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
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/1955—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by an alcohol, ether, aldehyde, ketonic, ketal, acetal radical
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
  • C10L1/2368—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing heterocyclic compounds containing nitrogen in the ring
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
  • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
  • C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • 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
  • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L2200/00—Components of fuel compositions
  • C10L2200/04—Organic compounds
  • C10L2200/0461—Fractions defined by their origin
  • C10L2200/0469—Renewables or materials of biological origin
  • C10L2200/0484—Vegetable or animal oils

Definitions

• the present invention relates to the use of particular cross-linked polymers for lowering the filterability limit temperature of fuels during storage and / or their use at low temperatures.
• the present invention also relates to additive compositions (or "additive packages") containing these polymers, as well as fuel and fuel compositions supplemented with such polymers in combination with a cold-flow additive (CFI).
• additive compositions or "additive packages” containing these polymers, as well as fuel and fuel compositions supplemented with such polymers in combination with a cold-flow additive (CFI).
• CFI cold-flow additive
• Fuels or fuels containing paraffinic compounds especially compounds containing n-alkyl, isoalkyl or n-alkenyl groups, such as paraffin waxes, are known to have deteriorated flow properties at low temperatures. temperature, typically below 0 ° C.
• temperature typically below 0 ° C.
• 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 according to their origin. These compounds tend to crystallize at low temperatures, clogging pipes, pipes, pumps and filters, for example in motor vehicle fuel systems.
• CFI cold flow improvers
• TLF Temperature Limit of Filtration
• EVA or EVP polymers of ethylene and vinyl acetate and / or vinyl propionate
• TLF additives This type of additive, widely known by those skilled in the art, is systematically added to conventional middle distillates at the refinery outlet. 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 at service stations, in particular to meet the so-called "Big Cold" specifications.
• EP0857776 proposes to use alkylphenol-aldehyde resins derived from the condensation of alkylphenol and aldehyde in combination with copolymers or terpolymers ethylene / vinyl ester, 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 carboxylic acid ester of 3 to 12 carbon atoms and a fatty alcohol comprising a chain of more of 16 carbon atoms and possibly an olefinic double bond and a cold-cooling additive (CFI) of the EVA or EVP type, to increase the effectiveness of the CFI additives by amplifying their effect on the TLF.
• CFI cold-cooling additive
• a block A consisting of a chain of structural units derived from one or more ⁇ , ⁇ -unsaturated acrylate or alkyl methacrylate monomers
• a block B consisting of a chain of structural units derived from one or more ⁇ , ⁇ -unsaturated monomers containing at least one aromatic ring.
• This additive is especially useful as a TLF booster in combination with a cold-flow additive (CFI).
• CFI cold-flow additive
• This need is particularly important for fuels comprising one or more paraffinic compounds, for example compounds containing n-alkyl, isoalkyl or n-alkenyl groups exhibiting a tendency to crystallize at low temperature.
• distillates used in fuels are increasingly derived from more complex refining operations than those resulting from the direct distillation of petroleum, and can come in particular from cracking, hydrocracking and catalytic cracking processes. visbreaking processes. With the increasing demand for diesel fuels, the refiner tends to introduce into these fuels cuts more difficult to exploit, such as the heaviest cuts from cracking and visbreaking processes which are rich in long-chain paraffins.
• the present invention applies to fuels containing not only conventional distillates such as those derived from the direct distillation of crude oils, but also bases derived from other sources, such as those described above.
• the object of the present invention is to propose novel additives and concentrates containing them which may advantageously be used as additives to improve the cold-holding properties of these fuels, when they are stored and / or when they are used low temperature, typically below 0 ° C.
• the object of the present invention is to propose new additives for fuels and fuels, and concentrates containing such additives, acting on the Temperature Limit of Filtration (TLF).
• TLF Temperature Limit of Filtration
• Another object of the invention is to provide a fuel or fuel composition having improved cold-holding properties, particularly at temperatures below 0 ° C, preferably below -5 ° C.
• the present invention thus relates to the use, for lowering the filterability limit temperature of a fuel or fuel composition, of one or more crosslinked polymers comprising at least one unit of formula (I) below:
• R 1 represents a hydrogen atom or a methyl group
• E represents -O-CO-, or -CO-O- or -NH-CO- or -CO-NH-, and
• G represents a C1-C34 alkyl group
• said copolymer having a degree of crosslinking, corresponding to the molar amount of crosslinking agent relative to the total molar amount of monomers in the polymer, crosslinking agent not included, in the range of 0.5% to 30% .
• the polymer defined above is used as a so-called “TLF booster” additive, that is to say in combination with a flow-enhancing additive or cold-flow additive (in English “cold”). flow improvers “or CFI), which improves performance.
• the invention also relates to an additive composition comprising such a polymer in combination with a cold-cooling additive as described hereinafter, as well as an additive concentrate comprising such a composition.
• the cold-cooling additive chosen from copolymers and terpolymers of ethylene and of vinyl ester (s) and / or acrylic (s), alone or as a mixture.
• the invention also relates to a composition of fuel or fuel, comprising:
• At least one cold-cooling additive selected from copolymers and terpolymers of ethylene and of vinyl ester (s) and / or acrylic (s).
• compound C N denotes a compound containing in its chemical structure N carbon atoms.
• the crosslinked polymer is a crosslinked polymer:
• the invention uses a crosslinked polymer, comprising at least one unit of formula (I) below:
• R 1 represents a hydrogen atom or a methyl group
• E represents -O-CO-, or -CO-O- or -NH-CO- or -CO-NH-,
• G represents a C1-C34 alkyl group.
• the group E of the formula (I) is chosen from:
• the group E of the formula (I) is preferably the group -O- CO-.
• the group E of the formula (I) is chosen from: -CO-O- and -CO-NH-, it being understood that the group E is connected to the vinyl carbon by the carbon atom.
• the group E of the formula (I) is preferably the -CO-O- group.
• the group E is a group -CO-O-, E being connected to the vinyl carbon by the carbon atom.
• the group G of the formula (I) is a C 1 to C 34 alkyl group, preferably a C 4 to C 34 alkyl radical, preferably a C 4 to C 30 alkyl radical, more preferably a C 6 to C 24 alkyl radical, more preferably in Cs to C 22 .
• the alkyl radical is a linear or branched radical, cyclic or acyclic, preferably acyclic. This alkyl radical can comprise a linear or branched part and a cyclic part.
• the group G of formula (I) is advantageously a linear or branched C 1 to C 34 , preferably C 4 to C 34 , more preferably C 4 to C 30 , more preferably C 6 to C 24, alkyl acyclic radical. More preferably Cs to C22, and more preferably C12 to C14 or C14 to C22.
• the embodiment in which the group G is a linear or branched C 12 to C 14 acyclic alkyl radical is particularly preferred.
• alkyl groups such as butyl, octyl, decyl, dodecyl, ethyl-2-hexyl, isooctyl, isodecyl and isododecyl, and alkyl groups.
• alkyl groups such as butyl, octyl, decyl, dodecyl, ethyl-2-hexyl, isooctyl, isodecyl and isododecyl, and alkyl groups.
• alkyl groups such as butyl, octyl, decyl, dodecyl, ethyl-2-hexyl, isooctyl, isodecyl and isododecyl, and alkyl groups.
• the group E is a group -CO-O-, E being connected to the vinyl carbon by the carbon atom
• the group G is a linear or branched acyclic alkyl radical C1 to C34. , preferably C 4 -C 30, more preferably C 6 -C 24, more preferably Cs to C 22, more preferably C 12 -C 14 or -C s to C 22.
• the embodiment in which the group G is a linear or branched C 12 to C 14 acyclic alkyl radical is particularly preferred.
• the units according to this embodiment correspond to those resulting from monomers chosen from acrylates and methacrylates of C 1 to C 34, preferably C 4 to C 30 , more preferably C 6 to C 24 , even more preferentially in Cs to C 22 , and more preferably in C12 to C14 or in C s to C22.
• the crosslinked polymer may be a homopolymer or a copolymer.
• the polymer according to the invention may comprise several (at least two) different units of formula (I) as described above and / or additional units, different from the units of formula (I) above.
• Such additional units are preferably derived from polar monomers, such as in particular from one or more polar-substituted vinyl monomers.
• Preferred polar monomers include:
• the copolymer according to the invention advantageously contains at least 50 mol% of units of formula (I), preferably at least 70 mol%.
• the copolymer contains from 50 to 80 mol% of units of formula (I).
• the polymer according to the invention is a copolymer
• it may be chosen from block copolymers and random copolymers, preferably random copolymers.
• the polymer according to the invention has the particularity of being crosslinked.
• the degree of crosslinking corresponding to the quantity in moles of crosslinking agent relative to the total amount by mole of monomers of the polymer, crosslinking agent not included, is from 0.5% to 30%, preferably from 1% to 20%, more preferably from 2% to 10%, and even better from 3% to 6%.
• the crosslinking agent may be any compound capable of allowing the crosslinking of polymers comprising units of formula (I) as described above. Many crosslinking agents exist, and are well known to those skilled in the art.
• the crosslinking agent is chosen from di-vinyl compounds, and more preferentially from the diacrylates and dimethacrylates of formula (III) below:
• R representing a hydrocarbon chain comprising from 2 to 16 and preferably from 3 to 12 carbon atoms, which may be interrupted by one or more heteroatoms chosen from N and O, and which may be substituted with one or more -OZ groups with Z representing a hydrogen atom or a C 1 -C 4 alkyl radical, and
• R 2 and R 3 represent, independently of one another, a hydrogen atom or a methyl group.
• Nonlimiting examples of particularly preferred crosslinking agents include:
• 1,6-hexanediol dimethacrylate of formula:
• glycerol dimethacrylate of formula:
• 1,6 hexanediol diacrylate of formula:
• di (ethylene glycol) diacrylate of formula: the 1,6 hexanediol ethoxylate diacrylate of formula:
• the polymer employed in the present invention may be obtained by homopolymerization or copolymerization of at least one monomer corresponding to the following formula (II):
• R 1, E and G are as defined above, the preferred variants of R 1, E and G according to formula (I) described above being also preferred variants of formula (II).
• the monomer of formula (II) is preferably selected from alkyl vinyl esters Ci-C34, preferably C 4 to C 30, more preferably C 6 to C 24, more preferably C 8 to C22, more preferably C12-C14 or Ci 8 at C22 and even more preferably at C12 to C14.
• the alkyl radical of the alkyl vinyl ester is linear or branched, cyclic or acyclic, preferably acyclic.
• alkyl vinyl ester monomers mention may be made, for example, of vinyl octanoate, vinyl decanoate, vinyl dodecanoate, vinyl tetradecanoate, vinyl hexadecanoate, vinyl octodecanoate and docosanoate. vinyl, 2-ethylhexanoate vinyl.
• the monomer of formula (II) is preferably selected from acrylates or methacrylates of alkyl to C34, preferably C 4 to C 30, more preferably C 6 to C 24, more preferably Cs to C22 and more preferably C12 to C14, or Cis at C22, and even more preferably at C12 to C14.
• the alkyl radical of the acrylate or methacrylate is linear or branched, cyclic or acyclic, preferably acyclic.
• alkyl (meth) acrylates that can be used as monomers in the manufacture of the polymer of the invention, mention may be made, by way of non-limiting examples: n-octyl acrylate, n-octyl methacrylate, n-decyl acrylate, methacrylate, n-decyl, n-dodecyl acrylate, n-dodecyl methacrylate, ethyl-2-hexyl acrylate, ethyl-2-hexyl methacrylate, isooctyl acrylate, methacrylate, isooctyl, isodecyl acrylate, isodecyl methacrylate, alkyl acrylates, C 1 2 to 4 or a 1 is C to C22 alkyl methacrylates of C 12 to C i 4 or i C 8 -C 22. It is particularly preferred to employ alkyl acrylate,
• the polymer according to the invention was obtained from monomers different from those of formula (II) above, insofar as the final polymer corresponds to a crosslinked polymer as defined above.
• the units of formula (I) can be obtained from acrylic acid, by transesterification reaction.
• the polymer according to the invention can be prepared according to 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 those skilled in the art.
• the polymerization is, advantageously, a controlled radical polymerization; for example, by atom transfer radical polymerization (ATRP in English “Atom Transfer Radical Polymerization”); the radical polymerization by nitroxide (NMP in English “Nitroxide-mediated polymerization”); degenerative transfer processes (degenerative transfer processes) such as degenerative iodine transfer polymerization (ITRP-iodine polymerization ”) or radical polymerization by reversible addition-fragmentation chain transfer (RAFT) (Reversible Addition-Fragmentation Chain Transfer); polymerizations derived from ATRP such as polymerizations using initiators for the continuous regeneration of the activator (ICAR -Initiators for continuous activator regeneration) or using electron-regenerated activators regenerated by electron (ARGET) transfer ").
• ATRP atom transfer radical polymerization
• NMP nitroxide
• degenerative transfer processes degenerative transfer processes
• IRP-iodine polymerization degenerative iodine transfer poly
• the reversible Addition-Fragmentation Chain Transfer (RAFT) radical polymerization is a living radical polymerization technique.
• the RALT technique was discovered in 1988 by the Australian scientific research organization CSIRO (J. Chiefari et al., Macromolecules, 1998, 31, 5559).
• the RALT technique has very rapidly been the subject of intensive research by the scientific community as it allows the synthesis of macromolecules with complex architectures, including structures in blocks, grafts, combs or even stars. by controlling the molecular weight of the macromolecules obtained (G. Moad et al., Aust J. Chem, 2005, 58, 379).
• RALT polymerization can be applied to a very broad range of vinyl monomers and under various experimental conditions, including for the preparation of water-soluble materials (McCormick, C. et al., Acc., Chem Res., 2004, 37, 3, 12). ).
• the RALT method includes the conventional radical polymerization of a substituted monomer in the presence of a suitable chain transfer agent (RALT agent or CTA in English "Chain Transfer Agent").
• RALT agents include thiocarbonylthio compounds such as dithioesters (J. Chiefari et al., Macromolecules, 1998, 1, 5559), dithiocarbamates (R. T. A. Mayadunne et al.,
• radical radicalization description RAFT examples include the following documents WO 1998/01478, W01999 / 114 144, WO2001 / 77198, WO2005 / 003 19,
• the crosslinked polymer according to the invention advantageously has a weight average molecular weight (Mw) of between 10 000 and 100 000 g. mol 1 , preferably between 10,000 and 50,000 g. mol 1 , and more preferably between 1 000 and 35 000 g. mol 1 .
• Mw weight average molecular weight
• the crosslinked polymer according to the invention advantageously has a number-average molecular weight (Mn) of between 2,000 and 16,000 g. mol 1 .
• the average molar masses by number and by weight are measured by Size Exclusion Chromatography (SEC).
• the crosslinked polymer described above is used to lower the temperature limit of filterability of a fuel composition or fuel, in particular, of a composition selected from gas oils, biodiesel, type B x gas oils and fuel oils preferably, domestic fuel oils (FOD).
• a fuel composition or fuel in particular, of a composition selected from gas oils, biodiesel, type B x gas oils and fuel oils preferably, domestic fuel oils (FOD).
• FOD domestic fuel oils
• the filterability limit temperature, or TLF is measured according to standard NF EN 1 16.
• the fuel or fuel composition is as described below and advantageously comprises at least one hydrocarbon fraction from one or more sources selected from the group consisting of mineral sources, preferably petroleum, animal, vegetable and synthetic.
• the crosslinked polymer according to the invention is used as a TLF booster additive, that is to say in combination with at least one flow-enhancing additive or cold-flow additive (in English “cold”). flow improvers "or CFI).
• the cold-flow additive is chosen from copolymers and terpolymers of ethylene and of vinyl ester (s) and / or acrylic (s), alone or as a mixture.
• the crosslinked polymer according to the invention is used to amplify the fluidifying effect of the cold-flow additive, by lowering the filterability limit temperature (TLF).
• TLF filterability limit temperature
• TLF booster This effect is usually called the "TLF booster" effect insofar as the presence of the crosslinked polymer improves the fluidifying nature of the CFI additive.
• This improvement is reflected, in particular, by a significant decrease in the TLF of the fuel composition or fuel additive with this combination compared to the same fuel composition or fuel additive only with the CFI additive, at the same rate of treatment.
• a significant decrease in the TLF results in a reduction of at least 3 ° C of the TLF according to standard NF EN 1 16.
• the crosslinked polymer is used to amplify the fluidizing (flow) effect of the cold-flow-making additive (CFI) by improving the temperature limit of filterability (TLF) of the fuel or fuel, the TLF being measured according to standard NF EN 1 16.
• the crosslinked polymer may be added to the fuels within the refinery, and / or be incorporated downstream of the refinery, optionally mixed with other additives, in the form of an additive concentrate, also called according to the use "additive package".
• the crosslinked polymer is advantageously used in the fuel or fuel at a content of at least 2 ppm by weight, preferably at least 3 ppm by weight, and more preferably at least 5 ppm by weight.
• ppm by weight more preferably at a content ranging from 2 to 100 ppm by weight, still more preferably from 3 to 50 ppm by weight and more preferably from 3 to 10 ppm by weight, relative to the total weight of the fuel composition or of fuel.
• the units mentioned in ppm in the present application correspond to ppm by weight unless otherwise indicated.
• the invention also relates to an additive composition comprising a crosslinked polymer as described above, and one or more additive (s) fluidifying (s) cold.
• the cold-flow additive is chosen from copolymers and terpolymers of ethylene and of vinyl ester (s) and / or acrylic (s), alone or as a mixture.
• copolymers of ethylene and of unsaturated ester such as ethylene / vinyl acetate (EVA), ethylene / vinylpropionate (EVP), ethylene / vinyl ethanoate (EVE) copolymers ethylene / methyl methacrylate (EMMA), and ethylene / alkyl fumarate described, for example, in US3048479,
• the cold-flow-making additive is chosen from copolymers of ethylene and of vinyl ester (s), alone or as a mixture, in particular ethylene / vinyl acetate copolymers.
• EVA ethylene / vinyl acetate copolymers
• EDP ethylene / vinyl propionate
• EVA ethylene / vinyl acetate copolymers
• the additive composition may also comprise one or more other additives commonly used in fuels or fuels, different from the cross-linked polymer and cold-flow-reducing additives described above.
• the additive composition may typically comprise one or more other additives selected from detergents, anti-corrosion agents, dispersants, demulsifiers, anti-foam agents, biocides, deodorants, procetane additives, friction modifiers, lubricity additives or lubricity additives, combustion assistants (catalytic combustion promoters and soot), anti-sedimentation agents, anti-wear agents and / or conductivity modifiers.
• additives selected from detergents, anti-corrosion agents, dispersants, demulsifiers, anti-foam agents, biocides, deodorants, procetane additives, friction modifiers, lubricity additives or lubricity additives, combustion assistants (catalytic combustion promoters and soot), anti-sedimentation agents, anti-wear agents and / or conductivity modifiers.
• procetane additives in particular (but not limited to) selected from alkyl nitrates, preferably 2-ethyl hexyl nitrate, aryl peroxides, preferably benzyl peroxide, and alkyl peroxides, preferably ter-butyl peroxide;
• anti-foam additives in particular (but not limited to) selected from polysiloxanes, oxyalkylated polysiloxanes, and fatty acid amides from vegetable or animal oils. Examples of such additives are given in EP 861 882, EP663000, EP736590;
• detergent and / or anti-corrosion additives in particular (but not limited to) selected from the group consisting of amines, succinimides, alkenylsuccinimides, polyalkylamines, polyalkylamines, polyetheramines, quaternary ammonium salts and triazole derivatives; examples of such additives are given in the following documents: EP0938535,
• lubricity additives or anti-wear agents in particular (but not limited to) selected from the group consisting of fatty acids and their ester or amide derivatives, in particular glycerol monooleate, and monocarboxylic acid derivatives and polycyclic.
• lubricity additives or anti-wear agents are given in the following documents: EP680506, EP860494, WO98 / 04656, EP915944, FR2772783, FR2772784.
• anti-sedimentation additives and / or paraffin dispersants in particular (but not exclusively) chosen from the group consisting of polyamine-amidated (meth) acrylic acid / alkyl (meth) acrylate copolymers, alkenylsuccinimides of polyamine, phthalamic acid derivatives and double fatty amine chain; alkylphenol resins.
• examples of such additives are given in the following documents: EP261959, EP59333 1, EP674689, EP327423, EP512889, EP832172; US2005 / 022363 1;
• the additive composition may advantageously comprise from 0.3 to 30% by weight of crosslinked polymer as described above, relative to the total weight of the additive composition.
• the present invention also relates to an additive concentrate comprising an additive composition as described above, 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, especially those from one or more sources selected 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 marketed under the name "SOLVESSO", alcohols, ethers and other oxygenated compounds, and paraffinic solvents such as hexane, pentane or isoparaffins, alone. or in mixture.
• aromatic hydrocarbon solvents such as the solvent marketed under the name "SOLVESSO”
• alcohols, ethers and other oxygenated compounds such as hexane, pentane or isoparaffins, alone. or in mixture.
• the fuel or fuel composition is:
• the invention also relates to a fuel or fuel composition, comprising:
• At least one cold-cooling additive selected from copolymers and terpolymers of ethylene and of vinyl ester (s) and / or acrylic (s).
• the fuel composition according to the invention advantageously comprises the crosslinked polymer (s) in a content of at least 2 ppm by weight, preferably at least 3 ppm, and more preferably at least 5 ppm. ppm, more preferably at a content ranging from 2 to 100 ppm, still more preferably from 3 to 50 ppm, and more preferably from 3 to 10 ppm by weight.
• the cold-reducing additive (s) is (are) chosen from ethylene / vinyl acetate (EVA), ethylene / vinylpropionate (EVP), ethylene copolymers.
• EVE vinyl ethanoate
• EMMA ethylene / methyl methacrylate
• EVE ethylene / vinyl acetate
• EVP ethylene / vinyl propionate copolymers
• the composition advantageously contains at least 20 ppm by weight, preferably at least 50 ppm, advantageously between 20 and 5000 ppm, more preferably between 50 and 1000 ppm by weight of cold-flow additive (s).
• the fuels or fuels may be chosen from liquid hydrocarbon fuels or liquid fuels alone or as a mixture.
• the liquid hydrocarbon fuels or fuels comprise, in particular, middle distillates having a boiling point of between 100 and 500 ° C.
• These distillates may for example be chosen from distillates obtained by direct distillation of crude hydrocarbons, vacuum distillates, hydrotreated distillates, distillates obtained from catalytic cracking and / or hydrocracking of distillates under vacuum, distillates resulting from ARDS (by atmospheric residue desulphurisation) and / or visbreduction type conversion processes, the distillates resulting from the recovery 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 by weight, preferably less than 500
• the fuel or fuel is preferably selected from gas oils, biodiesels, gasolines type B x and fuel oils, preferably domestic fuel oils (FOD).
• FOD domestic fuel oils
• Diesel fuel of type B x for a diesel engine means a diesel fuel which contains x% (v / v) of vegetable or animal oil esters (including used cooking oils) converted by a process chemical called transesterification reacting this oil with an alcohol to obtain fatty acid esters (EAG). With methanol and ethanol, fatty acid methyl esters (EMAG) and fatty acid ethyl esters (EEAG) are obtained respectively.
• EAG fatty acid methyl esters
• EEAG fatty acid ethyl esters
• the letter "B” followed by a number x ranging from 0 to 100 indicates the percentage of EAG contained in the diesel fuel.
• a B99 contains 99% of EAG and 1% of middle distillates of fossil origin, the B20, 20% of EAG and 80% of middle distillates of fossil origin, etc.
• the diesel fuels of Bo type are distinguished. which do not contain oxygenated compounds, type Bx gasolines which contain x% (v / v) of vegetable oil esters or fatty acids, most often methyl esters (EMHV or EMAG).
• EAG methyl esters
• the fuel is designated by the term B 100.
• the fuel or fuel may also contain hydrogenated vegetable oils known to those skilled in the art as HVO (hydrogenated vegetable oil) or HDRD (hydrogenation-derived renewable diesel). .
• HVO hydrogenated vegetable oil
• HDRD hydrogenation-derived renewable diesel
• the fuel or fuel is selected from gas oils, biodiesels and gas oils type B x , hydrogenated vegetable oils (HVO), and mixtures thereof.
• the fuel or fuel composition may also contain one or more additional additives, different from the cross-linked polymers and cold-flow-reducing additives described above.
• additives may be chosen from detergents, anti-corrosion agents, dispersants, demulsifiers, anti-foam agents, biocides, re-deodorants, procetane additives, friction modifiers, lubricant additives or additives. lubricity, combustion assistants (catalytic combustion promoters and soot), anti-settling agents, anti-wear agents and / or conductivity modifiers.
• additives may generally be present in an amount ranging from 50 to 1000 ppm by weight (each).
• a method for lowering the filterability limit temperature of a fuel or fuel composition comprises a step of treating said composition with at least one crosslinked polymer as described above, and with one or more cold-flow additive (s) chosen from copolymers and terpolymers of ethylene and of vinyl ester (s) and / or acrylic (s).
• s cold-flow additive
• such a method comprises the successive steps of:
• an additive composition (s) most suitable for the fuel composition or fuel to be treated and the treatment rate necessary to achieve a maximum value of filterability limit temperature for the specific fuel or fuel composition
• said additive composition (s) comprising at least cross-linked polymer according to the invention and at least one cold-flow-forming additive (CFI);
• step b) treating the fuel or fuel composition with the amount determined in step a) of said additive composition (s).
• the process according to the invention is typically intended for a fuel or fuel composition as described above.
• Step a) is carried out according to any known process and is common practice in the field of fuel additives. This step involves defining a target value and then to determine the improvement that is required to achieve the specification.
• the specification is a maximum TLF according to standard NF EN 1 16.
• the determination of the amount of additive composition (s) to be added to the fuel or fuel composition in order to reach the specification will be carried out typically by comparison with the composition. fuel or fuel without said additive composition (s).
• the cross-linked polymer amount needed to process the fuel or fuel composition may vary depending on the nature and origin of the fuel or fuel, particularly depending on the rate and nature of the paraffinic compounds it contains. The nature and origin of the fuel or fuel may therefore also be a factor to be taken into account for step a).
• the above method may also include an additional step after step b) of checking the target reached and / or adjusting the treatment rate with the additive composition (s).
• AIBN azobis isobutyronotrile
• the AIBN solution is then transferred using a nitrogen purged syringe into the 50 mL flask, preheated to 80 ° C, to initiate polymerization.
• the reaction is left 24h.
• the solvent is evaporated under reduced pressure (55mbar) at 60 ° C to recover the crosslinked copolymer.
• Example 1 The polymers described in Example 1 were tested as cold-holding additives in a composition G diesel fuel type particularly difficult to treat, and whose characteristics are detailed in the table below:
• the gas oil composition G was added with a package containing the following two commercial cold flow-forming additives (CFI additives) in solvent Solvesso 150:
• additive CP7956C ethylene-vinyl acetate copolymer
• Dodiflow D4134 marketed by Clariant, and which is an ethylene-vinyl acetate-vinyl neodecanoate terpolymer.
• This package was incorporated into the composition of diesel G at a content of 300 ppm by weight of active ingredient (ie 150 ppm by weight of each additive) relative to the total weight of the gas oil composition.
• Each polymer was added at a content of 3 ppm by weight to the composition G 1, to give the G 2 gas oil, which was then measured TLF, according to the standard EN 1 16.

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• 2017
  • 2017-12-21 FR FR1762700A patent/FR3075813B1/fr active Active
• 2018
  • 2018-12-17 WO PCT/EP2018/085152 patent/WO2019121485A1/fr unknown
  • 2018-12-17 EP EP18815750.7A patent/EP3728524A1/de active Pending
  • 2018-12-17 US US16/955,369 patent/US20210095217A1/en not_active Abandoned

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