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
  • 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
  • C10L1/16—Hydrocarbons
  • C10L1/1625—Hydrocarbons macromolecular compounds
  • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
  • C10L1/165—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aromatic monomers
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, 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
• • 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
  • C10L1/18—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
  • C10L1/234—Macromolecular compounds
  • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives 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
  • C10L1/2364—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amide and/or imide groups
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/234—Macromolecular compounds
  • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
  • C10L1/2366—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof homo- or copolymers derived from unsaturated compounds containing amine groups
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • 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

Definitions

• the present invention relates to the use of copolymers and additive concentrates containing such copolymers for improving the properties of low-temperature fuels or fuels, also known as cold-holding properties, in particular their flow properties during storage and / or their use at low temperature.
• the present invention relates in particular to the use of copolymers to enhance the fluidizing (flow) effect of the cold-flow additive (CFI) by improving the Filterability Limit Temperature (TLF) of the fuel or fuel.
• CFI fluidizing
• TEZ Filterability Limit Temperature
• the present invention also relates to the use of copolymers as an anti-sedimentation additive, also called WASA or "Wax Anti-Settling Additive", for retarding and / or preventing the sedimentation of crystals of n-alkyl, isoalkyl or n-alkyl substituted compounds. alkenyl.
• WASA anti-sedimentation additive
• Wax Anti-Settling Additive for retarding and / or preventing the sedimentation of crystals of n-alkyl, isoalkyl or n-alkyl substituted compounds. alkenyl.
• the present invention also relates to fuel and fuel compositions additive with a cold-flow additive (CFI) comprising such copolymers.
• CFI cold-flow additive
• Fuels containing n-alkyl, iso-alkyl or n-alkenyl substituted compounds such as paraffin waxes are known to exhibit deteriorated flow properties at low temperatures, typically below 0 ° C.
• the middle distillates obtained from crude oils of petroleum origin by distillation such as diesel or heating oil contain different amounts of n-alkanes or n-paraffins according to their origin.
• These n-alkyl, iso-alkyl or n-alkenyl substituted compounds tend to crystallize by lowering the temperature, clogging pipes, lines, pumps and filters, for example in motor vehicle fuel systems.
• the phenomenon of crystallization can lead to the decrease of the flow properties of fuels and, consequently, difficulties during their transport, storage and / or their use.
• the cold operability of fuels is important, especially for starting cold engines. If the paraffins are crystallized at the bottom of the tank, they can be driven to start in the fuel system and particularly clog the filters and prefilters arranged upstream systems injection pump and injectors. Similarly, for the storage of domestic fuel oils, paraffins precipitate at the bottom of the tank and can be driven and obstruct the pipes upstream of the pump and the boiler supply system (nozzle and filter).
• CFI cold flow improvers
• CFI Cold Flow Additives
• TLF Filtration Limit Temperature
• PE pour point
• TLF additives Temporal Limit of Filtration
• TLF Temperature Limit of Filtration
• JP 2003 286495 A describes the use as cold-flow additive of copolymers obtained by copolymerization of ethylene and of a monomer comprising an aromatic ring.
• JP 2003 286495 A describes the use as cold-flow additive of copolymers obtained by copolymerization of ethylene and of a monomer comprising an aromatic ring.
• EP0857776 the alkylphenol-aldehyde resins resulting from the condensation of alkylphenol and aldehyde have been proposed in association with copolymers or terpolymers ethylene / vinyl ester, to improve the fluidity of mineral oils.
• the document FR2903418 describes in particular the use of a combination of a polyacrylate or polymethacrylate with a cold-cooling additive (CFI) of the EVA or EVP type, to reveal the effectiveness of the CFI additives by amplifying their effect on the TLF.
• CFI cold-cooling additive
• Another purpose of the flow enhancement additives is to ensure the dispersion of the paraffin crystals, so as to retard or prevent the sedimentation of the crystals of the crystals.
• paraffins and thus the formation of a paraffin-rich layer in the bottom of containers, tanks or storage tanks; these paraffin-dispersing additives are referred to as anti-settling additives or WASA (acronym for Wax Anti-Settling Additive).
• Modified alkylphenol aldehyde resins have been described in FR2969620 as an anti-sedimentation additive in combination with a TLF additive.
• the object of the present invention is to provide novel additives and concentrates containing them which can advantageously be used as additives to improve cold-holding properties, in particular the cold-flow properties of these fuels, during their storage and / or their use at low temperature, typically below 0 ° C.
• the object of the present invention is furthermore to propose new additives and concentrates containing them acting both on the TLF and retarding and / or preventing the sedimentation of the crystals of n-alkyl, isoalkyl or n-substituted-substituted compounds. alkenyl, in particular paraffins.
• 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 Applicant has discovered that the copolymers mentioned below and additive concentrates containing such copolymers, have remarkable properties as an additive for improving the cold-holding properties of fuels during their storage and / or their use. at low temperature.
• the invention relates to the use of a copolymer as an additive for improving the cold-holding properties of a fuel or a fuel, this copolymer being obtained by copolymerization of at least: (i) an apolar monomer (m a ) having the following formula I):
• G represents a group chosen from a C1-C4 alkyl, an aromatic ring, an aralkyl comprising at least one aromatic ring and at least one C1-C34 alkyl group, and
• an ⁇ , ⁇ -unsaturated polar monomer (m b ) containing at least one styrene derivative or an alpha-methylstyrene derivative is distinct.
• the polar monomer (m b ) is chosen from styrene and alpha-methylstyrene derivatives whose aromatic nucleus is substituted by at least one R group or at least one C 1 to C hydrocarbon chain.
• 2 linear or branched, preferably acyclic, substituted by at least one R group, said R group being chosen from:
• y is an integer from 2 to 8
• f is an integer from 1 to 10
• Q is selected from C 1 to C 24 alkyl chains.
• the group R is chosen from groups having a primary, secondary or tertiary amine function.
• the group R is chosen from the group consisting of: -NH 2 ; groups having at least one amine, imine, amidine, guanidine, aminoguanidine or biguanidine function; heterocyclic groups having from 3 to 34 atoms and at least one nitrogen atom.
• the polar monomer (m b ) is chosen from styrene and alpha-methylstyrene derivatives, the aromatic nucleus of which is substituted by at least one linear or branched C 1 -C 12 hydrocarbon-based chain, preferably acyclic, preferably selected from alkyl groups, said chain being substituted by one or more groups containing a quaternary ammonium.
• the group R is chosen from groups having at least one quaternary ammonium function, preferably chosen from tertiary quaternary ammoniums.
• the quaternary ammonium function is chosen from quaternary ammoniums of iminium, amidinium, formamidinium, guanidinium and biguanidinium.
• the quaternary ammonium function is chosen from quaternary ammoniums of pyrrolinium, pyridinium, imidazolium, triazolium, triazinium, oxazolium and isoxazolium.
• the group R is chosen from trialkylammonium groups, preferably the polar monomer (m b ) is chosen from the isomers of (vinylbenzyl) trialkylammoniums, alone or as a mixture.
• the polar monomer (m b ) is chosen from monomers derived from styrene or alpha-methylstyrene whose aromatic nucleus is substituted by at least one -O- (CO) -Q group, Q being selected from C1 to C4 alkyls
• the polar monomer (m b ) is chosen from monomers derived from styrene or alpha-methylstyrene whose aromatic nucleus is substituted by at least one hydroxyl group or by a C 1 to C 3 hydrocarbon chain. C12, linear or branched, preferably acyclic, substituted by at least one hydroxyl group.
• the group E of the apolar monomer (m a ) is chosen from -O-, -NH (Z) - with Z represents H or a C 1 -C 6 alkyl group, and -O- Where E is connected to the vinyl carbon by the oxygen atom.
• w is equal to 0.
• the group G is a C4-C30 alkyl.
• the group G is an aralkyl comprising at least one aromatic ring and at least one C4-30 alkyl group.
• the copolymer is a block or random copolymer, preferably a block copolymer.
• the copolymer is a block copolymer obtained by block copolymerization and controlled.
• the copolymer is a diblock copolymer.
• the block copolymer is represented by the following formula (III) or (IV):
• n is an integer ranging from 2 to 50, preferably from 3 to 20,
• p is an integer ranging from 2 to 50, preferably from 3 to 20,
• R 0 is chosen from hydrogen or the methyl group, preferably R 0 is H,
• R 3 is a substituent in the ortho, meta or para position on the aromatic ring, preferably in the para position, chosen from the group consisting of at least one R group or at least one linear or branched C 1 -C 12 hydrocarbon-based chain; , preferably acyclic, substituted by at least one R group, said R group being chosen from:
• a group comprising from 1 to 40 atoms chosen independently from C, N, and optionally O, and comprising at least one primary, secondary, tertiary or quaternary ammonium amine function,
• - polyalkoxy groups - (OC y H 2y O) rH where y is an integer from 2 to 8, preferably 2 to 4, more preferably from 2 to 3 and f is an integer ranging from 1 to 10, preferably of
• - polyalkoxy groups - (OC y H 2y O) RR8 where y is an integer from 2 to 8, preferably 2 to 4, more preferably from 2 to 3 and f is an integer ranging from 1 to 10, preferably from 2 to 8, more preferably from 2 to 4, and R 8 represents a C 1 to C 24 alkyl, preferably C1 to C12 ,
• R 9 is chosen from C 1 to C 24 , preferably C 1 to C 12 , more preferably C 1 to C 6 , linear or branched, preferably acyclic, and
• R 4 is selected from the group consisting of:
• halogens preferably bromine
• R 5 and R 6 are identical or different and independently selected from the group consisting of hydrogen and alkyl groups C1 to Ci 0, preferably -C C 4 , linear or branched, more preferably acyclic, even more preferentially the methyl group,
• R 7 is selected from hydrogen or methyl, preferably R 7 is H.
• the invention also relates to the use of a copolymer as defined above as an anti-sedimentation additive, in particular for retarding and / or preventing the sedimentation of crystals of n-alkyl, isoalkyl or n-substituted-substituted compounds. alkenyl during storage and / or use at low temperatures.
• the invention further relates to the use of a copolymer as defined above as an additive for improving the cold-holding properties of a fuel or fuel from one or more sources selected from the group consisting of mineral, animal, vegetable and synthetic sources, said copolymer being used with at least one cold-cooling additive (CFI) improving the low-temperature flow properties of said fuel or fuel during its storage and / or its use at low temperature .
• CFI cold-cooling additive
• said fuel or fuel comprises one or more n-alkyl, iso-alkyl or n-alkenyl substituted compounds having a tendency to crystallize in said fuel or a fuel during storage and / or use at low temperature.
• the use is intended to amplify the fluidifying effect of the cold-flow-making additive (CFI) by improving the Filtration Limit Temperature (TLF) according to standard NF EN 1 16 of said fuel or fuel.
• CFI cold-flow-making additive
• TEZ Filtration Limit Temperature
• the invention also relates to an additive concentrate comprising a copolymer as defined above and comprising at least one cold-cooling additive (CFI), preferably chosen from ethylene and ester (s) copolymers and terpolymers.
• CFI cold-cooling additive
• the additive concentrate further comprises at least one organic liquid, said organic liquid being inert with respect to the copolymer and miscible with fuels or fuels derived from one or more sources chosen from group consisting of mineral, animal, vegetable and synthetic sources.
• the invention also relates to the use of a concentrate as defined above, for retarding or preventing the sedimentation of the crystals of the n-alkyl, isoalkyl or n-alkenyl substituted compounds of the fuel or fuel during its storage. and / or its use at low temperature.
• the invention also relates to the use of a concentrate as defined above to improve the fluidizing (flow) effect by improving the filterability limit temperature (TLF) of the fuel or fuel.
• TEZ filterability limit temperature
• the invention also relates to the use of a concentrate as defined above, in which the fuel or fuel is chosen from diesel fuel, bio-gas oils, gas oil and bio-diesel fuel mixtures of type B x and fuel oils, preferably domestic fuel oils (FOD).
• the fuel or fuel is chosen from diesel fuel, bio-gas oils, gas oil and bio-diesel fuel mixtures of type B x and fuel oils, preferably domestic fuel oils (FOD).
• the invention further relates to a fuel or fuel composition
• a fuel or fuel composition comprising: (1) a fuel or fuel from one or more sources selected from the group consisting of mineral, animal, plant and synthetic sources,
• CFI cold-improving cold-forming additive
• EVA and or EVP cold-improving cold-forming additive
• the fuel or fuel in the fuel or fuel composition: (1) the fuel or fuel is derived from one or more sources selected from the group consisting of mineral, animal, plant and synthetic sources, includes one or a plurality of n-alkyl, isoalkyl or n-alkenyl substituted compounds having a tendency to crystallize in said fuel or fuel during storage and / or use at a low temperature,
• the copolymer as defined above is present in the composition in an amount sufficient to retard or prevent the sedimentation of the crystals of said n-alkyl, iso-alkyl or n-alkenyl substituted compounds, during storage and / or the low temperature use of said fuel or fuel (1).
• the composition contains at least 10 ppm, preferably between 10 and 5000 ppm of the copolymer and at least 10 ppm, preferably between 10 and 5000 ppm of the cold-flow additive.
• the fuel or fuel is selected from gas oils, bio-diesel, blends of diesel and bio-diesel type B x and fuel oils, more preferably from gas oils, biodiesel, diesel and bio-diesel fuel mixtures type B x .
• copolymers mentioned below and the additive concentrates containing such copolymers can be used as an anti-settling additive, also called WASA or "Wax Anti-Settling Additive", to retard and / or prevent sedimentation of crystals of n-alkyl, isoalkyl or n-alkenyl substituted compounds during storage and / or use at low temperatures.
• WASA Wood Anti-Settling Additive
• the copolymer used as an additive improving the cold properties of a fuel or a fuel is obtained by copolymerization of at least one apolar (m a ) and at least one styrenic monomer (m b ).
• the copolymer is chosen from block copolymers and random copolymers.
• the copolymer is a block copolymer.
• the copolymer can be obtained by copolymerizing at least one apolar monomer (m a ), and at least one polar monomer (m b )
• the olaire monomer (m a ) has the following formula (I):
• the group E of the apolar monomer (m a ) is chosen from
• - E -NH (Z) - with Z represents H or a linear or branched, cyclic or acyclic, preferably acyclic, C 1 -C 6 alkyl group,
• the copolymer is a block copolymer.
• E -NH (Z) - with Z represents H or a linear or branched, cyclic or acyclic, preferably acylic, C 1 -C 6 alkyl group, preferably CH 3 , and
• the group (G) of the apolar monomer (m a ) may be a C 1 -C 3 alkyl, preferably a C 4 -C 30 alkyl radical, more preferably a C 6 -C 24, still more preferably a C 8 -C 18 alkyl radical.
• 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 the apolar monomer (m a ) is advantageously an acyclic alkyl in C1-C34, preferably an alkyl radical C4-C30, more preferably C6-C24, still more preferably C8-C18, linear or branched, preferably linear.
• alkyl groups such as octyl, decyl, dodecyl, ethyl-2-hexyl, isooctyl, isodecyl and isododecyl.
• 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 group (G) of the apolar monomer (m a ) may also be an aromatic ring, preferably a phenyl or aryl group.
• aromatic groups there may be mentioned, without limitation, the phenyl or naphthyl group, preferably the phenyl group.
• the group (G) of the apolar monomer (m a ) may, according to another preferred variant, be an aralkyl comprising at least one aromatic ring and at least one C 1 -C 34 alkyl group.
• the group (G) is an aralkyl comprising at least one aromatic ring and one or more C4-C30 alkyl groups, advantageously C6-C24, still more preferably C8-C18.
• the aromatic ring may be mono-substituted or substituted on a number of its carbon atoms. Preferably, the aromatic ring is monosubstituted.
• the C1-C34 alkyl group may be in the ortho, meta or para position on the aromatic ring, preferably in para.
• the alkyl radical is a linear or branched radical, cyclic or acyclic, preferably acyclic.
• the alkyl radical is preferably an acyclic radical, linear or branched, preferably linear.
• the aromatic ring may be directly attached to the E group or the vinyl carbon but may also be connected to it via an alkyl substituent.
• group (G) mention may be made of a benzyl group substituted in para with a C 4 -C 30 alkyl group.
• the group (G) of the apolar monomer (m a ) is an aralkyl comprising at least one aromatic ring and at least one C 4 -C 30 alkyl group, advantageously C 6 -C 24, still more preferably C 8 at C18.
• the polar monomer (m b ) is chosen from styrene and alpha-methylstyre derivatives whose aromatic ring is substituted with at least one R group or with at least one C 1 -C 12 and preferably C 1 -C 8 hydrocarbon-based chain. 4 , linear or branched, preferably acyclic, advantageously -CH 2 -, substituted by at least one R group.
• hydrocarbon chain is meant a chain consisting exclusively of carbon and hydrogen atoms, said chain being linear or branched, cyclic, polycyclic or acyclic, saturated or unsaturated, and optionally aromatic or polyaromatic.
• a hydrocarbon chain may comprise a linear or branched part and a cyclic part. It may include an aromatic part and an aromatic part.
• substitution on the aromatic ring of the styrenic group is ortho, meta or para, preferably para.
• the aromatic ring of the styrenic group is substituted by a single substituent.
• the group R is chosen from:
• - alkoxy groups -OQ, Q is an alkyl to C 24,
• the group R is preferably chosen from:
• - polyalkoxy groups - (OC y H 2y O) rH where y is an integer ranging from 2 to 4, most preferably from 2 to 3 and f is an integer ranging from 2 to 8, more preferably from 2 to 4,
• - polyalkoxy groups - (OC y H 2y O) rQ
• y is an integer preferably ranging from 2 to 4, more preferably from 2 to 3 and f is an integer ranging from 2 to 8, more preferably from 2 to 4
• Q is an alkyl to C 2
• alkyl carboxylates or alkyl esters -O- (CO) -Q, Q representing a C1-C12 alkyl.
• R is selected from alkyl carboxylates: -0- (CO) -Q, Q is an alkyl to C 24, preferably Ci-Ci 2.
• the group R is the acetoxy group.
• the group R is the hydroxyl group.
• the polar monomer (m b ) is chosen from monomers derived from styrene or alpha-methylstyrene whose aromatic ring is substituted with a -CH 2 -R group.
• the group R is preferably chosen from: - the hydroxyl group and,
• the alkyl carboxylates -O- (CO) -Q, Q representing a C 1 to C 24 alkyl, preferably C 1 to C 2, more preferably C 1 to C 8 , still more preferably C 1 to C 4 , example the acetoxy group.
• the R group is preferably the hydroxyl group.
• the polar monomer (m b ) may, in particular, be chosen from monomers derived from styrene or alpha-methylstyrene, the aromatic ring of which is substituted by at least one alkyl carboxylate group -O- (CO) -Q, Q is an alkyl to C 24, preferably Ci to Ci 2, most preferably C, to C 8, more preferably to C 4, for example the acetoxy group.
• the alkyl carboxylate group -O- (CO) -Q may be in the ortho, meta or para position on the aromatic ring, preferably in the para position.
• the polar monomer (m b ) is chosen from monomers derived from styrene or alpha-methylstyrene whose aromatic nucleus is substituted in the ortho, meta or para position by at least one hydroxyl group or by a linear or branched, preferably acyclic, C 1 to C 12 , preferably C 1 to C 4 , hydrocarbon chain substituted by at least one hydroxyl group.
• the group R is chosen from groups having at least one primary, secondary or tertiary amine function.
• the group R is chosen from the group consisting of: -NH 2 ; groups having at least one amine, imine, amidine, guanidine, aminoguanidine or biguanidine function; heterocyclic groups having from 3 to 34 atoms and at least one nitrogen atom.
• the group R is connected to the aromatic group or the hydrocarbon chain, preferably via a nitrogen atom present in the group R,
• the group R is chosen from the group consisting of:
• alkyl-amines groups having at least one amine, imine, amidine, guanidine, aminoguanidine or biguanidine function, such as alkyl-amines, polyalkylene polyamines, polyalkylenimines, alkylimines, alkylamidines, alkylguanidines and alkyl-biguanidines, alkyl substituent preferably having 1 to 34 carbon atoms, preferably 1 to 12 and being linear or branched, cyclic or acyclic.
• monocyclic or polycyclic heterocyclic groups having from 3 to 34 atoms, preferably from 5 to 12 atoms, more preferably from 6 to 10 atoms, and at least one nitrogen atom, it being understood that the polycyclic heterocyclic groups have, if appropriate , merged cycles.
• the number of atoms includes hetero atoms.
• fused rings are meant rings having at least two atoms in common.
• the heterocyclic groups may further comprise an oxygen atom and / or a carbonyl group and / or one or more unsaturations.
• heterocyclic R group By way of example of heterocyclic R group, mention may be made of the following radicals: triazole, aminotriazole, pyrrolidone, piperidine imidazole, morpholine, isoxazole, oxazole and indole, said radical preferably being linked to the hydrocarbon chain or to the aryl group by an atom nitrogen.
• group R is chosen from the group consisting of:
• R ', R ", R'", R '"andR”" are independently from each other an alkyl group HC 3 6, preferably C 2 Ci, optionally comprising one or more functions NH 2 and one or more -NH- bridges;
• R a represents a C 1 -C 6 alkyl group, preferably C 2 -C 4 alkyl
• k represents an integer ranging from 1 to 20, preferably from 2 to 12.
• R groups having an amino function include polyamines and polyalkylene polyamines, for example ethylene diamine, diethylene triamine, triethylene tetramine, tetraethylene pentamine.
• the group R is chosen from groups having at least one quaternary ammonium function obtained by quaternization of the primary amines, secondary or tertiary as described above, according to any known method.
• the group R may, in particular, be chosen from groups having at least one quaternary ammonium function obtained by quaternization of at least one amine, imine, amidine, guanidine, aminoguanidine or biguanidine function; heterocyclic groups having from 3 to 34 atoms and at least one nitrogen atom.
• the group R is chosen from groups having at least one quaternary ammonium function obtained by quaternization of the tertiary amines.
• the quaternary ammonium is selected from the quaternary ammonium of iminium, amidinium, formamidinium, guanidinium and biguanidinium.
• the group R is chosen from groups having at least one quaternary ammonium functional group chosen from heterocyclic groups having from 3 to 34 atoms and at least one nitrogen atom, preferably from quaternary ammoniums of pyrrolinium. , pyridinium, imidazolium, triazolium, triazinium, oxazolium and isoxazolium.
• the group R is chosen from quaternary ammoniums, preferably comprising at least one C 1 to C 4 , preferably C 1 to C 4 , hydrocarbon chain, linear or branched, cyclic or acyclic, preferably acyclic, said chain optionally comprising one or more oxygen atoms in the form of an ether function or in substitution, preferably in substitution.
• the hydrocarbon chain may, for example, be an alkyl chain substituted with a hydroxyl group, this type of quaternary ammonium salt being obtainable by reaction of a tertiary amine with an epoxide according to any known method.
• the group R is chosen from trialkylammonium groups.
• the alkyl substituents of trialkylammonium are preferably selected from alkyl groups having from 1 to 10 carbon atoms, preferably from 1 to 4 carbon atoms, and being linear or branched, cyclic or acyclic, preferably acyclic.
• the R group is selected from quaternary ammonium substituted with at least one hydrocarbon chain, preferably alkyl, Ci-Ci 0, still more preferably C 1 -C 4 linear or branched, cyclic or acyclic, preferably acyclic, comprising one or more hydroxyl groups.
• the polar monomer (m b ) is represented by the following formula (II):
• X represents a C 1 to C 12 , preferably C 1 to C 4 , hydrocarbon chain, more preferably the -CH 2 group,
• R is as described above .
• the monomer derived from styrene (m b ) is, for example, selected from vinyl phenols and (vinyl phenyl) methanols in the ortho, meta and para position, preferably para.
• the monomer derived from styrene (m b ) is, for example, chosen from acetoxystyrene in the ortho, meta and para position, preferably para.
• the monomer (m b ) is chosen from the (vinylbenzyl) trialkylammonium isomers in the ortho, meta or para position, preferably in para, alone or as a mixture.
• the copolymer may be a block copolymer, a random copolymer or any other form of copolymer.
• the block copolymer comprises at least a block A consisting of a chain of structural units derived from one or more apolar monomers selected from apolar monomers (m a ) of formula (I) and a block B consisting of a chain of structural units derived from one or more polar monomers selected from polar monomers (m b ),
• block A is derived solely from apolar monomers (m a ) and that block B contains only polar blocks (m b ).
• the block copolymer comprises at least: a block A consisting of a chain of structural units derived from an apolar monomer chosen from apolar monomers (m a ) of formula (I) and,
• a B block consisting of a chain of structural units derived from a polar monomer selected from polar monomers (m b).
• the block copolymer is represented by one of the following formulas (III) and (IV):
• n is an integer ranging from 2 to 50, preferably from 3 to 20,
• p is an integer ranging from 2 to 50, preferably from 3 to 20,
• R 0 is chosen from hydrogen or the methyl group, preferably R 0 is H,
• Ri is chosen from hydrocarbon chains, preferably alkyl groups, cyclic or acyclic, saturated or unsaturated, linear or branched Ci to C32, preferably C 4 -C 24, more preferably a Cio to C 24 and groups resulting from a reversible addition-fragmentation chain transfer agent (RAFT), a reversible additive-fragmentation chain transfer agent
• RAFT reversible addition-fragmentation chain transfer agent
• RAFT transfer agents are well known to those skilled in the art. A wide variety of RAFT transfer agents are available or quite easily synthesizable. By way of example, mention may be made of thiocarbonylthio, dithiocarbonate, xanthate, dithiocarbamate and trithiocarbonate transfer agents, for example S, S-bis ( ⁇ , ⁇ '-dimethyl- ⁇ -acetic acid) trithiocarbonate (BDMAT ) or 2-cyano-2-propylbenzodithioate R 2 represents the group - (E) u -G
• R 3 is a substituent in the ortho, meta or para position on the aromatic ring, preferably in the para position, chosen from the group consisting of at least one R group or at least one linear or branched C 1 -C 12 hydrocarbon-based chain, preferably acyclic, substituted by at least one group R, said group R being chosen from:
• a group comprising from 1 to 40 atoms chosen independently from C, N, and optionally O, and comprising at least one primary, secondary, tertiary or quaternary ammonium amine function,
• polyalkoxy groups - (OC y H 2y O) rH where y is an integer from 2 to 8, preferably 2 to 4, more preferably from 2 to 3 and f is an integer ranging from 1 to 10, preferably 2 to 8, more preferably 2 to 4,
• polyalkoxy groups - (OC y H 2y O) RR8 where y is an integer from 2 to 8 preferably from 2 to 4, more preferably from 2 to 3 and f is an integer ranging from 1 to 10, preferably from 2 to 8, more preferably from 2 to 4, and R 8 represents a C 1 -C 4 alkyl, preferably Ci-Ci 2
• R 9 is chosen from C 1 to C 24 , preferably C 1 to C 12, more preferably C 1 to C 6 alkyl groups, which are linear or branched, preferably acyclic,
• Z " is chosen from hydroxide ions, halides and organic anions, in particular the acetate ion,
• Rio, Ru and R 12 are, identical or different, and chosen independently from C 1 to C 10 , preferably C 1 to C 4 , alkyl groups, linear or branched, cyclic or acyclic, preferably acyclic,
• R-13 is chosen from groups comprising from 1 to 40 atoms chosen from C, N, and optionally O, and comprising at least one primary, secondary or tertiary amine function,
• R 4 is selected from the group consisting of:
• halogens preferably bromine
• R 5 and R 6 are identical or different and independently selected from the group consisting of hydrogen and C 1 to C 10 , preferably C 1 to C 4 , alkyl groups, linear or branched, more preferably acyclic, even more preferably methyl group,
• R 7 is selected from hydrogen or methyl group, preferably R 7 is H.
• R 1 is preferably chosen from linear or branched, C 1 to C 32, preferably C 4 to C 24, more preferably C 10 alkyl, cyclic or acyclic groups;
• R 3 is, according to a first preferred variant, a substituent in the ortho, meta or para position on the aromatic ring, preferably in the para position, chosen from the groups - OCOR 9 where R 9 is as described above.
• At least one of the groups R 3 , R 4 and R 13 is a group having at least one primary, secondary or tertiary amine function chosen independently from the group consisting of:
• alkyl-amines groups having at least one amine, imine, amidine, guanidine, aminoguanidine or biguanidine function, such as alkyl-amines, polyalkylene polyamines, polyalkylenimines, alkylimines, alkylamidines, alkylguanidines and alkyl-biguanidines, alkyl substituent preferably having 1 to 34 carbon atoms, preferably 1 to 12 and being linear or branched, cyclic or acyclic.
• monocyclic or polycyclic heterocyclic groups having from 3 to 34 atoms, preferably from 5 to 12 atoms, more preferably from 6 to 10 atoms, and at least one nitrogen atom, it being understood that the polycyclic heterocyclic groups have, if appropriate , merged cycles.
• the number of atoms includes hetero atoms.
• fused rings are meant rings having at least two atoms in common.
• the heterocyclic groups may further comprise an oxygen atom and / or a carbonyl group and / or one or more unsaturations.
• heterocyclic group By way of example of a heterocyclic group, mention may be made of the following radicals: triazole, aminotriazole, pyrrolidone, piperidine imidazole, morpholine, isoxazole, oxazole and indole, said radical preferably being linked by a nitrogen atom.
• At least one of the groups R 3 , R 4 and R 13 is chosen from the group consisting of:
• R ', R ", R” ⁇ R “” and R “” are independently from each other an alkyl group HC 3 6, preferably C 2 Ci, optionally comprising one or more functions and NH 2 one or more bridges -NH-;
• R a represents an alkyl group Ci-C 6, preferably C 2 -C 4, k represents an integer ranging from 1 to 20, preferably 2 to 12.
• groups comprising an amino function include polyamines and polyalkylene polyamines, for example ethylene diamine, diethylene triamine, triethylene tetramine and tetraethylene pentamine.
• the copolymer may be prepared by any known method of polymerization. The various techniques and polymerization conditions are widely described in the literature and fall within the general knowledge of those skilled in the art.
• the poly (vinyl phenol) blocks can be obtained from poly (acetoxystyrene) blocks obtained by copolymerization of acetoxystyrene polar monomers (m b ), followed by hydrolysis according to any known method.
• the poly (styrene alkyl ester block) can be obtained from a poly (vinyl phenol) moiety by esterification reaction.
• a block copolymer comprising a quaternary ammonium group of formula (V) with Rio, u and R 12 being methyl groups and Z a chlorine
• the chloride counterion may be substituted by treatment of the thus obtained block copolymer in an ion exchange column according to any known method.
• the block copolymers can be obtained by sequential polymerization, preferably by sequential and controlled polymerization and, optionally followed by one or more post-functionalizations.
• the controlled polymerizations can be radical controlled polymerizations or ionic controlled polymerizations.
• the block copolymer described above is obtained by sequenced and controlled polymerization.
• the polymerization is advantageously chosen from controlled radical polymerization; for example, by atom transfer radical polymerization (ATRP in English “Atom Transfer Radical Polymerization”); radical polymerization with nitroxide (NMP).
• ATRP atom transfer radical polymerization
• NMP radical polymerization with nitroxide
• degenerative transfer processes such as degenerative iodine transfer polymerization (ITRP-iodine transfer radical polymerization) or radical polymerization by reversible addition-fragmentation chain transfer (RAFT in English "Reversible Addition-Fragmentation Chain Transfer”
• RAFT in English "Reversible Addition-Fragmentation Chain Transfer”
• polymerizations derived from ATRP such as polymerizations using initiators for the continuous regeneration of the activator (ICAR -Initiators for continuous activator regeneration) or using electron-regenerated activators regenerated by electron (ARGET) transfer ").
• Block copolymers can be synthesized by living cationic polymerization.
• the living cationic polymerization is characterized by a decrease in the reactivity of the cationic propagating species, which makes it possible to suppress the termination and transfer reactions while keeping a sufficient reactivity for the propagation.
• the sequenced and controlled polymerization is typically carried out in a solvent, under an inert atmosphere, at a reaction temperature generally ranging from 0 to 200 ° C, preferably from 50 ° C to 130 ° C.
• the solvent may be chosen from polar solvents, in particular ethers such as anisole (methoxybenzene) or tetrahydrofuran or apolar solvents, in particular paraffins, cycloparaffins, aromatics and alkylaromatics having from 1 to 19 carbon atoms. carbon, for example, benzene, toluene, cyclohexane, methylcyclohexane, n-butene, n-hexane, n-heptane and the like.
• the reaction is generally carried out under vacuum in the presence of an initiator, a ligand and a catalyst.
• a ligand mention may be made of N, N, N ', N ", N" -Pentamethyldiethylenetriamine (PMDETA), 1,1,4,7,10,10-hexamethyltriethylene tetramine (HMTETA), 2,2'-Bipyridine (BPY) and Tris (2-pyridylmethyl) amine (TPMA).
• the ATRP polymerization is preferably carried out in a solvent chosen from polar solvents. According to the sequenced and controlled polymerization technique, it can also be envisaged to work under pressure.
• the numbers of apolar monomer equivalents (m a ) of block A and of polar monomer (m b ) of block B reacted during the polymerization reaction are identical or different.
• the number of apolar monomer equivalents (m a ) of block A is preferably from 2 to 50, preferably from 3 to 20.
• the number of polar monomer equivalents (m b ) of block B is preferably from 2 to 50, preferably from 3 to 20.
• the number of equivalents of apolar monomer (m a ) of block A is advantageously greater than or equal to that of the polar monomer (b m) of the block B.
• the molar mass in weight M w of block A or block B is preferably less than or equal to 15,000 g. mol "1 , more preferably less than or equal to 10,000 g. mol. " 1 .
• the block copolymer advantageously comprises at least one sequence of AB, ABA or BAB blocks in which said blocks A and B are linked together without the presence of an intermediate block of a different chemical nature.
• Other blocks may optionally be present in the block copolymer described above insofar as these blocks do not fundamentally change the character of the block copolymer.
• block copolymers containing only blocks A and B will be preferred.
• a and B represent at least 70% by weight, preferably at least 90% by weight, more preferably at least 95% by weight, more preferably at least 99% by weight of the block copolymer.
• the block copolymer is a diblock copolymer.
• the block copolymer is an alternating block triblock copolymer comprising two blocks A and a block B (ABA) or comprising two blocks B and a block A (BAB).
• the block copolymer also comprises a terminal chain I consisting of a linear or branched, C 1 to C 32, preferably C 4 to C 24 , hydrocarbon, cyclic or acyclic, saturated or unsaturated hydrocarbon chain, more preferably preferentially at C1 0 to C 24 .
• cyclic hydrocarbon chain means a hydrocarbon chain at least a part of which is cyclic, in particular aromatic. This definition does not exclude hydrocarbon chains comprising both an acyclic and a cyclic moiety.
• the terminal chain I may comprise an aromatic hydrocarbon chain, for example a benzene chain and / or a linear or branched, saturated and acyclic hydrocarbon-based chain, in particular an alkyl chain.
• the terminal chain I is, preferably, selected from alkyl chains, preferably linear, more preferably alkyl chains of at least 4 carbon atoms, even more preferably of at least 12 carbon atoms.
• the terminal chain I is located in the terminal position of the block copolymer. It can be introduced into the block copolymer by means of the polymerization initiator.
• the terminal chain I may, advantageously, constitute at least a part of the polymerization initiator and is positioned within the polymerization initiator in order to introduce, during the first polymerization initiation step. , the terminal chain I in the terminal position of the block copolymer.
• the polymerization initiator is, for example, chosen from free radical initiators used in the ATRP polymerization process. These free radical initiators well known to those skilled in the art are described in particular in the article "Atom Transfer Radical Polymerization: Current Status and Future Prospects, Macromolecules, 45, 4015-4039, 2012 ".
• the polymerization initiator is, for example, chosen from alkyl esters of a carboxylic acid substituted by a halide, preferably a bromine in the alpha position, for example ethyl 2-bromopropionate or ⁇ -bromoisobutyrate.
• a halide preferably a bromine in the alpha position
• ethyl 2-bromopropionate or ⁇ -bromoisobutyrate ethyl chloride, benzyl choride or bromide, ethyl ⁇ -bromophenylacetate and chloroethylbenzene.
• ethyl 2-bromopropionate may make it possible to introduce into the copolymer the terminal chain I in the form of a C 2 alkyl chain and benzyl bromide in the form of a benzyl group.
• the transfer agent can conventionally be removed from the copolymer at the end of the polymerization according to any known method.
• the terminal chain I can also be obtained in the copolymer by RAFT polymerization according to the methods described in the article by Moad, G. et al., Australian Journal of Chemistry, 2012, 65, 985-1076.
• the terminal chain I may, for example, be modified by aminolysis when a transfer agent is used to give a thiol function.
• thiocarbonylthio, dithiocarbonate, xanthate, dithiocarbamate and trithiocarbonate transfer agents for example S, S-bis ( ⁇ , ⁇ '-dimethyl- ⁇ -acetic acid) trithiocarbonate (BDMAT or 2-cyano-2-propyl benzodithioate.
• the block copolymer is a diblock copolymer (also called diblocks).
• the block copolymer structure may be of the IAB or IBA type, advantageously IAB.
• the terminal chain I may be directly linked to block A or B according to the structure IAB or IBA respectively, or to be linked via a linking group, for example an ester, amide, amine or ether function.
• the linking group then forms a bridge between the terminal chain I and the block A or B.
• the block copolymer can also be functionalized at the end of the chain according to any known method, in particular by hydrolysis, aminolysis and / or nucleophilic substitution.
• aminolysis any chemical reaction in which a molecule is split into two parts by reaction of a molecule of ammonia or an amine.
• a general example of aminolysis is to replace a halogen of an alkyl group by reaction with an amine, with elimination of hydrogen halide.
• the aminolysis can be used, for example, for an ATRP polymerization which produces a copolymer having a terminal halide or for a RAFT polymerization to transform the thio, dithio or trithio bond introduced into the copolymer by the RAFT transfer agent.
• thiol function is meant any chemical reaction in which a molecule is split into two parts by reaction of a molecule of ammonia or an amine.
• a general example of aminolysis is to replace a halogen of an alkyl group by reaction with an amine, with elimination of hydrogen halide.
• the aminolysis can be used, for example, for an ATRP polymerization which produces a copolymer having a terminal halide or
• the terminal chain I comprises a hydrocarbon chain, linear or branched, cyclic or acyclic, C 1 to C 32, preferably C 1 to C 24 , more preferably C 1 to C 0 , even more preferably an alkyl group, optionally substituted. by one or more groups containing at least one heteroatom selected from N and O, preferably N.
• this functionalization may, for example, be carried out by treating the copolymer IAB or IBA obtained by ATRP with a primary alkylamine to C 32 or an alcohol to C 32 under conditions soft so as not to modify the functions present on blocks A, B and I.
• block A corresponds to the repeating pattern n times and block B to the repeating pattern p times.
• the R- ⁇ group may consist of the terminal chain I as described above and / or the R 4 group may consist of the end chain I as described above.
• the molar and / or mass ratio between block A and B in the block copolymer and in particular the m, n and p values of formulas (III) and (IV), will be chosen so that the block copolymer is soluble in the fuel or fuel and / or the organic liquid of the concentrate for which it is intended.
• this ratio and these values m, n and p will be optimized according to the fuel or fuel and / or the organic liquid so as to obtain the best properties when cold.
• the optimization of the molar and / or mass ratio, in particular for defining the values m, n and p of the formulas (III) and (IV) can be carried out by routine tests accessible to those skilled in the art.
• the molar ratio between the apolar monomer (m a ) and the polar monomer (m b ), or between the blocks A and B in molar percentage between the apolar monomer (m a ) of the block A and the polar monomer (m b ) of block B is preferably between 95: 5 and 5: 95, more preferably between 70:30 and 30:70.
• block copolymers may optionally be present in the block copolymer insofar as they do not fundamentally change the character of the block copolymer.
• block copolymers containing only blocks A and B will be preferred.
• the block copolymer comprising at least one block A and at least one block B is prepared according to any known process for block copolymerization and controlled from only two types. of ⁇ , ⁇ -unsaturated monomers.
• the equivalents of the monomers of the block A and of the block B reacted during the polymerization reaction are identical or different and, independently, between 2 and 20, preferably between 3 and 16.
• number of equivalents is meant the ratio between the amounts of material (in moles) of the monomers of the block A and the block B during the polymerization reaction.
• the copolymer described above is used as a cold-holding additive for the fuel or fuel.
• the term cold-holding additive an additive that improves the cold-holding properties of a fuel or fuel, especially the cold operability during storage and / or its use at low temperature, typically less than 0 ° C, preferably below -5 ° C.
• the copolymer is particularly advantageous as a fuel or fuel additive comprising one or more n-alkyl, iso-alkyl or n-alkenyl substituted compounds having a tendency to crystallize in the fuel or fuel, during storage and / or use at low temperature.
• the fuels or fuels may be chosen from liquid hydrocarbon fuels or liquid fuels alone or as a mixture.
• the liquid fuel is advantageously derived from one or more sources selected from the group consisting of mineral, animal, vegetable and synthetic sources. Oil will preferably be chosen as a mineral source.
• the liquid fuel is preferably chosen from hydrocarbon fuels and non-essentially hydrocarbon fuels, alone or as a mixture.
• Hydrocarbon fuel is a fuel consisting of one or more compounds consisting solely of carbon and hydrogen.
• non-substantially hydrocarbon fuel is understood to mean a fuel consisting of one or more compounds consisting essentially of carbon and hydrogen, that is to say which also contain other atoms, in particular oxygen atoms.
• the hydrocarbon fuels or fuels include in particular middle distillates boiling temperature ranging from 100 to 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 vacuum distillates, distillates resulting from ARDS type conversion processes (in English "atmospheric residue desulfuration") and / or visbreaking, the distillates from the valuation of Fischer Tropsch cuts. Hydrocarbon fuels or fuels are typically gasoline and diesel (also called diesel fuel).
• Gas oils include, in particular, any commercially available diesel fuel compositions. As a representative example, mention may be made of gas oils that comply with the NF EN 590 standard.
• Non-essentially hydrocarbon fuels or fuels include oxygenates, for example distillates resulting from BTL conversion (in English "biomass to liquid") of plant biomass and / or animal, taken alone or in combination; biofuels, for example oils and / or esters of vegetable and / or animal oils; biodiesels of animal and / or vegetable origin and bioethanols.
• Diesel gasoline type B x for diesel engines a diesel fuel which contains x% (v / v) of vegetable or animal oil esters (including used cooking oils) transformed by a chemical process called transesterification, obtained by reacting this oil with an alcohol to obtain fatty acid esters (EAG).
• EAG fatty acid esters
• EMAG fatty acid methyl esters
• EEAG fatty acid ethyl esters
• a B99 contains 99% of EAG and 1% of middle distillates of fossil origin (mineral source), B20, 20% of EAG and 80% of middle distillates of fossil origin, etc.
• Type B 0 gas oils which do not contain oxygenated compounds
• Bx type gas oils which contain x% (v / v) of vegetable oil or fatty acid esters, most often methyl esters (EMHV or EMAG) .
• EAG EAG
• EMAG methyl esters
• the sulfur content of the liquid fuel is preferably less than or equal to 5000 ppm, preferably less than or equal to 500 ppm, and more preferably less than or equal to 50 ppm, or even less than or equal to 10 ppm and advantageously without sulfur. .
• the copolymer described above is also used as an anti-sedimentation additive.
• the copolymer advantageously makes it possible to retard or prevent the sedimentation of the crystals of the n-alkyl, iso-alkyl or n-alkenyl substituted compounds.
• the copolymer may advantageously be used to retard or prevent the sedimentation of the crystals of n-alkanes, preferably n-alkanes containing at least 12 carbon atoms, more preferably at least 20 carbon atoms, even more preferably at minus 24.
• the copolymer is furthermore used as a cold-holding additive in combination with at least one cold-cooling additive (CFI) improving the low-temperature flow properties of the fuel or fuel during its operation. storage and / or use at low temperatures.
• the cold-flow-making 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.
• copolymers of ethylene and of unsaturated ester such as ethylene / vinyl acetate copolymers (EVA), ethylene / vinyl propionate (EVP), ethylene / vinyl ethanoate (EVE), ethylene / methyl methacrylate (EMMA), and ethylene / alkyl fumarate described, for example, in US3048479, US3627838, US3790359, US3961961 and EP261957.
• the cold-flow additive (CFI) is advantageously chosen from copolymers of ethylene and of vinyl ester (s), alone or as a mixture, in particular ethylene / vinyl acetate (EVA) and ethylene / ethylene copolymers.
• vinyl propionate (EVP) more preferably ethylene / vinyl acetate copolymers (EVA).
• the copolymer is used to amplify the fluidizing (flow) effect of the cold-flow additive (CFI) by improving the temperature limit of filterability (TLF) of the fuel or fuel, the TLF being measured according to the NF EN 1 standard. 16.
• TLF booster Filtration Limit Temperature
• the copolymer 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 the use "additive package".
• the copolymer is used as a cold-running additive in the fuel or fuel at a content, advantageously at least 10 ppm, preferably at least 50 ppm, more preferably at a content of between 10 and 5 000 ppm, more preferably between 10 and 1 OOOppm.
• an additive concentrate comprises the copolymer as described above, mixed with an organic liquid.
• the organic liquid must be inert with respect to the copolymer and miscible with the fuels or fuels as described above.
• miscible means that the copolymer, as described according to the invention, and the organic liquid form a solution or a dispersion so as to facilitate the mixing of the copolymer in the fuels according to the conventional methods of additive fuels.
• the organic liquid must be miscible with fuels comprising one or more n-alkyl, iso-alkyl or n-alkenyl substituted compounds having a tendency to crystallize in said fuel or a fuel during its storage and / or of its use at low temperature.
• the fuel or fuel is preferably selected from gas oils, biodiesel, gasolines type B x and fuel oils, preferably domestic fuel oils (FOD).
• the fuel or fuel is preferably selected from gas oils, biodiesel, gasolines type B x .
• the organic liquid is advantageously chosen from aromatic hydrocarbon solvents such as the solvent sold under the name "SOLVESSO", alcohols, ethers and other oxygenated compounds and paraffinic solvents such as hexane, pentane or isoparaffins. alone or in mixture.
• the additive concentrate advantageously comprises at least one cold-cooling additive (CFI) improving the cold-resistance, preferably improving the low-temperature flow properties of the fuel or fuel during its storage and / or its use at low temperature. low temperature.
• CFI cold-cooling additive
• the cold-flow-making 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 as described herein. -above.
• the additive concentrate may also comprise one or more other additives commonly used in fuels or fuels and different from the copolymer described above.
• the additive concentrate may typically comprise one or more other additives selected from detergents, anti-corrosion agents, dispersants, demulsifiers, defoamers, biocides, re-deodorants, procetane additives, modifiers lubricant additives or lubricity additives, combustion assistants (catalytic combustion and soot promoters), cloud point improvers, pour point, TLF, agents anti-settling agents, anti-wear agents and / or conductivity modifiers.
• additives selected from detergents, anti-corrosion agents, dispersants, demulsifiers, defoamers, biocides, re-deodorants, procetane additives, modifiers lubricant additives or lubricity additives, combustion assistants (catalytic combustion and soot promoters), cloud point improvers, pour point, TLF, agents anti-settling 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 EP861882, 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, US2012 / 00101 12 and WO2012 / 004300.
• lubricity additives or anti-wear agents in particular (but not limited to) selected from the group consisting of fatty acids and their ester or amide derivatives, in particular glycerol monooleate, and monocarboxylic acid derivatives and polycyclic.
• lubricity additives or anti-wear agents are given in the following documents: EP680506, EP860494, WO98 / 04656, EP915944, FR2772783, FR2772784.
• cloud point additives including (but not limited to) selected from the group consisting of long-chain olefin terpolymers / (meth) acrylic ester / maleimide, and fumaric acid / maleic acid ester polymers. Examples of such additives are given in FR2528051, FR2528051, FR2528423, EP1 12195, EP172758, EP271385, EP291367;
• anti-sedimentation additives and / or paraffin dispersants in particular (but not exclusively) selected from the group consisting of polyamine-amidated (meth) acrylic acid / alkyl (meth) acrylate copolymers, alkenylsuccinimides of polyamine, phthalamic acid derivatives and double chain fatty amine; alkylphenol resins.
• examples of such additives are given in the following documents: EP261959, EP593331, EP674689, EP327423, EP512889, EP832172; US2005 / 0223631; US5998530; W093 / 14178.
• polyfunctional cold operability additives selected from the group consisting of olefin and alkenyl nitrate polymers as described in EP573490; These other additives are generally added in an amount ranging from 100 to 1000 ppm (each).
• the use of such an additive concentrate may be the same as that of the copolymer described above, in particular, the concentrate may be used to retard or prevent the sedimentation of the crystals of the n-alkyl, iso-substituted compounds, alkyl or n-alkenyl of the fuel or fuel during storage and / or use at low temperatures.
• the additive concentrate may advantageously comprise between 5 and 99% by weight, preferably between 10 and 80%, more preferably between 25 and 70% of copolymer as described above.
• the additive concentrate comprises from 5 to 94% by weight of cold-flow additive (CFI), preferably from 10 to 80%, more preferably from 30 to 70%, the percentages being expressed relative to the mass. total additive concentrate.
• CFI cold-flow additive
• the ratio between the mass of copolymer and the mass of cold-flow additive (CFI) present in the additive concentrate is from 1: 99 to 99: 1, preferably from
• the additive concentrate may, typically, comprise between 1 and 95% by weight, preferably 10 to 70%, more preferably 25 to 60% of organic liquid, the remainder corresponding to the copolymer and, optionally, to the other additives different from the copolymer such as as described above.
• the solubility of the copolymer in the organic liquids, the fuels or the fuels described above will depend in particular on the average molar masses by weight and by number, respectively M w and M n, of the copolymer.
• the average molar masses M w and M n of the copolymer will be chosen so that the copolymer is soluble in the fuel or fuel and / or the organic liquid of the concentrate for which it is intended.
• the average molar masses M w and M n of the copolymer may also have an influence on the effectiveness of this copolymer as cold-holding additive.
• the copolymer advantageously has a weight average molecular weight (Mw) of between 1,000 and 30,000 g. mol "1 , preferably between 4000 and 10,000 g, mol " 1 , more preferably less than 4000 g. mol "1 , and / or a number-average molar mass (Mn) of between 1,000 and 15,000 g. mol- 1 , preferably between 4,000 and 10,000 g. mol "1 , more preferably less than 4000 g, mol " 1 .
• Mw weight average molecular weight
• Mw weight average molecular weight
• Mn number-average molar mass
• the number and weight average molar masses are measured by Size Exclusion Chromatography (SEC).
• SEC Size Exclusion Chromatography
• a fuel or fuel composition is prepared according to any method known for adding:
• CFI cold-cooling additive
• the copolymer is present in the fuel or fuel composition in an amount sufficient to retard or prevent the sedimentation of the crystals of said n-alkyl, iso-alkyl or n-alkenyl substituted compounds during storage and / or use at low temperatures. temperature of said fuel or fuel (1).
• the fuel or fuel composition advantageously comprises at least 10 ppm, preferably at least 50 ppm, advantageously between 10 and 5000 ppm, more preferably between 10 and 1000 ppm of the copolymer described above.
• the cold-flow-making 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.
• the cold-flow additive (CFI) is advantageously chosen from copolymers of ethylene and of vinyl ester (s), alone or as a mixture, in particular ethylene / vinyl acetate copolymers (EVA) and ethylene / vinyl propionate (EVP), more preferably ethylene / vinyl acetate copolymers (EVA).
• the coolant additive (CFI) is present in the fuel or fuel composition in an amount sufficient to improve the low temperature flow behavior of the fuel or fuel (1) during storage and / or use at low temperature.
• the fuel or fuel composition advantageously comprises at least 10 ppm, preferably at least 50 ppm, more preferably between 10 and 5000 ppm, even more preferably between 10 and 1000 ppm of the cold-flow additive (CFI). .
• the fuel or fuel composition (1) may also contain one or more other additives different from the additives (2) and (3) chosen from detergents, anti-corrosion agents, dispersants, demulsifiers, defoamers, biocides, deodorants, friction modifiers, lubricity additives or lubricity additives, combustion assistants (Catalytic combustion promoters and soot), cloud point improving agents, pour point, TLF, anti-sedimentation agents, anti-wear agents and / or conductivity modifiers.
• additives different from the additives (2) and (3) chosen from detergents, anti-corrosion agents, dispersants, demulsifiers, defoamers, biocides, deodorants, friction modifiers, lubricity additives or lubricity additives, combustion assistants (
• additives different from additives (2) and (3) are, for example, those mentioned above.
• a method for improving the cold-holding properties of a fuel or fuel composition derived from one or more sources selected from the group consisting of mineral sources, preferably oil, animal, vegetable and synthetic comprises the successive stages of:
• the additive composition is constituted by the additive concentrate according to the invention.
• Step a) treating the fuel or fuel composition with the amount determined in step a) of the copolymer and, optionally, with the cold-flow additive (CFI).
• CFI cold-flow additive
• the determination of the amount of copolymer to be added to the fuel or fuel composition to achieve the specification will typically be made by comparison with the fuel or fuel composition containing the CFI additive but without block copolymer or statistic.
• the amount of copolymer required to treat the fuel or fuel composition may vary depending on the nature and origin of the fuel or fuel, particularly depending on the level of n-alkyl, iso-alkyl or n-alkenyl substituted compounds. .
• the nature and origin of the fuel or fuel may therefore also be a factor to be taken into account for step a).
• the method for improving the cold-holding properties may also comprise an additional step after step b) of checking the target reached and / or adjusting the treatment rate with the copolymer as a cold-holding additive and, optionally, with cold-flow additive (CFI).
• CFI cold-flow additive
• the performance of the copolymers as an anti-sedimentation additive is evaluated by testing their ability to avoid the sedimentation of fuel compositions additive with conventional EVA.
• the anti-settling properties of the fuel compositions can be evaluated by the following ARAL sedimentation test: 250mL of the fuel composition are cooled in 250mL test pieces in a climatic chamber at -13 ° C. according to the following temperature cycle: change from + 10 ° C to -13 ° C in 4h then isothermal at -13 ° C for 16h. At the end of the test, a visual quotation of the sample appearance and the sedimented phase volume is performed, then 20% of the lower volume is taken, for PTR (ASTM D7689) and temperature point characterization.
• each copolymer as a TLF booster additive can also be evaluated by testing their ability to lower the TLF of the fuel compositions additive with conventional EVA.
• the medium is stirred for 2 h at 0 ° C. and then brought to ambient temperature. Methyl 2-bromopropionate is introduced into the reaction medium at one time. The medium is stirred for 2 hours. The solvent is evaporated under reduced pressure. The solid obtained is dissolved in 200 mL of ethyl acetate. The organic phase is washed with 3 ⁇ 200 ml of distilled water with neutral pH control on the last aqueous phase, and then dried over Na 2 SO 4 sodium sulphate. The product is then purified on a silica column (450 g of silica). 26.7 g (Yield: 93%) of a pale yellow solid with a purity of 94% (measured by 1 H NMR) are obtained.
• Block A Block A
• CMS Block B
• BlockA - 4950 10.0 0.0020 1
• a copolymer according to the invention is tested as an anti-sedimentation additive in a diesel engine distillate.
• the motor distillate may be of type B 7 , GOM whose characteristics are listed in Table 5 below: GOM GOM (B 7 )
• a composition C is prepared by solubilizing 100 ppm by weight of the copolymer (100% of active material) in a gas oil composition containing 300 ppm by weight of a cold-flow additive (CFI).
• the cold-reducing additive may be an additive marketed by the company TOTAL under the name CP7936C, which is an ethylene-vinyl acetate (EVA of Ethylene-vinyl acetate) comprising 30.5% w / w vinyl acetate and concentrated to 70% w / w in an aromatic solvent (Solvesso 150, sold by ExxonMobil).
• EVA ethylene-vinyl acetate
• Solvesso 150 sold by ExxonMobil
• the performance of the copolymer as an anti-sedimentation additive is evaluated by testing its ability to avoid sedimentation of the fuel composition C additive with conventional EVA.
• the anti-settling properties of the fuel composition C are evaluated by the following ARAL sedimentation test: 250mL of the fuel composition C are cooled in 250mL test pieces in a climatic chamber conditioned at -13 ° C. according to the cycle of next temperature: change from + 10 ° C to -13 ° C in 4h then isothermal at -13 ° C for 16h.
• the copolymer performance is also evaluated as a TLF booster additive by testing its ability to lower the Cold Filter Plugging Point (CFPP) of the fuel composition C additive with conventional EVA.
• CFPP Cold Filter Plugging Point

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• General Chemical & Material Sciences (AREA)
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• 2016
  • 2016-07-21 FR FR1656976A patent/FR3054240B1/fr not_active Expired - Fee Related
• 2017
  • 2017-07-20 WO PCT/FR2017/051977 patent/WO2018015667A1/fr unknown
  • 2017-07-20 EP EP17751441.1A patent/EP3487962A1/de not_active Withdrawn

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