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    • 专利摘要:
    Copolymer obtained by copolymerization of at least: - an apolar monomer (ma) of formula (I) With u = 0 or 1, w = 0 or 1, E = -O- or -NH (Z) -, or -O -CO-, or -NH-CO- or -CO-NH-, where Z is H or an alkyl group, G is a group selected from alkyl, aromatic ring, aralkyl, and - polar monomer (mb) of formula (II): with t = 0 or 1 Q selected from the oxygen atom and the group -NR'- with R 'being chosen from a hydrogen atom and the hydrocarbon chains, R is a substituted hydrocarbon chain by at least one quaternary ammonium group and optionally one or more hydroxyl groups. Use of such a copolymer as a detergent additive in a liquid fuel of an internal combustion engine.
    公开号:FR3054225A1
    申请号:FR1656974
    申请日:2016-07-21
    公开日:2018-01-26
    发明作者:Julie Prevost
    申请人:Total Marketing Services SA；
    IPC主号:
    专利说明:

    054 225
    56974 ® FRENCH REPUBLIC
    NATIONAL INSTITUTE OF INDUSTRIAL PROPERTY © Publication number:
    (to be used only for reproduction orders)
    ©) National registration number
    COURBEVOIE
    ©) Int Cl 8 : C 08 F220 / 34 (2017.01), C 08 F220 / 60, 210/00, 212/00, 216/12, 218/04, 220/54, 220/02, C10L 1/195, 1/236, 10/04, 10/02
    A1 PATENT APPLICATION
    ©) Date of filing: 21.07.16.(30) Priority: © Applicant (s): TOTAL MARKETING SERVICES - FR. ©) Inventor (s): PREVOST JULIE. @) Date of public availability of the request: 26.01.18 Bulletin 18/04. (56) List of documents cited in the preliminary search report: See the end of this brochure @) References to other related national documents: ©) Holder (s): TOTAL MARKETING SERVICES. ©) Extension request (s): @) Agent (s): INNOVATION COMPETENCE GROUP.
    COPOLYMER FOR USE AS A FUEL DETERGENT ADDITIVE.
    (U /) Copolymer obtained by copolymerization of at least: - an apolar monomer (m a ) of formula (I)
    U
    FR 3 054 225 - A1 (O
    H ° (I)
    With u = 0 or 1, w = 0 or 1,
    E = -O- or -NH (Z) -, or -O-CO-, or -NH-CO- or -CO-NH, with Z represents H or an alkyl group,
    G represents a group chosen from an alkyl, an aromatic ring, an aralkyl, and - a polar monomer (m b ) of formula (II):
    (II) with t = 0 or 1
    Q chosen from the oxygen atom and the group - NR 'with R' being chosen from a hydrogen atom and the hydrocarbon chains,
    R is a hydrocarbon chain substituted by at least one quaternary ammonium group and optionally one or more hydroxyl groups.
    Use of such a copolymer as a detergent additive in a liquid fuel of an internal combustion engine.
    ICG70098 text deposit
    COPOLYMER FOR USE AS A FUEL DETERGENT ADDITIVE
    The present invention relates to a copolymer and its use as a detergent additive in a liquid fuel of an internal combustion engine. The invention also relates to a method for maintaining the cleanliness and / or cleaning of at least one of the internal parts of an internal combustion engine.
    PRIOR STATE OF THE ART
    Liquid fuels for internal combustion engines contain components that can degrade during engine operation. The problem of deposits in the internal parts of combustion engines is well known to engine manufacturers. It has been shown that the formation of these deposits has consequences on engine performance and in particular has a negative impact on consumption and particle emissions. Advances in fuel additive technology have made it possible to deal with this problem. So-called detergent additives used in fuels have already been proposed to keep the engine clean by limiting deposits ("Keep-clean" effect) or by reducing deposits already present in the internal parts of the combustion engine (" clean-up ”. By way of example, mention may be made of document US4171959 which describes a detergent additive for petrol fuel containing a quaternary ammonium 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. However, engine technology is constantly evolving and fuel requirements must evolve to meet these technological advances in combustion engines. 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 spraying, in particular, more numerous holes having smaller diameters but which, on the other hand, induce a greater sensitivity to deposits. The presence of deposits can affect combustion performance, in particular increasing polluting emissions and particulate emissions. Other consequences of excessive deposits have been reported in the literature, such as increased fuel consumption and handling problems.
    ICG70098 text deposit
    Preventing and reducing deposits in these new engines is essential for optimal operation of today's engines. There is therefore a need to provide detergent additives for fuel promoting optimal operation of combustion engines, in particular for new engine technologies.
    There is also a need for a universal detergent additive capable of acting on deposits regardless of the engine technology and / or the nature of the fuel.
    OBJECT OF THE INVENTION
    The object according to the invention relates to new copolymers.
    The Applicant has discovered that the copolymers according to the invention have remarkable properties as a detergent additive in the liquid fuels of an internal combustion engine. The copolymers according to the invention used in these fuels make it possible to maintain the cleanliness of the engine, in particular, by limiting or avoiding the formation of deposits (“Keep-clean” effect in English) or by reducing the deposits already present in the internal parts of the combustion engine ("clean-up" effect in English).
    The advantages associated with the use of such copolymers according to the invention are:
    - optimal engine operation,
    - a reduction in fuel consumption,
    - better handling of the vehicle,
    - reduced pollutant emissions, and
    - savings due to less maintenance of the engine.
    The subject of the present invention relates to a copolymer obtained by copolymerization of at least:
    - an apolar monomer (m a ) corresponding to the following formula (I)
    (I)
    With u = 0 or 1,
    ICG70098 text deposit w = 0 or 1,
    E = -O- or -NH (Z) -, or -O-CO-, or -NH-CO- or -CO-NH-, with Z represents H or a C1-C6 alkyl group, it being understood that when E = -O-CO- E is linked to the vinyl carbon by the oxygen atom,
    G represents a group chosen from C1-C34 alkyl, an aromatic ring, an aralkyl comprising at least one aromatic ring and at least one C1-C34 alkyl group, and
    a polar monomer (m b ) chosen from those of formula (II) below:
    (II) in which t = 0 yes
    Q is chosen from the oxygen atom and the group -NR’- with R ’being chosen from a hydrogen atom and the C 1 to C 12 hydrocarbon chains,
    R is a C 1 to C 34 hydrocarbon chain substituted with at least one quaternary ammonium group and optionally one or more hydroxyl groups.
    According to an advantageous embodiment, the group E of the apolar monomer (m a ) is -O-.
    According to another advantageous embodiment, the group E of the apolar monomer (m a ) is -NH (Z) - with Z represents H or a C1-C6 alkyl group.
    According to yet another advantageous embodiment, the group E of the apolar monomer (m a ) is and -O-CO- where E is linked to the vinyl carbon by the oxygen atom.
    Advantageously, the apolar monomer (m a ) is such that w is equal to 0.
    According to a first preferred variant, the group G of the apolar monomer (m a ) is a C4-C30 alkyl.
    ICG70098 text deposit
    According to another preferred variant, the group G of the apolar monomer (m a ) is an aralkyl comprising at least one aromatic nucleus and at least one C4-30 alkyl group.
    Advantageously, in the polar monomer (m b ), the quaternary ammonium group is chosen from quaternary ammoniums of pyrrolinium, pyridinium, imidazolium, triazolium, triazinium, oxazolium and isoxazolium.
    According to a variant, the quaternary ammonium group is chosen from quaternary ammoniums of trialkylammonium, of minimium, of amidinium, of formamidinium, of guanidinium and of biguanidinium, preferably of trialkylammonium.
    According to a particular preferred embodiment, the polar monomer (m b ) is represented by one of the following formulas (III) and (IV):
    (III) (IV) in which t and Q are as defined in formula (II) above,
    X is chosen from hydroxide ions, halides and organic anions,
    R 2 is chosen from C 1 to C 34 hydrocarbon chains, optionally substituted with at least one hydroxyl group,
    R 3 , R 4 and R 5 are identical or different and chosen, independently, from the C 1 to C 8 hydrocarbon chains, it being understood that the alkyl groups R 3 , R 4 and R 5 may contain one or more groups chosen from: a nitrogen atom, an oxygen atom and a carbonyl group and the groups R 3 , R 4 and R 5 can be linked together in pairs to form one or more rings,
    R 6 and R 7 are identical or different and chosen independently from the C 1 to C 8 hydrocarbon chains, it being understood that the groups R 6 and R 7 may contain one or more groups chosen from: a nitrogen atom, a d atom oxygen and a carbonyl group and that the groups R 6 and R 7 may be
    ICG70098 text deposit linked together to form a cycle.
    Advantageously, the group R 2 is represented by one of the following formulas (V) and (VI):
    »Liaison with N
    bond with Q (V) bond with N bond with Q
    R9 OH (VI)
    In which
    R 8 is chosen from C 1 to C 32 hydrocarbon chains,
    R g is selected from hydrogen, alkyl to C 6.
    According to a particular embodiment, the monomer (m b ) is obtained by reaction:
    - a tertiary amine of formula NR3R4R5 or R 6 N = R 7 in which R 3 , R 4 , R 5 , R 6 and R 7 are as defined above in formulas (III) and (IV), and
    - an intermediate (meth) acrylate or (meth) acrylamide (m,) monomer of formula (VII) below:
    ex
    8 w
    (VII)
    In which,
    Q, t, R 8 and R g are as defined in formulas (II), (V) and (VI) above.
    According to a preferred embodiment, the copolymer is chosen from block copolymers and random copolymers.
    According to a particularly preferred embodiment, the copolymer is a block copolymer.
    In particular, the block copolymer comprises at least:
    a block A consisting of a chain of structural units derived from one or more apolar monomers chosen from apolar monomers (m a ) of formula (I) and,
    ICG70098 text deposit
    - a block B consisting of a chain of structural units derived from one or more polar monomers chosen from polar monomers (m b ).
    Advantageously, the copolymer comprises at least one block sequence AB, ABA or BAB where said blocks A and B are linked without the presence of an intermediate block of different chemical nature.
    According to a particular development, the block copolymer is obtained by block polymerization, optionally, followed by one or more post-functionalizations.
    According to a particular embodiment, the block B is obtained by post-functionalization of an intermediate polymer P / resulting from the polymerization of an intermediate monomer (meth) acrylate or (meth) acrylamide (m,) of formula (VII) defined above and in which said post-functionalization corresponds to the reaction of said intermediate polymer P / with a tertiary amine NR3R4R5 where R 6 N = R 7 where R 3 , R 4 , R 5 , R 6 and R 7 are such that defined above in formulas (III) and (IV).
    Advantageously, the intermediate polymer P / also comprises at least one block A as defined in above.
    According to a particular embodiment, the block copolymer is obtained by block 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 the presence of an intermediate block of different chemical nature.
    The object of the present invention also relates to a fuel concentrate comprising one or more copolymers as described above, in admixture with an organic liquid, said organic liquid being inert with respect to the copolymer (s) and miscible with said fuel .
    The subject of the present invention also relates to a fuel composition comprising:
    (1) a fuel from one or more sources chosen from the group consisting of mineral, animal, plant and synthetic sources, and
    ICG70098 text deposit (2) one or more copolymers as defined above.
    Advantageously, the composition comprises at least 5 ppm of copolymer (s) (2).
    According to a particular embodiment, the fuel (1) is chosen from hydrocarbon fuels; non-essentially hydrocarbon fuels and their mixtures.
    The object of the present invention also relates to the use of one or more copolymers as defined above, as a detergent additive in a liquid fuel of internal combustion engines, said copolymer being used alone, as a mixture or in the form of 'a concentrate as defined above.
    According to a particular embodiment, the copolymer is used in the liquid fuel to maintain the 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 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 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 emissions of particles from 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 chosen 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 diesel engine with direct injection.
    ICG70098 text deposit
    Advantageously, the copolymer is used to avoid and / or reduce the formation of deposits in the injection system of the diesel engine.
    In particular, the copolymer is used to avoid and / or reduce the formation of deposits linked to the coking phenomenon 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 loss of power being determined according to the method d standard CEC F-98-08 engine test.
    According to a particular embodiment, the copolymer is used to reduce and / or avoid the restriction of the flow of fuel emitted by the injector during the operation of said diesel engine, said restriction of flow being determined according to the standardized engine test method CEC F-23-1-01.
    The invention also relates to a process for maintaining the cleanliness and / or cleaning of at least one of the internal parts of an internal combustion engine comprising at least the following steps:
    the preparation of a fuel composition by additivation of a fuel with one or more copolymers as described above and,
    - the combustion of said fuel composition in said internal combustion engine.
    According to a first embodiment, the internal combustion engine is a spark-ignition engine.
    Advantageously, according to this embodiment, the internal part of the positive-ignition engine kept clean and / or cleaned is chosen from the engine intake system, in particular the intake valves (IVD), the combustion chamber (CCD or TCD) and the fuel injection system, in particular the injectors of an indirect injection system (PFI) or the injectors of a direct injection system (DISI).
    According to another embodiment, the internal combustion engine is a diesel engine, preferably a direct injection diesel engine.
    ICG70098 text deposit
    Advantageously, according to this embodiment, the internal part of the diesel engine kept clean and / or cleaned is the injection system of the diesel engine.
    DETAILED DESCRIPTION
    Other advantages and characteristics will emerge more clearly from the description which follows. The particular embodiments of the invention are given by way of nonlimiting examples.
    According to a particular embodiment, a copolymer is obtained by copolymerization of at least one apolar monomer (m a ) and at least one polar monomer (m b ).
    According to one embodiment, the copolymer is chosen from block or random copolymers.
    According to a particularly preferred embodiment, the copolymer is a block copolymer.
    The apolar monomer (m a ) corresponds to the following formula (I):
    With u = 0 or 1 w = 0 or 1
    Advantageously, the apolar monomer (m a ) is such that w = 0.
    The group E of the apolar monomer (m a ) is chosen from
    - E = -O-,
    E = -NH (Z) - with Z represents H or a C1-C6 alkyl group, linear or branched, cyclic or acyclic, preferably acylic,
    ICG70098 text deposit
    E = -O-CO- it being understood that E is then connected to the vinyl carbon by the oxygen atom,
    - E = -NH-CO-, and
    - E = -CO-NH-.
    According to a variant, the apolar monomer (m a ) is chosen from those verifying u = 0
    According to a preferred variant, the apolar monomer (m a ) is chosen from those satisfying: u = 1, and the group E is chosen from
    - E = -O-,
    E = -NH (Z) - with Z represents H or a C1-C6 alkyl group, linear or branched, cyclic or acyclic, preferably acylic, preferably CH3, and E = -O-CO- where E is connected to vinyl carbon by the oxygen atom.
    According to a more preferred variant, the apolar monomer (m a ) is chosen from those verifying:
    u = 1, and the group E is chosen from: ο E = -O-, and ο E = -O-CO- where E is linked to the vinyl carbon by the oxygen atom.
    The group (G) of the apolar monomer (m a ) may be a C1-C34 alkyl, preferably a C4-C30 alkyl radical, even better in C6-C24, even more preferably in C8 to C18. The alkyl radical is a linear or branched radical, cyclic or acyclic, preferably acyclic. This alkyl radical can comprise a linear or branched part and a cyclic part.
    The group (G) of the apolar monomer (m a ) is advantageously an acyclic C1-C34 alkyl, preferably a C4-C30 alkyl radical, even better in C6-C24, even more preferably in C8 to C18, linear or branched , preferably linear.
    Mention may be made, without limitation, of alkyl groups such as octyl, decyl, dodecyl, ethyl-2-hexyl, isooctyl, isodecyl and isododecyl.
    Among the vinyl ester alkyl monomers that may be mentioned, for example, vinyl octanoate, vinyl decanoate, vinyl dodecanoate, vinyl tetradecanoate, vinyl hexadecanoate, vinyl octodecanoate, docosanoate of vinyl, vinyl 2ethylhexanoate.
    ICG70098 text deposit
    The group (G) of the apolar monomer (m a ) can also be an aromatic ring, preferably a phenyl or aryl group. Among the aromatic groups, non-limiting mention may be made of the phenyl or naphthyl group, preferably the phenyl group.
    According to another preferred variant, the group (G) of the apolar monomer (m a ) can be an aralkyl comprising at least one aromatic nucleus and at least one C1-C34 alkyl group. Preferably, according to this variant, the group (G) is an aralkyl comprising at least one aromatic ring and one or more alkyl groups C4-C30, advantageously C6-C24, even more preferably C8 to C18.
    The aromatic ring can be mono-substituted or be substituted on several of its carbon atoms. Preferably, the aromatic nucleus is monosubstituted.
    The C1-C34 alkyl group may be in the ortho, meta or para position on the aromatic ring, preferably in para.
    The alkyl radical is a linear or branched radical, cyclic or acyclic, preferably acyclic.
    The alkyl radical is preferably an acyclic radical, linear or branched, preferably linear.
    The aromatic ring can be directly linked to the group E or to vinyl carbon, but it can also be linked to it via an alkyl substituent.
    Mention may be made, by way of example of group G, of a benzyl group substituted in para with a C4-C30 alkyl group.
    Preferably, according to this variant, the group (G) of the apolar monomer (m a ) is an aralkyl comprising at least one aromatic ring and at least one alkyl group in C4-C30, advantageously in C6-C24, even more preferably in C8 to C18.
    The polar monomer (m b ) is chosen from those of formula (II):
    ICG70098 text deposit
    O
    Ft
    R (II) in which t = 0 or 1, preferably t = 0,
    Q is selected from oxygen atom and the -NR 'group with R' being selected from hydrogen and hydrocarbon chains -C 12, preferably C, to C 6, said chains being linear or branched, cyclic or acyclic, preferably acyclic. Q is preferably chosen from the oxygen atom and the group -NH-.
    R is a hydrocarbon chain Ci-C34, preferably Ci to C 8, more preferably Ci to C10 linear or branched, cyclic or acyclic, preferably acyclic, substituted with at least one quaternary ammonium group preferably having from 4 with 50 atoms and possibly one or more hydroxyl groups.
    According to a particular embodiment, the group R comprises a quaternary ammonium group and one or more hydroxyl groups.
    According to a variant, the group R is chosen from groups having at least one quaternary ammonium function obtained by quaternization of a primary, secondary or tertiary amine according to any known process.
    The group R can, in particular, be chosen from groups having at least one quaternary ammonium function obtained by quaternization of at least one amine, imine, amidine, guanidine, aminoguanidine or biguanidine function; heterocyclic groups having 3 to 34 atoms and at least one nitrogen atom.
    Advantageously, the group R is chosen from groups having at least one quaternary ammonium function obtained by quaternarization of a tertiary amine.
    According to a particular embodiment, the polar monomer (m b ) is represented by
    ICG70098 text deposit one of the following formulas (III) and (IV):
    in which t and Q are as described above,
    X is chosen from hydroxide ions, halides and organic anions, in particular acetate ion,
    R 2 is chosen from C1 to C34, preferably C1 to Cw hydrocarbon chains, cyclic or acyclic, linear or branched, optionally substituted with at least one hydroxyl group; preferably R 2 is chosen from alkyl groups, optionally substituted with at least one hydroxyl group,
    R 3 , R 4 and R 5 are identical or different and chosen, independently, from the C1 to Cw, preferably C1 to C12 hydrocarbon chains, linear or branched, cyclic or acyclic, it being understood that the alkyl groups R 3 , R 4 and R 5 may contain one or more nitrogen and / or oxygen atoms and / or carbonyl groups and may be linked together in pairs to form one or more rings,
    R 6 and R 7 are identical or different and chosen, independently, from the C1 to Cw, preferably C1 to C12 hydrocarbon chains, linear or branched, cyclic or acyclic, it being understood that the groups R 6 and R 7 may contain one or more nitrogen and / or oxygen atoms and / or carbonyl groups and can be linked together to form a ring.
    The nitrogen and / or oxygen atom (s) may be present in the groups R 3 , R 4 and R 5 in the form of ether bridges, amine bridges or in the form of an amine or hydroxyl substituent.
    The organic anions of group X are generally the conjugate bases of organic acids, preferably the conjugate bases of carboxylic acids, in particular the acids chosen from monocarboxylic, polycarboxylic, cyclic or acyclic acids. Preferably the organic anions of group X are
    ICG70098 text deposit chosen from the conjugate bases of saturated acyclic or cyclic aromatic carboxylic acids. Examples include methanoic acid, acetic acid, adipic acid, oxalic acid, malonic acid, succinic acid, citric acid, benzoic acid, acid phthalic, isophthalic acid and terephthalic acid.
    According to a particular embodiment, the group R 2 is chosen from acyclic C1 to C34, preferably C1 to Ci 8 alkyl groups, linear or branched, substituted by at least one hydroxyl group.
    According to a particular embodiment, the group R 2 is represented by one of the following formulas (V) and (VI):
    RS
    liaison with N '| bond with Q
    OH bond with N
    bond with Q
    R9 OH (V) (VI)
    In which
    R 8 is chosen from C 1 to C 32 , preferably C 1 to C 6 hydrocarbon chains, cyclic or acyclic, preferably acyclic, linear or branched, preferably alkyl groups,
    R g is chosen from hydrogen and C 1 to C 6 , C 1 to C 4 alkyl groups, more preferably hydrogen.
    The copolymer can be prepared according to any known method of polymerization. The various techniques and conditions of polymerization are widely described in the literature and fall within the general knowledge of those skilled in the art.
    It is understood that one would not depart from the invention if the copolymer according to the invention were obtained from monomers other than (m a ) and (m b ), insofar as the final copolymer corresponds to that of the invention, that is to say obtained by copolymerization of at least (m a ) and (m b ). For example, one would not depart from the invention, if the copolymer were obtained by copolymerization of monomers other than (m a ) and (m b ) followed by post-functionalization.
    For example, the blocks deriving from an apolar monomer (m a ) can be obtained from vinyl alcohol or acrylic acid, respectively by transesterification or amidation reaction.
    ICG70098 text deposit
    For example, the blocks deriving from a polar monomer (m b ) can be obtained by post-functionalization of an intermediate polymer P / resulting from the polymerization of an intermediate monomer (meth) acrylate or (meth) acrylamide (m, ) of formula (VII) defined above and in which said post-functionalization corresponds to the reaction of said intermediate polymer P / with a tertiary amine NR 3 R 4 R 5 where R 6 N = R 7 where R 3 , R 4 , R 5 , R 6 and R 7 are as defined above in formulas (III) and (IV).
    The block copolymer can be obtained by block polymerization, preferably by block 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 block and controlled polymerization. The polymerization is advantageously chosen from controlled radical polymerization; for example, by atomic transfer radical polymerization (ATRP in English "Atom Transfer Radical Polymerization"); radical polymerization with nitroxide (NMP in English "Nitroxide-mediated polymerization"); degenerative transfer processes (in English “degenerative transfer processes”) such as degenerative iodine transfer polymerization (in English “ITRP- iodine transfer radical polymerization”) or radical polymerization by reversible chain transfer by addition-fragmentation ( RAFT in English “Reversible Addition-Fragmentation Chain Transfer); polymerizations derived from ATRP such as polymerizations using initiators for continuous regeneration of the activator (ICAR -Initiators for continuous activator regeneration) or using activators regenerated by electron transfer (ARGET in English "activators regenerated by electron transfer ”).
    By way of example, mention may be made of the publication "Macromolecular Engineering by atom transfer radical polymerization", JACS, 136, 6513-6533 (2014) which describes a sequenced and controlled polymerization process for forming block copolymers.
    The sequenced and controlled polymerization is typically carried out in a solvent, under an inert atmosphere, at a reaction temperature generally ranging from 0 to 200 ° C, preferably from 50 ° C to 130 ° C. The solvent can be chosen from polar solvents, in particular ethers such as anisole (methoxybenzene) or tetrahydrofuran or non-polar solvents, in particular, paraffins, cycloparaffins, aromatics and alkylaromatics having from 1 to 19 atoms of carbon, for example, benzene,
    ICG70098 text deposit toluene, cyclohexane, methylcyclohexane, n-butene, n-hexane, n-heptane and the like.
    For radical polymerization by atom transfer (ATRP in English "Atom Transfer Radical Polymerization"), the reaction is generally carried out under vacuum in the presence of an initiator, a ligand and a catalyst. By way of example of a ligand, mention may be made of Ν, Ν, Ν ', Ν'',Ν''- Pentamethyldiethylenetriamine (PMDETA), 1,1,4,7,10,10hexamethyltriethylene tetramine (HMTETA), 2,2'-Bipyridine (BPY) and Tris (2pyridylmethyl) amine (TPMA). Examples of catalysts that may be mentioned include: CuX, CuX 2 , with X = CI, Br and ruthenium-based complexes Ru 2+ / Ru 3+ .
    The ATRP polymerization is preferably carried out in a solvent chosen from polar solvents.
    According to the sequenced and controlled polymerization technique, it can also be envisaged to work under pressure.
    The numbers of equivalents of apolar monomer (m a ) of block A and of polar monomer (m b ) of block B reacted during the polymerization reaction are identical or different.
    The number of equivalents of apolar monomer (m a ) of block A is preferably from 2 to 50, preferably from 5 to 50, more preferably from 10 to 50.
    The number of polar monomer equivalents (m b ) of block B is preferably from 2 to 50, preferably from 2 to 40, more preferably from 2 to 20.
    The number of equivalents of monomer (m a ) of block A is advantageously greater than or equal to that of the monomer (m b ) of block B.
    In addition, the molar mass by weight M w of block A or block B is preferably less than or equal to 15,000 g.mol. 1 , more preferably less than or equal to 10,000 g.mol. ' 1 .
    The block copolymer advantageously comprises at least one block sequence AB, ABA or BAB where said blocks A and B are linked without the presence of an intermediate block of different chemical nature.
    ICG70098 text deposit
    Other blocks may possibly be present in the block copolymer described above insofar as these blocks do not fundamentally change the character of the block copolymer. However, block copolymers containing only blocks A and B will be preferred.
    Advantageously, A and B represent at least 70% by mass, preferably at least 90% by mass, more preferably at least 95% by mass, even more preferably at least 99% by mass of the block copolymer.
    According to a particular embodiment, the block copolymer is a sequenced copolymer.
    According to another particular embodiment, the block copolymer is a triblock copolymer with alternating blocks comprising two blocks A and a block B (ABA) or comprising two blocks B and a block A (BAB).
    According to a particular embodiment, the block copolymer also comprises a terminal chain I consisting of a hydrocarbon chain, cyclic or acyclic, saturated or unsaturated, linear or branched, in Ci to C 32 , preferably in C 4 to C 24 , more preferably in Cw to C 24 .
    The term cyclic hydrocarbon chain is understood to mean a hydrocarbon chain of which at least part is cyclic, in particular aromatic. This definition does not exclude hydrocarbon chains comprising both an acyclic part and a cyclic part.
    The terminal chain I can comprise an aromatic hydrocarbon chain, for example benzene and / or a hydrocarbon chain, saturated and acyclic, linear or branched, in particular an alkyl chain.
    The terminal chain I is preferably chosen from alkyl chains, preferably linear, more preferably alkyl chains of at least 4 carbon atoms, even more preferably of at least 12 carbon atoms.
    For ATRP polymerization, the terminal chain I is located in the terminal position of the block copolymer. It can be introduced into the block copolymer using the polymerization initiator. Thus, the terminal chain I can, advantageously,
    ICG70098 text deposit constitute at least part of the polymerization initiator and is positioned within the polymerization initiator in order to allow the introduction, during the first polymerization initiation step, of the terminal chain I in position terminal of the block copolymer.
    The polymerization initiator is, for example, chosen from the 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 perspectives, Macromolecules, 45, 4015-4039, 2012".
    The polymerization initiator is, for example, chosen from alkyl esters of carboxylic acid substituted with a halide, preferably a bromine in the alpha position, for example, ethyl 2-bromopropionate, α-bromoisobutyrate ethyl, benzyl choride or bromide, ethyl α-bromophenylacetate and chloroethylbenzene. Thus, for example, ethyl 2-bromopropionate may make it possible to introduce into the copolymer the terminal chain I in the form of a C 2 alkyl chain and the benzyl bromide in the form of a benzyl group.
    For RAFT polymerization, the transfer agent can conventionally be removed from the copolymer at the end of polymerization according to any known process.
    Alternatively, the terminal chain I can also be obtained in the copolymer by RAFT polymerization according to the methods described in the article by Moad, G. and co., Australian Journal of Chemistry, 2012, 65, 985-1076. The terminal chain I can, for example, be introduced by aminolysis when a transfer agent is used. By way of example, mention may be made of transfer agents of the thiocarbonylthio, dithiocarbonate, xanthate, dithiocarbamate and trithiocarbonate type, for example S, S-bis (a, a'-dimethyl-a ”acetic acid) trithiocarbonate (BDMAT) or 2-cyano-2-propyl benzodithioate.
    According to a particular embodiment, the block copolymer is a sequenced copolymer (also called diblocks). The block copolymer structure can be of the IAB or IBA type, advantageously IAB. The terminal chain I can be directly linked to block A or B according to the structure respectively IAB or IBA or, can 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.
    ICG70098 text deposit
    According to a particular embodiment, the block copolymer can also be functionalized at the end of the chain according to any known process, in particular by hydrolysis, aminolysis and / or nucleophilic substitution.
    By aminolysis is meant any chemical reaction in which a molecule is split into two parts by reaction of an ammonia molecule or an amine. A general example of aminolysis consists in replacing a halogen of an alkyl group by reaction with an amine, with elimination of hydrogen halide. Aminolysis can be used, for example, for an ATRP polymerization which produces a copolymer having a halide in the terminal position or for a RAFT polymerization to remove the thio, dithio or trithio bond introduced into the copolymer by the RAFT transfer agent.
    It is thus possible to introduce a terminal chain I ′ by post-functionalization of the block copolymer obtained by sequenced and controlled polymerization of the monomers m a and m b described above.
    The terminal chain I ′ advantageously comprises a hydrocarbon chain, linear or branched, cyclic or acyclic, C 1 to C 32, preferably C 1 to C 24 , more preferably C 1 to C 8, even more preferably an alkyl group, optionally substituted by one or more groups containing at least one heteroatom chosen from N and O, preferably N.
    For an ATRP polymerization using a metal halide as catalyst, this functionalization can, for example, be carried out by treating the IAB or IBA copolymer obtained by ATRP with a primary C1 to C 32 alkylamine or a C1 to C 32 alcohol under conditions soft so as not to modify the functions present on blocks A, B and l.
    The quaternary ammonium group of block B described above can be acyclic or cyclic.
    The acyclic quaternary ammonium group is advantageously chosen from quaternary ammoniums of trialkylammonium, minimium, amidinium, formamidinium, guanidinium and biguanidinium, preferably trialkylammonium.
    ICG70098 text deposit
    The cyclic quaternary ammonium group is advantageously chosen from heterocyclic compounds containing at least one nitrogen atom, in particular chosen from quaternary ammoniums of pyrrolinium, pyridinium, imidazolium, triazolium, triazinium, oxazolium and isoxazolium.
    The quaternary ammonium group in block B is advantageously a quaternary ammonium, advantageously a quaternary trialkylammonium.
    According to a particular embodiment, the block B is preferably derived from a monomer (m b ) obtained by reaction:
    a tertiary amine of formula NR 3 R 4 R 5 or R 6 N = R 7 in which R 3 , R 4 , R 5 , R 6 and R 7 are as described above, and
    - an intermediate (meth) acrylate or (meth) acrylamide m monomer, of formula (VII) below:
    ® O (VII)
    In which,
    Q, t, R 8 and R g are as described above.
    According to another particular embodiment, block B is obtained by post-functionalization of an intermediate polymer P / comprising at least one block P of formula (VIII) below:
    In which,
    Q, R 8 and Rg are as described above, Ri represents H or CH 3 , n represents a
    ICG70098 full deposit text ranging from 2 to 50, preferably from 2 to 40, more preferably from 2 to 20.
    Post-functionalization corresponds to the reaction of the intermediate polymer P / with a tertiary amine of formula NR 3 R 4 R 5 or R 6 N = R 7 in which R 3 , R 4 , R 5 and R 6 , R 7 are such as previously described.
    The tertiary amine can, for example, be chosen from acyclic tertiary amines, preferably trialkylamines, guanidines and quaternizable imines. The tertiary amine is advantageously chosen from trialkylamines, in particular those in which the alkyl groups are identical or different and chosen, independently, from C1 to Cw alkyl, preferably from C1 to C12, linear or branched, cyclic or acyclic, preferably acyclic.
    According to a variant, the tertiary amine can be chosen from cyclic tertiary amines, preferably pyrrolines, pyridines, imidazoles, triazoles, guanidines, imines, triazines, oxazoles and quaternizable isoxazoles.
    The intermediate polymer P / can also comprise at least one block A as described above.
    The copolymer described above is particularly advantageous when it is used as a detergent additive in a liquid fuel of an internal combustion engine.
    The term “detergent additive for liquid fuel” is understood to mean an additive which is incorporated in small quantity into the liquid fuel and has an effect on the cleanliness of said engine compared to said liquid fuel which is not specially additive.
    The liquid fuel advantageously comes from one or more sources chosen from the group consisting of mineral, animal, plant and synthetic sources. Preferably, petroleum will be chosen as the mineral source.
    The liquid fuel is preferably chosen from hydrocarbon fuels and non-essentially hydrocarbon fuels, alone or as a mixture.
    Hydrocarbon fuel is understood to mean a fuel consisting of one or more compounds consisting solely of carbon and hydrogen.
    ICG70098 text deposit
    Non-essentially hydrocarbon fuel is understood to mean a fuel consisting of one or more compounds consisting not essentially of carbon and hydrogen, that is to say which also contain other atoms, in particular oxygen atoms.
    Hydrocarbon fuels include in particular middle distillates with a boiling point ranging from 100 to 500 ° C or lighter distillates with a boiling temperature in the range of gasolines. These distillates can, for example, be chosen from distillates obtained by direct distillation of crude hydrocarbons, vacuum distillates, hydrotreated distillates, distillates from catalytic cracking and / or hydrocracking of vacuum distillates, distillates resulting from ARDS-type conversion processes (in English "atmospheric residue desulfurization") and / or visbreaking, the distillates from the recovery of Fischer Tropsch cuts. Hydrocarbon fuels are typically gasolines and diesel fuels (also called diesel fuel).
    The gasolines include, in particular, all fuel compositions for spark ignition engines commercially available. As a representative example, mention may be made of gasolines meeting the NF EN 228 standard. Gasolines generally have octane numbers high enough to avoid the knocking phenomenon. Typically, gasoline-type fuels sold in Europe, compliant with standard NF EN 228, have an engine octane number (MON in English “Motor Octane Number”) greater than 85 and a research octane number (RON in English “ Research Octane Number ") with a minimum of 95. Gasoline fuels generally have an RON ranging from 90 to 100 and a MON ranging from 80 to 90, the RON and MON being measured according to standard ASTM D 2699- 86 or D 2700-86.
    Diesel oils (diesel fuels) include, in particular, all fuel compositions for diesel engines commercially available. As a representative example, mention may be made of diesel oils meeting the N F EN 590 standard.
    Fuels which are not essentially hydrocarbon-based include in particular oxygenates, for example distillates resulting from the BTL (in English "biomass to liquid") conversion of plant and / or animal biomass, taken alone or in combination; biofuels, for example oils and / or esters of vegetable and / or animal oils; biodiesel of animal and / or vegetable origin and bioethanols.
    ICG70098 text deposit
    The mixtures of hydrocarbon fuel and non-essentially hydrocarbon fuel are typically gas oils of type B x or gasolines of type E x .
    By diesel fuel type B x means a diesel fuel, a diesel fuel that contains x% (v / v) of vegetable or animal oil esters (including used cooking oils) transformed by a chemical process called transesterification, obtained by reacting this oil with an alcohol in order to obtain fatty acid esters (EAG). With methanol and ethanol, methyl esters of fatty acids (EMAG) and ethyl esters of fatty acids (EEAG) are obtained, respectively. The letter B followed by a number indicates the percentage of EAG contained in diesel. Thus, a B99 contains 99% EAG and 1% of middle distillates of fossil origin (mineral source), B20, 20% of EAG and 80% of middle distillates of fossil origin, etc. type B o gas oils which do not contain oxygenated compounds, type Bx gas oils which contain x% (v / v) of vegetable oil esters or fatty acids, most often methyl esters (EMHV or EMAG) . When the EAG is used alone in engines, the fuel is designated by the term B100.
    The expression “E x type petrol for positive ignition engine” is understood to mean a petrol fuel which contains x% (v / v) of oxygenates, generally ethanol, bioethanol and / or ethyl-tertio-butyl-ether (ETBE).
    The sulfur content of the liquid fuel is preferably less than or equal to 5000 ppm, preferably less than or equal to 500 ppm, and more preferably less than or equal to 50 ppm, or even even less than 10 ppm and advantageously without sulfur.
    The copolymer described above is used as a detergent additive in liquid fuel at a content, advantageously at least 10 ppm, preferably at least 50 ppm, more preferably at a content of 10 to 5000 ppm, even more preferably from 10 to 1000 ppm.
    According to a particular embodiment, the use of a copolymer as described above in the liquid fuel makes it possible to maintain the cleanliness of at least one of the internal parts of the internal combustion engine and / or to clean at least one of the parts internal combustion engine.
    The use of the copolymer in 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 (effect
    ICG70098 deposit text “keep-clean” in English) and / or reduce deposits existing in at least one of the internal parts of said engine (“clean-up” effect in English).
    Thus, the use of the copolymer in the liquid fuel makes it possible, compared to the liquid fuel not specially additive, to limit or avoid the formation of deposits in at least one of the internal parts of said engine or to reduce the deposits existing in at least one of the internal parts of said motor.
    Advantageously, the use of the copolymer in liquid fuel makes it possible to observe both the two effects, limitation (or prevention) and reduction of deposits ("keep-clean" and "clean-up" effects).
    A distinction is made between deposits depending on the type of internal combustion engine and the location of deposits in the internal parts of said engine.
    According to a particular embodiment, the internal combustion engine is a spark-ignition engine, preferably with direct injection (DISI in English "Direct Injection Spark Ignition engine"). The targeted deposits are located in at least one of the internal parts of said positive-ignition engine. The internal part of the spark-ignition engine kept clean (keep-clean) and / or cleaned (clean-up) is advantageously chosen from the engine intake system, in particular the intake valves (IVD in English). Intake Valve Deposit ”), the combustion chamber (CCD in English“ Combustion Chamber Deposit ”or TCD in English“ Total Chamber Deposit ”) and the fuel injection system, in particular the injectors of an indirect injection system (PFI in English "Port Fuel Injector") or the injectors of a direct injection system (DISI).
    According to another particular embodiment, the internal combustion engine is a diesel engine, preferably a diesel engine with direct injection, in particular a diesel engine with common-rail injection system (CRDI in English "Common Rail Direct Injection" ), The target depots are located in at least one of the internal parts of said Diesel engine.
    Advantageously, the targeted deposits are located in the injection system of the diesel engine, preferably located on an external part of an injector of said injection system, for example the nose of the injector and / or on an internal part. an injector of said injection system (IDID in English "Internai Diesel Injector Deposits"), by
    ICG70098 text deposit example on the surface of an injector needle.
    The deposits may consist of deposits linked to the phenomenon of coking (“coking” in English) and / or deposits of the soap and / or varnish type (in English “lacquering”).
    The copolymer as described above can advantageously be used in liquid fuel to reduce and / or avoid the loss of power due to the formation of deposits in the internal parts of a direct injection diesel engine, said loss of power being determined according to CEC F-98-08 standardized engine test method.
    The copolymer as described above can advantageously be used in liquid fuel to reduce and / or avoid the restriction of the flow of fuel emitted by the injector of a diesel engine with direct injection during its operation, said restriction of flow being determined according to the standard CEC F-23-101 engine test method.
    Advantageously, the use of the copolymer as described above makes it possible, compared with the liquid fuel not specially additive, to limit or avoid the formation of deposits on at least one type of deposits described above and / or reduce the deposits existing on at least a type of deposits described above.
    According to a particular embodiment, the use of the copolymer described above also makes it possible to reduce the fuel consumption of the internal combustion engine.
    According to another particular embodiment, the use of the copolymer described above also makes it possible to reduce the emissions of pollutants, in particular, the emissions of particles from the internal combustion engine.
    Advantageously, the use of the copolymer according to the invention makes it possible to reduce both the fuel consumption and the pollutant emissions.
    The copolymer described above can be used alone, in the form of a mixture of at least two of said copolymers or in the form of a concentrate.
    The copolymer can be added to the liquid fuel within a refinery and / or be incorporated downstream of the refinery and / or optionally, mixed with other additives
    ICG70098 text deposit in the form of a concentrate of additives, also commonly called "additive package".
    The 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, in admixture 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” is understood to mean the fact that the copolymer and the organic liquid form a solution or a dispersion so as to facilitate the mixing of the copolymer in the liquid fuels according to the conventional methods of fuel additivation.
    The organic liquid is advantageously chosen from aromatic hydrocarbon solvents such as the solvent sold under the name "SOLVESSO", alcohols, ethers and other oxygenated compounds and paraffinic solvents such as hexane, pentane or isoparaffins, alone or as a mixture.
    The concentrate can advantageously comprise from 5 to 99% by mass, preferably from 10 to 80%, more preferably from 25 to 70% of copolymer as described above.
    The concentrate can, typically, comprise from 1 to 95% by mass, preferably from 10 to 70%, more preferably from 25 to 60% of organic liquid, the remainder corresponding to the copolymer, it being understood that the concentrate can comprise one or more copolymers with 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 in number, respectively M w and M n of the copolymer. The average molar masses M w and M n of the copolymer according to the invention will be chosen so that the copolymer is soluble in the liquid fuel and / or the organic liquid of the concentrate for which it is intended.
    The average molar masses M w and M n of the copolymer according to the invention can also have an influence on the effectiveness of this copolymer as a detergent additive.
    ICG70098 text deposit
    The average molar masses M w and M n will therefore be chosen so as to optimize the effect of the copolymer according to the invention, in particular the detergency effect (engine cleanliness) in the liquid fuels described above.
    Optimization of the average molar masses M w and M n can be carried out by routine tests accessible to those skilled in the art.
    According to a particular embodiment, the copolymer advantageously has a weight-average molar mass (M w ) ranging from 500 to 30,000 g.mol 1 , preferably from 1000 to 10,000 g.mol ' 1 , more preferably lower or equal to 4000 g.mol ' 1 , and / or a number-average molar mass (Mn) ranging from 500 to 15,000 g.mol 1 , preferably from 1000 to 10,000 g.mol' 1 , more preferably lower or equal to 4000 g.mol 1 . The number and weight average molar masses are measured by size exclusion chromatography (SEC in English “Size Exclusion Chromatography). The operating conditions of the SEC, in particular, the choice of the solvent will be chosen as a function of the chemical functions present within the block copolymer.
    According to a particular embodiment, the copolymer according to the invention is used in the form of an additive concentrate in combination with at least one other additive for internal combustion engine fuel different from the copolymer described above.
    The additive concentrate can typically comprise one or more other additives chosen from detergent additives different from the copolymer described above, for example from anti-corrosion agents, dispersants, demulsifiers, anti-foaming agents, biocides, reodorants, procetane additives, friction modifiers, lubricant additives or oiliness additives, combustion aid agents (catalytic combustion and soot promoters), cloud point improving agents, pour point, TLF ("Filterability limit temperature"), anti-sedimentation agents, anti-wear agents and agents modifying conductivity.
    Among these additives, there may be mentioned in particular:
    a) procetane additives, in particular (but not limited to) chosen from alkyl nitrates, preferably 2-ethyl hexyl nitrate, aryl peroxides, preferably benzyl peroxide, and alkyl peroxides, preferably ter-butyl peroxide;
    b) anti-foam additives, in particular (but not limited to) chosen from polysiloxanes, oxyalkylated polysiloxanes, and fatty acid amides derived from oils
    ICG70098 text depot for plants or animals. Examples of such additives are given in EP861882, EP663000, EP736590;
    c) Cold fluidizing additives (CFI in English “Cold Flow Improver”) chosen from ethylene and unsaturated ester copolymers, such as ethylene / vinyl acetate (EVA), ethylene / vinyl propionate (TEU) copolymers , ethylene / vinyl ethanoate (EVE), ethylene / methyl methacrylate (EMMA), and ethylene / alkyl fumarate described, for example, in US3048479, US3627838, US3790359, US3961961 and EP261957.
    d) lubricating additives or antiwear agents, in particular (but not limited to) chosen from the group consisting of fatty acids and their ester or amide derivatives, in particular glycerol monooleate, and derivatives of mono- and carboxylic acids polycyclic. Examples of such additives are given in the following documents: EP680506, EP860494, WO98 / 04656, EP915944, FR2772783, FR2772784.
    e) cloud point additives, in particular (but not limited to) chosen from the group consisting of long chain olefin / (meth) acrylic ester / maleimide terpolymers, and polymers of fumaric / maleic acid esters. Examples of such additives are given in FR2528051, FR2528051, FR2528423, EP112195, EP172758, EP271385, EP291367;
    f) detergent additives in particular (but not limited to) chosen from the group consisting of succinimides, polyetheramines and quaternary ammonium salts; for example those described in documents US4171959 and WO2006135881.
    g) the polyfunctional additives for cold operability selected from the group consisting of polymers based on olefin and alkenyl nitrate as described in EP573490.
    These other additives are generally added in an amount ranging from 100 to 1000 ppm (each).
    The molar and / or mass ratio between the polar monomer (m b ) and the apolar monomer (m a ) and / or between block A and B in the block copolymer described above will be chosen so that the copolymer block is soluble in the fuel and / or the organic liquid of the concentrate for which it is intended. Similarly, this ratio can be optimized as a function of the fuel and / or of the organic liquid so as to obtain the best effect on engine cleanliness.
    Optimization of the molar and / or mass ratio can be carried out by routine tests accessible to a person skilled in the art.
    ICG70098 text deposit
    According to a particular embodiment, the molar ratio between the apolar monomer (m a ) and the polar monomer (m b ), or between the blocks A and B in molar percentage between the apolar monomer (m a ) of the block A and the polar monomer (m b ) of block B is preferably between 95: 5 and 70:30, more preferably between 85: 15 to 75: 25.
    According to a particular embodiment, a fuel composition is prepared according to any known process by adding the liquid fuel described above with at least one copolymer as described above.
    According to a particular embodiment, a fuel composition comprising:
    (1) a fuel as described above, and (2) one or more copolymers as described above.
    The fuel (1) is, in particular, chosen from hydrocarbon fuels and non-essentially hydrocarbon fuels described above, taken alone or as a mixture.
    The combustion of this fuel composition comprising such a copolymer in an internal combustion engine produces an effect on the cleanliness of the engine compared to liquid fuel not specially additivated and makes it possible, in particular, to prevent or reduce fouling of the internal parts of said engine . The effect on the cleanliness of the engine is as described above in the context of the use of the copolymer.
    According to a particular embodiment, the combustion of the fuel composition comprising such a copolymer in an internal combustion engine also makes it possible to reduce the fuel consumption and / or the pollutant emissions.
    The copolymer according to the invention is preferably incorporated in a small amount in the liquid fuel described above, the amount of copolymer being sufficient to produce a detergent effect as described above and thus improve engine cleanliness.
    The fuel composition advantageously comprises at least 5 ppm, preferably from 10 to 5,000 ppm, more preferably from 20 to 2,000 ppm, in particular from 50 to 500 ppm of copolymer (s) (2).
    In addition to the copolymer described above, the fuel composition can also
    ICG70098 text deposit include one or more other additives different from the copolymer according to the invention chosen from other known detergent additives, for example from anticorrosion agents, dispersants, demulsifiers, anti-foaming agents, biocides, reodorants, procetane additives, friction modifiers, lubricant additives or oiliness additives, combustion aid agents (catalytic combustion and soot promoters), cloud point improving agents, pour point, TLF, anti-sedimentation agents, anti-wear agents and / or agents modifying conductivity.
    The additives other than the copolymer according to the invention are, for example, the fuel additives listed above.
    According to a particular embodiment, a method of maintaining the cleanliness (keepclean) and / or cleaning (clean-up) of at least one of the internal parts of an internal combustion engine comprises the preparation of a composition of fuel by additivation of a fuel with one or more copolymers as described above and the combustion of said fuel composition in the internal combustion engine.
    According to a particular embodiment, the internal combustion engine is a spark-ignition engine, preferably with direct injection (DISI).
    The internal part kept clean and / or cleaned of the positive-ignition engine is preferably chosen from the engine's intake system, in particular the intake valves (IVD), the combustion chamber (CCD or TCD) and the fuel injection system, in particular the injectors of an indirect injection system (PFI) or the injectors of a direct injection system (DISI).
    According to another particular embodiment, the internal combustion engine is a diesel engine, preferably a direct injection diesel engine, in particular a diesel engine with common-rail injection systems (CRDI).
    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.
    ICG70098 text deposit
    The process of maintaining cleanliness (keep-clean) and / or cleaning (clean-up) comprises the successive stages of:
    a) determining the most suitable additive for the fuel, said additive corresponding to the selection of the copolymer (s) described above to be incorporated in combination, optionally, with other fuel additives as described above and the determination of the rate of treatment necessary to reach a given specification relating to the detergency of the fuel composition.
    b) incorporation into the fuel of the copolymer (s) selected at the rate determined in step a) and, optionally, of the other fuel additives.
    The copolymer (s) can be incorporated into the fuel, alone or as a mixture, successively or simultaneously.
    Alternatively, the copolymer (s) can be used in the form of a concentrate or a concentrate of additives as described above.
    Step a) is carried out according to any known process and is part of current practice in the field of fuel additivation. This step involves defining at least one characteristic representative of the detergency properties of the fuel composition.
    The characteristic characteristic of the detergency properties of the fuel will depend on the type of internal combustion engine, for example Diesel or by positive ignition, on the direct or indirect injection system and on the location in the engine of the deposits targeted for cleaning and / or maintaining cleanliness.
    For diesel engines with direct injection, the characteristic representative of the detergency properties of the fuel may, for example, correspond to the loss of power due to the formation of deposits in the injectors or the restriction of the flow of fuel emitted by the injector at during operation of said engine.
    The characteristic characteristic of detergency properties can also correspond to the appearance of lacquering deposits at the level of the injector needle (IDID).
    Methods for evaluating the detergent properties of fuels have been widely described in the literature and fall within the general knowledge of those skilled in the art
    ICG70098 business filing text. Mention will be made, by way of nonlimiting example, of the tests standardized or recognized by the profession or the methods described in the following literature:
    For direct injection diesel engines:
    - the DW10 method, CEC F-98-08 standard engine test method, for measuring the power loss of direct injection diesel engines
    - the XUD9 method, CEC F-23-1-01 Issue 5 standardized engine test method, to measure the fuel flow restriction emitted by the injector
    - The method described by the applicant in application W02014 / 029770 page 17 to 20, for the evaluation of lacquering deposits (IDID), this method being cited by way of example and / or incorporated by reference into the present application.
    For indirect injection ignition engines:
    - the Mercedes Benz M102E method, CEC F-05-A-93 standardized test method, and
    - the Mercedes Benz M111 method, CEC F-20-A-98 standardized test method.
    These methods allow the measurement of deposits on the intake valves (IVD), the tests generally being carried out on a Eurosuper petrol meeting the EN228 standard.
    For direct injection ignition engines:
    - the method described by the applicant in the article "Evaluating Injector Fouling in
    Direct Injection Spark Ignition Engines ”, Mathieu Arondel, Philippe China, Julien Gueit; Conventional and future energy for automobiles; 10th international colloquium; January 20-22, 2015, p.375-386 (Technische Akademie Esslingen by Techn. Akad. Esslingen, Ostfildern), for the evaluation of coking deposits on the injector, this method being cited as an example and / or incorporated by reference into this application.
    - The method described in document US20130104826, for the evaluation of deposits of the coking type on the injector, this method being cited by way of example and / or incorporated by reference into the present application.
    The amount of copolymer to be added to the fuel composition to reach the specification will typically be determined by comparison with the fuel composition but without the block copolymer according to the invention.
    The determination of the quantity of copolymer to be added to the fuel composition to reach the specification (step a) described above) will typically be carried out by comparison with the fuel composition but without the copolymer according to
    ICG70098 text deposit the invention, the given specification relating to detergency can for example be a target value of power loss according to the DW10 method or a flow restriction value according to the XUD9 method mentioned above.
    The amount of copolymer can also vary depending on the nature and origin of the fuel, in particular depending on the level of compounds containing n-alkyl, isoalkyl or n-alkenyl substituents. Thus, the nature and origin of the fuel can also be a factor to take into account for step a).
    The method of maintaining cleanliness (keep-clean) and / or cleaning (clean-up) may also include an additional step after step b) of verifying the target reached and / or of adjusting the rate of additivation with the copolymer (s) as detergent additive.
    The copolymers according to the invention have remarkable properties as a detergent additive in a liquid fuel, in particular in a diesel or petrol fuel.
    The copolymers according to the invention are particularly remarkable in particular because they are effective as a detergent additive for a wide range of liquid fuel and / or for one or more types of motorization and / or against one or more types of deposit which form in the internal parts of internal combustion engines.
    ICG70098 text deposit
    权利要求:
    Claims (32)
    [1" id="c-fr-0001]
    1. Copolymer obtained by copolymerization of at least:
    - an apolar monomer (m a ) corresponding to the following formula (I) η2 ° <© - © η
    T w (^)
    L
    G (l)
    With u = 0 or 1, w = 0 or 1,
    E = -O- or -NH (Z) -, or -O-CO-, or -NH-CO- or -CO-NH-, with Z represents H or a C1-C6 alkyl group, it being understood that when E = -O-CO- E is linked to the vinyl carbon by the oxygen atom,
    G represents a group chosen from C1-C34 alkyl, an aromatic ring, an aralkyl comprising at least one aromatic ring and at least one C1-C34 alkyl group, and
    a polar monomer (m b ) chosen from those of formula (II) below:
    H (il) in which t = 0 or 1
    20 Q is chosen from the oxygen atom and the group —NR’- with R ’being chosen from a hydrogen atom and the C 1 to C 12 hydrocarbon chains,
    R is a C 1 to C 34 hydrocarbon chain substituted by at least one quaternary ammonium group and optionally one or more hydroxyl groups.
    ICG70098 text deposit
    [2" id="c-fr-0002]
    2. Copolymer according to claim 1, in which the group E of the apolar monomer (m a ) is chosen from -O-, -NH (Z) - with Z represents H or a C1-C6 alkyl group, and -O- CO- where E is linked to vinyl carbon by the oxygen atom.
    [3" id="c-fr-0003]
    3. Copolymer according to one of claims 1 and 2, in which w is equal to 0.
    [4" id="c-fr-0004]
    4. Copolymer according to any one of the preceding claims, in which the group G is a C4-C30 alkyl.
    [5" id="c-fr-0005]
    5. Copolymer according to any one of claims 1 to 3, in which the group G is an aralkyl comprising at least one aromatic nucleus and at least one C4-30 alkyl group.
    [6" id="c-fr-0006]
    6. Copolymer according to any one of the preceding claims, in which in the polar monomer (m b ), the quaternary ammonium group is chosen from quaternary ammoniums of pyrrolinium, pyridinium, imidazolium, triazolium, triazinium, d 'oxazolium and isoxazolium.
    [7" id="c-fr-0007]
    7. Copolymer according to any one of claims 1 to 5, in which the quaternary ammonium group is chosen from quaternary ammoniums of trialkylammonium, iminium, amidinium, formamidinium, guanidinium and biguanidinium, preferably trialkylammonium .
    [8" id="c-fr-0008]
    8. Copolymer according to any one of the preceding claims, in which the polar monomer (m b ) is represented by one of the following formulas (III) and (IV):
    (III) (IV) in which t and O are as defined in formula (II),
    X is chosen from hydroxide ions, halides and organic anions,
    ICG70098 text deposit
    R 2 is chosen from C 1 to C 34 hydrocarbon chains, optionally substituted with at least one hydroxyl group,
    R 3 , R 4 and R 5 are identical or different and chosen, independently, from the Ci to Ci 3 hydrocarbon chains, it being understood that the alkyl groups R 3 , R 4 and R 5 may contain one or more groups chosen from: a nitrogen atom, an oxygen atom and a carbonyl group and the groups R 3 , R 4 and R 5 can be linked together in pairs to form one or more rings,
    R 6 and R 7 are identical or different and chosen independently from the C1 to C 3 hydrocarbon chains, it being understood that the groups R 6 and R 7 may contain one or more groups chosen from: a nitrogen atom, a d atom oxygen and a carbonyl group and that the groups R 6 and R 7 can be linked together to form a ring.
    [9" id="c-fr-0009]
    9. Copolymer according to claim 8, in which the group R 2 is represented by one of the formulas (V) and (VI) below:
    (V) (VI)
    In which
    R 3 is chosen from C 1 to C 32 hydrocarbon chains,
    R g is selected from hydrogen, alkyl to C 6.
    [10" id="c-fr-0010]
    10. Copolymer according to claim 9, in which the monomer (m b ) is obtained by reaction:
    - a tertiary amine of formula NR 3 R 4 R 5 or R 6 N = R 7 in which R 3 , R 4 , R 5 , R 6 and R 7 are as defined in formulas (III) and (IV ), and
    - an intermediate (meth) acrylate or (meth) acrylamide (m,) monomer of formula (VII) below:
    ICG70098 text deposit
    In which,
    Q, t, R 8 and R g are as defined in formulas (II), (V) and (VI).
    [11" id="c-fr-0011]
    11. Copolymer according to any one of the preceding claims, in which the copolymer is chosen from block copolymers and random copolymers.
    [12" id="c-fr-0012]
    12. Copolymer according to any one of the preceding claims, in which the copolymer is a block copolymer.
    [13" id="c-fr-0013]
    13. Copolymer according to claim 12, in which the block copolymer comprises at least:
    a block A consisting of a chain of structural units derived from one or more apolar monomers chosen from apolar monomers (m a ) of formula (I) and,
    - a block B consisting of a chain of structural units derived from one or more polar monomers chosen from polar monomers (m b ).
    [14" id="c-fr-0014]
    14. The copolymer according to claim 13, wherein the copolymer comprises at least one block sequence AB, ABA or BAB where said blocks A and B are linked without the presence of an intermediate block of different chemical nature.
    [15" id="c-fr-0015]
    15. Copolymer according to any one of claims 12 to 14, in which the block copolymer is obtained by block polymerization, optionally followed by one or more post-functionalizations.
    [16" id="c-fr-0016]
    16. Copolymer according to any one of claims 13 to 14, in which the block B is obtained by post-functionalization of an intermediate polymer P / resulting from the polymerization of an intermediate monomer (meth) acrylate or (meth) acrylamide (m,) of formula (VII) defined above and in which said post-functionalization corresponds to the reaction of said intermediate polymer P / with a tertiary amine NR 3 R 4 R 5 where R 6 N = R 7 where R 3 , R4, R5, R 6 and R 7 are as defined in formulas (III) and (IV).
    ICG70098 text deposit
    [17" id="c-fr-0017]
    17. Copolymer according to claim 16, in which the intermediate polymer P / also comprises at least one block A as defined in claim 13.
    [18" id="c-fr-0018]
    18. A fuel concentrate comprising one or more copolymers according to any one of claims 1 to 17, in mixture with an organic liquid, said organic liquid being inert with respect to the copolymer (s) and miscible with said fuel.
    [19" id="c-fr-0019]
    19. Fuel composition comprising:
    (1) a fuel obtained from one or more sources chosen from the group consisting of mineral, animal, vegetable and synthetic sources, and (2) one or more copolymers according to any one of claims 1 to 17.
    [20" id="c-fr-0020]
    20. Composition according to claim 19, which comprises at least 5 ppm of copolymer (s) (2).
    [21" id="c-fr-0021]
    21. Composition according to claim 19 or according to claim 20, in which the fuel (1) is chosen from hydrocarbon fuels, non-essentially hydrocarbon fuels and their mixtures.
    [22" id="c-fr-0022]
    22. Use of one or more copolymers according to any one of claims 1 to 17, as a detergent additive in a liquid fuel of internal combustion engines, said copolymer being used alone, in mixture or in the form of a concentrate such as defined in claim 18.
    [23" id="c-fr-0023]
    23. Use according to claim 22, in which the copolymer is used in liquid fuel to maintain the cleanliness and / or clean at least one of the internal parts of said internal combustion engine.
    [24" id="c-fr-0024]
    24. Use according to any one of claims 22 and 23, wherein the copolymer is used in 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 deposits existing in the at least one of the internal parts of said engine.
    [25" id="c-fr-0025]
    25. Use according to one of claims 22 to 24, for reducing the fuel consumption of the internal combustion engine.
    ICG70098 text deposit
    [26" id="c-fr-0026]
    26. Use according to any one of claims 22 to 25, for reducing the emission of pollutants, in particular, the emission of particles from the internal combustion engine.
    [27" id="c-fr-0027]
    27. Use according to any one of claims 22 to 26, in which the internal combustion engine is a spark-ignition engine.
    [28" id="c-fr-0028]
    28. Use according to claim 27, in which the deposits are located in at least one of the internal parts chosen from the engine intake system, the combustion chamber and the fuel injection system.
    [29" id="c-fr-0029]
    29. Use according to any one of claims 22 to 26, in which the internal combustion engine is a diesel engine, preferably a direct injection diesel engine.
    [30" id="c-fr-0030]
    30. Use according to claim 29, to avoid and / or reduce the formation of deposits in the injection system of the diesel engine.
    [31" id="c-fr-0031]
    31. Use according to claim 30, to avoid and / or reduce the formation of deposits linked to the coking phenomenon and / or deposits of soap and / or varnish type.
    [32" id="c-fr-0032]
    32. Process for maintaining the cleanliness and / or cleaning of at least one of the internal parts of an internal combustion engine comprising at least the following steps:
    the preparation of a fuel composition by additivation of a fuel with one or more copolymers according to any one of claims 1 to 17 or a concentrate according to claim 18 and,
    - the combustion of said fuel composition in said internal combustion engine.
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    同族专利:
    公开号 | 公开日
    EP3487894A1|2019-05-29|
    FR3054225B1|2019-12-27|
    CN109689708A|2019-04-26|
    US10767128B2|2020-09-08|
    MX2019000915A|2019-07-01|
    WO2018015666A1|2018-01-25|
    BR112019001157A2|2019-04-30|
    ZA201900369B|2019-10-30|
    EA201990117A1|2019-07-31|
    US20190169516A1|2019-06-06|
    CA3031315A1|2018-01-25|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US3226373A|1959-12-28|1965-12-28|Gulf Research Development Co|Oil-soluble copolymers of acrylic acid esters and quaternary ammonium salts of acrylic acids|
    US5011504A|1989-09-08|1991-04-30|E. I. Du Pont De Nemours And Company|Fuel oil additives|
    EP1533359A1|2003-11-13|2005-05-25|Infineum International Limited|A method of inhibiting deposit formation in a jet fuel at high temperature|
    US20130274369A1|2012-04-13|2013-10-17|Basf Se|New cationic polymers|
    US3048479A|1959-08-03|1962-08-07|Exxon Research Engineering Co|Ethylene-vinyl ester pour depressant for middle distillates|
    NL124842C|1959-08-24|
    NL124306C|1959-08-24|
    US3231587A|1960-06-07|1966-01-25|Lubrizol Corp|Process for the preparation of substituted succinic acid compounds|
    US3627838A|1964-12-11|1971-12-14|Exxon Research Engineering Co|Process for manufacturing potent pour depressants|
    US3790359A|1969-03-17|1974-02-05|Exxon Research Engineering Co|Middle distillate fuel having increased low temperature flowability|
    US3961961A|1972-11-20|1976-06-08|Minnesota Mining And Manufacturing Company|Positive or negative developable photosensitive composition|
    US4171959A|1977-12-14|1979-10-23|Texaco Inc.|Fuel composition containing quaternary ammonium salts of succinimides|
    FR2528051B1|1982-06-08|1986-05-02|Inst Francais Du Petrole|NITROGEN ADDITIVES FOR USE AS DISORDERS TO REDUCE THE POINT OF MEDIUM HYDROCARBON DISTILLATES AND COMPOSITIONS OF MEDIUM HYDROCARBON DISTILLATES CONTAINING THE ADDITIVES|
    FR2528423B1|1982-06-10|1987-07-24|Inst Francais Du Petrole|NITROGEN ADDITIVES FOR USE AS DISORDERS TO REDUCE THE POINT OF MEDIUM HYDROCARBON DISTILLATES AND COMPOSITIONS OF MEDIUM HYDROCARBON DISTILLATES CONTAINING THE ADDITIVES|
    FR2535723B1|1982-11-09|1985-01-18|Inst Francais Du Petrole|
    FR2567536B1|1984-07-10|1986-12-26|Inst Francais Du Petrole|ADDITIVE COMPOSITIONS, IN PARTICULAR FOR IMPROVING THE COLD FILTRABILITY PROPERTIES OF MEDIUM OIL DISTILLATES|
    IN184481B|1986-09-24|2000-08-26|Exxon Chemical Patents Inc|
    FR2607139B1|1986-11-21|1989-08-18|Inst Francais Du Petrole|POLYMERS WITH NITROGEN FUNCTIONS DERIVED FROM UNSATURATED POLYESTERS AND THEIR USE AS ADDITIVES FOR LOWERING THE FLOW POINT OF MEDIUM HYDROCARBON DISTILLATES|
    US4755563A|1986-12-29|1988-07-05|E. I. Du Pont De Nemours And Company|Block copolymer dispersants containing ionic moieties|
    FR2613371B1|1987-04-01|1989-07-07|Inst Francais Du Petrole|NITROGENATED COPOLYMERS, THEIR PREPARATION AND THEIR USE AS ADDITIVES FOR IMPROVING THE FLOW PROPERTIES OF MEDIUM HYDROCARBON DISTILLATES|
    GB9104138D0|1991-02-27|1991-04-17|Exxon Chemical Patents Inc|Polymeric additives|
    GB9219962D0|1992-09-22|1992-11-04|Exxon Chemical Patents Inc|Additives for organic liquids|
    GB9301119D0|1993-01-21|1993-03-10|Exxon Chemical Patents Inc|Fuel composition|
    FR2751982B1|1996-07-31|2000-03-03|Elf Antar France|ONCTUOSITY ADDITIVE FOR ENGINE FUEL AND FUEL COMPOSITION|
    JPH10237467A|1997-02-26|1998-09-08|Tonen Corp|Fuel oil composition for diesel engine|
    US5730029A|1997-02-26|1998-03-24|The Lubrizol Corporation|Esters derived from vegetable oils used as additives for fuels|
    FR2772784B1|1997-12-24|2004-09-10|Elf Antar France|ONCTUOSITY ADDITIVE FOR FUEL|
    FR2772783A1|1997-12-24|1999-06-25|Elf Antar France|New additives compositions for improving the lubricating power of low sulfur petrol, diesel and jet fuels|
    US6749651B2|2001-12-21|2004-06-15|Chevron Oronite Company Llc|Fuel additive compositions containing a mannich condensation product, a poly monool, and a carboxylic acid|
    US20040261313A1|2003-06-25|2004-12-30|The Lubrizol Corporation, A Corporation Of The State Of Ohio|Gel additives for fuel that reduce soot and/or emissions from engines|
    KR101143114B1|2003-11-13|2012-05-08|인피늄 인터내셔날 리미티드|A method of inhibiting deposit formation in a jet fuel at high temperatures|
    KR101314378B1|2005-06-16|2013-10-15|더루우브리졸코오포레이션|Quaternary ammonium salt detergents for use in fuels|
    GB201007756D0|2010-05-10|2010-06-23|Innospec Ltd|Composition, method and use|
    US9487719B2|2010-05-18|2016-11-08|The Lubrizol Corporation|Methods and compositions that provide detergency|
    FR2983484B1|2011-12-01|2015-02-20|Arkema France|CONTROLLED RADICAL CONTROL COPOLYMERIZATION OF MONOMERS FLUORINATED BY XANTHATE OR TRITHIOCARBONATE|
    FR2987052B1|2012-02-17|2014-09-12|Total Raffinage Marketing|ADDITIVES ENHANCING WEAR AND LACQUERING RESISTANCE OF GASOLINE OR BIOGAZOLE FUEL|
    CA2880415A1|2012-04-13|2013-10-17|Basf Se|New cationic polymers|
    EP2676974A1|2012-06-21|2013-12-25|BYK-Chemie GmbH|Ionic adhesive groups containing comb copolymers|
    FR2994695B1|2012-08-22|2015-10-16|Total Raffinage Marketing|ADDITIVES ENHANCING WEAR AND LACQUERING RESISTANCE OF GASOLINE OR BIOGAZOLE FUEL|
    CA2889031A1|2012-10-23|2014-05-01|Basf Se|Quaternized ammonium salts of hydrocarbyl epoxides and use thereof as additives in fuels and lubricants|
    EP3019579B1|2013-07-12|2019-03-06|Basf Se|Use of a hydrocarbyl-substituted dicarboxylic acid for improving or boosting the separation of water from gasoline fuels|
    SG11201609849WA|2014-05-30|2016-12-29|Lubrizol Corp|Coupled quaternary ammonium salts|FR3072095B1|2017-10-06|2020-10-09|Total Marketing Services|COMPOSITION OF FUEL ADDITIVES|
    FR3074499B1|2017-12-06|2020-08-28|Total Marketing Services|USE OF A SPECIAL COPOLYMER TO PREVENT DEPOSITS ON THE VALVES OF INDIRECT GASOLINE INJECTION ENGINES|
    GB201805238D0|2018-03-29|2018-05-16|Innospec Ltd|Composition, method and use|
    FR3087788B1|2018-10-24|2021-06-25|Total Marketing Services|FUEL ADDITIVES ASSOCIATION|
    FR3101882A1|2019-10-14|2021-04-16|Total Marketing Services|Use of particular cationic polymers as fuel and fuel additives|
    法律状态:
    2017-06-20| PLFP| Fee payment|Year of fee payment: 2 |
    2018-01-26| PLSC| Publication of the preliminary search report|Effective date: 20180126 |
    2018-06-21| PLFP| Fee payment|Year of fee payment: 3 |
    2019-06-21| PLFP| Fee payment|Year of fee payment: 4 |
    2020-06-23| PLFP| Fee payment|Year of fee payment: 5 |
    2021-07-27| PLFP| Fee payment|Year of fee payment: 6 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1656974A|FR3054225B1|2016-07-21|2016-07-21|COPOLYMER FOR USE AS A FUEL DETERGENT ADDITIVE|
    FR1656974|2016-07-21|FR1656974A| FR3054225B1|2016-07-21|2016-07-21|COPOLYMER FOR USE AS A FUEL DETERGENT ADDITIVE|
    US16/319,788| US10767128B2|2016-07-21|2017-07-20|Copolymer suitable for use as a detergent additive for fuel|
    BR112019001157-9A| BR112019001157A2|2016-07-21|2017-07-20|copolymer suitable for use as a fuel detergent additive|
    PCT/FR2017/051976| WO2018015666A1|2016-07-21|2017-07-20|Copolymer suitable for use as a detergent additive for fuel|
    EP17751440.3A| EP3487894A1|2016-07-21|2017-07-20|Copolymer suitable for use as a detergent additive for fuel|
    EA201990117A| EA201990117A1|2016-07-21|2017-07-20|COPOLYMER SUITABLE FOR APPLICATION AS A WASHING FUEL ADDITIVE|
    CA3031315A| CA3031315A1|2016-07-21|2017-07-20|Copolymer suitable for use as a detergent additive for fuel|
    CN201780053772.3A| CN109689708A|2016-07-21|2017-07-20|It is suitable as the copolymer of the detergent additive of fuel|
    MX2019000915A| MX2019000915A|2016-07-21|2017-07-20|Copolymer suitable for use as a detergent additive for fuel.|
    ZA201900369A| ZA201900369B|2016-07-21|2019-01-18|Copolymer suitable for use as a detergent additive for fuel|
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