m _a ) is chosen from -O-, -NH (Z) - with Z represents H or a C1-C6 alkyl group, and -O- CO- where E is linked to the vinyl carbon by the oxygen atom. 3. Copolymer according to one of claims 1 and 2, in which w is equal to 0. 4. Copolymer according to any one of the preceding claims, in which the group G is a C4-C30 alkyl. 5. Copolymer according to any one of claims 1 to 3, in which the group G is an aralkyl comprising at least one aromatic ring and at least one C4-30 alkyl group. 6. Copolymer according to any one of the preceding claims, in which the copolymer is a block or random copolymer, preferably a block copolymer. 7. Block copolymer according to any one of the preceding claims, in which the copolymer comprises at least: a block A consisting of a chain of structural units derived from one or more apolar monomers chosen from apolar monomers (m _a ) of formula (I) and, - a block B consisting of a chain of structural units derived from one or more polar monomers chosen from polar monomers (m _b ). 8. Block copolymer according to claim 7, in which the copolymer comprises at least one block sequence AB, ABA or BAB where said blocks A and B are linked without the presence of an intermediate block of different chemical nature. 9. Block copolymer according to claim 7, in which the copolymer is obtained by block polymerization, optionally, followed by one or more post-functionalizations. 10. Copolymer according to any one of claims 1 to 9, in which the polar monomer (m _b ) is chosen from monomers derived from styrene or from alphamethylstyrene in which the aromatic ring is substituted by at least one group -O ( CO) -R ', R' being selected from alkyl to C ₄ February. ICG70096 FR text deposit 11. Copolymer according to any one of claims 1 to 9, in which the polar monomer (m _b ) is chosen from monomers derived from styrene or from alphamethylstyrene, the aromatic nucleus of which is substituted by at least one hydroxyl group or by a linear or branched C1 to C12 hydrocarbon chain, preferably acyclic, substituted by at least one hydroxyl group. 12. A fuel concentrate comprising one or more copolymers according to any one of claims 1 to 11, in admixture with an organic liquid, said organic liquid being inert with respect to the copolymer (s) and miscible with said fuel, said fuel being from one or more sources chosen from the group consisting of mineral, animal, plant and synthetic sources. 13. Fuel composition which includes: (1) a fuel from one or more sources chosen from the group consisting of mineral, animal, plant and synthetic sources, and (2) one or more copolymers as defined in any one of claims 1 to 11 . 14. The composition of claim 13, wherein the fuel composition comprises at least 5 ppm of copolymer (s) (2). 15. Composition according to either of Claims 13 and 14, comprising the copolymer (s) in the form of a concentrate according to Claim 12. 16. Use of a copolymer according to any one of claims 1 to 11, as a detergent additive in a liquid fuel of an internal combustion engine. 17. Use according to claim 16, for maintaining the cleanliness and / or cleaning at least one of the internal parts of the internal combustion engine. 18. Use according to one of claims 16 and 17, to limit or avoid the formation of deposits in at least one of the internal parts of the internal combustion engine and / or reduce the deposits existing in at least one of the internal parts of said engine. 19. Use according to any one of claims 16 to 18, for reducing the fuel consumption of the internal combustion engine. ICG70096 FR text deposit 20. Use according to any one of claims 16 to 19, to reduce the emission of pollutants, in particular, the emission of particles from the internal combustion engine. 21. Use according to any one of claims 16 to 20, in which the internal combustion engine is a spark-ignition engine. 22. Use according to any one of claims 16 to 20, in which the internal combustion engine is a diesel engine, preferably a direct injection diesel engine. 23. Use according to claim 22, to limit or avoid and / or reduce deposits linked to the coking phenomenon and / or deposits of soap and / or varnish type. 24. Method for maintaining the cleanliness and / or cleaning of at least one of the internal parts of an internal combustion engine comprising at least the following steps: the preparation of a fuel composition by additivation of a fuel with one or more copolymers as described in any one of claims 1 to 11 or a concentrate according to claim 12 and, - the combustion of said fuel composition in said internal combustion engine.