Use of a fuel composition comprising three additives for cleaning the internal parts of a gasoline engine

Abstract

The present invention relates to the use of a fuel composition for reducing deposits in internal parts of a spark ignition engine, the fuel composition comprising at least three additives: a quaternary ammonium salt, a non-quaternary polyisobutylene succinimide, and a Mannich base different from the other additives. The composition is such that the mass ratio of the amount of the first additive to the amount of the second additive is in the range of 0.2:1 to 2.5:1.

Description

[0001] The present invention relates to the use of a fuel composition for reducing and / or preventing deposits in the internal parts of a spark ignition (spark ignition type) engine, the fuel composition comprising at least three additives: a quaternary ammonium salt, a non-quaternary polyisobutylene succinimide, and a Mannich base different from the other two additives. The composition is such that the mass ratio of the amount of the first additive to the amount of the second additive is in the range of 0.2:1 to 2.5:1.

[0002] The invention also relates to the use of a fuel concentrate comprising at least the three additives described in admixture with an organic liquid inert towards the additives for improving the detergency properties of a gasoline fuel.

[0003] The composition is also used to keep deposits in the engine clean (keep clean effect) and / or to clean them (cleaning effect), as well as to reduce the fuel consumption of the engine ("Fuel Eco" effect) and / or to minimize the power loss of the engine, and / or to reduce the emission of pollutants, in particular particulate matter from an internal combustion engine, and / or to reduce fouling of the pistons of the engine, preferably in gasoline direct injection (GDI) (or GDI). Background Art

[0004] Liquid fuels for internal combustion engines contain components that can degrade during engine operation. The problem of deposits in the internal components of internal combustion engines is well known to engine manufacturers. It has been shown that the formation of these deposits has an impact on engine performance and has a negative impact on fuel consumption and particulate emissions in particular (Gueit, J. et al., "Injector Fouling in Direct Injection Spark Ignition Engines-A New Test Procedure for the Evaluation of Gasoline Additives," SAE Technical Paper 2017-01-2294). Advances in fuel additive technology have made it possible to solve this problem. So-called decontamination additives for use in fuels have been provided to keep the engine clean by limiting deposits ("keep clean" effect) or by reducing deposits already present in the internal components of the internal combustion engine ("cleaning" effect). The document US4171959 can be mentioned as an example, which describes a decontamination additive for gasoline fuel containing a quaternary ammonium functional group.

[0005] However, engine technology continues to change over time, and fuel requirements must change to account for these technological advances in internal combustion engines.

[0006] In particular, new gasoline direct injection systems expose injectors to more severe pressure and temperature conditions that favor the formation of deposits.

[0007] Furthermore, these new injection systems have more complex geometries to optimize the spray, especially more holes with smaller diameters, which, on the other hand, lead to greater sensitivity to deposits. The presence of deposits can affect the combustion performance, especially in terms of increased pollutant emissions and particulate matter emissions.

[0008] Other consequences of excessive deposits have been reported in the literature, such as increased fuel consumption, and therefore particulate matter emissions, and drivability problems.

[0009] The prevention and reduction of deposits in these new engines is critical to the optimal operation of today's engines. Therefore, there is a need to provide a detergent fuel additive that promotes optimal performance of internal combustion engines, particularly for new engine technologies as well as for older / conventional engine technologies.

[0010] In the case of spark-ignition engines (or gasoline engines) with indirect injection, particular problems arise due to the formation of deposits on external components of the engine and in particular on the stems of the intake valves of the air / fuel mixture upstream of the combustion chamber, which leads to valve sticking phenomena.

[0011] This phenomenon, known to those skilled in the art as "valve sticking," is described in a reference publication by Seppo Mikkonen, Reino Karlsson and Jouni Kivi entitled "Intake Valve Stiking in Some Carburetor Engines," SAE Technical Paper Series n°881643, International Fuels and Lubricants Meeting and Exposition, Portland, Oregon, October 10-13, 1988.

[0012] This phenomenon is caused by the accumulation of high viscosity deposits at the interface between the intake valve stem and the valve guide (guide) in an indirect injection spark ignition engine during low temperature engine operation (e.g. in cold weather). The accumulation of such deposits on the valve stem impedes valve movement, the stem sticks to the valve guide, which results in poor valve closure, creates sealing problems in the combustion chamber, and can significantly affect engine operation, and in particular can prevent starting in cold weather.

[0013] Generally speaking, there are different types of deposits on the intake valves of indirect injection spark ignition engines. These types of deposits are well known to engine manufacturers, and the appearance of some of them depends on the treatment options for others.

[0014] On the one hand, the first type of deposits consists of deposits formed at high temperatures on the intake valves of indirect injection spark-ignition engines when using fuels without detergent additives. These deposits consist in particular of carbon residues associated with the coking phenomenon and may also include soap and / or varnish type ("lacquered") deposits. These deposits are usually treated by using detergent additives added to the fuel (additized fuel).

[0015] On the other hand, the second type of deposits consists of the above-mentioned sticky deposits which form at low temperatures when using additived fuels and which occur on the intake valves of indirect injection spark-ignition engines, leading to the above-mentioned valve sticking phenomenon.

[0016] Thus, fuel additives designed to treat and prevent deposits that form at high temperatures can result in sticky deposits at low temperatures.

[0017] As described in the above-mentioned publication (SAE Technical Paper Series No. 881643), the composition of gasoline and the additives it contains have a crucial influence on the valve sticking phenomenon. In particular, detergent additives, which are traditionally introduced into gasoline to keep the valves clean, have been shown, paradoxically, to promote valve sticking. In a manner known per se, when fuels without detergent additives are used, the problem of valve sticking does not occur or occurs only to a very limited extent. Furthermore, the above-mentioned publication shows that polymeric additives which may be used in gasoline and / or engine oils are known to be valve sticking promoters.

[0018] WO2006135881 describes a detergent additive containing a quaternary ammonium salt for reducing or cleaning deposits, in particular on intake valves.

[0019] The solutions provided in the prior art are not entirely satisfactory.Therefore, there is a need to provide fuel additives which promote optimal performance of spark ignition engines and which are effective in preventing all types of deposits, including deposits on intake valves.

[0020] There is also a need for a universal detergency additive which is able to act on deposits regardless of the engine technology (direct or indirect injection) and / or fuel properties while minimizing the treat rate, ie the amount of additive employed. Summary of the invention

[0021] The Applicant has found that the use of a fuel composition comprising at least three additives as described below has remarkable and unexpected detergency properties for internal combustion engines, preferably gasoline engines (known as spark-ignition engines). This combination of additives makes it possible to ensure and improve the detergency of fuels intended for use in internal combustion engines. It also produces an unexpected synergistic effect.

[0022] Further advantages of the fuel additive composition used according to the invention are:

[0023] - Protect pumps, injection systems, piston areas, rings, bushings and all moving parts that the additive comes into contact with in the engine,

[0024] - Optimal engine operation,

[0025] - Reduced fuel consumption,

[0026] - Savings due to less engine maintenance and lower fuel consumption,

[0027] - Reduced particulate matter emissions,

[0028] -Efficiency of gasoline direct and indirect injection.

[0029] One object of the present invention is therefore the use of a fuel composition for reducing and / or preventing deposits in internal components of a spark-ignition engine, said fuel composition comprising:

[0030] (1) at least one first additive consisting of a quaternary ammonium salt,

[0031] (2) at least one second additive consisting of a non-quaternary polyisobutylene succinimide,

[0032] (3) at least one third additive consisting of a Mannich base different from additives (1) and (2), and

[0033] The mass ratio of the amount of the first additive to the amount of the second additive is in the range of 0.2:1 to 2.5:1.

[0034] Preferably, the mass ratio of the amount of the first additive to the amount of the second additive in the composition is in the range of 1:1 to 2:1 and preferably 1.25:1 to 1.5:1.

[0035] Another object of the invention is also the use of said composition for keeping clean (keeping clean effect) and / or cleaning (cleaning effect) deposits in internal parts of a spark-ignition engine, said internal parts being chosen from the following: combustion chamber and fuel injection system, and preferably the fuel injection system.

[0036] Yet another object of the invention is the use of a fuel concentrate comprising at least three additives as defined above mixed with an organic liquid which is inert with respect to the first, second and third additives and which is miscible with said fuel for improving the detergency properties of a gasoline fuel.

[0037] The present invention also relates to a method for keeping clean and / or cleaning the internal parts of a spark ignition engine (or internal combustion gasoline engine), said method comprising at least the following steps:

[0038] - preparing a fuel composition by additively treating a fuel with at least three additives as defined above or a concentrate comprising them, and then

[0039] - combusting said fuel composition in said spark ignition engine.

[0040] Further objects, features, aspects and advantages of the present invention will become more apparent upon reading the following description.

[0041] In the following, and unless otherwise stated, the boundaries of a range of values ​​are included in the range, especially in the expressions “between” and “a range of ... to . . . .”

[0042] In addition, the expressions "at least one" and "at least" used in the present specification are equivalent to the expressions "one or more" and "greater than or equal to", respectively.

[0043] Finally, in a manner known per se, C N A compound or group is one that contains N carbon atoms in its chemical structure. DETAILED DESCRIPTION

[0044] First additive: quaternary ammonium salt

[0045] The composition according to the invention comprises a first additive consisting of a quaternary ammonium salt obtained in a first embodiment by reaction of a nitrogen compound comprising a tertiary amine function, which is the product of the reaction of an acylating agent substituted with a hydrocarbon group and a compound comprising at least one tertiary amine group and at least one group selected from primary amines, secondary amines and alcohols, with a quaternizing agent.

[0046] In a second embodiment, the quaternary ammonium salt is selected from quaternized PIBA (polyisobutylene amine) compounds, or from quaternized polyetheramines.

[0047] According to a first and preferred embodiment, the nitrogen compound is the reaction product of a hydrocarbon-substituted acylating agent and a compound comprising both an oxygen atom or a nitrogen atom capable of condensing with the acylating agent (i.e. the compound comprises at least one group selected from primary amines, secondary amines and alcohols) and a tertiary amine group.

[0048] The acylating agent is advantageously selected from monocarboxylic acids or polycarboxylic acids and their derivatives, in particular their ester, amide or anhydride derivatives. The acylating agent is preferably selected from succinic acid, phthalic acid and propionic acid and the corresponding anhydrides.

[0049] In this embodiment, the acylating agent is substituted with a hydrocarbon group.A "hydrocarbon" group means any group having a carbon atom directly attached to the remainder of the molecule (ie, to the acylating agent) and having predominantly aliphatic hydrocarbon character.

[0050] Hydrocarbon groups according to the present invention may also contain non-hydrocarbon groups. For example, they may contain up to one non-hydrocarbon group per ten carbon atoms, provided that the non-hydrocarbon group does not significantly change the main hydrocarbon characteristics of the group. Examples of such groups well known to those skilled in the art are hydroxyl, halogen (particularly chloro and fluoro groups), alkoxy, alkyl mercapto (alkylthio) and alkylsulfinyl (alkylsulphoxy).

[0051] In one embodiment, preferably, the hydrocarbon substituents contain no such non-hydrocarbon groups and are purely aliphatic hydrocarbons.

[0052] The hydrocarbon substituent of the acylating agent preferably contains at least 8, preferably at least 12 carbon atoms. The hydrocarbon substituent may contain up to about 200 carbon atoms.

[0053] The hydrocarbon substituent of the acylating agent preferably has a number average molecular weight (Mn) of 160 to 2800, such as 250 to 2000, more preferably 500 to 1500 and even more preferably 500 to 1300. A range of Mn values ​​between 700 and 1300 is particularly preferred, such as 700 to 1200.

[0054] Examples of hydrocarbon substituents for the acylating agent include n-octyl, n-decyl, n-dodecyl, tetrapropenyl, n-octadecyl, oleyl, octadecyl or triacontyl.

[0055] The hydrocarbon substituent of the acylating agent may also be obtained from homopolymers or interpolymers (e.g., copolymers, terpolymers) of mono- and di-olefins having 2 to 10 carbon atoms, such as ethylene, propylene, 1-butene, isobutylene, butadiene, isoprene, 1-hexene or 1-octene. Preferably, these olefins are 1-mono-olefins.

[0056] The hydrocarbon substituents of the acylating agent may also be selected from derivatives of the halogenated (eg, chlorinated or brominated) analogs of these homopolymers or interpolymers.

[0057] According to an alternative, the hydrocarbon substituent of the acylating agent may be obtained from other sources, such as high molecular weight olefin monomers (e.g., 1-tetradecene) and their chlorinated or hydrochlorinated analogs, aliphatic petroleum fractions (e.g., paraffins, their cracked, chlorinated and / or hydrochlorinated analogs), white oils, synthetic olefins (e.g., produced by the Ziegler-Natta process (e.g., polyethylene fats)), and other sources known to those skilled in the art.

[0058] Any unsaturation present in the hydrocarbon group of the acylating agent may optionally be reduced or removed by hydrogenation according to any known method.

[0059] The hydrocarbon substituent of the acylating agent is preferably substantially saturated, ie, it contains no more than one unsaturated carbon-carbon bond for every ten carbon-carbon single bonds present.

[0060] The hydrocarbon substituent of the acylating agent advantageously contains no more than one non-aromatic carbon-carbon unsaturated bond for every 50 carbon-carbon single bonds present.

[0061] According to a preferred embodiment, the hydrocarbon substituent of the acylating agent is a polyisobutylene group, also referred to as polyisobutene (PIB). In particular, so-called highly reactive polyisobutylenes (PIB) are preferred. Highly reactive polyisobutylenes (PIB) are understood to be polyisobutylenes (PIB) in which at least 50 mol %, preferably at least 70 mol % or more of the terminal olefinic double bonds are of the vinylidene (vinylidene) type, as described in document EP0565285. In particular, preferred PIBs are those having more than 80 mol % and up to 100 mol % of vinylidene end groups, as described in document EP1344785.

[0062] According to a particularly preferred embodiment, the hydrocarbon-substituted acylating agent is polyisobutenyl succinic anhydride (PIBSA).

[0063] The preparation of polyisobutenyl succinic anhydride is known per se and is widely described in the literature. Mention may be made, by way of example, of the processes described in documents US Pat. Nos. 3,361,673 and 3,018,250 involving the reaction between polyisobutylene (PIB) and maleic anhydride, or of the processes involving the reaction of halogenated, in particular chlorinated, polyisobutylene (PIB) with maleic anhydride (US Pat. No. 3,172,892).

[0064] According to one alternative, polyisobutenyl succinic anhydride can be prepared by mixing a polyolefin with maleic anhydride and then passing chlorine through the mixture (GB949981).

[0065] Other hydrocarbon groups comprising internal olefins, such as described in application WO2007 / 015080, can also be used as substituents for the acylating agent. Internal olefins are understood to mean any olefin containing mainly non-alpha double bonds, which are olefins in the beta position or higher.

[0066] Preferably, these materials are substantially beta-olefins or higher order olefins, for example containing less than 10% by weight of alpha-olefins, advantageously less than 5% or less than 2% by weight.

[0067] Internal olefins can be prepared by isomerization of alpha-olefins according to any known method.

[0068] The compound containing both an oxygen atom or a nitrogen atom and a tertiary amine group capable of condensing with the acylating agent can, for example, be selected from: dimethylaminopropylamine, N,N-diethylaminopropylamine, N,N-dimethylamino-ethylamine, N,N-dimethyl-aminoethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, butanediamine (isomers), diethylenetriamine, dipropylenetriamine, dibutylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, hexamethylenetetramine, bis(hexamethylene)triamine, diaminobenzene, and pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, and preferably N,N-dimethylaminopropylamine.

[0069] The compound may be further selected from alkylamine-substituted heterocyclic compounds such as 1-(3-aminopropyl)-imidazole, 4-(3-aminopropyl)morpholine, 1-(2-aminoethyl)piperidine, 3,3-diamino-N-methyldipropylamine, diaminopyridine, and 3,3-bisamino(N,N-dimethylpropylamine).

[0070] Compounds containing both an oxygen atom or a nitrogen atom capable of condensing with an acylating agent and a tertiary amine group may also be selected from alkanolamines, including, but not limited to, triethanolamine, trimethanolamine, N,N-dimethylaminopropanol, N,N-dimethylaminoethanol, N,N-diethylaminopropanol, N,N-diethylaminoethanol, N,N-diethylaminobutanol, N,N,N-tris(hydroxyethyl)amine, N,N,N-tris(hydroxymethyl)amine, N,N,N-tris(aminoethyl)amine, N , N-dibutylaminopropylamine and N,N,N'-trimethyl-N'-hydroxyethyl-bisaminoethyl ether, N,N-bis(3-dimethylamino-propyl)-N-isopropanolamine, N-(3-dimethylamino-propyl)-N,N-diisopropanolamine, N'-(3-(dimethylamino)propyl)-N,N-dimethyl-1,3-propanediamine 2-(2-dimethylaminoethoxy)ethanol and N,N,N'-trimethylaminoethylethanolamine, or mixtures thereof.

[0071] According to a preferred embodiment, the compound comprising at least one tertiary amine group and at least one group selected from primary amines, secondary amines and alcohols is selected from amines of the following formula (I) or (II):

[0072]

[0073] in:

[0074] R6 and R7 are the same or different and independently represent an alkyl group having 1 to 22 carbon atoms, preferably 1 to 5 carbon atoms;

[0075] X is an alkylene group having 1 to 20 carbon atoms, preferably 1 to 5 carbon atoms;

[0076] m is an integer between 1 and 5;

[0077] n is an integer from 0 to 20; and

[0078] R8 is a hydrogen atom or a C1-C22 alkyl group.

[0079] The compound is preferably selected from the amines of formula (I).

[0080] When the nitrogen compound comprises an amine of formula (I), R8 is advantageously a hydrogen atom or a C1-C16 alkyl group, preferably a C1-C10 alkyl group, even more preferably a C1-C6 alkyl group.

[0081] R8 can be selected from hydrogen, methyl, ethyl, propyl, butyl and isomers thereof, for example. Preferably, R8 is a hydrogen atom.

[0082] When the nitrogen compound comprises an amine of formula (II), m is preferably equal to 2 or 3, more preferably equal to 2; n is preferably an integer between 0 and 15, more preferably between 0 and 10, even more preferably between 0 and 5. Advantageously, n is 0.

[0083] According to a preferred embodiment, the nitrogen compound is the reaction product of an acylating agent substituted with a hydrocarbon group and a diamine of formula (I).

[0084] In this embodiment, preferably:

[0085] - R6 and R7 independently represent C1-C16 alkyl, preferably C1-C10 alkyl;

[0086] - R6 and R7 independently represent methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl or isomers thereof. Advantageously, R6 and R7 independently represent a C1-C4 group, preferably a methyl group;

[0087] -X represents an alkylene group having 1 to 16 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, for example 2 to 6 carbon atoms or 2 to 5 carbon atoms. X particularly preferably represents ethylene, propylene or butylene, in particular propylene.

[0088] According to a particularly preferred embodiment, the nitrogen compound is the reaction product of a succinic acid derivative substituted by a hydrocarbon group, preferably polyisobutenyl succinic anhydride, and an alcohol or amine which also comprises a tertiary amine group, in particular a compound of formula (I) or (II) as described above and more preferably a compound of formula (I).

[0089] According to a first alternative, the succinic acid derivative substituted with a hydrocarbon group is reacted with an amine also containing a tertiary amine group under such conditions to form succinimide (closed form, closed type). The reaction of the succinic acid derivative and the amine can also produce succinamide under certain conditions, i.e., a compound containing an amide group and a carboxylic acid group (open form, open type).

[0090] According to a second alternative, an alcohol further comprising a tertiary amine group is reacted with a succinic acid derivative to form an alcohol further comprising a free carboxyl group -CO 2 Thus, in some embodiments, the nitrogen compound may be a reaction product of a succinic acid derivative and an amine or an alcohol, which is an ester or an amide and which further comprises an unreacted carboxyl group -CO 2 H (open form).

[0091] The quaternary ammonium salt forming the first additive according to the invention is obtained directly by the reaction between the above-mentioned nitrogen compound comprising a tertiary amine function and a quaternizing agent.

[0092] According to a particular embodiment, the quaternizing agent is selected from the following substances, alone or in admixture (in the form of a mixture): dialkyl sulfates, carboxylates, alkyl halides, benzyl halides, hydrocarbon carbonates, and hydrocarbon epoxides, optionally mixed with acids, preferably carboxylates.

[0093] In fuel compositions, it is often desirable to reduce the levels of halogens, sulfur and phosphorus containing compounds.

[0094] Therefore, if a quaternizing agent containing such an element is used, it may be advantageous to perform a subsequent reaction to exchange the counterion. For example, the quaternary ammonium salt formed by reaction with the alkyl halide may then be reacted with sodium hydroxide and the sodium halide salt filtered off.

[0095] Quaternizing agents may include halides such as chlorides, iodides or bromides; hydroxides; sulfonates; bisulfites; alkyl sulfates such as dimethyl sulfate; sulfones; phosphates; C1-C12 alkyl phosphates; C1-C12 dialkyl phosphates; borates; C1-C12 alkyl borate; nitrites; nitrates; carbonates; bicarbonates; alkanoates; O,O-dialkyl dithiophosphates, alone or in admixture.

[0096] According to a particular embodiment, the quaternizing agent can be chosen from dialkyl sulfate derivatives such as dimethyl sulfate, N-oxides, sulfones such as propane and butane-sulfone, alkyl, acyl or aralkyl halides such as methyl and ethyl chlorides, benzyl bromides, iodides or chlorides, and hydrocarbon carbonates (or alkyl carbonates).

[0097] If the acyl halide is benzyl chloride, the aromatic ring is optionally substituted with one or more alkyl or alkenyl groups.

[0098] The hydrocarbon (alkyl) groups of the hydrocarbon carbonate may contain 1 to 50, 1 to 20, 1 to 10 or 1 to 5 carbon atoms per group. According to one embodiment, the hydrocarbon carbonate contains two hydrocarbon groups, which may be the same or different. Examples of hydrocarbon carbonates include dimethyl carbonate or diethyl carbonate.

[0099] According to a preferred embodiment, the quaternizing agent is selected from hydrocarbon epoxides represented by the following formula (III):

[0100]

[0101] Wherein R9, R10, R11 and R12 may be the same or different and independently represent a hydrogen atom or a C 1 -C 50 As non-limiting examples, mention may be made of styrene oxide, ethylene oxide, propylene oxide, butylene oxide, stilbene oxide (stilbene oxide) and C 1 -C 50 Epoxides. Styrene oxide and propylene oxide are particularly preferred, and more preferably, the quaternizing agent is propylene oxide.

[0102] Such hydrocarbon epoxides can be used as quaternizing agents in combination with an acid, such as acetic acid. Hydrocarbon epoxides can also be used alone as quaternizing agents, especially in the absence of an additional acid.

[0103] Without being bound by this hypothesis, it appears that the presence of carboxylic acid functional groups in the molecule promotes the formation of quaternary ammonium salts. In such an embodiment where no additional acid is used, a protic solvent is used to prepare the quaternary ammonium salt. For example, protic solvents such as water, alcohols (including polyols) can be used alone or in admixture. Preferred protic solvents have a dielectric constant greater than 9.

[0104] The corresponding quaternary ammonium salts prepared from amides or esters and succinic acid derivatives are described in WO2010 / 132259 or EP1896555.

[0105] According to another embodiment, the quaternizing agent is selected from compounds of formula (IV):

[0106]

[0107] wherein R13 is optionally substituted alkyl, alkenyl, aryl and aralkyl, and R14 is C 1 To C 22 Alkyl, aryl or alkylaryl.

[0108] The compound of formula (IV) is a carboxylic acid ester capable of reacting with a tertiary amine to form a quaternary ammonium salt. The compound of formula (IV) is selected from, for example, carboxylic acid esters having a pKa of 3.5 or less. The compound of formula (IV) is preferably selected from substituted aromatic carboxylic acids, α-hydroxy carboxylic acids and polycarboxylic acid esters.

[0109] According to one embodiment, the ester is a substituted aromatic carboxylic acid ester of formula (IV), wherein R13 is a substituted aryl. Preferably, R13 is a substituted aryl having 6 to 10 carbon atoms, preferably phenyl or naphthyl, more preferably phenyl. R13 is advantageously selected from alkoxycarbonyl (carboalkoxy), nitro, cyano, hydroxyl, SR 15 and NR 15 R 16 One or more groups are substituted. 15 and R 16 The groups may each be a hydrogen atom or an optionally substituted alkyl, alkenyl, aryl or alkoxycarbonyl group. 15 and R 16 The groups each advantageously represent a hydrogen atom or an optionally substituted C 1-22 Alkyl, preferably a hydrogen atom or a C l-16 Alkyl, more preferably a hydrogen atom or a C 1-10 Alkyl, even more preferably a hydrogen atom or a C 1-4 Alkyl. 15 Preferably, it is a hydrogen atom, and R 16 is a hydrogen atom or C 1 To C 4 Advantageously, R 15 and R 16 They are all hydrogen atoms.

[0110] According to one embodiment, R13 is selected from hydroxy, alkoxycarbonyl, nitro, cyano and NH 2 R13 may be a polysubstituted aryl group, for example a trihydroxyphenyl group. Advantageously, R13 is a monosubstituted aryl group, preferably ortho-substituted. For example, R13 is selected from OH, NH 2 、NO 2 or COOMe, preferably OH or NH 2 R13 is preferably hydroxy-aryl, especially 2-hydroxyphenyl.

[0111] According to a particular embodiment, R14 is alkyl or alkylaryl. R14 may be C 1 To C 16 , preferably C 1 To C 10 , advantageously C 1 To C 8 Alkyl. R14 can be C 1 To C 16 , preferably C 1 To C 10 , advantageously C 1 To C 8 R14 can be selected from methyl, ethyl, propyl, butyl, pentyl, benzyl or isomers thereof. Preferably, R14 is benzyl or methyl, more preferably methyl.

[0112] A particularly preferred compound is methyl salicylate.

[0113] According to a particular embodiment, the compound of formula (IV) is an α-hydroxycarboxylate having the following formula (V):

[0114]

[0115] Wherein R17 and R18 are identical or different and are independently selected from hydrogen atom, alkyl, alkenyl, aryl or aralkyl. Such compounds are described, for example, in EP 1254889.

[0116] Examples of compounds of formula (IV) in which R13COO is the residue of an α-hydroxycarboxylic acid include: methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, phenyl-, benzyl- or allyl- esters of 2-hydroxy-isobutyric acid; methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-, phenyl- or allyl- esters of 2-hydroxy-2-methylbutyric acid; methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-, phenyl- or allyl- esters of 2-hydroxy-2-ethylbutyric acid; methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, benzyl-, phenyl- or allyl- esters of lactic acid, and methyl-, ethyl-, propyl-, butyl-, pentyl-, hexyl-, allyl-, benzyl- or phenyl- esters of glycolic acid. Of the above, the preferred compound is methyl 2-hydroxyisobutyrate.

[0117] According to a particular embodiment, the compound of formula (IV) is an ester of a polycarboxylic acid selected from dicarboxylic acids and carboxylic acids having more than two acid functions. The carboxylic acid functions are preferably all in esterified form. Preferred esters are C 1 To C 4 Alkyl esters.

[0118] The compound of formula (IV) may be selected from oxalic acid diesters, phthalic acid diesters, maleic acid diesters, malonic acid diesters or citric acid diesters. Preferably, the compound of formula (IV) is dimethyl oxalate.

[0119] According to a preferred alternative, the compound of formula (IV) is a carboxylic acid ester having a pKa of less than 3.5. In case the compound comprises more than one acid group, reference will be made to the first dissociation constant.

[0120] The compound of formula (IV) can be selected from one or more carboxylic acid esters selected from oxalic acid, phthalic acid, salicylic acid, maleic acid, malonic acid, citric acid, nitrobenzoic acid, aminobenzoic acid and 2,4,6-trihydroxybenzoic acid. Preferred compounds of formula (IV) are dimethyl oxalate, methyl 2-nitrobenzoate and methyl salicylate.

[0121] According to a particularly preferred embodiment, the quaternary ammonium salt employed in the present invention is formed by the reaction of a hydrocarbon epoxide, preferably selected from those of formula (III) above and more preferably propylene oxide, a reaction product between polyisobutenyl succinic anhydride having a number average molecular weight (Mn) between 700 and 1000 with its polyisobutylene (PIB) group and dimethylaminopropylamine.

[0122] According to a particularly preferred embodiment, the additive (1) is selected from polyisobutylene succinimides functionalized with quaternary ammonium groups.

[0123] The composition according to the invention comprises the first additive as described above in a preferred content ranging from 5 to 10,000 ppm by weight, preferably from 5 to 1000 ppm by weight, more preferably from 10 to 500 ppm by weight, more preferably from 15 to 200 ppm by weight, and even more preferably from 20 to 150 ppm by weight, based on the total weight of the fuel composition.

[0124] Second additive: polyisobutylene succinimide

[0125] The composition according to the invention comprises a second additive (2) consisting of a non-quaternary polyisobutylene succinimide, ie it does not contain quaternary ammonium groups.

[0126] According to a preferred embodiment, the second additive is obtained from the condensation of:

[0127] - a compound A consisting of a carboxylic diacid substituted by a polyisobutylene group or an anhydride of such a diacid,

[0128] - with a compound B consisting of a primary poly(poly)amine of the following general formula (VI):

[0129] H 2 N-[-(CHR1-(CH 2 ) p -CHR2) n -NH] m -H (VI)

[0130] wherein R1 and R2 are the same or different and represent hydrogen or a hydrocarbon group containing 1 to 4 carbon atoms, n is an integer ranging from 1 to 3, m is an integer ranging from 1 to 10, preferably 1 to 4; and p is an integer equal to 0 or 1.

[0131] In a preferred embodiment, the additive (2) is obtained by condensation of compound A and compound B used in such amounts that the A / B molar ratio is in the range of 1:1 to 1:3.

[0132] Preferably, the molar ratio A / B is in the range of 1:1.1 to 1:2, even more preferably, the molar ratio A / B is in the range of 1:1.1 to 1:1.5.

[0133] The additive (2) is obtainable in particular by condensation of 60 to 90% by weight of compound A and 10 to 30% by weight of compound B.

[0134] The average molar mass of the compounds A according to the invention ranges from 200 to 3000, preferably from 200 to 2000 g / mol, more preferably from 200 to 1500 g / mol, even more preferably from 900 to 1300 g / mol. These compounds are well known in the prior art.

[0135] Among the primary polyamines according to formula (VI), preference is given to polyamines from the group consisting of diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine and substituted derivatives thereof, or mixtures thereof.

[0136] The mixing of these compounds A and B can be carried out in the order detailed below, or in a different order.

[0137] In a preferred embodiment, compound B (ie the primary polyamine of formula (VI)) is added to compound A (ie the carboxylic acid or anhydride).

[0138] The polyamine B is gradually added in an organic solvent at room temperature and then added to the solution of the carboxylic hydrocarbon mixture, and the mixture is then heated to between 65 and 250° C., and preferably between 80 and 220° C., for 5 to 30 hours.

[0139] The organic solvent required for dissolving the primary polyamine is selected to have a boiling point between 65 and 250° C. and preferably between 80 and 220° C. and which is capable of removing, by azeotropic distillation of the water / solvent mixture, the water formed by the condensation of the polyamine on compound A. The solvent is selected from benzene, toluene, xylene, ethylbenzene and commercial hydrocarbon cuts, for example those which distill from 190 to 209° C. and contain 99% by weight of aromatic compounds.

[0140] According to another embodiment of the invention, mixtures of solvents may be used, in particular mixtures of xylenes, or xylene / alcohol mixtures, preferably the alcohol being 2-ethylhexanol, in order to promote the homogeneity of the medium on the one hand and the kinetics of the reaction on the other hand.

[0141] After the addition of the primary polyamine B has ended, heating is maintained under reflux until the water has been completely removed, for 0.5 to 7 hours, preferably 1 to 5 hours.

[0142] In one embodiment, the composition according to the invention comprises the second additive as described above, in a preferred content ranging from 5 to 10,000 ppm by weight, preferably 5 to 1000 ppm by weight, more preferably 10 to 500 ppm by weight, more preferably 15 to 200 ppm by weight, and most preferably 20 to 150 ppm by weight, based on the total weight of the fuel composition.

[0143] The third additive: Mannich base

[0144] The fuel composition according to the invention comprises a third additive (3) consisting of a Mannich base, different from additives (1) and (2). The preparation of Mannich bases is known per se and is described, for example, in documents US 2008 / 0052985 or US Pat. No. 8,016,898.

[0145] Advantageously, the third additive is prepared by reacting a hydrocarbon-substituted phenol (phenol), an aldehyde and an amine.

[0146] The hydrocarbon substituent of the phenol may contain from 6 to 400 carbon atoms, advantageously from 30 to 180 carbon atoms, preferably from 10 to 110 carbon atoms, more preferably from 40 to 110 carbon atoms.

[0147] The hydrocarbon substituent of the phenol may be derived from an olefin or a polyolefin. By way of example, α-olefins such as nl-decene (normal-1-decene) may be mentioned. Preferably, the hydrocarbon substituent of the phenol is a polyisobutylene group.

[0148] The polyolefins forming the hydrocarbon substituents of the phenols may be prepared by polymerization of olefin monomers according to any known polymerization method.

[0149] Advantageously, the polyolefin is chosen from polyisobutylenes having a number average molar mass (Mn) between 400 and 3000, preferably between 400 and 2500, more preferably between 400 and 1500, between 500 and 1500 or between 500 and 1000.

[0150] The polyisobutene is preferably highly reactive, which differs from low-reactivity polyisobutene in that it has a low amount of terminal ethylene double bonds. The reactive polyisobutene according to the invention comprises at least 85% by weight, preferably at least 90% by weight, most preferably at least 95% by weight of isobutene units.

[0151] Preferably, the polyisobutene, which is preferably highly reactive, has a polydispersity, which is the quotient of the weight-average molar mass Mw and the number-average molar mass Mn, of less than 1.9, preferably less than 1.7 and even more preferably less than 1.5.

[0152] The hydrocarbon-substituted phenols can be prepared by alkylating phenols with the above-mentioned olefins or polyolefins (eg polyisobutylene or polypropylene, preferably polyisobutylene) using conventional alkylation methods.

[0153] According to one alternative, the phenol may be substituted with one or more low molecular weight alkyl groups, for example phenols carrying one or more alkyl chains of less than 28 carbon atoms, preferably less than 24 carbon atoms, more preferably less than 20 carbon atoms, even more preferably less than 18 carbon atoms, even more preferably 16 carbon atoms and even more preferably 14 carbon atoms.

[0154] Monoalkylphenols having 4 to 20 carbon atoms, preferably 6 to 18, more preferably 8 to 16, still more preferably 10 to 14 carbon atoms, such as phenols substituted with C12 alkyl groups, will be preferred.

[0155] The aldehyde used to form the Mannich reaction product may contain from 1 to 10 carbon atoms and is typically formaldehyde or a reactive equivalent thereof such as formalin (methanol and formaldehyde), trioxane or paraformaldehyde (paraformaldehyde), and preferably paraformaldehyde.

[0156] The amine used to form the Mannich reaction product can be a monoamine or a polyamine.

[0157] As non-limiting examples of monoamines, mention may be made of ethylamine, dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, n-butylamine, dibutylamine, allylamine, isobutylamine, coconut amine (cocoamine), stearylamine, laurylamine, methyllaurylamine, oleylamine, N-methyl-octylamine, dodecylamine, diethanolamine, morpholine, dimethylmorpholine, dicyclohexylamine, pyrrolidine, piperidine, diethylenetriamine, triethylenetetramine, N,N-diethylethylenediamine, N,N,N',N'-tetramethyldiethylenetriamine, polyethyleneimine and octadecylamine. The polyamines are selected from compounds comprising two or more amino groups.

[0158] As non-limiting examples, polyalkylene polyamines may be mentioned, wherein the alkylene group has, for example, 1 to 6, preferably 1 to 4, more preferably 2 to 3 carbon atoms. Preferred polyamines are polyethylene polyamines. The polyamines may contain 2 to 15 nitrogen atoms, preferably 2 to 10 nitrogen atoms, more preferably 2 to 8 nitrogen atoms. Examples of polyamines are: 3-(dimethylamino)-n-propylamine, di[3-(dimethylamino)-n-propyl]amine, di[3-(diethylamino)-n-propyl]amine, di[2-(dimethylamino)ethyl]amine, N-methylpiperazine.

[0159] According to one alternative, the amine used to form the Mannich reaction product comprises a diamine, which preferably comprises a primary or secondary amine functionality involved in the Mannich reaction, and a tertiary amine functionality.

[0160] According to another alternative, additive (3) can be obtained by a Mannich reaction and then subjected to a reaction for obtaining a tertiary amine function; for example, a process using an intermediate compound comprising a secondary amine and obtained by a Mannich reaction which is then modified, for example by alkylation, to give a tertiary amine.

[0161] According to one embodiment, the content of additive (3) ranges from 5 to 10,000 ppm by weight, preferably 5 to 1000 ppm by weight, more preferably 50 to 500 ppm by weight, more preferably 100 to 500 ppm by weight, and most preferably 150 to 450 ppm by weight, based on the total weight of the fuel composition.

[0162] Fuel Concentrate

[0163] Another object of the invention is the use of a fuel concentrate comprising at least the additives (1), (2) and (3) as defined above, mixed with an organic liquid which is inert with respect to the first, second and third additives and which is miscible with said fuel, for improving the detergency properties of a gasoline fuel.

[0164] The organic liquid is advantageously miscible with liquid fuels, especially those from one or more sources selected from mineral, preferably petroleum, animal, vegetable and synthetic sources. Miscible means that the additive and the organic liquid form a solution or dispersion to facilitate mixing the additive according to the invention in the liquid fuel according to conventional fuel additive methods.

[0165] The organic liquid is preferably chosen from aromatic hydrocarbon solvents, for example the solvents sold under the name "SOLVESSO", alcohols, ethers and other oxygenates, and paraffinic solvents such as hexane, pentane or isoparaffins, alone or in mixtures.

[0166] fuel

[0167] The fuel according to the invention contains a base from one or more sources selected from mineral, animal, vegetable and synthetic sources, and preferably selected from hydrocarbon fuels, non-essentially hydrocarbon fuels and mixtures thereof.

[0168] Preferably, petroleum will be chosen as the mineral source.

[0169] The fuel is advantageously chosen from hydrocarbon fuels and non-essentially hydrocarbon fuels, alone or in admixture.

[0170] Hydrocarbon fuel means a fuel composed of one or more compounds consisting only of carbon and hydrogen. Gasoline is a hydrocarbon fuel.

[0171] By non-essentially hydrocarbon fuel is meant a fuel composed of one or more compounds which do not consist essentially of carbon and hydrogen, ie which also contain other atoms, in particular oxygen atoms.

[0172] Hydrocarbon fuels include in particular light distillates having a boiling point in the gasoline range, preferably between 30 and 210°C.

[0173] For example, these light distillates can 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 obtained from ARDS (atmospheric residue desulfurization) type conversion processes.

[0174] In other words, the hydrocarbon fuel is selected from gasoline.

[0175] Gasoline particularly includes all commercially available spark ignition engine fuel compositions. As a representative example, the gasoline that meets the NF EN 228 standard can be mentioned. Gasoline usually has a sufficiently high octane number to avoid slight knocking (pinking) phenomena. Typically, gasoline-type fuels sold in Europe according to the NF EN 228 standard have a motor octane number (MON) of more than 85 and a research octane number (RON) of at least 95. Gasoline-type fuels usually have a RON in the range of 90 to 100 and a MON in the range of 80 to 90, wherein RON and MON are measured according to standard ASTM D 2699-86 or D 2700-86.

[0176] Non-essential hydrocarbon fuels include, inter alia, oxygenates, such as distillates from BTL (biomass to liquid) conversion of plant and / or animal biomass, alone or in combination; biofuels, such as oils and / or esters of plant and / or animal oils; and bioethanol.

[0177] The mixture of hydrocarbon fuel and non-essentially hydrocarbon fuel is typically Ex type gasoline.

[0178] Ex type gasoline for spark ignition engines means gasoline fuel containing x% (v / v) oxygenates, typically ethanol, bioethanol and / or ethyl tert-butyl ether (ETBE).

[0179] The fuel composition may comprise only the new distillate source, or may consist of a blend with lighter conventional petroleum distillates as the basis for gasoline-type fuels.

[0180] Preferably, the content of each additive (1) and (2) in the fuel composition according to the present invention ranges from 5 to 10,000 ppm by weight, preferably 5 to 1000 ppm by weight, more preferably 10 to 500 ppm by weight, more preferably 15 to 200 ppm by weight, and most preferably 20 to 150 ppm by weight, based on the total weight of the fuel composition.

[0181] Preferably, the content of additive (3) in the fuel composition according to the present invention ranges from 5 to 10,000 ppm by weight, preferably 5 to 1000 ppm by weight, more preferably 50 to 500 ppm by weight, more preferably 100 to 500 ppm by weight, and most preferably 150 to 450 ppm by weight, based on the total weight of the fuel composition.

[0182] Preferably, the sulphur content of the fuel composition is less than or equal to 1500 ppm by weight, preferably less than or equal to 1000 ppm by weight, preferably less than or equal to 500 ppm by weight and preferentially less than or equal to 50 ppm by weight, even more preferably less than or equal to 10 ppm by weight, based on the total weight of the composition, and is advantageously sulphur-free.

[0183] Other fuel composition additives

[0184] The fuel composition may also comprise one or more further additives other than the additives according to the invention.

[0185] The (these) additional one or more additives can be selected, for example, in a non-limiting manner: detergent additives, corrosion inhibitors, antioxidants, carrier oils, dispersants, demulsifiers, tracers or markers, deodorants, friction modifiers, lubricity additives or lubricity additives, combustion aids (catalytic combustion and smoke promoters), anti-settling agents, anti-wear agents and conductivity modifiers.

[0186] These further additives are more preferably selected from:

[0187] (a) lubricity additives or anti-wear agents, in particular (but not limited to) selected from fatty acids and their ester or amide derivatives, in particular glycerol monooleate, and monocyclic and polycyclic carboxylic acid derivatives. Examples of such additives are given in the following documents: EP680506, EP860494, WO98 / 04656, EP915944, FR2772783, FR2772784;

[0188] b) soil release additives, especially (but not exclusively) selected from polyetheramines;

[0189] c) friction or friction modifiers, in particular (but not limited to) selected from fatty acids or fatty acid esters or mixtures of fatty acids or fatty acid esters, such as oleic acid, linoleic acid, resin acid, palmitic acid; or from fatty acid dimers, or monopropoxylated or dipropoxylated esters; sorbitan esters; sucrose stearate; or from glycerol and its derivatives; or pentaerythritol esters; or amines; and preferably from glycerol or polyglycerol esters, or fatty acids or esters, or mixtures thereof;

[0190] d) anticorrosion additives, in particular (but not exclusively) chosen from fatty acids or fatty acid esters or mixtures of fatty acids or fatty acid esters, or from fatty acid dimers;

[0191] e) antioxidants, in particular (but not limited to) selected from 2,6-di-tert-butyl-4-methylphenol, tert-butylhydroquinone, 2,6 and 2,4-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, pyrogallol, tocopherol, 4,4'-methylenebis(2,6-di-tert-butylphenol), alone or in mixtures;

[0192] f) Carrier oils, especially (but not exclusively) chosen from polyoxyalkylenes, such as poly-1-butene oxide or polypropylene oxide.

[0193] These further additives may be present in amounts ranging from 3 to 1000 ppm by weight (each), preferably from 5 to 500 ppm, based on the total weight of the fuel composition.

[0194] use

[0195] A further object of the present invention is the use of the fuel composition for keeping clean (keeping clean effect) and / or cleaning (cleaning effect) deposits in internal parts of an engine, said internal parts being selected from the group consisting of: a combustion chamber and a fuel injection system, and preferably a fuel injection system.

[0196] The compositions according to the invention are effective in conventional engines or in more modern engines such as GDI, BMW B48, Renault HSFT and HR13DDT, PSA EB2DTS, Volkswagen EA111, etc. and IIE Mercedes M102E and M111E, PSA EW10A and EB2, etc.

[0197] Another object of the present invention is the use of a fuel composition comprising at least one first additive, at least one second additive and at least one third additive as defined above for preventing and / or reducing coking (i.e. coke deposits), especially in gasoline direct injection (GDI) and / or varnishing (i.e. deposits of soap and / or varnish), especially in gasoline indirect injection (GII), and especially on valves.

[0198] Thus, the present invention makes it possible to prevent and / or reduce coke and / or soap deposits on fuel intake valves in indirect injection spark ignition engines.

[0199] Another object of the present invention is the use of a fuel composition comprising at least one first additive, at least one second additive and at least one third additive as defined above for preventing and / or reducing the sticking (or valve sticking) of a fuel intake valve in an engine, in particular a gasoline indirect injection (GII) spark ignition engine. In this embodiment, the composition advantageously further comprises a fourth additive, which is a carrier oil.

[0200] In the case of use against valve sticking, the composition preferably further comprises a carrier oil. The carrier oil may be selected from poly(oxyalkylene) type oils, such as poly-1-butene oxide or polypropylene oxide. In one embodiment, the weight ratio of the amount of carrier oil to the amount of the detergency additive is in the range of 0.1 to 2.5, preferably 0.3 to 1.5, even more preferably 0.5 to 1.

[0201] Another object of the invention is the use of said fuel composition for reducing the fuel consumption of an engine ("fuel economy" effect) and / or minimizing the power losses of said engine, and / or reducing pollutant emissions, in particular particulate matter emissions of an internal combustion engine.

[0202] Another object of the present invention is the use of said additive composition for reducing fouling in the area of ​​pistons, rings and liners of an engine, preferably a gasoline direct injection (or GDI) engine.

[0203] The quaternary ammonium additive (1) as defined in the present invention is particularly effective in combating piston fouling, especially in GDI.

[0204] The combination of additives (1) and (2) is also very effective in combating piston fouling, especially in GDI.

[0205] The fuel composition can be used for gasoline indirect injection (GII) or gasoline direct injection (GDI), preferably GDI. In one embodiment, the GDI is centrally mounted, and in another embodiment, the GDI is side mounted. Therefore, the present invention is effective and is used for centrally and / or side mounted GDI.

[0206] The fuel composition can also be used to combat corrosion in engines. The additive (2) polyisobutylene succinimide defined in the present invention is particularly effective in combating corrosion.

[0207] The use according to the invention is applicable to engines used in light vehicles (LV), heavy goods vehicles (HGV), stationary machines, agricultural machines, thermal vehicles or hybrid (rechargeable or non-rechargeable) vehicles, petrol / gas dual-fuel engines, such as petrol / NGV (natural gas for vehicles) or petrol / LPG; petrol / NGV or petrol / LPG companion injection engines, etc.

[0208] The additive composition, fuel or concentrate may be used in a "severe" or "easier to treat" gasoline. A "severe" gasoline is distinguished from an "easy to treat" gasoline in that a severe gasoline requires a higher treat rate of the additive composition to be effective than an "easy to treat" gasoline. Gasos similar to reference gasolines CEC RF12-09 and CEC RF-83 may be referred to as "severe" gasolines.

[0209] Process for preparing a fuel composition

[0210] The fuel composition according to the invention may be prepared according to any known method by additives to a liquid hydrocarbon fraction as described above with at least three additives as described above and optionally one or more further additives as described above which are different from the additives according to the invention.

[0211] Methods for improving engine cleanliness

[0212] The invention also relates to a method for keeping clean and / or cleaning at least one of the internal components of a spark-ignition engine, said method comprising at least the following steps:

[0213] - preparing a fuel composition by additives to a fuel with at least three additives as described above or with a concentrate containing them, and then

[0214] - combusting said fuel composition in said spark ignition engine.

[0215] All characteristics of the additive, fuel or application apply to this method.

[0216] According to one alternative, the above-mentioned step of preparing the fuel composition is preceded by a preliminary step of determining the respective contents of the three additives to be introduced into said fuel composition in order to achieve given specifications relating to the detergency properties of the fuel composition.

[0217] This preliminary step is common practice in the field of fuel additives and involves defining at least one characteristic representative of the detergency properties of the fuel composition and a target value.

[0218] Methods for evaluating the decontamination properties of fuels are widely described in the literature and are within the general knowledge of the skilled person. As non-limiting examples, the following standardized or professionally recognized tests or methods described in the literature may be cited for indirect injection spark ignition engines:

[0219] -Mercedes Benz Method M102E, Standard Test Method CEC F-05-A-93, and

[0220] - Mercedes Benz method M111E, Standard Test Method CEC F-20-A-98.

[0221] These methods make it possible to measure intake valve deposits (IVD), wherein the test is typically carried out on Eurosuper gasoline meeting standard EN228.

[0222] For direct injection spark ignition engines:

[0223] - the method described by the applicant in the following paper: "Evaluating Injector Fouling in Direct Injection Spark Ignition Engines", Mathieu Arondel, Philippe China, Julien Gueit; Conventional and future energy for automobiles; 10th International Symposium; January 20-22, 2015, pages 375-386 (Technische Akademie Esslingen by Techn. Akad. Esslingen, Ostfildern), for evaluating coking type deposits on injectors,

[0224] - the method described in US20130104826 for evaluating coking type deposits on injectors,

[0225] - Method developed within the framework of CEC TDG-F-113 based on the VW EA111 engine (Glawar, A. et al., "Development of a Fuel System Cleanliness Test Method in a Euro 4 Direct-Injection Gasoline Engine (VW 1.4L TSI 90kW)," SAE Int. J. Fuels Lubr. 10(3):2017, doi:10.4271 / 2017-01-2296).

[0226] Reference may also be made to the method CEC L111-16 for evaluating fouling in the area of ​​pistons, rings and liners of gasoline direct injection engines.

[0227] The following examples are given to illustrate the present invention and should not be construed as limiting the scope thereof.

[0228] Example

[0229] The following examples are based on gasoline E, the properties of which are described in detail in Table 1 below.

[0230] Table 1: Characteristics of gasoline E

[0231]

[0232]

[0233]

[0234] A fuel composition was prepared by adding the following additives A1, A2 and A3 to gasoline G:

[0235] -Al: quaternary ammonium salt formed by reacting propylene oxide with the condensation product of polyisobutenyl succinic anhydride and dimethylaminopropylamine having a number average molecular weight (Mn) of 1000 g / mol of its polyisobutylene (PIB) groups;

[0236] - A2: polyisobutylene succinimide obtained by condensation of polyisobutylene succinic anhydride whose polyisobutylene groups (PIB) have a number average molecular weight (Mn) of 1000 g / mol and tetraethylene pentamine;

[0237] - A3: Mannich base obtained by reacting a phenol substituted with polyisobutylene (PIB) groups having a number average molecular weight (Mn) of 1000 g / mol with formaldehyde and dimethylaminopropylamine.

[0238] The amounts of additives added to each composition are detailed in Table 2 below, where the content of each additive is expressed in ppm by weight based on the total weight of the final composition:

[0239] Table 2: Fuel composition from gasoline G

[0240]

[0241]

[0242] Composition G1 is according to the invention. Compositions G2, G3 and G4 are comparative. For all three compositions G1, G2 and G3, the additive rate is the same (433 ppm).

[0243] The fouling performance of each of the above fuel compositions G1 to G4 and the unadditized reference fuel G have been evaluated using a test for determining the fouling level of injectors for gasoline direct injection (GDI) engines.

[0244] The engine used is the PSA EB2DTS engine, which is a 3-cylinder 1199cm 3 Turbocharged direct injection petrol engine with centrally located injectors.

[0245] Before the tests were carried out, the injector flow rates were determined using an injector flow meter test machine model EFS IFR 600, which makes it possible to measure the fuel mass flow rate of the injector in a manner known per se.

[0246] The principle of the test is to run the engine at 4300 rpm and 11 bar mean effective pressure (hereinafter referred to as MEP) for 5 hours, after a 20 minute warm-up period and a 10 minute stabilization period, fed with the test gasoline at an injection pressure of 70 bar.

[0247] This test is used to determine the average flow rate loss, defined as the average restriction of the flow rate of gasoline from the engine injectors corresponding to the end of the test. The higher the average flow rate loss, the greater the fouling effect of the fuel on the engine injectors and the poorer its defouling performance.

[0248] The test steps are as follows:

[0249] - a heating step;

[0250] - Stabilization step;

[0251] - Scaling step;

[0252] - Procedure for determining the flow rate loss of an ejector.

[0253] The test conditions are as follows:

[0254] temperature:

[0255] -Water at engine outlet: 90±2℃

[0256] -Oil: 110±5℃

[0257] - Air in intake manifold: 40±2℃

[0258] - Fuel in low pressure loop: 50±2℃

[0259] Fuel injection pressure: 70 bar

[0260] For the warm-up phase, the engine was subjected to a gradual increase in speed, for a period of 20 minutes, until it reached a speed of 4000 rpm and a MEP of 8 bar.

[0261] For the stabilization phase, the engine was kept under the operating conditions of the test at a speed of 4300 rpm, a MEP of 11 bar and a fuel injection pressure of 70 bar for a period of 10 minutes.

[0262] For the fouling phase, the engine was then run at 4300 rpm and 11 bar MEP with a fuel injection pressure of 70 bar for 5 hours.

[0263] At the end of the test, the injectors were removed for evaluation using an EFS IFR 600 injector flowmeter test machine, which measured the injector fuel mass flow rate at the end of the test. The injector average flow rate loss was calculated by comparing it to the injector mass fuel flow rate value measured before the test.

[0264] The results obtained are described in detail in Table 3 below.

[0265] Table 3: Results

[0266] Composition G1 G2 G3 G4 G Average flow rate loss 5.2％ 6.7％ 14.3％ 16.2％ 17.5％

[0267] The above results show that the composition G1 according to the invention containing a combination of the three additives A1, A2 and A3 achieves very good results in reducing injector fouling ("keep clean" effect). At the same total additive content (433 ppm), these results are significantly better than those obtained with the comparative compositions G2 and G3 containing only two of the three additives. The results obtained with the composition G4 containing only one of the three additives and with the reference fuel G are even worse.

[0268] These results illustrate the synergistic effect provided by the combination of the two additives according to the invention.

Claims

1. Use of a fuel composition for reducing and / or preventing deposits in internal components of a spark ignition engine, the fuel composition comprising: (1) at least one first additive consisting of a quaternary ammonium salt, wherein the first additive consisting of a quaternary ammonium salt is obtained by reacting a nitrogen compound comprising a tertiary amine functional group with a quaternizing agent, the nitrogen compound being the product of the reaction of a polyisobutenyl succinic anhydride with a compound comprising at least one tertiary amine group and at least one group selected from the group consisting of a primary amine, a secondary amine and an alcohol, the polyisobutenyl succinic anhydride having a number average molecular weight Mn of 1000 to 2800 g / mol, (2) at least one second additive consisting of a polyisobutylene succinimide free of quaternary ammonium groups, (3) at least one third additive consisting of a Mannich base different from the first additive and the second additive, and wherein the mass ratio of the amount of the first additive to the amount of the second additive is in the range of 0.2:1 to 2.5:1, and The third additive, which consists of a Mannich base, is prepared using a phenol substituted with a polyisobutylene group.

2. The use according to claim 1, wherein the mass ratio of the amount of the first additive to the amount of the second additive is in the range of 1:1 to 2:

1.

3. The use according to claim 1, wherein the compound comprising at least one tertiary amine group and at least one group selected from primary amines, secondary amines and alcohols is selected from amines of the following formula (I) or (II): in: R6 and R7 are the same or different and independently represent an alkyl group having 1 to 22 carbon atoms; X is an alkylene group having 1 to 20 carbon atoms; m is an integer between 1 and 5; n is an integer from 0 to 20; and R8 is a hydrogen atom or a C1-C 22 alkyl.

4. The use according to claim 3, wherein the compound comprising at least one tertiary amine group and at least one group selected from primary amines, secondary amines and alcohols is selected from amines of formula (I).

5. The method according to claim 1, wherein the quaternizing agent is selected from the group consisting of dialkyl sulfates, carboxylates, alkyl halides, benzyl halides, hydrocarbon carbonates, and hydrocarbon epoxides, alone or in admixture, optionally in admixture with an acid.

6. The method according to claim 1 , wherein the second additive consisting of polyisobutylene succinimide free of quaternary ammonium groups is obtained by condensation of: - a compound A consisting of a carboxylic diacid substituted by a polyisobutylene group or an anhydride of such a diacid; - and a compound B consisting of a primary polyamine of the following general formula (VI): H2N-[-(CHR1-(CH2)p-CHR2)n-NH]mH(VI) wherein R1 and R2 are the same or different, represent hydrogen or a hydrocarbon group containing 1 to 4 carbon atoms, n is an integer ranging from 1 to 3, m is an integer ranging from 1 to 10; and p is an integer equal to 0 or 1.

7. The use according to claim 6, wherein the second additive is obtained by condensation of compound A and compound B used in such amounts that the molar ratio A / B is in the range of 1:1 to 1:

3.

8. The method according to claim 1, wherein the third additive consisting of a Mannich base is obtained by reacting a phenol substituted with a polyisobutylene group, an aldehyde and an amine, the polyisobutylene group substituent of the phenol containing 6 to 400 carbon atoms.

9. Use according to any one of claims 1 to 3, wherein the fuel contains a base from one or more sources selected from mineral, animal, vegetable and synthetic sources.

10. The use according to any one of claims 1 to 3, wherein the content of each of the first additive and the second additive ranges from 5 to 10,000 ppm by weight, based on the total weight of the fuel composition.

11. The use according to claim 10, wherein the content of the first additive ranges from 10 to 500 ppm by weight, based on the total weight of the fuel composition.

12. The use according to claim 10, wherein the content of the second additive ranges from 10 to 500 ppm by weight.

13. The use according to any one of claims 1 to 3, wherein the content of the third additive ranges from 5 to 10,000 ppm by weight, based on the total weight of the fuel composition.

14. The use according to claim 13, wherein the content of the third additive ranges from 50 to 500 ppm by weight.

15. Use according to any one of claims 1 to 3, wherein the fuel further comprises one or more additional additives different from the first, second and third additives, which are selected from detergent additives, corrosion inhibitors, antioxidants, carrier oils, dispersants, demulsifiers, tracers or markers, deodorants, lubricity additives, combustion aids and conductivity modifiers.

16. Use according to any one of claims 1 to 3 for keeping clean and / or cleaning deposits in internal parts of a spark ignition engine, said internal parts being selected from the group consisting of: combustion chambers and fuel injection systems.

17. Use according to claim 16, wherein the internal component is a fuel injection system.

18. Use according to any one of claims 1 to 3 for preventing and / or reducing coke and / or soap deposits on fuel intake valves in an indirect injection spark ignition engine.

19. Use according to any one of claims 1 to 3 for preventing and / or reducing valve sticking of a fuel inlet valve in an indirect injection spark ignition engine.

20. Use according to any one of claims 1 to 3, wherein the additive composition is used in a fuel to reduce the fuel consumption of an engine and / or to minimize power losses of said engine, and / or to reduce pollutant emissions.

21. Use according to any one of claims 1 to 3 for reducing fouling in the area of ​​pistons, rings and liners of an engine.

22. Use of a fuel concentrate for improving the detergency properties of a gasoline fuel, the fuel concentrate comprising at least one first additive, at least one second additive and at least one third additive mixed with an organic liquid, the organic liquid being inert with respect to the first additive, the second additive and the third additive and being miscible with the fuel, wherein (1) the at least one first additive consists of a quaternary ammonium salt, wherein the first additive consisting of a quaternary ammonium salt is obtained by reacting a nitrogen compound containing a tertiary amine functional group with a quaternizing agent, the nitrogen compound being the product of the reaction of polyisobutenyl succinic anhydride with a compound containing at least one tertiary amine group and at least one group selected from primary amines, secondary amines and alcohols, the polyisobutenyl succinic anhydride having a number average molecular weight Mn of 1000 to 2800 g / mol, (2) the at least one second additive consists of polyisobutylene succinimide free of quaternary ammonium groups, (3) the at least one third additive is different from the first additive and the second additive and consists of a Mannich base, and wherein the mass ratio of the amount of the first additive to the amount of the second additive is in the range of 0.2:1 to 2.5:1, and The third additive, which consists of a Mannich base, is prepared using a phenol substituted with a polyisobutylene group.

23. A method for maintaining cleanliness and / or cleaning at least one of the internal components of a spark ignition engine, the method comprising at least the following steps: - preparing a fuel composition by additives to a fuel with at least one first additive, at least one second additive and at least one third additive or with a concentrate as defined in claim 22, and then - combusting said fuel composition in said spark ignition engine, wherein (1) the at least one first additive consists of a quaternary ammonium salt, wherein the first additive consisting of a quaternary ammonium salt is obtained by reacting a nitrogen compound containing a tertiary amine functional group with a quaternizing agent, the nitrogen compound being the product of the reaction of polyisobutenyl succinic anhydride with a compound containing at least one tertiary amine group and at least one group selected from primary amines, secondary amines and alcohols, the polyisobutenyl succinic anhydride having a number average molecular weight Mn of 1000 to 2800 g / mol, (2) the at least one second additive consists of polyisobutylene succinimide free of quaternary ammonium groups, (3) the at least one third additive is different from the first additive and the second additive and consists of a Mannich base, and wherein the mass ratio of the amount of the first additive to the amount of the second additive is in the range of 0.2:1 to 2.5:1, and The third additive, which consists of a Mannich base, is prepared using a phenol substituted with a polyisobutylene group.

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