EP3692117A1 - Composition d'additifs pour carburant - Google Patents
Composition d'additifs pour carburantInfo
- Publication number
- EP3692117A1 EP3692117A1 EP18796711.2A EP18796711A EP3692117A1 EP 3692117 A1 EP3692117 A1 EP 3692117A1 EP 18796711 A EP18796711 A EP 18796711A EP 3692117 A1 EP3692117 A1 EP 3692117A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fuel
- group
- copolymer
- chosen
- additive composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
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
-
- 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
- C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
- C10L1/224—Amides; Imides carboxylic acid amides, imides
-
- 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
- C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
-
- 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
- C10L10/18—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
- 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
- C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide 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, 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
- C10L1/2366—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, 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
- C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
- C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
-
- 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
- C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
- C10L2200/0295—Water
-
- 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
- C10L2200/0461—Fractions defined by their origin
- C10L2200/0469—Renewables or materials of biological origin
- C10L2200/0484—Vegetable or animal oils
Definitions
- the present invention relates to an additive composition for 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 ("Keep-clean” effect) or by reducing the deposits already present in the internal parts of the combustion engine (effect " clean-up "in English).
- US 4,171,959 which describes a detergent additive for petrol fuel containing a quaternary ammonium function.
- WO 2006135881 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.
- WO 2017/046526 discloses the use as a detergent additive in a liquid fuel of an internal combustion engine of a copolymer comprising at least one block A and at least one block B.
- the block A is obtained from monomers (meth) acrylates alkyl.
- Block B is obtained from alkyl (meth) acrylate monomers or alkyl (meth) acrylamide, said alkyl group being substituted by at least one quaternary ammonium group.
- Another important problem associated with liquid fuels of internal combustion engines is related to the presence of residual water in these fuels.
- the fuels comprise a variable amount of water that can range from a few parts per million to a few percent by weight in relation to the total mass of the fuel.
- the presence of this residual water generally results in the formation of stable emulsions which, being suspended in the fuel, are the cause of many problems occurring during transport and / or during the combustion of these fuels. For example, these emulsions can cause clogging of the engine filters or accelerate engine corrosion.
- the detergent additives currently used in fuels tend to stabilize the emulsions present in the fuel.
- demulsifier additives or demulsifier
- US 2016/0160144 proposes to use a polyisobutenyl succinic acid in combination with one or more detergent additives to improve the separation of water and fuel.
- Many documents of the prior art describe the "dehazing” (dehazing) of fuels comprising water. This "debris” phenomenon actually corresponds to the stabilization of the water-in-fuel emulsion in order to obtain a fuel composition of monophasic appearance (emulsification).
- the “debridging”, unlike the demulsification, does not allow the separation of water and fuel and therefore does not constitute a solution to the disadvantages described above.
- the invention firstly relates to a fuel additive composition
- a fuel additive composition comprising: (a) one or more copolymer (s) comprising:
- R 1 is chosen from hydrogen and the methyl group
- R '2 is selected from hydrocarbon chains to C 34, an aromatic ring, an aralkyl having at least one aromatic ring and at least one alkyl group in Ci to C34, and
- Ri is chosen from hydrogen and the methyl group
- Z is chosen from the oxygen atom and the group -NR'- with R 'being chosen from a hydrogen atom and the C 1 -C 12 hydrocarbon chains,
- G comprises a hydrocarbon chain -C 34 substituted by at least one quaternary ammonium group and optionally one or more hydroxyl groups, the group G possibly also containing one or more nitrogen and / or oxygen atoms and / or carbonyl groups
- the group G of the formula (I I) is represented by one of the following formulas (I I I) and (IV):
- X " is chosen from hydroxide ions, halides and organic anions, preferably organic anions,
- R 2 is chosen from C 1 to C 34 hydrocarbon chains, optionally substituted with at least one hydroxyl group, it being understood that the R 2 group is connected to Z in formula (II),
- R 3 , R 4 and R 5 are identical or different and chosen, independently, from C 1 to C 8 hydrocarbon chains, it being understood that the alkyl groups R 3 , R 4 and R 5 may contain one or more groups chosen from: a nitrogen atom, an oxygen atom and a carbonyl group and that the groups R 3 , R 4 and R 5 may be connected together in pairs to form one or more rings,
- R 6 and R 7 are identical or different and independently selected from C 1 -C 18 hydrocarbon chains, it being understood that the R 6 and R 7 groups may contain one or more groups chosen from: a nitrogen atom, a hydrogen atom, oxygen and a carbonyl group and that the groups R 6 and R 7 may be joined together to form a ring.
- X " is chosen from organic anions, preferably conjugated bases of carboxylic acids,
- R 2 is chosen from C 1 to C 34 hydrocarbon chains, preferably C 1 to C 18 alkyl groups ,
- R 3 , R 4 and R 5 are identical or different and chosen, independently, from the chains
- the copolymer (s) consist exclusively of units of formula (I) and of units of formula (II).
- the copolymer is obtained by copolymerization of at least:
- R 1, Z and G are as defined above.
- the copolymer is a block copolymer.
- the block copolymer comprises at least one block A and at least one block B.
- the block copolymer comprises:
- p is an integer ranging from 2 to 100
- R 1 and R ' 2 are as defined above.
- n is an integer ranging from 2 to 40
- Ri, Z and G are as defined above.
- the succinimide compound substituted with a hydrocarbon chain (b) is selected from polyisobutenes succinimides.
- the mass ratio between the copolymer (s) and the succinimide compound (b) ranges from 5: 95 to 95: 5, preferably from 10: 90 to 90:10.
- the invention also relates to a fuel concentrate comprising a fuel additive composition as defined above and in detail below, in admixture with an organic liquid, said organic liquid being inert with respect to or copolymers (a) and succinimide compound (s) (b) and miscible with said fuel.
- the invention also relates to a fuel composition
- a fuel composition comprising:
- a fuel from one or more sources selected from the group consisting of mineral, animal, plant and synthetic sources, and
- the fuel composition according to the invention comprises at least 5 ppm of copolymer (s) (a).
- the copolymer or copolymers (a) are present in the composition according to the invention in an amount ranging from 1 to 1000 ppm, preferably ranging from 5 to 500 ppm, more preferably ranging from 10 to 200 ppm, and even more preferentially from 20 to 100 ppm.
- the succinimide compound (b) is present in the fuel composition according to the invention in an amount ranging from 1 to 1000 ppm, preferably ranging from 5 to 500 ppm, more preferably ranging from 10 to 200 ppm. and even more preferably from 20 to 100 ppm.
- the fuel (1) is selected from hydrocarbon fuels, non-substantially hydrocarbon fuels and mixtures thereof.
- the invention also relates to the use of a fuel additive composition as described above as a detergent additive in a liquid fuel of internal combustion engines, said fuel additive composition being used alone or under the form of a concentrate as defined above and in detail below.
- the fuel additive composition 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 fuel additive composition according to the invention is used in the liquid fuel to limit or prevent the formation of deposits in at least one of the internal parts of said engine and / or to reduce the deposits existing in the engine. least one of the internal parts of said internal combustion engine.
- the fuel additive composition according to the invention is used in the liquid fuel to reduce the fuel consumption of the internal combustion engine.
- the fuel additive composition according to the invention is used in the liquid fuel to reduce the emissions of pollutants, in particular the particulate emissions of the combustion engine.
- the invention finally relates to the use of a fuel additive composition as described above, for improving the separation of water and fuel when the latter contains water, said fuel additive composition being used alone or in the form of a concentrate as defined above and in detail below.
- alkyl (meth) acrylate to denote an alkyl acrylate or an alkyl methacrylate (alkyl (meth) acrylate),
- alkyl (meth) acrylamide to designate an alkyl acrylamide or an alkyl methacrylamide (alkyl (meth) acrylamide),
- the term "unit” means a group of atoms constituting part of the structure of the copolymer and corresponding to a monomer employed in the synthesis of the copolymer.
- the invention relates to a fuel additive composition
- a fuel additive composition comprising:
- R 1 is chosen from hydrogen and the methyl group, preferably R 1 'is a hydrogen atom,
- R '2 is selected from hydrocarbon chains to C 34, an aromatic ring, an aralkyl having at least one aromatic ring and at least one alkyl
- Ri is chosen from hydrogen and the methyl group
- Z is chosen from the oxygen atom and the group -NR'- with R 'being chosen from a hydrogen atom and the C 1 -C 6 hydrocarbon-based chains; 2 ,
- G comprises a C 1 to C 34 hydrocarbon-based chain substituted with at least one quaternary ammonium group and optionally one or more hydroxyl groups, the G group possibly also containing one or more nitrogen and / or oxygen atoms and / or carbonyl groups , and
- the units of formula (I) and the units of formula (II) defined above represent at least 70 mol% of the copolymer (a), relative to the number of moles of units entering the the composition of the copolymer (a), preferably at least 80 mol%, more preferably at least 90 mol%, even more preferably at least 95 mol%, and advantageously at least 98 mol%.
- the copolymer (a) comprises only units of formula (I) and units of formula (II).
- the copolymer (a) is chosen from block copolymers or statistics.
- the copolymer (a) is a block copolymer.
- the group R ' 2 of the formula (I) is chosen from C 1 to C 34 , preferably C 4 to C 3 o, more preferably C 6 to C 24 , still more preferably C 8 to C, hydrocarbon chains. 22 , said chains being linear or branched, cyclic or acyclic, preferably acyclic
- hydrocarbon-based chain means a chain consisting exclusively of carbon and hydrogen atoms, said chain possibly being linear or branched, cyclic, polycyclic or acyclic, saturated or unsaturated, and optionally aromatic or polyaromatic.
- a hydrocarbon chain may comprise a linear or branched part and a cyclic part. It may comprise an aliphatic part and an aromatic part.
- the group R 2 'of the formula (I) can be a C 1 -C 3 alkyl, preferably a C 4 -C 3 4 alkyl, preferably a C 4 -C 30 alkyl, more preferably a C 6 -C 2 4 alkyl radical, even more preferentially in C 8 to C 8 .
- the alkyl radical is a linear or branched radical, cyclic or acyclic, preferably acyclic. This alkyl radical can comprise a linear or branched part and a cyclic part.
- the group R 2 'of the formula (I) is advantageously a C 1 -C 3 acyclic alkyl, preferably a C 4 -C 3 4 alkyl, preferably a C 4 -C 30 alkyl, more preferably a C 6 -C 2 4 alkyl radical, and even more preferably C 8 to C 8 linear or branched, preferably branched.
- alkyl groups such as butyl, octyl, decyl, dodecyl, ethyl-2-hexyl, isooctyl, isodecyl and isododecyl.
- the group R 2 'of formula (I) may also be an aromatic ring, preferably a phenyl or aryl group.
- aromatic groups there may be mentioned, without limitation, the phenyl or naphthyl group, preferably the phenyl group.
- the group R 2 'of the formula (I) may, according to another preferred variant, be an aralkyl comprising at least one aromatic ring and at least one C 1 -C 34 alkyl group.
- the group R 2 ' is an aralkyl comprising at least one aromatic nucleus and one or more C 4 -C 34, preferably C 4 -C 30, more preferably C 6 -C 24 alkyl groups, and even more preferably C 8 to C 8.
- the aromatic ring may be mono-substituted or substituted on a number of its carbon atoms.
- the aromatic ring is monosubstituted.
- the C1-C34 alkyl group may be in the ortho, meta or para position on the aromatic ring, preferably in para.
- the alkyl radical is a linear or branched radical, cyclic or acyclic, preferably acyclic.
- the alkyl radical is preferably an acyclic radical, linear or branched, preferably branched.
- the aromatic ring may be directly attached to the oxygen atom but may also be connected to it via an alkyl substituent.
- R 2 'group By way of example of an R 2 'group, mention may be made of a benzyl group substituted in para with a C 4 -C 34, preferably C 4 -C 3, alkyl group.
- the R 2 'group of formula (I) is an aralkyl comprising at least one aromatic ring and at least one C 4 -C 34 , preferably C 4 -C 30, alkyl group, more preferably C 6 -C 24 , even more preferentially
- the Z group of formula (II) is the oxygen atom.
- the group G of formula (II) comprises a quaternary ammonium group and one or more hydroxyl groups.
- the group G is chosen from groups having at least one quaternary ammonium function obtained by quaternization of a primary, secondary or tertiary amine according to any known method.
- the group G 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.
- the group G is chosen from groups having at least one quaternary ammonium function obtained by quaternization of a tertiary amine.
- the group G of the formula (II) is represented by one of the following formulas (III) and (IV):
- X " is chosen from hydroxide ions, halides and organic anions, in particular the acetate ion,
- R 2 is selected from C 1 to C 34 , preferably C 1 to C 8 , more preferably C 1 to C 8 , still more preferably C 2 to C 4 , cyclic or acyclic, linear or branched, optionally substituted hydrocarbon chains; by at least one hydroxyl group; preferably, R 2 is chosen from alkyl groups, optionally substituted with at least one hydroxyl group, it being understood that the group R 2 is connected to the Z group in formula (II),
- R 3, R 4 and R 5 are identical or different and independently selected from hydrocarbon chains Ci to C 8, preferably Ci-Ci 2 linear or branched, cyclic or acyclic, it being understood that the alkyl groups R 3 , R 4 and R 5 may contain one or more nitrogen atoms and / or oxygen and / or carbonyl groups and may be connected together in pairs to form one or more rings,
- R 6 and R 7 are identical or different and independently selected among the channels hydrocarbon Ci to C 8, preferably Ci-Ci 2 linear or branched, cyclic or acyclic, it being understood that R 6 and R groups 7 may contain one or more nitrogen atoms and / or oxygen and / or carbonyl groups and may be joined together to form a ring.
- the nitrogen atom (s) and / or oxygen (s) may be present in the R 3 , R 4 and R 5 groups in the form of ether bridges, amine bridges or in the form of an amino or hydroxyl substituent.
- the organic anions of the group X ' are advantageously the conjugate bases of the organic acids, preferably the conjugate bases of the carboxylic acids, in particular the acids chosen from monocarboxylic, polycarboxylic, cyclic or acyclic acids.
- the organic anions of the group X " are selected from conjugated bases of saturated acyclic or cyclic aromatic carboxylic acids.
- the group R 2 is chosen from C 1 to C 34 , preferably C 1 to C 8 , more preferably C 1 to C 8 , even more preferably C 2 to C 4 , acyclic alkyl groups. linear or branched, substituted by at least one hydroxyl group.
- the group G of formula (II) comprises a hydrocarbon chain substituted with at least one quaternary ammonium group and one or more hydroxyl groups.
- the group G of formula (II) is represented by formula (III) in which:
- X " is chosen from organic anions, preferably conjugated bases of carboxylic acids,
- R 2 is selected from hydrocarbon chains to C 34, preferably the alkyl groups Ci to C 8,
- R 3 , R 4 and R 5 are identical or different and are chosen, independently, from C 1 to C 8 hydrocarbon chains, optionally substituted with at least one hydroxyl group, it being understood that at least one of the groups R 3 , R 4 and R 5 contains at least one hydroxyl group.
- the group R 2 is represented by one of the following formulas (V) and (VI):
- R 8 is selected from hydrocarbon chains to C 32, preferably Ci to C 6 cyclic or acyclic, preferably acyclic, linear or branched, preferably alkyl groups,
- R 9 is selected from hydrogen and C 1 to C 6 lower alkyl groups preferentially hydrogen.
- the unit of formula (I) is obtained from a monomer (m a ).
- the monomer (m a ) corresponds to the following formula (VII):
- the group R 1 ' is a hydrogen atom.
- the monomer (m a ) is preferably chosen 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 24 alkyl acrylates or methacrylates. 22.
- the alkyl radical of the acrylate or methacrylate is linear or branched, cyclic or acyclic, preferably acyclic.
- alkyl (meth) acrylates which may be used in the manufacture of the copolymer, mention may be made, in a nonlimiting manner, of n-octyl acrylate, n-octyl methacrylate, n-octyl acrylate and the like.
- the unit of formula (II) is obtained from a monomer (m b ).
- the monomer (m b ) is chosen from those of formula (VIII)
- R 1, Z and Q are as defined above, preferred variants of R 1, Z and Q according to formula (II) as defined above are also preferred variants of formula (VIII).
- the monomer (m b ) is represented by the formulas
- R 1 and Z are as defined above, the preferred variants of R 1 and Z according to formula (II) as defined above are also preferred variants of formulas (IX) and (X),
- X " , R 2 , R 3, R 4 , R 5 , R 6 and R 7 are as defined above, the preferred variants of X " , R 2 , R 3, R 4 , R 5 , R 6 and R 7 according to the formulas III) and (IV) as defined above are also preferred variants of formulas (IX) and (X).
- the copolymer (a) is chosen from the monomers (ma) and the monomers (mb) defined above, preferably at least 80% by weight. moles, more preferably at least 90 mol%, even more preferably at least 95 mol%, and advantageously at least 98 mol%.
- the copolymer (a) is obtained solely from monomers (m a ) and monomers (m b ).
- the copolymer (a) can 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 (a) is a block copolymer comprising at least one block A and at least one block B.
- block A is represented by (XI):
- p is an integer ranging from 2 to 100, preferably from 5 to 80, preferably from 10 to 70, more preferably from 20 to 60,
- R 1 'and R 2 ' are as defined above, the variants of R 1 'and R 2 ' according to formula (I) as defined above are also preferred variants of formula (XI).
- p is an integer ranging from 2 to 40, and R ' 2 is chosen from C 4 to C 3 hydrocarbon chains.
- p is an integer ranging from 2 to 40
- R ' 2 is chosen from C 4 to C 30 hydrocarbon chains
- the copolymer has a number-average molecular weight (M n) ranging from 1000 to 10,000 g. mol "1 .
- p is an integer greater than 40 and less than or equal to 100, preferably greater than 40 and less than or equal to 80, still more preferably 41 to 70, still more preferably 41 to 50.
- p is an integer greater than 40 and less than or equal to 100
- R ' 2 is chosen from C 4 to C 30 hydrocarbon chains.
- block B is represented by the following formula (XII):
- n is an integer ranging from 2 to 50, preferably from 3 to 40, more preferably from 4 to 20, even more preferably from 5 to 10,
- R 1, Z and G are as defined above, the preferred variants of R 1, Z and Q according to formula (II) as defined above are also preferred variants of formula (XII).
- block B is represented by one of the following formulas (XIII) and (XIV):
- n, Z and R 1 are as described above, the preferred variants of n, Z and R-1 according to formulas (II) and (XII) as defined above are also preferred variants of formulas (XIII) and (XIV),
- X ', R2, R3, R 4, R 5, R 6 and R 7 are as defined above, the preferred variants of X', R 2,
- R 3, R 4, R 5, R 6 and R 7 of the formulas (III) and (IV) as defined above are also preferred embodiments of formulas (XIII) and (XIV).
- the block A consists of a chain of structural units derived from at least one monomer (m a ) as described above.
- the block B consists of a chain of patterns Structural derivatives derived from at least one monomer (m b ) as described above.
- the block A consists of a chain of structural units derived from an alkyl acrylate or alkyl methacrylate monomer (m a ) and the block B corresponds to the formula (XI I) described above. above.
- the block copolymer is obtained by copolymerization of at least one alkyl (meth) acrylate monomer (m a ) and at least one monomer (m b ).
- 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. It is understood that it would not go beyond the invention if the copolymer according to the invention was obtained from monomers different from (m a ) and (m b ), insofar as the final copolymer corresponds to that of the invention, that is to say comprising at least one unit of formula (I) and at least one unit of formula (II) as defined above. For example, it would not go beyond the invention, if one obtained the copolymer by copolymerization of monomers different from (m a ) and (m b ) followed by post-functionalization.
- 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 chain length chosen to form the expected alkyl group.
- 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
- degenerative transfer processes degenerative transfer processes
- IRP-iodine transfer radical polymerization degenerative iod
- the reversible Addition-Fragmentation Chain Transfer (RAFT) radical polymerization is a living radical polymerization technique.
- the RAFT technique was discovered in 1988 by the Australian scientific research organization CSIRO (J. Chiefari et al., Macromolecules, 1998, 31, 5559).
- the RAFT technique has very rapidly been the subject of intensive research by the scientific community as it allows the synthesis of macromolecules with complex architectures, including structures in blocks, grafts, combs or even stars. by controlling the molecular weight of the macromolecules obtained (G. Moad et al., Aust J. Chem, 2005, 58, 379).
- the RAFT polymerization can be applied to a very wide range of vinyl monomers and under various experimental conditions, including for the preparation of water-soluble materials (CL McCormick et al., Acc. Chem. Res. 2004, 37, 312).
- the RAFT method includes the conventional radical polymerization of a substituted monomer in the presence of a suitable chain transfer agent (RAFT agent or CTA in English "Chain Transfer Agent").
- RAFT agent thiocarbonylthio compounds
- dithioesters J.
- RAFT agent allows the synthesis of polymers having a high degree of functionality and having a narrow distribution of molecular weights, that is to say a low polydispersity index (PDI in English "Polydispersity index”) .
- radical radicalization description RAFT examples include the following documents W01998 / 01478, W01999 / 31144, WO2001 / 77198, WO2005 / 00319, WO2005 / 000924.
- 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.
- the number of monomer equivalents (m a ) of the block A is preferably from 2 to 100 eq, preferably from 5 to 80 eq, preferably from 10 to 70 eq, more preferably from 20 to 60 eq.
- the number of monomer equivalents (m b ) of the block B is preferably from 2 to 50 eq, preferably from 3 to 40 eq, more preferably from 4 to 20 eq, still more preferably from 5 to 10 eq. .
- 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 in 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 preferably comprises at least a sequence of blocks AB, ABA or BAB, where said blocks A and B are connected without the presence of such intermediate block different chemical.
- 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 linear or branched, C 1 to C 32, preferably C 4 to C 24, hydrocarbon, cyclic or acyclic, saturated or unsaturated hydrocarbon chain , more preferably preferentially at 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, 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.
- ethyl chloride benzyl chloride or bromide
- ethyl ⁇ -bromophenylacetate 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 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 to give a thiol function.
- 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-propyl benzodithioate (CPD).
- DBTTC N-dibenzyltrithiocarbonate
- BDMAT S-bis (a, a'- dimethyl- ⁇ -acetic acid) trithiocarbonate
- CPD 2-cyano-2-propyl benzodithioate
- the transfer agent can be cleaved at the end of the polymerization by reacting a cleavage agent such as C2-C6 alkylamines, the terminal function of the copolymer can in this case be a thiol -SH group.
- a cleavage agent such as C2-C6 alkylamines
- the sulfur of the copolymer obtained by RAFT polymerization introduced by the sulfur transfer agent such as thiocarbonylthio, dithiocarbonate, xanthate, dithiocarbamate and trithiocarbonate, can be converted in order to eliminate the sulfur of the copolymer.
- 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 an alkyl group by reaction with an amine, with removal of hydrogen halide.
- Aminolysis can be used, for example, for an ATRP polymerization which produces a copolymer having a terminal halide or for a RAFT polymerization to transform the thio, dithio or trithio linkage introduced into the copolymer by the RAFT transfer agent into the copolymer. thiol function.
- the terminal chain I 'advantageously comprises a hydrocarbon chain, linear or branched, cyclic or acyclic, C 1 to C 32, preferably C 1 to C 24, more preferably C 1 to C 0 , still 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 quaternary ammonium group of block B described above may be acyclic or cyclic.
- the acyclic quaternary ammonium group is advantageously chosen from quaternary salts of trialkylammonium, iminium, amidinium, formamidinium, guanidinium and biguanidinium, preferably trialkylammonium.
- the cyclic quaternary ammonium group is advantageously chosen from heterocyclic compounds containing at least one nitrogen atom, in particular chosen from the quaternary salts of pyrrolinium, pyridinium, imidazolium, triazolium, triazinium, oxazolium and isoxazolium.
- the quaternary ammonium group of the B block is, advantageously, a quaternary ammonium, still more preferably a quaternary trialkylammonium salt.
- At least one of the alkyl groups of the quaternary ammonium of block B is substituted by a hydroxyl group.
- the block B is preferably derived from a monomer (m b ) obtained by reaction:
- a tertiary amine of formula NR 3 R 4 R 5 or R 6 N R 7 in which R 3 , R 4, R 5 , R 6 and R 7 are as described above, and
- Z, R 1; R 8 and R 9 are as described above, preferred variants of Z, R 1; R 8 and R 9 according to the formulas (II), (V) and (VI) as defined above are also preferred variants of the formula (XV).
- the block B is obtained by post-functionalization of an intermediate polymer Pi comprising at least one block P of formula (XVI) below:
- n, Z, R 1; R 8 and R 9 are as described above, preferred variants of n, Z, R 1; and R 9 according to the formulas (II), (V), (VI) and (XVI I) as defined above are also preferred variants of the formula (XVI).
- the tertiary amine may, for example, be selected from acyclic tertiary amines, preferably quaternizable trialkylamines, guanidines and imines.
- the tertiary amine is preferably selected from trialkylamines, especially those whose alkyl groups are identical or different and independently selected from alkyl Cl to C 8, preferably Ci-C12, linear or branched, cyclic or acyclic, preferably acyclic.
- the tertiary amine may be chosen from cyclic tertiary amines, preferably pyrrolines, pyridines, imidazoles, triazoles, guanidines, imines, triazines, oxazoles and quaternizable isoxazoles.
- the intermediate polymer Pi may also comprise at least one block A as described above.
- the quaternization step may be carried out before the copolymerization reaction, on an intermediate monomer carrying the tertiary amine, for example, by reaction with an alkyl halide or an epoxide (oxirane) according to any known process, optionally followed by a anion exchange reaction.
- the quaternization step can also be carried out by post-functionalization of an intermediate polymer carrying the tertiary amine, for example by reaction with an alkyl halide optionally followed by an anion exchange reaction.
- an alkyl halide optionally followed by an anion exchange reaction.
- a post-functionalization reaction of an intermediate polymer bearing the tertiary amine by reaction with an epoxide (oxirane) according to any known method.
- the fuel additive composition may advantageously comprise from 5 to 99% by weight, preferably from 10 to 80%, more preferably from 25 to 70% of copolymer (a) as described above.
- the fuel additive composition according to the invention also comprises at least one chemical compound selected from succinimides substituted with a hydrocarbon chain (b).
- the succinimide compound (b) is substituted by a hydrocarbon chain, preferably C 8 -C 5 oo, more preferably C 1 -C 5
- the succinimide compound substituted with a hydrocarbon chain (b) is chosen from polyisobutenes succinimides.
- Polyisobutene succinimides can be obtained by the reaction of a polyisobutenyl substituted succinic acid or anhydride with an amino compound.
- the polyisobutenyl chain substituting the succinic acid or anhydride has a number-average molecular mass ranging from 200 to 5000 g / mol, preferably ranging from 400 to 3000, more preferably ranging from 500 to 2500, even more preferentially ranging from of 800 and 1500, the number average molecular weight being determined by gel permeation chromatography (GPC), also called size exclusion chromatography (CES), from the starting polymer.
- GPC gel permeation chromatography
- CES size exclusion chromatography
- the product obtained consists of a complex mixture of unreacted polymers and succinic anhydrides substituted by a polyisobutene chain in which the polyisobutenyl substituent is bonded to at least one of the carbon atoms located in alpha groups carbonyls of succinic anhydride.
- the amine compound used for the preparation of the polyisobutene succinimide is NH 3 ammonia.
- the amine compound used for the preparation of polyisobutene succinimide is a hydrocarbon compound C1-C50, preferably C 2 -C 3 o and comprising at least one amine function, preferably a primary amine function.
- the amine function is substituted by at least one optionally substituted heterocycle, said heterocycle comprising at least 2 carbon atoms and at least 1 nitrogen atom, preferably at least 2 nitrogen atoms, more preferentially at least three nitrogens.
- the amine function is substituted by an optionally substituted triazole group.
- the amine compound has the following formula XVII):
- R13 is selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group to C 8 linear or branched, a carboxylic acid group (-C0 2 H).
- R13 is a hydrogen atom.
- the amine compound consists of a linear or branched hydrocarbon chain C1-C50, preferably C 2 -C 30 comprising at least one amino group.
- the amine compound is chosen from
- the Rio groups are all identical.
- polyalkylenepolyamine is chosen from the polyethylenepolyamines of formula (XIX) below:
- q is an integer from 1 to 10, preferably from 3 to 5.
- the polyethylenepolyamine is chosen from ethylenediamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine. More preferably, the polyethylenepolyamine is tetraethylenepentamine.
- the succinic acid or succinic anhydride, substituted by a polyisobutene chain, and the amine compound are introduced in a molar ratio ranging from 0.2: 1 to 5: 1, preferably ranging from 0.2: 1 to 2.5: 1, even more preferably from 1: 1 to 2: 1.
- the reaction between the polyisobutenyl-substituted succinic acid or anhydride and the amine compound is preferably carried out at a temperature of at least 80 ° C, preferably at a temperature of 125 to 250 ° C.
- polyisobutene succinimide compound has the following formula (XX):
- R12 is a polyisobutenyl chain
- R11 is a hydrogen atom or a hydrocarbon group C1-C50, preferably C 2 -C 3 o comprising at least one nitrogen atom.
- the Ru group comprises at least one heterocycle, optionally substituted, said heterocycle comprising at least 2 carbon atoms and at least 1 nitrogen atom, preferably at least 2 nitrogen atoms, more preferably at least minus 3 nitrogen atoms.
- the Ru group consists of an optionally substituted triazole group.
- the group Ru corresponds to the following formula (XXI):
- R13 is selected from the group consisting of a hydrogen atom, an aliphatic hydrocarbon group to C 8 linear or branched, a carboxylic acid group (-C0 2 H).
- R13 is a hydrogen atom.
- the Ru group consists of a linear or branched hydrocarbon group C1-C50, preferably C 2 -C 3 o and comprising at least one amino group.
- the Ru group consists of a polyalkylenepolyamine chain of formula (XXI I) below:
- the groups Ri 0 are chosen independently from the C1-C5, preferably C 2 -C 3 , alkylene chains, and
- q is an integer ranging from 1 to 10, preferably from 3 to 5.
- polyalkylene polyamines are commercially available in the form of complex mixtures further comprising, in small amounts, cyclic compounds such as piperazines. Therefore, the detergent additives of The polyisobutenes succinimides described above are available in the form of mixtures which may additionally comprise, in a minor way, unreacted polyolefins, reaction solvent or by-products. It is common in the literature to refer to these mixtures as "alkenyl succinimide detergent".
- the fuel additive composition may advantageously comprise from 5 to 99% by weight, preferably from 10 to 80%, more preferably from 25 to 70% of succinimide compound (b) as described above.
- the mass ratio between the copolymer (s) (a) and the succinimide compound (b) ranges from 5: 95 to 95: 5, preferably 10: 90 to 90: 10.
- the fuel additive composition described above is particularly advantageous when 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 fuel additive composition described above is also particularly advantageous when it is used as a demulsifying additive in a liquid fuel of an internal combustion engine.
- demulsifying additive an additive which is incorporated in a small amount in the liquid fuel and improves the separation of water and fuel when the latter contains water.
- the use of the fuel additive composition according to the invention in a liquid fuel makes it possible both 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 internal parts of the internal combustion engine, with respect to a fuel not specially additivé.
- the use of the additive composition according to the invention also makes it possible to improve the separation of water and fuel when the latter contains water.
- “Improving the separation of water and fuel” means accelerating the separation, and / or increasing the rate of separation of the fuel and the residual water present in the fuel compared to a fuel comprising only:
- 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-substantially hydrocarbon fuel is understood to mean a fuel consisting of one or more compounds consisting essentially of carbon and hydrogen, that is to say which also contain other atoms, in particular oxygen atoms.
- Hydrocarbon fuels include in particular medium distillates boiling temperature ranging from 100 to 500 ° C or lighter distillates having a boiling point in the range of gasolines. These distillates may, for example, be chosen from distillates obtained by direct distillation of crude hydrocarbons, vacuum distillates, hydrotreated distillates, distillates obtained from catalytic cracking and / or hydrocracking of vacuum distillates, distillates resulting from methods of conversion type ARDS (in English "atmospheric residue desulfuration") and / or visbreaking, 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.
- species that comply with the NF EN 228 standard The essences generally have octane numbers that are sufficiently high to avoid the phenomenon of rattling.
- gasoline fuels marketed in Europe, compliant with the NF EN 228 standard have a motor octane number (MON) of greater than 85 and a research octane number (RON in English). Research Octane Number ”) of a minimum of 95.
- Gasoline fuels generally have an RON of 90 to 100 and a MON of 80 to 90, with RON and MON being measured according to ASTM D 2699- 86 or D 2700-86.
- Gas oils 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
- Mixtures of hydrocarbon fuel and hydrocarbon fuel are not essentially typically type diesel B or type E x x essences.
- 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
- the term fuel is designated by the term B100.
- 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 fuel additive composition described above is used 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, still more preferably from 10 to 1000 ppm.
- the use of a fuel additive composition 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 internal parts of the internal combustion engine.
- the use of the fuel additive composition 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 reduce existing deposits in at least one of the internal parts of said engine ("clean-up" effect).
- the use of the additive composition according to the invention 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 of said engine.
- the use of the fuel additive composition according to the invention in the liquid fuel makes it possible to observe both the effects, limitation (or prevention) and reduction of deposits (keep-clean and clean-up ").
- 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 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 Valve Deposit (IVD), the Combustion Chamber Deposit (CCD). Deposit ”) and the fuel injection system, in particular the injectors of an indirect fuel injection system (PFI) 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 fuel additive composition 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 power loss being determined according to the CEC F-98-08 normed engine test method.
- the fuel additive composition as described above may 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. operation, said flux restriction being determined according to the CEC standard engine test method F-23-1 -01.
- the use of the fuel additive composition as described above makes it possible, in comparison with the liquid fuel with no particular additive, to limit or avoid the formation of deposits on at least one type of deposits described above and / or to reduce existing deposits on at least one type of deposits described previously.
- the use of the fuel additive composition described above also makes it possible to reduce the fuel consumption of the internal combustion engine.
- the use of the fuel additive composition described above also makes it possible to reduce pollutant emissions, in particular the particulate emissions of the internal combustion engine.
- the use of the fuel additive composition according to the invention makes it possible to reduce both the fuel consumption and the pollutant emissions.
- the fuel additive composition described above may be used alone or in admixture with other fuel additives in the form of an additive concentrate.
- the fuel additive composition according to the invention can be added to the liquid fuel in a refinery and / or be incorporated downstream of the refinery and / or optionally mixed with other additives in the form of a fuel.
- a concentrate of additives also called according to the use "additive package”.
- a fuel concentrate comprises one or more copolymers (a) and one or more succinimide compounds (b) as described above, mixed with an organic liquid.
- the organic liquid is inert with respect to the copolymer (a) and the succinimide compound (b) described above and miscible in the liquid fuel described above.
- miscible means that the copolymer (a), the succinimide compound (b) and the organic liquid form a solution or a dispersion so as to facilitate the mixing of the additive composition according to the invention in liquid fuels. according to conventional methods of additive fuel.
- the organic liquid is advantageously chosen from aromatic hydrocarbon solvents such as the solvent sold under the name "SOLVESSO", alcohols, ethers and other oxygenated compounds and paraffinic solvents such as hexane, pentane or isoparaffins, alone or as a mixture.
- 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 as a 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 (a) 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 copolymer (a) and succinimide compound (b) being understood that the concentrate may comprise one or more copolymers (a) and one or more succinimide compounds (b) as described above.
- solubility of the copolymer (a) 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 copolymer (a) will be chosen so that the copolymer (a) 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 (a) may also have an influence on the effectiveness of the fuel additive composition according to the invention as a detergent additive.
- the average molar masses M w and M n will be chosen so as to optimize the effect of the copolymer (a), in particular the detergency effect (engine cleanliness) in the liquid fuels described above.
- the copolymer (a) 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 from 3000 to 8000 g, mol -1, even more preferably from 3000 to 7000 g. mol "1, particularly 4000 to 5000 g.mol" 1.
- Mw weight average molecular weight
- the average molar mass (Mn) is less than or equal to 4000 g. mol "1.
- the weight average molecular weight and number are measured by size exclusion chromatography (SEC English" Size Exclusion Chromatography ").
- SEC English Size Exclusion Chromatography ".
- the operating conditions of the SEC, including the choice of solvent will be chosen based on chemical functions present within the copolymer
- the fuel additive composition according to the invention 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 (a). and the succinimide compound (b) previously described.
- the additive concentrate may typically comprise one or more other additives selected from detergent additives different from the above-described copolymer and succinimide compound, for example from anti-corrosion agents, dispersants, demulsifiers other than the succinimide compound. described above, antifoam 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-settling agents, anti-wear agents and conductivity modifiers.
- detergent additives different from the above-described copolymer and succinimide compound
- demulsifiers other than the succinimide compound.
- antifoam agents biocides, deodorants, procetane additives, friction modifiers, lubricity additives or lubricity additives
- combustion assistants catalytic combustion promoters and soot
- 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 group consisting of long-chain olefin terpolymers / (meth) acrylic ester / maleimide ester, and fumaric / 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 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 10 to 1000 ppm (each), preferably from 100 to 1000 ppm (each).
- the molar ratio 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 copolymer is soluble in the fuel and or the organic liquid of the concentrate for which it is intended. Likewise, this ratio can be optimized according to the fuel and / or the organic liquid so as to obtain the best effect on engine cleanliness. The optimization of the molar and / or mass ratio can be carried out by routine tests accessible to those skilled in the art.
- the molar ratio between the monomer 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.
- a fuel composition is prepared according to any known method by adding the liquid fuel described above with a fuel additive composition as described above.
- a fuel composition comprises:
- the fuel (1) is, in particular, chosen from hydrocarbon fuels and non-essentially hydrocarbon fuels previously described, taken alone or as a mixture.
- the introduction, in particular the combustion, of this fuel composition comprising a fuel additive composition according to the invention in an internal combustion engine has an effect on the cleanliness of the engine compared to the liquid fuel that is not specially additive.
- the combustion of this fuel composition makes it possible, in particular, to prevent and / or reduce the fouling of the internal parts of said engine.
- the introduction of the additive composition according to the invention into an internal combustion engine fuel as defined above makes it possible to produce an effect on the demulsification of said fuel, compared to a fuel comprising only the copolymer ( a) or only the succinimide compound (b).
- the combustion of the fuel composition comprising such a fuel additive composition in an internal combustion engine also makes it possible to reduce the fuel consumption and / or the pollutant emissions.
- the fuel additive composition according to the invention is preferably incorporated in a small amount in the liquid fuel described above, the amount of fuel additive composition being sufficient to produce on the one hand a detergent effect and on the other hand a demulsifying effect as described above.
- the fuel composition advantageously comprises at least 1 ppm, preferably from 10 to 5 000 ppm, more preferably from 20 to 2000 ppm, in particular from 50 to 500 ppm of copolymer (s) (a).
- the fuel composition advantageously comprises from 1 to 1000 ppm, preferably from 5 to 500 ppm, more preferably from 10 to 200 ppm, and even more preferably from 20 to 100 ppm of copolymer (s). (at).
- the fuel composition advantageously comprises from 1 to 1000 ppm, preferably from 5 to 500 ppm, more preferably from 10 to 200 ppm, even more preferably from 20 to 100 ppm of succinimide compounds substituted with a hydrocarbon chain (b).
- the composition of The fuel may also comprise one or more other additives different from the copolymer (a) and the succinimide compound (b) present in the fuel additive composition according to the invention.
- additives are chosen in particular from the other known detergent additives, for example from anti-corrosion agents, dispersants, other demulsifying agents, antifoam agents, biocides, deodorants, procetane additives, friction modifiers, lubricant additives or lubricity additives, combustion assistants (catalytic combustion and soot promoters), cloud point improvers, pour point, TLF, anti-sedimentation agents, anti-wear agents and / or conductivity modifiers.
- 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 a fuel additive composition as described above and introduction, including 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 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 a 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 method comprises the successive steps of:
- step 2) incorporation into the fuel of the selected fuel additive composition at the rate determined in step 1) and, optionally, other fuel additives.
- the selection of the fuel additive composition corresponds more particularly to the selection on the one hand of one or more copolymers (a) as described above and on the other hand of one or more succinimide compounds (b). ) as described above but also to the determination of the ratio according to which these compounds will be introduced in order to prepare a fuel additive composition according to the invention.
- copolymer or copolymers (a) and the succinimide compound (s) (b) may be incorporated in the fuel, alone or as a mixture, successively or simultaneously.
- the fuel additive composition may be used in the form of an additive concentrate or concentrate as described above.
- Step 1) is carried out according to any known process and is a common practice in the field of fuel additives.
- This step involves defining at least one representative characteristic of the detergency properties of the fuel composition.
- the representative characteristic of the fuel detergency properties will depend on the type of internal combustion engine, for example diesel or spark ignition, the direct or indirect injection system and the location in the engine of the targeted deposits for cleaning and / or maintaining cleanliness.
- the characteristic characteristic of the fuel detergency properties may, for example, correspond to the loss of power due 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 determination of the amount of copolymer (a) and the amount of succinimide compound (b) to be added to the fuel composition to meet the specification (step 1) described above will typically be performed by comparison with the fuel composition.
- the specification relating to the detergency may for example be a target power loss value according to the DW10 method or a flow restriction value according to XUD9 method mentioned above.
- the keep-clean and / or clean-up method may also include an additional step after step 2) of checking the target reached and / or adjusting the rate of additive with the fuel additive composition and / or adjustment of the ratio according to which the copolymer (a) and the succinimide compound (b) are present in the fuel additive composition.
- a process for demulsifying or separating water from a fuel comprises:
- the process for demulsifying the fuel or for separating the water from the fuel comprises, between the step 1 ') and the step 2') defined above, a step a ') of determining the additive the most suitable for fuel, said additive corresponding to the selection of the fuel additive composition described above to be incorporated in combination, optionally, with other fuel additives as described above and the determination of the necessary treatment rate to achieve a given specification relating to the demulsification of the fuel composition.
- the selection of the fuel additive composition corresponds more particularly to the selection on the one hand of one or more copolymers (a) as described above and on the other hand of one or more succinimide compounds (b). ) as described above but also to the determination of the ratio according to which these compounds will be introduced in order to prepare a fuel additive composition according to the invention.
- the copolymer or copolymers (a) and the succinimide compound (s) (b) may be incorporated in the fuel, alone or as a mixture, successively or simultaneously.
- the fuel additive composition may be used in the form of a concentrate or an additive concentrate as described above.
- Stage a ' is carried out according to any known process and is a common practice in the field of fuel additives. This step involves defining at least one representative characteristic of the demulsification properties of the fuel composition.
- the representative characteristic of the demulsibility properties may for example correspond to a measurement of the volume of aqueous phase extracted from the fuel according to the ASTM D 1094 standard.
- Step 3 ') is also carried out according to any method known to those skilled in the art.
- step 3 ') can be carried out by decantation and separation of the additive fuel composition.
- the determination of the amount of fuel additive composition to be added to the fuel composition to achieve the specification (step a ') described above) will be typically performed by comparison with a fuel composition comprising only the copolymer (a) or only the succinimide compound (b).
- the determination of the amount of copolymer (a) and the amount of succinimide compound (b) to be added to the fuel composition to achieve the specification (steps a ') described above) will be typically performed by comparison with a composition of fuel comprising only the copolymer (a) or only the succinimide compound (b) present in the fuel additive composition according to the invention, the given specification relating to the dememulsion may for example be an aqueous phase volume extracted from the composition of fuel according to ASTM D 1094.
- the dememulsion process may also comprise an additional step after step 4 ') of checking the target reached and / or adjusting the additive rate with the additive composition and / or adjusting the ratio according to which copolymer (a) and succinimide compound (b) are present in the fuel additive composition.
- the amount of copolymer (a) and succinimide compound (b) may also vary depending on the nature and origin of the fuel, in particular depending on the level of n-alkyl, isoalkyl or n-alkenyl substituted compounds. . Thus, the nature and origin of the fuel may also be a factor to take into account for step a) and / or for step a ').
- the fuel additive composition according to the invention has remarkable properties as a detergent additive in a liquid fuel, particularly in a diesel or gasoline fuel.
- the fuel additive composition according to the invention is also remarkable in that it makes it possible to obtain fuel compositions having improved demulsification properties, with respect to that of fuel compositions comprising only a copolymer (a) or only a succinimide compound (b) as defined above.
- EXAMPLES 1 Synthesis of a block copolymer from 2-ethylhexyl acrylate (EHA) and 2-dimethylaminoethyl acrylate (ADAME) and quaternization with 1,2-epoxybutane
- the copolymer is obtained by radical polymerization by reversible addition-fragmentation chain transfer (RAFT) according to the following protocol.
- RAFT reversible addition-fragmentation chain transfer
- the chromatograph used is an UltiMate 300 HPLC marketed by Thermo Fischer.
- the stationary phase is a column of Symmetry Shield RP 18 type.
- the mobile phase consists of:
- the flow rate of the mobile phase is equal to 1 mL / min.
- the temperature of the oven is recorded at 40 ° C.
- the injection volume is 5 ⁇ L.
- the products are detected via a diode array detector.
- the 1 H and 13 C NMR spectroscopy analyzes were carried out in deuterated chloroform CDCl 3 with a BRUKER Avance III 400 MHz NMR spectrometer ( 1 H Larmor frequency) operating under TopSpin 3.2: 13 C SEXI Omm probe with pulsed magnetic field gradient z and lock 2 H operating at 300K and probe 1 H BBI 5mm with pulsed magnetic field gradient z and lock 2 H operating at 300K.
- an external standard (1,2,4,5-tetrachloro-3-nitrobenzene or TCNB) is used.
- the GPC analyzes are carried out in THF (tetrahydrofuran) using a WATERS Styragel type column operating at a temperature of 40 ° C. and at a pressure equal to 645 psi and equipped with an RI (refractive index) detector.
- the flow rate of THF is equal to 1 mL / min.
- M n The number average molar masses (M n ) are determined from calibration curves constructed from PMMA standards (poly (methyl methacrylate)). C-Copolymerization - Obtaining an EHA / ADAME Block Copolymer
- the AIBN solution is added to the EHA / CPDTTC mixture by means of a syringe previously purged with nitrogen.
- the reaction medium is stirred for 24 h at 70 ° C. under an inert atmosphere (N 2 ).
- the reaction medium is stirred for 24 h at 70 ° C. under an inert atmosphere (N 2 ). 250 ⁇ l of the reaction mixture are taken at t 0 (just after the addition of ⁇ ) and t f (after stirring 24h) and are analyzed by HPLC to measure the residual content of ADAME monomers present in the medium, before and after reaction. The ratio of the peak areas relative to the ADAME monomer makes it possible to determine an ADAME monomer conversion rate equal to 97%.
- the residual monomer levels of EHA and ADAME are determined by 1 H NMR spectroscopy and the relative composition of the copolymer (EHA / ADAME molar ratio) and the number of EHA and ADAME units by 13 C NMR.
- ADAME for ADAME residual monomers, a main series of signals obtained for chemical shift values equal to 6.43 ppm, 6.15 ppm and 5.82 ppm (AMX system). The assignment of these signals to the monomers ADAME is confirmed by the observation of two triplets of comparable intensity obtained for chemical shift values equal to 4.3 ppm and 2.7 ppm and linked to the groups -OCH 2 and -NCH 2 of the residual monomer.
- ADAME
- the Residual EHA is 0.1% by mass and the residual ADAME rate is 0.5% by mass.
- the signal obtained at 22.8 ppm attributed to the CH 3 CH 2 grouping of the RAFT terminal group is used.
- an integral of 0.95 is obtained for the broad signal obtained at 180.6 ppm and bound to the -COOH group of the RAFT agent.
- the block copolymer EHA / q-ADAME is obtained.
- the quaternization rate of the obtained copolymer was determined by NMR 13 C the solid obtained to 70 ppm is assigned to the CH 2 group of -CH2CHOHCH2CH 3 situated in the alpha position with respect to the quaternized nitrogen atom.
- EHA / ADAME 86/114
- Additive A2 succinimide compound substituted by a polyisobutyl chain corresponding to formula (XX) defined above in which Ru represents a triazole group corresponding to formula (XXI) and in which R13 is a hydrogen atom.
- Ru represents a triazole group corresponding to formula (XXI) and in which R13 is a hydrogen atom.
- the C 0 to C 5 fuel compositions are prepared by additivation of a virgin diesel fuel (GOM B7) meeting the EN590 standard containing 7% (vol / vol) or (v / v) of fatty acid methyl esters (FAMEs).
- GOM B7 virgin diesel fuel
- FAMEs fatty acid methyl esters
- composition C 0 corresponds to the virgin fuel which is not particularly additive: it constitutes a reference composition.
- compositions Ci to C 3 are comparative.
- compositions C 4 and C 5 are according to the invention.
- the detergency properties of the C 0 and C 3 to C 5 fuel compositions are evaluated according to the XUD9 engine test.
- 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.
- the objective of this XUD9 test is to evaluate the ability of the diesel fuel and / or the additive and / or the 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.
- Additivation of the fuel with the copolymer obtained above thus makes it possible to reduce the quantity of deposits formed at the level of the injectors during the operation of the engine, with respect to the non-additive fuel composition (composition C 0 ).
- the introduction into the fuel of the combination of the copolymer as defined above with one of the additives A1 or A2 (compositions C 4 and C 5 ) also significantly reduces the loss of flow of the engine.
- the demulsification properties of the C 0 to C 5 fuel compositions are also evaluated according to ASTM D 1094.
- compositions Ci to C 3 After 5 minutes of rest, the volume of water recovered from the compositions Ci to C 3 is zero. Even after 30 minutes of rest, no significant volume of water is recovered from the composition Ci. With regard to the compositions C 2 and C 3 , 2.5 ml of water are recovered after respectively 30 minutes and 15 minutes of rest.
- the additivation of the fuel with a succinimide additive or the copolymer as defined above results in a significant degradation of the demulsification properties of the fuel.
- the introduction into an internal combustion engine of such a fuel composition is likely to cause clogging of the engine filters or premature corrosion of the engine.
- the additive compositions according to the invention have remarkable properties as a detergent additive in a liquid fuel, in particular in a diesel fuel.
- the additive compositions according to the invention are also remarkable in that they make it possible to obtain fuel compositions having improved demulsification properties, with respect to that of fuel compositions comprising only a copolymer (a) or only one succinimide compound (b) as defined above.
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Graft Or Block Polymers (AREA)
- Liquid Carbonaceous Fuels (AREA)
- Solid Fuels And Fuel-Associated Substances (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1759201A FR3071850B1 (fr) | 2017-10-02 | 2017-10-02 | Composition d’additifs pour carburant |
PCT/FR2018/052424 WO2019069010A1 (fr) | 2017-10-02 | 2018-10-02 | Composition d'additifs pour carburant |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3692117A1 true EP3692117A1 (fr) | 2020-08-12 |
Family
ID=60450870
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP18796711.2A Withdrawn EP3692117A1 (fr) | 2017-10-02 | 2018-10-02 | Composition d'additifs pour carburant |
Country Status (4)
Country | Link |
---|---|
US (1) | US20200208070A1 (fr) |
EP (1) | EP3692117A1 (fr) |
FR (1) | FR3071850B1 (fr) |
WO (1) | WO2019069010A1 (fr) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR3087788B1 (fr) | 2018-10-24 | 2021-06-25 | Total Marketing Services | Association d'additifs pour carburant |
EP3887488B1 (fr) | 2018-11-30 | 2023-01-04 | TotalEnergies OneTech | Composé amidoamine gras quaternaire destiné à être utilisé en tant qu'additif pour carburant |
CA3175760A1 (fr) | 2020-04-22 | 2021-10-28 | Totalenergies One Tech | Compositions de piegeage de sulfure d'hydrogene et de mercaptans |
Family Cites Families (37)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3048479A (en) | 1959-08-03 | 1962-08-07 | Exxon Research Engineering Co | Ethylene-vinyl ester pour depressant for middle distillates |
NL124306C (fr) | 1959-08-24 | |||
NL124842C (fr) | 1959-08-24 | |||
US3231587A (en) | 1960-06-07 | 1966-01-25 | Lubrizol Corp | Process for the preparation of substituted succinic acid compounds |
US3627838A (en) | 1964-12-11 | 1971-12-14 | Exxon Research Engineering Co | Process for manufacturing potent pour depressants |
US3790359A (en) | 1969-03-17 | 1974-02-05 | Exxon Research Engineering Co | Middle distillate fuel having increased low temperature flowability |
US3961961A (en) | 1972-11-20 | 1976-06-08 | Minnesota Mining And Manufacturing Company | Positive or negative developable photosensitive composition |
US4129508A (en) | 1977-10-13 | 1978-12-12 | The Lubrizol Corporation | Demulsifier additive compositions for lubricants and fuels and concentrates containing the same |
US4171959A (en) * | 1977-12-14 | 1979-10-23 | Texaco Inc. | Fuel composition containing quaternary ammonium salts of succinimides |
FR2528051B1 (fr) | 1982-06-08 | 1986-05-02 | Inst Francais Du Petrole | Additifs azotes utilisables comme agents d'abaissement du point de trouble des distillats moyens d'hydrocarbures et compositions de distillats moyens d'hydrocarbures renfermant lesdits additifs |
FR2528423B1 (fr) | 1982-06-10 | 1987-07-24 | Inst Francais Du Petrole | Additifs azotes utilisables comme agents d'abaissement du point de trouble des distillats moyens d'hydrocarbures et compositions de distillats moyens d'hydrocarbures renfermant lesdits additifs |
FR2535723A1 (fr) | 1982-11-09 | 1984-05-11 | Inst Francais Du Petrole | Additifs azotes utilisables comme agents d'abaissement du point de trouble des distillats moyens d'hydrocarbures et compositions de distillats moyens d'hydrocarbures renfermant lesdits additifs |
FR2567536B1 (fr) | 1984-07-10 | 1986-12-26 | Inst Francais Du Petrole | Compositions d'additifs destinees notamment a ameliorer les proprietes de filtrabilite a froid des distillats moyens de petrole |
IN184481B (fr) | 1986-09-24 | 2000-08-26 | Exxon Chemical Patents Inc | |
FR2607139B1 (fr) | 1986-11-21 | 1989-08-18 | Inst Francais Du Petrole | Polymeres a fonctions azotees derives de polyesters insatures et leur utilisation comme additifs d'abaissement du point d'ecoulement des distillats moyens d'hydrocarbures |
FR2613371B1 (fr) | 1987-04-01 | 1989-07-07 | Inst Francais Du Petrole | Copolymeres azotes, leur preparation et leur utilisation comme additifs pour ameliorer les proprietes d'ecoulement des distillats moyens d'hydrocarbures |
GB9104138D0 (en) | 1991-02-27 | 1991-04-17 | Exxon Chemical Patents Inc | Polymeric additives |
GB9219962D0 (en) | 1992-09-22 | 1992-11-04 | Exxon Chemical Patents Inc | Additives for organic liquids |
GB9301119D0 (en) | 1993-01-21 | 1993-03-10 | Exxon Chemical Patents Inc | Fuel composition |
WO1998001478A1 (fr) | 1996-07-10 | 1998-01-15 | E.I. Du Pont De Nemours And Company | Polymerisation presentant des caracteristiques vivantes |
FR2751982B1 (fr) | 1996-07-31 | 2000-03-03 | Elf Antar France | Additif d'onctuosite pour carburant moteurs et composition de carburants |
JPH10237467A (ja) | 1997-02-26 | 1998-09-08 | Tonen Corp | ディーゼルエンジン用燃料油組成物 |
US5730029A (en) | 1997-02-26 | 1998-03-24 | The Lubrizol Corporation | Esters derived from vegetable oils used as additives for fuels |
IL136389A0 (en) | 1997-12-18 | 2001-06-14 | Du Pont | Polymerization process with living characteristics and polymers made therefrom |
FR2772784B1 (fr) | 1997-12-24 | 2004-09-10 | Elf Antar France | Additif d'onctuosite pour carburant |
FR2772783A1 (fr) | 1997-12-24 | 1999-06-25 | Elf Antar France | Additif d'onctuosite pour carburant |
AUPQ679400A0 (en) | 2000-04-07 | 2000-05-11 | Commonwealth Scientific And Industrial Research Organisation | Microgel synthesis |
EP1390455A2 (fr) | 2001-02-14 | 2004-02-25 | The Lubrizol Corporation | Composition d'additifs pour carburants, composition de carburants et procede associe |
WO2005000924A1 (fr) | 2003-06-26 | 2005-01-06 | Symyx Technologies, Inc. | Polymeres a base de photoresist |
TWI329024B (en) | 2003-06-26 | 2010-08-21 | Suntory Holdings Ltd | Composition for skin, kit for skin and skin permeation enhancer |
DE602005003352T2 (de) | 2004-05-12 | 2008-09-04 | Commonwealth Scientific And Industrial Research Organisation | Verfahren zur entfernung von schwefelhaltigen endgruppen |
CN102174340B (zh) * | 2005-06-16 | 2013-01-30 | 卢布里佐尔公司 | 润滑组合物所用的季铵盐清洁剂 |
GB201007756D0 (en) | 2010-05-10 | 2010-06-23 | Innospec Ltd | Composition, method and use |
FR2994695B1 (fr) | 2012-08-22 | 2015-10-16 | Total Raffinage Marketing | Additifs ameliorant la resistance a l'usure et au lacquering de carburants de type gazole ou biogazole |
US10174269B2 (en) * | 2013-07-12 | 2019-01-08 | Basf Se | Use of a hydrocarbyl-substituted dicarboxylic acid for improving or boosting the separation of water from fuel oils and gasoline fuels |
FR3017876B1 (fr) | 2014-02-24 | 2016-03-11 | Total Marketing Services | Composition d'additifs et carburant de performance comprenant une telle composition |
FR3041349B1 (fr) * | 2015-09-18 | 2020-01-24 | Total Marketing Services | Copolymere utilisable comme additif detergent pour carburant |
-
2017
- 2017-10-02 FR FR1759201A patent/FR3071850B1/fr active Active
-
2018
- 2018-10-02 WO PCT/FR2018/052424 patent/WO2019069010A1/fr unknown
- 2018-10-02 EP EP18796711.2A patent/EP3692117A1/fr not_active Withdrawn
- 2018-10-02 US US16/645,998 patent/US20200208070A1/en not_active Abandoned
Also Published As
Publication number | Publication date |
---|---|
FR3071850A1 (fr) | 2019-04-05 |
WO2019069010A1 (fr) | 2019-04-11 |
US20200208070A1 (en) | 2020-07-02 |
FR3071850B1 (fr) | 2020-06-12 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP3350232B1 (fr) | Composition de carburant comprenant un copolymere blocs comme additif detergent | |
WO2018015666A1 (fr) | Copolymere utilisable comme additif detergent pour carburant | |
EP3692117A1 (fr) | Composition d'additifs pour carburant | |
EP3487892A1 (fr) | Copolymere et son utilisation comme additif detergent pour carburant | |
EP3350293A1 (fr) | Additif detergent pour carburant | |
WO2017109370A1 (fr) | Utilisation d'un additif detergent pour carburant | |
WO2019091950A1 (fr) | Nouveau copolymère et son utilisation comme additif pour carburant | |
WO2019068845A1 (fr) | Composition d'additifs pour carburant | |
WO2019110911A1 (fr) | Composition d'additifs pour carburant | |
EP3720931A1 (fr) | Utilisation d'un copolymere particulier pour prevenir les depôts sur les soupapes des moteurs a injection indirecte essence | |
EP3394225A1 (fr) | Additif détergent pour carburant | |
WO2017109369A1 (fr) | Additif détergent pour carburant et copolymères utilisables dans cette application | |
WO2018015667A1 (fr) | Utilisation de copolymeres pour ameliorer les proprietes a froid de carburants ou combustibles | |
EP3870684A1 (fr) | Association d'additifs pour carburant | |
FR3041361A1 (fr) | Additif detergent pour carburant | |
WO2019110912A1 (fr) | Composition d'additifs pour carburant |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: UNKNOWN |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20200324 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN |
|
18W | Application withdrawn |
Effective date: 20220331 |