Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
  • C10L1/2368—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing heterocyclic compounds containing nitrogen in the ring
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
  • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/02—Use of additives to fuels or fires for particular purposes for reducing smoke development
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L2200/00—Components of fuel compositions
  • C10L2200/04—Organic compounds
  • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
  • C10L2200/0415—Light distillates, e.g. LPG, naphtha
  • C10L2200/0423—Gasoline
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L2200/00—Components of fuel compositions
  • C10L2200/04—Organic compounds
  • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
  • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
  • C10L2200/0446—Diesel

Definitions

• the present invention relates to the use of monomer-based copolymers comprising an ester function, such as for example (meth) acrylates or olefinic alkyl esters, and monomers comprising a heterocycle comprising at least six atoms including at least one atom. nitrogen and at least one functionalization with at least one oxygen atom, as detergent additives in a liquid fuel of an internal combustion engine.
• 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 (in English effect "Keep-clean") or by reducing the deposits already present in the internal parts of the combustion engine (in English). clean-up effect).
• mention may be made of US4171959 which describes a detergent additive for petrol fuel containing a quaternary ammonium function.
• WO2006135881 discloses a detergent additive containing a quaternary ammonium salt used to reduce or clean deposits including the intake valves.
• US-3,015,546 discloses the use of polymeric additives in fuel compositions as a dispersant to prevent the formation of deposits, sludge and varnish in engines. These terpolymers result from the copolymerization of a long chain ester of a conjugated unsaturated diacid, a vinyl ester of a short chain fatty acid and an N-vinyl amide which may be a heterocyclic compound.
• WO99 / 58580 discloses polymeric compounds and their use in an oil as wax dispersant. These copolymers comprise a monomer alcohol, or acid or unsaturated ester, a carboxylic ester monomer unsaturated with a polar group in the ester, and at least one unsaturated amide. The purpose is to reduce wax deposits in these cold fuels
• DE 15 45 342 discloses fuel and lubricant compositions in which copolymers of N-vinyl-piperazinones acting as dispersants are incorporated.
• the invention relates to the use of copolymers comprising an ester function, for example (meth) acrylates or olefinic alkyl esters, in particular vinyl esters, and monomers functionalized with a heterocycle comprising at least six atoms, including at least one atom. nitrogen, and at least one functionalization with at least one oxygen atom, as additives detergents in a liquid fuel of an internal combustion engine.
• copolymers comprising an ester function, for example (meth) acrylates or olefinic alkyl esters, in particular vinyl esters, and monomers functionalized with a heterocycle comprising at least six atoms, including at least one atom. nitrogen, and at least one functionalization with at least one oxygen atom, as additives detergents in a liquid fuel of an internal combustion engine.
• These copolymers can be used in the form of an additive concentrate.
• copolymers including the copolymers of the invention, have remarkable properties as a detergent additive in internal combustion engine liquid fuels.
• the copolymers according to the invention used in these fuels make it possible to maintain the cleanliness of the engine, in particular by avoiding or limiting the formation of the deposits (Keep-clean effect) and / or by reducing the deposits already present in the internal parts. combustion engine ("clean-up" effect).
• the object of the present invention therefore relates to the use of a copolymer as a detergent additive in a liquid fuel of an internal combustion engine, said copolymer comprising at least one repeating unit comprising an alkyl ester or alkyl ester function and a repeating unit comprising at least one heterocycle comprising at least six atoms, of which at least one nitrogen atom, and at least one functionalization with at least one oxygen atom.
• the functionalization with at least one oxygen atom consists of the presence of at least one oxygen atom in the heterocyclic chain.
• the copolymer is a block copolymer comprising at least:
• a block A consisting of a chain of structural units derived from an alkyl acrylate or alkyl methacrylate monomer (m a ) and
• a block B consisting of a chain of structural units derived from an olefinic monomer (m b ) comprising at least one heterocycle comprising at least six atoms, of which at least one nitrogen atom, and at least one functionalization with at least one atom; oxygen.
• the block copolymer is obtained by sequential polymerization, preferably by sequential and controlled polymerization and, optionally followed by one or more post-functionalizations.
• the copolymer is obtained by copolymerization of at least:
• an olefinic monomer (m b ) comprising at least one heterocycle comprising at least six atoms, of which at least one nitrogen atom and at least one functionalization with at least one oxygen atom.
• the alkyl (meth) acrylate monomer (m a ) is chosen from (C 1 to C 34 ) alkyl (meth) acrylates.
• the monomer m b corresponds to formula (I) below:
• n an integer selected from 0 and 1
• Rb is chosen from rings comprising six atoms and rings comprising seven atoms, these rings comprising one or two nitrogen atoms, zero, one or two oxygen atoms and three, four, five or six carbon atoms.
• Rb is chosen from rings comprising six atoms and rings containing seven atoms, these rings comprising one or two nitrogen atoms, one or two oxygen atoms and three, four, five or five atoms. six carbon atoms.
• Rb is selected from rings comprising six atoms, these rings comprising at least one nitrogen atom and at least one oxygen atom in the heterocyclic chain.
• the monomer (m b ) is chosen from
• N-acryloyl morpholine N-methacryloyl morpholine, N-vinyl-e-caprolactam
• the monomer (m b ) is chosen from
• the copolymer is a block copolymer comprising at least:
• a block A consisting of a chain of structural units derived from the alkyl (meth) acrylate monomer (m a ) and,
• a block Bi consisting of a chain of structural units derived from a monomer (m b ) chosen from: N-acryloyl morpholine, N-methacryloyl morpholine and N-vinyl-e-caprolactam, even more preferably ( mb ) is chosen from: N-acryloyl morpholine and N-methacryloyl morpholine.
• the copolymer is used in a fuel concentrate comprising one or more copolymers as described above, mixed with an organic liquid, said organic liquid being inert with respect to the copolymers and miscible with said fuel.
• the copolymer is implemented in a fuel composition which comprises:
• a fuel from one or more sources selected from the group consisting of mineral, animal, plant and synthetic sources, and
• the fuel composition comprises at least 5 ppm of at least one copolymer as defined above.
• the fuel is selected from hydrocarbon fuels and non-essentially hydrocarbon fuels alone or as a mixture.
• 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.
• the copolymer is used in the liquid fuel to avoid and / or reduce 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 .
• the copolymer is used to reduce the fuel consumption of the internal combustion engine.
• the copolymer is used to limit and / or reduce and / or avoid and / or prevent pollutant emissions, in particular the particulate emissions of the internal combustion engine.
• the internal combustion engine is a spark ignition engine.
• the copolymer is used to limit and / or reduce and / or avoid and / or prevent the formation of deposits in at least one internal part of the spark ignition engine chosen from the engine intake system. , in particular the intake valves, the combustion chamber, the fuel injection system, in particular the injectors of an indirect injection system or the injectors of a direct injection system.
• the internal combustion engine is a diesel engine.
• the copolymer is used to limit and / or reduce and / or avoid and / or prevent the formation of deposits in the injection system of the diesel engine, preferably located on an external part of an engine. 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, for example on the surface of an injector needle.
• the copolymer is used to limit and / or reduce and / or avoid and / or prevent the formation of deposits related to the phenomenon of coking and / or soap-like deposits and / or varnish.
• the copolymer is used to limit and / or reduce and / or avoid and / or prevent 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 standard CEC engine test method
• the copolymer is used to limit and / or reduce and / or avoid and / or prevent the restriction of the fuel flow emitted by the injector of the direct injection diesel engine during its operation, said restriction flow rate determined by standard engine test method
• the copolymer comprises at least one repeating unit comprising an alkyl ester or alkyl ester function and a repeating unit comprising at least one heterocycle comprising at least 6 atoms including at least one nitrogen atom, and at least one functionalization. by at least one oxygen atom.
• alkyl ester refers to an alkyl carboxylate A1-CO-O-A2 with A 2 alkyl and A-1 any group.
• alkyl ester denotes an alkyl carboxylate A CO-O-A 2 with A 1 alkyl and A 2 any group.
• the repeating unit comprising an alkyl ester or alkyl ester function is an olefinic unit.
• the repeating unit comprising at least one heterocycle comprising at least 6 atoms, of which at least one nitrogen atom, and at least one functionalization with at least one oxygen atom, is an olefinic unit.
• the repeating unit comprising an alkyl ester function may be derived from an alkyl acrylate, alkyl methacrylate monomer.
• the repeating unit comprising an alkyl ester function may be derived from an alkyl vinyl ester or propene-2-yl alkyl ester monomer.
• the repeating unit comprising an alkyl ester function is derived from at least one monomer selected from alkyl acrylate and alkyl methacrylate monomers (m a ).
• Alkyl (meth) acrylate denotes a monomer chosen from alkyl acrylates and alkyl methacrylates.
• the monomer (m a ) is preferably chosen from (C 1 to C 34) alkyl, preferably C 4 to C 3 o, more preferably C 6 to C 24 alkyl, more preferably C 8 to C22.
• the alkyl radical of the alkyl acrylate or methacrylate is linear, branched, cyclic or acyclic, preferably acyclic.
• alkyl (meth) acrylates that may be used in the manufacture of the copolymer of the invention, mention may be made, in a nonlimiting manner: n-octyl acrylate, n-octyl methacrylate, n-decyl acrylate, n-decyl methacrylate, n-dodecyl acrylate, n-dodecyl methacrylate, ethyl-2-hexyl acrylate, 2-ethylhexyl methacrylate, isooctyl acrylate, isooctyl methacrylate, isodecyl acrylate, isodecyl methacrylate.
• R ' is a linear C 1 to C 34 , preferably C 4 to C 3 o, more preferably C 6 to C 24 , even more preferably C 8 to C 2 2 alkyl.
• alkyl vinyl ester monomers mention may be made, for example, of vinyl octanoate, vinyl decanoate, vinyl dodecanoate, vinyl tetradecanoate, vinyl hexadecanoate, vinyl octodecanoate and vinyl docosanoate.
• the repeating unit comprising a heterocyclic group is derived from at least one olefinic monomer (m b ) comprising at least one heterocycle comprising at least 6 atoms including at least one nitrogen atom and at least one functionalization with at least one atom. oxygen.
• the olefinic monomer (m b ) comprising at least one heterocyclic group corresponds to formula (I) below:
• n an integer selected from 0 and 1
• Rb represents a nitrogen heterocycle comprising at least six atoms, including at least one nitrogen atom and comprising at least one functionalization with at least one oxygen atom,
• R1 represents H or CH3.
• n 0.
• n 1.
• Ra represents a group chosen from -CO- and a straight or branched C1-C8 alkyl chain optionally comprising a carbonyl bridge. Even more preferably, Ra represents -CO-.
• Rb can be a unicycle or a polycyclic compound.
• Rb is monocyl or bicyclic, even more preferentially
• Rb is monocyclic. Rb may be saturated or unsaturated, possibly aromatic.
• Rb represents a heterocycle comprising at least six atoms, of which at least one nitrogen atom and at least three carbon atoms.
• the functionalization with at least one oxygen atom consists of the presence of at least one oxygen atom in the heterocyclic chain.
• the functionalisation by at least one oxygen atom consists in the presence of at least one oxygenated function on an atom of the heterocyclic chain.
• Rb comprises at least six atoms. Preferentially, Rb is chosen from rings comprising six atoms and rings containing seven atoms.
• Rb is chosen from rings comprising six atoms and rings containing seven atoms, these rings comprising one or two nitrogen atoms, zero, one or two oxygen atoms and three, four, five or six carbon atoms.
• Rb is chosen from rings comprising six atoms and rings containing seven atoms, these rings comprising one or two nitrogen atoms, one or two oxygen atoms and three, four, five or six carbon atoms.
• the 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.
• units derived from an alkyl (meth) acrylate monomer (m a ) can be obtained from a poly (meth) acrylate moiety by transesterification reaction using an alcohol of chosen chain length to form the expected alkyl group.
• the repeating unit comprising a nitrogenous heterocycle may be obtained from a polyvinyl moiety functionalized with a precursor group of the heterocycle.
• the repeating unit comprising a nitrogenous heterocycle can be obtained by reacting morpholine with chloromethyl polystyrene divinylbenzene as described in US6506701 (Example 13). Such conversion reactions are well known to those skilled in the art.
• the copolymer may be a random copolymer or a block copolymer.
• the copolymer is a block copolymer comprising at least: A block consisting of a chain of repeating units comprising an alkyl ester function,
• the copolymer is a block copolymer comprising at least:
• a block A consisting of a chain of structural units derived from the monomer (m a ) and
• a block B consisting of a chain of structural units derived from the monomer (m b ).
• the block copolymer is obtained by copolymerization of at least the alkyl (meth) acrylate monomer (m a ) and at least the heterocyclic monomer (m b ).
• the block copolymer can be obtained by sequential polymerization, preferably by sequential and controlled polymerization and optionally followed by one or more post-functionalizations.
• the block copolymer described above is obtained by sequenced and controlled polymerization.
• the polymerization is advantageously chosen from controlled radical polymerization; by for example, by atom transfer radical polymerization (ATRP in English “Atom Transfer Radical Polymerization”); the radical polymerization by nitroxide (NMP in English “Nitroxide-mediated polymerization”); degenerative transfer processes (degenerative transfer processes) such as degenerative iodine transfer polymerization (ITRP-iodine transfer radical polymerization) or radical polymerization by reversible addition-fragmentation chain transfer ( RAFT in English "Reversible Addition-Fragmentation Chain Transfer”); polymerizations derived from ATRP such as polymerizations using initiators for the continuous regeneration of the activator (ICAR in English “Initiators for continuous activator regeneration") or using activators regenerated by electron transfer (ARGET in English "activators regenerated by electron transfer ").
• ATRP atom transfer radical polymerization
• NMP nitroxide
• 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.
• atom transfer radical polymerization For atom transfer radical polymerization (ATRP), the reaction is generally carried out under vacuum in the presence of an initiator, a ligand and a catalyst.
• a ligand mention may be made of N, N, N ', N ", N" -pentamethyldiethylenetriamine (PMDETA), 1,1,7,7,10,10-hexamethyltriethylene tetramine (HMTETA), 2,2'-Bipyridine (BPY) and Tris (2-pyridylmethyl) amine (TPMA).
• PMDETA N, N, N ', N ", N" -pentamethyldiethylenetriamine
• HMTETA 1,1,7,7,10,10-hexamethyltriethylene tetramine
• BPY 2,2'-Bipyridine
• TPMA Tris (2-pyridylmethyl) amine
• TPMA Tris (2-pyridylmethyl) amine
• TPMA Tris (2
• the ATRP polymerization is preferably carried out in a solvent chosen from polar solvents.
• the monomer equivalents (m a ) of the A block and the monomer (m b ) of the B block reacted during the polymerization reaction are identical or different and, independently, range from 2 to 40, preferably 3 to 30, more preferably from 5 to 20, even more preferably from 5 to 10.
• the number of monomer equivalents (m a ) of block A is advantageously greater than or equal to that of monomer (m b ) of block B.
• 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 sequence of AB, ABA or BAB blocks in which said blocks A and B are linked together without the presence of an intermediate block of a different chemical nature.
• block copolymers 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.
• the blocks A and B represent at least 70% by weight of the total mass of the monomers used in the polymerization reaction, preferably at least 90% by weight, advantageously at least 95% by weight, and even more preferably at least 99% by weight.
• the block copolymer is a diblock copolymer.
• the block copolymer is a alternating block triblock copolymer comprising two A blocks and one B block (ABA) or comprising two B blocks and one A block (BAB).
• the block copolymer also comprises a terminal chain I consisting of a saturated or unsaturated, linear, branched or cyclic, C 1 to C 32, preferably C 4 to C 24, hydrocarbon-based chain , more preferably C1 0 to C 24.
• 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.
• 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.
• the terminal chain I may, advantageously, constitute at least a part of the polymerization initiator and is positioned within the polymerization initiator in order to introduce, during the first polymerization initiation step. , the terminal chain I in the terminal position of the block copolymer.
• the polymerization initiator is, for example, chosen from free radical initiators used in the ATRP polymerization process. These free radical initiators well known to those skilled in the art are described in particular in the article "Atom Transfer Radical Polymerization: current status and future prospects, Macromolecules, 45, 4015-4039, 2012".
• the polymerization initiator is, for example, selected from alkyl esters of a halide-substituted carboxylic acid, preferably a bromine in the alpha position, for example ethyl 2-bromopropionate, a-bromoisobutyrate.
• ethyl chloride benzyl choride or bromide
• ethyl ⁇ -bromophenylacetate chloroethylbenzene
• ethyl 2-bromopropionate may make it possible to introduce into the copolymer the terminal chain I in the form of a C 2 alkyl chain and benzyl bromide in the form of a benzyl group.
• the transfer agent can conventionally be removed from the copolymer at the end of the polymerization according to any known method.
• the terminal chain I may be obtained by 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.
• thiocarbonylthio, dithiocarbonate, xanthate, dithiocarbamate and trithiocarbonate transfer agents for example S, S-bis ( ⁇ , ⁇ '-dimethyl- ⁇ -acetic acid) trithiocarbonate (BDMAT or 2-cyano-2-propyl benzodithioate.
• 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 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.
• 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.
• aminolysis any chemical reaction in which a molecule is split into two parts by reaction of a molecule of ammonia or an amine.
• a general example of aminolysis is to replace a halogen of a alkyl group by reaction with an amine, with elimination 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.
• the terminal chain ⁇ preferably comprises a hydrocarbon chain, linear, branched or cyclic, C 1 to C 32, preferably C 1 to C 24 , more preferably C 1 to C 0 , still more preferably an alkyl group, optionally substituted with one or several groups containing at least one heteroatom selected from N and O, preferably N.
• 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 monomer (m b ) is chosen from:
• the monomer (m b ) is chosen from
• N-acryloyl morpholine N-methacryloyl morpholine
• block copolymer is as described above and block B is a block Bi consisting of a chain of structural units derived from a monomer selected from N-acryloylmorpholine, N-methacryloyl morpholine and N-vinyl- ⁇ -caprolactam, even more preferably from N-acryloylmorpholine and N-methacryloyl morpholine.
• the block copolymer comprises, in particular, at least one block sequence ABi, ABiA or ⁇ where blocks A and Bi are linked together without the presence of intermediate blocks of different chemical nature.
• the block copolymer comprises, in particular, at least one block sequence ABi, ABiA or ⁇ where blocks A and Bi are linked together without the presence of intermediate blocks of different chemical nature.
• the block copolymer is represented by the following formula (Ma) or (Mb):
• Ri, Ra, Rb and n are as defined above in formula (I)
• y is an integer ranging from 2 to 40, preferably from 3 to 30, more preferably from 4 to 20, even more preferably from 5 to 10,
• z is an integer ranging from 2 to 40, preferably from 3 to 30, more preferably from 4 to 20, even more preferably from 5 to 10,
• R 2 is chosen from linear, branched or cyclic, preferably acyclic, C 1 to C 34 , preferably C 4 to C 3 o, more preferably C 6 to C 24 , still more preferably C 8 , alkyl groups; at C 22 , R 3 is chosen from hydrogen and the methyl group,
• R 4 is selected from the group consisting of:
• halogens preferably bromine
• hydrocarbon chains saturated or unsaturated, linear, branched or cyclic Ci to C3 2, preferably C, to C 24, more preferably to C 1 0, preferably alkyl groups, said hydrocarbon chains optionally being substituted by one or more groups containing at least one heteroatom selected from N and O,
• R 5 and R 6 are identical or different and independently selected from the group consisting of hydrogen and C 1 to C 10 alkyl groups, preferably linear or branched C 1 to C 4 alkyls, even more preferably the group methyl,
• RAFT Addition-Fragmentation Chain Transfer
• RAFT transfer agents are well known to those skilled in the art. A wide variety of RAFT transfer agents are available or quite easily synthesizable. By way of example, mention may be made of thiocarbonylthio, dithiocarbonate, xanthate, dithiocarbamate and trithiocarbonate transfer agents, for example S, S-bis ( ⁇ , ⁇ '-dimethyl- ⁇ -acetic acid) trithiocarbonate (BDMAT or 2-cyano-2-propyl benzodithioate.
• S, S-bis ( ⁇ , ⁇ '-dimethyl- ⁇ -acetic acid) trithiocarbonate BDMAT or 2-cyano-2-propyl benzodithioate.
• a block copolymer synthesis using a RAFT agent is, for example, described in the article by Zhishen Ge et al. entitled “Stimuli-Responsive Double Hydrophilic Block Copolymer Micelleswith Switchable Catalytic Activity",
• the block A corresponds to the repeated pattern y times and the block B to the repeated pattern z times.
• the R- ⁇ group may consist of the terminal chain I as described above and / or the R 4 group may consist of the end chain I as described above.
• the copolymer described above is particularly advantageous when it is used, alone or as a mixture, as a detergent additive in a liquid fuel of an internal combustion engine.
• the block copolymer described above has remarkable properties as a detergent additive in a liquid fuel of an internal combustion engine.
• detergent additive liquid fuel an additive which is incorporated in a small amount in the liquid fuel and has an effect on the cleanliness of said engine compared to said 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.
• the hydrocarbon fuels include, in particular, middle distillates having a boiling point of between 100 and 500 ° C. or lighter distillates having a boiling point in the gasoline range.
• 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 conversion processes like ARDS
• Hydrocarbon fuels are typically gasolines and gas oils (also called diesel fuel).
• the gasolines include, in particular, any commercially available gasoline engine fuel compositions.
• any commercially available gasoline 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.
• MON motor octane number
• RON research octane number
• Gas oils include, in particular, any commercially available diesel fuel compositions.
• gas oils that comply with the NF EN 590 standard.
• Non-essentially hydrocarbon fuels include, in particular, oxygenated fuels, for example distillates resulting from BTL conversion (in English "biomass to liquid") 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.
• hydrocarbon fuel and hydrocarbon fuel are not essentially typically type B x gas oils or of type E x species.
• Diesel gasoline type B x for a diesel engine means a diesel fuel which contains x% (v / v) of vegetable or animal oil esters (including used cooking oils) converted by a chemical process called transesterification, obtained by 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.
• EAG fatty acid methyl esters
• EEAG fatty acid ethyl esters
• the letter “B” followed by a number indicates the percentage of EAG contained in the diesel fuel.
• 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 B 0 gas oils which do not contain oxygenated compounds
• Bx type gas oils which contain x% (v / v) of vegetable oil or fatty acid esters, most often methyl esters (EMHV or EMAG) .
• EAG methyl esters
• B100 the term fuel is designated by the term B100.
• Gasoline type E x for petrol engines means a petrol fuel which 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 or equal to 10 ppm and advantageously without sulfur. .
• the 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 content ranging from 10 to 5000 ppm, more preferably from 10 to 1000 ppm.
• 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.
• 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 deposits existing in least one of the internal parts of said engine (effect "clean-up" in English).
• the use of the copolymer in the liquid fuel makes it possible to observe an effect of limiting or preventing the formation of deposits in at least one of the internal parts of said engine or an effect of reducing deposits existing in at least one of the parts internal of said engine, compared to liquid fuel not specially additivé.
• 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.
• the internal combustion engine is a spark ignition engine, preferably a direct injection engine (DISI).
• DISI direct injection 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
• 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.
• 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
• 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 copolymer as described above may advantageously be used in the liquid fuel to reduce and / or prevent 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 Standard F-98-08 Engine Test Method.
• the copolymer as described above may advantageously be used in the liquid fuel to reduce and / or prevent 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 engine test method F-23-1 -01.
• copolymer as described above advantageously makes it possible to obtain an effect of limiting or preventing the formation of deposits in at least one of the internal parts of said engine or a deposit-reducing effect. existing in at least one of the internal parts of said engine, on at least one type of depots described above.
• the use of the copolymer described above also makes it possible to reduce the fuel consumption of the internal combustion engine.
• the use of the copolymer described above also makes it possible to reduce the emissions of pollutants, in particular the particulate emissions of the internal combustion engine.
• the use of the copolymer makes it possible to reduce both the fuel consumption and the pollutant emissions.
• the copolymer described above may 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 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, also called the use "additive package".
• copolymer described above can be used as a mixture in an organic liquid in the form of a concentrate.
• 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 copolymer described above and miscible in the liquid fuel described above.
• miscible means that the copolymer and the organic liquid form a solution or a dispersion so as to facilitate the mixing of the copolymer in liquid fuels according to the conventional fuel additive processes.
• miscible is meant in the sense of the present invention that the organic liquid and the liquid fuel, when mixed, in all proportions, to room temperature, form a solution.
• 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.
• aromatic hydrocarbon solvents such as the solvent sold under the name "SOLVESSO”
• alcohols, ethers and other oxygenated compounds 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 (s) as described above.
• the concentrate may, typically, comprise from 1 to 95% by weight, preferably from 10 to 70%, more preferably from 25 to 60% of organic liquid, the remainder corresponding to the copolymer defined above, it being understood that the concentrate may comprise one or several copolymers as described above.
• solubility of the copolymer in the organic liquids and liquid fuels described above will depend in particular on the average molar masses by weight and by number, respectively M w and M n of the copolymer.
• the average molar masses M w and M n of the copolymer 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 may also have an influence on the effectiveness of this copolymer as a detergent additive.
• the average molar masses M w and M n will therefore be chosen so as to optimize the effect of the copolymer, in particular the detergency effect (engine cleanliness) in the liquid fuels described above.
• the copolymer advantageously has a weight average molecular weight M w ranging from 500 to 30,000 g. mol "1 , of preferably from 1000 to 10,000 g. mol "1 , more preferably less than or equal to 4000 g. mol " 1 , 1 and / or an average molar mass in number M n ranging from 500 to 15 000 g. mol "1 , preferably from 1000 to 10,000 g, mol " 1 , more preferably less than or equal to 4000 g.
• the copolymer is used in the form of an additive concentrate in combination with at least one other fuel additive for an internal combustion engine different from the copolymer described above.
• the additive concentrate may typically comprise one or more other additives selected from detergent additives different from the 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), cloud point improvers, pour point, TLF ("Filterability Limit Temperature”), anti-sedimentation agents, anti-wear agents and conductivity modifiers.
• detergent additives different from the 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), cloud point improvers, pour point, TLF ("Filterability Limit Temperature”), anti
• procetane additives in particular (but not limited to) selected from alkyl nitrates, preferably 2-ethyl hexyl nitrate, aryl peroxides, preferably benzyl peroxide, and alkyl peroxides, preferably ter-butyl peroxide;
• 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;
• CFI Cold Flow Improver
• EVA ethylene / vinyl acetate copolymers
• EVE ethylene / vinyl propionate
• EMMA ethylene / vinyl ethanoate
• alkyl fumarate described, for example, in US3048479, US3627838, US3790359, US3961961 and EP261957;
• 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.
• lubricity additives or anti-wear agents are given in the following documents: EP680506, EP860494, WO98 / 04656, EP915944, FR2772783, FR2772784;
• 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, EP1 12195, EP172758, EP271385, EP291367;
• 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;
• polyfunctional cold operability additives selected from the group consisting of olefin and alkenyl nitrate polymers as described in EP573490.
• additives are generally added in an amount ranging from 100 ppm to 1000 ppm (each).
• the molar and / or mass ratio between the monomer mb and the monomer m a and / or between the block A and B or Bi in the 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 molar ratio between the monomer mb and the monomer m a or between the blocks A and B or Bi in the 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.
• a fuel composition is prepared according to any known method by adding the liquid fuel described above with at least one copolymer as described above.
• the fuel composition comprises: (1) a fuel as described above, and
• the fuel (1) is, in particular, chosen from hydrocarbon fuels and non-essentially hydrocarbon fuels previously described, taken alone or as a mixture.
• 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 copolymer.
• 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 (2) 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 10 ppm, preferably at least 50 ppm, more preferably from 10 to 5000 ppm, in particular from 10 to 1000 ppm of copolymer (s) (2).
• the fuel composition may also comprise one or more other additives different from the copolymer according to the invention chosen from the other known detergent additives, for example from anti-corrosion agents, dispersants, demulsifiers, antifoaming agents, biocides, re-deodorants, procetane additives, friction modifiers, lubricity additives or lubricity additives, combustion assistants (catalytic combustion and soot promoters), improving agents cloud point, pour point, TLF, anti-sedimentation agents, anti-wear agents and / or conductivity modifiers.
• the other additives different from the copolymer according to the invention chosen from the other known detergent additives, for example from anti-corrosion agents, dispersants, demulsifiers, antifoaming agents, biocides,
• the various additives of the copolymer according to the invention are, for example, the fuel additives listed above.
• a method of keeping clean (keep-clean) and / or cleaning (clean-up) of at least one of the internal parts of an internal combustion engine comprises at least the following steps :
• the internal combustion engine is a spark ignition engine, preferably direct injection (DISI).
• DISI direct injection
• 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).
• 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.
• IDRC Common Rail injection systems
• the keep-clean and / or clean-up process advantageously comprises the successive steps of:
• step b) incorporation into the fuel of the selected copolymer or copolymers at the rate determined in step a) and, optionally, the other fuel additives.
• copolymer or copolymers can be incorporated in the fuel, alone or in mixture, successively or simultaneously.
• the 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's detergency properties will depend on the type of internal combustion engine, for example diesel or gasoline, the direct or indirect injection system and the location in the engine of the targeted deposits for cleaning and / or maintenance. cleanliness.
• the representative characteristic of the fuel detergency properties may, for example, correspond to the loss. of power due to the formation of deposits in the injectors or the restriction of the fuel flow emitted by the injector during 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).
• the amount of 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.
• copolymers according to the invention have remarkable properties as a detergent additive in a liquid fuel, in particular in a diesel or gasoline fuel, in particular block copolymers.
• 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 or against one or more types of deposits that form in the internal parts of the internal combustion engines.

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• 2015
  • 2015-12-22 FR FR1563101A patent/FR3045658A1/fr active Pending
• 2016
  • 2016-12-19 US US16/065,319 patent/US20190153343A1/en not_active Abandoned
  • 2016-12-19 WO PCT/FR2016/053558 patent/WO2017109370A1/fr active Application Filing
  • 2016-12-19 EP EP16826404.2A patent/EP3394226A1/de not_active Withdrawn

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