EP3720932A1

EP3720932A1 - Additive composition for fuel

Info

Publication number: EP3720932A1
Application number: EP18836831.0A
Authority: EP
Inventors: Jérôme OBIOLS
Original assignee: Total Marketing Services SA
Current assignee: TotalEnergies Marketing Services SA
Priority date: 2017-12-06
Filing date: 2018-12-04
Publication date: 2020-10-14
Also published as: US11225620B2; FR3074497B1; WO2019110911A1; US20200392422A1; FR3074497A1

Abstract

The invention relates to an additive composition for fuel, comprising: (a) one or more copolymer(s) comprising: - at least one unit of the following formula (I), where u = 0 or 1, E = –O– or –N(Z)–, or –O-CO-, or –CO-O- or –NH-CO- or -CO-NH-, where Z represents H or a C₁-C₆ alkyl group, G represents a group selected between a C₁-C₃₄ alkyl group, an aromatic ring, an aralkyl comprising at least one aromatic ring and at least one C₁-C₃₄ alkyl group, and - at least one unit of the following formula (II), where R₁" is selected between a hydrogen atom and a methyl group, Q is selected between an oxygen atom and a group -NR'-, where R' is selected between a hydrogen atom and C₁ to C₁₂ hydrocarbon chains, R comprises a C₁ to C₃₄ hydrocarbon chain substituted with at least one quaternary ammonium group and, optionally, one or more hydroxyl groups, the group R also optionally containing one or more nitrogen and/or oxygen atoms and/or carbonyl groups, (b) one or more amines substituted with a polyalkenyl group, and (c) at least one carrier oil.

Description

COMPOSITION OF FUEL ADDITIVES

The present invention relates to an additive composition for liquid fuel of spark ignition engine or gasoline engine with compression ignition also called GCI engine (for "Gasoline Compression Ignition" in English).

STATE OF THE PRIOR ART

Liquid fuels from spark ignition engines or GCI engines contain components that may degrade during engine operation. The issue of deposits in the internal parts of spark ignition engines or GCI 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 fuel consumption and particulate emissions. Advances in fuel additive technology have addressed this problem. Additives known as detergents 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 spark ignition engine or the engine. GCI engine ("clean-up" effect). By way of example, US 4,171,959 describes a gasoline fuel detergent additive containing a quaternary ammonium function. WO 2006/135881 discloses a detergent additive containing a quaternary ammonium salt used to reduce or clean deposits including the intake valves. Nevertheless, engine technology is constantly evolving and fuel requirements must evolve to meet these advances in spark ignition engines and GCI engines. In particular, the new gasoline direct injection systems expose the injectors to more severe pressure and temperature conditions which promotes the formation of deposits. In addition, these new injection systems have more complex geometries to optimize the spraying, including more holes with smaller diameters but, on the other hand, induce greater sensitivity to deposits. The presence of deposits can alter the performance of combustion including increasing pollutant emissions and particulate emissions. Other consequences of the excessive presence of deposits have been reported in the literature, such as increased fuel consumption and maneuverability problems.

Compression ignition gasoline engines also called GCI engines (for "Gasoline Compression Ignition" in English) having the same architecture as conventional spark ignition engines, they are subject to the same problems fouling. Like conventional spark ignition engines, GCI engines can be direct injection or indirect injection. The deposits recorded in conventional spark ignition engines can thus also be formed in GCI engines.

There are several types of deposits well known to engine manufacturers. In particular, the high-temperature deposits on the fuel injectors of spark-ignition engines or GCI direct injection engines and on the intake valves of spark-ignition engines or GCI engines with indirect injection can be mentioned. when using virgin fuel (that is to say, not additive). The formation of this type of deposits is well known to those skilled in the art and occurs mainly when the engine operates in the so-called "normal" mode. This "normal" operating mode is characterized for example by an engine coolant temperature greater than or equal to 90 ° C.

In order to prevent the formation of this type of high temperature deposit, it is known to motorists to introduce detergent additives into the fuel. However, the use of fuels with additives, in particular with detergent additives, may in certain cases lead to the formation of deposits on the surface of the stems of intake valves of spark-ignition engines or GCI engines, with indirect injection, in particular at low temperature. The formation of this type of deposit, unlike those defined above, occurs when the engine has not operated long enough to reach its "normal" operating regime. This operating regime is mainly found in engines used on short trips, and more particularly in cold weather. It is characterized by a coolant temperature of less than or equal to 80 ° C, preferably less than or equal to 60 ° C, or even lower than or equal to 30 ° C. The accumulation of these deposits then causes the adhesion of said rods to the valve guide and prevents the closing of the intake valves. This phenomenon of valve sticking (in English "valve sticking") is thus at the origin of sealing problems in the combustion chamber, responsible for a reduction in the compression force and therefore the efficiency of the engines.

In extreme cases, the inlet valve, left open by the accumulation of deposits, may collide with the piston. This collision can then cause the deformation of the valve and / or the valve stem and thus the engine failure.

S. Mlkkonen et al., SAE Technical Paper Sériés, SAE 881643, 1988 studies this phenomenon in detail and concludes that the use of polymeric additives in fuels appears to promote this phenomenon of valve sticking. In order to prevent the formation of this type of deposit, it is known to use the detergent additives of the prior art in combination with a carrier oil.

Characterized by a high boiling temperature, a high viscosity and a remarkable thermal stability, this carrier oil makes it possible on the one hand to solubilize the additives, and in particular the detergent additives, and on the other hand to form on the surface of the hot parts the motor a thin layer of carrier oil. This thin layer of carrier oil in which the detergent additives are solubilized makes it possible to effectively clean the surface of the hot parts of the engine and to prevent the formation of deposits on these same surfaces. This thin layer of carrier oil, including detergent additives, thus prevents valve sticking phenomena that can occur in spark-ignition engines or GCI engines with indirect injection.

However, carrier oils are very expensive and therefore represent a significant part of the cost of additives used in spark ignition engine or GCI engine fuels.

Moreover, the addition of a carrier oil does not prevent the sticking of the valves with any type of detergents. In particular, the use of a carrier oil does not prevent the sticking phenomenon of the valves that may occur in the presence of a detergent additive selected from amino compounds substituted by a polyalkenyl chain. WO 201 1/134923 discloses the use as a detergent additive in a direct injection diesel engine of a quaternized terpolymer obtained from ethylene (A), alkyl ester or alkenyl monomers (B) and of ethylenically unsaturated monomers comprising at least one tertiary nitrogen atom at least partially quaternized.

Preventing and reducing deposits in these new engines is essential for optimal operation of today's engines. There is therefore a need to provide fuel additive compositions that promote optimal operation of spark ignition engines or GCI engines, especially for new engine technologies.

There is also a need for a universal additive composition capable of acting on deposits regardless of the type of engine, spark ignition or compression ignition (GCI), and / or the engine technology and / or the fuel composition. Spark ignition engine or GCI engine technology means a gasoline direct injection (FDI) engine or an indirect fuel injection (ME) engine.

There is more particularly the need for an additive composition based on polyalkenyl amine compounds and which is capable of acting on the deposits forming in the spark ignition or compression ignition engines both at high temperature and low temperature.

In particular, there remains the need to provide a fuel additive composition, usable both in spark-ignition engines and / in GCI engines, direct injection and indirect injection, both for preventing and / or or to limit the formation of deposits at the intake valves and injectors.

More particularly, there remains the need to provide a fuel additive composition for use in spark-ignition engines and / or GCI engines with indirect injection, to clean and keep the hot parts of engines clean and to prevent valve sticking phenomena with a reduced content of carrier oil.

OBJECT OF THE INVENTION

The subject of the invention relates to novel fuel additive compositions.

The applicant has discovered that the additive compositions according to the invention have remarkable properties as a detergent additive in spark ignition engine liquid fuels or GCI engines. 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 the deposits ("Keep-clean" effect) or by reducing the deposits already present in the internal parts. spark ignition engine or GCI engine ("clean-up" effect).

In particular, the Applicant has discovered that the use in a spark-ignition engine or in a GCI engine additive compositions according to the invention limits the formation of deposits at the injectors of gasoline direct injection engines ( IDE) and at the intake valves of engines with indirect fuel injection (ME) while preventing the occurrence of the phenomenon of sticking valves (in English "valve sticking") indirect injection petrol (ME).

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

- optimal operation of the motor,

- a reduction in fuel consumption,

- better handling of the vehicle,

- reduced pollutant emissions, and

- economy due to less engine maintenance.

The subject of the invention relates to a fuel additive composition comprising:

(a) one or more copolymer (s) comprising: at least one unit of formula (I) below:

With

u = 0 or 1,

R 1 represents a hydrogen atom or a methyl group,

E = -O- or -N (Z) -, or -O-CO-, or -CO-O- or -NH-CO- or -CO-NH-, where Z is H or a C ₁ -C ₆ alkyl group ,

G represents a group chosen from a C ₁ -C ₃₄ alkyl, an aromatic ring, an aralkyl comprising at least one aromatic ring and at least one C ₁ -C ₃₄ alkyl group, and

at least one unit of formula (II) below:

in which

R 1 is chosen from the hydrogen atom and the methyl group,

Q is chosen from the oxygen atom and the group -NR'- with R 'being chosen from a hydrogen atom and the C ₁ -C ₁₂ hydrocarbon chains,

R comprises a C 1 to C ₃₄ hydrocarbon-based chain substituted with at least one quaternary ammonium group and optionally with one or more hydroxyl groups, the R group possibly also containing one or more nitrogen and / or oxygen atoms and / or groups carbonyl, and

(b) one or more amines substituted by a polyalkenyl group.

Preferably, the additive composition according to the invention comprises:

(a) one or more copolymer (s) comprising:

at least one unit of formula (I) below:

With

u = 0 or 1,

R 1 represents a hydrogen atom or a methyl group,

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

at least one unit of formula (II) below:

in which

R 1 is chosen from the hydrogen atom and the methyl group,

Q is chosen from the oxygen atom and the group -NR'- with R 'being chosen from a hydrogen atom and the C1-C12 hydrocarbon chains,

R comprises a C 1 to C ₃₄ hydrocarbon-based chain substituted with at least one quaternary ammonium group and optionally with one or more hydroxyl groups, the R group possibly also containing one or more nitrogen and / or oxygen atoms and / or groups carbonyl,

(b) one or more amines substituted with a polyalkenyl group, and

(c) at least one carrier oil.

Preferably, the units of formula (I) and the units of formula (II) defined above represent at least 70 mol% of the copolymer (a), relative to the number of moles of units used in the composition of the copolymer ( a), preferably at least 80 mol%, more preferably at least 90 mol%, even more preferably at least 95 mol%, and advantageously at least 98 mol%. Preferably, the group G of formula (I) is selected from a C ₄ -C _34, an aromatic ring, an aralkyl having at least one aromatic ring and at least one alkyl group -C _34, preferably C ₄ -C ₃₄ .

According to a first variant, the group G of formula (I) is a C 1 -C ₃ alkyl.

According to a second variant, the group G of the formula (I) is an aralkyl comprising at least one aromatic ring and at least one C 1 -C ₃₀ alkyl group.

According to a first embodiment, the group E of the formula (I) is chosen from: -O- and -N (Z) -, with Z representing H or a C ₁ -C ₆ alkyl group.

According to a second embodiment, the group E of the formula (I) is chosen from: O-CO- and -NH-CO-, preferably the group E is the group -O-CO-, it being understood that the group E = -O-CO- is connected to the vinyl carbon by the oxygen atom and that the group E = -NH-CO- is connected to the vinyl carbon by the nitrogen atom.

According to a third embodiment, the group E of the formula (I) is chosen from: -CO-O- and -CO-NH-, preferably the group E is the group -CO-O-, it being understood that the group E is connected to the vinyl carbon by the carbon atom.

Advantageously, in formula (II), the quaternary ammonium group is chosen from quaternary ammoniums of pyrrolinium, pyridinium, imidazolium, triazolium, triazinium, oxazolium and isoxazolium.

According to one variant, the quaternary ammonium group of formula (II) is chosen from quaternary ammoniums of trialkylammonium, iminium, amidinium, formamidinium, guanidinium and biguanidinium, preferably trialkylammonium.

According to a preferred embodiment, the group R of formula (II) is represented by one of the following formulas (III) and (IV):

in which

X is chosen from hydroxide ions, halides and organic anions, preferably organic anions,

R ₂ is chosen from C 1 to C ₃₄ hydrocarbon chains, optionally substituted with at least one hydroxyl group, it being understood that the R ₂ group is connected to Q in formula (II),

R ₃ , R ₄ and R ₅ are identical or different and chosen, independently, from C 1 to C ₈ hydrocarbon chains, it being understood that the alkyl groups R ₃ , R ₄ and R ₅ may contain one or more groups chosen from: a nitrogen atom, an oxygen atom and a carbonyl group and that the groups R ₃ , R ₄ and R ₅ may be connected together in pairs to form one or more rings,

R ₆ and R ₇ are identical or different and independently selected from C ₁ -C ₁₈ hydrocarbon chains, it being understood that the R ₆ and R _{7 groups} may contain one or more groups chosen from: a nitrogen atom, a hydrogen atom, oxygen and a carbonyl group and that the groups R ₆ and R ₇ may be joined together to form a ring.

According to a first variant of this preferred embodiment, the group R of the unit of formula (II) is represented by formula (III) in which:

X is chosen from organic anions, preferably conjugated bases of carboxylic acids,

R ₂ is selected from C 1 to C ₃₄ hydrocarbon chains, preferably C ₁ to C 18 alkyl groups _,

R _3, R and R ₅ are identical or different and independently selected from hydrocarbon chains Ci to C _8, optionally substituted by at least one hydroxyl group, provided that at least one of R _3, R and R ₅ contains at least one hydroxyl group.

According to a second variant of this preferred embodiment, the group R ₂ is represented by one of the following formulas (V) and (VI):

bond

(V) (VI)

in which

R ₈ is selected from C 1 to C ₃₂ hydrocarbon chains, R ₉ is selected from hydrogen and C _1-6 alkyl groups.

According to a particular embodiment, the copolymer (a) is obtained by copolymerization of at least:

a monomer (m _a ) corresponding to the following formula (VII):

in which

Ri ', u, E and G are as defined above,

a monomer (m _b ) corresponding to the following formula (VIII):

in which

Ri ", Q and R are as defined above.

According to a preferred embodiment, the monomer (m _a) is selected from alkyl acrylates to C ₃₄ alkyl methacrylates and Ci-C _34.

According to a particular embodiment, the monomer (m _b ) is obtained by reaction:

a tertiary amine of formula NR ₃ R ₄ R ₅ or R ₆ N = R ₇ in which R ₃ , R _4, R ₅ , R ₆ and R ₇ are as defined above, and

an intermediate monomer (meth) acrylate or (meth) acrylamide (m,) of formula (XV) below:

in which,

Q, R 1, R ₈ and R ₉ are as defined above.

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

Preferably, the copolymer is a block copolymer comprising:

a block A corresponding to the following formula (XI):

in which

p is an integer ranging from 2 to 100, preferably ranging from 5 to 80, preferably ranging from 10 to 70, more preferably ranging from 20 to 60,

Ri ', u, E and G are as defined above,

a block B corresponding to the following formula (XII):

in which

n is an integer ranging from 2 to 50, preferably from 3 to 40, more preferably from 4 to 20, even more preferably from 5 to 10,

Ri ", Q and R are as defined above.

Preferably, the block copolymer comprises at least:

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

a block B consisting of a chain of structural units derived from one or more monomers chosen from the monomers (m _b ) of formula (VIII). More preferably, the block copolymer comprises at least:

block A consisting of a chain of structural units derived from a single monomer chosen from the monomers (m _a ) of formula (VII), and

- Block B consisting of a chain of structural units derived from a single monomer selected from the monomers (m _b ) of formula (VIII).

Even more preferably, the block copolymer comprises at least:

block A consisting of a chain of structural units derived from a C1-C34 alkyl (meth) acrylate monomer (m _a ), and

- Block B consisting of a chain of structural units derived from an alkyl (meth) acrylate monomer or alkyl (meth) acrylamide (m _b ), the alkyl radical is constituted by a hydrocarbon chain C 1 -C ₃₄ substituted with at least one quaternary ammonium group and optionally one or more hydroxyl groups.

Preferably, the number of monomer equivalents (m _a ) of block A is from 2 to 100 moles.

Preferably, the number of monomer equivalents (m) of block B is from 2 to 50 moles.

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

Preferably, the block copolymer is obtained by sequential polymerization, optionally followed by one or more post-functionalizations.

According to a particular embodiment, the block B is obtained by post-functionalization of an intermediate polymer Pi resulting from the polymerization of an intermediate monomer (meth) acrylate or (meth) acrylamide (m,) of formula (XV) defined above and wherein said post-functionalization corresponds to the reaction of said intermediate polymer Pi with a tertiary amine NR ₃ R ₄ R ₅ where R ₆ N = R ₇ where R ₃ , R _, R ₅ , R ₆ and R ₇ are as defined above.

Advantageously, the intermediate polymer Pi also comprises at least one block A as defined above.

Preferably, the amine (s) substituted with a polyalkenyl group (b) are selected from polyisobutene amines.

Preferably, the mass ratio between the copolymer or copolymers (a) as defined above and the amine (s) substituted with a polyalkenyl group (b) ranges from 5: 95 to 95: 5, preferably from 10: 90 to 90: 10.

According to one embodiment, in the additive composition according to the invention, the ratio between the mass of carrier oil (c) and the sum of the masses of copolymers (a) and amines substituted by a polyalkenyl group (b ) described above and in detail below ranges from 0, 1 to 2, preferably from 0.3 to 1, 2, more preferably from 0.4 to 0.8.

The invention also relates to a fuel concentrate comprising a fuel additive composition as defined above and in detail below, in admixture with an organic liquid. According to the use in the field, the said organic liquid is inert with respect to the copolymer (s) (a), the amine (s) substituted with a polyalkenyl group (b) and the carrier oil (s) (c), if appropriate. present, and miscible with said fuel.

The invention also relates to a fuel composition comprising:

(1) a fuel from one or more sources selected from the group consisting of mineral, animal, plant and synthetic sources, and

(2) an additive composition as described above and in detail below.

Preferably, the fuel composition according to the invention comprises at least 5 ppm of copolymer (s) (a).

Preferably, the amine (s) substituted with a polyalkenyl group (b) are present in the fuel composition according to the invention in an amount ranging from 1 to 1000 ppm, preferably ranging from 5 to 500 ppm, more preferably ranging from 50 to 500 ppm, and even more preferably from 100 to 300 ppm.

Preferably, the copolymer or copolymers (a) are present in the fuel composition according to the invention in an amount ranging from 1 to 1000 ppm, preferably from 5 to 500 ppm, more preferably from 10 to 200 ppm, and even more preferably ranging from 20 to 100 ppm.

Preferably, the fuel (1) is chosen from hydrocarbon fuels, non-essentially hydrocarbon fuels and mixtures thereof.

Advantageously, the hydrocarbon fuel is chosen from gasolines.

The invention also relates to the use of a fuel additive composition as described above and in detail below, as a detergent additive in a spark ignition engine liquid fuel or in an ignition gasoline engine. by compression, said fuel additive composition being used alone or in the form of a concentrate as defined above and in detail below.

In a particular embodiment, the fuel additive composition is used in the liquid fuel to maintain cleanliness and / or clean at least one of the internal parts of said spark ignition engine or said compression ignition engine.

According to a particular embodiment, the fuel additive composition is used in the liquid fuel to limit or prevent the formation of deposits in at least one of the internal parts of said spark ignition engine or said compression ignition engine and / or to reduce deposits in at least one of the internal parts of said spark ignition engine or said compression ignition engine.

In a particular embodiment, the fuel additive composition is used in the liquid fuel to reduce the fuel consumption of the spark ignition engine or the compression ignition engine.

In a particular embodiment, the fuel additive composition is used in the liquid fuel to reduce pollutant emissions, particularly particulate emissions from the spark ignition engine or the compression ignition engine.

Advantageously, the deposits are located in at least one of the internal parts selected from the engine intake system, the combustion chamber and the fuel injection system.

Preferably, the additive composition is used to prevent and / or reduce the formation of deposits related to the phenomenon of coking and / or soap-like deposits and / or varnish. According to a first embodiment, the fuel additive composition according to the invention is used in a spark ignition engine or in a direct injection injection gasoline engine to maintain the cleanliness and / or clean the injectors of the engine. engine.

According to a second embodiment, the fuel additive composition according to the invention is used in a spark-ignition engine or in a gasoline engine with compression ignition, with indirect injection to maintain the cleanliness and / or clean the valves of the engine. engine intake.

According to one embodiment, the fuel additive composition according to the invention is used to prevent and / or prevent and / or limit and / or delay the bonding of the intake valves in a spark-ignition engine or in an engine gasoline with compression ignition, indirect injection.

According to a first embodiment, the engine is a spark ignition engine.

According to a second embodiment, the engine is a compression-ignition gasoline engine (GCI engine).

The invention finally relates to a method for maintaining the cleanliness and / or cleaning of at least one of the internal parts of a spark-ignition engine or a compression-ignition gasoline engine comprising at least the following steps:

the preparation of a fuel composition by additivation of a fuel with an additive composition or a concentrate as described above and in a detailed manner below, and

the introduction, and in particular the combustion, of said fuel composition in said spark ignition engine or in said gasoline engine with compression ignition.

DETAILED DESCRIPTION

Other advantages and features will emerge more clearly from the following description. The particular embodiments of the invention are given by way of non-limiting examples.

For reasons of simplification, we will use in the rest of the description the terms:

alkyl (meth) acrylate to designate an alkyl acrylate or an alkyl methacrylate,

alkyl (meth) acrylamide to designate an alkyl acrylamide or an alkyl methacrylamide, and

quaternary ammonium to designate a quaternary ammonium salt.

For the purposes of the invention, the term "unit" means a group of atoms constituting part of the structure of the copolymer and corresponding to a monomer employed in the synthesis of the copolymer.

The invention relates to a fuel additive composition comprising:

(a) one or more copolymer (s) comprising:

at least one unit of formula (I) below:

With

u = 0 or 1,

R 1 represents a hydrogen atom or a methyl group, preferably R 1 'is a hydrogen atom,

at least one unit of formula (II) below:

in which

R 1 is chosen from the hydrogen atom and the methyl group,

R comprises a C 1 to C ₃₄ hydrocarbon-based chain substituted with at least one quaternary ammonium group and optionally one or more hydroxyl groups, the R group possibly also containing one or more nitrogen and / or oxygen atoms and / or carbonyl groups .

(b) one or more amine (s) substituted with a polyalkenyl group.

The copolymer (a)

According to a particular embodiment, the units of formula (I) and the units of formula (II) defined above represent at least 70 mol% of the copolymer (a), relative to the number of moles of units entering the the composition of the copolymer (a), preferably at least 80 mol%, more preferably at least 90 mol%, even more preferably at least 95 mol%, and advantageously at least 98 mol%.

According to a preferred embodiment, the copolymer (a) comprises only units of formula (I) and units of formula (II).

According to a particular embodiment, the copolymer (a) is chosen from block copolymers or statistics.

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

According to a first variant, the unit of formula (I) is chosen from those verifying u = 0. Preferably, and according to this first variant, the copolymer is in blocks.

According to another variant, the unit of formula (I) is chosen from those verifying u = 1.

The group E of the formula (I) is chosen from:

- E = -O-,

E = -N (Z) - with Z represents H or a linear or branched, cyclic or acyclic, preferably acyclic, C ₁ -C ₆ alkyl group,

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

- E = -NH-CO-, and

- E = -CO-NH-.

According to a second embodiment, the group E of the formula (I) is chosen from: O-CO- and -NH-CO-, it being understood that the group E-O-CO- is linked to the vinyl carbon by oxygen atom and that the group E = -NH-CO- is connected to the vinyl carbon by the nitrogen atom.

According to this same embodiment, the group E of the formula (I) is preferably the -O-CO- group, it being understood that the -O-CO- group is connected to the vinyl carbon by the oxygen atom.

According to a third embodiment, the group E of the formula (I) is chosen from: -CO-O- and -CO-NH-, it being understood that the group E is connected to the vinyl carbon by the carbon atom.

According to this third embodiment, the group E of the formula (I) is preferably the -CO-O- group, it being understood that the -CO-O- group is connected to the vinyl carbon by the carbon atom.

According to a preferred embodiment, the unit of formula (I) is such that u = 1, and the group E is a group -CO-O-, E being connected to the vinyl carbon by the carbon atom.

The group (G) of the formula (I) may be a C ₁ -C ₃ alkyl, preferably a C ₄ -C ₃ 4 alkyl, preferably a C ₄ -C ₃₀ alkyl, more preferably a C ₆ -C ₂ 4 alkyl radical, even more preferentially in C ₈ to C ₈ . 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.

The group (G) of the formula (I) is advantageously a C ₁ -C ₃₄ acyclic alkyl, preferably a C ₄ -C ₃₄ alkyl radical, preferably a C ₄ -C ₃₀ alkyl radical, more preferably C ₆ -C ₂ 4, more preferably C ₈ to C ₈ linear or branched, preferably branched.

Mention may be made, without limitation, of alkyl groups such as butyl, octyl, decyl, dodecyl, ethyl-2-hexyl, isooctyl, isodecyl and isododecyl.

The group (G) of formula (I) may also be an aromatic ring, preferably a phenyl or aryl group. Among the aromatic groups, there may be mentioned, without limitation, the phenyl or naphthyl group, preferably the phenyl group.

The group (G) of the formula (I) may, according to another preferred variant, be an aralkyl comprising at least one aromatic ring and at least one C 1 -C 34 alkyl group. Preferably, according to this variant, the group (G) is an aralkyl comprising at least one aromatic ring and one or more C ₄ -C ₃₄ , preferably C ₄ -C ₃₀ , more preferably C ₆ -C alkyl groups. _24, more preferably C ₈ to C _8.

The aromatic ring may be mono-substituted or substituted on a number of its carbon atoms. Preferably, the aromatic ring is monosubstituted.

The C ₁ -C ₃₄ alkyl group may 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 branched.

The aromatic ring may be directly attached to the E group or the vinyl carbon but may also be connected to it via an alkyl substituent.

By way of example of group G, there may be mentioned a benzyl group substituted in para with a C ₄ -C ₃₄ , preferably C ₄ -C _30, alkyl group. Preferably, according to this variant, the group (G) of formula (I) is an aralkyl comprising at least one aromatic ring and at least one C 1 -C ₃ alkyl group, preferably C ₄ -C ₃₀ , more preferably C ₆ -C _24, more preferably C ₈ to C _8.

According to a particular embodiment, the group Q of formula (II) is the oxygen atom.

According to a particular embodiment, the group R of formula (II) comprises a quaternary ammonium group and one or more hydroxyl groups.

According to one variant, the group R is chosen from groups having at least one quaternary ammonium function obtained by quaternization of a primary, secondary or tertiary amine according to any known method.

The group R may, in particular, be chosen from groups having at least one quaternary ammonium function obtained by quaternization of at least one amine, imine, amidine, guanidine, aminoguanidine or biguanidine function; heterocyclic groups having from 3 to 34 atoms and at least one nitrogen atom.

Advantageously, the group R is chosen from groups having at least one quaternary ammonium function obtained by quaternizing a tertiary amine.

According to one particular embodiment, the group R of formula (II) is represented by one of the following formulas (III) and (IV):

(III) (IV)

in which

X is chosen from hydroxide ions, halides and organic anions, in particular the acetate ion,

R ₂ is selected from C 1 to C ₃₄ , preferably C 1 to C ₈ , more preferably C 1 to C ₈ , still more preferably C ₂ to C ₄ , cyclic or acyclic, linear or branched, optionally substituted hydrocarbon chains; by at least one hydroxyl group; preferably, R ₂ is chosen from alkyl groups, optionally substituted with at least one hydroxyl group, it being understood that the group R ₂ is connected to the group Q in formula (II),

R _3, R ₄ and R ₅ are identical or different and independently selected from hydrocarbon chains Ci to C _8, preferably Ci-Ci ₂ linear or branched, cyclic or acyclic, it being understood that the alkyl groups R ₃ , R ₄ and R ₅ may contain one or more nitrogen atoms and / or oxygen and / or carbonyl groups and may be connected together in pairs to form one or more rings,

R ₆ and R ₇ are identical or different and independently selected among the channels hydrocarbon Ci to C _8, preferably Ci-Ci ₂ linear or branched, cyclic or acyclic, it being understood that R ₆ and R groups ₇ may contain one or more nitrogen atoms and / or oxygen and / or carbonyl groups and may be joined together to form a ring.

The nitrogen atom (s) and / or oxygen (s) may be present in the groups R ₃ , R and R ₅ as ether bridges, amine bridges or in the form of an amine or hydroxyl substituent.

The organic anions of the X group are advantageously the conjugate bases of the organic acids, preferably the conjugate bases of the carboxylic acids, in particular the acids chosen from monocarboxylic, polycarboxylic, cyclic or acyclic acids. Preferably, the organic anions of the X group are chosen from conjugated bases of saturated acyclic or cyclic aromatic carboxylic acids. By way of example, mention may be made of methanoic acid, acetic acid, adipic acid, oxalic acid, malonic acid, succinic acid, citric acid, benzoic acid and phthalic acid, isophthalic acid and terephthalic acid.

According to one particular embodiment, the group R ₂ is chosen from C 1 to C ₃₄ , preferably C 1 to C ₈ , more preferably C 1 to C ₈ , even more preferably C ₂ to C, linear acyclic groups. or branched, substituted by at least one hydroxyl group.

According to a particular embodiment, the group R of formula (II) comprises a hydrocarbon chain substituted with at least one quaternary ammonium group and one or more hydroxyl groups.

Advantageously, the group R of formula (II) is represented by formula (III) in which :

According to a particular embodiment, the group R ₂ is represented by one of the following formulas (V) and (VI):

(V) (VI)

In which

R ₈ is selected from hydrocarbon chains to C _32, preferably Ci to C ₆ cyclic or acyclic, preferably acyclic, linear or branched, preferably alkyl groups,

R ₉ is chosen from hydrogen and C ₁ -C ₆ alkyl groups _, C ₁ -C _4, more preferably hydrogen.

According to a particular embodiment, the unit of formula (I) is obtained from a monomer (m _a ).

Preferably, the monomer (m _a ) corresponds to the following formula (VII):

With

Ri ', E, G and u are as defined above, the preferred variants of R 1', E, G and u according to the formula (I) as defined above are also preferred variants of the formula (VII ). Advantageously, the group R 1 'is a hydrogen atom.

When the group E of the monomer (m _a ) is the group -O-CO-, it being understood that the group -O-CO- is connected to the vinyl carbon by the oxygen atom, the monomer (m _a ) is, preferably, chosen from vinyl esters of C 1 to C ₃₄ , preferably C ₄ to C ₃ o, more preferably C ₆ to C _24, more preferably C ₈ to C ₂ 2- alkyl of the The vinyl ester alkyl is linear or branched, cyclic or acyclic, preferably acyclic.

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

When the group E of the monomer (m _a ) is the group -CO-O-, it being understood that the group -CO-O- is connected to the vinyl carbon by the carbon atom, the monomer (m _a ) is preferably selected from alkyl acrylates or methacrylates to C _34, preferably C ₄ -C _30, more preferably C ₆ to C _24, more preferably C ₈ to C _22. The alkyl radical of the acrylate or methacrylate is linear or branched, cyclic or acyclic, preferably acyclic.

Among the alkyl (meth) acrylates which may be used in the manufacture of the copolymer of the invention, mention may be made, in a nonlimiting manner: n-octyl acrylate, n-octyl methacrylate, n-decyl acrylate, n-decyl methacrylate, n-dodecyl acrylate, n-dodecyl methacrylate, ethyl-2-hexyl acrylate, ethyl-2-hexyl methacrylate, isooctyl acrylate, isooctyl methacrylate, isodecyl acrylate, isodecyl methacrylate.

According to a particular embodiment, the unit of formula (II) is obtained from a monomer (m _b ).

Preferably, the monomer (m _b ) is chosen from those of formula (VIII):

in which

R 1 ", Q and R are as defined above, preferred variants of R 1", Q and R according to formula (II) as defined above are also preferred variants of formula (VIII).

According to a particular embodiment, the monomer (m _b ) is represented by one of the following formulas (IX) and (X):

(IX) (X)

in which

R 1 "and Q are as defined above, preferred variants of R 1" and Q according to formula (II) as defined above are also preferred variants of formulas (IX) and (X),

X, R 2, R 3, R ₄ , R ₅ , R 6 and R ₇ are as defined above, the preferred variants of X, R ₂ , R ₃ , R ₄ , R ₅ , R 6 and R ₇ according to formulas (III) and (IV) as defined above are also preferred variants of formulas (IX) and (X).

According to a particular embodiment, the copolymer (a) can be obtained by copolymerization of at least one monomer (m _a ) and at least one monomer (m).

According to a particular embodiment, at least 70 mol% of the monomers used for the preparation of the copolymer (a) are chosen from the monomers (m _a ) and the monomers (m _b ) defined above, preferably at least 80 % in moles, plus preferably at least 90 mol%, even more preferably at least 95 mol%, and advantageously at least 98 mol%.

According to a particular preferred embodiment, the copolymer (a) is obtained solely from monomers (m _a ) and monomers (m _b ).

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

According to a particular embodiment, the copolymer (a) is a block copolymer comprising at least one block A and at least one block B.

Block A corresponds to the following formula (XI):

in which

p is an integer ranging from 2 to 100, preferably from 5 to 80, preferably from 10 to 70, more preferably from 20 to 60.

Ri ', E, G and u are as defined above, the preferred variants of R 1', E, G and u according to formula (I) as defined above are also preferred variants of the formula (XI ).

Block B corresponds to the following formula (XII):

in which

n is an integer ranging from 2 to 50, preferably from 3 to 40, more preferably from 4 to 20, still more preferably from 5 to 10,

R 1 ", Q and R are as defined above, preferred variants of R 1", Q and R according to formula (II) as defined above are also preferred variants of formula (XII).

According to a particular embodiment, block B is represented by one of the following formulas (XIII) and (XIV):

(XIII) (XIV) in which

n, Q and R _\ "are as described above, the preferred variants of n, Q and R _\" according to the formulas (II) and (XII) as defined above are also preferred embodiments of formulas (XIII) and (XIV),

X, R 2, R 3, R ₄ , R ₅ , R 6 and R ₇ are as defined above, the preferred variants of X, R ₂ , R ₃ , R ₄ , R ₅ , R 6 and R ₇ according to formulas (III) and (IV) as defined above are also preferred variants of formulas (XIII) and (XIV).

According to a particular embodiment, the block A consists of a chain of structural units derived from at least one monomer (m _a ) as described above.

According to a particular embodiment, the block B consists of a chain of structural units derived from at least one monomer (m _b ) as described above.

According to a particular embodiment, block A consists of a chain of structural units derived from an alkyl acrylate or alkyl methacrylate monomer (m _a ) and block B corresponds to formula (XII) described above. .

According to a particular embodiment, the block copolymer is obtained by copolymerization of at least the alkyl (meth) acrylate monomer (m _a ) and at least the monomer (m).

It is understood that it would not go beyond the invention if the copolymer (a) according to the invention was obtained from monomers different from (m _a ) and (m _b ), insofar as the final copolymer corresponds to that of the invention, that is to say comprising at least one unit of formula (I) and at least one unit of formula (II) as defined above _. For example, it would not go beyond the invention, if one obtained the copolymer by copolymerization of monomers different from (m _a ) and (m _b ) followed by post-functionalization.

For example, units derived from a monomer (m _a ) can be obtained from vinyl alcohol or acrylic acid, respectively by transesterification or amidification reaction.

For example, the units deriving from a monomer (m _b ) can be obtained by post-functionalization of an intermediate polymer P 1 resulting from the polymerization of an intermediate monomer (meth) acrylate or (meth) acrylamide (m 2) of formula (XV) defined below and wherein said post-functionalization corresponds to the reaction of said intermediate polymer Pi with a tertiary amine NR ₃ R ₄ R ₅ where R ₆ N = R ₇ where R ₃ , R _4, R ₅ , R ₆ and R ₇ are as defined above in formulas (III) and (IV).

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

According to a particular embodiment, the block copolymer described above is obtained by sequenced and controlled polymerization. The polymerization is advantageously chosen from controlled radical polymerization; for example, by atom transfer radical polymerization (ATRP in English "Atom Transfer Radical Polymerization"); the radical polymerization by nitroxide (NMP in English "Nitroxide-mediated polymerization"); degenerative transfer processes (degenerative transfer processes) such as degenerative iodine transfer polymerization (ITRP-iodine transfer radical polymerization) or radical polymerization by reversible addition-fragmentation chain transfer ( RAFT in English "Reversible Addition-Fragmentation Chain Transfer"); polymerizations derived from ATRP such as polymerizations using initiators for the continuous regeneration of the activator (ICAR -Initiators for continuous activator regeneration) or using electron-regenerated activators regenerated by electron (ARGET) transfer ").

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 method of sequenced and controlled polymerization to form block copolymers.

As an example for NMP, mention may be made of the identification by CJ Hawker of an alkoxyamine capable of acting as a unimolecular agent, providing both the initiator reactive radical and the intermediate nitroxide radical in stable form (CJ Hawker, J. Am., Chem., 1994, 116, 1185). Hawker has also developed a universal NMP initiator (D. Benoit et al., J. Am Chem Soc., 1999, 121, 3904).

The reversible Addition-Fragmentation Chain Transfer (RAFT) radical polymerization is a living radical polymerization technique. The RAFT technique was discovered in 1988 by the Australian scientific research organization CSIRO (J. Chiefari et al., Macromolecules, 1998, 31, 5559). The RAFT technique has very rapidly been the subject of intensive research by the scientific community as it allows the synthesis of macromolecules with complex architectures, including structures in blocks, grafts, combs or even stars. by controlling the molecular weight of the macromolecules obtained (G. Moad et al., Aust J. Chem, 2005, 58, 379). The RAFT polymerization can be applied to a very wide range of vinyl monomers and under various experimental conditions, including for the preparation of water-soluble materials (McCormick, C. L. et al., Acc.Chem.Res.2004, 37, 312). The RAFT method includes the conventional radical polymerization of a substituted monomer in the presence of a suitable chain transfer agent (RAFT agent or CTA in English "Chain Transfer Agent"). Commonly used RAFT agents include thiocarbonylthio compounds such as dithioesters (J. Chiefari et al., Macromolecules, 1998, 31, 5559), dithiocarbamates (RTA Mayadunne et al., Macromolecules, 1999, 32, 6977; et al., Macromol Rapid, Commun., 2000, 21, 1035), trithiocarbonates (RTA Mayadunne et al., Macromolecules, 2000, 33, 243) and xanthates (R. Francis et al., Macromolecules, 2000, 33, 4699), which operate the polymerization by a reversible chain transfer method. The use of a suitable RAFT agent allows the synthesis of polymers having a high degree of functionality and having a narrow distribution of molecular weights, that is to say a low polydispersity index (PDI in English "Polydispersity index") .

Examples of radical RAFT polymerization description include the following documents WO 1998/01478, WO 1999/31144, WO 2001/77198, WO 2005/00319, WO 2005/000924. 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 may be chosen from polar solvents, in particular ethers such as anisole (methoxybenzene) or tetrahydrofuran or apolar solvents, in particular paraffins, cycloparaffins, aromatics and alkylaromatics having from 1 to 19 carbon atoms. carbon, for example, benzene, toluene, cyclohexane, methylcyclohexane, n-butene, n-hexane, n-heptane and the like.

For the Atom Transfer Radical Polymerization (ATRP), 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 N, N, N ', N ", N" -Pentamethyldiethylenetriamine (PMDETA), 1,1,7,7,10,10-hexamethyltriethylene tetramine (HMTETA), 2,2'-Bipyridine (BPY) and Tris (2-pyridylmethyl) amine (TPMA). As an example of a catalyst, mention may be made of: CuX, CuX ₂ , with X = Cl, Br and ruthenium 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 monomer equivalents (m _a ) of block A and monomer (m _b ) of block B reacted during the polymerization reaction may be the same or different.

By number of equivalents is meant the amounts of material (in moles) of the monomers (m _a ) of the block A and of the monomers (m _b ) of the block B, used during the polymerization reaction.

The number of monomer equivalents (m _a ) of the block A is preferably from 2 to 100 eq, preferably from 5 to 80 eq, preferably from 10 to 70 eq, more preferably from 20 to 60 eq.

The number of monomer equivalents (m) of the block B is preferably from 2 to 50 eq, preferably from 3 to 40 eq, more preferably from 4 to 20 eq, still more preferably from 5 to 10 eq. The number of monomer equivalents (m _a ) of the block A is advantageously greater than or equal to that of the monomer (m _b ) of the block B.

Preferably, when the group E of the monomer (m _a ) is a group -CO-O-, E being connected to the vinyl carbon by the carbon atom, the number of monomer equivalents (m _a ) of the block A is between 20 and 60 moles, and G is selected from C ₄ to C ₃₀ hydrocarbon chains.

Even more preferentially, when the group E of the monomer (m _a ) is a group -CO-O-, E being connected to the vinyl carbon by the carbon atom, the number of monomer equivalents (m _a ) of the block A is between 20 and 60 moles, and G is selected from C ₄ -C ₃ hydrocarbon chains, and the copolymer has a number average molecular weight (Mn) of from 1000 to 10,000 g. mol ¹ .

In addition, the molar mass in weight M _w of block A or 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 together without the presence of intermediate blocks of different chemical nature.

Other blocks may optionally 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 A and B blocks will be preferred.

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

According to a particular embodiment, the block copolymer is a diblock copolymer.

According to another particular embodiment, the block copolymer is an alternating block triblock copolymer comprising two blocks A and one block B (ABA) or comprising two blocks B and a block A (BAB). According to one particular embodiment, the block copolymer also comprises a terminal chain I consisting of a linear or branched, C ₁ to C 32, preferably C ₄ to C _24, hydrocarbon, cyclic or acyclic, saturated or unsaturated hydrocarbon chain _, more preferably preferentially in C10 to C24 _.

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

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

The terminal chain I is, preferably, selected 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 the ATRP polymerization, the terminal chain I is located in the terminal position of the block copolymer. It can be introduced into the block copolymer by means of the polymerization initiator. Thus, the terminal chain I may, advantageously, constitute at least a part of the polymerization initiator and is positioned within the polymerization initiator in order to introduce, during the first polymerization initiation step. , the terminal chain I in the terminal position of the block copolymer.

The polymerization initiator is, for example, chosen from free radical initiators used 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 prospects, Macromolecules, 45, 4015-4039, 2012".

The polymerization initiator is, for example, selected from alkyl esters of a halide-substituted carboxylic acid, preferably a bromine in the alpha position, for example ethyl 2-bromopropionate, a-bromoisobutyrate. ethyl chloride, benzyl chloride 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 benzyl bromide in the form of a benzyl group. For the RAFT polymerization, the transfer agent can conventionally be removed from the copolymer at the end of the polymerization according to any known method.

According to one 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. et al., Australian Journal of Chemistry, 2012, 65, 985-1076. The terminal chain I may, for example, be modified by aminolysis when a transfer agent is used to give a thiol function. By way of example, mention may be made of transfer agents of the thiocarbonylthio, dithiocarbonate, xanthate, dithiocarbamate and trithiocarbonate type, for example S, N-dibenzyltrithiocarbonate (DBTTC), S, S-bis (a, a'- dimethyl-α -acetic acid) trithiocarbonate (BDMAT) or 2-cyano-2-propyl benzodithioate (CPD).

According to a known method, the transfer agent can be cleaved at the end of the polymerization by reacting a cleavage agent such as C ₂ -C ₆ alkylamines, the terminal function of the copolymer can in this case be a thiol group -SH .

According to another process described in patent EP 1751 194, the sulfur of the copolymer obtained by RAFT polymerization introduced by the sulfur transfer agent such as thiocarbonylthio, dithiocarbonate, xanthate, dithiocarbamate and trithiocarbonate, can be converted in order to eliminate sulfur. of the copolymer.

According to a particular embodiment, the block copolymer is a diblock copolymer (also called diblocks). The block copolymer structure may be of the IAB or IBA type, advantageously IAB. The terminal chain I may be directly linked to the block A or B according to the structure IAB or IBA, respectively, or to 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 method, in particular by hydrolysis, aminolysis and / or nucleophilic substitution.

By aminolysis is meant any chemical reaction in which a molecule is split into two parts by reaction of an ammonia molecule or an amine. A general example of aminolysis is to replace a halogen of an alkyl group by reaction with an amine, with removal of hydrogen halide. Aminolysis can be used, for example, for an ATRP polymerization which produces a copolymer having a terminal halide or for a RAFT polymerization to transform the thio, dithio or trithio bond introduced into the copolymer by the thiol-functional transfer agent RAFT.

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 ₂₄ , more preferably C 1 to C ₁₀ , still more preferably an alkyl group, optionally substituted with one or more groups containing at least one heteroatom selected from N and O, preferably N.

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

The quaternary ammonium group of block B described above may be acyclic or cyclic.

The acyclic quaternary ammonium group is advantageously chosen from quaternary ammoniums of trialkylammonium, iminium, amidinium, formamidinium, guanidinium and biguanidinium, preferably trialkylammonium.

The cyclic quaternary ammonium group is advantageously chosen from heterocyclic compounds containing at least one nitrogen atom, in particular chosen from quaternary ammoniums of pyrrolinium, pyridinium, imidazolium, triazolium, triazinium and oxazolium. isoxazolium.

The quaternary ammonium group of the B block is, advantageously, a quaternary ammonium, still more advantageously a quaternary trialkylammonium.

According to a preferred variant, at least one of the alkyl groups of the quaternary ammonium of block B is substituted by a hydroxyl group. According to a particular embodiment, the block B is preferably derived from a monomer (m _b ) obtained by reaction:

a tertiary amine of formula NR ₃ R ₄ R ₅ or R ₆ N = R ₇ in which R ₃ , R _, R ₅ , R ₆ and R ₇ are as described above, and

an intermediate monomer (meth) acrylate or (meth) acrylamide m, of formula (XV) below:

In which,

Q, R 1, R ₈ and R ₉ are as described above, the preferred variants of Q, R 1, R ₈ and R ₉ according to formulas (II), (V) and (VI) as defined herein. above are also preferred variants of the formula (XV).

According to another particular embodiment, the block B is obtained by post-functionalization of an intermediate polymer Pi comprising at least one block P of formula (XVI) below:

In which,

R 1, n, Q, R ₈ and R ₉ are as described above, the preferred variants of R 1, n, Q, R ₈ and R ₉ according to formulas (II), (V), (VI) and (XII) as defined above are also preferred variants of formula (XVI).

The post-functionalization corresponds to the reaction of the intermediate polymer Pi with a tertiary amine of formula NR ₃ R ₄ R ₅ or R ₆ N = R ₇ in which R ₃ , R _4, R ₅ and R ₆ , R ₇ are such that previously described.

The tertiary amine may, for example, be selected from the acyclic tertiary amines of preferably trialkylamines, guanidines and quaternizable imines. The tertiary amine is preferably selected from trialkylamines, especially those whose alkyl groups are identical or different and independently selected from alkyl Cl to C _8, preferably C, to C _12, linear or branched, cyclic or acyclic, preferably acyclic.

According to one variant, the tertiary amine may be chosen from cyclic tertiary amines, preferably pyrrolines, pyridines, imidazoles, triazoles, guanidines, imines, triazines, oxazoles and isoxazoles which are quaternizable.

The intermediate polymer Pi may also comprise at least one block A as described above.

According to a particular embodiment, the block B of formula (XII) is obtained by quaternization, according to any known method, of a tertiary amine corresponding to the quaternary ammonium group of block B of formula NR ₃ R ₄ R ₅ or R ₆ N = R ₇ wherein R ₃ , R _4, Rs, F¾ and R ₇ are as defined above.

The quaternization step may be carried out before the copolymerization reaction, on an intermediate monomer carrying the tertiary amine, for example, by reaction with an alkyl halide or an epoxide (oxirane) according to any known process, optionally followed by a anion exchange reaction.

The quaternization step can also be carried out by post-functionalization of an intermediate polymer carrying the tertiary amine, for example by reaction with an alkyl halide optionally followed by an anion exchange reaction. By way of an example of quaternization, mention may be made of a post-functionalization reaction of an intermediate polymer bearing the tertiary amine, by reaction with an epoxide (oxirane) according to any known method.

It is preferred to copolymerize intermediate monomers carrying a tertiary amine function and then in a second step to functionalize the intermediate copolymer obtained by quaternization of the tertiary amine present in the intermediate copolymer, rather than to copolymerize already quaternized monomers.

In addition, it will be preferred to carry out quaternarization involving an epoxide. The fuel additive composition may advantageously comprise from 5 to 99% by weight, preferably from 10 to 80% by weight, more preferably from 25 to 70% by weight of copolymer as described above with respect to the mass. total of the additive composition.

Amine substituted with a polyalkenyl group (b)

The fuel additive composition according to the invention also comprises at least one amine substituted with a polyalkenyl or polyalkene group (b).

In the remainder of the description, the terms "polyalkenyl group" and "polyalkene group" will be used in an undifferentiated manner to designate a group derived from a polyalkene.

The amines substituted with a polyalkene group (b) may be prepared from at least one polyolefin and at least one amine, said amine being chosen in particular from ammonia, monoamines, polyamines and their mixtures. The amines substituted with a polyalkene group may be prepared according to any known process, in particular those described in US 2008/01 13890.

As non-limiting examples, mention may be made of the reaction of a halogenated olefinic polymer with an amine; reacting a hydroformylated olefin with a polyamine followed by hydrogenation of the reaction product; converting a polyalkene to the corresponding epoxide followed by conversion of the epoxide to polyalkene amine by reductive amination; hydrogenation of a b-aminonitrile; and hydroformylation of a polybutene or polyisobutylene in the presence of a catalyst, carbon monoxide CO and dihydrogen H ₂ at elevated pressure and temperature.

The olefinic monomers from which the olefinic polymers are prepared include the polymerizable olefinic monomers characterized by the presence of one or more ethylenic unsaturations, for example ethylene, propylene, 1-butene, isobutene, 1-butene, and the like. octene, 1,3-butadiene and isoprene.

The olefinic monomers are generally polymerizable terminal olefins. However, polymerizable internal olefinic monomers can also be used to form polyalkenes.

Without limitation, among the terminal and / or internal olefinic monomers which can be used to prepare the polyalkenes according to any known process, there may be mentioned in particular: ethylene; propylene; butenes, including 1-butene, 2-butene and isobutylene or isobutene; 1-pentene; 1-hexene; 1-heptene; 1-octene; 1-nonene; 1-decene; 2-pentene; propylene tetramer; diisobutylene; isobutylene trimer; 1,2-butadiene; 1,3-butadiene; 1,2-pentadiene; 1,3-pentadiene; 1,4-pentadiene; isoprene; 5-hexadiene, 2-methyl-5-propyl-1-hexene; 3-pentene; 4-octene and 3,3-dimethyl-1-pentene.

Preferably, the amine substituted with a polyalkenyl group (b) is substituted with a C ₈ -C ₅ polyalkene group, more preferably with C ₁₂ -C 150.

More preferentially, the polyalkene group has a number-average molecular mass ranging from 200 to 5000 g / mol, preferably from 400 to 3000, more preferably from 500 to 2500, even more preferentially from 800 to 1500, the number-average molecular mass being determined by gel permeation chromatography (GPC), also called size exclusion chromatography (CES), from the starting polymer.

The amine used to prepare the amine substituted with a polyalkenyl group (b) can be chosen from ammonia, monoamines, polyamines, alone or in mixtures, including mixtures of different monoamines, mixtures of different polyamines, and mixtures of monoamines and polyamines (including diamines).

The monoamine or polyamine advantageously comprises at least one primary or secondary amine.

Preferably, the monoamine or polyamine is substituted with at least one hydrocarbon group chosen from an aliphatic group, possibly cyclic; an aromatic group or a heterocyclic group.

According to a first embodiment, the amine is a monoamine.

Preferably, the monoamine is substituted with at least one hydrocarbon group having 1 to 50 carbon atoms, preferably 1 to 30 carbon atoms.

According to a first variant, the monoamine is substituted by at least one aliphatic hydrocarbon group, preferably saturated.

By way of example, mention may be made of: methylamine, ethylamine, diethylamine, 2-ethylhexylamine, di- (2-ethylhexyl) amine, n-butylamine, di-n-butylamine, allylamine, isobutylamine, cocoamine, stearylamine, laurylamine, methyllaurylamine and oleylamine.

According to a second variant, the monoamine is substituted by at least one optionally substituted aromatic group, the aromatic group being connected to the nitrogen atom of the amine by one of the carbon atoms of the aromatic ring.

Preferably, when the aromatic group is substituted, the substituent group is chosen from an aliphatic hydrocarbon chain, linear or branched, cyclic or acyclic, optionally comprising one or more heteroatoms.

As the monoamine substituted by an aromatic group, there may be mentioned by way of example: aniline, di- (para-methylphenyl) amine and naphthylamine.

As monoamine substituted by a substituted aromatic group, there may be mentioned by way of example: N- (n-butyl) aniline, para-dodecylaniline, cyclohexyl-naphthylamine and thienylaniline.

According to a third variant, the monoamine is substituted by at least one group comprising a hydroxyl group -OH.

Preferably, according to this third variant, the monoamine is substituted with at least one hydroxyalkyl chain.

By way of example, mention may be made of ethanolamine, di-3-propanolamine, 4-hydroxybutylamine, diethanolamine and N-methyl-2-hydroxypropylamine.

According to a fourth variant, the monoamine is substituted by a heterocyclic group, the heterocyclic group not comprising an amino nitrogen atom. Heterocyclic monoamines are known to those skilled in the art.

According to a second embodiment, the amine is a polyamine.

Preferably, the polyamine is chosen from polyamines substituted with polyalkene groups.

The polyamine may be substituted with one or more aliphatic, cycloaliphatic, heterocyclic or aromatic hydrocarbon groups.

By way of example, mention may be made of polyalkylene polyamines, hydroxylated polyamines, aryl polyamines and heterocyclic polyamines.

According to a first variant, the polyamine is chosen from the polyalkylene polyamines of formula (XVII) below:

H ₂ N- (R ₁ NH) _q -H (XVII) in which :

the Rio groups are independently selected from C ₁ -C 5, preferably C ₂ -C ₃ , alkylene chains, and

q is an integer from 1 to 10, preferably from 3 to 5.

Preferably, the groups R10 are all identical.

Even more preferentially, the polyalkylenepolyamine is chosen from the polyethylenepolyamines of formula (XVIII) below:

H ₂ N- (OH ₂ OH ₂ NH) _V -H (XVIII)

wherein q is an integer from 1 to 10, preferably from 3 to 5.

Advantageously, the polyethylenepolyamine is chosen from ethylenediamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine.

More preferably, the polyethylenepolyamine is tetraethylenepentamine.

According to a second variant, the polyamine is chosen from hydroxylated polyamines. By "hydroxylated polyamine" is meant in the sense of the invention a polyamine substituted by at least one group comprising at least one hydroxyl function -OH.

Preferably, the polyamine is chosen from polyamines substituted with one or more polyalkene groups and of which at least one or more nitrogen atoms is substituted with a hydroxyalkyl chain. These compounds may be prepared according to any known process and in particular by the reaction of polyamines substituted with one or more polyalkene groups with one or more alkene oxides.

By way of example, mention may be made of N- (2-hydroxyethyl) ethylenediamine, N, N-bis (2-hydroxyethyl) ethylene diamine, 1- (2-hydroxyethyl) piperazine, and monohydroxypropyl-diethylene triamine, dihydroxypropyl tetraethylene pentamine and N- (3-hydroxybutyl) tetramethylenediamine.

According to a third variant, the polyamine is chosen from arylpolyamines.

The arylpolyamines are analogous to the aromatic group-substituted monoamines described above with the exception of the presence in their structure of another amino nitrogen.

By way of example, mention may be made of N, N'-di-n-butyl-para-phenylenediamine and bis (para-aminophenyl) methane. Preferably, the polyamine is chosen from polyalkylenepolyamines, more preferably from polyethylenepolyamines for reasons of cost and efficiency.

Examples of amines substituted with polyalkene groups may include polypropylene amine, polybutene amine, N, N-dimethylpolyisobutylene amine, N-polybutene-morpholine, N-polybutene-ethylenediamine, N-polypropylene trimethylenediamine, and the like. N-polybutene-diethylene triamine, N ', N'-polybutene-tetraethylenepentamine and N, N-dimethyl-N'-polypropylene-1,3-propylenediamine.

According to a preferred embodiment, the amines substituted with a polyalkenyl group (b) are selected from polyisobutenyl amines.

For the purposes of the invention, the term "polyisobutene amine" means an amine, monoamine or polyamine substituted with at least one polyisobutenyl chain. The polyisobutene amines are also called polyisobutylene amines or PIB-amines or PIBA.

Preferably, the polyisobutenyl chain is a homopolymer obtained from isobutylene monomers.

According to one particular embodiment, the polyisobutenyl chain may contain up to 20% by weight, based on the total weight of the polymer, of units derived from one or more monomers other than isobutylene, for example n-butene. , propene and their mixtures.

Examples of polyisobutene amine compounds include those obtained by carrying out the methods described in US 4,832,702, US 6, 140,541, US 6,909,017 or US 7,753,970.

Preferably, the polyisobutene amine corresponds to the following formula (XIX):

R12

/

R1- CH _? - NOT

\

R13

(XIX)

in which

Ru is a polyisobutenyl chain as described above, R-12 and R ₁₃ are independently selected from:

a hydrogen atom,

a hydrocarbon group, aliphatic or aromatic, preferably chosen from an alkyl, aryl and aralkyl group,

an aminoalkylene or polyalkylenepolyamine group, primary or secondary, aliphatic or aromatic,

a polyoxyalkylene group,

a heterocyclic group, optionally substituted, or

R 12 and R ₁₃ form with the nitrogen atom through which they are linked a heterocycle, said heterocycle can optionally comprise further heteroatoms and may be optionally substituted.

Preferably, at least one of the groups R12 and R ₁₃ is selected from polyoxyalkylene groups.

Preferably, the polyoxyalkylene group is represented by the following formula (XX):

- (Ri ₈ -O-) _O -X (XX)

in which

the groups Ris are independently selected from alkylene groups of C ₂ -C ₆ , preferably C ₂ -C ₃ ,

X is a hydrogen atom or an alkyl group, and

o is an integer ranging from 1 to 30.

According to a particular embodiment, the Ru group comprises from 20 to 400 carbon atoms.

Preferably, according to this particular embodiment, the Ru group consists of a chain of structural units derived from a mixture of monomers comprising isobutene monomers and up to 20% by weight, relative to the total weight of monomers, n-butene.

The fuel additive composition according to the invention may advantageously comprise from 5 to 99% by weight, preferably from 10 to 80% by weight, more preferably from 25 to 70% by weight of group-substituted amine compound. polyalkenyl (b) based on the total weight of the additive composition.

Advantageously, in the fuel additive composition according to the invention, the mass ratio between the copolymer (s) (a) and the amine compound (s) substituted by a polyalkenyl group (b) described above. is from 5: 95 to 95: 5, preferably from 10: 90-90: 10.

The carrier oil (c)

According to a particular embodiment, the fuel additive composition as described above is used in combination with at least one carrier oil (c), also called carrier fluid, induction adjuvant or fluidizer.

According to a first variant, the fuel additive composition according to the invention comprises at least one carrier oil (c), preferably solubilized in a carrier oil (c).

According to a second variant, the carrier oil (c) and the fuel additive composition as defined above are provided separately.

Examples of suitable carrier oils are described in US 2009/0071065 in paragraphs [0038] to § [0053].

Thus, by way of examples of carrier oils, mention may be made of: liquid oligomers of poly-α-olefins; liquid hydrocarbons of polyalkenes, especially polypropylene, polybutene and polyisobutene and their derivatives; liquid hydrocarbons of hydrotreated polyalkenes, especially hydrotreated polypropylene, hydrotreated polybutene, hydrotreated polyisobutene and their derivatives; mineral oils; poly (oxyalkylene) type liquid compounds; liquid alcohols and polyols; liquid esters, their derivatives and their mixtures.

Preferably, the carrier oil is chosen from:

(1) a mineral oil or a mixture of mineral oils, preferably having a viscosity number, determined according to ASTM D2270, less than 120,

(2) a poly-α-olefin (PAO) or a mixture of poly-α-olefins, preferably having a weight average molecular weight of from 500 to 1500 g. mol ¹ ,

(3) a polyether or a mixture of polyethers, and especially poly (oxyalkylene) compounds, preferably having a weight average molecular weight of 500 to 1500 g. mol ¹ ,

(4) one or more liquid polyalkylenes, and

(5) their mixtures. When the carrier oil is chosen from mineral oils, it is preferably selected from paraffinic oils, naphthenic oils, asphaltic oils and mixtures thereof.

Preferably, the mineral oil is chosen from hydrotreated oils.

When the carrier oil is selected from poly-α-olefins, it is preferably selected from hydrotreated poly-α-olefins and non-hydrolyzed poly-α-olefins.

More preferably, the poly-α-olefins are chosen from trimers, tetramers or even pentamers of α-olefinic monomers, said α-olefinic monomers each comprising from 6 to 12 carbon atoms.

When the carrier oil is selected from polyethers, it is preferably selected from poly (oxyalkylene).

More preferably, the poly (oxyalkylenes) have a weight average molecular weight ranging from 500 to 1500 g. mol ¹ .

As an example of a polyether, there may be mentioned hydrocarbyl-terminated poly (oxyalkylene) mono-alcohols.

By way of example of poly (oxyalkylene) compounds, mention may be made especially of mono-alcohols and mixtures of poly (oxyalkylene) mono-alcohols substituted with an alkyl group. In the undiluted state, these compounds are in the form of a liquid soluble in gasoline and have a viscosity of at least 70 cSt at 40 ° C and at least 13 cSt at 100 ° C. These compounds include in particular the monols formed by the propoxylation of one or more alkanols each comprising at least 8 carbon atoms, preferably from 10 to 18 carbon atoms.

Preferably, the poly (oxyalkylene) type carrier oils have an undiluted viscosity, determined according to ASTM D445, of at least 60 cSt at 40 ° C., more preferably at least 70 cSt, and at least 11 cSt at 100 ° C, more preferably at least 13 cSt.

Preferably, the poly (oxyalkylene) type carrier oils have an undiluted viscosity of at most 400 cSt at 40 ° C., more preferably at most 300 cSt, and not more than 50 cSt at 100 ° C., more preferably not more than 40 cSt.

Among the poly (oxyalkylene) s, there may be mentioned poly (oxyalkylene) glycols and their monoether type derivatives, especially those meeting the viscosity requirements. described above. This includes in particular compounds obtained or obtainable by the reaction between an alcohol or polyalcohol and an alkylene oxide, such as for example propylene oxide and / or butylene oxide, with or without the use of of ethylene oxide. Typically, at least 80 mole percent of the oxyalkylene groups present in these compounds are derived or derivable from 1,2-propylene groups.

Examples of poly (oxyalkylene) compounds also include those described in and / or obtained or obtainable by carrying out the methods described in US 2,425,845, US 2,425,755 and US 2,457,139.

Poly (oxyalkylene) bearing oils must contain sufficient branched oxyalkylene units, for example methyldimethyleneoxy and / or ethyldimethyleneoxy units, so that the latter is sufficiently soluble in the fuel.

When the carrier oil is selected from polyalkylenes, it is preferably selected from polypropenes, polybutenes, polyisobutenes, polyamylenes, copolymers of propene and butene, butene and isobutene copolymers, copolymers of propene and isobutene and copolymers of propene, butene and isobutene and mixtures thereof.

As examples of polyalkylene, there may be mentioned hydrotreated polypropylenes, hydrotreated polybutenes, hydrotreated polyisobutenes and their derivatives.

Preferably, the polybutenes have a narrow molecular weight distribution, for example expressed as the ratio Mw on Mn, Mw denoting the weight average molecular weight of polybutene and Mn denoting the number average molecular weight of polybutene. This ratio is sometimes referred to as polydispersity index of polybutene.

Preferably, the ratio Mw to Mn of the polybutenes is at most 1, 4, Mw denoting the weight average molecular weight of the polybutene and Mn denoting the number average molecular weight of the polybutene.

By way of example, mention may be made of the polybutenes described in US Pat. No. 6,048,373.

Methods for determining the mass average molecular weight include static light scattering, small angle neutron scattering, diffusion of X-rays and sedimentation rate. The number average molecular weight (Mn) can be determined by Gel Permeation Chromatography (GPC).

Preferably, the carrier oil is chosen from polyethers, more preferably from poly (oxyalkylene) s.

Advantageously, in the additive composition according to the invention, the ratio between the mass of carrier oil (c) and the total mass of detergent additives present in the additive composition ranges from 0.4 to 2, preferably from 0.6 to 1, 4.

Included in the category of detergent additives are both the copolymer (s) and the amine (s) substituted by a polyalkenyl group (b) defined above, but also all the other optional detergent additives which may be added and such as defined in the application below.

Preferably, the ratio between the carrier oil mass (c) and the sum of the copolymer (s) (a) and polyalkenyl group-substituted amine compound (s) masses described above is from 0 , 1 to 2, preferably from 0.3 to 1, 2, more preferably from 0.4 to 0.8.

According to an alternative embodiment, the additive composition according to the invention is devoid of carrier oil.

uses

The fuel additive composition described above is particularly advantageous when used as a detergent additive in a spark ignition engine fuel or a compression ignition gasoline engine (GCI engine).

By detergent additive liquid fuel is meant an additive which is incorporated in a small amount in the liquid fuel and has an effect on the cleanliness of said engine compared to said non-additive liquid fuel.

The liquid fuel is advantageously derived from one or more sources selected from the group consisting of mineral, animal, vegetable and synthetic sources. Oil will preferably be chosen as a mineral source.

The liquid fuel is preferably chosen from hydrocarbon fuels and non-essentially hydrocarbon fuels, alone or as a mixture. Hydrocarbon fuel is a fuel consisting of one or more compounds consisting solely of carbon and hydrogen.

The term "non-substantially hydrocarbon fuel" is understood to mean a fuel consisting of one or more compounds consisting essentially of carbon and hydrogen, that is to say which also contain other atoms, in particular oxygen atoms.

The hydrocarbon fuels include in particular medium distillates boiling temperature ranging from 100 ° C to 500 ° C or lighter distillates having a boiling point in the range of gasolines. These distillates may, for example, be chosen from distillates obtained by direct distillation of crude hydrocarbons, vacuum distillates, hydrotreated distillates, distillates obtained from catalytic cracking and / or hydrocracking of vacuum distillates, distillates resulting from ARDS type conversion processes (in English "atmospheric residue desulphurization") and / or visbreaking, the distillates from the valuation of Fischer Tropsch cuts. There may also be mentioned hydrocarbon fuels resulting from the conversion BTL (in English "biomass to liquid"), available especially from the company EKOBENZ. Hydrocarbon fuels are typically gasolines.

Advantageously, the hydrocarbon fuel is chosen from gasolines.

The gasolines include, in particular, any commercially available spark ignition engine or GCI engine fuel compositions. As a representative example, mention may be made of species that comply with the NF EN 228 standard. The essences generally have octane numbers that are sufficiently high to prevent the phenomenon of knocking. Typically, gasoline fuels marketed in Europe, compliant with the NF EN 228 standard, have a motor octane number (MON) of greater than 85 and a research octane number (RON in English). Research Octane Number ") of a minimum of 95. Gasoline fuels generally have an RON of 90 to 100 and a MON of 80 to 90, with RON and MON being measured according to ASTM D 2699- 86 or D 2700-86.

Non-essentially hydrocarbon fuels include oxygenates, for example bioethanols resulting from BTL (biomass to liquid) conversion of plant and / or animal biomass, in particular the conversion of sugars and / or lignocellulose from biomass or even biofuels, consisting of example of ether compounds such as methyl-tert-butyl-ether (MTBE), ethyl-tert-butyl ether (ETBE) or diisopropyl ether or DIPE (in English "diisopropyl ether").

Mixtures of hydrocarbon fuel and non-essentially hydrocarbon fuel are typically E _x type gasolines.

Gasoline type E _x for a spark ignition engine or GCI engine means a petrol fuel which contains x% (v / v) oxygenates, usually ethanol, bioethanol, methyl tertiary butyl ether (MTBE) and / or ethyl tertiary butyl ether (ETBE).

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 less than 10 ppm and advantageously without sulfur.

The fuel additive composition described above is used in the liquid fuel at a content, preferably at least 10 ppm, preferably at least 50 ppm, more preferably at a level of 10 to 5000 ppm, still more preferably from 10 to 1000 ppm.

According to a particular embodiment, the use of a fuel additive composition as described previously in the liquid fuel makes it possible to maintain the cleanliness of at least one of the internal parts of the spark ignition engine or the GCI engine and / or cleaning at least one of the internal parts of the spark ignition engine or the GCI engine.

The use of the fuel additive composition according to the invention 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 to reduce the deposits existing in at least one of the internal parts of said engine ("clean-up" effect).

Thus, the use of the fuel additive composition according to the invention in the liquid fuel makes it possible, in comparison with the liquid fuel with no particular additive, to limit or avoid the formation of deposits in at least one of the internal parts of said engine or of reduce the deposits existing in at least one of the internal parts of said engine. Advantageously, the use of the fuel additive composition according to the invention in the liquid fuel makes it possible to observe both the effects, limitation (or prevention) and reduction of deposits (keep-clean and clean-up ").

Deposits are distinguished according to the type of spark ignition engine or GCI engine and the location of deposits in the internal parts of said engine.

The targeted deposits are located in at least one of the internal parts of said spark ignition engine or GCI engine. The internal part of the spark-ignition engine or GCI engine kept clean (keep-clean) and / or cleaned (clean-up) is advantageously chosen from the intake system of the engine, in particular the intake valves ( IVD in English "Intake Valve Deposit"), the combustion chamber (CCD in English "Total Chamber Deposit" or TCD) and the fuel injection system, in particular the injectors of a system indirect injection (Port Fuel Injector) or the injectors of a direct injection system (DISI).

According to a first embodiment, the spark ignition engine or the GCI engine is a direct injection injection engine (DISI). The use of the fuel additive composition according to the invention in a spark-ignition engine or in a direct injection GCI engine makes it possible to limit or avoid the formation at high temperature of deposits in at least one of the internal parts of said motor or reduce existing deposits in at least one of the internal parts of said engine. Preferably, according to this first embodiment, the targeted deposits are located at the level of the injectors (GDI in English "Gasoline Direct Injector").

According to a second embodiment, the spark ignition engine or the GCI engine is an indirect injection engine.

The use of the fuel additive composition according to the invention in a spark-ignition engine or in a GCI engine with indirect injection then makes it possible to limit or avoid the formation at high temperature of deposits in at least one of the internal parts. said engine or reduce the existing deposits in at least one of the internal parts of said engine.

Preferably, according to this second embodiment, the targeted deposits are located at the level of the Intake Valve Deposit (IVD).

The use of the fuel additive composition according to the invention in an engine with Ignition controlled or in a GCI engine, indirect injection also prevents and / or prevent and / or limit and / or retard the formation of deposits, especially at low temperatures, at the intake valves.

More particularly, the use of the additive composition according to the invention in a spark-ignition engine or in a GCI engine with indirect injection makes it possible to prevent and / or prevent and / or limit and / or delay the sticking phenomenon. valves (in English "Valve Sticking").

The deposits may consist of deposits related to the phenomenon of coking ("coking" in English) and / or deposits soap and / or varnish (in English "lacquering").

Advantageously, the use of the fuel additive composition as described above makes it possible, in comparison with the liquid fuel with no particular additive, to limit or avoid the formation of deposits on at least one type of deposits described above and / or reduce existing deposits on at least one type of deposits described above.

According to a particular embodiment, the use of the fuel additive composition described above also makes it possible to reduce the fuel consumption of the spark ignition engine or the GCI engine.

According to another particular embodiment, the use of the fuel additive composition described above also makes it possible to reduce pollutant emissions, in particular the particulate emissions of the spark ignition engine or the GCI engine.

Advantageously, the use of the fuel additive composition according to the invention makes it possible to reduce both the fuel consumption and the pollutant emissions.

The fuel additive composition described above may be used alone or in admixture with other additives in the form of an additive concentrate.

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

According to one embodiment, the fuel additive composition described above is used in admixture with an organic liquid in the form of a concentrate.

According to a particular embodiment, a fuel concentrate comprises one or more copolymers (a), one or more amines substituted by a polyalkenyl group (b) and optionally one or more carrier oils (c), as described above, in admixture with an organic liquid.

The organic liquid is inert with respect to the copolymer (a), the amine (s) substituted by a polyalkenyl group (b) and the optional carrier oil (s) (c) described above and miscible with the fuel. liquid described above. The term "miscible" means that the copolymer (a), the amine substituted with a polyalkenyl group (b), optionally the carrier oil (c), and the organic liquid form a solution or a dispersion so as to facilitate mixing. of the fuel additive composition according to the invention in liquid fuels according to conventional fuel additive processes.

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 in mixture.

The concentrate may advantageously comprise from 5 to 99% by weight, preferably from 10 to 80%, more preferably from 25 to 70% of copolymer (a) as described above.

The concentrate may typically comprise from 1 to 95% by weight, preferably from 10 to 70%, more preferably from 25 to 60% of organic liquid, the remainder corresponding to copolymer (a), amine substituted by a grouping. polyalkenyl (b) and optionally carrier oil (c), it being understood that the concentrate may comprise one or more copolymers (a), one or more amines substituted by a polyalkenyl group (b) and optionally one or more carrier oils ( c) as described above.

In general, the solubility of the copolymer in the organic liquids and liquid fuels described above will depend in particular on the average molar masses by weight and by number, respectively M _w and M _n of the copolymer. The average molar masses M _w and M _n of the copolymer according to the invention 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 according to the invention can also have an influence on the effectiveness of the fuel additive composition according to the invention as a detergent additive. The average molar masses M _w and M _n will thus be chosen so as to optimize the effect of the copolymer according to the invention, in particular the detergency effect (engine cleanliness) in the liquid fuels described above.

The 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 (a) has a weight average molecular weight (M _w ) ranging from 500 to 30,000 g. mol ¹ , preferably from 1000 to 10,000 g. mol ¹ , more preferably less than 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 less than or equal to 4000 g. mol ¹ . The number and weight average molar masses are measured by Size Exclusion Chromatography (SEC). The operating conditions of the SEC, in particular, the choice of the solvent will be chosen according to the chemical functions present within the block copolymer.

According to a particular embodiment, the fuel additive composition according to the invention is used in the form of an additive concentrate in combination with at least one other spark-ignition engine fuel additive or a GCI engine other than copolymer (a), amine substituted with a polyalkenyl group (b) and any carrier oil (c), described above.

The additive concentrate may typically comprise one or more other additives selected from detergent additives different from the copolymer (a) and amine substituted by a polyalkenyl group (b) described above, among the anti-corrosion agents. , dispersants, demulsifiers, biocides, deodorants, friction modifiers, lubricity additives or lubricity additives, combustion assistants (catalytic combustion promoters and soot), anti-corrosion agents, sedimentation, anti-wear agents and conductivity modifiers.

Among these additives, mention may be made in particular of:

a) lubricity additives or anti-wear agents, in particular (but not exclusively) chosen from the group consisting of fatty acids and their ester or amide derivatives, in particular glycerol monooleate, and mono- and polycyclic carboxylic acid derivatives. Examples of such additives are given in the following documents: EP 680506, EP 860494, WO 98/04656, EP 915944, FR 2772783, FR 2772784.

b) detergent additives including (but not limited to) selected from the group consisting of succinimides, polyetheramines, Mannich bases and quaternary ammonium salts; for example those described in US 4, 171, 959 and WO 2006/135881.

These other additives are generally added in an amount ranging from 10 to 1000 ppm (each), preferably from 100 to 1000 ppm.

The molar and / or mass ratio between the monomer (m _b ) and the monomer (m _a ) in the copolymer described above and / or between the blocks A and B when the copolymer is in blocks will be chosen so that the copolymer is soluble in the fuel and / or the organic liquid of the concentrate for which it is intended. Likewise, this ratio can be optimized according to the fuel and / or the organic liquid so as to obtain the best effect on engine cleanliness.

The optimization of the molar and / or mass ratio can be carried out by routine tests accessible to those skilled in the art.

According to a particular embodiment, the molar ratio between the monomer (m _a ) and the monomer (m _b ), or between the blocks A and B in molar percentage is preferably between 95: 5 and 50:50, more preferably between 90:10 and 75:25, still more preferably between 85:15 and 70:30.

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 fuel additive composition as described above.

According to a particular embodiment, a fuel composition comprises:

(1) a fuel as described above, and

(2) a fuel additive composition as described above.

The fuel (1) is, in particular, chosen from hydrocarbon fuels and non-essentially hydrocarbon fuels previously described, taken alone or in mixed.

The introduction, and in particular combustion, of this fuel composition comprising such a fuel additive composition in a spark ignition engine or in a GCI engine has an effect on the cleanliness of the engine compared to the liquid fuel not specially additive. The introduction, and especially the combustion, of this fuel composition makes it possible, in particular, to prevent and / or reduce the fouling of the internal parts of said engine. These effects on the cleanliness of the engine are as previously described in the context of the use of the fuel additive composition according to the invention.

According to a particular embodiment, the introduction, and in particular combustion, of the fuel composition comprising such additive composition in a spark-ignition engine or in a GCI engine also makes it possible to reduce the fuel consumption and / or pollutant emissions.

The fuel additive composition according to the invention is preferably incorporated in a small amount in the liquid fuel described above, the amount of additive composition being sufficient to produce a detergent effect as described above and thereby improve the cleanliness of the engine.

According to one particular embodiment, the fuel composition comprises at least 1 ppm, preferably from 10 to 5 000 ppm, more preferably from 20 to 2000 ppm, in particular from 50 to 500 ppm of copolymer (s) (a), by weight. relative to the total mass of the fuel composition.

According to an advantageous embodiment, the fuel composition comprises from 1 to 1000 ppm, preferably from 5 to 500 ppm, more preferably from 10 to 200 ppm, and still more preferably from 20 to 100 ppm of copolymer (s) ( a), in mass relative to the total mass of the fuel composition.

The fuel composition advantageously comprises from 1 to 1000 ppm of amine substituted with an alkenyl group (b), by weight relative to the total weight of the fuel composition, preferably from 5 to 500 ppm, more preferably from 50 to 500 ppm, even more preferably from 100 to 300 ppm.

According to a preferred embodiment, the fuel composition further comprises at least one less carrier oil (c).

Preferably, according to this embodiment, the fuel composition comprises at least 10 ppm of carrier oil (c), by weight relative to the total weight of the fuel composition, preferably at least 20 ppm.

More preferably, according to this embodiment, the fuel composition comprises from 10 to 1000 ppm of carrier oil (c), the contents being expressed by weight relative to the total mass of the fuel composition, preferably from 20 to 500 ppm, more preferably 50 to 300 ppm.

According to a second alternative embodiment, the fuel composition is devoid of carrier oil.

In addition to the fuel additive composition described above, the fuel composition may also comprise one or more other additives different from the copolymer (a), the amine substituted with a polyalkenyl group (b) and the optional oil. carrier (c) present in the fuel additive composition according to the invention. These additives are chosen in particular from other known detergent additives, for example from anti-corrosion agents, dispersants, demulsifiers, biocides, deodorants, friction modifiers, lubricity additives or lubricity additives, agents and the like. combustion aids (catalytic combustion promoters and soot), anti-sedimentation agents, anti-wear agents and / or conductivity modifiers.

The additives different from the copolymer (a), the amine substituted with a polyalkenyl group (b) and the carrier oil (c) present in the fuel additive composition according to the invention are, for example, the additives for fuel listed above.

According to a particular embodiment, a method of keeping clean (keep-clean) and / or cleaning (clean-up) of at least one of the internal parts of a spark ignition engine or a GCI engine comprises preparing a fuel composition by adding a fuel with a fuel additive composition as described above and introducing, and in particular burning, said fuel composition into the spark ignition engine or in the GCI engine.

The inner part kept clean and / or cleaned of the spark ignition engine or GCI engine is preferably selected 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 (IFP) or the injectors of a direct injection system (DISI).

The keep-clean and / or clean-up method comprises the successive steps of:

a) determining the additive most suitable for the fuel, said additive corresponding to the selection of the fuel additive composition described above to be incorporated in combination, optionally, with other fuel additives as described above and determining 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 selected fuel additive composition at the rate determined in step a) and, optionally, the other fuel additives.

The selection of the fuel additive composition corresponds more particularly to the selection on the one hand of one or more copolymers (a) as described above, on the other hand of one or more amines substituted by a polyalkenyl group. (b) as previously described, and optionally of one or more carrier oils defined above, for preparing a fuel additive composition according to the invention.

The copolymer (s) (a), the amine (s) substituted with a polyalkenyl group (b) and the optional carrier oil (s) (c) may be incorporated in the fuel, alone or as a mixture, successively or simultaneously.

Alternatively, the fuel additive composition may be used in the form of a concentrate or an additive concentrate as described above.

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

The representative characteristic of the fuel's detergency properties will depend on the type of engine, for example by positive ignition or compression ignition (GCI engine), the type of direct or indirect fuel injection system and the location in the engine of the targeted deposits. for cleaning and / or maintaining cleanliness.

The representative characteristic of the detergency properties may for example correspond to the appearance of deposits inside or on the external parts of the injector.

Methods for evaluating the detergent properties of fuels have been widely described in the literature and are subject to general knowledge of those skilled in the art. By way of non-limiting example, the tests standardized or recognized by the profession or the methods described in the following literature are:

For indirect injection controlled ignition engines:

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

- the Mercedes Benz M 1 1 1 method, standardized test method CEC F-20-A-98.

These methods make it possible to measure the deposits on the intake valves (IVD) and in the combustion chambers (CCD), the tests being generally carried out on a Eurosuper gasoline meeting the EN228 standard.

For direct injection spark ignition engines:

- the method described by the plaintiff 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.

the method described in the document US20130104826, for the evaluation of coking deposits on the injector, this method being cited as an example.

the so-called "VW DISI" method described in the article "Characterization of Gasoline Fuels in a DISI Engine", D. Weissenberger, J. Pibeam; 1 1 th international colloquium; June 27-27, 2017, p.97 (Technische Akademie Esslingen by Techn Akad, Esslingen, Ostfildern), for the evaluation of coking deposits on the injector, this method being cited as an example. A European standard for evaluating coking deposits on the injector is currently being developed on the basis of this method.

In order to evaluate the safety of a fuel vis-à-vis the appearance of the sticking phenomenon of the valves indirect injection ("valve sticking"), that is to say the ability of it to preventing and / or preventing and / or limiting and / or delaying the formation, in particular at low temperature, of deposits at the intake valves, it is possible to evaluate the quality of the sealing of the chamber valve (s). combustion, for example by performing compression measurements.

By way of non-limiting example, the test method described in the CEC standard F- 16-T-96.

The determination of the amount of copolymer (a), the amount of amine substituted by a polyalkenyl group (b), and the possible amount of carrier oil (c) to be added to the fuel composition to meet the specification will be typically performed by comparison with the fuel composition but without the copolymer (a), without the amine substituted with a polyalkenyl group (b) and without the carrier oil (c).

The determination of the amount of fuel additive composition to be added to the fuel composition to achieve the specification (step a) described above) will typically be performed by comparison with the fuel composition but without the copolymer (a), without the fuel composition. amine substituted with a polyalkenyl group (b) and without the carrier oil (c) present in the fuel additive composition according to the invention, the specification given for the detergency may for example be a target fouling value intake valve (IVD) according to method M102E or a drift value injection time or loss of injector flow according to the so-called "VW DISI" method mentioned above.

The amount of copolymer (a), amine substituted by a polyalkenyl group (b) and carrier oil (c) may also vary depending on the nature and origin of the fuel, in particular depending on the rate n-alkyl, iso-alkyl or n-alkenyl substituted compounds. Thus, the nature and origin of the fuel may also be a factor to consider for step a).

The keep-clean and / or clean-up method may also include an additional step after step b) of checking the target reached and / or adjusting the rate of additivation with the additive composition as a detergent additive.

The fuel additive composition according to the invention has remarkable properties as a detergent additive in a liquid fuel, particularly in a petrol fuel.

The fuel additive composition according to the invention is particularly remarkable in particular because it is effective as a detergent additive for a wide range of liquid fuel and / or for one or more types of engine and / or against one or more types of fuel. deposit that form in the internal parts of ignition engines ordered or GCI engine.

In particular, the fuel additive composition according to the invention is particularly effective in spark ignition engines or GCI engines, with direct injection to clean and limit the formation of deposits at the injectors but also in the ignition engines controlled or in GCI engines, with indirect injection to clean and limit the formation of deposits in the intake valves, thus avoiding engine damage.

The invention is illustrated by the following examples given without limitation.

EXAMPLES

1. Synthesis of a block copolymer from 2-ethylhexyl acrylate (EHA) and 2-dimethylaminoethyl acrylate (ADAME) and quaternization with 1,2-epoxybutane

The copolymer is obtained by radical polymerization by reversible addition-fragmentation chain transfer (RAFT) according to the following protocol.

A- Hardware

Reaction products:

Polymerization initiator: α, α'-azoisobutyronitrile, AIBN (CAS 78-67-1),

- RAFT transfer agent: 2-cyano-2-propyl dodecyl trithiocarbonate> 97%, CPDTTC (CAS 870196-83-1),

For obtaining the A - monomers block (m _a ):

2-ethylhexyl acrylate 98%, EHA (CAS 103-11-7),

For obtaining the B - monomers block (m _b ):

2-dimethylaminoethyl acrylate 98%, ADAME (CAS 2439-35-2)

Quaternarization agent:

99% 1,2-epoxybutane (CAS 106-88-7).

B- Devices

The different devices used for the characterization of the copolymer are described below. in high or HPLC in

"Hiqh pressure liouid chromatoqraphy"):

The chromatograph used is an UltiMate 300 HPLC marketed by Thermo Fischer.

The stationary phase is a column of Symmetry Shield RP 18 type.

The mobile phase consists of:

a water / methanol mixture at a ratio by volume 95/5, added with methanolic acid CH ₂ 0 ₂ (CAS 64-18-6) so as to fix the pH of the mixture at 5, or

of methanol additive with methanoic acid so as to fix the pH of the mixture at 5.

The flow rate of the mobile phase is equal to 1 mL / min. The temperature of the oven is recorded at 40 ° C. The injection volume is 5 μL. The products are detected via a diode array detector.

Nuclear magnetic resonance spectroscopy or NMR:

The ¹ H and ¹³ C NMR spectroscopy analyzes are carried out in deuterated chloroform CDCl ₃ with a BRUKER Avance III 400 MHz NMR spectrometer ( ¹ H Larmor frequency) operating under TopSpin 3.2: ¹³ C SEXI Omm probe with pulsed magnetic field gradient z and lock ² H operating at 300K and probe ¹ H BBI 5mm with pulsed magnetic field gradient z and lock ² H operating at 300K. For measurements, an external standard (1,2,4,5-tetrachloro-3-nitrobenzene or TCNB) is used.

Gel permeation chromatography (GPC in English for "gel permeation cnromatoqrapny"):

The GPC analyzes are carried out in THF (tetrahydrofuran) using a WATERS Styragel type column operating at a temperature of 40 ° C. and at a pressure equal to 645 psi and equipped with an RI (refractive index) detector.

The flow rate of THF is equal to 1 mL / min.

In a typical analysis, 100 μl of 0.5% m / m sample previously filtered on a 0.45 μm millipore filter are injected into the column.

The number average molar masses (M _n ) are determined from calibration curves constructed from PMMA standards (poly (methyl methacrylate)).

C-Copolymerization - Obtaining an EHA / ADAME Block Copolymer

Step 1 - Synthesis of Block A (EHA):

30.0 g (163.0 mmol) of 2-ethylhexyl acrylate (EHA), 0.94 g (2.72 mmol) of 2-cyano-2-propyl dodecyltrithiocarbonate (CPDTTC) and 35 ml of toluene are introduced into a 250 ml balloon. 44.3 mg (0.27 mmol) of AIBN are weighed in a 20 ml flask and then solubilized in 4 ml of toluene. Both solutions are degassed with nitrogen for 30 minutes. The solution containing the EHA monomer is heated to 70 ° C. When the temperature is reached, the AIBN solution is added to the EHA / CPDTTC mixture by means of a syringe previously purged with nitrogen. The reaction medium is stirred for 24 h at 70 ° C. under an inert atmosphere (N ₂ ).

250 μl of the reaction mixture are taken at t ₀ (just after the addition of GAIBN) and at t _f (after 24h stirring) and are analyzed by HPLC to measure the content of residual monomers EHA present in the medium, before and after reaction. The ratio of the peak areas relative to the monomer EHA allows the determination of the conversion rate of the monomers EHA. In this case, the conversion rate of the monomers EHA is equal to 98%.

Step 2 - Synthesis of Block B (ADAME):

3.89 g (27.0 mmol) of 2- (dimethylamino) ethyl acrylate (ADAME) are weighed in a 50 ml flask. 11 ml of toluene are added. On the other hand, 44.3 mg (0.27 mmol) of AIBN are weighed in a 20 ml flask and then solubilized in 3 ml of toluene. Both solutions are degassed with nitrogen for 30 minutes. The ADAME solution is then added, by means of a syringe previously purged with nitrogen, to the mixture obtained at the end of step 1 and maintained at 70 ° C. The AIBN solution is finally added to the reaction medium also by means of a syringe previously purged with nitrogen. The reaction medium is stirred for 24 h at 70 ° C. under an inert atmosphere (N ₂ ).

250 μl of the reaction mixture are taken at t ₀ (just after the addition of GAIBN) and at t _f (after stirring for 24 h) and are analyzed by HPLC in order to measure the content of residual ADAME monomers present in the medium, before and after reaction. The ratio of the peak areas relative to the ADAME monomer makes it possible to determine an ADAME monomer conversion rate equal to 97%.

The residual monomer levels of EHA and ADAME are determined by ¹ H NMR spectroscopy and the relative composition of the copolymer (EHA / ADAME molar ratio) and the number of EHA and ADAME units by ¹³ C NMR.

For the determination of residual monomer levels, the following are detected:

- for ADAME residual monomers, a main series of signals obtained for chemical shift values equal to 6.43 ppm, 6.15 ppm and 5.82 ppm (AMX system). The assignment of these signals to ADAME monomers is confirmed by observation two triplets of comparable intensity obtained for chemical shift values equal to 4.3 ppm and 2.7 ppm and linked to the groups -OCH ₂ and -NCH ₂ of the residual monomer ADAME,

for the residual monomers EHA, three low intensity ethylenic signals obtained for chemical shift values equal to 6.39 ppm, 6.13 ppm and 5.80 ppm.

Using the integral of the singlet related BNCT (7.7 ppm) as a reference unit, and considering the molecular weights of the compounds involved (184, 143, and 261 g. Mol ¹ EHA, DMAEA and BNCT), the rate of Residual EHA is 0.1% by mass and the residual ADAME rate is 0.5% by mass.

For the determination of the relative composition (EHA / ADAME molar ratio), the signal obtained at 22.8 ppm attributed to the CH ₃ CH ₂ grouping of the RAFT terminal group is used. By setting its integral to 1, an integral of 0.95 is obtained for the broad signal obtained at 180.6 ppm and bound to the -COOH group of the RAFT agent. An integral of 3.35 is also measured for the ¹³ C NMR signal of the C = H group of the TCNB. With this same reference we obtain average integrals (corrected for the presence of residual monomers) equal to 62 for EHA and 10 for ADAME corresponding to the number of units (molar ratio EHA / ADAME 86/14).

Finally, the molar masses in number M _n and in mass M _w , as well as the index of dispersity, which reflects the dispersity in size D (D = MJM _n ), are determined by GPC:

M _n = 13800 g / mol; M _w = 15900 g / mol; D = 1, 15.

D- Quaternarization - Obtaining a block copolymer EHA / q-ADAME

To the reaction medium obtained at the end of step 2 above are added successively:

46 ml of n-butanol,

7.79 g (108 mmol) of 1,2-epoxybutane, and

- 6.48 g (108 mmol) of acetic acid.

The reaction medium is stirred 24h at 60 ° C. After returning to ambient temperature, the solvent is evaporated to dryness.

The block copolymer EHA / q-ADAME is obtained.

The degree of quaternarization of the copolymer obtained is determined by ¹³ C NMR. The mass obtained around 70 ppm is assigned to CH ₂ of the -CH ₂ CHOHCH ₂ CH _{3 group} located in the alpha position relative to the quaternized nitrogen atom. On the basis of the molar proportion EHA / ADAME (86/14) determined above, and comparing the integral of this solid to the integral of the characteristic signals of the carbons linked to the EHA units, a quaternarization rate equal to 95% is determined.

2. Preparation of different fuel compositions

A - Material

• Additive A: additive A is a monoamine substituted by a polyisobutylene group of molecular weight Mn = 1000 g / mol and whose polydispersity index (Mw / Mn) is equal to 1, 6. This compound is commercially available from BASF under the commercial reference Kerocom® PIBA-03,

• HP carrier oil: HP carrier oil is a polyether polymer consisting mainly of aliphatic hydrocarbon compounds and propylene oxide. This carrier oil is commercially available from CHEVRON ORONITE under the trade name OLOA 2509H.

• Fuel :

- The C1 fuel is a RON 98 premium unleaded premium gasoline fuel containing 15% v / v of ETBE (ethyl tertiobutyl ether) and meeting the EN228 standard.

The C1 fuel is commercially available from the company TOTAL under the commercial brand Supercarburant SP98 E5.

C1 fuel is a fuel conventionally used in European countries in which the climatic conditions favor the appearance of low temperature deposits likely to cause the sticking of the valves. It is therefore a reference fuel for valve sticking tests.

- The C2 fuel is a CEC type RF12-09 gasoline fuel available commercially from Halterman.

C2 fuel is a fuel known to those skilled in the art to lead to the formation of high temperature deposits. It is therefore a reference fuel for detergency tests carried out in the context of high temperature deposits.

B - Compositions

The C11 to C14 fuel compositions, defined in the following Table 1, are prepared by additivation of the virgin gasoline fuel C1.

The fuel compositions C21 to C24, defined in the following Table 1, are prepared by additivation of the virgin gasoline fuel C2.

In the following Table 1, the contents are given in ppm by weight relative to the total mass of the fuel compositions obtained. Table 1

¹ EHA / q-ADAME block copolymer synthesized above

3. Evaluation of the ability of fuel compositions to cause sticking of the valves ("valve stickinq").

The ability of the fuel compositions C1 and C11 to C14 to cause the bonding of the valves of an indirect injection engine is evaluated according to CEC standard F16-96 (+ 5 ° C). The measurement is repeated 3 times. The results obtained for the bonding test of the valves are summarized in the following Table 2.

The mention "1" indicates that no sticking phenomenon of the valves was observed during the 3 tests carried out.

"0" indicates that valve bonding was observed in at least one test. Table 2

No sticking phenomenon of the valves is observed with the virgin fuel (composition C1).

No sticking phenomenon of the valves is observed during the tests carried out with the fuel composition additive with the copolymer obtained previously and the carrier oil HP (composition C12).

Conversely, the operation of the engine with the fuel composition additive with the additive A and the carrier oil HP results in bonding of the engine valves (composition C11).

No phenomenon of sticking of the valves is observed during the tests carried out from the fuel composition additive with both the copolymer synthesized above, the additive A and the carrier oil HP (compositions C13 and C14 according to the invention).

The addition of the copolymer obtained above in a fuel composition comprising both the additive A and the HP carrier oil thus makes it possible to prevent the sticking of the valves occurring during the operation of the engine with a fuel composition that is additive only with the fuel. additive A and the carrier oil HP.

4. Evaluation of the detergent properties of fuel compositions

The detergency properties of the C2 and C21 to C24 fuel compositions are evaluated according to CEC standard F05-93.

The results of the detergency test are given in Table 3 below.

Table 3

The operation of the engine from the virgin C2 fuel composition results in the formation of 328 mg of deposits on the surface of the engine valves. Additive fuel with additive A and HP carrier oil significantly reduces the amount of deposits (composition C21: 4 mg deposits per valve). The deposition mass formed at the injectors is divided by more than 80.

Conversely, the additivation of the fuel with the copolymer prepared above and the carrier oil HP leads to a significant increase in the mass of deposits formed in the valves (composition C22: 683 mg of deposits per valve): the amount of deposits has more than doubled.

The combination of the copolymer and the carrier oil HP therefore does not have any detergent activity.

However, the joint introduction of the additive A, the copolymer obtained above and the HP carrier oil into the fuel makes it possible to significantly reduce the mass of deposits formed in the valves (compositions C23 and C24: 8 and 17 mg of respective way). The amount of deposition formed during the use of the C23 and C24 fuel compositions is reduced by more than 20-fold with respect to the non-additive C2 fuel, particularly more than 40-fold for the C23 composition.

Claims

A fuel additive composition comprising:

(a) one or more copolymer (s) comprising:

at least one unit of formula (I) below:

With

u = 0 or 1,

R 1 'is selected from hydrogen and methyl,

G represents a group selected from C ₁ -C _34, an aromatic ring, an aralkyl having at least one aromatic ring and at least one alkyl group C _r C _34, and

at least one unit of formula (II) below:

in which

R 1 is chosen from the hydrogen atom and the methyl group,

R comprises a C 1 to C ₃₄ hydrocarbon-based chain substituted with at least one quaternary ammonium group and optionally one or more hydroxyl groups, the R group possibly also containing one or more nitrogen and / or oxygen atoms and / or carbonyl groups ,

(b) one or more amines substituted with a polyalkenyl group, and

(c) at least one carrier oil.

2. fuel additive composition according to claim 1, wherein the units of formula (I) and the units of formula (II) represent at least 70 mol% of the copolymer (a), relative to the number of moles of units involved in the composition of the copolymer (a).

A fuel additive composition according to any of claims 1 and 2 wherein the copolymer is obtained by copolymerization of at least:

a monomer (m _a ) corresponding to the following formula (VII)

in which

R 1, u, E and G are as defined in claim 1, and

a monomer (m _b ) corresponding to the following formula (VIII):

in which

R 1, Q and R are as defined in claim 1.

The fuel additive composition according to any one of claims 1 to 3, wherein the copolymer (a) is a block copolymer comprising:

a block A corresponding to the following formula (XI):

in which

p is an integer ranging from 2 to 100 R 1, u, E and G are as defined in claim 1, and

a block B corresponding to the following formula (XII):

in which

n is an integer ranging from 2 to 50,

R 1, Q and R are as defined in claim 1.

The fuel additive composition according to claim 4, wherein:

block A consists of a chain of structural units derived from a (C 1 -C 3) alkyl (meth) acrylate monomer (m _a ), and

- Block B consists of a chain of structural units derived from an alkyl (meth) acrylate monomer or alkyl (meth) acrylamide (m _b ), the alkyl radical of which consists of a hydrocarbon chain C 1 to C ₃₄ substituted with at least one quaternary ammonium group and optionally one or more hydroxyl groups.

The fuel additive composition according to any one of claims 1 to

5, wherein the one or more amines substituted by a polyalkenyl group (b) are chosen from polyisobutene amines.

The fuel additive composition according to any one of claims 1 to

6, in which the mass ratio between the copolymer (s) and the amine (s) substituted with a polyalkenyl group (b) ranges from 5: 95 to 95: 5, preferably from 10: 90 to 90: 10.

The fuel additive composition according to any one of claims 1 to

7, wherein the ratio of the carrier oil mass (c) to the sum of the copolymer (a) and polyalkenyl (b) substituted amine masses is from 0.1 to 2, preferably from 0 to , 3 to 1, 2, more preferably 0.4 to 0.8.

A fuel concentrate comprising an additive composition according to any one of claims 1 to 8, in admixture with an organic liquid.

10. Fuel composition comprising:

(2) A fuel additive composition according to any one of claims 1 to 8.

The use of a fuel additive composition according to any one of claims 1 to 8 as a detergent additive in a spark ignition engine liquid fuel or in a compression-ignition gasoline engine, said fuel additive composition. fuel additives being used alone, or in the form of a concentrate as defined in claim 9.

Use according to claim 11, wherein the fuel additive composition is used in the liquid fuel for:

- maintain the cleanliness and / or cleanliness of at least one of the internal parts of the spark ignition engine or said compression-ignition gasoline engine, and / or

- reduce the fuel consumption of the positive-ignition engine or compression-ignition gasoline engine, and / or

- reduce pollutant emissions, in particular, particulate emissions from the spark ignition engine or compression-ignition gasoline engine.

13. Use according to any one of claims 1 1 and 12 in a spark ignition engine or in a direct injection fuel injection gasoline engine to maintain cleanliness and / or clean the injectors of the engine.

14. Use according to any one of claims 1 1 and 12 in a spark ignition engine or in a compression-ignition gasoline engine, indirect injection to maintain cleanliness and / or clean the intake valves of the engine.

15. Use according to claim 14, for preventing the sticking of the intake valves in a spark-ignition engine or in a gasoline engine with compression ignition, indirect injection.