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    • 专利摘要:
    The invention relates to a block copolymer comprising: at least one block A of formula (I) below: in which p is an integer ranging from 2 to 40, R 1 'is chosen from hydrogen and the methyl group, R2 is chosen from hydrocarbon chains C1 to C34, - at least one block B of formula (II) below: in which n is an integer ranging from 2 to 40, R1 is chosen from hydrogen and the methyl group, Z is chosen among the oxygen atom and the -NR'- group with R 'being chosen from a hydrogen atom and the C1 to C12 hydrocarbon chains, G is a C1 to C34 hydrocarbon chain substituted with at least one ammonium group; quaternary and optionally one or more hydroxyl groups. The invention also relates to the use of such a block copolymer as a detergent additive in a liquid fuel of an internal combustion engine.
    公开号:FR3041349A1
    申请号:FR1558831
    申请日:2015-09-18
    公开日:2017-03-24
    发明作者:Julie Prevost
    申请人:Total Marketing Services SA；
    IPC主号:
    专利说明:

    COPOLYMER USEFUL AS DETERGENT ADDITIVE FOR FUEL
    The present invention relates to a block copolymer and its use as a detergent additive in a liquid fuel of an internal combustion engine. The invention also relates to a method for maintaining the cleanliness and / or cleaning of at least one of the internal parts of an internal combustion engine.
    STATE OF THE PRIOR ART
    Liquid fuels from internal combustion engines contain components that can degrade during engine operation. The problem of deposits in the internal parts of combustion engines is well known to motorists. It has been shown that the formation of these deposits has consequences on engine performance and in particular has a negative impact on fuel consumption and particulate emissions. Advances in fuel additive technology have addressed this problem. Additives known as detergents used in fuels have already been proposed to maintain the cleanliness of the engine by limiting the deposits ("Keep-clean" effect) or by reducing the deposits already present in the internal parts of the combustion engine (effect " clean-up "in English). By way of example, mention may be made of US4171959 which describes a detergent additive for petrol fuel containing a quaternary ammonium function. The document WO2006135881 describes a detergent additive containing a quaternary ammonium salt used to reduce or clean the deposits, in particular on the intake valves. Nevertheless, engine technology is constantly evolving and fuel requirements must evolve to cope with these advances in combustion engine technology. In particular, the new petrol or diesel direct injection systems expose the injectors to more severe pressure and temperature conditions, which favors the formation of deposits. In addition, these new injection systems have more complex geometries to optimize the spraying, including more holes with smaller diameters but, on the other hand, induce greater sensitivity to deposits. The presence of deposits can alter the performance of combustion including increasing pollutant emissions and particulate emissions. Other consequences of the excessive presence of deposits have been reported in the literature, such as increased fuel consumption and maneuverability problems.
    Preventing and reducing deposits in these new engines is essential for optimal operation of today's engines. There is therefore a need to provide detergent fuel additives promoting optimal operation of combustion engines, especially for new engine technologies.
    There is also a need for a universal detergent additive capable of acting on the deposits whatever the engine technology and / or the nature of the fuel.
    OBJECT OF THE INVENTION The object according to the invention relates to novel block copolymers.
    The Applicant has discovered that the block copolymers according to the invention have remarkable properties as a detergent additive in liquid fuels of an internal combustion engine. The block copolymers according to the invention used in these fuels make it possible to maintain the cleanliness of the engine, in particular by limiting or avoiding the formation of the deposits ("Keep-clean" effect) or by reducing the deposits already present in the internal parts of the combustion engine ("clean-up" effect).
    The advantages associated with the use of such copolymers according to the invention are: optimum operation of the engine, reduced fuel consumption, improved vehicle handling, reduced pollutant emissions, and economy. due to less engine maintenance. The subject of the present invention relates to a block copolymer comprising: at least one block A of formula (I) below:
    (I) wherein p is an integer from 2 to 40,
    Ri is chosen from hydrogen and the methyl group, R2 is chosen from C1-C34 hydrocarbon chains, at least one block B of formula (II) below:
    (II) wherein n is an integer from 2 to 40,
    Ri is chosen from hydrogen and the methyl group, Z is chosen from the oxygen atom and the group -NR'- with R 'being chosen from a hydrogen atom and the C12 to C12 hydrocarbon chains, G is a C1-C34 hydrocarbon chain substituted with at least one quaternary ammonium group and optionally one or more hydroxyl groups.
    According to one particular embodiment, the block copolymer comprises: block A consists of a chain of structural units derived from an alkyl (meth) acrylate monomer (ma), and block B consists of a chain of structural units derived from an alkyl (meth) acrylate monomer or alkyl (meth) acrylamide (mb), the alkyl radical of which consists of a C1-C34 hydrocarbon chain substituted with at least one quaternary ammonium group and optionally one or more hydroxyl groups.
    Advantageously, the monomer (a1) is chosen from C1-C34 alkyl acrylates and C1-C34 alkyl methacrylates.
    According to a particular embodiment, the alkyl radical of the monomer (mb) is substituted by at least one quaternary ammonium group and one or more hydroxyl groups.
    Advantageously, the quaternary ammonium group is chosen from quaternary salts of pyrrolinium, pyridinium, imidazolium, triazolium, triazinium, oxazolium and isoxazolium.
    According to one variant, the quaternary ammonium group is chosen from quaternary trialkylammonium, guanidinium and iminium salts.
    According to a particular preferred embodiment, block B is represented by one of the following formulas (III) and (IV):
    (III) (IV) wherein η, Z and R! are as defined in formula (II) above, X 'is selected from hydroxide ions, halides and organic anions, R2 is selected from C1-C34 hydrocarbon chains, optionally substituted by at least one hydroxyl group, R3, R4 and R5 are identical or different and chosen, independently, from C18 to C18 hydrocarbon chains, it being understood that the alkyl groups R3, R4 and R5 may contain one or more groups chosen from: a nitrogen atom, an atom of oxygen and a carbonyl group and that the groups R3, R4 and R5 may be connected together in pairs to form one or more rings, R6 and R7 are the same or different and independently selected from C1-C18 hydrocarbon chains, being understood that the groups R6 and R7 may contain one or more groups chosen from: a nitrogen atom, an oxygen atom and a carbonyl group and that the R6 groups and R7 can be connected together to form a ring.
    Advantageously, the group R2 is represented by one of the following formulas (V) and (VI):
    (V) (VI)
    In which R 8 is selected from C 1 -C 32 hydrocarbon chains, R 9 is selected from hydrogen and C 1-6 alkyl groups.
    According to a particular embodiment, the block B of formula (III), (IV), (V) or (VI) is derived from a monomer (mb) obtained by reaction of: a tertiary amine of formula NR3R4R5 or R6N = R7 wherein R3, R4i, R5, R6 and R7 are as defined above in formulas (III) and (IV), and - an intermediate (meth) acrylate or (meth) acrylamide monomer (m, ) of formula (VII) below:
    (VII)
    Wherein, Z, Ri, Rset R9 are as defined in formulas (II), (V) and (VI) above.
    According to another particular embodiment, the block B is obtained by post-functionalization of an intermediate polymer Pi comprising at least one block P of formula (VIII) below: (VIII)
    Wherein, η, Z, R1, R8 and Rg are as defined in formulas (II), (V) and (VI) above, and wherein said post-functionalization corresponds to the reaction of said intertwentyx polymer Pi with a tertiary amine NR3R4R5 where R6N = R7 where R1, R4, R5, R8 and R7 are as defined above in formulas (III) and (IV).
    Advantageously, the intermediate polymer Pi also comprises at least one block A as defined in the above.
    According to a particular embodiment, the block copolymer is obtained by sequential polymerization, optionally followed by one or more post-functionalizations.
    According to a particular embodiment, the copolymer is a copolymer comprising at least one block sequence AB, ABA or BAB where said blocks A and B are linked without presence of intermediate block of different chemical nature. The object of the present invention also relates to a fuel concentrate comprising one or more block copolymers as described above, mixed with an organic liquid, said organic liquid being inert with respect to the block copolymer or copolymers. and miscible with said fuel. The object of the present invention also relates to a fuel composition comprising: (1) a fuel from one or more sources selected from the group consisting of mineral, animal sources; vegetable and synthetic, and (2) one or more block copolymers as defined above.
    Advantageously, the composition comprises at least 5 ppm of block copolymer (s) (2).
    According to a particular embodiment, the fuel (1) is selected from hydrocarbon fuels; non-essentially hydrocarbon fuels and mixtures thereof. The object of the present invention also relates to a use of one or more block copolymers as defined above, as a detergent additive in a liquid fuel of internal combustion engines, said copolymer being used alone, in a mixture or under form of a concentrate as defined above.
    According to a particular embodiment, the copolymer is used in the liquid fuel to maintain cleanliness and / or clean at least one of the internal parts of said internal combustion engine.
    According to a particular preferred embodiment, the copolymer is used in the liquid fuel to limit or prevent the formation of deposits in at least one of the internal parts of said engine and / or reduce the deposits existing in at least one of the internal parts of said engine.
    According to a particular embodiment, the copolymer is used to reduce the fuel consumption of the internal combustion engine.
    According to a particular embodiment, the copolymer is used to reduce the emissions of pollutants, in particular the particulate emissions of the internal combustion engine.
    According to a particular embodiment, the internal combustion engine is a spark ignition engine.
    Advantageously, the deposits are located in at least one of the internal parts selected from the engine intake system, the combustion chamber and the fuel injection system.
    According to another particular embodiment, the internal combustion engine is a diesel engine, preferably a direct injection diesel engine.
    Advantageously, the copolymer is used to prevent and / or reduce the formation of deposits in the injection system of the diesel engine.
    In particular, the copolymer is used to prevent and / or reduce the formation of deposits related to the phenomenon of coking and / or deposits of the soap and / or varnish type.
    According to a particular embodiment, the copolymer is used to reduce and / or avoid the loss of power due to the formation of said deposits in the internal parts of a direct injection diesel engine, said power loss being determined according to the method of the invention. CEC F-98-08 engine test.
    According to one particular embodiment, the copolymer is used to reduce and / or avoid the restriction of the fuel flow emitted by the injector during the operation of said diesel engine, said flow restriction being determined according to the standard engine test method. CEC F-23-1-01.
    DETAILED DESCRIPTION Other advantages and features will become more clearly apparent from the following description. The particular embodiments of the invention are given by way of non-limiting examples.
    According to a particular embodiment, a block copolymer comprises at least one block A and at least one block B.
    Block A is represented by the following formula (I):
    (I) in which p is an integer ranging from 2 to 40, preferably from 3 to 30, more preferably from 4 to 20, still more preferably from 5 to 10, is chosen from hydrogen and the methyl group, R2 is chosen from C1-C34, preferably C4-C30, more preferably C6-C24, still more preferably C8-C22, hydrocarbon chains, said chains being linear or branched, cyclic or acyclic, preferably acyclic. Alkyl groups will be preferred.
    The term "hydrocarbon-based chain" means a chain consisting exclusively of carbon and hydrogen atoms, said chain possibly being linear or branched, cyclic, polycyclic or acyclic, saturated or unsaturated, and optionally aromatic or polyaromatic. A hydrocarbon chain may comprise a linear or branched part and a cyclic part. It may comprise an aliphatic part and an aromatic part.
    Block B is represented by the following formula (II):
    (II) wherein n is an integer ranging from 2 to 40, preferably from 3 to 30, more preferably from 4 to 20, still more preferably from 5 to 10,
    R 1 is chosen from hydrogen and the methyl group, Z is chosen from the oxygen atom and the group -NR '- with R' being chosen from a hydrogen atom and the C 1 -C 12 hydrocarbon chains, from preferably C1 to C6, said chains being linear or branched, cyclic or acyclic, preferably acyclic. Z is preferably selected from the oxygen atom and the -NH- group. G is a C1 to C34, preferably C1 to C18, more preferably C1 to Cio, hydrocarbon chain, linear or branched, cyclic or acyclic, preferably acyclic, substituted by at least one quaternary ammonium group, preferably having from 4 to 50 atoms and optionally one or more hydroxyl groups.
    According to a particular embodiment, the group G comprises the quaternary ammonium group and one or more hydroxyl groups.
    According to a particular embodiment, the block B is represented by one of the following formulas (III) and (IV):
    (III) (IV) in which η, Z and Ri are as described above, X 'is chosen from hydroxide ions, halides and organic anions, in particular the acetate ion, R2 is chosen from hydrocarbon chains C 1 to C 34, preferably C 1 to C 18, cyclic or acyclic, linear or branched, optionally substituted with at least one hydroxyl group; preferably R2 is chosen from alkyl groups, optionally substituted with at least one hydroxyl group, R3, R4 and R5 are identical or different and chosen, independently, from C1-C18, preferably C1-C12, hydrocarbon chains, linear or branched, cyclic or acyclic, it being understood that the alkyl groups R3, R4 and R5 may contain one or more nitrogen atoms and / or oxygen and / or carbonyl groups and may be connected together in pairs to form one or more several rings, R6 and R7 are identical or different and are chosen independently from C1-C18, preferably C1-C12, linear or branched, cyclic or acyclic hydrocarbon chains, it being understood that the R6 and R7 groups may contain one or more nitrogen and / or oxygen atoms and / or carbonyl groups and can be connected together to form a ring.
    The nitrogen atom (s) and / or oxygen (s) may be present in the R3, R4 and R5 groups in the form of ether bridges, amine bridges or in the form of an amine or hydroxyl substituent.
    The organic anions of the X 'group are generally the conjugate bases of the organic acids, preferably the conjugate bases of the carboxylic acids, in particular the acids chosen from monocarboxylic, polycarboxylic, cyclic or acyclic acids. The organic anions of the X 'group are preferably chosen from conjugated bases of saturated acyclic or cyclic aromatic carboxylic acids. By way of example, mention may be made of methanoic acid, acetic acid, adipic acid, oxalic acid, malonic acid, succinic acid, citric acid, benzoic acid and phthalic acid, isophthalic acid and terephthalic acid.
    According to a particular embodiment, the group R2 is chosen from linear or branched C 1 to C 34, preferably C 1 to C 18, alkyl groups substituted with at least one hydroxyl group.
    According to a particular embodiment, the group R2 is represented by one of the following formulas (V) and (VI):
    (V) (VI)
    In which R 8 is chosen from C 1 to C 32, preferably C 1 to C 16, hydrocarbon chains, cyclic or acyclic, preferably acyclic, linear or branched, preferably alkyl groups, R 9 is chosen from hydrogen and alkyl groups. C1 to C6, C1 to C4i, more preferably hydrogen.
    According to a particular embodiment, the block A consists of a chain of structural units derived from an alkyl acrylate or alkyl methacrylate monomer ma and the block B consists of a chain of structural units derived from an acrylate monomer. alkyl, alkyl methacrylate, alkyl acrylamide or alkyl methacrylamide mb, the alkyl radical of which consists of a saturated C 1 to C 34, preferably C 1 to C 18, saturated hydrocarbon chain, linear or branched, preferably acyclic, substituted with at least one quaternary ammonium group and optionally one or more hydroxyl groups.
    For reasons of simplification, we will use in the rest of the description the terms alkyl (meth) acrylate and alkyl (meth) acrylamide to indicate alkyl acrylate or alkyl methacrylate (alkyl) (meth) acrylate ) and alkyl acrylamide or alkyl methacrylamide (alkyl (meth) acrylamide).
    The block copolymer may be prepared by any known method of polymerization. The various techniques and polymerization conditions are widely described in the literature and fall within the general knowledge of those skilled in the art.
    According to a particular embodiment, the block copolymer is obtained by copolymerization of at least the alkyl (meth) acrylate monomer ma and at least the monomer mb.
    The monomer ma is preferably chosen from alkyl acrylates or methacrylates C1 to C34, preferably C4 to C30, more preferably C6 to C24, more preferably C8 to C22. The alkyl radical of the acrylate or methacrylate is linear or branched, cyclic or acyclic, preferably acyclic.
    Among the alkyl (meth) acrylates which may be used in the manufacture of the block copolymer of the invention, mention may be made, in a nonlimiting manner: n-octyl acrylate, n-octyl methacrylate, n-decyl acrylate, n-decyl methacrylate, n-dodecyl acrylate, n-dodecyl methacrylate, ethyl-2-hexyl acrylate, ethyl-2-hexyl methacrylate , isooctyl acrylate, isooctyl methacrylate, isodecyl acrylate, isodecyl methacrylate.
    According to a particular embodiment, the alkyl radical of the monomer mb is substituted by at least one quaternary ammonium group and one or more hydroxyl groups.
    It is understood that it would not go beyond the invention if the copolymer according to the invention was obtained from monomers different from ma and mb, insofar as the final copolymer corresponds to that of the invention. that is, obtained by copolymerization of at least 1 mb and 1 mb. For example, it would not go beyond the invention, if one obtained the copolymer by copolymerization of monomers different from ma and mb followed by post-functionalization.
    For example, units derived from an alkyl (meth) acrylate monomer may be obtained from a poly (meth) acrylate moiety by transesterification reaction using a chain chosen to form the expected alkyl group.
    An example of post-functionalization of the monomers mb is illustrated below.
    The block copolymer can be obtained by sequential polymerization, preferably by sequential and controlled polymerization and optionally followed by one or more post-functionalizations.
    According to a particular embodiment, the block copolymer described above is obtained by sequenced and controlled polymerization. The polymerization is advantageously chosen from controlled radical polymerization; for example, by radical polymerization by atom transfer (ATRP in English "Atom Transfer
    Radical Polymerization "); the radical polymerization by nitroxide (NMP in English "Nitroxide-mediated polymerization"); degenerative transfer processes (degenerative transfer processes) such as degenerative iodine transfer polymerization (ITRP-iodine transfer radical polymerization) or radical polymerization by reversible addition-fragmentation chain transfer ( RAFT in English "Reversible Addition-Fragmentation Chain Transfer"; polymerizations derived from ATRP such as polymerizations using initiators for the continuous regeneration of the activator (ICAR -Initiators for continuous activator regeneration) or using electron-regenerated activators regenerated by electron (ARGET) transfer ").
    By way of example, mention may be made of the publication "Macromolecular Engineering by atom transfer radical polymerization", JACS, 136, 6513-6533 (2014) which describes a controlled and sequenced polymerization process for forming block copolymers.
    The sequenced and controlled polymerization is typically carried out in a solvent, under an inert atmosphere, at a reaction temperature generally ranging from 0 to 200 ° C, preferably from 50 ° C to 130 ° C. The solvent may be chosen from polar solvents, in particular ethers such as anisole (methoxybenzene) or tetrahydrofuran or apolar solvents, in particular paraffins, cycloparaffins, aromatics and alkylaromatics having from 1 to 19 carbon atoms. carbon, for example, benzene, toluene, cyclohexane, methylcyclohexane, n-butene, n-hexane, n-heptane and the like.
    For the Atom Transfer Radical Polymerization (ATRP), the reaction is generally carried out under vacuum in the presence of an initiator, a ligand and a catalyst. By way of example of ligand, mention may be made of Ν, Ν, Ν ', Ν' ', Ν' '- pentamethyldiethylenetriamine (PMDETA), 1,1,4,7,10,10-hexamethyltriethylene tetramine (HMTETA ), 2,2'-bipyridine (BPY) and Tris (2-pyridylmethyl) amine (TPMA). As an example of a catalyst, mention may be made of: CuX, CuX2, with X = Cl, Br and ruthenium complexes Ru2 + / Ru3 +.
    The ATRP polymerization is preferably carried out in a solvent chosen from polar solvents.
    According to the sequenced and controlled polymerization technique, it can also be envisaged to work under pressure.
    According to a particular embodiment, the numbers of monomer equivalents ma of block A and of monomer mb of block B reacted during the polymerization reaction are identical or different and have a value ranging, independently, from 2 to 40, preferably from 3 to 30, more preferably from 4 to 20, even more preferably from 5 to 10. By number of equivalents, the ratio between the amounts of material (in moles) of the monomers ma of block A and monomers mb of block B, during the polymerization reaction.
    The number of equivalents of monomer ma of block A is advantageously greater than or equal to that of monomer mb of block B. In addition, the molar mass by weight Mw of block A or block B is preferably lower or equal to 15,000 g.mol.'1, more preferably less than or equal to 10,000 g.mol.'1.
    The block copolymer advantageously comprises at least one block sequence AB, ABA or BAB where said blocks A and B are linked together without the presence of intermediate blocks of different chemical nature. Other blocks may optionally be present in the block copolymer described above insofar as these blocks do not fundamentally change the character of the block copolymer. However, block copolymers containing only A and B blocks will be preferred.
    Advantageously, A and B represent at least 70% by weight, preferably at least 90% by weight, more preferably at least 95% by weight, more preferably at least 99% by weight of the block copolymer.
    According to a particular embodiment, the block copolymer is a diblock copolymer.
    According to another particular embodiment, the block copolymer is an alternating block triblock copolymer comprising two blocks A and one block B (ABA) or comprising two blocks B and a block A (BAB).
    According to one particular embodiment, the block copolymer also comprises a terminal chain I consisting of a linear or branched, cyclic or acyclic, saturated or unsaturated, linear or branched hydrocarbon chain, in C 1 to C 32, preferably in C 4 to C 24, more preferentially in C10 to C24.
    The term "cyclic hydrocarbon chain" means a hydrocarbon chain at least a part of which is cyclic, in particular aromatic. This definition does not exclude hydrocarbon chains comprising both an acyclic and a cyclic moiety.
    The terminal chain I may comprise an aromatic hydrocarbon chain, for example a benzene chain and / or a linear or branched, saturated and acyclic hydrocarbon-based chain, in particular an alkyl chain.
    The terminal chain I is, preferably, selected from alkyl chains, preferably linear, more preferably alkyl chains of at least 4 carbon atoms, even more preferably of at least 12 carbon atoms.
    For the ATRP polymerization, the terminal chain I is located in the terminal position of the block copolymer. It can be introduced into the block copolymer by means of the polymerization initiator. Thus, the terminal chain I may, advantageously, constitute at least a part of the polymerization initiator and is positioned within the polymerization initiator in order to introduce, during the first polymerization initiation step. , the terminal chain I in the terminal position of the block copolymer. The polymerization initiator is, for example, chosen from free radical initiators used in the ATRP polymerization process. These free radical initiators well known to those skilled in the art are described in particular in the article "Atom Transfer Radical Polymerization: current status and future prospects, Macromolecules, 45, 4015-4039, 2012". The polymerization initiator is, for example, chosen from alkyl esters of a carboxylic acid substituted by a halide, preferably a bromine in the alpha position, for example ethyl 2-bromopropionate or α-bromoisobutyrate. ethyl chloride, benzyl choride or bromide, ethyl α-bromophenylacetate and chloroethylbenzene. Thus, for example, ethyl 2-bromopropionate may make it possible to introduce into the copolymer the terminal chain I in the form of a C2 alkyl chain and benzyl bromide in the form of a benzyl group.
    For the RAFT polymerization, the transfer agent can conventionally be removed from the copolymer at the end of the polymerization according to any known method.
    According to one variant, the terminal chain I can also be obtained in the copolymer by RAFT polymerization according to the methods described in the article by Moad, G. et al., Australian Journal of Chemistry, 2012, 65, 985-1076. The terminal chain I may, for example, be introduced by aminolysis when a transfer agent is used. By way of example, mention may be made of thiocarbonylthio, dithiocarbonate, xanthate, dithiocarbamate and trithiocarbonate transfer agents, for example S, S-bis (α, α'-dimethyl-α-acetic acid) trithiocarbonate (BDMAT or 2-cyano-2-propyl benzodithioate.
    According to a particular embodiment, the block copolymer is a diblock copolymer (also called diblocks). The block copolymer structure may be of the IAB or IBA type, advantageously IAB. The terminal chain I may be directly linked to the block A or B according to the structure IAB or IBA, respectively, or to be linked via a linking group, for example an ester, amide, amine or ether function. The linking group then forms a bridge between the terminal chain I and the block A or B.
    According to a particular embodiment, the block copolymer can also be functionalized at the end of the chain according to any known method, in particular by hydrolysis, aminolysis and / or nucleophilic substitution.
    By aminolysis is meant any chemical reaction in which a molecule is split into two parts by reaction of an ammonia molecule or an amine. A general example of aminolysis is to replace a halogen of an alkyl group by reaction with an amine, with removal of hydrogen halide. Aminolysis can be used, for example, for ATRP polymerization which produces a copolymer having a terminal halide or for RAFT polymerization to remove the thio, dithio or trithio linkage introduced into the copolymer by the RAFT transfer agent.
    It is thus possible to introduce a terminal chain Γ by post-functionalization of the block copolymer obtained by sequenced and controlled polymerization of the monomers ma and mb described above.
    The terminal chain I 'advantageously comprises a hydrocarbon chain, linear or branched, cyclic or acyclic, C 1 to C 32, preferably C 1 to C 24, more preferably C 1 to C 10, still more preferably an alkyl group, optionally substituted by a or more groups containing at least one heteroatom selected from N and O, preferably N.
    For ATRP polymerization using a metal halide as a catalyst, this functionalization can, for example, be carried out by treating the ATRP-derived IAB or IBA copolymer with a C 1 -C 32 primary alkylamine or a C 1 -C 32 alcohol under mild conditions. do not modify the functions present on blocks A, B and I.
    The quaternary ammonium group of block B described above may be acyclic or cyclic.
    The acyclic quaternary ammonium group is advantageously chosen from quaternary salts of trialkylammonium, guanidinium and iminium.
    The cyclic quaternary ammonium group is advantageously chosen from heterocyclic compounds containing at least one nitrogen atom, in particular chosen from the quaternary salts of pyrrolinium, pyridinium, imidazolium, triazolium, triazinium, oxazolium and isoxazolium.
    The quaternary ammonium group of the block B is, advantageously, a quaternary trialkylammonium salt.
    According to a particular embodiment, the block B is preferably derived from a monomer (mb) obtained by reaction of: a tertiary amine of formula NR3R4R5 or R6N = R7 in which R3, R4, R5, R6 and R7 are as described above, and - an intermediate monomer (meth) acrylate or (meth) acrylamide m, of formula (VII) below:
    (VN)
    Wherein, Z, R 1, R 8 and R 9 are as described above.
    According to another particular embodiment, the block B is obtained by post-functionalization of an intermediate polymer Pi comprising at least one block P of formula (VIII) below:
    (WINE)
    Wherein, η, Z, R 1, R 8 and R 8 are as described above.
    The post-functionalization corresponds to the reaction of the intermediate polymer Pi with a tertiary amine of formula NR3R4R5 or R6N = R7 in which R3, R4, R5 and R6, R7 are as previously described. The tertiary amine may, for example, be selected from acyclic tertiary amines, preferably trialkylamines, guanidines and quaternizable amines. The tertiary amine is advantageously chosen from trialkylamines, in particular those whose alkyl groups are identical or different and chosen, independently, from C 1 to C 18 and preferably C 1 to C 12 alkyls, which are linear or branched, cyclic or acyclic, preferably acyclic.
    According to one variant, the tertiary amine may be chosen from cyclic tertiary amines, preferably pyrrolines, pyridines, imidazoles, triazoles, guanidines, imines, triazines, oxazoles and isoxazoles which are quaternizable.
    The intermediate polymer Pi may also comprise at least one block A as described above.
    The block copolymer described above is particularly advantageous when it is used as a detergent additive in a liquid fuel of an internal combustion engine.
    By detergent additive liquid fuel is meant an additive that is incorporated in a small amount in the liquid fuel and has an effect on the cleanliness of said engine compared to said liquid fuel not specially additivé.
    The liquid fuel is advantageously derived from one or more sources selected from the group consisting of mineral, animal, vegetable and synthetic sources. Oil will preferably be chosen as a mineral source.
    The liquid fuel is preferably chosen from hydrocarbon fuels and non-essentially hydrocarbon fuels, alone or as a mixture.
    Hydrocarbon fuel is a fuel consisting of one or more compounds consisting solely of carbon and hydrogen.
    The term "non-substantially hydrocarbon fuel" is understood to mean a fuel consisting of one or more compounds consisting essentially of carbon and hydrogen, that is to say which also contain other atoms, in particular oxygen atoms.
    The hydrocarbon fuels include in particular medium distillates boiling temperature ranging from 100 to 500 ° C or lighter distillates having a boiling point in the range of gasolines. These distillates may, for example, be chosen from distillates obtained by direct distillation of crude hydrocarbons, vacuum distillates, hydrotreated distillates, distillates obtained from catalytic cracking and / or hydrocracking of vacuum distillates, distillates resulting from ARDS type conversion processes (in English "atmospheric residue desulphurization") and / or visbreaking, the distillates from the valuation of Fischer Tropsch cuts. Hydrocarbon fuels are typically gasolines and gas oils (also called diesel fuel).
    The gasolines include, in particular, all commercially available spark ignition engine fuel compositions. As a representative example, mention may be made of species that comply with the NF EN 228 standard. The essences generally have octane numbers that are sufficiently high to prevent the phenomenon of knocking. Typically, gasoline fuels marketed in Europe, compliant with the NF EN 228 standard, have a motor octane number (MON) of greater than 85 and a research octane number (RON in English). Research Octane Number ") of a minimum of 95. Gasoline fuels generally have an RON of 90 to 100 and a MON of 80 to 90, with RON and MON being measured according to ASTM D 2699- 86 or D 2700-86.
    Gas oils (diesel fuels) include, in particular, any commercially available diesel fuel compositions. As a representative example, mention may be made of gas oils that comply with the NF EN 590 standard.
    Non-essentially hydrocarbon fuels include oxygenates, for example distillates resulting from BTL (biomass to liquid) conversion of plant and / or animal biomass, taken alone or in combination; biofuels, for example oils and / or esters of vegetable and / or animal oils; biodiesels of animal and / or vegetable origin and bioethanols.
    The mixtures of hydrocarbon fuel and non-essentially hydrocarbon fuel are typically type B gas oils or Ex type gasolines.
    Diesel gasoline of type Bx for a diesel engine, a diesel fuel which contains x% (v / v) of vegetable or animal oil esters (including used cooking oils) transformed by a chemical process called transesterification, obtained in reacting this oil with an alcohol to obtain fatty acid esters (EAG). With methanol and ethanol, fatty acid methyl esters (EMAG) and fatty acid ethyl esters (EEAG) are obtained respectively. The letter "B" followed by a number indicates the percentage of EAG contained in the diesel fuel. Thus, a B99 contains 99% of EAG and 1% of middle distillates of fossil origin (mineral source), B20, 20% of EAG and 80% of middle distillates of fossil origin, etc. type B0 gas oils which do not contain oxygenated compounds, type Bx gas oils which contain x% (v / v) of vegetable oil esters or fatty acids, most often methyl esters (EMHV or EMAG). When the EAG is used alone in the engines, the term fuel is designated by the term B100.
    Ex-type gasoline for a spark ignition engine is a gasoline fuel that contains x% (v / v) oxygenates, usually ethanol, bioethanol and / or ethyl tertiary butyl ether ( ETBE).
    The sulfur content of the liquid fuel is preferably less than or equal to 5000 ppm, preferably less than or equal to 500 ppm, and more preferably less than or equal to 50 ppm, or even less than 10 ppm and advantageously without sulfur.
    The block copolymer described above is used as a detergent additive in the liquid fuel at a content, preferably at least 10 ppm, preferably at least 50 ppm, more preferably at a level of 10 to 5000 ppm, even more preferably from 10 to 1 000 ppm.
    According to a particular embodiment, the use of a block copolymer as described above in the liquid fuel makes it possible to maintain the cleanliness of at least one of the internal parts of the internal combustion engine and / or to clean at least one internal parts of the internal combustion engine. The use of the block copolymer in the liquid fuel makes it possible, in particular, to limit or avoid the formation of deposits in at least one of the internal parts of said engine ("keep-clean" effect) and / or to reduce the existing deposits in at least one of the internal parts of said engine ("clean-up" effect).
    Thus, the use of the copolymer in the liquid fuel makes it possible, in comparison with the liquid fuel with no particular additives, to limit or avoid the formation of deposits in at least one of the internal parts of said engine or to reduce the deposits existing in at least one of the internal parts. said engine.
    Advantageously, the use of the copolymer in the liquid fuel makes it possible to observe both the effects, limitation (or prevention) and reduction of deposits ("keep-clean" and "clean-up" effects).
    Deposits are distinguished according to the type of internal combustion engine and the location of deposits in the internal parts of said engine.
    According to a particular embodiment, the internal combustion engine is a spark ignition engine, preferably direct injection (DISI in English "Direct Injection Spark Ignition Engine"). The targeted deposits are located in at least one of the internal parts of said spark ignition engine. The internal part of the spark-ignition engine kept clean (keep-clean) and / or cleaned (clean-up) is advantageously chosen from the intake system of the engine, in particular the intake valves (IVD). Intake Valve Deposit "), the" Combustion Chamber Deposit "(CCD) and the fuel injection system, in particular the injectors of an indirect injection system (PFI in English "Port Fuel Injector") or the injectors of a direct injection system (DISI).
    According to another particular embodiment, the internal combustion engine is a diesel engine, preferably a direct injection diesel engine, in particular a diesel engine with Common Rail Direct Injection (IDRC) system. The targeted deposits are located in at least one of the internal parts of said diesel engine.
    Advantageously, the targeted deposits are located in the injection system of the diesel engine, preferably located on an external part of an injector of said injection system, for example the nose of the injector and / or on an internal part. of an injector of said injection system (IDID in English "Internai Diesel Injector Deposits"), for example on the surface of an injector needle.
    The deposits may consist of deposits related to the phenomenon of coking ("coking" in English) and / or deposits soap and / or varnish (in English "lacquering").
    The block copolymer as described above may advantageously be used in the liquid fuel to reduce and / or avoid the loss of power due to the formation of deposits in the internal parts of a direct injection diesel engine, said loss of fuel. power being determined using the CEC F-98-08 Standard Engine Test Method.
    The block copolymer as described above can advantageously be used in the liquid fuel to reduce and / or avoid the restriction of the fuel flow emitted by the injector of a direct injection diesel engine during its operation, said flux restriction being determined according to the CEC Standard F-23-1-01 engine test method.
    Advantageously, the use of the copolymer as described above makes it possible, in comparison with the liquid fuel that is not particularly additive, to limit or avoid the formation of deposits on at least one type of deposits previously described and / or to reduce the deposits existing on at least one of a type of depots previously described.
    According to a particular embodiment, the use of the block copolymer described above also makes it possible to reduce the fuel consumption of the internal combustion engine.
    According to another particular embodiment, the use of the block copolymer described above also makes it possible to reduce the emissions of pollutants, in particular the particulate emissions of the internal combustion engine.
    Advantageously, the use of the block copolymer makes it possible to reduce both the fuel consumption and the pollutant emissions.
    The block copolymer described above may be used alone, in the form of a mixture of at least two of said block copolymers or in the form of a concentrate.
    The block copolymer may be added to the liquid fuel within a refinery and / or incorporated downstream of the refinery and / or optionally mixed with other additives in the form of an additive concentrate, further called according to the use "additive package".
    The block copolymer described above is used in admixture with an organic liquid in the form of a concentrate.
    According to a particular embodiment, a fuel concentrate comprises one or more copolymers as described above, mixed with an organic liquid.
    The organic liquid is inert with respect to the block copolymer described above and miscible in the liquid fuel described above. The term "miscible" means that the block copolymer and the organic liquid form a solution or a dispersion so as to facilitate the mixing of the block copolymer in liquid fuels according to the conventional methods of fuel additive.
    The organic liquid is advantageously chosen from aromatic hydrocarbon solvents such as the solvent sold under the name "SOLVESSO", alcohols, ethers and other oxygenated compounds and paraffinic solvents such as hexane, pentane or isoparaffins. alone or in mixture.
    The concentrate may advantageously comprise from 5 to 99% by weight, preferably from 10 to 80%, more preferably from 25 to 70% of copolymer as described above.
    The concentrate may typically comprise from 1 to 95% by weight, preferably from 10 to 70%, more preferably from 25 to 60% of organic liquid, the balance corresponding to the copolymer, it being understood that the concentrate may comprise one or more copolymers. in blocks as described above.
    In general, the solubility of the block copolymer in the organic liquids and the liquid fuels described above will depend in particular on the average molar masses by weight and by number, respectively Mw and Mn of the copolymer. The average molar masses Mw and Mn of the block copolymer will be chosen so that the copolymer is soluble in the liquid fuel and / or the organic liquid of the concentrate for which it is intended.
    The average molar masses Mw and Mn of the block copolymer may also have an influence on the effectiveness of this copolymer as a detergent additive. The average molar masses Mw and Mn will therefore be chosen so as to optimize the effect of the block copolymer, in particular the detergency effect (engine cleanliness) in the liquid fuels described above. The optimization of the average molar masses Mw and Mn can be carried out by routine tests accessible to those skilled in the art.
    According to one particular embodiment, the copolymer advantageously has a weight average molecular weight (Mw) ranging from 500 to 30,000 g / mol, preferably from 1,000 to 10,000 g / mol, more preferably lower. or equal to 4000 g.mol -1, and / or a number-average molar mass (M n) ranging from 500 to 15,000 g / mol, preferably from 1,000 to 10,000 g / mol, more preferably lower. or 4000 g.mol -1. The number and weight average molar masses are measured by Size Exclusion Chromatography (SEC). The operating conditions of the SEC, in particular, the choice of the solvent. will be chosen according to the chemical functions present within the block copolymer.
    According to a particular embodiment, the block copolymer is used in the form of an additive concentrate in combination with at least one other fuel additive for an internal combustion engine other than the block copolymer described above.
    The additive concentrate may typically comprise one or more other additives selected from detergent additives other than the block copolymer described above, for example from anti-corrosion agents, dispersants, demulsifiers, anti-foam agents , biocides, deodorants, procetane additives, friction modifiers, lubricity additives or lubricity additives, combustion assistants (catalytic combustion promoters and soot), point-of-use improvers cloudiness, pour point, TLF ("Filterability Limit Temperature"), anti-settling agents, anti-wear agents and conductivity modifiers.
    Among these additives, mention may be made in particular of: a) procetane additives, in particular (but not limited to) selected from alkyl nitrates, preferably 2-ethyl hexyl nitrate, aryl peroxides, preferably peroxide; benzyl, and alkyl peroxides, preferably ter-butyl peroxide; b) anti-foam additives, in particular (but not limited to) selected from polysiloxanes, oxyalkylated polysiloxanes, and fatty acid amides from vegetable or animal oils. Examples of such additives are given in EP861882, EP663000, EP736590; c) Cold Flow Improver (CFI) selected from copolymers of ethylene and unsaturated ester, such as ethylene / vinyl acetate copolymers (EVA), ethylene / vinyl propionate (EVP) ethylene / vinyl ethanoate (EVE), ethylene / methyl methacrylate (EMMA), and ethylene / alkyl fumarate described, for example, in US3048479, US3627838, US3790359, US3961961 and EP261957. d) lubricity additives or anti-wear agents, in particular (but not limited to) selected from the group consisting of fatty acids and their ester or amide derivatives, in particular glycerol monooleate, and monocarboxylic acid derivatives and polycyclic. Examples of such additives are given in the following documents: EP680506, EP860494, WO98 / 04656, EP915944, FR2772783, FR2772784. e) cloud point additives, including (but not limited to) selected from the group consisting of long-chain olefin terpolymers / (meth) acrylic ester / maleimide, and fumaric acid / maleic acid ester polymers. Examples of such additives are given in FR2528051, FR2528051, FR2528423, EP112195, EP172758, EP271385, EP291367; f) detergent additives including (but not limited to) selected from the group consisting of succinimides, polyetheramines and quaternary ammonium salts; for example those described in US4171959 and WO2006135881. g) polyfunctional cold operability additives selected from the group consisting of olefin and alkenyl nitrate polymers as described in EP573490.
    These other additives are generally added in an amount ranging from 100 to 1000 ppm (each).
    The molar and / or mass ratio between the monomer mb and the monomer ma and / or between the block A and B in the block copolymer described above will be chosen so that the block copolymer is soluble in the fuel and or the organic liquid of the concentrate for which it is intended. Likewise, this ratio can be optimized according to the fuel and / or the organic liquid so as to obtain the best effect on engine cleanliness. The optimization of the molar and / or mass ratio can be carried out by routine tests accessible to those skilled in the art.
    The molar ratio between the monomer mb and the monomer ai or between the blocks A and B in the block copolymer described above is advantageously from 1:10 to 10: 1, preferably from 1: 2 to 2: 1 more preferably from 1: 0.5 to 0.5: 2.
    According to a particular embodiment, a fuel composition is prepared according to any known method by adding the liquid fuel described above with at least one block copolymer as described above.
    According to a particular embodiment, a fuel composition comprising: (1) a fuel as described above, and (2) one or more block copolymers as described above.
    The fuel (1) is, in particular, chosen from hydrocarbon fuels and non-essentially hydrocarbon fuels previously described, taken alone or as a mixture.
    The combustion of this fuel composition comprising such a copolymer in an internal combustion engine has an effect on the cleanliness of the engine compared to the liquid fuel that is not particularly additive and allows, in particular, to prevent or reduce the fouling of the internal parts of said engine. . The effect on the cleanliness of the engine is as previously described in the context of the use of the block copolymer.
    According to a particular embodiment, the combustion of the fuel composition comprising such a block copolymer in an internal combustion engine also makes it possible to reduce the fuel consumption and / or the pollutant emissions.
    The block copolymer is preferably incorporated in a small amount in the liquid fuel described above, the amount of block copolymer being sufficient to produce a detergent effect as described above and thus improve the engine cleanliness.
    The fuel composition advantageously comprises at least 5 ppm, preferably from 10 to 5 000 ppm, more preferably from 20 to 2000 ppm, in particular from 50 to 500 ppm of block copolymer (2).
    In addition to the block copolymer described above, the fuel composition may also comprise one or more other additives different from the block copolymer according to the invention chosen from the other known detergent additives, for example from anti-corrosion agents, dispersants , demulsifiers, defoamers, biocides, deodorants, procetane additives, friction modifiers, lubricity additives or lubricity additives, combustion assistants (catalytic soot), cloud point improvers, pour point, TLF, anti-settling agents, anti-wear agents and / or conductivity modifiers.
    The additives different from the block copolymer according to the invention are, for example, the fuel additives listed above.
    According to a particular embodiment, a method of keeping the cleanliness (keep-clean) and / or cleaning (clean-up) of at least one of the internal parts of an internal combustion engine comprises the preparation of a fuel composition by additivation of a fuel with one or more block copolymers as described above and combustion of said fuel composition in the internal combustion engine.
    According to a particular embodiment, the internal combustion engine is a spark ignition engine, preferably direct injection (DISI).
    The inner part kept clean and / or cleaned of the spark ignition engine is preferably selected from the engine intake system, in particular the intake valves (IVD), the combustion chamber (CCD or TCD) and the fuel injection system, in particular the injectors of an indirect injection system (IFP) or the injectors of a direct injection system (DISI).
    According to another particular embodiment, the internal combustion engine is a diesel engine, preferably a direct injection diesel engine, in particular a diesel engine with Common Rail injection systems (IDRC).
    The internal part kept clean (keep-clean) and / or cleaned (clean-up) of the diesel engine is preferably the injection system of the diesel engine, preferably an external part of an injector of said injection system for example the nose of the injector and / or one of the internal parts of an injector of said injection system, for example the surface of an injector needle.
    The method of maintaining cleanliness (keep-clean) and / or cleaning (clean-up) comprises the successive steps of: a) determining the additivation most suitable for the fuel, said additivation corresponding to the selection of the The above-described block copolymers to be incorporated in combination, optionally, with other fuel additives as described above and the determination of the rate of treatment necessary to achieve a given specification for the detergency of the fuel composition. b) incorporation into the fuel of the selected block copolymer or copolymers at the rate determined in step a) and, optionally, the other fuel additives.
    The one or more block copolymers can be incorporated in the fuel, alone or in a mixture, successively or simultaneously.
    Alternatively, the block copolymer (s) may be used in the form of a concentrate or an additive concentrate as described above. Step a) is carried out according to any known method and is common practice in the field of additive fuel. This step involves defining at least one representative characteristic of the detergency properties of the fuel composition.
    The representative characteristic of the fuel detergency properties will depend on the type of internal combustion engine, for example diesel or spark ignition, the direct or indirect injection system and the location in the engine of the targeted deposits for cleaning and / or maintaining cleanliness.
    For direct injection diesel engines, the characteristic characteristic of the fuel detergency properties may, for example, correspond to the power loss due to the formation of the deposits in the injectors or the restriction of the fuel flow emitted by the injector at the fuel injector. during the operation of said engine.
    The representative characteristic of the detergency properties may also correspond to the appearance of lacquering deposits at the injector needle (IDID).
    Methods for evaluating the detergent properties of fuels have been widely described in the literature and are subject to general knowledge of those skilled in the art. By way of non-limiting example, the tests standardized or recognized by the profession or the methods described in the following literature are:
    For direct injection diesel engines: - the DW10 method, CEC engine test method F-98-08, to measure the power loss of direct injection diesel engines - the XUD9 method, standard engine test method CEC E-23-1-01 Issue 5, to measure the restriction of fuel flow emitted by the injector - the method described by the applicant in the application W02014 / 029770 page 17 to 20, for the evaluation of deposits lacquering ( IDID), this method being cited by way of example and / or incorporated by reference in the present application.
    For indirect-injection spark ignition engines: - the Mercedes Benz M102E method, standard test method CEC F-05-A-93, and - the Mercedes Benz M111 method, standardized test method CEC F-20-A -98.
    These methods make it possible to measure the deposits on the intake valves (IVD), the tests being generally carried out on a Eurosuper gasoline meeting the EN228 standard.
    For direct injection spark ignition engines: - the method described by the Applicant in the article "Evaluating Injector Fouling in
    Direct Injection Spark Ignition Engines ", Mathieu Arondel, Philippe China, Julien Gueit; Conventional and future energy for automobiles; 10th international colloquium; January 20-22, 2015, p.375-386 (Technische Akademie Esslingen by
    Techn. Akad. Esslingen, Ostfildern), for the evaluation of coking deposits on the injector, this method being cited as an example and / or incorporated by reference in the present application. the method described in the document US20130104826, for the evaluation of coking deposits on the injector, this method being cited by way of example and / or incorporated by reference into the present application.
    The determination of the amount of block copolymer to be added to the fuel composition to achieve the specification will typically be made by comparison with the fuel composition but without the block copolymer according to the invention.
    The determination of the amount of copolymer to be added to the fuel composition to reach the specification (step a) described above) will be carried out typically by comparison with the fuel composition but without the copolymer according to the invention, the specification given for the detergency may for example be a target value of power loss according to the DW10 method or a flow restriction value according to XUD9 method mentioned above.
    The amount of block copolymer may also vary depending on the nature and origin of the fuel, particularly depending on the level of n-alkyl, iso-alkyl or n-alkenyl substituted compounds. Thus, the nature and origin of the fuel may also be a factor to consider for step a).
    The keep-clean and / or clean-up method may also include an additional step after step b) of checking the target reached and / or adjusting the rate of additivation with the copolymer (s) as a detergent additive.
    The block copolymers according to the invention have remarkable properties as a detergent additive in a liquid fuel, in particular in a diesel or gasoline fuel.
    The block copolymers according to the invention are particularly remarkable, in particular because they are effective as a detergent additive for a wide range of liquid fuels and / or for one or more types of motorization and / or against one or more types of deposit which are form in the internal parts of internal combustion engines.
    权利要求:
    Claims (29)
    [1" id="c-fr-0001]
    A block copolymer comprising: at least one block A of formula (I) below:

    (I) wherein p is an integer ranging from 2 to 40, R 1 is chosen from hydrogen and the methyl group, R 2 is chosen from C 1 to C 34 hydrocarbon chains, at least one B block of formula (II) next :

    (II) in which n is an integer ranging from 2 to 40, R 1 is chosen from hydrogen and the methyl group, Z is chosen from the oxygen atom and the group -NR '- with R' being chosen from a hydrogen atom and the C1-C12 hydrocarbon chains, G is a C1-C34 hydrocarbon chain substituted with at least one quaternary ammonium group and optionally one or more hydroxyl groups.
    [2" id="c-fr-0002]
    2. Block copolymer according to claim 1, in which: block A consists of a chain of structural units derived from an alkyl (meth) acrylate monomer (ma), and block B consists of a chain of structural units derived from an alkyl (meth) acrylate monomer or alkyl (meth) acrylamide (mb), the alkyl radical of which consists of a C1-C34 hydrocarbon chain substituted with at least one quaternary ammonium group and optionally one or more hydroxyl groups.
    [3" id="c-fr-0003]
    The block copolymer according to claim 2, wherein the monomer (a1) is selected from C1 to C4 alkyl acrylates. C1 to C34 alkyl methacrylates.
    [4" id="c-fr-0004]
    4. Block copolymer according to any one of claims 2 to 3, wherein the alkyl radical of the monomer (mb) is substituted by at least one quaternary ammonium group and one or more hydroxyl groups.
    [5" id="c-fr-0005]
    5. Block copolymer according to any one of claims 1 to 4, wherein the quaternary ammonium group is selected from quaternary salts of pyrrolinium, pyridinium, imidazolium, triazolium, triazinium, oxazolium and isoxazolium.
    [6" id="c-fr-0006]
    6. Block copolymer according to any one of claims 1 to 4, wherein the quaternary ammonium group is selected from quaternary trialkylammonium, guanidinium and iminium salts.
    [7" id="c-fr-0007]
    Block copolymer according to any one of claims 1 to 6, wherein the block B is represented by one of the following formulas (III) and (IV):



    (III) (IV) wherein η, Z and R 1 are as defined in claim 1, X 'is selected from hydroxide ions, halides and organic anions, R2 is Ghoisi from Ct to C34 hydrocarbon chains, optionally substituted by at least one hydroxyl group, R3, R4 and R5 are the same or different and independently selected from C1-C8 hydrocarbon chains, it being understood that the alkyl groups R3, R4 and R5 may contain one or more several groups chosen from: a nitrogen atom, an oxygen atom and a carbonyl group and that the groups R3, R4 and R5 can be connected together in pairs to form one or more rings, R6 and R7 are identical or different and chosen independently from the C-1 to C 18 hydrocarbon chains, it being understood that the R 6 and R 7 groups may contain one or more groups chosen from: a nitrogen atom, an oxygen atom and a group carbonyl and that the groups R6 and R7 can be joined together to form a ring.
    [8" id="c-fr-0008]
    Block copolymer according to claim 7, wherein the group R2 is represented by one of the following formulas (V) and (VI):

    (V) (VI) wherein R 8 is selected from C 1 -C 32 hydrocarbon chains, R 9 is selected from hydrogen and C 1-6 alkyl groups.
    [9" id="c-fr-0009]
    9. Block copolymer according to one of claims 7 and 8, wherein the block B of formula (III), (IV), (V) or (VI) is derived from a monomer (mb) obtained by reaction: a tertiary amine of formula NR 3 R 4 R 5 or R 6 N = R 7 in which R 3, R 4, R 5, R 8 and R 7 are as defined in claim 7, and

    Wherein, Z, R 1, R 8 and R 8 are as defined in claims 1, 7 and 8 - an intermediate monomer (meth) aerylate or (meth) acrylamide (m 1) of the following formula (VII): )
    [10" id="c-fr-0010]
    10. Block copolymer according to one of claims 7 and 8, wherein the block B is obtained by post-functionalization of an intermediate polymer Pi comprising at least one block P of formula (VIII) below:

    (VIII) wherein, η, Z, R1f R8 and R9 are as defined in claims 1, 7 and 8, and wherein said post-functionalization corresponds to the reaction of said intermediate polymer Pi with a tertiary amine NR3R4R5 where R6N = R7 where R3> R4, R5, R6 and R7 are as defined in claim 7.
    [11" id="c-fr-0011]
    11. Block copolymer according to claim 10, wherein the intermediate polymer Pi also comprises at least one block A as defined in any one of claims 1 to 3.
    [12" id="c-fr-0012]
    12. Block copolymer according to any one of claims 1 to 11, wherein the block copolymer is obtained by sequential polymerization, optionally followed by one or more post-functionalizations.
    [13" id="c-fr-0013]
    13. Block copolymer according to any one of claims 1 to 12, wherein the copolymer is a copolymer comprising at least one block sequence AB, ABA or BAB where said blocks A and B are linked without presence of intermediate block of different chemical nature.
    [14" id="c-fr-0014]
    14. Fuel concentrate comprising one or more block copolymers as described in any one of claims 1 to 13, in admixture with an organic liquid, said organic liquid being inert with respect to the block copolymer or copolymers. miscible to said fuel.
    [15" id="c-fr-0015]
    A fuel composition comprising: (1) a fuel from one or more sources selected from the group consisting of mineral, animal sources; vegetable and synthetic, and (2) one or more block copolymers as defined in any one of claims 1 to 13.
    [16" id="c-fr-0016]
    16. Composition according to claim 15, comprising at least 5ppm of block copolymer (s) (2).
    [17" id="c-fr-0017]
    17. Composition according to one of claims 15 and 16, wherein the fuel (1) is selected from hydrocarbon fuels; non-essentially hydrocarbon fuels and mixtures thereof.
    [18" id="c-fr-0018]
    18. Use of one or more block copolymers as defined in any one of claims 1 to 13, as a detergent additive in a liquid fuel of internal combustion engines, said copolymer being used alone, in mixture or in form of a concentrate as defined in claim 14.
    [19" id="c-fr-0019]
    The use of claim 18, wherein the copolymer is used in the liquid fuel to maintain cleanliness and / or clean at least one of the internal parts of said internal combustion engine.
    [20" id="c-fr-0020]
    20. Use according to any one of claims 18 and 19, wherein the copolymer is used in the liquid fuel to limit or avoid the formation of deposits in at least one of the internal parts of said engine and / or reduce the existing deposits in least one of the internal parts of said engine.
    [21" id="c-fr-0021]
    21. Use according to one of claims 19 and 20, for reducing the fuel consumption of the internal combustion engine.
    [22" id="c-fr-0022]
    22. Use according to any one of claims 19 to 21 for reducing the emissions of pollutants, in particular the particulate emissions of the internal combustion engine.
    [23" id="c-fr-0023]
    23. Use according to any one of claims 19 to 22, wherein the internal combustion engine is a spark ignition engine.
    [24" id="c-fr-0024]
    24. Use according to claim 23, wherein the deposits are located in at least one of the internal parts selected from the engine intake system, the combustion chamber and the fuel injection system.
    [25" id="c-fr-0025]
    25. Use according to any one of claims 19 to 22, wherein the internal combustion engine is a diesel engine, preferably a direct injection diesel engine,
    [26" id="c-fr-0026]
    26. Use according to claim 25, to avoid and / or reduce the formation of deposits in the injection system of the diesel engine.
    [27" id="c-fr-0027]
    27. Use according to claim 25, to prevent and / or reduce the formation of deposits related to the phenomenon of coking and / or soap-like deposits and / or varnish.
    [28" id="c-fr-0028]
    28. Use according to claim 26, for reducing and / or avoiding the loss of power due to the formation of said deposits in the internal parts of a direct injection diesel engine, said power loss being determined according to the engine test method. CEC CEC F-98-08.
    [29" id="c-fr-0029]
    29. Use according to claim 26, for reducing and / or avoiding the restriction of the flow of fuel emitted by the injector during operation of said diesel engine, said flow restriction being determined according to the engine test method CEC CEC F- 23-1-01.
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    同族专利:
    公开号 | 公开日
    CN108026204A|2018-05-11|
    EA201890509A1|2018-08-31|
    WO2017046526A1|2017-03-23|
    MX2018003273A|2018-06-07|
    BR112018005334A2|2018-10-09|
    EP3350232A1|2018-07-25|
    CN108026204B|2020-08-28|
    FR3041349B1|2020-01-24|
    CA2998442A1|2017-03-23|
    US20180265793A1|2018-09-20|
    ZA201801711B|2019-01-30|
    US10752853B2|2020-08-25|
    AR106046A1|2017-12-06|
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    法律状态:
    2016-08-22| PLFP| Fee payment|Year of fee payment: 2 |
    2017-03-24| PLSC| Publication of the preliminary search report|Effective date: 20170324 |
    2017-08-22| PLFP| Fee payment|Year of fee payment: 3 |
    2018-08-22| PLFP| Fee payment|Year of fee payment: 4 |
    2019-08-20| PLFP| Fee payment|Year of fee payment: 5 |
    2020-08-19| PLFP| Fee payment|Year of fee payment: 6 |
    2021-09-21| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1558831|2015-09-18|
    FR1558831A|FR3041349B1|2015-09-18|2015-09-18|COPOLYMER FOR USE AS A FUEL DETERGENT ADDITIVE|FR1558831A| FR3041349B1|2015-09-18|2015-09-18|COPOLYMER FOR USE AS A FUEL DETERGENT ADDITIVE|
    EP16774975.3A| EP3350232A1|2015-09-18|2016-09-15|Copolymer that can be used as detergent additive for fuel|
    US15/761,400| US10752853B2|2015-09-18|2016-09-15|Copolymer that can be used as detergent additive for fuel|
    BR112018005334-1A| BR112018005334A2|2015-09-18|2016-09-15|copolymer that can be used as a fuel detergent additive|
    CN201680054419.2A| CN108026204B|2015-09-18|2016-09-15|Copolymers useful as detergent additives for fuels|
    EA201890509A| EA201890509A1|2015-09-18|2016-09-15|COPOLYMER USED AS WASHING FUEL ADDITIVE|
    PCT/FR2016/052327| WO2017046526A1|2015-09-18|2016-09-15|Copolymer that can be used as detergent additive for fuel|
    CA2998442A| CA2998442A1|2015-09-18|2016-09-15|Copolymer that can be used as detergent additive for fuel|
    MX2018003273A| MX2018003273A|2015-09-18|2016-09-15|Copolymer that can be used as detergent additive for fuel.|
    ARP160102825A| AR106046A1|2015-09-18|2016-09-16|DETERGENT ADDITIVE FOR FUEL|
    ZA2018/01711A| ZA201801711B|2015-09-18|2018-03-13|Copolymer that can be used as detergent additive for fuel|
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