Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
  • C10L1/2366—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amine groups
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/146—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
  • 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
  • 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
  • C10L1/196—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
  • C10L1/18—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
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L2200/00—Components of fuel compositions
  • C10L2200/04—Organic compounds
  • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
  • C10L2200/0438—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
  • C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
  • C10L2230/14—Function and purpose of a components of a fuel or the composition as a whole for improving storage or transport of the fuel
• • 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
  • C10L2270/00—Specifically adapted fuels
  • C10L2270/02—Specifically adapted fuels for internal combustion engines
  • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine

Definitions

• TITLE Use of particular cationic polymers as cold strength additives for fuels and fuels
• the present invention relates to the use of particular cationic polymers as cold strength additives in fuel and fuel compositions, for example to improve their cold resistance properties during storage and / or use at low temperature.
• the present invention also relates to fuel and fuel compositions supplemented with such polymers.
• the present invention finally relates to additive compositions (or "additive packages”) containing these polymers, in combination with at least one cold thinning additive (CFI), as well as a method for lowering the limit temperature of filterability d. a fuel or fuel composition using such a polymer.
• additive compositions or "additive packages” containing these polymers, in combination with at least one cold thinning additive (CFI), as well as a method for lowering the limit temperature of filterability d. a fuel or fuel composition using such a polymer.
• CFI cold thinning additive
• Fuels or fuels containing paraffinic compounds are known to exhibit deteriorated flow properties at low temperatures, typically below 0 ° C.
• the middle distillates obtained by distillation from crude oils of petroleum origin such as gas oil or domestic fuel oil contain different amounts of n-alkanes or n-paraffins depending on their origin. These compounds tend to crystallize at low temperature, blocking pipes, conduits, pumps and filters, for example in the fuel circuits of motor vehicles.
• CFI cold flow improvers
• s vinyl ester
• acrylic s
• TLF Limit Temperature of Filterability
• PE pour point
• EVA polymers of ethylene and vinyl acetate and / or vinyl propionate
• TLF additives polymers of ethylene and vinyl acetate and / or vinyl propionate
• Document EP0857776 proposes to use 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 with 3 to 12 carbon atoms and a fatty alcohol comprising one more chain. of 16 carbon atoms and optionally an olefinic double bond and of a cold liquefying 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 liquefying additive
• Patent application WO 2016/128379 describes the use, as an additive for the cold resistance of a fuel or fuel, of a block copolymer comprising:
• an A block consisting of a chain of structural units derived from one or more ⁇ , b-unsaturated alkyl acrylate or methacrylate monomers
• a B block 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 in particular useful as a TLF booster in combination with a cold thinning additive (CFI).
• CFI cold thinning additive
• another object of cold-resistance additives is to ensure the dispersion of the paraffin crystals, so as to delay or prevent the sedimentation of such crystals and of avoid the formation of a layer rich in paraffins at the bottom of containers, tanks or storage tanks; these paraffin dispersing additives are called anti-sedimentation additives or WASA (acronym for the English term “Wax Anti-Settling Additive”).
• 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 derived from more complex refining operations than those derived from the direct distillation of petroleum, and may 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 exploit, 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 fuels containing not only conventional distillates such as those obtained from the direct distillation of crude oils, but also to bases obtained from other sources, such as those described above.
• the aim of the present invention is to provide new additives and concentrates containing them, which can be used as additives in fuel compositions and other fuels in order to improve their cold resistance properties, in particular their properties. cold flow at low temperature typically less than 0 ° C, and better still less than -5 ° C.
• the object of the present invention is furthermore to provide new additives for fuels and fuels, and concentrates containing such additives, acting on the Limit Filtrability Temperature (TLF), the pour point (PE), and retarding and / or preventing the sedimentation of crystals of hydrocarbon compounds, in particular paraffins.
• TEZ Limit Filtrability Temperature
• PE pour point
• these polymers possess unexpected properties for improving the cold resistance of fuel and fuel compositions, including those which are particularly difficult to process.
• a subject of the present invention is thus the use, to improve the cold resistance properties of a fuel or fuel composition, of one or more polymers comprising at least 70% by moles of units of formula (I) below : in which 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 group of formula -R2-Q in which R2 denotes a C 1 -C 34 hydrocarbon chain and Q denotes a group comprising a quaternary ammonium function and optionally one or more hydroxyl groups.
• the polymer defined above is used as an additive called “TLF booster”, that is to say in combination with an additive for improving flow or cold liquefying additive (in English “cold flow improvers ”or CFI) whose performance it improves.
• TEZ booster an additive for improving flow or cold liquefying additive
• a subject of the invention is also a fuel or fuel composition, comprising: at least one cut of hydrocarbons obtained from one or more sources chosen from the group consisting of mineral (preferably petroleum), animal sources. , vegetable and synthetic,
• At least one cold thinning additive chosen from copolymers of ethylene and vinyl ester (s).
• a subject of the invention is also an additive composition (or “additive package”) comprising such a polymer in combination with at least one cold resistance additive different from the polymers according to the invention, as well as a concentrate of additives containing such a composition.
• the cold resistance additive is chosen from copolymers and terpolymers of ethylene and of vinyl ester (s) and / or acrylic (s), alone or as a mixture.
• a subject of the invention is a method for lowering the limit filterability temperature of a fuel or fuel composition, comprising adding to said fuel or fuel composition of a polymer according to the invention.
• C N compound or group denotes a compound or a group containing in its chemical structure N carbon atoms.
• the invention uses a polymer comprising at least 70 mol% of units of formula (I) below: in which 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 group of formula -R2-Q in which R2 denotes a C 1 to C34 hydrocarbon chain, and Q denotes a group comprising a quaternary ammonium function and optionally one or more hydroxyl groups.
• the group E of formula (I) is chosen from:
• the group E is preferably the group -O-CO-.
• the group E of formula (I) is chosen from: -CO-O- and -CO-NH-, it being understood that the group E is linked to the vinyl carbon via the carbon atom.
• the group E is preferably the group -CO-O-.
• the group E is a -CO-O- group, E being linked to the vinyl carbon via the carbon atom.
• the group G of formula (I) contains an R2 hydrocarbon chain chosen from C1 to C34, cyclic or acyclic, linear or branched hydrocarbon chains.
• R2 denotes a linear or branched C 1 to C 18, more preferably C 1 to C 8, hydrocarbon chain, even more preferably a linear C 2 to C 4 hydrocarbon chain.
• the quaternary ammonium function (s) of the group Q can be chosen from quaternary ammoniums of pyrrolinium, pyridinium, imidazolium, triazolium, triazinium, oxazolium, isoxazolium, trialkylammonium, iminium, of amidinium, of formamidinium, of guanidinium and of biguanidinium, and preferably of trialkylammonium.
• the group G is represented by one of the following formulas (II) and (III): in which :
• R 2 is as defined above;
• X is an anion, preferably chosen from hydroxide ions, halides and organic anions, preferably from organic anions,
• R 3 , R 4 and R 5 are identical or different and chosen, independently of one another, from C 1 to C 24 hydrocarbon chains, preferably from C 4 to C 5, it being understood that the groups R 3 , R 4 and R 5 may contain one or more nitrogenous and / or oxygenated groups and in particular be substituted by one or more hydroxyl group (s) and that the R 3 , R 4 and R 5 groups can be linked together in pairs to form one or more cycles,
• R O and R 7 are identical or different and independently selected from hydrocarbon chains to C 24, preferably C 4 to C, it being understood that R O and R 7 groups may contain one or more nitrogenous groups and / or oxygenated and in particular be substituted by one or more hydroxyl group (s) and that the R ⁇ and R 7 groups can be linked together to form a ring.
• the group G is represented by formula (II) above, in which: R 2 denotes a linear or branched C 1 to C 18 hydrocarbon chain, more preferably C 1 to C 8, even more preferably a linear C 2 to C 4 hydrocarbon chain;
• R 3 , R 4 and R 5 represent, independently of one another, C 1 to C 18, preferably C 1 to C 12 , alkyl groups, optionally substituted by at least one hydroxyl group, it being understood that at least one of the groups R 3 , R 4 and R 5 contains one or more hydroxyl group (s);
• X is the conjugate base of a carboxylic acid, preferably a monocarboxylic acid containing from 1 to 24 carbon atoms, more preferably from 2 to 18, even more preferably from 2 to 8.
• X corresponds to the formula R-COO with R a linear or branched alkyl group , preferably linear, C1 to C24, more preferably C2 to Cis, even more preferably C2 to Cs.
• the polymer according to the invention comprises at least 70% by moles of units of formula (I), preferably at least 80% by moles, and better still at least 90% by moles.
• the polymer according to the invention is formed from units of formula (I), ie it does not contain units different from the units of formula (I) above.
• the polymer according to the invention is a homopolymer, that is to say that it is formed from a single repeating unit of formula (I).
• the polymer used in the present invention can be obtained by homopolymerization or copolymerization of one or more monomer (s) corresponding to the following formula (IV): in which
• Ri, E and G are as defined above, the preferred variants of Ri, E and G according to formula (I) described above also being preferred variants of formula (IV).
• the polymer used in the invention is obtained by homopolymerization of a single monomer of formula (IV).
• the polymer according to the invention is obtained by polymerization of intermediate monomers corresponding to the following formula (V): in which
• Ri and E are as defined above according to formula (I) and G 'represents a group of formula -R2-P in which R2 denotes a C 1 to C 34 hydrocarbon chain optionally substituted by one or more hydroxyl group (s) , as defined above, and P denotes a group comprising a tertiary amine function capable of leading to the Q group as defined above, by reaction with a quaternization agent.
• the quaternizing agent is preferably an epoxide, and preferably an epoxide in combination with a monocarboxylic acid which is preferably a monocarboxylic acid containing from 2 to 12 carbon atoms as described above, preferably 4 to 8 atoms. of carbon.
• the polymerization is advantageously a block polymerization.
• the sequenced polymerization may be of the group transfer polymerization (GTP) or controlled radical polymerization type; for example, by atom transfer radical polymerization (ATRP); radical polymerization by nitroxide (NMP in English "Nitroxide-mediated polymerization”); degenerative transfer processes such as degenerative iodine transfer polymerization (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 the 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 ”).
• GTP group transfer polymerization
• ATRP atom transfer radical polymerization
• NMP radical polymerization by nitroxide
• the polymer according to the invention advantageously has a number-average molar mass (Mn) of between 500 and 5,000 g. mol 1 , more preferably between 1200 and 3000 g. mol 1 .
• Mn number-average molar mass
• the number-average molar masses of a polymer are, in a manner known per se, measured by nuclear magnetic resonance (NMR).
• the polymer described above is used to improve the cold resistance properties of a fuel or fuel composition, in particular, of a composition chosen from gas oils, biodiesels, type B x gas oils and fuel oils. such as in particular domestic fuel oils (FOD).
• FOD domestic fuel oils
• the fuel or fuel composition is as described below and advantageously comprises at least one cut of hydrocarbons obtained from one or more sources chosen from the group consisting of mineral sources, preferably petroleum, animal sources. , vegetable and synthetic.
• the polymer according to the invention is used to improve the low-temperature flow properties of the fuel or of the fuel during its storage and / or its use at low temperature, by lowering its limit filterability temperature (or TLF, measured according to standard NF EN 116) and / or its pour point (or PE, measured according to standard ASTM D 7346) and / or by delaying or preventing the sedimentation of crystals, and preferably by lowering its limit filterability temperature (TLF, measured according to standard NF EN 116).
• TLF limit filterability temperature
• PE measured according to standard ASTM D 7346
• TLF limit filterability temperature
• the polymer 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. , even more preferably preferably at least 24.
• the polymer according to the invention is used as a TLF booster additive, that is to say in combination with at least one flow improvement additive or cold flow additive. improvers ”or CFI).
• the cold thinning additive (CFI) is preferably chosen from copolymers and terpolymers of ethylene and of vinyl ester (s) and / or acrylic (s), alone or as a mixture, preferably from among ethylene / vinyl acetate (EVA) copolymers and their mixtures with a terpolymer of ethylene, vinyl acetate and a other vinyl ester.
• the polymer according to the invention is used to amplify the fluidifying effect of the cold fluidifying additive, in particular by lowering the limit filterability temperature (TLF) and / or the pour point, and / or the pour point. or by delaying or preventing the sedimentation of crystals, such as those containing paraffins.
• TLF limit filterability temperature
• TLF booster This effect is usually referred to as the "TLF booster" effect insofar as the presence of the polymer according to the invention improves the fluidifying nature of the CFI additive.
• This improvement is reflected, in particular, by a significant reduction in the TLF of the fuel composition or fuel additive with this combination compared to the same fuel or fuel composition additive only with the additive CFI, at the same treatment rate.
• a significant drop in TLF results in a decrease of at least 3 ° C in TLF according to standard NF EN 116.
• the polymer is used to amplify the liquefying (flow) effect of the cold liquefying additive (CFI) by improving the Limit Filterability Temperature (TLF) of the fuel or fuel, the TLF being measured according to standard NF EN 116.
• CFI cold liquefying additive
• TLF Limit Filterability Temperature
• the polymer can be added to the fuels or fuels within the refinery, and / or be incorporated downstream of the refinery, optionally, in admixture with other additives, in the form of a concentrated composition of additives, also called according to usage "additive package”.
• the polymer is advantageously used in a content of at least 0.0001% by weight, relative to the total weight of the fuel or fuel composition.
• the content of said polymer ranges from 0.0001 to 0.01% by weight, preferably from 0.0002 to 0.005% by weight, and more preferably from 0.0003 to 0.002% by weight, relative to the total weight. fuel or fuel composition.
• a subject of the invention is also a composition of additives comprising a polymer as described above, and at least one cold thinning additive (CFI) chosen from copolymers of ethylene and of vinyl ester (s). ), the weight ratio between the content of polymer (s) formed from units of formula (I) on the one hand, and the content of copolymer (s) of ethylene and vinyl ester (s) ) on the other hand, being included in the range from 0.1: 100 to 10: 100.
• CFI cold thinning additive
• Said copolymers of ethylene and vinyl ester (s) are different from polymers formed from units of formula (I).
• copolymers and terpolymers of ethylene and of vinyl ester (s) and / or acrylic (s) can be used alone or as a mixture.
• copolymers of ethylene and of unsaturated ester such as ethylene / vinyl acetate (EVA), ethylene / vinyl propionate (EVP), ethylene / vinyl ethanoate (EVE) copolymers.
• EVA ethylene / vinyl acetate
• EVE ethylene / vinyl ethanoate
• EMMA ethylene / methyl methacrylate
• the copolymers of ethylene and of vinyl ester (s) are chosen from ethylene / vinyl acetate (EVA) copolymers, ethylene / vinyl propionate (EVP) copolymers and terpolymers.
• EVA ethylene / vinyl acetate
• EDP ethylene / vinyl propionate
• ethylene, vinyl acetate and another vinyl ester more preferably from ethylene / vinyl acetate (EVA) copolymers and their mixtures with a terpolymer of ethylene, of vinyl acetate and of another vinyl ester, such as in particular vinyl neodecanoate.
• the weight ratio between the content of polymer (s) according to the invention on the one hand, and the content of copolymer (s) of ethylene and of vinyl ester (s) on the other hand, is included in the range from 0.1: 100 to 10: 100, preferably from 0.5: 100 to 5: 100.
• a particularly preferred weight ratio is 1: 100 ⁇ 10%.
• the additive composition may also comprise one or more several anti-sedimentation additives and / or paraffin dispersants (WASA), different from the polymer according to the invention and from the cold thinning additives described above.
• WASA paraffin dispersants
• These additives may be in particular, but not limited to, chosen from the group consisting of (meth) acrylic acid / (meth) acrylate copolymers of alkyl amidified with a polyamine, polyamine alkenylsuccinimides, derivatives of phthalamic acid and of double chain fatty amine; optionally grafted alkylphenol resins. Examples of such additives are given in the following documents: EP261959, EP593331, EP674689, EP327423, EP512889, EP832172;
• WASA paraffin dispersant additives
• the additive composition may also include one or more other additives commonly used in fuels or fuels, other than the polymer according to the invention and cold resistance additives described above.
• the additive composition may typically comprise one or more other additives chosen from detergents, anti-corrosion agents, dispersants, demulsifiers, biocides, reodorants, procetane additives, friction modifiers, lubricity additives. or lubricity additives, combustion aid agents (catalytic combustion and soot promoters), antiwear agents and / or conductivity modifiers.
• procetane additives in particular (but not limited to) chosen from alkyl nitrates, preferably 2-ethylhexyl nitrate, aryl peroxides, preferably peroxide benzyl, 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 obtained from vegetable oils or animal.
• additives examples include EP861882, EP663000, EP736590; c) detergent and / or anti-corrosion additives, in particular (but not limited to) chosen from the group consisting of amines, succinimides, alkenylsuccinimides, polyalkylamines, polyalkyl polyamines, polyetheramines, quaternary ammonium salts and triazole derivatives; examples of such additives are given in the following documents: EP0938535, US2012 / 0010112 and W02012 / 004300.
• block copolymers formed from at least one polar unit and one non-polar 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 mono- and carboxylic acid derivatives. polycyclic. Examples of such additives are given in the following documents: EP680506, EP860494, WO98 / 04656, EP915944, FR2772783,
• the additive composition can advantageously comprise from 0.1 to 50% by weight of polymer as described above, preferably from 0.2 to 20% by weight, and more preferably from 0.5 to 10% by weight. , relative to the total weight of additives present in said additive composition.
• a subject of the present invention is also an additive concentrate comprising an additive composition as described above, mixed with an organic liquid.
• the organic liquid is advantageously inert with respect to the constituents of the additive composition, and miscible with fuels or fuels, in particular those obtained from one or more sources chosen from the group consisting of mineral sources, preferably petroleum, animal, vegetable and synthetic.
• the organic liquid is preferably chosen from aromatic hydrocarbon solvents such as the solvent sold under the name “SOLVESSO”, alcohols, ethers and other oxygenated compounds, and paraffinic solvents such as hexane, pentane or isoparaffins, alone or as a mixture.
• aromatic hydrocarbon solvents such as the solvent sold under the name “SOLVESSO”
• alcohols, ethers and other oxygenated compounds such as hexane, pentane or isoparaffins, alone or as a mixture.
• paraffinic solvents such as hexane, pentane or isoparaffins
• the invention also relates to a fuel or fuel composition, comprising:
• At least one cold thinning additive chosen from copolymers of ethylene and vinyl ester (s).
• the mineral sources are preferably petroleum.
• the fuel or fuel composition according to the invention advantageously comprises said polymer (s) formed from units of formula (I) in a content of at least 0.0001% by weight, relative to the total weight. fuel or fuel composition.
• the content of such polymer (s) ranges from 0.0001 to 0.01% by weight, preferably from 0.0002 to 0.005% by weight, and more preferably from 0.0003 to 0.002% by weight. weight, relative to the total weight of the fuel or fuel composition.
• the cold thinning additives (CLI) chosen from copolymers of ethylene and vinyl ester (s) are as described above. They are different (s) from the polymers according to the invention formed from units of formula (I).
• the fuel composition preferably contains at least 20 ppm (0.002% by weight), preferably at least 50 ppm (0.005% by weight), preferably between 20 and 5000 ppm (between 0.002% and 0.5% by weight), more preferably between 50 and 1000 ppm (between 0.005% and 0.1% by weight) in total of cold thinning additive (s) chosen from copolymers of ethylene and of ester (s) vinyl (s).
• the composition may also contain one or more anti-sedimentation additives and / or paraffin dispersants (WASA), different from the polymers according to the invention formed from units of formula (I) and ethylene copolymers and vinyl ester (s).
• WASA paraffin dispersants
• the fuels or fuels can be chosen from liquid hydrocarbon fuels or fuels, alone or as a mixture.
• Liquid hydrocarbon fuels or fuels include in particular middle distillates with a boiling point of between 100 and 500 ° C. These distillates can for example be chosen from the distillates obtained by direct distillation of crude hydrocarbons, the vacuum distillates, the hydrotreated distillates, the distillates resulting from the catalytic cracking and / or the hydrocracking of vacuum distillates, the distillates resulting from ARDS-type conversion processes (by desulphurization of atmospheric residue) and / or visbreaking, distillates resulting from the upgrading of Fischer Tropsch cuts, 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 combustibles is preferably less than 5000 ppm, preferably less than 500 ppm, and more preferably less than 50 ppm, or even less than 10 ppm, and advantageously sulfur free.
• the fuel or fuel is preferably chosen from gas oils, biodiesels, type B x gas oils and fuel oils, preferably domestic fuel oils (FOD).
• diesel type B x diesel compression engine
• a diesel fuel which contains x% (v / v) of esters of vegetable or animal oils (including used cooking oils) transformed by a process chemical called transesterification by reacting this oil with an alcohol to obtain fatty acid esters (EAG).
• EAG fatty acid esters
• FAME fatty acid methyl esters
• EEAG fatty acids
• B followed by a number x ranging from 0 to 100, which indicates the percentage of EAG contained in the diesel fuel.
• a B99 contains 99% of EAG and 1% of middle distillates of fossil origin, B20, 20% of EAG and 80% of middle distillates of fossil origin etc.
• type Bx diesel fuels which contain x% (v / v) of esters of vegetable or animal oils or of fatty acids, most often methyl esters (EMHV or FAME).
• EAG methyl esters
• FAME methyl esters
• the fuel or fuel may also contain hydrogenated vegetable oils, known to those skilled in the art under the name HVO (standing for “hydrotreated vegetable oil”) or HDRD (standing for “hydrogenation-derived renewable diesel”).
• HVO hydrogenated vegetable oil
• HDRD hydrogenation-derived renewable diesel
• the fuel or fuel is chosen from gas oils, biodiesels, type B x gas oils, hydrogenated vegetable oils (HVO), and mixtures thereof.
• the fuel or fuel composition may also contain one or more additional additives, different from the polymers according to the invention and from the cold resistance additives described above.
• additives can in particular be chosen from detergents, anti-corrosion agents, dispersants, demulsifiers, anti-foam agents, biocides, reodorants, procetane additives, friction modifiers, lubricity additives or additives. lubricity, combustion aid agents (catalytic combustion and soot promoters), antiwear agents and / or conductivity modifiers, as described above.
• a method of improving the cold resistance properties of a fuel or fuel composition comprises a step of adding to said composition a polymer formed from units of formula (I ) as defined above.
• this method comprises the successive steps of: a) determining a composition of additive (s) suitable for the composition of the fuel or fuel to be treated as well as the rate of treatment, said composition of additive ( s) comprising at least one polymer according to the invention formed from units of formula (I) and, optionally, at least one cold-thinning additive chosen from copolymers of ethylene and of vinyl ester (s), different from polymers formed from units of formula (I); b) treatment of the fuel or fuel composition with the quantity determined in step a) of said composition of additive (s).
• the process for improving the cold resistance properties is typically intended for a fuel or fuel composition as described above.
• Step a) is carried out according to any known process and falls within common practice in the field of fuel or fuel additives.
• This step involves defining a characteristic representative of the cold resistance properties of the fuel or fuel, for example the low temperature flow characteristics, setting the target value (in particular a given specification relating to the cold resistance properties), then determine the improvement that is required to achieve such a target value.
• a specification relating to cold resistance can be a European Deep Cold specification defining, in particular, a maximum TLF according to standard NF EN 116. Determination of the quantity of additive composition (s) to be added to the Fuel or fuel composition to achieve the specification will typically be achieved by comparison with the fuel or fuel composition without said composition of additive (s).
• the amount of additive composition required to treat the fuel or fuel composition may vary depending on the nature and origin of the fuel or fuel, in particular depending on the rate and nature of the paraffinic compounds that it contains. contains. The nature and origin of the fuel or fuel can therefore also be a factor to be taken into account for step a).
• the method of improving the cold resistance properties may also include an additional step after step b) of verifying the target reached and / or adjusting the rate of treatment with the composition of additive (s).
• RAFT 2-cyano-2-propyl dodecyl trithiocarbonate
• the intermediate polymer thus obtained has a number-average molar mass Mn of 1500 G. mol 1 which corresponds to an average of 8 units of formula (I) per polymer chain.
• the conversion rate is 99% by weight (ie 1% by weight of residual monomer).
• Two polymers PI and P2 according to the invention were prepared, by quaternization of the intermediate amino polymer above, in accordance with the protocols below.
• Example 1 The PI and P2 polymers described in Example 1 were tested as cold-resistance additives in a fuel composition G of diesel fuel type which is particularly difficult to process, and the characteristics of which are detailed in Table 1 below:
• the gas oil composition G was additivated with a conventional cold-resistance additive A, which consists of the following two commercial cold-thinning additives (CFI additives), in Solvesso 150 solvent:
• CFI additives commercial cold-thinning additives
• additive marketed by the company Total Additives Carburants Spéciaux, and which is an ethylene / vinyl acetate (EVA) copolymer having a molecular mass of between 2000 and 6000 gmol 1 ; - 0.5% by weight of Dodiflow D4134 additive marketed by the company
• EVA ethylene / vinyl acetate
• Clariant and which is an ethylene / vinyl acetate / vinyl ester terpolymer.
• Additive A has been incorporated into the diesel fuel composition G at a content of 300 ppm by weight of active material relative to the total weight of the diesel fuel composition.
• the gas oil composition with additive Gl This has a limit filterability temperature (TLF, standard EN 116) of -6 ° C.
• TLF limit filterability temperature
• the performances as cold-resistance additives of each of the polymers PI and P2 of Example 1 were tested, by evaluating their ability to lower the limit filterability temperature (TFL) of the additive gas oil composition G l.
• TLF limit filterability temperature
• Each polymer was added at a content of 3 ppm by weight (0.0003% by weight) to composition Gl, to give gas oil G2, the TLF of which was then measured, in accordance with standard EN 116.

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• 2019
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