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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F12/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
  • C08F12/02—Monomers containing only one unsaturated aliphatic radical
  • C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
  • C08F12/14—Monomers containing only one unsaturated aliphatic radical containing one ring substituted by hetero atoms or groups containing heteroatoms
  • C08F12/26—Nitrogen
  • C08F12/28—Amines
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
  • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/16—Hydrocarbons
  • C10L1/1625—Hydrocarbons macromolecular compounds
  • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
  • C10L1/165—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aromatic monomers
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/20—Organic compounds containing halogen
  • C10L1/206—Organic compounds containing halogen macromolecular compounds
  • C10L1/207—Organic compounds containing halogen macromolecular compounds containing halogen with or without hydrogen
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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
  • C10L1/2366—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amine groups
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/18—Use of additives to fuels or fires for particular purposes use of detergents or dispersants for purposes not provided for in groups C10L10/02 - C10L10/16
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2438/00—Living radical polymerisation
  • C08F2438/03—Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX]
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2250/00—Structural features of fuel components or fuel compositions, either in solid, liquid or gaseous state
  • C10L2250/04—Additive or component is a polymer
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2270/00—Specifically adapted fuels
  • C10L2270/02—Specifically adapted fuels for internal combustion engines
  • C10L2270/023—Specifically adapted fuels for internal combustion engines for gasoline engines
• • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L2270/00—Specifically adapted fuels
  • C10L2270/02—Specifically adapted fuels for internal combustion engines
  • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine

Definitions

• the present invention relates to the use of a copolymer as a detergent additive in a liquid fuel of an internal combustion engine.
• the invention also relates to a method of maintaining cleanliness (keep-clean) and / or cleaning (clean-up) of at least one of the internal parts 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 deposits (keep-clean effect) or by reducing the deposits already present in the internal parts of the combustion engine (“clean-up effect"). ).
• cleaning-up effect By way of example, 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.
• engine technology is constantly evolving and fuel requirements must evolve to cope with these advances in combustion engine technology.
• the new petrol or diesel direct injection systems expose the injectors to more severe pressure and temperature conditions, which favors the formation of deposits.
• these new injection systems have more complex geometries to optimize the spraying, including more holes with smaller diameters but, on the other hand, induce greater sensitivity to deposits.
• the presence of deposits can alter the performance of combustion including increasing pollutant emissions and particulate emissions.
• Other consequences of the excessive presence of deposits have been reported in the literature, such as increased fuel consumption and maneuverability problems.
• Preventing and reducing deposits in these new engines is essential for optimal operation of today's engines. There is therefore a need to provide detergent fuel additives promoting optimal operation of combustion engines, especially for new engine technologies.
• the Applicant has discovered that the block copolymers according to the invention have remarkable properties as a detergent additive in liquid fuels of an internal combustion engine.
• the block copolymers according to the invention used in these fuels make it possible to maintain the cleanliness of the engine, in particular by limiting or avoiding the formation of the deposits ("Keep-clean” effect) or by reducing the deposits already present in the internal parts of the combustion engine (“clean-up” effect).
• the subject of the present invention relates to the use of a block copolymer as a detergent additive in a liquid fuel of internal combustion engines, said block copolymer comprising:
• n is an integer ranging from 2 to 100
• Ri is chosen from hydrogen and the methyl group
• R 2 is selected from C 1 to C 34 hydrocarbon chains
• p is an integer from 2 to 40
• G is selected from:
• a hydrocarbon chain Ci to Ci 2 A hydrocarbon chain Ci to Ci 2 .
• 2 substituted by at least one R group, said R group being selected from the group consisting of:
• said group R being connected to the aryl group or the hydrocarbon chain, preferably by a nitrogen atom present in the R group.
• n is an integer ranging from 2 to 40.
• n is an integer greater than 40 and less than or equal to 100.
• the block B is represented by the formula (II) in which G is a substituted aryl group.
• the group R is chosen from groups having at least one primary, secondary or tertiary amine function.
• the group R is chosen from the group consisting of: -NH 2 ; groups having at least one amine, imine, amidine, guanidine, aminoguanidine or biguanidine function; groupings heterocyclic compounds having from 3 to 34 atoms and at least one nitrogen atom.
• the group R represents, preferably, a heterocyclic group further comprising at least one element chosen from: an oxygen atom, a carbonyl group and one or more unsaturations.
• the group R is chosen from trialkylammonium groups.
• the block copolymer comprises:
• 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 a styrene monomer (m b ) chosen from styrene and styrenic derivatives whose aromatic ring is substituted with at least one R group or at least one C 1 hydrocarbon chain; C12, linear or branched, preferably acyclic, optionally substituted with at least one R group.
• m b styrene monomer
• the monomer (m a ) is chosen from acrylates or C 1 -C 3 alkyl methacrylate.
• the monomer (m b ) is preferably chosen from the isomers of (vinylbenzyl) trialkylammoniums, alone or as a mixture.
• the block copolymer is represented by the following formula (IV) or (V):
• n, p, R 1 and R 2 are as described above in formulas (I) and (II),
• R 3 is a substituent on the aromatic ring selected from the group consisting of:
• X " is chosen from hydroxide ions, halides and organic anions and R 7 , R 8 and R 9 are identical or different and are chosen independently from C 1 to C 10 alkyl groups,
• Rio is chosen from groups comprising from 1 to 40 atoms chosen from C, N, and optionally O, and comprising at least one primary, secondary or tertiary amine function, or a quaternary ammonium function, and
• R 4 is selected from the group consisting of:
• R 5 and R 6 are identical or different and chosen independently from the group consisting of hydrogen and alkyl groups C1 to Ci 0.
• RAFT additive-fragmentation reversible chain transfer radical transfer agent
• the block copolymer is obtained by sequential polymerization, optionally followed by one or more post-functionalizations.
• the block copolymer is preferably a diblock copolymer.
• the block copolymer is an alternating block triblock copolymer comprising two blocks A and one block B (ABA) or comprising two blocks B and a block A (BAB).
• the block copolymer comprises at least one block sequence AB, ABA or BAB where said blocks A and B are linked together without the presence of intermediate block of different chemical nature.
• the block copolymer is used in a liquid fuel chosen from hydrocarbon fuels and non-essentially hydrocarbon fuels, alone or as a mixture.
• the block copolymer is used in admixture with an organic liquid in the form of a concentrate, said organic liquid being inert with respect to the block copolymer and miscible in the fuel.
• the block copolymer is used in the form of an additive concentrate in combination with at least one fuel additive for an internal combustion engine different from said block copolymer.
• the block copolymer is used in the liquid fuel to maintain cleanliness and / or clean at least one of the internal parts of the internal combustion engine.
• the block copolymer is used in the liquid fuel to limit or prevent the formation of deposits in at least one of the internal parts of the internal combustion engine and / or to reduce the deposits existing in at least one of the parts internal of said engine.
• the block copolymer is used to reduce the fuel consumption of the internal combustion engine.
• the block copolymer is also used to reduce the emissions of pollutants, in particular the particulate emissions of the internal combustion engine.
• the internal combustion engine is a spark ignition engine.
• the internal combustion engine is a diesel engine, preferably a direct injection diesel engine.
• the block copolymer is used to limit or avoid and / or reduce deposits related to the phenomenon of coking and / or soap-like deposits and / or varnish.
• the block copolymer is used 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 power loss being determined according to the CEC engine test method F-98-08.
• the block copolymer is used to reduce and / or avoid the restriction of the fuel flow emitted by the injector of a direct injection diesel engine during its operation, said restriction of flux being determined by the CEC standard engine test method F-23-1 -01.
• the subject of the present invention also relates to a method of maintaining the cleaning and / or cleaning at least internal parts of an internal combustion engine comprising at least the following steps:
• the internal combustion engine is a spark ignition engine.
• the inner part kept clean and / or cleaned of the spark ignition engine is selected from the engine intake system, in particular the intake valves (IVD), the combustion chamber (CCD or TCD) and the system fuel injectors, 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.
• the inner part kept clean and / or cleaned of the diesel engine is the injection system of said diesel engine.
• a block copolymer comprises at least one block A and at least one block B.
• Block A is represented by the following formula (I)
• n is an integer ranging from 2 to 100.
• n 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,
• n is an integer ranging from more than 40 to 100, preferably from more than 40 to 80, still more preferably from 41 to 70, even more preferably from 41 to 50.
• Ri is chosen from hydrogen and the methyl group
• R 2 is selected from C 1 to C 34 , preferably C 4 to C 3 o, more preferably C 6 to C 24 , more preferably C 8 to C 22 , said chains being linear or branched, cyclic or acyclic, preferably acyclic. Alkyl groups will be preferred.
• hydrocarbon-based chain means a chain consisting exclusively of carbon and hydrogen atoms, said chain possibly being linear or branched, cyclic, polycyclic or acyclic, saturated or unsaturated, and optionally aromatic or polyaromatic.
• a hydrocarbon chain may comprise a linear or branched part and a cyclic part. It may include an aromatic part and an aromatic part.
• Block B is represented by the form:
• p is an integer ranging from 2 and 40, preferably from 3 to 30, more preferably from 4 to 20, still more preferably from 5 to 10, and
• G is a substituted or unsubstituted aryl group, preferably C 5 to C 3 o, more preferably C 5 to C 6 , still more preferably C 6 to C 0 .
• G is an unsubstituted aryl group, for example a naphthyl or phenyl radical.
• G is a substituted aryl group comprising an aromatic ring substituted with at least one R group or at least one C 1 -C 12, preferably C 1 -C 4 , linear or branched, cyclic hydrocarbon chain. or acyclic, preferably acyclic, optionally substituted with at least one R, said aromatic ring preferably having from 5 to 30 atoms, more preferably from 5 to 16 atoms, even more preferably from 6 to 10 atoms.
• the group R is chosen from the group consisting of:
• the aromatic ring of the aryl group is substituted with a hydrocarbon chain, or with a group R, or with a hydrocarbon chain substituted by R, in the ortho, meta or para position, preferably in para.
• the R group is connected to the aryl group or linked to the hydrocarbon chain, preferably by a nitrogen atom present in the R group.
• the group R is chosen from groups having at least one primary, secondary or tertiary amine function.
• the group R is chosen from the group consisting of:
• alkyl-amines groups having at least one amine, imine, amidine, guanidine, aminoguanidine or biguanidine function, such as alkyl-amines, polyalkylene polyamines, polyalkylenimines, alkylimines, alkylamidines, alkylguanidines and alkyl-biguanidines, alkyl substituent preferably having 1 to 34 carbon atoms, preferably 1 to 12 and being linear or branched, cyclic or acyclic.
• monocyclic or polycyclic heterocyclic groups having from 3 to 34 atoms, preferably from 5 to 12 atoms, more preferably from 6 to 10 atoms, and at least one nitrogen atom, it being understood that the polycyclic heterocyclic groups have, optionally, fused rings.
• the number of atoms includes hetero atoms. By fused rings are meant rings having at least two atoms in common.
• the heterocyclic groups may further comprise an oxygen atom and / or a carbonyl group and / or one or more unsaturations.
• heterocyclic R group By way of example of heterocyclic R group, mention may be made of the following radicals: triazole, aminotriazole, pyrrolidone, piperidine imidazole, morpholine, isoxazole, oxazole and indole, said radical preferably being linked to the hydrocarbon chain or to the aryl group by an atom nitrogen.
• the group R is chosen from the group consisting of:
• R ', R ", R'", R '"andR”" are independently from each other an alkyl group HC 3 6, preferably C1-C12, optionally comprising one or more functions NH 2 and one or more -NH- bridges;
• R a represents a C 1 -C 6 , preferably C 2 -C 4 , alkyl group, k represents an integer ranging from 1 to 20, preferably from 2 to 12;
• R groups having an amino function include polyamines and polyalkylene polyamines, for example ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine.
• the group R is chosen from quaternary ammoniums, preferably comprising at least one C 1 to C 10 , preferably C 1 to C 4 , hydrocarbon chain, linear or branched, cyclic or acyclic, preferably acyclic, said chain optionally comprising one or more oxygen atoms in the form of an ether function or in substitution, preferably in substitution.
• the hydrocarbon chain may, for example, be an alkyl chain substituted with a hydroxyl group, this type of quaternary ammonium salt being obtainable by reaction of a tertiary amine with an epoxide according to any known method.
• the group R is chosen from trialkylammonium groups.
• alkyl substituents of trialkylammonium are preferably selected from alkyl groups having from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, and being linear or branched, cyclic or acyclic, preferably acyclic.
• the R group is chosen from quaternary ammoniums substituted with at least one hydrocarbon chain, preferably C 1 -C 10 alkyl, still more preferably C 1 -C 4 , linear or branched, cyclic or acyclic, preferably acyclic. comprising one or more hydroxyl groups.
• the block copolymer comprises at least:
• a block A consisting of a chain of structural units derived from an alkyl acrylate monomer or alkyl methacrylate m a, and
• B block consisting of a chain of structural units derived from a styrenic monomer b m selected from styrene and styrene derivatives, the aromatic ring is substituted by at least the R group described above or by at least one chain hydrocarbon Ci-Ci 2, preferably to C 4, linear or branched, preferably acyclic, optionally substituted with at least said group R.
• the styrenic monomer m b is represented by the following formula (III):
• g 0 or 1
• L is selected from hydrocarbon chains Ci to Ci 2, preferably to C 4, linear or branched, acyclic and preferably saturated, particularly preferably the group -CH 2 -,
• the block copolymer is obtained by copolymerization of at least one alkyl acrylate or alkyl methacrylate monomer m a and at least one styrenic monomer m b as described above.
• the monomer m a is, preferably, selected from alkyl acrylates or methacrylates C 1 to C 34 , preferably C 4 to C 3 o, more preferably C 6 to C 24 , more preferably C 8 to C 22.
• the alkyl radical of the acrylate or methacrylate is linear or 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, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, isooctyl acrylate, isooctyl methacrylate, isodecyl acrylate, isodecyl methacrylate.
• the monomer mb is preferably chosen from styrenic derivatives whose aromatic ring is substituted by at least the R group or by at least the hydrocarbon chain described above substituted by at least the R group.
• the monomer mb is preferably chosen from styrenic derivatives whose aromatic nucleus is substituted with the group R or -CH 2 R, preferably with -CH 2 R.
• the m monomer b is selected from the isomers of (vinylbenzyl) trialkylammoniums ortho, meta or para, preferably in para, alone or in admixture.
• the block copolymer is represented by one of the following formulas (IV) and (V):
• n, p, Ri and R 2 are as described above,
• R 3 is a substituent in the ortho, meta or para position on the aromatic ring selected from the group consisting of:
• Ci-C 12 preferably Ci-C 4, alkyl groups, preferably acyclic;
• X " is chosen from hydroxide ions, halides and organic anions, in particular the acetate ion,
• R 7 , R 8 and R 9 are identical or different and are chosen independently from C 1 to C 10 , preferably C 1 to C 4 , alkyl groups, linear or branched, cyclic or acyclic, preferably acyclic,
• R 1 0 is chosen from groups having at least one primary, secondary or tertiary amine function, or a quaternary ammonium function
• R 4 is chosen from the group consisting of:
• Ci-C32 preferably C, to C 24, more preferably Ci-C1 0, cyclic or acyclic, saturated or unsaturated, linear or branched, preferably alkyl groups, said chains being optionally substituted by a 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 alkyl groups C1 to Ci 0 linear or branched, cyclic or acyclic, more preferably acyclic.
• RAFT reversible addition-fragmentation chain transfer agent
• 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 transfer agents of the thiocarbonylthio, dithiocarbonate, xanthate, dithiocarbamate and trithiocarbonate type, for example S, N-dibenzyltrithiocarbonate (DBTTC), S, S-bis (a, a'- dimethyl- ⁇ -acetic acid) trithiocarbonate (BDMAT) or 2-cyano-2-propylbenzodithioate
• T can be a sulfur-containing group
• the transfer can be cleaved at the end of polymerization by reacting a cleavage agent such as alkyl amines, C 2 -C 6 T may in this case be a thiol group -.. SH
• at least one of R 3, R 4 and R 10 is a group having
• alkyl-amines groups having at least one amine, imine, amidine, guanidine, aminoguanidine or biguanidine function, such as alkyl-amines, polyalkylene polyamines, polyalkylenimines, alkylimines, alkylamidines, alkylguanidines and alkyl-biguanidines, alkyl substituent preferably having 1 to 34 carbon atoms, preferably 1 to 12 and being linear or branched, cyclic or acyclic.
• monocyclic or polycyclic heterocyclic groups having from 3 to 34 atoms, preferably from 5 to 12 atoms, more preferably from 6 to 10 atoms, and at least one nitrogen atom, it being understood that the polycyclic heterocyclic groups have, if appropriate , merged cycles.
• the number of atoms includes hetero atoms.
• fused rings are meant rings having at least two atoms in common.
• the heterocyclic groups may further comprise an oxygen atom and / or a carbonyl group and / or one or more unsaturations.
• heterocyclic group By way of example of a heterocyclic group, mention may be made of the following radicals: triazole, aminotriazole, pyrrolidone, piperidine imidazole, morpholine, isoxazole, oxazole and indole, said radical preferably being linked by a nitrogen atom.
• at least one of the groups R 3 , R 4 and R 10 is chosen from the group consisting of: - groupings:
• R ', R ", R'", R '"andR”" are independently from each other an alkyl group HC 3 6, preferably C 2 Ci, optionally comprising one or more functions NH 2 and one or more -NH- bridges;
• R a represents a C 1 -C 6 , preferably C 2 -C 4 , alkyl group, k represents an integer ranging from 1 to 20, preferably from 2 to 12;
• groups comprising an amino function include polyamines and polyalkylene polyamines, for example ethylene diamine, diethylene triamine, triethylene tetramine and tetraethylene pentamine.
• At least one of the groups R 3 , R 4 and R 10 is chosen from groups having at least one quaternary ammonium function obtained by quaternization of the primary, secondary or tertiary amines as described above. above, according to any known method.
• At least one of the groups R 3 , R 4 and R 10 may, 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 from 3 to 34 atoms and at least one nitrogen atom.
• At least one of the groups R 3 , R 4 and R 10 is chosen from groups having at least one quaternary ammonium function obtained by quaternization of the tertiary amines.
• the quaternary ammonium is selected from the quaternary ammonium of iminium, amidinium, formamidinium, guanidinium and biguanidinium.
• At least one of the groups R 3 , R 4 and R 10 is chosen from groups having at least one quaternary ammonium function chosen from heterocyclic groups having from 3 to 34 atoms and at least one atom from nitrogen, preferably from the quaternary ammoniums of pyrrolinium, pyridinium, imidazolium, triazolium, triazinium, oxazolium and isoxazolium.
• At least one of the groups R 3 , R 4 and R 10 is chosen from groups having at least one quaternary ammonium function, preferably comprising at least one C 1 to C 10 hydrocarbon chain, preferably C 1 to C 4 , linear or branched, cyclic or acyclic, preferably acyclic, said chain optionally comprising one or more oxygen atoms in the form of an ether function or in substitution, preferably in substitution.
• the hydrocarbon chain may, for example, be an alkyl chain substituted with a hydroxyl group, this type of quaternary ammonium may be obtained by reaction of a tertiary amine with an epoxide according to any known method.
• At least one of the groups R 3 , R 4 and R 10 is chosen from trialkylammonium groups.
• the alkyl substituents of trialkylammonium are preferably chosen from alkyl groups having from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, and being linear or branched, cyclic or acyclic, preferably acyclic
• At least one of R 3, R 4 and R 10 is selected from quaternary ammonium substituted with at least one hydrocarbon chain, preferably alkyl, Ci-Ci 0, more preferably to C 4, linear or branched, cyclic or acyclic, preferably acyclic, comprising one or more hydroxyl groups.
• the block copolymer may be prepared by any known method of polymerization.
• the various techniques and polymerization conditions are widely described in the literature and fall within the general knowledge of those skilled in the art.
• the copolymer according to the invention was obtained from monomers different from m a and m b , inasmuch 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.
• the copolymer by copolymerization of monomers different from m a and m b followed by post-functionalization.
• units derived from a (meth) acrylate has m can be obtained from a fragment poly (meth) acrylate, by a transesterification reaction with an alcohol of length selected chain to form the expected alkyl group.
• a block copolymer comprising a quaternary ammonium group of formula (VI) with R 7 , R 8 and R 9 being methyl groups and X a chlorine can be obtained from a copolymer of formula (IV) or (V ) in which R 3 is a -CH 2 Cl group, by reaction with trimethylamine.
• the chloride counterion may be substituted by treatment of the thus obtained block copolymer in an ion exchange column according to any known method. This reaction scheme makes it possible to synthesize numerous quaternary ammoniums simply and at low cost.
• the block copolymer can be obtained by sequential polymerization, preferably by sequential and controlled polymerization and optionally followed by one or more post-functionalizations. According to a particular embodiment, the block copolymer described above is obtained by sequenced and controlled polymerization.
• the polymerization is advantageously chosen from controlled radical polymerization; for example, by 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 -Initiators for continuous activator regeneration) or using electron-regenerated activators regenerated by electron (ARGET) transfer ").
• ATRP atom transfer radical polymerization
• NMP nitroxide
• RAFT reversible Addition-Fragmentation Chain Transfer
• polymerizations derived from ATRP
• 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.
• 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).
• the ATRP polymerization is preferably carried out in a solvent chosen from polar solvents.
• the numbers of monomer equivalents m a of block A and of monomer m b of block B reacted during the polymerization reaction are identical or different and, independently, from 2 to 40, of preferably from 3 to 30, more preferably from 4 to 20, even more preferably from 5 to 10.
• the amounts of material (in moles) of monomers m a of block A and monomers m b of block B, during the polymerization reaction are identical or different and, independently, from 2 to 40, of preferably from 3 to 30, more preferably from 4 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.
• a and B represent at least 70% by weight, preferably at least 90% by weight, more preferably at least 95% by weight, more preferably at least 99% by weight of the block copolymer.
• the block copolymer is a diblock copolymer.
• the block copolymer is an alternating block triblock copolymer comprising two blocks A and one block B (ABA) or comprising two blocks B and a block A (BAB).
• the block copolymer also comprises a terminal chain I consisting of a hydrocarbon chain, cyclic or acyclic, saturated or unsaturated, linear or branched, C 1 -C 12 , preferably C 4 -C 24 , more preferably C 1 0 -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, chosen from alkyl esters of a carboxylic acid substituted by a halide, preferably a bromine in the alpha position, for example ethyl 2-bromopropionate or ⁇ -bromoisobutyrate.
• a halide preferably a bromine in the alpha position
• ethyl 2-bromopropionate may be able 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 can also be obtained in the copolymer by RAFT polymerization according to the methods described in the article by Moad, G. et al., Australian Journal of Chemistry, 2012, 65, 985-1076.
• the terminal chain I may, for example, be introduced by aminolysis when a transfer agent is used, in particular thiocarbonylthio, dithiocarbonate, xanthate, dithiocarbamate and trithiocarbonate transfer agents, for example S, S-bis.
• the block copolymer is a diblock copolymer (also called diblocks).
• the block copolymer structure may be of the IAB or IBA type, advantageously IAB
• the terminal chain I may be directly linked to the block A or B according to the IAB or IBA structure respectively, or be connected 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 an alkyl group by reaction with an amine, with removal of hydrogen halide.
• Aminolysis can be used, for example, for ATRP polymerization which produces a copolymer having a terminal halide or for RAFT polymerization to remove the thio, dithio or trithio linkage introduced into the copolymer by the RAFT transfer agent.
• the terminal chain I 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 0 , even more preferably an alkyl group, optionally substituted. by one or more groups containing at least one heteroatom selected from N and O, preferably N.
• this functionalization may, for example, be carried out by treating the copolymer IAB or IBA obtained by ATRP with a primary alkylamine to C 32 or an alcohol to C 32 under conditions soft so as not to modify the functions present on blocks A, B and I.
• the block A corresponds to the repeated pattern n times and the block B to the pattern repeated p times.
• the group T may consist of the terminal chain I as described above and / or the group R 4 may consist of the terminal chain as described above.
• the block copolymer described above is particularly advantageous when it is used as a detergent additive in a liquid fuel of an internal combustion engine.
• detergent additive liquid fuel is meant an additive that is incorporated in a small amount in the liquid fuel and has an effect on the cleanliness of said engine compared to said liquid fuel not specially additivé.
• the liquid fuel is advantageously derived from one or more sources selected from the group consisting of mineral, animal, vegetable and synthetic sources. Oil will preferably be chosen as a mineral source.
• the liquid fuel is preferably chosen from hydrocarbon fuels and non-essentially hydrocarbon fuels, alone or as a mixture.
• Hydrocarbon fuel is a fuel consisting of one or more compounds consisting solely of carbon and hydrogen.
• non-essentially hydrocarbon fuel is meant a fuel consisting of one or more compounds consisting essentially of carbon and hydrogen. that also contain other atoms, especially oxygen atoms.
• 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 ARDS type conversion processes (in English "atmospheric residue desulfuration") and / or visbreaking, the distillates from the valuation of Fischer Tropsch cuts.
• Hydrocarbon fuels are typically gasolines and gas oils (also called diesel fuel).
• the gasolines include, in particular, all commercially available spark ignition engine fuel compositions.
• gasoline fuels marketed in Europe, compliant with the NF EN 228 standard have a motor octane number (MON) of greater than 85 and a research octane number (RON in English). Research Octane Number ") of a minimum of 95.
• Gasoline fuels generally have an RON between 90 and 100 and a MON between 80 and 90, the RON and MON being measured according to ASTM D 2699- 86 or D 2700-86.
• Gas oils (diesel fuels) include, in particular, any commercially available diesel fuel compositions. As a representative example, mention may be made of gas oils that comply with the NF EN 590 standard.
• Non-essentially hydrocarbon fuels include oxygenates, for example distillates resulting from BTL (biomass to liquid) conversion of plant and / or animal biomass, taken alone or in combination; biofuels, for example oils and / or esters of vegetable and / or animal oils; biodiesels of animal and / or vegetable origin and bioethanols.
• oxygenates for example distillates resulting from BTL (biomass to liquid) conversion of plant and / or animal biomass, taken alone or in combination
• biofuels for example oils and / or esters of vegetable and / or animal oils
• biodiesels of animal and / or vegetable origin and bioethanols bioethanol
• 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
• 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 EAG
• EMAG methyl esters
• E x type gasoline for a spark ignition engine 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 10 ppm and advantageously without sulfur.
• the block copolymer described above is used as a detergent additive in the liquid fuel at a content, preferably at least 10 ppm, preferably at least 50 ppm, more preferably at a level of 10 to 5000 ppm, even more preferably from 10 to 1 000 ppm.
• the use of a block copolymer as described above in the liquid fuel makes it possible to maintain the cleanliness of at least one of the internal parts of the internal combustion engine and / or to clean at least one internal parts of the internal combustion engine.
• the use of the block copolymer in the liquid fuel makes it possible, in particular, to limit or avoid the formation of deposits in at least one of the internal parts of said engine ("keep-clean” effect) and / or to reduce the existing deposits in at least one of the parts internal of said engine (“keep-clean” effect).
• the use of the copolymer in the liquid fuel makes it possible, in comparison with the liquid fuel with no particular additives, to limit or avoid the formation of deposits in at least one of the internal parts of said engine or to reduce the deposits existing in at least one of the internal parts. said engine.
• 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).
• the internal combustion engine is a spark ignition engine, preferably direct injection (DISI in English "Direct Injection Spark Ignition Engine”).
• the targeted deposits are located in at least one of the internal parts of said spark ignition engine.
• the internal part of the spark-ignition engine kept clean (keep-clean) and / or cleaned (clean-up) is advantageously chosen from the intake system of the engine, in particular the intake valves (IVD). Intake Valve Deposit "), the" Combustion Chamber Deposit “(CCD) and the fuel injection system, in particular the injectors of an indirect injection system (PFI in English "Port Fuel Injector") or the injectors of a direct injection system (DISI).
• 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 Deposits"), for example on the surface of an injector needle.
• the deposits may consist of deposits related to the phenomenon of coking ("coking" in English) and / or deposits soap and / or varnish (in English "lacquering”).
• the block copolymer as described above may advantageously be used in the liquid fuel to reduce and / or avoid the loss of power due to the formation of deposits in the internal parts of a direct injection diesel engine, said loss of fuel.
• the block copolymer as described above can advantageously be used in the liquid fuel to reduce and / or avoid the restriction of the fuel flow emitted by the injector of a direct injection diesel engine during its operation, said flux restriction being determined according to the CEC standard motor test method F-23-1-01.
• the use of the copolymer as described above makes it possible, in comparison with the liquid fuel that is not particularly additive, to limit or avoid the formation of deposits on at least one type of deposits previously described and / or to reduce the deposits existing on at least one of a type of depots previously described.
• the use of the block copolymer described above also makes it possible to reduce the fuel consumption of the internal combustion engine.
• the use of the block copolymer described above also makes it possible to reduce the emissions of pollutants, in particular the particulate emissions of the internal combustion engine.
• the use of the block copolymer makes it possible to reduce both the fuel consumption and the pollutant emissions.
• the block copolymer described above may be used alone, in the form of a mixture of at least two of said block copolymers or in the form of a concentrate.
• the block copolymer can be added to the liquid fuel within a refinery and / or be incorporated downstream of the refinery and / or optionally mixed with other refineries.
• additives in the form of an additive concentrate also referred to as "additive package”.
• the block copolymer described above is used in admixture of an organic liquid in the form of a concentrate.
• the organic liquid is inert with respect to the block copolymer described above and miscible in the liquid fuel described above.
• miscible means that the block copolymer and the organic liquid form a solution or a dispersion so as to facilitate the mixing of the block copolymer in liquid fuels according to the conventional methods of fuel additive.
• the organic liquid is advantageously chosen from aromatic hydrocarbon solvents such as the solvent sold under the name "SOLVESSO", alcohols, ethers and other oxygenated compounds and paraffinic solvents such as hexane, pentane or isoparaffins. alone or in mixture.
• 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 as described above.
• the concentrate may typically comprise from 1 to 95% by weight, preferably from 10 to 70%, more preferably from 25 to 60% of organic liquid, the balance corresponding to the copolymer, it being understood that the concentrate may comprise one or more copolymers. in blocks as described above.
• solubility of the block copolymer in the organic liquids and the liquid fuels described above will depend in particular on the average molar masses by weight and by number, respectively M w and M n of the copolymer.
• the average molar masses M w and M n of the block copolymer will be chosen so that the copolymer is soluble in the liquid fuel and / or the organic liquid of the concentrate for which it is intended.
• the average molar masses M w and M n of the block 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 block copolymer, in particular the detergency effect (engine cleanliness) in the liquid fuels described above.
• the 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.
• the copolymer advantageously has a weight average molecular weight (Mw) ranging from 500 to 30,000 g. mol "1 , preferably from 1000 to 10,000 g, mol " 1 , more preferably less than 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 less than or equal to 4000 g, mol " 1 .
• Mw weight average molecular weight
• Mn number-average molar mass
• the number and weight average molar masses are measured by Size Exclusion Chromatography (SEC).
• SEC Size Exclusion Chromatography
• the block copolymer is used in the form of an additive concentrate in combination with at least one other fuel additive for an internal combustion engine other than the block copolymer described above.
• the additive concentrate may typically comprise one or more other additives selected from detergent additives other than the block copolymer described above, for example from anti-corrosion agents, dispersants, demulsifiers, anti-foam agents , biocides, deodorants, procetane additives, friction modifiers, lubricity additives or lubricity additives, combustion assistants (catalytic combustion promoters and soot), point-of-use improvers cloudiness, pour point, TLF ("Filterability Limit Temperature”), anti-settling agents, anti-wear agents and conductivity modifiers.
• detergent additives other than the block copolymer described above, for example from anti-corrosion agents, dispersants, demulsifiers, anti-foam agents , biocides, deodorants, procetane additives, friction modifiers, lubricity additives or lubricity additives, combustion assistants (catalytic combustion promoters and soot), point-of-use improvers cloudiness, pour point, TLF (“
• 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 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 in the block copolymer described above will be chosen so that the block copolymer is soluble in the fuel and / or the organic liquid of the concentrate for which it is intended. Likewise, this ratio can be optimized according to the fuel and / or the organic liquid so as to obtain the best effect on engine cleanliness.
• the molar ratio between the monomer m b and the monomer m a or between the blocks A and B in the block copolymer described above is advantageously from 1: 10 to 10: 1, preferably from 1: 2 to 2 : 1, more preferably from 1: 0.5 to 0.5: 2.
• the molar ratio between the number of apolar monomer equivalents (m a ) and the number of polar monomer equivalents (m b ), or between the A and B blocks in molar percentage between the monomer apolar (m a ) of block A and the polar monomer (m b ) of block B is preferably from 95: 5 to 70:30, more preferably from 85:15 to 70:30.
• a fuel composition is prepared according to any known method by adding the liquid fuel described above with at least one block copolymer as described above.
• this fuel composition comprising such a copolymer in an internal combustion engine has an effect on the cleanliness of the engine compared to the liquid fuel that is not particularly additive and allows, in particular, to prevent or reduce the fouling of the internal parts of said engine. .
• the effect on the cleanliness of the engine is as previously described in the context of the use of the block copolymer.
• the combustion of the fuel composition comprising such a block copolymer in an internal combustion engine also makes it possible to reduce the fuel consumption and / or the pollutant emissions.
• the block copolymer is preferably incorporated in a small amount in the liquid fuel described above, the amount of block copolymer being sufficient to produce a detergent effect as described above and thus improve the engine cleanliness.
• the fuel composition advantageously comprises at least 10 ppm, preferably at least 50 ppm, advantageously from 10 to 5000 ppm, more preferably from 10 to 1000 ppm of the copolymer described above.
• the fuel composition may also comprise one or more other additives different from the block copolymer according to the invention chosen from the other known detergent additives, for example from anti-corrosion agents, dispersants , demulsifiers, defoamers, biocides, deodorants, procetane additives, friction modifiers, lubricity additives or lubricity additives, combustion assistants (catalytic soot), cloud point improving agents, point flow, TLF, anti-settling agents, anti-wear agents and / or conductivity modifiers.
• the additives different from the block copolymer according to the invention are, for example, the fuel additives listed above.
• 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 the preparation of a fuel composition by additivation of a fuel with one or more block copolymers as described above and combustion of said fuel composition in the internal combustion engine.
• 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 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).
• a direct injection diesel engine in particular a diesel engine with Common Rail injection systems (IDRC).
• IDRC Common Rail injection systems
• the internal part kept clean (keep-clean) and / or cleaned (clean-up) of the diesel engine is preferably the injection system of the diesel engine, preferably an external part of an injector of said injection system for example the nose of the injector and / or one of the internal parts of an injector of said injection system, for example the surface of an injector needle.
• the keep-clean and / or clean-up method comprises the successive steps of:
• step b) incorporation into the fuel of the selected block copolymer or copolymers at the rate determined in step a) and, optionally, the other fuel additives.
• the one or more block copolymers can be incorporated in the fuel, alone or in a mixture, successively or simultaneously.
• the block copolymer (s) may be used in the form of a concentrate or an additive concentrate as described above.
• Step a) is carried out according to any known method and is common practice in the field of additive fuel. This step involves defining at least one representative characteristic of the detergency properties of the fuel composition.
• the characteristic characteristic of the fuel detergency properties will depend on the type of internal combustion engine, for example diesel or spark ignition, the direct or indirect injection system and the location in the engine of the targeted deposits for cleaning and / or maintaining cleanliness.
• the characteristic characteristic of the fuel detergency properties may, for example, correspond to the power loss due to the formation of the deposits in the injectors or the restriction of the fuel flow emitted by the injector at the fuel injector. during the operation of said engine.
• the representative characteristic of the detergency properties may also correspond to the appearance of lacquering deposits at the injector needle (IDID).
• the determination of the amount of copolymer to be added to the fuel composition to reach the specification (step a) described above) will be carried out typically by comparison with the fuel composition but without the copolymer according to the invention, the specification given for the detergency may for example be a target value of power loss according to the DW10 method or a flow restriction value according to XUD9 method mentioned above.
• the amount of block copolymer may also vary depending on the nature and origin of the fuel, particularly depending on the level of n-alkyl, iso-alkyl or n-alkenyl substituted compounds. Thus, the nature and origin of the fuel may also be a factor to consider for step a).
• the keep-clean and / or clean-up method may also include an additional step after step b) of checking the target reached and / or adjusting the rate of additivation with the copolymer (s) as a detergent additive.
• THF is evaporated on a rotary evaporator and octadecyl 2-bromopropionate is dissolved in 100 ml of dichloromethane.
• the organic phase is washed twice with a 10% aqueous solution of hydrochloric acid, three times with water, twice with an aqueous solution of 1 M sodium hydroxide and then three times with water.
• the organic phase is dried with sodium sulfate.
• a solution of initiator I is prepared by dissolving 1 equivalent of octadecyl 2-bromopropionate (1 g, 405 gmol -1 ) in 4 ml of anisole, the solution is degassed by bubbling nitrogen before use.
• a monomer solution m a / catalyst / ligand is obtained by dissolving in 8 ml of anisole, 14 equivalents of dodecyl acrylate (8.30 g, 240 g mol -1 ), 0.4 equivalent of copper bromide ( 142 mg, 143 g.mol "1) and 0.4 equivalents of 1, 1, 4,7, 10, 10- hexaméthyltriéthylène tetramine (227 mg, 230 g.mol” 1) and degassing the solution thus obtained by nitrogen bubbling.
• a monomeric solution m b / catalyst / ligand is obtained by dissolving in 4 ml of anisole, 6 equivalents of chloride ⁇ , ⁇ , ⁇ -trimethylammonium vinylbenzene (3,14g, 212 g.mol "1), 0.4 equivalent copper bromide (142 mg, 143 g.mol "1) and 0.4 equivalents of 1, 1, 4,7, 10, 10-hexaméthyltriéthylène tetramine (227 mg, 230 g.mol” 1).
• the solution The mixture is placed under vacuum, with magnetic stirring, at 90 ° C., under the exclusion of light, under a stream of nitrogen to the monomer solution m a / catalyst / ligand.
• reaction is followed by spectroscopic analysis 1 H NMR (Bruker 400 MHz spectrometer). After 25h of reaction, the entire dodecyl acrylate is consumed. After degassing by bubbling nitrogen, the monomer solution m b / catalyst / ligand is then After 52h at 90 ° C., the reaction is stopped by immersing the flask in liquid nitrogen, and 100 ml of tetrahydrofuran are added to the reaction mixture. It is then reacted and the solution thus obtained is passed through a column of basic alumina.
• m, n and p values are determined by 1 H NMR spectroscopy analysis (Bruker 400 MHz spectrometer).
• the molar masses are measured by a Viscotek GPC Max TDA 305 from Malvern equipped with two columns PLGel Mixed C column gel from Agilent and detects ionizing radiation.
• the solvent used is chloroform (+1% triethylamine) and the flux is set at 1 ml.min -1 Calibration is performed with standard polystyrene samples of low dispersity.
• the values are measured by a Varian device equipped with TOSOHAAS TSK gel columns and an ionizing radiation detector.
• the solvent used is THF and the flux is set at 1 ml.min -1 Calibration is carried out with standard samples of polystyrene with low dispersities.
• DBTTC S O -dibenzyl trithiocarbonate 98%
• DBTTC CAS 26504-29-0
• DBTTC is used in 50% by weight solution in ethyl acetate.
• the conversion of DDA is followed by integration of the monomers -OCH 2 of the monomer DDA ( ⁇ (ppm): 4.1 (t, 2H)) in comparison with the integration of the methylenes -OCH 2 of the polymerized DDA units ( ⁇ (ppm): 4.0 (m, 2H)) and the conversion of the CMS is followed by integration of the CH 2 Cl monomers of the CMS monomer ( ⁇ (ppm): 4.58 (s, 2H)) in comparison with the integration of the CH 2 Cl 2 methylenes ( ⁇ (ppm): 4.51 (m, 2H)).
• the medium After an NMR check of the conversion, the medium is cooled to room temperature. The solvent is evaporated under reduced pressure.
• the number-average molar mass (Mn), the weight-average molar mass (Mw) and the dispersity (D) of the copolymer are measured by SEC equipped with a detector of the refractive index (RI) type. with a calibration with polymethylmethacrylate (PMMA). 66 g of copolymer are obtained (Mn: 8410 g / mol, Mp: 1 1980 g / mol, D: 1.43).
• n and p are determined from the conversion rate and the number of starting moles (determination of the molar ratio of the two monomers) and the molar masses M n of the copolymer determined by SEC. Values are rounded to the integer.
• the copolymer obtained above is precipitated in methanol.
• the precipitate is dissolved in 400 mL of toluene.
• the solution is washed 3 times with 200 ml of a saturated solution of sodium acetate and 1 time with 200 ml of ultra-purified water.
• the organic phase is evaporated, allowing the elimination of the residual water by azeotropic entrainment.
• the copolymer is dissolved in 200 mL of toluene and filtered through a Buchner filter. The volatiles are evaporated and the copolymer is dried under vacuum. 53.0 g of blOCS RAFT bA 12 26 B aq 2 copolymer are obtained.
• the copolymer is analyzed by 1 H NMR in the presence of 1, 2.4 . 5-tetrachloro-3-nitrobenzene (TCNB) to assay the residual toluene (14% by mass).
• TCNB 5-tetrachloro-3-nitrobenzene
• the 1 H NMR results show a complete disappearance of the CH2 resonance of the CMS block at 4.51 ppm. There then appear two broad masses at 3.24 and 4 ppm corresponding to the methyl and ethyl groups of the quaternary ammonium group present in the RAFT bA 12 26 B aq 2 copolymer.
• the XUD9 test makes it possible to determine the restriction of the flow of diesel fuel emitted by the injector of a prechamber diesel engine during its operation, according to the engine test method CEC CEC F-23-1 -01.
• This XUD9 test is to evaluate the ability of the diesel fuel and / or additive and / or additive composition tested to maintain cleanliness, the so-called "Keep Clean" effect, of injectors of a Peugeot XUD9 A / L engine with four cylinders and diesel prechamber injection, in particular to evaluate its ability to limit the formation of deposits on the injectors.
• the tests were carried out on a virgin diesel (GOM B7) meeting the EN590 standard containing 7% (vol / vol) or (v / v) of fatty acid methyl ester (EMAG) and said GMO B7 gas oil additive, rated GOM x at two additive treatment rates, 50ppm and 250ppm in mass dry matter.
• GOM B7 virgin diesel
• EMAG fatty acid methyl ester
• the diesel compositions additive with the copolymer according to the present invention GOM1 to GOM5 have a loss of flow rate lower than that of the GOM B7 tested.
• the additivation of GOM B7 with the copolymer according to the invention makes it possible to obtain an average flow loss of less than 60% and an average flow rate gain of greater than 10%.
• the block copolymers RAFT 4 -bA 12 31 B aq 4 and RAFT 5 -bA 12 25 B aq 6 are particularly effective as a detergent additive even at a low additivation level.
• the measurements give for the GOM5 and GOM6 a mean flow loss of less than 60% at 50ppm of additive rate and less than 25% at 250ppm of additive rate and an average flow gain greater than 10% at 50ppm additivation rate and over 40% at 250ppm additive rate.
• the copolymers according to the invention have remarkable properties as a detergent additive in a liquid fuel, in particular in a diesel or gasoline fuel.
• the block copolymers according to the invention are particularly remarkable in particular because they are effective as a detergent additive for a wide range of liquid fuels and / or for one or more types of motorization and / or against one or more types of deposit which form in the internal parts of internal combustion engines.

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• 2015
  • 2015-09-18 FR FR1558830A patent/FR3041362B1/fr not_active Expired - Fee Related
• 2016
  • 2016-09-15 US US15/761,378 patent/US20180258357A1/en not_active Abandoned
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