EP3844251A1 - Composition of additives, comprising at least one copolymer, one cold-flow improver and one anti-settling additive - Google Patents

Composition of additives, comprising at least one copolymer, one cold-flow improver and one anti-settling additive

Info

Publication number
EP3844251A1
EP3844251A1 EP19758410.5A EP19758410A EP3844251A1 EP 3844251 A1 EP3844251 A1 EP 3844251A1 EP 19758410 A EP19758410 A EP 19758410A EP 3844251 A1 EP3844251 A1 EP 3844251A1
Authority
EP
European Patent Office
Prior art keywords
composition
additive
weight
fuel
copolymer
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.)
Pending
Application number
EP19758410.5A
Other languages
German (de)
French (fr)
Inventor
Frédéric Tort
Thomas Dubois
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
TotalEnergies Onetech SAS
Original Assignee
Total Marketing Services SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Total Marketing Services SA filed Critical Total Marketing Services SA
Publication of EP3844251A1 publication Critical patent/EP3844251A1/en
Pending legal-status Critical Current

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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
    • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
    • 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
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
    • 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
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
    • C10L10/16—Pour-point depressants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
    • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/221—Organic compounds containing nitrogen compounds of uncertain formula; reaction products where mixtures of compounds are obtained
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C10L1/2368—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing heterocyclic compounds containing nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
    • C10L2200/0446—Diesel
    • 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
    • C10L2200/0476—Biodiesel, i.e. defined lower alkyl esters of fatty acids first generation biodiesel

Definitions

  • Additive composition comprising at least one copolymer, a cold-thinning additive and an anti-sedimentation additive
  • the present invention relates to a composition of particular additives and its use for improving the cold-keeping properties of fuels and combustibles during their storage and / or their use at low temperature.
  • the present invention also relates to fuel compositions and fuel containing such an additive composition.
  • Fuels or combustibles containing paraffinic compounds in particular compounds containing n-alkyl, iso-alkyl or n-alkenyl groups such as paraffinic waxes, are known to exhibit deteriorated flow properties at low temperature, typically below 0 ° C.
  • the middle distillates obtained by distillation from crude oils of petroleum origin such as diesel or heating oil, contain different amounts of n-alkanes or n-paraffins depending on their origin. These compounds tend to crystallize at low temperatures, clogging hoses, pipes, pumps and filters, for example in the fuel circuits of motor vehicles.
  • cold flow improvers in English “cold flow improvers” or CFI
  • CFI cold thinning additives
  • TLF Filterability Limit Temperature
  • PE pour point
  • TLF additives polymers of ethylene and vinyl acetate and / or vinyl propionate
  • an additive consisting of 90 to 10% by mass of an ethylene copolymer comprising from 10 to 30% of vinyl acetate units with a molecular weight by weight of between 1000 and 3000 g.mol and from 10 to 90% by weight of a lauryl polyacrylate and / or of a polymethyl lauryl methacrylate of varying weight by weight from 760 to 100,000 g.mol- l.
  • Document EP0857776 proposes using alkylphenol-aldehyde resins resulting from the condensation of alkylphenol and aldehyde in combination with ethylene / vinyl ester copolymers or terpolymers, to improve the fluidity of mineral oils.
  • Patent application WO 2008/006965 describes the use of a combination of a homopolymer obtained from an olefinic ester of carboxylic acid of 3 to 12 carbon atoms and a fatty alcohol comprising a chain of 16 carbon atoms and possibly an olefinic double bond and of a cold fluidizing additive (CFI) of EVA or EVP type, to increase the effectiveness of CFI additives by amplifying their effect on TLF.
  • CFI cold fluidizing additive
  • Patent application WO 2016/128379 describes the use, as a cold-keeping additive of a fuel or combustible, of a block copolymer comprising:
  • a block A consisting of a chain of structural units derived from one or more ⁇ , b-unsaturated acrylate or alkyl methacrylate monomers
  • a block B consisting of a chain of structural units derived from one or more a, b-unsaturated monomers containing at least one aromatic nucleus.
  • This additive is particularly useful as a TLF booster in combination with a cold thinning additive (CFI).
  • CFI cold thinning additive
  • Another object of the cold-keeping additives is to ensure the dispersion of the paraffin crystals, so as to delay or prevent the sedimentation of such crystals and of avoid training a layer rich in paraffins at the bottom of containers, tanks or storage tanks; these paraffin dispersant additives are called anti-sedimentation additives or WASA (acronym of the English term "Wax Anti-Settling Additive").
  • WASA anti-sedimentation additives
  • Modified alkylphenol-aldehyde resins have been described in document FR2969620 as an anti-sedimentation additive in combination with a TLF additive.
  • This need is particularly important for fuels or fuels comprising one or more paraffinic compounds, for example compounds containing n-alkyl, iso-alkyl or n-alkenyl groups exhibiting a tendency to crystallize at low temperature.
  • paraffinic compounds for example compounds containing n-alkyl, iso-alkyl or n-alkenyl groups exhibiting a tendency to crystallize at low temperature.
  • distillates used in fuels and fuels are increasingly produced from more complex refining operations than those resulting from direct petroleum distillation, and can originate in particular from cracking, hydrocracking, catalytic cracking and visbreaking processes.
  • the refiner tends to introduce into these fuels cuts that are more difficult to use, such as the heavier cuts resulting from cracking and visbreaking processes which are rich in long chain paraffins.
  • the present invention applies to fuels and combustibles containing not only conventional distillates such as those resulting from the direct distillation of crude oils, but also to bases obtained from other sources, such as those described above.
  • the object of the present invention is to propose a new composition of additives which can advantageously be used to improve the cold-keeping properties, in particular the cold-flow properties of these fuels or combustibles, during their storage. and / or their use at low temperature, typically below 0 ° C.
  • the aim of the present invention is further to propose a new composition of additives for fuels and combustibles, and concentrates containing such a composition, acting on the Filterability Limit Temperature (TLF), the pour point (PE), and delaying and / or preventing the sedimentation of crystals of hydrocarbon compounds, in particular paraffins.
  • TEZ Filterability Limit Temperature
  • PE pour point
  • Another object of the invention is to provide a fuel or fuel composition having improved cold-holding properties, in particular at temperatures below 0 ° C, preferably below -5 ° C.
  • composition of additives comprising:
  • Ri represents a hydrogen atom or a methyl group
  • X represents -O-CO-, or -CO-O- or -NH-CO- or -CO-NH-, and
  • R2 represents a C1 to C24 alkyl group
  • R represents a C 2 to C 34 group, comprising at least one nitrogen heterocycle
  • At least one cold-thinning additive chosen from copolymers of ethylene and of unsaturated ester (s);
  • the invention also relates to the use of the composition of additives according to the invention for improving the cold-keeping properties of a fuel or fuel composition.
  • the invention also relates to a concentrate of additives containing such a composition, as well as a fuel or fuel composition.
  • CN compound or group denotes a compound or group containing in its chemical structure N carbon atoms.
  • composition of additives is a composition of additives:
  • the invention uses an additive composition comprising at least one copolymer comprising at least one unit of formula (I) below:
  • Ri represents a hydrogen atom or a methyl group
  • X represents -O-CO-, or -CO-O- or -NH-CO- or -CO-NH-, and
  • R2 represents a C 1 to C 24 alkyl group.
  • X -O-CO-, it being understood that X is then linked to the vinyl carbon by the oxygen atom;
  • X -CO-O-, it being understood that X is then linked to the vinyl carbon by the carbon atom;
  • X -CO-NH-, it being understood that X is then linked to the vinyl carbon by the carbon atom.
  • the group X of formula (I) is preferably the group -O- CO-.
  • the group X of formula (I) is chosen from: -CO-O- and -CO-NH-, it being understood that the group X is linked to the vinyl carbon by the carbon atom.
  • the group X of formula (I) is preferably the group -CO-O-.
  • the group X is a group -CO-O-, X being linked to the vinyl carbon by the carbon atom.
  • the group R 2 of formula (I) is a C 1 to C 24 alkyl radical.
  • This alkyl radical can be linear or branched, cyclic or acyclic.
  • This alkyl radical can comprise a linear or branched part and a cyclic part.
  • the group R2 of formula (I) is an acyclic linear or branched C8-C24, preferably C10-C22, more preferably C12-C22, alkyl radical.
  • the group R2 of formula (I) is a linear or branched C12-C14 acyclic alkyl radical.
  • the group R2 of formula (I) is a linear or branched C18-C22 acyclic alkyl radical.
  • R2 groups of alkyl groups such as octyl, decyl, dodecyl, ethyl-2-hexyl, isooctyl, isodecyl, isododecyl. , lauryl, stearyl, octadecyl, behenyl, C 14 alkyl groups.
  • the group X is a group -CO-O-, X being linked to the vinyl carbon by the carbon atom, and the group R2 is a linear or branched C8-C24 acyclic alkyl radical, preferably in C10-C22, more preferably in C12-C22.
  • the units according to this embodiment correspond to those derived from monomers chosen from acrylates and alkyl methacrylates of C8-C24, preferably of C10-C22, more preferably of C12-C22.
  • the group X is a group -CO-O-, X being linked to the vinyl carbon by the carbon atom, and the group R2 is a linear or branched C12-C14 acyclic alkyl radical.
  • the patterns according to this embodiment correspond to those from monomers chosen from acrylates and C12-C14 alkyl methacrylates.
  • the group X is a group -CO-O-, X being linked to the vinyl carbon by the carbon atom, and the group R2 is an alkyl radical linear acyclic or branched C 1 8 - C 22.
  • the units according to this embodiment correspond to those derived from monomers chosen from acrylates and C 1 8 -C 22 alkyl methacrylates.
  • the copolymer used in the present invention also comprises at least one unit of formula (II) below:
  • R represents a group from C 2 to C 34, preferably from C 2 to C 1 2, more preferably from C 2 to Ce, and comprising at least one nitrogen heterocycle.
  • nitrogen heterocycle denotes, in a manner known per se, a cyclic group comprising carbon atoms and at least one nitrogen atom in the ring.
  • the group R can be saturated or unsaturated, monocyclic or polycyclic, it being possible for the ring or rings to be substituted or unsubstituted.
  • the substituent (s) optionally present on the cycle (s) may be saturated or unsaturated, and may in particular be chosen from hydrocarbon, oxygenated, nitrogenous, halogenated substituents, etc.
  • the nitrogen heterocycle (s) are chosen from rings formed from 5 to 7 atoms among which 1, 2, 3 or 4 atoms are nitrogen atoms, these cycles being saturated or unsaturated, substituted or unsubstituted.
  • nitrogen heterocycles the following cycles may be cited: pyrrolidine, pyrroline, pyrrole, pyrazolidine, imidazolidine, pyrazoline, imidazoline, pyrazole, imidazole, triazole, tetrazole, piperidine, pyridine, piperazine, pyridazine, pyrimidine, pyrazine, triazine.
  • the nitrogen hetero ring (s) may also contain, in addition to carbon and nitrogen atoms, one or more other heteroatoms such as in particular one or more oxygen atoms, which can be part of the cycle or be attached to it.
  • one or more other heteroatoms such as in particular one or more oxygen atoms, which can be part of the cycle or be attached to it.
  • the group R contains at least one nitrogen heterocycle having from one to three nitrogen atoms, more preferably two nitrogen atoms.
  • Preferred R groups are in particular chosen from the following rings: a substituted or unsubstituted imidazole ring, a substituted or unsubstituted triazole ring, a substituted or unsubstituted pyrrolidone ring.
  • the group R is a substituted or unsubstituted imidazole ring.
  • the units of formula (II) come from one or more vinyl monomers carrying an R group as described above.
  • Examples of preferred monomers that may be mentioned include:
  • the copolymer used in the present invention may or may not be crosslinked. Preferably, it is not crosslinked.
  • the copolymer according to the invention advantageously contains from 50 to 99 mol% of units of formula (I), preferably from 60 to 95 mol%, more preferably from 70 to 90 mol%, and better still from 75 to 85 % in moles.
  • the copolymer according to the invention advantageously contains from 1 to 50 mol% of units of formula (II), preferably from 5 to 40 mol%, more preferably from 10 to 30 mol%, and better still from 15 to 25 % in moles.
  • the copolymer used in the present invention contains only units of formula (I) and units of formula (II).
  • the copolymer used in the present invention is advantageously a random copolymer or a block copolymer. According to a particularly preferred embodiment, it is a random copolymer.
  • the copolymer used in the present invention can be obtained by copolymerization of:
  • Ri, X and R 2 are as defined above, the preferred variants of Ri, X and R 2 according to formula (I) described above also being preferred variants of formula (IA), and
  • the monomer of formula (IA) is preferably chosen from Cs to C 24 , preferably Cio to C 24 , more preferably C 2 to C 22 vinyl alkyl esters.
  • the monomer of formula (IA) is chosen from C 1 to C 4 alkyl vinyl esters.
  • the monomer of formula (IA) is chosen from C 1 to C 22 alkyl vinyl esters.
  • the alkyl radical of the vinyl alkyl ester is linear or branched, cyclic or acyclic, preferably acyclic.
  • vinyl ester alkyl monomers that may be mentioned, for example, vinyl octanoate, vinyl decanoate, vinyl dodecanoate, vinyl tetradecanoate, vinyl 2-ethylhexanoate.
  • the monomer of formula (IA) is typically chosen from Cs to C 24, preferably Cio to C 24, more preferably C 12 to C 22 alkyl acrylates and methacrylates. According to a particular embodiment, the monomer of formula (IA) is chosen from acrylates and C 1 2 to C 1 4 alkyl methacrylates. According to another particular embodiment, the monomer of formula (IA) is chosen from acrylates and C 1 to C 22 alkyl methacrylates.
  • alkyl (meth) acrylates which can be used as monomers in the manufacture of the copolymer used in the invention, mention may be made of C Ce to C 24 alkyl acrylates and of C à to C alkyl methacrylates 24, and in particular, by way of nonlimiting examples: n-octyl acrylate, n-octyl methacrylate, n-decyl acrylate, n-decyl methacrylate, n-dodecyl acrylate , n-dodecyl methacrylate, ethyl-2-hexyl acrylate, ethyl-2-hexyl methacrylate, isooctyl acrylate, isooctyl methacrylate, isodecyl acrylate, isodecyl methacrylate, lauryl acrylate, stearyl acrylate, octadecyl acrylate,
  • the monomers of formula (IIA) are vinyl monomers carrying an R group as described above.
  • the group R contains at least one unsaturated nitrogen heterocycle having from one to three nitrogen atoms, more preferably two atoms nitrogen, such as in particular an imidazole ring, substituted or unsubstituted.
  • the copolymer used in the invention were obtained from monomers different from those of formula (IA) and (IIA) above, insofar as the final copolymer corresponds to a polymer comprising units of formula (I) and units of formula (II) as defined above.
  • the polymer were obtained by polymerization of different monomers, followed by post-functionalization.
  • the units of formula (I) can be obtained from acrylic acid, by transesterification reaction.
  • the copolymer used in the invention can be prepared by any known method of polymerization.
  • the various techniques and conditions of polymerization and crosslinking are widely described in the literature and fall within the general knowledge of a person skilled in the art.
  • a polymerization is advantageously chosen from controlled radical polymerization; for example, by atomic transfer radical polymerization (ATRP in English “Atom Transfer Radical Polymerization”); radical polymerization with nitroxide (NMP in English “Nitroxide-mediated polymerization”); degenerative transfer processes (in English “degenerative transfer processes”) such as degenerative iodine transfer polymerization (in English “ITRP- iodine transfer radical polymerization ”) or radical polymerization by reversible chain transfer by addition-fragmentation (RAFT in English“ Reversible Addition-Fragmentation Chain Transfer ”); polymerizations derived from ATRP such as polymerizations using initiators for continuous regeneration of the activator (ICAR -Initiators for continuous activator regeneration) or using activators regenerated by electron transfer (ARGET in English "activators regenerated by electron transfer ”).
  • ATRP atomic transfer radical polymerization
  • NMP radical polymerization with nitroxide
  • degenerative transfer processes in English “de
  • the copolymer used in the invention advantageously has a weight-average molar mass (M w ) of between 1,000 and 50,000 g. mol 1 , more preferably between 1,000 and 20,000 g. mol 1 , even more preferably between 3,000 and 15,000 g. mol 1 .
  • the copolymer according to the invention advantageously has a number-average molar mass (Mn) of between 1,000 and 50,000 g. mol 1 , more preferably between 1,000 and 20,000 g. mol 1 , even more preferably between 2,000 and 10,000 g. mol 1 .
  • Mn number-average molar mass
  • the number and weight average molar masses are measured by size exclusion chromatography (SEC).
  • composition of additives according to the invention may advantageously comprise from 0.1 to 30% by weight of copolymer as described above, preferably from 1 to 20% by weight, more preferably from 2 to 10% by weight, per relative to the total weight of the additive composition.
  • the additive composition according to the invention also comprises at least one cold-thinning additive (CEI) chosen from copolymers of ethylene and of unsaturated ester (s).
  • CEI cold-thinning additive
  • the cold-thinning additive is chosen from copolymers of ethylene and of vinyl ester (s) and / or acrylic (s), such as ethylene / vinyl acetate (EVA), ethylene copolymers. / vinyl propionate (EVP), ethylene / vinyl ethanoate (EVE), ethylene / methyl methacrylate (EMMA), and ethylene / alkyl fumarate described, for example, in documents US3048479, US3627838, US3790359, US3961961 and EP261957 . We may also cite terpolymers of ethylene, vinyl acetate and another vinyl ester, for example vinyl neodecanoate.
  • EVA ethylene / vinyl acetate
  • EVE ethylene / vinyl ethanoate
  • EMMA ethylene / methyl methacrylate
  • alkyl fumarate described, for example, in documents US3048479, US3627838, US3790359, US3961961 and EP261957
  • the cold fluidizing additive is chosen from copolymers of ethylene and vinyl ester (s), preferably from ethylene / vinyl acetate (EVA) copolymers, ethylene vinyl propionate copolymers (TEUs) and terpolymers of ethylene, vinyl acetate and another vinyl ester; more preferably still, ethylene / vinyl acetate copolymers and their mixtures with a terpolymer of ethylene, vinyl acetate and another vinyl ester, such as in particular vinyl neodecanoate.
  • EVA ethylene / vinyl acetate
  • TOUs ethylene vinyl propionate copolymers
  • terpolymers of ethylene, vinyl acetate and another vinyl ester more preferably still, ethylene / vinyl acetate copolymers and their mixtures with a terpolymer of ethylene, vinyl acetate and another vinyl ester, such as in particular vinyl neodecanoate.
  • composition of additives according to the invention may advantageously comprise from 50 to 90% by weight of cold-thinning additive (CFI) as described above, preferably from 60 to 90% by weight, more preferably from 70 to 90% by weight relative to the total weight of the additive composition.
  • CFI cold-thinning additive
  • the additive composition according to the invention also comprises at least one paraffin dispersant and / or dispersant additive.
  • (WASA) can be in particular, but not limited to, chosen from the group consisting of acid copolymers
  • (meth) acrylic / (meth) acrylate amidified by a polyamine the condensation products of one or more carboxylic acids with one or more polyamines, alkenyl succinimides of polyamine, phthalamic acid and fatty amine derivatives double chain; optionally grafted alkylphenol resins, modified alkylphenol-aldehyde resins.
  • additives are given in the following documents: EP261959, EP59333 1, EP674689, EP327423, EP5 12889, EP832172; US2005 / 022363 1;
  • the particularly preferred anti-sedimentation and / or paraffin dispersant (WASA) additive is chosen from resins alkylphenol and alkylphenol resins grafted, for example, by functional groups such as polyamines.
  • the additive composition according to the invention may advantageously comprise from 1 to 50% by weight of anti-sedimentation additive and / or paraffin dispersant as described above, preferably from 2 to 30% by weight, more preferably from 5 to 20% by weight relative to the total weight of the additive composition.
  • the additive composition according to the invention may also comprise one or more other additives commonly used in fuels or combustibles, different from the copolymer, the cold-keeping additive, and the anti-sedimentation additive described above.
  • the additive composition can typically include one or more other additives chosen from detergents, anti-corrosion agents, dispersants, demulsifiers, biocides, reodorants, procetane additives, friction modifiers, lubricant additives or oiliness additives, combustion aid agents (catalytic combustion and soot promoters), antiwear agents and / or agents modifying conductivity.
  • additives chosen from detergents, anti-corrosion agents, dispersants, demulsifiers, biocides, reodorants, procetane additives, friction modifiers, lubricant additives or oiliness additives, combustion aid agents (catalytic combustion and soot promoters), antiwear agents and / or agents modifying conductivity.
  • procetane additives in particular (but not limited to) chosen from alkyl nitrates, preferably 2-ethyl hexyl nitrate, aryl peroxides, preferably benzyl peroxide, and alkyl peroxides, preferably tert-butyl peroxide;
  • anti-foam additives in particular (but not limited to) chosen from polysiloxanes, oxyalkylated polysiloxanes, and fatty acid amides derived from vegetable or animal oils. Examples of such additives are given in EP861882, EP663000, EP736590;
  • detergent and / or anti-corrosion additives in particular (but not limited to) chosen from the group consisting of amines, succinimides, alkenyl succinimides, polyalkylamines, polyalkyl polyamines, polyetheramines, ammonium salts quaternary and triazole derivatives; examples of such additives are given in the following documents: EP0938535,
  • the present invention also relates to the use, to improve the cold-keeping properties of a fuel or fuel composition, of the composition of additives according to the invention.
  • Said fuel or fuel composition can be a composition chosen from gas oils, biodiesel, gas oils of type B x containing x% (v / v) of vegetable or animal oil esters or fatty acids, oils hydrogenated vegetables, and fuel oils such as domestic fuel oils, x being a number strictly greater than 0 and less than or equal to 100.
  • the fuel or fuel composition is as described below and advantageously comprises at least one section of hydrocarbons obtained from one or more sources chosen from the group consisting of mineral sources, preferably petroleum, animal sources , vegetable and synthetic.
  • said additive composition is used to improve the low temperature flow properties of the fuel or fuel during its storage and / or use. at low temperature, by lowering its filterability limit temperature (or TLF, measured according to standard NF EN 1 16) and / or its pour point (or PE, measured according to standard ASTM D 7346) and / or by delaying or by preventing the sedimentation of crystals, and preferably by lowering its limit filterability temperature (TLF, measured according to standard NF EN 1 16).
  • TLF filterability limit temperature
  • PE pour point
  • the additive composition according to the invention can be used to delay or prevent the sedimentation of paraffin crystals and more particularly of n-alkanes, preferably, the n-alkanes containing at least 12 carbon atoms, more preferably at least 20 carbon atoms.
  • the present invention also relates to a concentrate of additives comprising the composition of additives according to the invention, in admixture with an organic liquid.
  • the organic liquid is advantageously inert with respect to the constituents of the additive composition, and miscible with fuels or combustibles, in particular those originating from one or more sources chosen from the group consisting of mineral sources, preferably the petroleum, animal, vegetable and synthetic.
  • the organic liquid is preferably chosen from aromatic hydrocarbon solvents such as the solvent sold under the name "Solvesso 150", alcohols, ethers and other oxygenated compounds, and paraffinic solvents such as hexane, pentane or isoparaffins, alone or as a mixture.
  • the invention also relates to a fuel or fuel composition, comprising: (1) at least one cut of hydrocarbons from one or more sources chosen from the group consisting of mineral, animal, plant and synthetic sources, and
  • the mineral sources are preferably petroleum.
  • the fuel or fuel composition according to the invention advantageously comprises the copolymer (s) in a content of at least 0.0001% by weight, relative to the total weight of the fuel or fuel composition.
  • the content of copolymer (s) ranges from 0.0001 to 0.01% by weight, more preferably from 0.0002 to 0.005% by weight relative to the total weight of the fuel or fuel composition.
  • the fuel or fuel composition according to the invention advantageously comprises the additive or additives cold thinning in a content ranging from 0.0005 to 0.2% by weight, preferably from 0.001 to 0.1% by weight, more preferably from 0.0015 to 0.05% by weight relative to the total weight of the fuel or fuel composition.
  • the fuel or fuel composition according to the invention advantageously comprises the anti-sedimentation additive or additives and / or paraffin dispersant (s) in a content ranging from 0.0001 to 0.1% by weight, preferably from 0 .0005 to 0.05% by weight, more preferably from 0.001 to 0.02% by weight, relative to the total weight of the fuel or fuel composition.
  • the fuels or fuels can be chosen from liquid hydrocarbon fuels or fuels, alone or as a mixture.
  • Fuels or liquid hydrocarbon fuels include in particular distillais with a boiling temperature of between 100 and 500 ° C.
  • These distillates can, for example, be chosen from distillates obtained by direct distillation of crude hydrocarbons, vacuum distillates, hydrotreated distillates, distillates resulting from catalytic cracking and / or hydrocracking of vacuum distillates, distillates resulting from ARDS type conversion processes (by residue desulfurization atmospheric) and / or visbreaking, the distillates resulting from the valorization of Fischer Tropsch cuts, the distillates resulting from the BTL (biomass to liquid) conversion of plant and / or animal biomass, taken alone or in combination, and / or biodiesels of animal and / or vegetable origin and / or oils and / or esters of vegetable and / or animal oils.
  • the sulfur content of the fuels or fuels is preferably less than 5000 ppm, more preferably less than 500 ppm, and more preferably still less than 50 ppm, or even even less than 10 ppm, and advantageously without sulfur.
  • the fuel or fuel is preferably chosen from gas oils, biodiesel, Bx type gas oils and fuel oils, preferably domestic fuel oils (FOD).
  • FOD domestic fuel oils
  • type B x diesel for diesel engine is meant a diesel fuel which contains x% (v / v) of vegetable or animal oil esters (including used cooking oils) transformed by a process chemical called transesterification reacting this oil with an alcohol in order to obtain fatty acid esters (EAG). With methanol and ethanol, methyl esters of fatty acids (EMAG) and ethyl esters of fatty acids (EEAG) are obtained respectively.
  • EMAG methyl esters of fatty acids
  • EEAG ethyl esters of fatty acids
  • the letter "B” followed by a number indicates the percentage of EAG contained in diesel, x being a number strictly greater than 0 and less than or equal to 100.
  • a B 99 contains 99% EAG and 1% distillates means of fossil origin, B 20, 20% EAG and 80% of middle distillates of fossil origin etc ...
  • diesel fuels of type Bo which do not contain oxygenated compounds
  • diesel fuels of type Bx which contain x% (v / v) of vegetable or animal oil esters or fatty acids, most often methyl esters (EMHV or EMAG).
  • EAG methyl esters
  • the fuel or combustible can also contain hydrogenated vegetable oils, known to the skilled person under the designation HVO (from the English “hydrogenated vegetable oil”) or HDRD (from the English “hydrogenation-derived renewable diesel”).
  • HVO from the English “hydrogenated vegetable oil”
  • HDRD from the English “hydrogenation-derived renewable diesel”.
  • the fuel or fuel is chosen from gas oils, biodiesel and gas oils of type B x , hydrogenated vegetable oils (HVO), and their mixtures.
  • the fuel or combustible composition can also contain one or more additional additives, different from the copolymers, of the cold-thinning additive and of the anti-sedimentation additive described above.
  • additional additives can in particular be chosen from detergents, anti-corrosion agents, dispersants, demulsifiers, anti-foaming agents, biocides, reodorants, procetane additives, friction modifiers, lubricant additives or additives oiliness, combustion aid agents (catalytic combustion and soot promoters), antiwear agents and / or agents modifying conductivity.
  • Additional additives can generally be present in an amount ranging from 0.005 to 0.1% by weight, relative to the weight of the fuel or fuel composition (each).
  • the subject of the invention is also a method of improving the cold-keeping properties of a fuel or fuel composition consisting in adding a composition of additives as described above.
  • the various polymers were synthesized by radical polymerization in solution.
  • the monomers were dissolved in a solvent chosen from toluene or dioxane, and the transfer agent was added to the mixture.
  • the system was degassed under nitrogen flow for 40 minutes and then allowed to heat until reaching 70 ° C. Once at this temperature, the initiator was added to start the polymerization. The reaction was left for 6 h. The system was then opened to air and allowed to cool until it reached room temperature. The polymer formed was recovered by drying under vacuum.
  • the recovered polymer was characterized by NMR spectroscopy and gas chromatography (GPC) in order to determine the composition and the molar mass of the copolymer, respectively.
  • composition G 1 and G 2 were prepared.
  • composition G l includes:
  • the G2 composition includes:
  • composition G l comprises a comparative additive composition.
  • the composition G l is therefore a comparative composition.
  • Composition G2 comprises an additive composition according to the invention.
  • the composition G2 is therefore a composition according to the invention.
  • Two levels of MDFI A additive are tested at 100 and 150 ppm.
  • composition G2 170 ppm of WASA 2 additive was added. Two levels of additive MDFI A are tested at 100 and 150 ppm.
  • the figure shows the TLF results obtained by adding each of the additives defined above, as a function of the additive rate MDFI A, the additive rate WASA 1, WASA 2 respectively, being constant (170 ppm).
  • Curve A corresponds to the results concerning the comparative composition G l.
  • Curve B corresponds to the results concerning the composition G2 according to the invention.
  • the TLF target to be reached is set at -28 ° C, as shown in the single figure (dotted lines).
  • the figure thus shows that the composition of additives according to the invention makes it possible to reach the TLF target of -28 ° C. with an MDFI A additive content of only 100 ppm.
  • This same TLF of -28 ° C. is reached with the composition of comparative additives with a higher rate of 50%, i.e. 150 ppm.
  • the use of the additive composition according to the invention makes it possible to reduce the treatment rate by 33%, compared with the comparative composition. Furthermore, at an identical treatment rate, the composition of additives according to the invention makes it possible to obtain better cold performance.
  • Example 3 Evaluation of the performance of cold resistance
  • composition G ’of diesel fuel type which is particularly difficult to process, and the characteristics of which are detailed in Table IV below:
  • compositions G’l, G’2 and G’3 were prepared.
  • composition G’l includes:
  • Composition G’2 includes:
  • Composition G’3 includes:
  • compositions G’l and G’2 include a comparative additive composition.
  • the compositions G’l and G’2 are therefore comparative compositions.
  • Composition G’3 comprises a composition of additives according to the invention.
  • Composition G’3 is therefore a composition according to the invention.
  • two levels of additive MDFI B are tested: 400 and 600 ppm.
  • composition G 200 ppm of WASA 1 additive was added.
  • composition G For composition G’3, 200 ppm of WASA 2 additive was added.

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Abstract

The present invention relates to a composition of additives, comprising: at least one copolymer having at least one motif of formula (I) and at least one motif of formula (II); at least one cold-flow improver selected from the copolymers of ethylene and unsaturated ester(s); and at least one anti-settling and/or paraffin dispersant additive.

Description

Composition d’additifs comprenant au moins un copolymère, un additif fluidifiant à froid et un additif anti-sédimentation  Additive composition comprising at least one copolymer, a cold-thinning additive and an anti-sedimentation additive
La présente invention concerne une composition d’additifs particuliers et son utilisation pour améliorer les propriétés de tenue à froid des carburants et des combustibles lors de leur stockage et/ou leur utilisation à basse température. The present invention relates to a composition of particular additives and its use for improving the cold-keeping properties of fuels and combustibles during their storage and / or their use at low temperature.
La présente invention concerne également des compositions de carburant et de combustible contenant une telle composition d’additifs.  The present invention also relates to fuel compositions and fuel containing such an additive composition.
ETAT DE L'ART ANTERIEUR PRIOR STATE OF THE ART
Les carburants ou combustibles contenant des composés paraffiniques, notamment des composés contenant des groupements n- alkyle, iso-alkyle ou n-alcényle telles que des cires paraffiniques, sont connus pour présenter des propriétés d'écoulement détériorées à basse température, typiquement en dessous de 0°C. En particulier, on sait que les distillais moyens obtenus par distillation à partir d'huiles brutes d'origine pétrolière comme le gazole ou le fioul domestique, contiennent différentes quantités de n-alcanes ou n-paraffines selon leur provenance. Ces composés ont tendance à cristalliser à basse température, bouchant les tuyaux, canalisations, pompes et filtres, par exemple dans les circuits du carburant des véhicules automobiles. En hiver ou dans des conditions d'utilisation des carburants ou combustibles à température inférieure à 0°C, le phénomène de cristallisation de ces composés peut conduire à la diminution des propriétés d’écoulement des carburants ou combustibles et, par conséquent engendrer des difficultés lors de leur transport, de leur stockage et/ou de leur utilisation. L'opérabilité à froid des carburants ou combustibles est une propriété très importante, notamment pour assurer le démarrage des moteurs à froid. Si des paraffines sont cristallisées au fond du réservoir, elles peuvent être entraînées au démarrage dans le circuit de carburant et colmater notamment les filtres et préfiltres disposés en amont des systèmes d'injection (pompe et injecteurs). De même, pour le stockage des fiouls domestiques, si des paraffines précipitent en fond de cuve, elles peuvent être entraînées et obstruer les conduites en amont de la pompe et du système d'alimentation de la chaudière (gicleur et filtre). Fuels or combustibles containing paraffinic compounds, in particular compounds containing n-alkyl, iso-alkyl or n-alkenyl groups such as paraffinic waxes, are known to exhibit deteriorated flow properties at low temperature, typically below 0 ° C. In particular, it is known that the middle distillates obtained by distillation from crude oils of petroleum origin such as diesel or heating oil, contain different amounts of n-alkanes or n-paraffins depending on their origin. These compounds tend to crystallize at low temperatures, clogging hoses, pipes, pumps and filters, for example in the fuel circuits of motor vehicles. In winter or under conditions of use of fuels or fuels at a temperature below 0 ° C, the crystallization phenomenon of these compounds can lead to a decrease in the flow properties of fuels or fuels and, consequently, cause difficulties during their transport, storage and / or use. The cold operability of fuels is a very important property, in particular for ensuring the starting of cold engines. If paraffins are crystallized at the bottom of the tank, they can be entrained at start-up in the fuel circuit and in particular clog the filters and prefilters placed upstream of the injection systems (pump and injectors). Likewise, for the storage of domestic heating oils, if paraffins precipitate at the bottom of the tank, they can be entrained and obstruct the pipes upstream of the pump and the boiler supply system (nozzle and filter).
Ces problèmes sont bien connus dans le domaine des carburants et combustibles, et de nombreux additifs ou mélanges d’additifs ont été proposés et commercialisés pour réduire la taille des cristaux de paraffines et/ou changer leur forme et/ou retarder leur formation. Une taille de cristaux la plus faible possible est préférée car elle minimise les risques de bouchage ou de colmatage des filtres.  These problems are well known in the field of fuels and fuels, and numerous additives or mixtures of additives have been proposed and marketed to reduce the size of the paraffin crystals and / or change their shape and / or delay their formation. The smallest possible crystal size is preferred since it minimizes the risk of clogging or clogging of the filters.
Les agents d'amélioration d'écoulement habituels dits fluidifiants à froid (en anglais « cold flow improvers » ou CFI) sont en général des co- et ter-polymères d’éthylène et d’ester(s) vinylique(s) et/ou acrylique(s), employés seuls ou en mélange. Ces additifs fluidifiants à froid (CFI), destinés à abaisser la Température Limite de Filtrabilité (TLF) et le point d’écoulement (PE), inhibent et/ou retardent la croissance des cristaux à basse température en favorisant la dispersion des cristaux de paraffine ; ce sont par exemple les polymères d’éthylène et d’acétate de vinyle et/ou de propionate de vinyle (EVA ou EVP), aussi communément appelés additifs de TLF. Ce type d’additifs, très largement connu par l’homme du métier, est systématiquement ajouté aux distillais moyens classiques en sortie de raffinerie durant les saisons hivernales. Ces distillais additivés sont utilisés comme carburant pour moteur Diesel ou comme combustible de chauffage. Des quantités supplémentaires de ces additifs peuvent être ajoutées aux carburants vendus en stations service notamment pour satisfaire les spécifications dites Grand Froid.  The usual flow improving agents known as cold flow improvers (in English "cold flow improvers" or CFI) are generally co-and ter-polymers of ethylene and of vinyl ester (s) and / or acrylic (s), used alone or as a mixture. These cold thinning additives (CFI), intended to lower the Filterability Limit Temperature (TLF) and the pour point (PE), inhibit and / or retard the growth of crystals at low temperature by promoting the dispersion of paraffin crystals ; these are, for example, polymers of ethylene and vinyl acetate and / or vinyl propionate (EVA or EVP), also commonly known as TLF additives. This type of additive, very widely known to those skilled in the art, is systematically added to conventional middle distillates at the end of the refinery during the winter seasons. These additive distillates are used as fuel for diesel engines or as heating fuel. Additional quantities of these additives can be added to the fuels sold in service stations, in particular to satisfy the so-called “Great Cold” specifications.
Pour améliorer à la fois la TLF et le point d'écoulement des distillais, il est connu d’ajouter à ces additifs CFI des additifs supplémentaires ou « boosters » ayant la fonction d'agir en combinaison avec les additifs CFI de manière à en augmenter l’efficacité. L'art antérieur décrit abondamment de telles combinaisons d’additifs. A titre d’exemple, on peut citer le brevet US 3 275427 décrivant un distillât moyen de coupe de distillation comprise entre 177 et 400°C contenant un additif constitué de 90 à 10 % massique d'un copolymère d'éthylène comprenant de 10 à 30% de motifs acétate de vinyle de masse molaire en poids comprise entre 1000 et 3000 g.mol- l et de 10 à 90 % massique d’un polyacrylate de lauryle et/ou d’un polyméthacrylate de lauryle de masse molaire en poids variant de 760 à 100.000 g.mol- l . To improve both the TLF and the pour point of the distillates, it is known to add to these CFI additives additional additives or “boosters” having the function of acting in combination with the CFI additives so as to increase them. efficiency. The prior art abundantly describes such combinations of additives. By way of example, mention may be made of US Pat. No. 3,274,427 describing an average distillate for a distillation cut between 177 and 400 ° C. containing an additive consisting of 90 to 10% by mass of an ethylene copolymer comprising from 10 to 30% of vinyl acetate units with a molecular weight by weight of between 1000 and 3000 g.mol and from 10 to 90% by weight of a lauryl polyacrylate and / or of a polymethyl lauryl methacrylate of varying weight by weight from 760 to 100,000 g.mol- l.
Le document EP0857776 propose d’employer des résines alkylphénol-aldéhyde issues de la condensation d’alkylphénol et d’aldéhyde en association avec des copolymères ou terpolymères éthylène /ester vinylique, pour améliorer la fluidité d’huiles minérales.  Document EP0857776 proposes using alkylphenol-aldehyde resins resulting from the condensation of alkylphenol and aldehyde in combination with ethylene / vinyl ester copolymers or terpolymers, to improve the fluidity of mineral oils.
La demande de brevet WO 2008/006965 décrit l’utilisation d’une combinaison d’un homopolymère obtenu à partir d'un ester oléfinique d’acide carboxylique de 3 à 12 atomes de carbone et d’un alcool gras comprenant une chaîne de plus de 16 atomes de carbone et éventuellement une double liaison oléfinique et d’un additif fluidifiant à froid (CFI) de type EVA ou EVP, pour augmenter l’efficacité des additifs CFI en amplifiant leur effet sur la TLF.  Patent application WO 2008/006965 describes the use of a combination of a homopolymer obtained from an olefinic ester of carboxylic acid of 3 to 12 carbon atoms and a fatty alcohol comprising a chain of 16 carbon atoms and possibly an olefinic double bond and of a cold fluidizing additive (CFI) of EVA or EVP type, to increase the effectiveness of CFI additives by amplifying their effect on TLF.
La demande de brevet WO 2016/128379 décrit l’utilisation, comme additif de tenue à froid d’un carburant ou combustible, d’un copolymère à blocs comprenant :  Patent application WO 2016/128379 describes the use, as a cold-keeping additive of a fuel or combustible, of a block copolymer comprising:
(i) un bloc A consistant en une chaîne de motifs structuraux dérivés d’un ou de plusieurs monomères a,b-insaturés acrylate ou méthacrylate d’alkyle,  (i) a block A consisting of a chain of structural units derived from one or more α, b-unsaturated acrylate or alkyl methacrylate monomers,
(ii) un bloc B consistant en une chaîne de motifs structuraux dérivés d’un ou de plusieurs monomères a,b-insaturés contenant au moins un noyau aromatique.  (ii) a block B consisting of a chain of structural units derived from one or more a, b-unsaturated monomers containing at least one aromatic nucleus.
Cet additif est notamment utile comme booster de TLF en association avec un additif fluidifiant à froid (CFI).  This additive is particularly useful as a TLF booster in combination with a cold thinning additive (CFI).
Outre l'amélioration de l'écoulement de la composition de carburant ou combustible, un autre but des additifs de tenue à froid est d’assurer la dispersion des cristaux de paraffines, de manière à retarder ou empêcher la sédimentation de tels cristaux et d’éviter la formation d'une couche riche en paraffines au fond des récipients, cuves ou réservoirs de stockage ; ces additifs dispersants de paraffines sont dénommés additifs anti-sédimentation ou WASA (acronyme du terme anglais « Wax Anti-Settling Additive »). In addition to improving the flow of the fuel or combustible composition, another object of the cold-keeping additives is to ensure the dispersion of the paraffin crystals, so as to delay or prevent the sedimentation of such crystals and of avoid training a layer rich in paraffins at the bottom of containers, tanks or storage tanks; these paraffin dispersant additives are called anti-sedimentation additives or WASA (acronym of the English term "Wax Anti-Settling Additive").
Des résines alkylphénol-aldéhyde modifiées ont été décrites dans le document FR2969620 comme additif anti-sédimentation en combinaison avec un additif de TLF.  Modified alkylphenol-aldehyde resins have been described in document FR2969620 as an anti-sedimentation additive in combination with a TLF additive.
Du fait de la diversification des sources de carburants et de combustibles, il existe toujours un besoin de trouver de nouveaux additifs pour améliorer les propriétés des carburants ou combustibles à basse température également dénommées propriétés de tenue à froid, et notamment leurs propriétés d’écoulement lors de leur stockage et/ou leur utilisation à basse température.  Due to the diversification of fuels and fuels sources, there is always a need to find new additives to improve the properties of fuels or fuels at low temperatures also called cold withstand properties, and in particular their flow properties during their storage and / or their use at low temperature.
Ce besoin est particulièrement important pour les carburants ou combustibles comprenant un ou plusieurs composés paraffiniques, par exemple des composés contenant des groupements n-alkyle, iso-alkyle ou n-alcényle présentant une tendance à la cristallisation à basse température.  This need is particularly important for fuels or fuels comprising one or more paraffinic compounds, for example compounds containing n-alkyl, iso-alkyl or n-alkenyl groups exhibiting a tendency to crystallize at low temperature.
Notamment, les distillais utilisés dans les carburants et combustibles sont de plus en plus issus d’opérations de raffinage plus complexes que ceux issus de la distillation directe du pétrole, et peuvent provenir notamment des procédés de craquage, d’hydrocraquage, de craquage catalytique et des procédés de viscoréduction. Avec la demande croissante en carburants Diesel, le raffineur a tendance à introduire dans ces carburants des coupes plus difficilement exploitables, comme les coupes les plus lourdes issues des procédés de craquage et de viscoréduction qui sont riches en paraffines à longues chaînes.  In particular, the distillates used in fuels and fuels are increasingly produced from more complex refining operations than those resulting from direct petroleum distillation, and can originate in particular from cracking, hydrocracking, catalytic cracking and visbreaking processes. With the growing demand for diesel fuels, the refiner tends to introduce into these fuels cuts that are more difficult to use, such as the heavier cuts resulting from cracking and visbreaking processes which are rich in long chain paraffins.
En outre, des distillais synthétiques issus de la transformation du gaz tels que ceux issus du procédé Fischer Tropsch, ainsi que des distillats résultant du traitement de biomasses d'origine végétale ou animale, comme notamment le NexBTL et des distillats comprenant des ester d'huiles végétales ou animales sont apparus sur le marché, et constituent une nouvelle gamme de produits utilisables comme base pour formuler des carburants et ou des fiouls domestiques. Ces produits comprenant également des hydrocarbures à chaînes paraffiniques longues. In addition, synthetic distillates from the transformation of gas such as those from the Fischer Tropsch process, as well as distillates resulting from the treatment of biomass of plant or animal origin, such as in particular NexBTL and distillates comprising esters of oils plants or animals have appeared on the market, and constitute a new range of products which can be used as a base to formulate fuels and / or fuel oils. These products also include hydrocarbons with long paraffinic chains.
De plus, on a constaté l'arrivée de nouveaux pétroles bruts sur le marché, beaucoup plus riches en paraffines que ceux communément raffinés et dont la température de filtrabilité des distillais issus de distillation directe était difficilement améliorée par les additifs de filtrabilité classique au même titre que ceux précédemment cités.  In addition, we have seen the arrival of new crude oils on the market, much richer in paraffins than those commonly refined and whose filterability temperature of distillates from direct distillation was hardly improved by conventional filterability additives in the same way than those previously cited.
On a constaté que les propriétés de tenue à froid des distillats obtenus par combinaison des anciennes bases et de ces nouvelles sources était difficilement améliorée par l'ajout d'additifs classiques de filtrabilité, entre autres du fait de la présence importante de paraffines à longue chaîne et de la distribution complexe en paraffines dans leur composition. On a pu noter en effet dans ces nouvelles combinaisons de distillats, des distributions discontinues en paraffines, en présence desquelles les additifs de filtrabilité connus ne sont pas toujours suffisamment efficaces.  It was found that the cold-keeping properties of the distillates obtained by combining the old bases and these new sources was hardly improved by the addition of conventional filterability additives, inter alia due to the significant presence of long-chain paraffins and the complex distribution of paraffins in their composition. It has been noted in fact in these new distillate combinations, discontinuous paraffin distributions, in the presence of which the known filterability additives are not always sufficiently effective.
Il existe donc un besoin d'adapter les additifs de tenue à froid à ces nouveaux types de bases pour carburants et combustibles, considérés comme particulièrement difficiles à traiter.  There is therefore a need to adapt the cold-keeping additives to these new types of bases for fuels and fuels, considered to be particularly difficult to treat.
La présente invention s'applique aux carburants et combustibles contenant non seulement des distillats classiques tels que ceux issus de la distillation directe des pétroles bruts, mais également aux bases issues d’autres sources, telles que celles décrites ci-avant.  The present invention applies to fuels and combustibles containing not only conventional distillates such as those resulting from the direct distillation of crude oils, but also to bases obtained from other sources, such as those described above.
Ainsi, le but de la présente invention est de proposer une nouvelle composition d’additifs qui peut avantageusement être utilisée pour améliorer les propriétés de tenue à froid, en particulier les propriétés d’écoulement à froid de ces carburants ou combustibles, lors de leur stockage et/ou leur utilisation à basse température, typiquement inférieure à 0°C.  Thus, the object of the present invention is to propose a new composition of additives which can advantageously be used to improve the cold-keeping properties, in particular the cold-flow properties of these fuels or combustibles, during their storage. and / or their use at low temperature, typically below 0 ° C.
Le but de la présente invention est en outre de proposer une nouvelle composition d’additifs pour carburants et combustibles, et des concentrés contenant une telle composition, agissant sur la Température Limite de Filtrabilité (TLF), le point d’écoulement (PE), et retardant et/ou empêchant la sédimentation de cristaux de composés hydrocarbonés, notamment des paraffines. The aim of the present invention is further to propose a new composition of additives for fuels and combustibles, and concentrates containing such a composition, acting on the Filterability Limit Temperature (TLF), the pour point (PE), and delaying and / or preventing the sedimentation of crystals of hydrocarbon compounds, in particular paraffins.
Enfin, un autre but de l’invention est de proposer une composition de carburant ou de combustible ayant des propriétés de tenue à froid améliorées, en particulier à des températures inférieures à 0°C, de préférence inférieures à -5°C.  Finally, another object of the invention is to provide a fuel or fuel composition having improved cold-holding properties, in particular at temperatures below 0 ° C, preferably below -5 ° C.
OBJET DE L’INVENTION OBJECT OF THE INVENTION
La demanderesse a maintenant découvert qu’une composition d’additifs particuliers, tels que décrits ci-après, possédait des propriétés inattendues pour améliorer la tenue à froid des compositions de carburants et de combustibles, y compris celles qui sont particulièrement difficiles à traiter. The Applicants have now discovered that a composition of particular additives, as described below, had unexpected properties for improving the cold resistance of fuel compositions, including those which are particularly difficult to process.
La présente invention a ainsi pour objet une composition d’additifs comprenant :  The subject of the present invention is therefore a composition of additives comprising:
- au moins un copolymère comprenant :  - at least one copolymer comprising:
- au moins un motif de formule (I) suivante :  - at least one motif of formula (I) below:
d d
Ri représente un atome d’hydrogène ou un groupement méthyle, X représente -O-CO-, ou -CO-O- ou -NH-CO- ou -CO-NH-, et  Ri represents a hydrogen atom or a methyl group, X represents -O-CO-, or -CO-O- or -NH-CO- or -CO-NH-, and
R2 représente un groupe alkyle en Ce à C 24 ; et R2 represents a C1 to C24 alkyl group; and
- au moins un motif de formule (II) suivante :  - at least one motif of formula (II) below:
(P),  (P),
dans laquelle R représente un groupe en C 2 à C34 , comprenant au moins un hétérocycle azoté ; in which R represents a C 2 to C 34 group, comprising at least one nitrogen heterocycle;
- au moins un additif fluidifiant à froid choisi parmi les copolymères d’éthylène et d’ester(s) insaturé(s) ;  - at least one cold-thinning additive chosen from copolymers of ethylene and of unsaturated ester (s);
- au moins un additif anti-sédimentation et/ou dispersant de paraffines.  - at least one anti-sedimentation and / or paraffin dispersant additive.
L'invention a également pour objet l’utilisation de la composition d’additifs selon l’invention pour améliorer les propriétés de tenue à froid d’une composition de carburant ou de combustible.  The invention also relates to the use of the composition of additives according to the invention for improving the cold-keeping properties of a fuel or fuel composition.
L’invention a également pour objet un concentré d’additifs contenant une telle composition, ainsi qu’une composition de carburant ou de combustible.  The invention also relates to a concentrate of additives containing such a composition, as well as a fuel or fuel composition.
D’autres objets, caractéristiques, aspects et avantages de l’invention apparaîtront encore plus clairement à la lecture de la description et des exemples qui suivent.  Other objects, characteristics, aspects and advantages of the invention will appear even more clearly on reading the description and the examples which follow.
Dans ce qui va suivre, et à moins d’une autre indication, les bornes d’un domaine de valeurs sont comprises dans ce domaine, notamment dans les expressions « compris entre » et « allant de ... à ... ».  In what follows, and unless otherwise indicated, the limits of a range of values are included in this range, in particular in the expressions "between" and "going from ... to ...".
Par ailleurs, les expressions « au moins un » et « au moins » utilisées dans la présente description sont respectivement équivalentes aux expressions « un ou plusieurs » et « supérieur ou égal ».  Furthermore, the expressions “at least one” and “at least” used in the present description are respectively equivalent to the expressions “one or more” and “greater than or equal”.
Enfin, de manière connue en soi, on désigne par composé ou groupe en CN un composé ou un groupe contenant dans sa structure chimique N atomes de carbone.  Finally, in a manner known per se, the term CN compound or group denotes a compound or group containing in its chemical structure N carbon atoms.
DE SCRIPTION DETAILLEE DETAILED DESCRIPTION
La composition d’additifs : The composition of additives:
L’invention met en œuvre une composition d’additifs comprenant au moins un copolymère comprenant au moins un motif de formule (I) suivante : The invention uses an additive composition comprising at least one copolymer comprising at least one unit of formula (I) below:
dans laquelle in which
Ri représente un atome d’hydrogène ou un groupement méthyle, Ri represents a hydrogen atom or a methyl group,
X représente -O-CO-, ou -CO-O- ou -NH-CO- ou -CO-NH-, et X represents -O-CO-, or -CO-O- or -NH-CO- or -CO-NH-, and
R2 représente un groupe alkyle en Ce à C 24 . R2 represents a C 1 to C 24 alkyl group.
Le groupement X de la formule (I) est choisi parmi :  The group X of formula (I) is chosen from:
X = -O-CO-, étant entendu que X est alors relié au carbone vinylique par l’atome d’oxygène ;  X = -O-CO-, it being understood that X is then linked to the vinyl carbon by the oxygen atom;
X = -CO-O-, étant entendu que X est alors relié au carbone vinylique par l’atome de carbone ;  X = -CO-O-, it being understood that X is then linked to the vinyl carbon by the carbon atom;
X = -NH-CO-, étant entendu que X est alors relié au carbone vinylique par l’atome d’azote ; et  X = -NH-CO-, it being understood that X is then linked to the vinyl carbon by the nitrogen atom; and
X = -CO-NH-, étant entendu que X est alors relié au carbone vinylique par l’atome de carbone.  X = -CO-NH-, it being understood that X is then linked to the vinyl carbon by the carbon atom.
Selon un premier mode de réalisation, le groupement X de la formule (I) est choisi parmi : -O-CO- et -NH-CO-, étant entendu que le groupement X= -O-CO- est relié au carbone vinylique par l’atome d’oxygène et que le groupement X= -NH-CO- est relié au carbone vinylique par l’atome d’azote. Dans ce mode de réalisation, le groupement X de la formule (I) est de préférence le groupement -O- CO-.  According to a first embodiment, the group X of formula (I) is chosen from: -O-CO- and -NH-CO-, it being understood that the group X = -O-CO- is linked to the vinyl carbon by the oxygen atom and that the group X = -NH-CO- is linked to the vinyl carbon by the nitrogen atom. In this embodiment, the group X of formula (I) is preferably the group -O- CO-.
Selon un deuxième mode de réalisation, le groupement X de la formule (I) est choisi parmi : -CO-O- et -CO-NH-, étant entendu que le groupement X est relié au carbone vinylique par l’atome de carbone. Dans ce mode de réalisation, le groupement X de la formule (I) est de préférence le groupement -CO-O-.  According to a second embodiment, the group X of formula (I) is chosen from: -CO-O- and -CO-NH-, it being understood that the group X is linked to the vinyl carbon by the carbon atom. In this embodiment, the group X of formula (I) is preferably the group -CO-O-.
Selon un mode de réalisation particulièrement préféré, le groupement X est un groupement -CO-O-, X étant relié au carbone vinylique par l’atome de carbone. Le groupement R2 de la formule (I) est un radical alkyle en Ce à C24. Ce radical alkyle peut être linéaire ou ramifié, cyclique ou acyclique. Ce radical alkyle peut comprendre une partie linéaire ou ramifiée et une partie cyclique. According to a particularly preferred embodiment, the group X is a group -CO-O-, X being linked to the vinyl carbon by the carbon atom. The group R 2 of formula (I) is a C 1 to C 24 alkyl radical. This alkyl radical can be linear or branched, cyclic or acyclic. This alkyl radical can comprise a linear or branched part and a cyclic part.
Avantageusement, le groupement R2 de la formule (I) est un radical alkyle acyclique linéaire ou ramifié en C8-C24, de préférence en C10-C22, plus préférentiellement en C12-C22. Selon un mode de réalisation particulier, le groupement R2 de la formule (I) est un radical alkyle acyclique linéaire ou ramifié en C12-C14. Selon un autre mode de réalisation particulier, le groupement R2 de la formule (I) est un radical alkyle acyclique linéaire ou ramifié en C18-C22.  Advantageously, the group R2 of formula (I) is an acyclic linear or branched C8-C24, preferably C10-C22, more preferably C12-C22, alkyl radical. According to a particular embodiment, the group R2 of formula (I) is a linear or branched C12-C14 acyclic alkyl radical. According to another particular embodiment, the group R2 of formula (I) is a linear or branched C18-C22 acyclic alkyl radical.
On peut citer, à titre d’exemples non limitatifs de groupements R2 préférés, les groupements alkyles tels que l’octyle, le décyle, le dodécyle, l’éthyl-2-hexyle, l’isooctyle, l’isodécyle, l’isododécyle, le lauryle, le stéaryle, l’octadécyle, le béhényle, les groupements alkyle en C 14.  Mention may be made, by way of nonlimiting examples of preferred R2 groups, of alkyl groups such as octyl, decyl, dodecyl, ethyl-2-hexyl, isooctyl, isodecyl, isododecyl. , lauryl, stearyl, octadecyl, behenyl, C 14 alkyl groups.
Selon un mode de réalisation particulièrement préféré, le groupement X est un groupement -CO-O-, X étant relié au carbone vinylique par l’atome de carbone, et le groupement R2 est un radical alkyle acyclique linéaire ou ramifié en C8-C24, de préférence en C10- C22, plus préférentiellement en C12-C22.  According to a particularly preferred embodiment, the group X is a group -CO-O-, X being linked to the vinyl carbon by the carbon atom, and the group R2 is a linear or branched C8-C24 acyclic alkyl radical, preferably in C10-C22, more preferably in C12-C22.
Les motifs selon ce mode de réalisation correspondent à ceux issus de monomères choisis parmi les acrylates et les méthacrylates d’alkyle en C8-C24, de préférence en C10-C22, plus préférentiellement en C12-C22.  The units according to this embodiment correspond to those derived from monomers chosen from acrylates and alkyl methacrylates of C8-C24, preferably of C10-C22, more preferably of C12-C22.
Selon un mode de réalisation particulier, le groupement X est un groupement -CO-O-, X étant relié au carbone vinylique par l’atome de carbone, et le groupement R2 est un radical alkyle acyclique linéaire ou ramifié en C12-C14. Les motifs selon ce mode de réalisation correspondent à ceux issus de monomères choisis parmi les acrylates et les méthacrylates d’alkyle en C12-C14.  According to a particular embodiment, the group X is a group -CO-O-, X being linked to the vinyl carbon by the carbon atom, and the group R2 is a linear or branched C12-C14 acyclic alkyl radical. The patterns according to this embodiment correspond to those from monomers chosen from acrylates and C12-C14 alkyl methacrylates.
Selon un autre mode de réalisation particulier, le groupement X est un groupement -CO-O-, X étant relié au carbone vinylique par l’atome de carbone, et le groupement R2 est un radical alkyle acyclique linéaire ou ramifié en C 1 8 - C 22 . Les motifs selon ce mode de réalisation correspondent à ceux issus de monomères choisis parmi les acrylates et les méthacrylates d’alkyle en C 1 8 - C 22 . According to another particular embodiment, the group X is a group -CO-O-, X being linked to the vinyl carbon by the carbon atom, and the group R2 is an alkyl radical linear acyclic or branched C 1 8 - C 22. The units according to this embodiment correspond to those derived from monomers chosen from acrylates and C 1 8 -C 22 alkyl methacrylates.
Le copolymère employé dans la présente invention comprend également au moins un motif de formule (II) suivante :  The copolymer used in the present invention also comprises at least one unit of formula (II) below:
(P),  (P),
dans laquelle in which
R représente un groupe en C 2 à C 34 , de préférence en C 2 à C 1 2 , plus préférentiellement en C 2 à Ce, et comprenant au moins un hétérocycle azoté.  R represents a group from C 2 to C 34, preferably from C 2 to C 1 2, more preferably from C 2 to Ce, and comprising at least one nitrogen heterocycle.
Par hétérocycle azoté, on désigne de manière connue en soi un groupement cyclique comprenant des atomes de carbone et au moins un atome d’azote dans le cycle.  The term “nitrogen heterocycle” denotes, in a manner known per se, a cyclic group comprising carbon atoms and at least one nitrogen atom in the ring.
Le groupement R peut être saturé ou insaturé, monocyclique ou polycyclique, le ou les cycles pouvant être substitués ou non substitués. Le ou les substituant(s) éventuellement présent(s) sur le ou les cycle(s) peuvent être saturés ou insaturés, et être notamment choisis parmi les substituants hydrocarbonés, oxygénés, azotés, halogénés, ...  The group R can be saturated or unsaturated, monocyclic or polycyclic, it being possible for the ring or rings to be substituted or unsubstituted. The substituent (s) optionally present on the cycle (s) may be saturated or unsaturated, and may in particular be chosen from hydrocarbon, oxygenated, nitrogenous, halogenated substituents, etc.
Selon un mode de réalisation préféré, le ou les hétérocycle(s) azoté(s) sont choisis parmi les cycles formés de 5 à 7 atomes parmi lesquels 1 , 2, 3 ou 4 atomes sont des atomes d’azote, ces cycles étant saturés ou insaturés, substitués ou non substitués.  According to a preferred embodiment, the nitrogen heterocycle (s) are chosen from rings formed from 5 to 7 atoms among which 1, 2, 3 or 4 atoms are nitrogen atoms, these cycles being saturated or unsaturated, substituted or unsubstituted.
On peut citer à titre d’exemples non limitatifs d’hétérocycles azotés les cycles suivants : pyrrolidine, pyrroline, pyrrole, pyrazolidine, imidazolidine, pyrazoline, imidazoline, pyrazole, imidazole, triazole, tétrazole, piperidine, pyridine, piperazine, pyridazine, pyrimidine, pyrazine, triazine.  As non-limiting examples of nitrogen heterocycles, the following cycles may be cited: pyrrolidine, pyrroline, pyrrole, pyrazolidine, imidazolidine, pyrazoline, imidazoline, pyrazole, imidazole, triazole, tetrazole, piperidine, pyridine, piperazine, pyridazine, pyrimidine, pyrazine, triazine.
Le ou les hétérocycles azotés peuvent également contenir, en plus des atomes de carbone et d’azote, un ou plusieurs autres hétéroatomes tels que notamment un ou plusieurs atomes d’oxygène, qui peuvent faire partie du cycle ou être rattachés à celui-ci. A titre d’exemple, on peut citer les cycles suivants : pyrrolidone, caprolactame. The nitrogen hetero ring (s) may also contain, in addition to carbon and nitrogen atoms, one or more other heteroatoms such as in particular one or more oxygen atoms, which can be part of the cycle or be attached to it. By way of example, mention may be made of the following cycles: pyrrolidone, caprolactam.
Selon un mode de réalisation préféré, le groupement R contient au moins un hétérocycle azoté ayant de un à trois atomes d’azote, plus préférentiellement deux atomes d’azote. Des groupements R préférés sont en particulier choisis parmi les cycles suivants : un cycle imidazole substitué ou non substitué, un cycle triazole substitué ou non substitué, un cycle pyrrolidone substitué ou non substitué.  According to a preferred embodiment, the group R contains at least one nitrogen heterocycle having from one to three nitrogen atoms, more preferably two nitrogen atoms. Preferred R groups are in particular chosen from the following rings: a substituted or unsubstituted imidazole ring, a substituted or unsubstituted triazole ring, a substituted or unsubstituted pyrrolidone ring.
Selon un mode de réalisation particulièrement préféré, le groupement R est un cycle imidazole substitué ou non substitué.  According to a particularly preferred embodiment, the group R is a substituted or unsubstituted imidazole ring.
Selon un mode de réalisation, les motifs de formule (II) sont issus d’un ou plusieurs monomères vinyliques portant un groupe R tel que décrit ci-avant.  According to one embodiment, the units of formula (II) come from one or more vinyl monomers carrying an R group as described above.
On peut citer à titre d’exemples de monomères préférés :  Examples of preferred monomers that may be mentioned include:
- les 1 ,2,3 et les 1 ,2,4 N-vinyltriazoles,  - 1,2,3 and 1,2,4 N-vinyltriazoles,
- la N-vinylpyrrolidone,  - N-vinylpyrrolidone,
- le 1 -vinylimidazole (ou N-vinylimidazole), ce dernier étant particulièrement préféré.  - 1 -vinylimidazole (or N-vinylimidazole), the latter being particularly preferred.
Le copolymère employé dans la présente invention peut être réticulé ou non. De préférence, il n’est pas réticulé.  The copolymer used in the present invention may or may not be crosslinked. Preferably, it is not crosslinked.
Le copolymère selon l’invention contient avantageusement de 50 à 99% en moles de motifs de formule (I), de préférence de 60 à 95% en moles, plus préférentiellement de 70 à 90% en moles, et mieux encore de 75 à 85% en moles.  The copolymer according to the invention advantageously contains from 50 to 99 mol% of units of formula (I), preferably from 60 to 95 mol%, more preferably from 70 to 90 mol%, and better still from 75 to 85 % in moles.
Le copolymère selon l’invention contient avantageusement de 1 à 50% en moles de motifs de formule (II), de préférence de 5 à 40% en moles, plus préférentiellement de 10 à 30% en moles, et mieux encore de 15 à 25% en moles.  The copolymer according to the invention advantageously contains from 1 to 50 mol% of units of formula (II), preferably from 5 to 40 mol%, more preferably from 10 to 30 mol%, and better still from 15 to 25 % in moles.
De préférence, le copolymère employé dans la présente invention contient uniquement des motifs de formule (I) et des motifs de formule (II).  Preferably, the copolymer used in the present invention contains only units of formula (I) and units of formula (II).
Le copolymère employé dans la présente invention est avantageusement un copolymère statistique ou un copolymère à blocs. Selon un mode de réalisation particulièrement préféré, il s’agit d’un copolymère statistique. The copolymer used in the present invention is advantageously a random copolymer or a block copolymer. According to a particularly preferred embodiment, it is a random copolymer.
Le copolymère employé dans la présente invention peut être obtenu par copolymérisation de :  The copolymer used in the present invention can be obtained by copolymerization of:
- au moins un monomère de formule suivante (IA) :  - at least one monomer of the following formula (IA):
dans laquelle in which
Ri , X et R2 sont tels que définis ci-dessus, les variantes préférées de Ri , X et R2 selon la formule (I) décrites ci-dessus étant également des variantes préférées de la formule (IA), et Ri, X and R 2 are as defined above, the preferred variants of Ri, X and R 2 according to formula (I) described above also being preferred variants of formula (IA), and
- au moins un monomère de formule suivante (IIA) : - at least one monomer of the following formula (IIA):
dans laquelle R est tel que défini ci-avant, les variantes préférées de R selon la formule (II) décrites ci-dessus étant également des variantes préférées de la formule (IIA). wherein R is as defined above, the preferred variants of R according to formula (II) described above are also preferred variants of formula (IIA).
Lorsque le groupement X du monomère de formule (IA) est le groupement -O-CO-, étant entendu que le groupement -O-CO- est relié au carbone vinylique par l’atome d’oxygène, le monomère de formule (IA) est, de préférence, choisi parmi les alkyl esters vinyliques en Cs à C24, de préférence en Cio à C24, plus préférentiellement en Ci2 à C22. Selon un mode de réalisation particulier, le monomère de formule (IA) est choisi parmi les alkyl esters vinyliques en Ci2 à Ci4. Selon un autre mode de réalisation particulier, le monomère de formule (IA) est choisi parmi les alkyl esters vinyliques en C is à C22. Le radical alkyle de l’alkyl ester vinylique est linéaire ou ramifié, cyclique ou acyclique, de préférence acyclique. Parmi les monomères ester vinylique d’alkyle, on peut citer par exemple l’octanoate de vinyle, le décanoate de vinyle, le dodécanoate de vinyle, le tétradécanoate de vinyle, le 2-éthylhexanoate de vinyle. When the group X of the monomer of formula (IA) is the group -O-CO-, it being understood that the group -O-CO- is linked to the vinyl carbon by the oxygen atom, the monomer of formula (IA) is preferably chosen from Cs to C 24 , preferably Cio to C 24 , more preferably C 2 to C 22 vinyl alkyl esters. According to a particular embodiment, the monomer of formula (IA) is chosen from C 1 to C 4 alkyl vinyl esters. According to another particular embodiment, the monomer of formula (IA) is chosen from C 1 to C 22 alkyl vinyl esters. The alkyl radical of the vinyl alkyl ester is linear or branched, cyclic or acyclic, preferably acyclic. Among the vinyl ester alkyl monomers that may be mentioned, for example, vinyl octanoate, vinyl decanoate, vinyl dodecanoate, vinyl tetradecanoate, vinyl 2-ethylhexanoate.
Lorsque le groupement X du monomère de formule (IA) est le groupement -CO-O-, étant entendu que le groupement -CO-O- est relié au carbone vinylique par l’atome de carbone, le monomère de formule (IA) est typiquement choisi parmi les acrylates et les méthacrylates d’alkyle en Cs à C 24 , de préférence en Cio à C 24 , plus préférentiellement en C 1 2 à C 22 . Selon un mode de réalisation particulier, le monomère de formule (IA) est choisi parmi les acrylates et les méthacrylates d’alkyle en C 1 2 à C 1 4 . Selon un autre mode de réalisation particulier, le monomère de formule (IA) est choisi parmi les acrylates et les méthacrylates d’alkyle en Cis à C 22 .  When the group X of the monomer of formula (IA) is the group -CO-O-, it being understood that the group -CO-O- is linked to the vinyl carbon by the carbon atom, the monomer of formula (IA) is typically chosen from Cs to C 24, preferably Cio to C 24, more preferably C 12 to C 22 alkyl acrylates and methacrylates. According to a particular embodiment, the monomer of formula (IA) is chosen from acrylates and C 1 2 to C 1 4 alkyl methacrylates. According to another particular embodiment, the monomer of formula (IA) is chosen from acrylates and C 1 to C 22 alkyl methacrylates.
Parmi les (méth)acrylates d’alkyle susceptibles d’être utilisés comme monomères dans la fabrication du copolymère employé dans l’invention, on peut citer les acrylates d’alkyle en Ce à C 24 et les méthacrylates d’alkyle en C à C 24 , et notamment, à titre d’exemples non limitatifs : l’acrylate de n-octyle, le méthacrylate de n-octyle, l’acrylate de n-décyle, le méthacrylate de n-décyle, l’acrylate de n- dodécyle, le méthacrylate de n-dodécyle, l’acrylate d’éthyl-2-hexyle, le méthacrylate d’éthyl-2-hexyle, l’acrylate d’isooctyle, le méthacrylate d’isooctyle, l’acrylate d’isodécyle, le méthacrylate d’isodécyle, l’acrylate de lauryle, l’acrylate de stéaryle, l’acrylate d’octadécyle, l’acrylate de béhényle, les acrylates d’alkyle en C 1 2 à C 1 4 et les méthacrylates d’alkyle en C 1 2 à C 14 . On préfère tout particulièrement employer les acrylates d’alkyle en C 1 2 à C 1 4 et les méthacrylates d’alkyle en C 1 2 à C 1 4 et également les acrylates d’alkyle en C is à C 22 et les méthacrylates d’alkyle en C is à C 22 .  Among the alkyl (meth) acrylates which can be used as monomers in the manufacture of the copolymer used in the invention, mention may be made of C Ce to C 24 alkyl acrylates and of C à to C alkyl methacrylates 24, and in particular, by way of nonlimiting examples: n-octyl acrylate, n-octyl methacrylate, n-decyl acrylate, n-decyl methacrylate, n-dodecyl acrylate , n-dodecyl methacrylate, ethyl-2-hexyl acrylate, ethyl-2-hexyl methacrylate, isooctyl acrylate, isooctyl methacrylate, isodecyl acrylate, isodecyl methacrylate, lauryl acrylate, stearyl acrylate, octadecyl acrylate, behenyl acrylate, C 1 2 to C 1 4 alkyl acrylates and alkyl methacrylates C 1 2 to C 14. It is particularly preferred to use C 1 2 to C 1 4 alkyl acrylates and C 1 2 to C 1 4 alkyl methacrylates and also C 1 to C 22 alkyl acrylates and methacrylates of C is to C 22 alkyl.
Les monomères de formule (IIA) sont des monomères vinyliques portant un groupe R tel que décrit ci-avant.  The monomers of formula (IIA) are vinyl monomers carrying an R group as described above.
Selon un mode de réalisation particulièrement préféré, le groupement R contient au moins un hétérocycle insaturé azoté ayant de un à trois atomes d’azote, plus préférentiellement deux atomes d’azote, tel qu’en particulier un cycle imidazole, substitué ou non substitué. According to a particularly preferred embodiment, the group R contains at least one unsaturated nitrogen heterocycle having from one to three nitrogen atoms, more preferably two atoms nitrogen, such as in particular an imidazole ring, substituted or unsubstituted.
On peut citer à titre de monomère de formule (IIA) particulièrement préféré le 1 -vinylimidazole (ou N-vinylimidazole).  Mention may be made, as monomer of formula (IIA) which is particularly preferred, of 1-vinylimidazole (or N-vinylimidazole).
II est entendu que l’on ne sortirait pas de l’invention si l’on obtenait le copolymère employé dans l’invention à partir de monomères différents de ceux de formule (IA) et (IIA) ci-avant, dans la mesure où le copolymère final correspond à un polymère comprenant des motifs de formule (I) et des motifs de formule (II) tels que définis ci-avant. Par exemple, on ne sortirait pas de l’invention, si l’on obtenait le polymère par polymérisation de monomères différents, suivie d’une post-fonctionnalisation. Par exemple, les motifs de formule (I) peuvent être obtenus à partir de l’acide acrylique, par réaction de transestérification.  It is understood that one would not depart from the invention if the copolymer used in the invention were obtained from monomers different from those of formula (IA) and (IIA) above, insofar as the final copolymer corresponds to a polymer comprising units of formula (I) and units of formula (II) as defined above. For example, it would not go beyond the invention, if the polymer were obtained by polymerization of different monomers, followed by post-functionalization. For example, the units of formula (I) can be obtained from acrylic acid, by transesterification reaction.
Le copolymère employé dans l’invention peut être préparé au moyen de tout procédé connu de polymérisation. Les différentes techniques et conditions de polymérisation et de réticulation sont largement décrites dans la littérature et relèvent des connaissances générales de l’homme du métier.  The copolymer used in the invention can be prepared by any known method of polymerization. The various techniques and conditions of polymerization and crosslinking are widely described in the literature and fall within the general knowledge of a person skilled in the art.
Dans le cas d’un copolymère statistique, on peut procéder notamment par polymérisation radicalaire classique : on procède généralement par mélange des différents monomères dans un solvant approprié, et la copolymérisation est amorcée au moyen d’un agent de polymérisation radicalaire.  In the case of a random copolymer, one can proceed in particular by conventional radical polymerization: one generally proceeds by mixing the different monomers in an appropriate solvent, and the copolymerization is initiated by means of a radical polymerization agent.
Dans le cas d’un copolymère à blocs, on peut procéder notamment par polymérisation séquencée et contrôlée. Une telle polymérisation est, avantageusement, choisie parmi la polymérisation radicalaire contrôlée ; par exemple, par polymérisation radicalaire par transfert d’atome (ATRP en anglais « Atom Transfer Radical Polymerization») ; la polymérisation radicalaire par le nitroxyde (NMP en anglais « Nitroxide-mediated polymerization ») ; les procédés de transfert dégénératif (en anglais « degenerative transfer processes ») tels que la polymérisation par transfert d'iode dégénérative (en anglais « ITRP- iodine transfer radical polymerization ») ou la polymérisation radicalaire par transfert de chaîne réversible par addition-fragmentation (RAFT en anglais « Réversible Addition-Fragmentation Chain Transfer ») ; les polymérisations dérivées de l’ATRP telles que les polymérisations utilisant des initiateurs pour la régénération continue de l'activateur (ICAR -Initiators for continuous activator régénération) ou utilisant des activateurs régénérés par transfert d’électron (ARGET en anglais « activators regenerated by électron transfer »). In the case of a block copolymer, one can proceed in particular by sequenced and controlled polymerization. Such a polymerization is advantageously chosen from controlled radical polymerization; for example, by atomic transfer radical polymerization (ATRP in English "Atom Transfer Radical Polymerization"); radical polymerization with nitroxide (NMP in English "Nitroxide-mediated polymerization"); degenerative transfer processes (in English “degenerative transfer processes”) such as degenerative iodine transfer polymerization (in English “ITRP- iodine transfer radical polymerization ”) or radical polymerization by reversible chain transfer by addition-fragmentation (RAFT in English“ Reversible Addition-Fragmentation Chain Transfer ”); polymerizations derived from ATRP such as polymerizations using initiators for continuous regeneration of the activator (ICAR -Initiators for continuous activator regeneration) or using activators regenerated by electron transfer (ARGET in English "activators regenerated by electron transfer ”).
Le copolymère employé dans l’invention a, avantageusement, une masse molaire moyenne en poids (Mw) comprise entre 1 000 et 50 000 g. mol 1 , plus préférentiellement entre 1 000 et 20 000 g. mol 1 , encore plus préférentiellement entre 3 000 et 15 000 g. mol 1. The copolymer used in the invention advantageously has a weight-average molar mass (M w ) of between 1,000 and 50,000 g. mol 1 , more preferably between 1,000 and 20,000 g. mol 1 , even more preferably between 3,000 and 15,000 g. mol 1 .
Le copolymère selon l’invention a, avantageusement, une masse molaire moyenne en nombre (Mn) comprise entre 1 000 et 50 000 g. mol 1 , plus préférentiellement entre 1 000 et 20 000 g. mol 1 , encore plus préférentiellement entre 2 000 et 10 000 g. mol 1. The copolymer according to the invention advantageously has a number-average molar mass (Mn) of between 1,000 and 50,000 g. mol 1 , more preferably between 1,000 and 20,000 g. mol 1 , even more preferably between 2,000 and 10,000 g. mol 1 .
Les masses molaires moyennes en nombre et en poids sont mesurées par chromatographie d’exclusion stérique (SEC en anglais « Size Exclusion Chromatography »).  The number and weight average molar masses are measured by size exclusion chromatography (SEC).
La composition d’additifs selon l’invention peut, avantageusement, comprendre de 0, 1 à 30% en poids de copolymère tel que décrit précédemment, de préférence de 1 à 20% en poids, plus préférentiellement de 2 à 10% en poids par rapport au poids total de la composition d’additifs.  The composition of additives according to the invention may advantageously comprise from 0.1 to 30% by weight of copolymer as described above, preferably from 1 to 20% by weight, more preferably from 2 to 10% by weight, per relative to the total weight of the additive composition.
La composition d’additifs selon l’invention comprend également au moins un additif fluidifiant à froid (CEI) choisi parmi les copolymères d’éthylène et d’ester(s) insaturé(s).  The additive composition according to the invention also comprises at least one cold-thinning additive (CEI) chosen from copolymers of ethylene and of unsaturated ester (s).
De préférence, l’additif fluidifiant à froid est choisi parmi les copolymères d’éthylène et d’ester(s) vinylique(s) et/ou acrylique(s), tels que les copolymères éthylène/acétate de vinyle (EVA), éthylène/propionate de vinyle (EVP), éthylène/éthanoate de vinyle (EVE), éthylène/méthacrylate de méthyle (EMMA), et éthylène/fumarate d’alkyle décrits, par exemple, dans les documents US3048479, US3627838, US3790359, US3961961 et EP261957. On peut également citer les terpolymères d’éthylène, d’acétate de vinyle et d’un autre ester vinylique, par exemple le néodécanoate de vinyle. Preferably, the cold-thinning additive is chosen from copolymers of ethylene and of vinyl ester (s) and / or acrylic (s), such as ethylene / vinyl acetate (EVA), ethylene copolymers. / vinyl propionate (EVP), ethylene / vinyl ethanoate (EVE), ethylene / methyl methacrylate (EMMA), and ethylene / alkyl fumarate described, for example, in documents US3048479, US3627838, US3790359, US3961961 and EP261957 . We may also cite terpolymers of ethylene, vinyl acetate and another vinyl ester, for example vinyl neodecanoate.
Selon un mode de réalisation préféré, l’additif fluidifiant à froid (CFI) est choisi parmi les copolymères d’éthylène et d’ester(s) vinylique(s), de préférence parmi les copolymères éthylène/acétate de vinyle (EVA), les copolymères éthylène/propionate de vinyle (EVP) et les terpolymères d’éthylène, d’acétate de vinyle et d’un autre ester vinylique ; plus préférentiellement encore les copolymères éthylène/acétate de vinyle et leurs mélanges avec un terpolymère d’éthylène, d’acétate de vinyle et d’un autre ester vinylique, tel que notamment le néodécanoate de vinyle.  According to a preferred embodiment, the cold fluidizing additive (CFI) is chosen from copolymers of ethylene and vinyl ester (s), preferably from ethylene / vinyl acetate (EVA) copolymers, ethylene vinyl propionate copolymers (TEUs) and terpolymers of ethylene, vinyl acetate and another vinyl ester; more preferably still, ethylene / vinyl acetate copolymers and their mixtures with a terpolymer of ethylene, vinyl acetate and another vinyl ester, such as in particular vinyl neodecanoate.
La composition d’additifs selon l’invention peut, avantageusement, comprendre de 50 à 90% en poids d’additif fluidifiant à froid (CFI) tel que décrit précédemment, de préférence de 60 à 90% en poids, plus préférentiellement de 70 à 90% en poids par rapport au poids total de la composition d’additifs.  The composition of additives according to the invention may advantageously comprise from 50 to 90% by weight of cold-thinning additive (CFI) as described above, preferably from 60 to 90% by weight, more preferably from 70 to 90% by weight relative to the total weight of the additive composition.
La composition d’additifs selon l’invention comprend également au moins un additif anti-sédimentation et/ou dispersant de paraffines.  The additive composition according to the invention also comprises at least one paraffin dispersant and / or dispersant additive.
L’additif anti-sédimentation et/ou dispersant de paraffines Anti-sedimentation and / or paraffin dispersant additive
(WASA) peut être notamment, mais non limitativement, choisi dans le groupe constitué par les copolymères acide(WASA) can be in particular, but not limited to, chosen from the group consisting of acid copolymers
(méth)acrylique/(méth)acrylate d'alkyle amidifiés par une polyamine, les produits de condensation d’un ou plusieurs acides carboxyliques avec une ou plusieurs polyamines, les alkénylsuccinimides de polyamine, les dérivés d'acide phtalamique et d'amine grasse à double chaîne; des résines alkylphénol éventuellement greffées, des résines alkylphénol-aldéhydes modifiées. Des exemples de tels additifs sont donnés dans les documents suivants : EP261959, EP59333 1 , EP674689, EP327423 , EP5 12889, EP832172 ; US2005/022363 1 ;(meth) acrylic / (meth) acrylate amidified by a polyamine, the condensation products of one or more carboxylic acids with one or more polyamines, alkenyl succinimides of polyamine, phthalamic acid and fatty amine derivatives double chain; optionally grafted alkylphenol resins, modified alkylphenol-aldehyde resins. Examples of such additives are given in the following documents: EP261959, EP59333 1, EP674689, EP327423, EP5 12889, EP832172; US2005 / 022363 1;
US5998530 ; W093/14178 ; WO2012/085865. US5998530; WO93 / 14178; WO2012 / 085865.
L’additif anti-sédimentation et/ou dispersant de paraffines (WASA) particulièrement préféré est choisi parmi les résines alkylphénol et les résines alkylphénol greffées par exemple par des groupes fonctionnels tels que des polyamines. The particularly preferred anti-sedimentation and / or paraffin dispersant (WASA) additive is chosen from resins alkylphenol and alkylphenol resins grafted, for example, by functional groups such as polyamines.
La composition d’additifs selon l’invention peut, avantageusement, comprendre de 1 à 50% en poids d’additif anti- sédimentation et/ou dispersant de paraffines tel que décrit précédemment, de préférence de 2 à 30% en poids, plus préférentiellement de 5 à 20% en poids par rapport au poids total de la composition d’additifs.  The additive composition according to the invention may advantageously comprise from 1 to 50% by weight of anti-sedimentation additive and / or paraffin dispersant as described above, preferably from 2 to 30% by weight, more preferably from 5 to 20% by weight relative to the total weight of the additive composition.
La composition d’additifs selon l’invention peut également comprendre un ou plusieurs autres additifs couramment utilisés dans les carburants ou combustibles, différents du copolymère, de l’additif de tenue à froid, et de l’additif anti-sédimentation décrits précédemment.  The additive composition according to the invention may also comprise one or more other additives commonly used in fuels or combustibles, different from the copolymer, the cold-keeping additive, and the anti-sedimentation additive described above.
La composition d’additifs peut, typiquement, comprendre un ou plusieurs autres additifs choisis parmi les détergents, les agents anti corrosion, les dispersants, les désémulsifiants, les biocides, les réodorants, les additifs procétane, les modificateurs de friction, les additifs de lubrifiance ou additifs d'onctuosité, les agents d'aide à la combustion (promoteurs catalytiques de combustion et de suie), les agents anti-usure et/ou les agents modifiant la conductivité.  The additive composition can typically include one or more other additives chosen from detergents, anti-corrosion agents, dispersants, demulsifiers, biocides, reodorants, procetane additives, friction modifiers, lubricant additives or oiliness additives, combustion aid agents (catalytic combustion and soot promoters), antiwear agents and / or agents modifying conductivity.
Parmi ces additifs, on peut citer en particulier :  Among these additives, there may be mentioned in particular:
a) les additifs procétane, notamment (mais non limitativement) choisis parmi les nitrates d’alkyle, de préférence le nitrate de 2-éthyl hexyle, les peroxydes d'aryle, de préférence le peroxyde de benzyle, et les peroxydes d'alkyle, de préférence le peroxyde de tert-butyle ;  a) procetane additives, in particular (but not limited to) chosen from alkyl nitrates, preferably 2-ethyl hexyl nitrate, aryl peroxides, preferably benzyl peroxide, and alkyl peroxides, preferably tert-butyl peroxide;
b) les additifs anti-mousse, notamment (mais non limitativement) choisis parmi les polysiloxanes, les polysiloxanes oxyalkylés, et les amides d'acides gras issus d'huiles végétales ou animales. Des exemples de tels additifs sont donnés dans EP861882, EP663000, EP736590 ;  b) anti-foam additives, in particular (but not limited to) chosen from polysiloxanes, oxyalkylated polysiloxanes, and fatty acid amides derived from vegetable or animal oils. Examples of such additives are given in EP861882, EP663000, EP736590;
c) les additifs détergents et/ou anti-corrosion, notamment (mais non limitativement) choisis dans le groupe constitué par les amines, les succinimides, les alkénylsuccinimides, les polyalkylamines, les polyalkyles polyamines, les polyétheramines, les sels d’ammonium quaternaire et les dérivés du triazole ; des exemples de tels additifs sont donnés dans les documents suivants : EP0938535 ,c) detergent and / or anti-corrosion additives, in particular (but not limited to) chosen from the group consisting of amines, succinimides, alkenyl succinimides, polyalkylamines, polyalkyl polyamines, polyetheramines, ammonium salts quaternary and triazole derivatives; examples of such additives are given in the following documents: EP0938535,
US2012/00101 12 et W02012/004300. On peut également avantageusement employer les copolymères blocs formés d’au moins un motif polaire et un motif apolaire, tels que par exemple ceux décrits dans la demande de brevet FR 1761700 au nom de la Demanderesse ; d) les additifs de lubrifiance ou agents anti-usure, notamment (mais non limitativement) choisis dans le groupe constitué par les acides gras et leurs dérivés ester ou amide, notamment le monooléate de glycérol, et les dérivés d'acides carboxyliques mono- et polycycliques. Des exemples de tels additifs sont donnés dans les documents suivants : EP680506, EP860494, WO98/04656, EP915944, FR2772783 , FR2772784. Utilisation US2012 / 00101 12 and W02012 / 004300. It is also advantageously possible to use block copolymers formed from at least one polar unit and one apolar unit, such as for example those described in patent application FR 1761700 in the name of the Applicant; d) lubricating additives or anti-wear agents, in particular (but not limited to) chosen from the group consisting of fatty acids and their ester or amide derivatives, in particular glycerol monooleate, and derivatives of mono- and carboxylic acids polycyclic. Examples of such additives are given in the following documents: EP680506, EP860494, WO98 / 04656, EP915944, FR2772783, FR2772784. use
La présente invention a également pour objet l’utilisation, pour améliorer les propriétés de tenue à froid d’une composition de carburant ou de combustible, de la composition d’additifs selon l’invention. The present invention also relates to the use, to improve the cold-keeping properties of a fuel or fuel composition, of the composition of additives according to the invention.
Ladite composition de carburant ou de combustible peut être une composition choisie parmi les gazoles, les biodiesel, les gazoles de type Bx contenant x% (v/v) d’esters d’huiles végétales ou animales ou d’acides gras, les huiles végétales hydrogénées, et les fiouls tels que les fiouls domestiques, x étant un nombre strictement supérieur à 0 et inférieur ou égal à 100. Said fuel or fuel composition can be a composition chosen from gas oils, biodiesel, gas oils of type B x containing x% (v / v) of vegetable or animal oil esters or fatty acids, oils hydrogenated vegetables, and fuel oils such as domestic fuel oils, x being a number strictly greater than 0 and less than or equal to 100.
La composition de carburant ou de combustible est telle que décrite ci-après et comprend avantageusement au moins une coupe d’hydrocarbures issue d’une ou de plusieurs sources choisies parmi le groupe consistant en les sources minérales, de préférence le pétrole, les sources animales, végétales et synthétiques.  The fuel or fuel composition is as described below and advantageously comprises at least one section of hydrocarbons obtained from one or more sources chosen from the group consisting of mineral sources, preferably petroleum, animal sources , vegetable and synthetic.
Avantageusement, ladite composition d’additifs est utilisée pour améliorer les propriétés d’écoulement à basse température du carburant ou du combustible lors de son stockage et/ou son utilisation à basse température, en abaissant sa température limite de filtrabilité (ou TLF, mesurée selon la norme NF EN 1 16) et/ou son point d’écoulement (ou PE, mesuré selon la norme ASTM D 7346) et/ou en retardant ou en empêchant la sédimentation de cristaux, et de préférence en abaissant sa température limite de filtrabilité (TLF, mesurée selon la norme NF EN 1 16). Advantageously, said additive composition is used to improve the low temperature flow properties of the fuel or fuel during its storage and / or use. at low temperature, by lowering its filterability limit temperature (or TLF, measured according to standard NF EN 1 16) and / or its pour point (or PE, measured according to standard ASTM D 7346) and / or by delaying or by preventing the sedimentation of crystals, and preferably by lowering its limit filterability temperature (TLF, measured according to standard NF EN 1 16).
La composition d’additifs selon l’invention peut être utilisée pour retarder ou empêcher la sédimentation des cristaux de paraffines et plus particulièrement de n-alcanes, de préférence, les n-alcanes contenant au moins 12 atomes de carbone, plus préférentiellement au moins 20 atomes de carbone.  The additive composition according to the invention can be used to delay or prevent the sedimentation of paraffin crystals and more particularly of n-alkanes, preferably, the n-alkanes containing at least 12 carbon atoms, more preferably at least 20 carbon atoms.
Concentré d’additifs : Concentrate of additives:
La présente invention a également pour objet un concentré d’additifs comprenant la composition d’additifs selon l’invention, en mélange avec un liquide organique. Le liquide organique est avantageusement inerte vis-à-vis des constituants de la composition d’additifs, et miscible aux carburants ou combustibles, notamment ceux issus d’une ou de plusieurs sources choisies parmi le groupe consistant en les sources minérale, de préférence le pétrole, animale, végétale et synthétique. The present invention also relates to a concentrate of additives comprising the composition of additives according to the invention, in admixture with an organic liquid. The organic liquid is advantageously inert with respect to the constituents of the additive composition, and miscible with fuels or combustibles, in particular those originating from one or more sources chosen from the group consisting of mineral sources, preferably the petroleum, animal, vegetable and synthetic.
Le liquide organique est de préférence choisi parmi les solvants hydrocarbonés aromatiques tels que le solvant commercialisé sous le nom « Solvesso 150 », les alcools, les éthers et autres composés oxygénés, et les solvants paraffiniques tels que l’hexane, pentane ou les isoparaffines, seuls ou en mélange.  The organic liquid is preferably chosen from aromatic hydrocarbon solvents such as the solvent sold under the name "Solvesso 150", alcohols, ethers and other oxygenated compounds, and paraffinic solvents such as hexane, pentane or isoparaffins, alone or as a mixture.
Composition de carburant ou de combustible : Fuel or fuel composition:
L’invention concerne également une composition de carburant ou de combustible, comprenant : ( 1 ) au moins une coupe d’hydrocarbures issue d’une ou de plusieurs sources choisies parmi le groupe consistant en les sources minérales, animales, végétales et synthétiques, et The invention also relates to a fuel or fuel composition, comprising: (1) at least one cut of hydrocarbons from one or more sources chosen from the group consisting of mineral, animal, plant and synthetic sources, and
(2) au moins une composition d’additifs selon l’invention.  (2) at least one additive composition according to the invention.
Les sources minérales sont de préférence le pétrole.  The mineral sources are preferably petroleum.
La composition de carburant ou de combustible selon l’invention comprend avantageusement le ou les copolymère(s) en une teneur d’au moins 0,0001 % en poids, par rapport au poids total de la composition de carburant ou de combustible. De préférence, la teneur en copolymère(s) va de 0,0001 à 0,01 % en poids, plus préférentiellement de 0,0002 à 0,005 % en poids par rapport au poids total de la composition de carburant ou de combustible.  The fuel or fuel composition according to the invention advantageously comprises the copolymer (s) in a content of at least 0.0001% by weight, relative to the total weight of the fuel or fuel composition. Preferably, the content of copolymer (s) ranges from 0.0001 to 0.01% by weight, more preferably from 0.0002 to 0.005% by weight relative to the total weight of the fuel or fuel composition.
La composition de carburant ou de combustible selon l’invention comprend avantageusement l’additif ou les additifs fluidifiant à froid en une teneur allant de 0,0005 à 0,2% en poids, de préférence de 0,001 à 0, 1 % en poids, plus préférentiellement de 0,0015 à 0,05% en poids par rapport au poids total de la composition de carburant ou de combustible.  The fuel or fuel composition according to the invention advantageously comprises the additive or additives cold thinning in a content ranging from 0.0005 to 0.2% by weight, preferably from 0.001 to 0.1% by weight, more preferably from 0.0015 to 0.05% by weight relative to the total weight of the fuel or fuel composition.
La composition de carburant ou de combustible selon l’invention comprend avantageusement l’additif ou les additifs anti sédimentation et/ou dispersant(s) de paraffines en une teneur allant de 0,0001 à 0, 1 % en poids, de préférence de 0,0005 à 0,05 % en poids, plus préférentiellement de 0,001 à 0,02% en poids, par rapport au poids total de la composition de carburant ou de combustible.  The fuel or fuel composition according to the invention advantageously comprises the anti-sedimentation additive or additives and / or paraffin dispersant (s) in a content ranging from 0.0001 to 0.1% by weight, preferably from 0 .0005 to 0.05% by weight, more preferably from 0.001 to 0.02% by weight, relative to the total weight of the fuel or fuel composition.
Les carburants ou combustibles peuvent être choisis parmi les carburants ou combustibles hydrocarbonés liquides, seuls ou en mélange. Les carburants ou combustibles hydrocarbonés liquides comprennent notamment des distillais moyens de température d'ébullition comprise entre 100 et 500°C. Ces distillais peuvent par exemple être choisis parmi les distillais obtenus par distillation directe d'hydrocarbures bruts, les distillais sous vide, les distillais hydrotraités, les distillais issus du craquage catalytique et/ou de l'hydrocraquage de distillais sous vide, les distillais résultant de procédés de conversion type ARDS (par désulfuration de résidu atmosphérique) et/ou de viscoréduction, les distillais issus de la valorisation des coupes Fischer Tropsch, les distillats résultant de la conversion BTL (biomass to liquid) de la biomasse végétale et/ou animale, prise seule ou en combinaison, et/ou les biodiesels d'origine animale et/ou végétale et/ou les huiles et/ou esters d'huiles végétales et/ou animales. The fuels or fuels can be chosen from liquid hydrocarbon fuels or fuels, alone or as a mixture. Fuels or liquid hydrocarbon fuels include in particular distillais with a boiling temperature of between 100 and 500 ° C. These distillates can, for example, be chosen from distillates obtained by direct distillation of crude hydrocarbons, vacuum distillates, hydrotreated distillates, distillates resulting from catalytic cracking and / or hydrocracking of vacuum distillates, distillates resulting from ARDS type conversion processes (by residue desulfurization atmospheric) and / or visbreaking, the distillates resulting from the valorization of Fischer Tropsch cuts, the distillates resulting from the BTL (biomass to liquid) conversion of plant and / or animal biomass, taken alone or in combination, and / or biodiesels of animal and / or vegetable origin and / or oils and / or esters of vegetable and / or animal oils.
La teneur en soufre des carburants ou combustibles est, de préférence, inférieure à 5000 ppm, plus préférentiellement inférieure à 500 ppm, et plus préférentiellement encore inférieure à 50 ppm, voire même inférieure à 10 ppm, et avantageusement sans soufre.  The sulfur content of the fuels or fuels is preferably less than 5000 ppm, more preferably less than 500 ppm, and more preferably still less than 50 ppm, or even even less than 10 ppm, and advantageously without sulfur.
Le carburant ou combustible est, de préférence, choisi parmi les gazoles, les biodiesel, les gazoles de type Bx et les fiouls, de préférence, les fiouls domestiques (FOD).  The fuel or fuel is preferably chosen from gas oils, biodiesel, Bx type gas oils and fuel oils, preferably domestic fuel oils (FOD).
On entend par gazole de type Bx pour moteur Diesel (moteur à compression), un carburant gazole qui contient x% (v/v) d’esters d’huiles végétales ou animale (y compris huiles de cuisson usagées) transformés par un procédé chimique appelé transestérification faisant réagir cette huile avec un alcool afin d'obtenir des esters d’acide gras (EAG). Avec le méthanol et l’éthanol, on obtient respectivement des esters méthyliques d’acides gras (EMAG) et des esters éthyliques d’acides gras (EEAG). La lettre "B" suivie par un nombre indique le pourcentage d’EAG contenu dans le gazole, x étant un nombre strictement supérieur à 0 et inférieur ou égal à 100. Ainsi, un B 99 contient 99% de EAG et 1 % de distillats moyens d’origine fossile, le B 20 , 20% de EAG et 80% de distillats moyens d’origine fossile etc...By type B x diesel for diesel engine (compression engine) is meant a diesel fuel which contains x% (v / v) of vegetable or animal oil esters (including used cooking oils) transformed by a process chemical called transesterification reacting this oil with an alcohol in order to obtain fatty acid esters (EAG). With methanol and ethanol, methyl esters of fatty acids (EMAG) and ethyl esters of fatty acids (EEAG) are obtained respectively. The letter "B" followed by a number indicates the percentage of EAG contained in diesel, x being a number strictly greater than 0 and less than or equal to 100. Thus, a B 99 contains 99% EAG and 1% distillates means of fossil origin, B 20, 20% EAG and 80% of middle distillates of fossil origin etc ...
On distingue donc les carburants gazoles de type Bo qui ne contiennent pas de composés oxygénés, des carburants gazoles de type Bx qui contiennent x% (v/v) d’esters d’huiles végétales ou animales ou d’acides gras, le plus souvent esters méthyliques (EMHV ou EMAG). Lorsque l’EAG est utilisé seul dans les moteurs, on désigne le carburant par le terme B 100. A distinction is therefore made between diesel fuels of type Bo which do not contain oxygenated compounds and diesel fuels of type Bx which contain x% (v / v) of vegetable or animal oil esters or fatty acids, most often methyl esters (EMHV or EMAG). When the EAG is used alone in engines, the fuel is designated by the term B 100.
Le carburant ou combustible peut également contenir des huiles végétales hydrogénées, connues de l’homme du métier sous l’appellation HVO (de l’anglais « hydrogenated vegetable oil ») ou HDRD (de l’anglais « hydrogenation-derived renewable diesel »). The fuel or combustible can also contain hydrogenated vegetable oils, known to the skilled person under the designation HVO (from the English “hydrogenated vegetable oil”) or HDRD (from the English “hydrogenation-derived renewable diesel”).
Selon un développement particulier, le carburant ou combustible est choisi parmi les gazoles, les biodiesel et les gazoles de type Bx, les huiles végétales hydrogénées (HVO), et leurs mélanges. According to a particular development, the fuel or fuel is chosen from gas oils, biodiesel and gas oils of type B x , hydrogenated vegetable oils (HVO), and their mixtures.
La composition de carburant ou combustible peut également contenir un ou plusieurs additifs additionnels, différents des copolymères, de l’additif fluidifiant à froid et de l’additif anti sédimentation décrits ci-avant. De tels additifs peuvent être notamment choisis parmi les détergents, les agents anti-corrosion, les dispersants, les désémulsifiants, les agents anti-mousse, les biocides, les réodorants, les additifs procétane, les modificateurs de friction, les additifs de lubrifiance ou additifs d'onctuosité, les agents d'aide à la combustion (promoteurs catalytiques de combustion et de suie), les agents anti-usure et/ou les agents modifiant la conductivité.  The fuel or combustible composition can also contain one or more additional additives, different from the copolymers, of the cold-thinning additive and of the anti-sedimentation additive described above. Such additives can in particular be chosen from detergents, anti-corrosion agents, dispersants, demulsifiers, anti-foaming agents, biocides, reodorants, procetane additives, friction modifiers, lubricant additives or additives oiliness, combustion aid agents (catalytic combustion and soot promoters), antiwear agents and / or agents modifying conductivity.
Ces additifs additionnels peuvent être en général présents en quantité allant de 0,005 à 0, 1 % en poids, par rapport au poids de la composition de carburant ou de combustible (chacun).  These additional additives can generally be present in an amount ranging from 0.005 to 0.1% by weight, relative to the weight of the fuel or fuel composition (each).
L’invention a également pour objet une méthode d’amélioration des propriétés de tenue à froid d’une composition de carburant ou de combustible consistant à ajouter une composition d’additifs telle que décrite ci-avant.  The subject of the invention is also a method of improving the cold-keeping properties of a fuel or fuel composition consisting in adding a composition of additives as described above.
Les exemples ci-après sont donnés à titre d’illustration de l’invention, et ne sauraient être interprétés de manière à en limiter la portée.  The examples below are given by way of illustration of the invention, and should not be interpreted so as to limit the scope thereof.
EXEMPLES Exemple 1 : Synthèse de différents polymères EXAMPLES Example 1: Synthesis of different polymers
Les différents polymères ont été synthétisés par polymérisation radicalaire en solution. Dans un exemple typique, les monomères ont été solubilisés dans un solvant choisi parmi le toluène ou le dioxane, et l’agent de transfert a été ajouté au mélange. Le système a été dégazé sous flux d’azote pendant 40 minutes et ensuite mis à chauffer jusqu’à atteindre 70°C. Une fois à cette température, l’amorceur a été ajouté pour démarrer la polymérisation. La réaction a été laissée pendant 6h. Le système a ensuite été ouvert à l’air et laissé refroidir jusqu’à atteindre la température ambiante. Le polymère formé a été récupéré par séchage sous vide. The various polymers were synthesized by radical polymerization in solution. In a typical example, the monomers were dissolved in a solvent chosen from toluene or dioxane, and the transfer agent was added to the mixture. The system was degassed under nitrogen flow for 40 minutes and then allowed to heat until reaching 70 ° C. Once at this temperature, the initiator was added to start the polymerization. The reaction was left for 6 h. The system was then opened to air and allowed to cool until it reached room temperature. The polymer formed was recovered by drying under vacuum.
Le polymère récupéré a été caractérisé par spectroscopie RMN et chromatographie en phase gazeuse (GPC) afin de déterminer la composition et la masse molaire du copolymère, respectivement.  The recovered polymer was characterized by NMR spectroscopy and gas chromatography (GPC) in order to determine the composition and the molar mass of the copolymer, respectively.
Les caractéristiques des polymères synthétisés selon le mode opératoire ci-avant sont rassemblées dans le tableau I ci-dessous :  The characteristics of the polymers synthesized according to the above procedure are collated in Table I below:
Tableau I Table I
Exemple 2 : Evaluation des performances de tenue à froid  Example 2: Evaluation of the performance of cold resistance
Une composition G de carburant de type gazole particulièrement difficile à traiter, et dont les caractéristiques sont détaillées dans le tableau II ci-dessous : Tableau II A composition G of diesel fuel type which is particularly difficult to process, and the characteristics of which are detailed in Table II below: Table II
a été additivée avec divers ingrédients. En particulier, deux compositions G l et G2 ont été préparées. has been added with various ingredients. In particular, two compositions G 1 and G 2 were prepared.
La composition G l comprend : The composition G l includes:
- l’additif MDFI A ;  - the additive MDFI A;
- l’additif WASA 1 . La composition G2 comprend : - the WASA 1 additive. The G2 composition includes:
- l’additif MDFI A ;  - the additive MDFI A;
- l’additif WASA 2. Les compositions des additifs sont reportées dans le tableau III ci-dessous, les teneurs indiquées étant en pourcentage en poids par rapport au poids total de l’additif :  - the WASA 2 additive. The compositions of the additives are given in Table III below, the contents indicated being in percentage by weight relative to the total weight of the additive:
Tableau III  Table III
Ainsi, la composition G l comprend une composition d’additifs comparative. La composition G l est donc une composition comparative. La composition G2 comprend une composition d’additifs selon l’invention. La composition G2 est donc une composition selon l’invention. Pour la composition G l , 170 ppm d’additif WASA 1 ont été ajoutés. Deux taux d’additif MDFI A sont testés à 100 et 150 ppm. Thus, composition G l comprises a comparative additive composition. The composition G l is therefore a comparative composition. Composition G2 comprises an additive composition according to the invention. The composition G2 is therefore a composition according to the invention. For composition G 1, 170 ppm of WASA 1 additive was added. Two levels of MDFI A additive are tested at 100 and 150 ppm.
Pour la composition G2, 170 ppm d’additif WASA 2 ont été ajoutés. Deux taux d’additif MDFI A sont testés à 100 et 150 ppm.  For composition G2, 170 ppm of WASA 2 additive was added. Two levels of additive MDFI A are tested at 100 and 150 ppm.
Les performances des compositions d’additifs ont été testées, en évaluant leur aptitude à abaisser la température limite de filtrabilité (TFL) des compositions de gazole additivées G l et G2. The performance of the additive compositions was tested, by evaluating their ability to lower the limit filterability temperature (TFL) of the diesel additive compositions G 1 and G 2.
Les résultats obtenus sont présentés dans la figure unique. On a mesuré les TLF des compositions G l et G2, conformément à la norme EN 1 16.  The results obtained are presented in the single figure. The TLFs of the compositions G 1 and G 2 were measured, in accordance with standard EN 1 16.
La figure présente les résultats de TLF obtenus en ajoutant chacun des additifs définis ci-avant, en fonction du taux d’additif MDFI A, le taux d’additif WASA 1 , WASA 2 respectivement, étant constant ( 170 ppm).  The figure shows the TLF results obtained by adding each of the additives defined above, as a function of the additive rate MDFI A, the additive rate WASA 1, WASA 2 respectively, being constant (170 ppm).
La courbe A correspond aux résultats concernant la composition G l comparative. La courbe B correspond aux résultats concernant la composition G2 selon l’invention.  Curve A corresponds to the results concerning the comparative composition G l. Curve B corresponds to the results concerning the composition G2 according to the invention.
La cible de TLF à atteindre est fixée à -28°C, tel que cela a été matérialisé sur la figure unique (pointillés).  The TLF target to be reached is set at -28 ° C, as shown in the single figure (dotted lines).
La figure montre ainsi que la composition d’additifs selon l’invention permet d’atteindre la cible de TLF de -28°C avec un taux en additif MDFI A de seulement 100 ppm. Cette même TLF de -28°C est atteinte avec la composition d’additifs comparative avec un taux supérieur de 50%, i.e 150 ppm. The figure thus shows that the composition of additives according to the invention makes it possible to reach the TLF target of -28 ° C. with an MDFI A additive content of only 100 ppm. This same TLF of -28 ° C. is reached with the composition of comparative additives with a higher rate of 50%, i.e. 150 ppm.
Ainsi, l’utilisation de la composition d’additifs selon l’invention permet de réduire de 33% le taux de traitement, par rapport à la composition comparative. Par ailleurs, à taux de traitement identique, la composition d’additifs selon l’invention permet d’obtenir de meilleures performances de tenue à froid. Exemple 3 : Evaluation des performances de tenue à froid Thus, the use of the additive composition according to the invention makes it possible to reduce the treatment rate by 33%, compared with the comparative composition. Furthermore, at an identical treatment rate, the composition of additives according to the invention makes it possible to obtain better cold performance. Example 3: Evaluation of the performance of cold resistance
Une composition G’ de carburant de type gazole particulièrement difficile à traiter, et dont les caractéristiques sont détaillées dans le tableau IV ci-dessous : A composition G ’of diesel fuel type which is particularly difficult to process, and the characteristics of which are detailed in Table IV below:
Tableau IV Table IV
a été additivée avec divers ingrédients. has been added with various ingredients.
En particulier, trois compositions G’l , G’2 et G’3 ont été préparées. In particular, three compositions G’l, G’2 and G’3 were prepared.
La composition G’l comprend :  The composition G’l includes:
- l’additif MDFI B, dans du solvant Solvesso 150 (28% en poids par rapport au poids de l’additif), commercialisé par la société Total Additifs Carburants Spéciaux, qui comprend 65% en poids d’un copolymère éthylène / acétate de vinyle (EVA), et 7% en poids d’un terpolymère alpha-oléfine / acrylate de stéaryle / anhydride maléique amidifié avec une amine de suif.  - the additive MDFI B, in Solvesso 150 solvent (28% by weight relative to the weight of the additive), sold by the company Total Additifs Carburants Spéciaux, which comprises 65% by weight of an ethylene / acetate copolymer vinyl (EVA), and 7% by weight of an alpha-olefin terpolymer / stearyl acrylate / maleic anhydride amidified with a tallow amine.
La composition G’2 comprend :  Composition G’2 includes:
- l’additif MDFI B tel que décrit ci-avant ;  - the additive MDFI B as described above;
- l’additif WASA 1 tel que décrit dans l’exemple 2.  - the WASA 1 additive as described in Example 2.
La composition G’3 comprend :  Composition G’3 includes:
- l’additif MDFI B tel que décrit ci-avant ;  - the additive MDFI B as described above;
- l’additif WASA 2 tel que décrit dans l’exemple 2.  - the WASA 2 additive as described in Example 2.
Ainsi, les compositions G’l et G’2 comprennent une composition d’additifs comparative. Les compositions G’l et G’2 sont donc des compositions comparatives. La composition G’3 comprend une composition d’additifs selon l’invention. La composition G’3 est donc une composition selon l’invention. Pour chacune des compositions G’l , G’2 et G’3 , deux taux d’additif MDFI B sont testés : 400 et 600 ppm. Thus, compositions G’l and G’2 include a comparative additive composition. The compositions G’l and G’2 are therefore comparative compositions. Composition G’3 comprises a composition of additives according to the invention. Composition G’3 is therefore a composition according to the invention. For each of the compositions G’l, G’2 and G’3, two levels of additive MDFI B are tested: 400 and 600 ppm.
Pour la composition G’2, 200 ppm d’additif WASA 1 ont été ajoutés.  For composition G’2, 200 ppm of WASA 1 additive was added.
Pour la composition G’3 , 200 ppm d’additif WASA 2 ont été ajoutés.  For composition G’3, 200 ppm of WASA 2 additive was added.
Les performances des compositions d’additifs ont été testées, en évaluant leur aptitude à abaisser la température limite de filtrabilité (TFL) des compositions de gazole additivées G’l , G’2 et G’3. On a mesuré les TLF des compositions G’l , G’2 et G’3 , conformément à la norme EN 1 16. The performance of the additive compositions was tested, by evaluating their ability to lower the limit filterability temperature (TFL) of the additive diesel compositions G'l, G'2 and G'3. We have measured the TLFs of compositions G'l, G'2 and G'3, in accordance with standard EN 1 16.
Les résultats obtenus sont présentés dans le tableau V ci- dessous :  The results obtained are presented in Table V below:
Tableau Y Table Y
Les résultats montrent clairement que la composition d’additifs selon l’invention conduit à un abaissement significatif de la TLL. The results clearly show that the composition of additives according to the invention leads to a significant lowering of the TLL.

Claims

REVENDICATIONS
1 . Composition d’additifs comprenant : 1. Composition of additives comprising:
au moins un copolymère comprenant :  at least one copolymer comprising:
- au moins un motif de formule (I) suivante :  - at least one motif of formula (I) below:
dans laquelle in which
Ri représente un atome d’hydrogène ou un groupement méthyle, X représente -O-CO-, ou -CO-O- ou -NH-CO- ou -CO-NH-, et  Ri represents a hydrogen atom or a methyl group, X represents -O-CO-, or -CO-O- or -NH-CO- or -CO-NH-, and
R2 représente un groupement alkyle en Ce à C 24 ; et R2 represents a C 1 to C 24 alkyl group; and
- au moins un motif de formule (II) suivante : - at least one motif of formula (II) below:
dans laquelle in which
R représente un groupe en C 2 à C 34 , comprenant au moins un hétérocycle azoté ;  R represents a C 2 to C 34 group, comprising at least one nitrogen heterocycle;
au moins un additif fluidifiant à froid choisi parmi les copolymères d’éthylène et d’ester(s) insaturé(s) ;  at least one cold-thinning additive chosen from copolymers of ethylene and of unsaturated ester (s);
au moins un additif anti-sédimentation et/ou dispersant de paraffines.  at least one anti-sedimentation and / or paraffin dispersant additive.
2. Composition selon la revendication 1 , caractérisée en ce que le groupement R contient au moins un hétérocycle azoté ayant de un à trois atomes d’azote, plus préférentiellement deux atomes d’azote, plus préférentiellement encore le groupement R est choisi parmi les cycles suivants : un cycle imidazole substitué ou non substitué, un cycle triazole substitué ou non substitué, un cycle pyrrolidone substitué ou non substitué ; et plus préférentiellement encore le groupement R est un cycle imidazole substitué ou non substitué. 2. Composition according to claim 1, characterized in that the group R contains at least one nitrogen heterocycle having from one to three nitrogen atoms, more preferably two nitrogen atoms, more preferably still the group R is chosen from rings following: a substituted or unsubstituted imidazole ring, a substituted or unsubstituted triazole ring, a substituted or unsubstituted pyrrolidone ring; and more preferably still the group R is a substituted or unsubstituted imidazole ring.
3. Composition selon les revendications 1 ou 2, caractérisée en ce que ledit copolymère contient uniquement des motifs de formule (I) et des motifs de formule (II). 3. Composition according to claims 1 or 2, characterized in that said copolymer contains only units of formula (I) and units of formula (II).
4. Composition selon l’une quelconque des revendications précédentes, caractérisée en ce que ledit copolymère est un copolymère statistique, ou un copolymère à blocs, et de préférence ledit copolymère est un copolymère statistique.  4. Composition according to any one of the preceding claims, characterized in that said copolymer is a random copolymer, or a block copolymer, and preferably said copolymer is a random copolymer.
5. Composition selon l’une quelconque des revendications précédentes, caractérisée en ce qu’elle comprend de 0, 1 à 30% en poids dudit copolymère, de préférence de 1 à 20% en poids, plus préférentiellement de 2 à 10% en poids par rapport au poids total de la composition d’additifs.  5. Composition according to any one of the preceding claims, characterized in that it comprises from 0.1 to 30% by weight of the said copolymer, preferably from 1 to 20% by weight, more preferably from 2 to 10% by weight. based on the total weight of the additive composition.
6. Composition selon l’une quelconque des revendications précédentes, caractérisée en ce qu’elle comprend de 50 à 90% en poids dudit additif fluidifiant à froid, de préférence de 60 à 90% en poids, plus préférentiellement de 70 à 90% en poids par rapport au poids total de la composition d’additifs.  6. Composition according to any one of the preceding claims, characterized in that it comprises from 50 to 90% by weight of said cold-thinning additive, preferably from 60 to 90% by weight, more preferably from 70 to 90% by weight relative to the total weight of the additive composition.
7. Composition selon l’une quelconque des revendications précédentes, caractérisée en ce qu’elle comprend de 1 à 50% en poids dudit additif anti-sédimentation et/ou dudit dispersant de paraffines, de préférence de 2 à 30% en poids, plus préférentiellement de 5 à 20% en poids par rapport au poids total de la composition d’additifs.  7. Composition according to any one of the preceding claims, characterized in that it comprises from 1 to 50% by weight of said anti-sedimentation additive and / or of said paraffin dispersant, preferably from 2 to 30% by weight, more preferably from 5 to 20% by weight relative to the total weight of the additive composition.
8. Composition selon l’une quelconque des revendications précédentes, caractérisée en ce que l’additif fluidifiant à froid est choisi parmi les copolymères d’éthylène et d’ester(s) vinylique(s) et/ou acrylique(s), de préférence parmi les copolymères d’éthylène et d’ester(s) vinylique(s), plus préférentiellement parmi les copolymères éthylène/acétate de vinyle, les copolymères éthylène/propionate de vinyle et les terpolymères d’éthylène, d’acétate de vinyle et d’un autre ester vinylique ; plus préférentiellement encore les copolymères éthylène/acétate de vinyle et leurs mélanges avec un terpolymère d’éthylène, d’acétate de vinyle et d’un autre ester vinylique, tel que notamment le néodécanoate de vinyle. 8. Composition according to any one of the preceding claims, characterized in that the cold-thinning additive is chosen from copolymers of ethylene and of vinyl ester (s) and / or acrylic (s), of preferably among the copolymers of ethylene and of vinyl ester (s), more preferably among the ethylene / vinyl acetate copolymers, the ethylene / vinyl propionate copolymers and the terpolymers of ethylene, vinyl acetate and another vinyl ester; more preferably still, ethylene / vinyl acetate copolymers and their mixtures with a terpolymer of ethylene, vinyl acetate and another vinyl ester, such as in particular vinyl neodecanoate.
9. Composition selon l’une quelconque des revendications précédentes, caractérisée en ce que l’additif anti-sédimentation est choisi dans le groupe constitué par les copolymères acide (méth)acrylique/(méth)acrylate d'alkyle amidifiés par une polyamine, les alkénylsuccinimides de polyamine, les dérivés d'acide phtalamique et d'amine grasse à double chaîne, les produits de condensation d’un ou plusieurs acides carboxyliques avec une ou plusieurs polyamines, des résines alkylphénol-aldéhydes modifiées et des résines alkylphénol éventuellement greffées, de préférence les résines alkylphénol et les résines alkylphénol greffées. 9. Composition according to any one of the preceding claims, characterized in that the anti-sedimentation additive is chosen from the group consisting of copolymers of (meth) acrylic acid / (meth) acrylate amidified by a polyamine, polyamine alkenyl succinimides, phthalamic acid and double chain fatty amine derivatives, the condensation products of one or more carboxylic acids with one or more polyamines, modified alkylphenol-aldehyde resins and optionally grafted alkylphenol resins, preferably alkylphenol resins and grafted alkylphenol resins.
10. Utilisation, pour améliorer les propriétés de tenue à froid d’une composition de carburant ou de combustible, de la composition d’additifs telle que définie à l’une quelconque des revendications précédentes.  10. Use, to improve the cold-keeping properties of a fuel or fuel composition, of the composition of additives as defined in any one of the preceding claims.
1 1 . Utilisation selon la revendication précédente, caractérisée en ce que la composition de carburant ou de combustible est choisie parmi les gazoles, les biodiesel, les gazoles de type Bx contenant x% (v/v) d’esters d’huiles végétales ou animales ou d’acides gras, les huiles végétales hydrogénées, et les fiouls tels que les fiouls domestiques. 1 1. Use according to the preceding claim, characterized in that the fuel or fuel composition is chosen from gas oils, biodiesel, gas oils of type B x containing x% (v / v) of vegetable or animal oil esters or fatty acids, hydrogenated vegetable oils, and fuel oils such as household fuel oils.
12. Utilisation selon les revendications 10 ou 1 1 pour abaisser la température limite de filtrabilité mesurée selon la norme NF EN 1 16 et/ou le point d’écoulement mesuré selon la norme ASTM D 7346, et/ou pour retarder ou en empêcher la sédimentation de cristaux, et de préférence pour abaisser la température limite de filtrabilité mesurée selon la norme NF EN 1 16.  12. Use according to claims 10 or 1 1 to lower the filterability limit temperature measured according to standard NF EN 1 16 and / or the pour point measured according to standard ASTM D 7346, and / or to delay or prevent the sedimentation of crystals, and preferably to lower the limit filterability temperature measured according to standard NF EN 1 16.
13. Concentré d’additifs comprenant une composition d’additifs telle que définie à l’une quelconque des revendications 1 à 9, en mélange avec un liquide organique.  13. Concentrate of additives comprising an additive composition as defined in any one of claims 1 to 9, in admixture with an organic liquid.
14. Composition de carburant ou de combustible, comprenant : 14. Fuel composition, comprising:
( 1 ) au moins une coupe d’hydrocarbures issue d’une ou de plusieurs sources choisies parmi le groupe consistant en les sources minérales, animales, végétales et synthétiques, et (2) au moins une composition d’additifs telle que définie à l’une quelconque des revendications 1 à 9. (1) at least one cut of hydrocarbons from one or more sources chosen from the group consisting of mineral, animal, plant and synthetic sources, and (2) at least one additive composition as defined in any one of claims 1 to 9.
15. Composition selon la revendication précédente, caractérisée en ce qu’elle contient le ou les copolymère(s) en une teneur d’au moins 0,0001 % en poids, de préférence en une teneur allant de 0,0001 à 0,01 % en poids, plus préférentiellement de 0,0002 à 0,005 % en poids par rapport au poids total de la composition.  15. Composition according to the preceding claim, characterized in that it contains the copolymer (s) in a content of at least 0.0001% by weight, preferably in a content ranging from 0.0001 to 0.01 % by weight, more preferably from 0.0002 to 0.005% by weight relative to the total weight of the composition.
EP19758410.5A 2018-08-28 2019-08-23 Composition of additives, comprising at least one copolymer, one cold-flow improver and one anti-settling additive Pending EP3844251A1 (en)

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PCT/EP2019/072602 WO2020043619A1 (en) 2018-08-28 2019-08-23 Composition of additives, comprising at least one copolymer, one cold-flow improver and one anti-settling additive

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US20210340453A1 (en) 2021-11-04
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FR3085383B1 (en) 2020-07-31

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