EP2977435A1 - Cyclic carbonate derivatives as anti-soot additives for fuel - Google Patents

Abstract

The present invention relates to the use of a compound of formula (I): in which: represents a single or double bond; - R 1 and R 2 represent, independently of one another, a group selected from a hydrogen atom or a linear or branched C 1-20 -alkyl or C 2-20 -alkenyl group, optionally interrupted by one or more oxygen atoms, and which may be substituted with one or more R 4 groups; or else R 1 and R 2 together with the carbon atoms to which they are bonded form an optionally substituted C 5-8 -cycloalkyl group as an anti-soot additive for a fuel, in particular for a fuel of aviation for turbine engines. The invention also relates to a fuel composition, in particular an aviation fuel composition, comprising at least one compound of formula (I).

Description

The subject of the present invention is the use of novel polyoxygenated compounds, more specifically cyclic carbonates derivatives, as anti-soot additives for a fuel, in particular for an aviation fuel.

Improving air quality is now a major concern for all industrialized countries. Among the referenced pollutants, the emission, during the combustion of fuel, for example a diesel fuel, of carbonaceous particles, more commonly known as "soot", remains a major problem for the environment and health.

In general, soot formation is related to a local oxygen deficiency during fuel combustion. The mechanisms leading to the formation of these soot particles are still poorly known. They involve complex reactions of nucleation, particle surface growth and coagulation. More specifically, macromolecules formed by pyrolysis or oxidation of hydrocarbons condense to give carbon cores less than 2 nm in diameter. On this core are then adsorbed particles from the gas phase, such as polycylic aromatic compounds or dioxins. Finally, the agglomeration of these primary carbon cores forms a set of particles of size between 10 and 300 nm at the exhaust outlet.

Studies have shown that soot particles are one of the causes of the degradation of air quality, and that they contribute to the phenomenon of global warming. It has also been suggested that soot particles are harmful to health, and more particularly that they are carcinogenic to humans.

For these health and environmental reasons, the limitation of soot emissions remains an important issue.

Currently, in the field of diesel vehicles, the use of particulate filters reduces the emissions of soot particles at the outlet of the muffler and to meet regulatory and health standards. Different so-called regenerative filter technologies have been developed to collect soot particles, and remove the soot so trapped to regenerate the pressure drop of the filters.

For obvious reasons, it is preferable to develop ways of not collecting and removing soot, but reducing or even preventing their formation.

To this end, a great deal of research has been conducted in the field of motor fuels, in particular for diesel engines, aimed at reducing the formation of soot by adding polyoxygenated additives.

For example, various studies ([1], [2]) analyze the influence of the implementation in diesel motor fuels, dimethyl carbonate (DMC) or diethyl carbonate (DEC) on the release of fumes, carbon monoxide carbon or nitrogen oxides.

Also, Guo et al. propose the addition, in diesel fuels, of di (2-ethoxyethyl) carbonate ([3], [4]) or methyl 2-ethoxyethyl carbonate [5], to reduce the formation of smoke particles.

We can also mention the document EP 1 321 503 which describes the use in diesel fuel compositions of glycerol acetal carbonates for the purpose of reducing particulate emissions.

Finally, it has been proposed, in particular to reduce the formation of soot and fumes emitted by diesel engines, various compounds of the (poly) ether type, such as alkyl ether alkylen glycol compounds ( US 3, 594,136 ), polyoxaalcanes ( US 2010/0005707 ), polyoxymethylene di (alkyl polyglycol) ethers ( US 2011/0131871 ) or dialkyl glycol ethers ( GB 1,246,853 ).

The soot emission problem is also encountered in the field of fuels used in aeronautics, mainly during take-off of aircraft (maximum thrust).

The use in aviation fuels of polyoxygenated compounds of the linear carbonate type has already been described. For example, dimethyl carbonate and diethyl carbonate have been proposed to adjust the volatility and flash point of an aviation fuel [6]. We can also mention the document WO 95/23836 which describes the use of linear carbonates derivatives, preferably dimethyl carbonate, in diesel fuels, diesel or jet fuel, as compounds called "ECS" (for "Enhanced Combustion Structure" in English), such for example, to increase the rate of combustion or to reduce the combustion temperature. The carbonates compounds described in these documents are however not proposed for the purpose of reducing the formation of soot in aviation fuels.

Finally, the document WO 2010/061223 proposes the use of an organic compound, in particular propylene carbonate, to improve the solubilization of a solid ferric compound in a fuel composition.

However, to the inventors' knowledge, it has never been proposed to use a cyclic carbonate derivative as an anti-soot additive in a fuel.

To meet the increasingly stringent standards for soot emissions, there remains a need for new additives for automotive and aviation fuels to reduce soot formation.

Such additives must meet several requirements.

First, they must of course be compatible with an implementation in the formulation of targeted fuel, gasoline, diesel or aviation fuel. In particular, they must be soluble in the desired fuel.

Also, it is imperative that these additives do not induce an increase in the melting point of the fuel formulation in which they are used, which, for obvious reasons, could have dramatic consequences. In aeronautics, for example, fuels must maintain a very low melting point to withstand extreme temperature conditions at high altitudes.

In addition, it is preferable that these additives do not lower the calorific value of the fuels.

Finally, it is important that these additives, during fuel combustion, do not cause the formation of toxic derivatives or related pollutants and, in the case of aviation fuels for turbine engines, do not induce the formation of layers polymeric or metallic on the surface of the turbine.

The purpose of the present invention is precisely to provide new polyoxygenated compounds as additives with anti-soot properties for a fuel, and advantageously for an aviation fuel, in particular a "jet fuel".

dans laquelle :

• 
  représente une liaison simple ou double ;
  • R₁ et R₂ représentent, indépendamment l'un de l'autre, un groupe choisi parmi :
    • ∘ un atome d'hydrogène ;
    • ∘ un groupe C_1-20-alkyle ou C_2-20-alcényle, en particulier C_1-12-alkyle ou C_2-12-alcényle, linéaire ou ramifié, lesdits groupes pouvant être interrompus par un ou plusieurs atomes d'oxygène, et pouvant être éventuellement substitués par un ou plusieurs groupes R₄ ;

R₄ étant choisi parmi un groupe hydroxyle, oxo, hétérocycloalkyle de 3 à 6 chaînons et comportant de 1 à 3 atomes d'oxygène, ledit groupe hétérocycloalkyle étant éventuellement substitué par un ou plusieurs groupes C_1-6-alkyle et/ou oxo ;

• ou bien, R₁ et R₂ forment ensemble, avec les atomes de carbone auxquels ils sont liés un groupe C_5-8-cycloalkyle, éventuellement substitué par un ou plusieurs groupes, identiques ou différents l'un de l'autre, choisis parmi un groupe C_1-6-alkyle et un groupe R₄ tel que défini précédemment ;

à titre d'additif anti-suies pour un carburant, en particulier pour un carburant d'aviation.The invention thus has, according to a first aspect, the use of a compound of formula (I):

in which :

• 
  represents a single or double bond;
  • R ₁ and R ₂ represent, independently of one another, a group chosen from:
    • ∘ a hydrogen atom;
    • A linear or branched C _1-20 -alkyl or C _2-20 -alkenyl, in particular C _1-12 -alkyl or C _2-12 -alkenyl group, said groups possibly being interrupted by one or more oxygen atoms; and may be optionally substituted with one or more R ₄ groups;

R ₄ being selected from hydroxyl, oxo, heterocycloalkyl of 3 to 6 members and having 1 to 3 oxygen atoms, said heterocycloalkyl group being optionally substituted with one or more C _1-6 alkyl and / or oxo groups;

• or else R ₁ and R ₂ together with the carbon atoms to which they are bonded form a C _5-8 -cycloalkyl group, optionally substituted by one or more groups, which are identical or different from one another, chosen from a C _1-6 alkyl group and a R ₄ group as defined above;

as an anti-soot additive for a fuel, particularly for an aviation fuel.

The term "anti-soot additive" is understood to mean a compound which, used in a fuel, for example an aviation fuel, makes it possible to reduce the formation of soot during the combustion of the fuel.

The inventors have thus discovered that such cyclic carbonate derivatives of general formula (I) prove particularly effective when added to fuel formulations, and in particular to aviation fuel, to improve their energy performance and to reduce the amount of soot emitted.

Without wishing to be bound by theory, the anti-soot effectiveness of these polyoxygenated compounds is due to their ability to easily trap the first radical species resulting from the thermal degradation of fuels, which are involved in the formation of soot. More specifically, the polyoxygenated compounds according to the invention are able to rapidly create thermodynamically stable radicals, mainly by stabilizing the radicals in the alpha position of the oxygen atoms.

The cyclic carbonate derivatives according to the invention can be added to automotive fuels, for example gasoline, diesel or diesel fuel, or to aviation fuels.

Cyclic carbonates derivatives are particularly effective anti-soot additives for aviation fuels for turbine engines used in aeronautics, as detailed more precisely in the following text.

The invention also relates, in another of its aspects, to a fuel composition, in particular aviation fuel, comprising at least one compound of formula (I) according to the invention.

• C_t-z où t et z peuvent prendre les valeurs de 1 à 20, une chaîne carbonée pouvant avoir de t à z atomes de carbone, par exemple C_1-3 une chaîne carbonée qui peut avoir de 1 à 3 atomes de carbone ;
• alkyle, un groupe aliphatique saturée, linéaire ou ramifié ; par exemple un groupe C_1-6-alkyle représente une chaîne carbonée de 1 à 6 atomes de carbone, linéaire ou ramifiée, plus particulièrement un méthyle, éthyle, propyle, isopropyle, butyle, isobutyle, tert-butyle, pentyle, hexyle ;
• alkylène, un groupe alkyle divalent, linéaire ou ramifié ; par exemple un groupe C_1-3-alkylène représente une chaîne carbonée divalente de 1 à 3 atomes de carbone, linéaire ou ramifiée, par exemple un méthylène, éthylène, 1-méthyléthylène, propylène ;
• alcényle, un groupe aliphatique, linéaire ou ramifié, comportant au moins une insaturation ; par exemple un groupe C_2-4-alcényle représente une chaîne carbonée, linéaire ou ramifiée, comprenant de 2 à 4 atomes de carbone et comportant 1 ou 2 insaturations. A titre d'exemple, on peut citer le groupe -CH=CH₂.
• cycloalkyle, un groupe alkyle cyclique, par exemple un groupe C_5-8-cycloalkyle représente un groupe carboné cyclique de 5 à 8 atomes de carbone, plus particulièrement un cyclopentyle, cyclohexyle, cycloheptyle ou cyclooctyle. De préférence, le groupe cycloalkyle est un groupe cyclohexyle.
• hétérocycloalkyle, un groupe alkyle cyclique de 3 à 6 chaînons contenant de 1 à 3 atomes d'oxygène. A titre d'exemple de groupe hétérocycle à 5 chaînons, on peut citer un groupe dioxolane, en particulier le 1,3-dioxolane.

In the context of the invention, the following terms mean:

• C _tz where t and z can take the values from 1 to 20, a carbon chain which can have from t to z carbon atoms, for example a C _1-3 carbon chain which can have from 1 to 3 carbon atoms;
• alkyl, a saturated, linear or branched aliphatic group; for example a C _1-6 -alkyl group represents a carbon chain of 1 to 6 carbon atoms, linear or branched, more particularly a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, hexyl;
• alkylene, a divalent, linear or branched alkyl group; for example a C _1-3 -alkylene group represents a divalent carbon chain of 1 to 3 carbon atoms, linear or branched, for example a methylene, ethylene, 1-methylethylene, propylene;
• alkenyl, an aliphatic group, linear or branched, having at least one unsaturation; for example a C _2-4 -alkenyl group represents a carbon chain, linear or branched, comprising from 2 to 4 carbon atoms and having 1 or 2 unsaturations. By way of example, mention may be made of the group -CH = CH ₂ .
• cycloalkyl, a cyclic alkyl group, for example C _5-8 -cycloalkyl represents a cyclic carbon group of 5 to 8 carbon atoms, more particularly a cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. Preferably, the cycloalkyl group is a cyclohexyl group.
• heterocycloalkyl, a 3- to 6-membered cyclic alkyl group containing from 1 to 3 oxygen atoms. As an example of a 5-membered heterocycle group, there may be mentioned a dioxolane group, in particular 1,3-dioxolane.

A 5-membered heterocycloalkyl group substituted with an oxo group may especially be 1,3-dioxolan-2-one (better known as ethylene carbonate).

For the purposes of the present invention, it should be noted that the terms "ranging from ... to ..." and "between ... and ..." mean that the terminals are included, unless otherwise specified.

Unless otherwise indicated, the expression "comprising / including a" shall be understood as "comprising / including at least one".

According to a particular embodiment, R ₄ is chosen from a hydroxyl group, an oxo group and a 4- to 6-membered cyclic carbonate group, in particular ethylene carbonate (1,3-dioxolan-2-one), cyclic carbonate being optionally substituted with one or more C _1-6 -alkyl groups, in particular C _1-4 -alkyl.

• R₁ et R₂ représentent, indépendamment l'un de l'autre, un groupe choisi parmi :
  • ∘ un atome d'hydrogène ;
  • ∘ un groupe C_1-20-alkyle ou C_2-20-alcényle, en particulier C_1-12-alkyle ou C_2-12-alcényle, linéaire ou ramifié, lesdits groupes pouvant être interrompus par un ou plusieurs atomes d'oxygène, un ou plusieurs groupements
• O-C(O)-O- et/ou un ou plusieurs groupements -C(O)O-; et pouvant être éventuellement substitués par un ou plusieurs groupes choisis parmi un groupe hydroxyle et un groupe carbonate cyclique de 4 à 6 chaînons, en particulier le carbonate d'éthylène, ledit carbonate cyclique pouvant être lui-même éventuellement substitué par un ou plusieurs groupes C_1-4-alkyle ;
• ou bien, R₁ et R₂ forment ensemble, avec les atomes de carbone auxquels ils sont liés un groupe C_5-8-cycloalkyle, en particulier cyclohexyle, éventuellement substitué par un ou plusieurs groupes choisis parmi un groupe C_1-4-alkyle et un groupe carbonate cyclique de 4 à 6 chaînons, en particulier carbonate d'éthylène, ledit carbonate cyclique pouvant être lui-même éventuellement substitué par un ou plusieurs groupes C_1-4-alkyle.

A preferred subgroup of cyclic carbonate derivatives according to the invention consists of the compounds of formula (I) above, in which:

• R ₁ and R ₂ represent, independently of one another, a group chosen from:
  • ∘ a hydrogen atom;
  • A linear or branched C _1-20 -alkyl or C _2-20 -alkenyl, in particular C _1-12 -alkyl or C _2-12 -alkenyl group, said groups possibly being interrupted by one or more oxygen atoms; , one or more groupings
• OC (O) -O- and / or one or more -C (O) O- groups; and which may be optionally substituted by one or more groups selected from a hydroxyl group and a 4- to 6-membered cyclic carbonate group, in particular ethylene carbonate, said cyclic carbonate being itself optionally substituted by one or more groups C _1-4 -alkyl;
• or else R ₁ and R ₂ together with the carbon atoms to which they are bonded form a C _5-8 -cycloalkyl group, in particular cyclohexyl, optionally substituted by one or more groups selected from a C _1-4 -alkyl group; and a 4- to 6-membered cyclic carbonate group, in particular ethylene carbonate, said cyclic carbonate being itself optionally substituted by one or more C _1-4 -alkyl groups.

• 
  représente une liaison simple ou double ;
  • R₁ et R₂ représentent, indépendamment l'un de l'autre, un groupe choisi parmi :
    • ∘ un atome d'hydrogène ;
    • ∘ un groupe C_1-4-alkyle ou C_2-4-alcényle, linéaire ou ramifié, en particulier méthyle ou éthylène ; et
    • ∘ un groupe -CH₂-OR₃, dans lequel R₃ réprésente :
      • un atome d'hydrogène, ou
      • un groupe A-R₆, dans lequel :
        • A représente une liaison covalente, un groupe -C(O)- ou un groupe - C(O)-O- ; et
        • R₆ représente un groupe C_1-12-alkyle, en particulier C_1-8-alkyle, linéaire ou ramifié, éventuellement interrompu par un ou plusieurs atomes d'oxygène, un ou plusieurs groupements -O-C(O)-O- et/ou un ou plusieurs groupements -C(O)O- ; et éventuellement substitué par un ou plusieurs groupes carbonates cycliques de 4 à 6 chaînons, en particulier carbonate d'éthylène, lesdits carbonates cycliques pouvant être éventuellement substitués par un ou plusieurs groupes C_1-4-alkyle ;
  • ou bien, R₁ et R₂ forment ensemble, avec les atomes de carbone auxquels ils sont liés un groupe C_5-8-cycloalkyle, en particulier cyclohexyle, éventuellement substitué par un ou plusieurs groupes choisis parmi un groupe C_1-4-alkyle et un groupe carbonate cyclique de 4 à 6 chaînons, en particulier carbonate d'éthylène, ledit carbonate cyclique pouvant être lui-même éventuellement substitué par un ou plusieurs groupes C_1-4-alkyle.

A more particularly preferred subgroup of cyclic carbonate derivatives according to the invention consists of the compounds of formula (I) above, in which:

• 
  represents a single or double bond;
  • R ₁ and R ₂ represent, independently of one another, a group chosen from:
    • ∘ a hydrogen atom;
    • A linear or branched C _1-4 -alkyl or C _2-4 -alkenyl group, in particular methyl or ethylene; and
    • A group -CH ₂ -OR ₃ , in which R ₃ represents:
      • a hydrogen atom, or
      • an AR group ₆ , in which:
        • A represents a covalent bond, a -C (O) - group or a -C (O) -O- group; and
        • R ₆ represents a linear or branched C _1-12 -alkyl, in particular C _1-8 -alkyl group, optionally interrupted by one or more oxygen atoms, one or more -OC (O) -O- and / or or one or more -C (O) O- groups; and optionally substituted with one or more cyclic 4- to 6-membered cyclic carbonate groups, in particular ethylene carbonate, said cyclic carbonates being optionally substituted by one or more C _1-4 -alkyl groups;
  • or else R ₁ and R ₂ together with the carbon atoms to which they are bonded form a C _5-8 -cycloalkyl group, in particular cyclohexyl, optionally substituted by one or more groups selected from a C _1-4 -alkyl group; and a 4- to 6-membered cyclic carbonate group, in particular ethylene carbonate, said cyclic carbonate being itself optionally substituted by one or more C _1-4 -alkyl groups.

représente une liaison simple.Among the compounds of general formula (I), a subgroup of compounds consists of compounds for which

represents a single link.

représente une double liaison.Among the compounds of general formula (I), another subgroup of compounds consists of compounds for which

represents a double bond.

dans la formule (I) précitée représente une double liaison, au moins l'un des R₁ et R₂ présente avantageusement une double liaison conjuguée avec la double liaison du cycle 1,3-dioxol-2-one (système conjugué π-σ-π).According to a particular embodiment, in the case where

in formula (I) above represents a double bond, at least one of R ₁ and R ₂ advantageously has a conjugated double bond with the double bond of the 1,3-dioxol-2-one ring (conjugated system π-σ -π).

dans la formule (I) précitée représente une double liaison, au moins l'un des R₁ et R₂ peut représenter un groupe C_2-4-alcényle, en particulier un groupe éthylène.For example, in the case where

in formula (I) above represents a double bond, at least one of R ₁ and R ₂ may represent a C _2-4 -alkenyl group, in particular an ethylene group.

According to a particular embodiment, the cyclic carbonate derivatives used according to the invention have the aforementioned formula (I) in which at least one of R ₁ and R ₂ comprises a linear, preferably saturated, chain of at least 6 carbon atoms, in particular at least 8 carbon atoms, more particularly at least 10 carbon atoms and preferably 10 to 15 carbon atoms, said sequence being interrupted by one or more oxygen atoms.

Advantageously, such compounds give the fuel in which they are used, in addition to good anti-soot properties, hot lubrication properties.

According to a particularly preferred embodiment, at least one of R ₁ and R ₂ comprises at least one polyether unit.

dans lequel :

• X, identiques ou différents, représentent un groupe C_1-4-alkylène, en particulier C_1-3-alkylène, de préférence X représentent -(CH₂)₂- et/ou -(CH₂-CH(CH₃))- ; et
• n est un entier allant de 2 à 10, en particulier de 2 à 8 et plus particulièrement de 2 à 4.

In particular, the polyether unit may be of the type

in which :

• X, which may be identical or different, represent a C _1-4 -alkylene group, in particular C _1-3 -alkylene, preferably X represent - (CH ₂ ) ₂ - and / or - (CH ₂ -CH (CH ₃ )) -; and
• n is an integer ranging from 2 to 10, in particular from 2 to 8 and more particularly from 2 to 4.

In particular, at least one of R ₁ and R ₂ may, for example, comprise at least one polyethylene glycol unit (X represents a - (CH ₂ ) ₂ - group) and / or a polypropylene glycol unit (X represents a group - (CH ₂ -CH (CH ₃ )) -).

Among the compounds of formula (I), a subgroup of compounds is composed of compounds for which R ₁ and R ₂ are identical.

According to a particular embodiment, R ₁ and R ₂ both represent a hydrogen atom or a C _1-4 alkyl group, in particular a methyl group.

Thus, among the compounds of formula (I) that can be used as anti-soot additives according to the invention, mention may be made of ethylene carbonate (IUPAC name: 1,3-dioxolan-2-one), vinylene carbonate (named IUPAC: 1,3-dioxol-2-one) or 4,5-dimethyl-1,3-dioxolan-2-one.

Among the compounds of formula (I), another subgroup of compounds consists of compounds for which R ₁ and R ₂ are different.

R ₁ and R ₂ , different, can be defined, independently of one another, according to any one of the above definitions.

According to a particularly preferred embodiment, one of R ₁ and R ₂ represents a hydrogen atom, and the other of R ₁ and R ₂ represents a group, different from a hydrogen atom, from the groups previously defined.

• l'un des R₁ et R₂ représente un atome d'hydrogène, et
• l'autre des R₁ et R₂ représente un groupe C_1-20-alkyle ou C_2-20-alcényle, en particulier C_1-12-alkyle ou C_2-12-alcényle, linéaire ou ramifié, éventuellement interrompu par un ou plusieurs atomes d'oxygène, un ou plusieurs groupements -O-C(O)-O- et/ou un ou plusieurs groupements -C(O)O- ; et éventuellement substitué par un ou plusieurs groupes choisis parmi un groupe hydroxyle et un carbonate cyclique de 4 à 6 chaînons, en particulier le carbonate d'éthylène, ledit carbonate cyclique pouvant être lui-même éventuellement substitué par un ou plusieurs groupes C_1-4-alkyle.

In particular, a subgroup of compounds according to the invention consists of the compounds of formula (I) above for which:

• one of R ₁ and R ₂ represents a hydrogen atom, and
• the other of R ₁ and R ₂ represents a linear or branched C _1-20 -alkyl or C _2-20 -alkenyl, in particular C _1-12 -alkyl or C _2-12 -alkenyl group, optionally interrupted by a or more oxygen atoms, one or more -OC (O) -O- groups and / or one or more -C (O) O- groups; and optionally substituted with one or more groups selected from a hydroxyl group and a cyclic carbonate of 4 to 6 members, in particular ethylene carbonate, said cyclic carbonate being itself possibly optionally substituted with one or more C _1-4 groups alkyl.

• l'un des R₁ et R₂ représente un atome d'hydrogène, et
• l'autre des R₁ et R₂ représente :
  • ∘ un groupe C_1-4-alkyle ou C_2-4-alcényle, linéaire ou ramifié, en particulier méthyle ou éthylène ; ou
  • ∘ un groupe -CH₂-OR₃, dans lequel R₃ réprésente :
    • un atome d'hydrogène, ou
    • un groupe A-R₆, dans lequel :
      • A représente une liaison covalente, un groupe -C(O)- ou un groupe -C(O)-O- ; et
      • R₆ représente un groupe C_1-12-alkyle, en particulier C_1-8-alkyle, linéaire ou ramifié, éventuellement interrompu par un ou plusieurs atomes d'oxygène, un ou plusieurs groupements -O-C(O)-O- et/ou un ou plusieurs groupements -C(O)O- ; et éventuellement substitué par un ou plusieurs groupes carbonates cycliques de 4 à 6 chaînons, en particulier carbonate d'éthylène, lesdits carbonates cycliques pouvant être éventuellement substitués par un ou plusieurs groupes C_1-4-alkyle.

Preferably, the cyclic carbonate derivatives according to the invention are of formula (I) above, in which:

• one of R ₁ and R ₂ represents a hydrogen atom, and
• the other of R ₁ and R ₂ represents:
  • A linear or branched C _1-4 -alkyl or C _2-4 -alkenyl group, in particular methyl or ethylene; or
  • A group -CH ₂ -OR ₃ , in which R ₃ represents:
    • a hydrogen atom, or
    • an AR group ₆ , in which:
      • A represents a covalent bond, a -C (O) - group or a -C (O) -O- group; and
      • R ₆ represents a linear or branched C _1-12 -alkyl, in particular C _1-8 -alkyl group, optionally interrupted by one or more oxygen atoms, one or more -OC (O) -O- and / or or one or more -C (O) O- groups; and optionally substituted by one or more cyclic 4- to 6-membered cyclic carbonate groups, in particular ethylene carbonate, said cyclic carbonates being optionally substituted by one or more C _1-4 -alkyl groups.

dans laquelle R₃ représente un groupe choisi parmi :

• un atome d'hydrogène ; et
• un groupe -A-R₆, dans lequel :
  • ∘ A représente une liaison covalente, un groupe -C(O)- ou un groupe -C(O)-O- ; et
  • ∘ R₆ représente un groupe C_1-12-alkyle, en particulier C_1-8-alkyle, linéaire ou ramifié, éventuellement interrompu par un ou plusieurs atomes d'oxygène, un ou plusieurs groupements -O-C(O)-O- et/ou un ou plusieurs groupements -C(O)O- ; et éventuellement substitué par un ou plusieurs groupes carbonates cyclique de 4 à 6 chaînons, en particulier carbonate d'éthylène, lesdits carbonates cycliques pouvant être éventuellement substitués par un ou plusieurs groupes C_1-4-alkyle.

Among the compounds of general formula (I) above, a subgroup of compounds is more particularly composed of compounds of formula (Ia):

in which R ₃ represents a group chosen from:

• a hydrogen atom; and
• a group -AR ₆ , in which:
  • ∘ A represents a covalent bond, a -C (O) - group or a -C (O) -O- group; and
  • R ₆ represents a linear or branched C _1-12 -alkyl, in particular C _1-8 -alkyl group, optionally interrupted by one or more oxygen atoms, one or more -OC (O) -O- groups and or one or more -C (O) O- groups; and optionally substituted with one or more cyclic carbonate groups of 4 to 6 linkages, in particular ethylene carbonate, said cyclic carbonates being optionally substituted by one or more C _1-4 -alkyl groups.

Other subgroups consisting of the compounds of formula (Ia) are also part of the present invention.

• un atome d'hydrogène ;
• un groupe -C(O)-O-R₇ ou -C(O)-R₇, avec R₇ représentant un groupe C_1-4-alkyle, en particulier méthyle ou éthyle ; et
• un groupe C_1-12-alkyle, en particulier C_1-8-alkyle, linéaire ou ramifié, éventuellement interrompu par un ou plusieurs atomes d'oxygène, un ou plusieurs groupements -O-C(O)-O- et/ou un ou plusieurs groupements -C(O)O- ; et éventuellement substitué par un ou plusieurs groupes carbonates cycliques de 4 à 6 chaînons, en particulier carbonate d'éthylène, lesdits carbonates cycliques pouvant être éventuellement substitués par un ou plusieurs groupes C_1-4-alkyle.

A subgroup of compounds of formula (Ia) is more particularly composed of compounds for which R ₃ represents a group chosen from:

• a hydrogen atom;
• a group -C (O) -OR ₇ or -C (O) -R ₇ , with R ₇ representing a C _1-4 alkyl group, in particular methyl or ethyl; and
• a linear or branched C _1-12 -alkyl, in particular C _1-8 -alkyl group, optionally interrupted by one or more oxygen atoms, one or more -OC (O) -O- and / or one or more several groups -C (O) O-; and optionally substituted by one or more cyclic 4- to 6-membered cyclic carbonate groups, in particular ethylene carbonate, said cyclic carbonates being optionally substituted by one or more C _1-4 -alkyl groups.

According to a particular embodiment, R ₃ in formula (Ia) above represents a hydrogen atom.

According to another particular embodiment, R ₃ in the formula (Ia) above represents a C _1-4 -alkyl group, in particular a methyl group, optionally substituted by a cyclic carbonate of 4 to 6 members, in particular the carbonate of 'ethylene.

According to another particular embodiment, R ₃ in formula (Ia) above represents a -C (O) -OR _{7 group} , with R ₇ representing a C _1-4 alkyl group, in particular methyl or ethyl.

According to yet another particular embodiment, R ₃ in the above formula (Ia) represents a C ₃ -C ₁₂ -alkyl, in particular C _4-7 -alkyl, linear group, interrupted by one or more oxygen atoms, said alkyl group being optionally substituted by one or more groups selected from a group -OC (O) OR ₈ , with R ₈ representing a C _1-4 alkyl group, in particular methyl, and a cyclic carbonate group of 4 to 6 members, in particular ethylene carbonate.

According to another particularly preferred embodiment, R ₃ in formula (Ia) above incorporates at least one polyether unit.

dans lequel :

• X, identiques ou différents, représentent un groupe C_1-4-alkylène, en particulier C_1-3-alkylène, de préférence X représentent -(CH₂)₂- et/ou -(CH₂-CH(CH₃))- ; et
• n est un entier allant de 2 à 10, en particulier de 2 à 8 et plus particulièrement de 2 à 4.

In particular, the polyether unit may be of the type

in which :

• X, which may be identical or different, represent a C _1-4 -alkylene group, in particular C _1-3 -alkylene, preferably X represent - (CH ₂ ) ₂ - and / or - (CH ₂ -CH (CH ₃ )) -; and
• n is an integer ranging from 2 to 10, in particular from 2 to 8 and more particularly from 2 to 4.

R ₃ may for example comprise at least one polyethylene glycol unit (X represents a - (CH ₂ ) ₂ - group) and / or a polypropylene glycol unit (X represents a group - (CH ₂ -CH (CH ₃ )) -) .

dans laquelle :

• Y représente un groupe C_1-4-alkyle, en particulier méthyle ou éthyle, portant éventuellement un groupe carbonate cyclique de 4 à 6 chaînons, en particulier carbonate d'éthylène ; et
• X et n sont tels que définis précédemment.

Among the compounds of formula (Ia) above, a subgroup of compounds thus consists of the compounds of formula (Ia-i) below:

in which :

• Y represents a C _1-4 alkyl group, in particular methyl or ethyl, optionally bearing a 4- to 6-membered cyclic carbonate group, in particular ethylene carbonate; and
• X and n are as defined above.

According to a particular embodiment, Y in the formula (Ia-i) above represents a C _1-4 -alkyl group, in particular methyl or ethyl.

According to another particular embodiment, Y in formula (Ia-i) above, represents a methyl bearing a cyclic carbonate group of 4 to 6 members, in particular ethylene carbonate.

dans laquelle B représente une liaison covalente ou un groupe C_1-10 alkylène, en particulier C_1-7-alkylène, linéaire ou ramifié, éventuellement interrompu par un ou plusieurs atomes d'oxygène, un ou plusieurs groupements -O-C(O)-O- et/ou un ou plusieurs groupements -C(O)O-.Among the compounds of formula (Ia) mentioned above, another subgroup of compounds is more particularly composed of compounds of formula (Ia-ii) below:

in which B represents a covalent bond or a C _1-10 alkylene group, in particular C _1-7 -alkylene, linear or branched, optionally interrupted by one or more oxygen atoms, one or more -OC (O) groups - O- and / or one or more -C (O) O- groups.

According to a particular embodiment, B represents a covalent bond.

According to another particular embodiment, B represents a C _3-8 -alkylene, in particular C _3-7 -alkylene, linear group, interrupted by one or more oxygen atoms and optionally substituted by one or more -OC groups ( O) OR ₈ with R ₈ representing a C _1-4 alkyl group, in particular methyl.

According to yet another particular embodiment, B represents a polyether unit is of type (̵X-O-) ̵ _n with X and n being as defined above.

• 
  représente une liaison simple ; et
• R₁ et R₂ forment ensemble, avec les atomes de carbone auxquels ils sont liés un groupe C_5-8-cycloalkyle éventuellement substitué par un ou plusieurs groupes choisis parmi un groupe C_1-4-alkyle et un groupe carbonate cyclique de 4 à 6 chaînons, en particulier le carbonate d'éthylène, ledit carbonate cyclique pouvant être lui-même éventuellement substitué par un ou plusieurs groupes C_1-4-alkyle.

Among the cyclic carbonate derivatives according to the invention, another subgroup consists of the compounds of general formula (I), in which:

• 
  represents a single link; and
• R ₁ and R ₂ together with the carbon atoms to which they are bonded form a C _5-8 -cycloalkyl group optionally substituted by one or more groups selected from a C _1-4 alkyl group and a cyclic carbonate group of 4 to 6-membered, in particular ethylene carbonate, said cyclic carbonate being itself optionally substituted by one or more C _1-4 -alkyl groups.

dans laquelle R₇ représente un groupe choisi parmi :

• ∘ un atome d'hydrogène,
• ∘ un groupe C_1-4-alkyle, et
• ∘ un groupe carbonate cyclique de 4 à 6 chaînons, en particulier carbonate d'éthylène, éventuellement substitué par un ou plusieurs groupes C_1-4-alkyle, en particulier méthyle.

In particular, a subgroup of compounds according to the invention consists of the compounds of general formula (Ib) below:

in which R ₇ represents a group chosen from:

• ∘ a hydrogen atom,
• ∘ a C _1-4 -alkyl group, and
• ∘ a 4- to 6-membered cyclic carbonate group, in particular ethylene carbonate, optionally substituted with one or more C _1-4 -alkyl groups, in particular methyl.

According to a particular embodiment, R ₇ in formula (Ib) above represents an ethylene carbonate group, optionally substituted with one or more methyl groups.

n°2

n°3

n°4

n°5

n°6

n°7

n°8

n°9

n°10

n°11

n°12

n°13

n°14

n°15

n°16

Among the compounds of formula (I), there may be mentioned the following derivatives, summarized in Table 1 below. <u> TABLE 1 </ u> # 1

# 2

# 3

# 4

# 5

# 6

# 7

# 8

# 9

# 10

# 11

# 12

# 13

# 14

# 15

# 16

It is understood that the specific compounds No. 1 to No. 16 presented above are only given by way of illustration and not limitation of the invention.

The cyclic carbonate derivatives may be commercially available or prepared according to synthetic methods described in the literature and known to those skilled in the art.

As examples of known synthetic routes for obtaining cyclic carbonates, mention may be made of cocyclisation reactions, for example between carbon dioxide and an allyl alcohol; transcarbonation reactions from a suitable linear alkyl carbonate and hydroxy compound; or the phosgenation reactions of dihydroxy compounds.

Application in a fuel

The compounds of formula (I) according to the invention may be used as anti-soot additives in a fuel formulation, in particular a diesel fuel, diesel or gasoline for the automobile, or an aviation fuel.

According to another of its aspects, the invention thus relates to a fuel composition comprising at least one compound of formula (I) as defined above.

The present invention further relates, according to another of its aspects, to a receptacle, in particular a fuel tank of an overhead or land vehicle, containing a fuel supplemented with at least one compound of formula (I) as defined above. .

The invention also relates to an aircraft or land vehicle, in particular an aircraft, comprising a fuel tank supplemented with at least one compound of formula (I) as defined above.

It is understood that a compound of formula (I) according to the invention may be added to a fuel formulation, alone or in combination with one or more other compounds of formula (I).

It is up to those skilled in the art to adapt the anti-soot additive (s) content of formula (I) according to the invention to be introduced into the fuel formulation, in particular with regard to the nature of the fuel, from or said anti-soot additives of formula (I) used, and expected anti-soot properties.

The said compound (s) of general formula (I) according to the invention are more particularly introduced into a fuel formulation in a content such that they are soluble in the fuel formulation.

In general, the said compounds of formula (I) can be used in a conventional formulation of fuel, in particular an aviation fuel, in a proportion of 1 to 40%, in particular from 1 to 20% , relative to the total volume of the fuel composition.

According to a particularly preferred embodiment, the fuel composition is an aviation fuel composition.

"Aviation fuel" means a fuel intended for use in an aircraft, in particular an airplane, and meeting the international specifications established for aviation fuels as set forth below.

In particular, the aviation fuel composition according to the invention may be a fuel intended for the operation of turbine engine engines (turbojet, turboprop engine), commonly known as "jet fuel" or "jet fuel" in English and, as such, can more particularly meet the standards required for jet fuels, for example those of Jet A-1 jet fuel.

According to an alternative embodiment, said one or more compounds of formula (I) may be added to a conventional fuel, for example an aviation fuel.

In practice, a conventional fuel can be supplemented with one or more compounds of formula (I) according to the invention by adding, for example, the compound (s) of formula (I) directly within the tank previously filled with fuel.

As aviation fuels, for example, the fuels known to those skilled in the art may be mentioned under the following names: JP-4 (MIL-T-5624), JP-5, JP-7 (MIL-T-38219), JP -8 (MIL-T-83133) in the field of military aviation, Jet A and Jet A-1 (ASTM-D 1655) in the field of civil aviation.

Aviation fuels are based on kerosene, alone or mixed with gasoline (eg 50% kerosene-50% gasoline for JP-4, 99.5% kerosene for JP-5 and JP-8, 100% kerosene for Jet A-1) and include additives adjusted for specific uses of the fuel, such as, for example, antioxidants, corrosion inhibitors, metal catalysis inhibitors, icing inhibitors, in limited quantities.

In general, jet fuels are produced from a fraction of kerosene derived directly from the atmospheric distillation of crude oil and whose distillation points are between 140 and 300 ° C, and from carbon chains of 9 to 16 carbon atoms. .

Aviation fuels have the particularity of having to meet the same levels of specifications worldwide, resulting directly from the particular conditions, in particular extreme temperature variations, in which they are used. The properties and specifications of these aviation fuels are more particularly detailed in the document: "Kerosene / Jet Fuel Category Assessment Document", submitted to the US EPA by the American Petroleum Institute, September 21, 2010 . Particularly advantageous aviation fuels are, for example, those conforming to the AFQRJOS specification ( "Fuel Fuel Quality Requirements for Jointly Operated Systems") Issue 18 for November 1999 Jet A-1 (this specification incorporates the most stringent criteria of ASTM Specification D 1655 and the British Specification DEF STAN 91-91).

In civil aviation, the most common fuel is Jet A1 jet fuel. This must have a defrost point below -47 ° C (typical value of -50 ° C). Jet-A with a defrost point of -40 ° C is of inferior quality to Jet A-1 and mainly used in the United States; Jet B with a defrost point below -50 ° C, the trade name for JP-4, is only used in very cold climates.

These aviation fuels all have a calorific value of between 42.8 and 43.6 MJ / kg. The minimum flash point is 60 ° C for JP-5, 38 ° C for Jet A-1 and JP-8 (typical value for Jet A-1 of 50 ° C). The characteristic densities are 810 kg / m ³ for the Jet A-1, 760 kg / m ³ for the Jet B.

Other specifications can still be quoted. For example, Jet A-1 must imperatively have a sulfur content of less than 0.30% by weight, and an aromatic content of less than 22% by volume.

Of course, the one or more compounds of formula (I) are added to the conventional fuel, for example a Jet A-1 fuel, in an amount such that they do not affect the specifications to which this fuel must meet.

Thus, according to a particular embodiment, an aviation fuel composition according to the invention has a freezing point below -40 ° C, in particular between -60 and -40 ° C, preferably below -47 ° C. ° C, and can thus be adapted to its potential use in cold conditions, for example in the context of use in civil aviation or military.

Preferably, an aviation fuel composition according to the invention has a good calorific value, in particular greater than 40 MJ / kg, in particular greater than 42.5 MJ / kg.

References :

1. [1] Rounce et al., "Comparison of Diesel and Biodiesel Emissions Using Dimethyl Carbonate and an Oxygenate Additive", UK. Energy & Fuels (2010), 24 (9), 4812-4819 ;
2. [2] Cheung et al., "Performance of diesel engine using diesel fuel blended with dimethyl carbonate," Southeast University Press, Nanjing, Peop. Rep. China CODEN: 69GNB5. CAN 142: 300536 ;
3. [3] Guo et al., "Development of di (2-ethoxyethyl) carbonate as a clean diesel fuel additive", American Chemical Society, Division of Petroleum Chemistry, CODEN: ACPCAT ISSN: 0569-3799. CAN 145: 491855 YEAR 2006: 270943 ;
4. [4] Guo et al. "Development of di (2-ethoxyethyl) carbonate used as a clean diesel fuel additive", American Chemical Society, Washington, DC CODEN: 69HYEC Conference; AN 2006: 249481 ;
5. [5] Guo et al. "Investigation of a novel oxygenate, methyl 2-ethoxyethyl carbonate, as a clean diesel fuel additive", Xi'an Research Institute of Hi-Tech, Xi'an, Peop. Rep. China. American Chemical Society, Washington, DC CODEN: 69GQMP Conference; YEAR 2005: 190024 ;
6. [6] Li Dan et al., Journal of Hazardous Materials (2009), 161 (2-3), 1193-1201 .

Claims (15)

Use of a compound of formula (I)

in which :

represents a single or double bond; - R ₁ and R ₂ represent, independently of one another, a group selected from: ∘ a hydrogen atom; A linear or branched C _1-20 -alkyl or C _2-20 -alkenyl group, said groups being capable of being interrupted by one or more oxygen atoms, and possibly substituted with one or more R ₄ groups; R ₄ being selected from hydroxyl, oxo, heterocycloalkyl of 3 to 6 members and having 1 to 3 oxygen atoms, said heterocycloalkyl group being optionally substituted with one or more C _1-6 alkyl and / or oxo groups; or R ₁ and R ₂ together with the carbon atoms to which they are bonded form a C _5-8 -cycloalkyl group optionally substituted with one or more groups, which are identical to or different from one another, chosen from a C _1-6 alkyl group and a R ₄ group as defined above; as an anti-soot additive for a fuel. Use according to claim 1, the fuel being an aviation fuel. Use according to claim 1 or 2, wherein: - R ₁ and R ₂ represent, independently of one another, a group selected from: ∘ a hydrogen atom; A linear or branched C _1-20 -alkyl or C _2-20 -alkenyl, in particular C _1-12 -alkyl or C _2-12 -alkenyl group, said groups possibly being interrupted by one or more atoms oxygen, one or more -OC (O) -O- groups and / or one or more -C (O) O- groups; and which may be optionally substituted by one or more groups selected from a hydroxyl group and a 4- to 6-membered cyclic carbonate group, particularly ethylene carbonate; or else R ₁ and R ₂ together with the carbon atoms to which they are bonded form a C _5-8 -cycloalkyl group, in particular cyclohexyl, optionally substituted with one or more groups selected from a C _1-4 group; alkyl and a cyclic carbonate group of 4 to 6 members, in particular ethylene carbonate;
said cyclic carbonate, in particular ethylene carbonate, which may itself be optionally substituted by one or more C _1-4 -alkyl groups. Use according to any one of the preceding claims, wherein: - R ₁ and R ₂ represent, independently of one another, a group selected from: ∘ a hydrogen atom; A linear or branched C _1-4 -alkyl or C _2-4 -alkenyl group, in particular methyl or ethylene; and A group -CH ₂ -OR ₃ , in which R ₃ represents: a hydrogen atom, or an AR group ₆ , in which: A represents a covalent bond, a -C (O) - group or a -C (O) -O- group; and R ₆ represents a linear or branched C _1-12 -alkyl, in particular C _1-8 -alkyl group, optionally interrupted by one or more oxygen atoms, one or more -OC (O) -O- and / or or one or more -C (O) O- groups; and optionally substituted with one or more cyclic 4- to 6-membered cyclic carbonate groups, in particular ethylene carbonate, said cyclic carbonates being optionally substituted by one or more C _1-4 -alkyl groups; or else R ₁ and R ₂ together with the carbon atoms to which they are bonded form a C _5-8 -cycloalkyl group, in particular cyclohexyl, optionally substituted with one or more groups selected from a C _1-4 group; alkyl and a cyclic carbonate group of 4 6-membered ring, in particular ethylene carbonate, said cyclic carbonate being itself optionally substituted by one or more C _1-4 -alkyl groups. Use according to any one of the preceding claims, wherein R ₁ and R ₂ , which are identical, represent a hydrogen atom or a C _1-4 alkyl group, in particular a methyl group. Use according to any one of claims 1 to 4, wherein: one of R ₁ and R ₂ represents a hydrogen atom; and - the other of R ₁ and R ₂ represents a C _1-20 -alkyl or C _2-20 -alkenyl, in particular C _1-12 -alkyl or C _2-12 -alkenyl, linear or branched group, said groups optionally interrupted by one or more oxygen atoms, one or more -OC (O) -O- groups and / or one or more -C (O) O- groups; and optionally substituted by one or more groups selected from a hydroxyl group and a cyclic carbonate of 4 to 6 members, in particular ethylene carbonate, said cyclic carbonate being itself possibly optionally substituted with one or more C _1-4 groups alkyl. Use according to any one of claims 1 to 4 and 6, said compound being of formula:

in which R ₃ represents a group chosen from: a hydrogen atom; and a group -AR ₆ , in which: ∘ A represents a covalent bond, a -C (O) - group or a -C (O) -O- group; and R ₆ represents a linear or branched C _1-12 -alkyl, in particular C _1-8 -alkyl group, optionally interrupted by one or more oxygen atoms, one or more -OC (O) -O- groups and or one or more -C (O) O- groups; and optionally substituted with one or more cyclic carbonate groups of 4 to 6 linkages, in particular ethylene carbonate, said cyclic carbonates being optionally substituted by one or more C _1-4 -alkyl groups. Use according to the preceding claim, in which R ₃ incorporates at least one polyether unit, in particular a unit

in which : X, which are identical or different, represent a C _1-4 -alkylene group, in particular C _1-3 -alkylene, preferably X represent - (CH ₂ ) ₂ - and / or - (CH ₂ -CH (CH ₃ ) ) -; and n is an integer ranging from 2 to 10, in particular from 2 to 8 and more particularly from 2 to 4. Use according to claim 7 or 8, said compound being of formula (Ia-i):

in which : Y represents a C _1-4 alkyl group, in particular methyl or ethyl, optionally bearing a 4- to 6-membered cyclic carbonate group, in particular ethylene carbonate; and X and n are as defined in claim 8. Use according to any one of claims 7 and 8, said compound being of formula (Ia-ii):

in which B represents: ∘ a covalent bond, or A linear or branched C _1-10 -alkylene, in particular C _1-7 -alkylene group, optionally interrupted by one or more oxygen atoms, one or more -OC (O) -O- groups and / or a or more -C (O) O- groups, in particular B represents a polyether unit, in particular a unit (̵X-O) ̵ _n with X and n being as defined in claim 8. Use according to any one of claims 1 to 4, said compound being of formula (Ib):

in which R ₇ represents a group chosen from: ∘ a hydrogen atom, ∘ a C _1-4 -alkyl group, and ∘ a 4- to 6-membered cyclic carbonate group, in particular ethylene carbonate, optionally substituted with one or more C _1-4 -alkyl groups, in particular methyl. Use according to any one of Claims 1 to 4, said compound of formula (I) being chosen from the following compounds: # 1

# 2

# 3

# 4

# 5

# 6

# 7

# 8

# 9

# 10

# 11

# 12

# 13

# 14

# 15

# 16

Fuel composition, in particular aviation fuel, comprising at least one compound of formula (I) as defined according to any one of claims 1 to 12. Receptacle containing a fuel composition as defined in claim 13, said receptacle being in particular a fuel tank of an overhead or land vehicle. Apparatus for locomotion overhead or overhead, in particular aircraft, comprising a fuel tank as defined in claim 14.