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

Abstract

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

Description

[0001] The present invention relates to a composition of particular additives and its use for improving the cold resistance properties of fuels and combustibles during their storage and / or use at low temperature.

[0002] The present invention also relates to fuel and combustible compositions containing such an additive composition. STATE OF THE PRIOR ART

[0003] Fuels or combustibles containing paraffinic compounds, in particular compounds containing n-alkyl, iso-alkyl or n-alkenyl groups such as paraffinic waxes, are known to have deteriorated flow properties at low temperatures, typically below 0°C. In particular, middle distillates obtained by distillation from crude oils of petroleum origin such as diesel or heating oil are known to contain different quantities of n-alkanes or n-paraffins depending on their origin. These compounds tend to crystallize at low temperatures, blocking pipes, lines, pumps and filters, for example in the fuel systems of motor vehicles.In winter or when fuels or combustibles are used at temperatures below 0°C, the crystallization of these compounds can lead to a reduction in the flow properties of the fuels or combustibles and, consequently, cause difficulties during their transport, storage and / or use. The cold operability of fuels or combustibles is a very important property, particularly to ensure cold engine starting. If paraffins are crystallized at the bottom of the tank, they can be carried along during start-up in the fuel circuit and clog, in particular, the filters and pre-filters located upstream of the injection systems (pump and injectors). Similarly, for the storage of domestic fuel oils, if paraffins precipitate at the bottom of the tank, they can be carried along and obstruct the pipes upstream of the pump and the boiler feed system (nozzle and filter).

[0004] These problems are well known in the field of fuels and combustibles, and many additives or additive mixtures have been proposed and marketed to reduce the size of paraffin crystals and / or change their shape and / or delay their formation. The smallest possible crystal size is preferred because it minimizes the risk of filter plugging or clogging.

[0005] Common flow improvers known as cold flow improvers (CFIs) are generally co- and ter-polymers of ethylene and vinyl and / or acrylic ester(s), used alone or in a mixture. These cold flow improvers (CFIs), intended to lower the Filterability Limit Temperature (FLT) and the pour point (FP), inhibit and / or delay the growth of crystals at low temperatures by promoting the dispersion of paraffin crystals; these are, for example, polymers of ethylene and vinyl acetate and / or vinyl propionate (EVA or EVP), also commonly called FLT additives. This type of additive, very widely known to those skilled in the art, is systematically added to conventional middle distillates at the refinery outlet during the winter seasons. These additivated distillates are used as diesel engine fuel or as heating fuel.Additional quantities of these additives can be added to fuels sold at service stations, in particular to meet the so-called Extreme Cold specifications.

[0006] To improve both the TLF and the pour point of distillates, it is known to add to these CFI additives additional additives or "boosters" having the function of acting in combination with the CFI additives so as to increase their effectiveness. The prior art describes such combinations of additives extensively.

[0007] By way of example, mention may be made of US patent 3,275,427 describing a middle distillate of a distillation cut between 177 and 400°C containing an additive consisting of 90 to 10% by mass of an ethylene copolymer comprising 10 to 30% of vinyl acetate units with a molar mass by weight of between 1000 and 3000 g.mol-1 and 10 to 90% by mass of a lauryl polyacrylate and / or a lauryl polymethacrylate with a molar mass by weight varying from 760 to 100,000 g.mol-1.

[0008] Document EP0857776 proposes to use alkylphenol-aldehyde resins resulting from the condensation of alkylphenol and aldehyde in association with ethylene / vinyl ester copolymers or terpolymers, to improve the fluidity of mineral oils.

[0009] Patent application WO 2008 / 006965 describes the use of a combination of a homopolymer obtained from an olefinic ester of a carboxylic acid of 3 to 12 carbon atoms and a fatty alcohol comprising a chain of more than 16 carbon atoms and optionally an olefinic double bond and a cold flow additive (CFI) of the EVA or EVP type, to increase the effectiveness of the CFI additives by amplifying their effect on the TLF.

[0010] Patent application WO 2016 / 128379 describes the use, as a cold resistance additive for a fuel or combustible, of a block copolymer comprising: (i) a block A consisting of a chain of structural units derived from one or more α,β-unsaturated alkyl acrylate or methacrylate monomers, (ii) a block B consisting of a chain of structural units derived from one or more α,β-unsaturated monomers containing at least one aromatic nucleus.

[0011] This additive is particularly useful as a TLF booster in association with a cold flow additive (CFI).

[0012] In addition to improving the flow of the fuel composition, another purpose of cold-holding additives is to ensure the dispersion of paraffin crystals, so as to delay or prevent the sedimentation of such crystals and to avoid the formation of a paraffin-rich layer at the bottom of containers, tanks or storage reservoirs; these paraffin dispersing additives are called anti-sedimentation additives or WASA (acronym for the English term "Wax Anti-Settling Additive").

[0013] Modified alkylphenol-aldehyde resins have been described in document FR2969620 as an anti-sedimentation additive in combination with a TLF additive.

[0014] Due to the diversification of fuel and combustible sources, there is always a need to find new additives to improve the low temperature properties of fuels or combustibles, also called cold holding properties, and in particular their flow properties during storage and / or use at low temperatures.

[0015] This need is particularly important for fuels or combustibles 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.

[0016] In particular, distillates used in fuels and combustibles are increasingly derived from more complex refining operations than those from direct distillation of petroleum, and can come in particular from cracking, hydrocracking, catalytic cracking and visbreaking processes. With the growing demand for diesel fuels, the refiner tends to introduce into these fuels more difficult to exploit cuts, such as the heavier cuts from cracking and visbreaking processes which are rich in long-chain paraffins.

[0017] In addition, synthetic distillates from gas processing such as those from the Fischer Tropsch process, as well as distillates resulting from the processing of biomass of plant or animal origin, such as NexBTL and distillates comprising esters of vegetable or animal oils have appeared on the market, and constitute a new range of products that can be used as a base for formulating fuels and / or domestic heating oils. These products also include long-chain paraffinic hydrocarbons.

[0018] In addition, we have seen the arrival of new crude oils on the market, much richer in paraffins than those commonly refined and whose filterability temperature of distillates from direct distillation was difficult to improve by conventional filterability additives like those previously mentioned.

[0019] It was found that the cold holding properties of distillates obtained by combining the old bases and these new sources were difficult to improve by adding conventional filterability additives, among other things due to the significant presence of long-chain paraffins and the complex distribution of paraffins in their composition. In fact, discontinuous distributions of paraffins were noted in these new combinations of distillates, in the presence of which the known filterability additives are not always sufficiently effective.

[0020] There is therefore a need to adapt cold-holding additives to these new types of fuel bases, which are considered particularly difficult to process.

[0021] The present invention applies to fuels and combustibles containing not only conventional distillates such as those from the direct distillation of crude oils, but also to bases from other sources, such as those described above.

[0022] Thus, the aim of the present invention is to propose a new additive composition which can advantageously be used to improve the 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.

[0023] The aim of the present invention is further to propose a new composition of additives for fuels and combustibles, and concentrates containing such a composition, acting on the Filterability Limit Temperature (FLT), the pour point (FP), and delaying and / or preventing the sedimentation of crystals of hydrocarbon compounds, in particular paraffins.

[0024] Finally, another aim of the invention is to provide a fuel or combustible composition having improved cold resistance properties, in particular at temperatures below 0°C, preferably below -5°C. SUBJECT OF THE INVENTION

[0025] The applicant has now discovered that a composition of particular additives, as described below, possesses unexpected properties for improving the cold performance of fuel and combustible compositions, including those which are particularly difficult to process.

[0026] The present invention thus relates to a composition of additives comprising: at least one copolymer comprising: at least one unit of the following formula (I): in which R 1 represents a hydrogen atom or a methyl group, X represents -O-CO-, or -CO-O- or -NH-CO- or -CO-NH-, and R 2 represents a linear or branched acyclic C 12 -C 22 alkyl radical, the copolymer containing from 70 to 95% by moles of said unit of formula (I) relative to the total number of moles of the copolymer; and at least one unit of the following formula (II): in which R is chosen from the following rings: a substituted or unsubstituted imidazole ring, a substituted or unsubstituted triazole ring, a substituted or unsubstituted pyrrolidone ring, the copolymer containing from 5 to 30% by mole of said unit of formula (II) relative to the total number of moles of the copolymer; said copolymer being present in a content of 0.1 to 30% by weight relative to the total weight of the additive composition; at least one cold-thinning additive chosen from copolymers of ethylene and unsaturated ester(s); from 1 to 50% by weight of at least one anti-sedimentation additive and / or paraffin dispersant relative to the total weight of the additive composition.

[0027] The invention also relates to the use of the additive composition according to the invention for improving the cold resistance properties of a fuel or combustible composition.

[0028] The invention also relates to a fuel or combustible composition.

[0029] Other objects, characteristics, aspects and advantages of the invention will appear even more clearly on reading the description and examples which follow.

[0030] In what follows, and unless otherwise indicated, the limits of a domain of values ​​are included in this domain, in particular in the expressions "between" and "ranging from ... to ...".

[0031] Furthermore, the expressions “at least one” and “at least” used in this description are respectively equivalent to the expressions “one or more” and “greater than or equal”.

[0032] Finally, in a manner known per se, the term CN compound or group refers to a compound or group containing N carbon atoms in its chemical structure. DETAILED DESCRIPTION

[0033] The present invention is disclosed in and by the appended claims. The composition of additives:

[0034] The invention uses an additive composition comprising at least one copolymer comprising at least one unit of the following formula (I): in which R 1 represents a hydrogen atom or a methyl group, X represents -O-CO-, or -CO-O- or -NH-CO- or -CO-NH-, and R 2 represents a linear or branched acyclic C 12 -C 22 alkyl radical.

[0035] The group X of formula (I) is chosen from: X = -O-CO-, it being understood that X is then linked to the vinyl carbon by the oxygen atom; X = -CO-O-, it being understood that X is then linked to the vinyl carbon by the carbon atom; X = -NH-CO-, it being understood that X is then linked to the vinyl carbon by the nitrogen atom; and X = -CO-NH-, it being understood that X is then linked to the vinyl carbon by the carbon atom.

[0036] According to a first embodiment, the group X of formula (I) is chosen from: -O-CO- and -NH-CO-, it being understood that the group X= -O-CO- is linked to the vinyl carbon by the oxygen atom and that the group X= -NH-CO- is linked to the vinyl carbon by the nitrogen atom. In this embodiment, the group X of formula (I) is preferably the group -O-CO-.

[0037] According to a second embodiment, the group X of formula (I) is chosen from: -CO-O- and -CO-NH-, it being understood that the group X is linked to the vinyl carbon by the carbon atom. In this embodiment, the group X of formula (I) is preferably the group -CO-O-.

[0038] According to a particularly preferred embodiment, the group X is a -CO-O- group, X being linked to the vinyl carbon by the carbon atom. . According to a particular embodiment, the group R 2 of formula (I) is a linear or branched acyclic C 12 -C 14 alkyl radical. According to another particular embodiment, the group R 2 of formula (I) is a linear or branched acyclic C 18 -C 22 alkyl radical.

[0039] Non-limiting examples of preferred R 2 groups include alkyl groups such as dodecyl, isododecyl, lauryl, stearyl, octadecyl, behenyl, C 14 alkyl groups.

[0040] According to a particularly preferred embodiment, the group X is a -CO-O- group, X being linked to the vinyl carbon by the carbon atom, and the group R 2 is a linear or branched acyclic C 12 -C 22 alkyl radical.

[0041] The patterns according to this embodiment correspond to those derived from monomers chosen from C 12 -C 22 alkyl acrylates and methacrylates.

[0042] According to a particular embodiment, the group X is a -CO-O- group, X being linked to the vinyl carbon by the carbon atom, and the group R 2 is a linear or branched acyclic C 12 -C 14 alkyl radical. The units according to this embodiment correspond to those derived from monomers chosen from C 12 -C 14 alkyl acrylates and methacrylates.

[0043] According to another particular embodiment, the group X is a -CO-O- group, X being linked to the vinyl carbon by the carbon atom, and the group R 2 is a linear or branched acyclic C 18 -C 22 alkyl radical. The units according to this embodiment correspond to those derived from monomers chosen from C 18 -C 22 alkyl acrylates and methacrylates.

[0044] The copolymer used in the present invention also comprises at least one unit of the following formula (II): in which R is selected from the following rings: a substituted or unsubstituted imidazole ring, a substituted or unsubstituted triazole ring, a substituted or unsubstituted pyrrolidone ring.

[0045] The substituent(s) possibly present on the cycle(s) may be saturated or unsaturated, and may be chosen in particular from hydrocarbon, oxygenated, nitrogenous, halogenated, etc. substituents.

[0046] According to a particularly preferred embodiment, the group R is a substituted or unsubstituted imidazole ring.

[0047] According to one embodiment, the units of formula (II) are derived from one or more vinyl monomers carrying a group R as described above.

[0048] Examples of preferred monomers include: 1,2,3 and 1,2,4 N-vinyltriazoles, N-vinylpyrrolidone, 1-vinylimidazole (or N-vinylimidazole), the latter being particularly preferred.

[0049] The copolymer used in the present invention may or may not be crosslinked. Preferably, it is not crosslinked.

[0050] The copolymer according to the invention contains from 70 to 95 mol% of units of formula (I) relative to the total number of moles of the copolymer, more preferably from 70 to 90 mol%, and better still from 75 to 85 mol%.

[0051] The copolymer according to the invention contains from 5 to 30 mol% of units of formula (II) relative to the total number of moles of the copolymer, more preferably from 10 to 30 mol%, and better still from 15 to 25 mol%.

[0052] Preferably, the copolymer employed in the present invention contains only units of formula (I) and units of formula (II).

[0053] The copolymer used in the present invention is advantageously a random copolymer or a block copolymer. According to a particularly preferred embodiment, it is a random copolymer.

[0054] The copolymer used in the present invention can be obtained by copolymerization of: at least one monomer of the following formula (IA): in which R 1 , X and R 2 are as defined above, the preferred variants of R 1 , X and R 2 according to formula (I) described above also being preferred variants of formula (IA), and at least one monomer of the following formula (IIA): wherein R is as defined above, the preferred variants of R according to formula (II) described above also being preferred variants of formula (IIA).

[0055] When the group X of the monomer of formula (IA) is the group -O-CO-, it being understood that the group -O-CO- is linked to the vinyl carbon by the oxygen atom, the monomer of formula (IA) is preferably chosen from C 12 to C 22 vinyl alkyl esters. According to a particular embodiment, the monomer of formula (IA) is chosen from C 12 to C 14 vinyl alkyl esters. According to another particular embodiment, the monomer of formula (IA) is chosen from C 18 to C 22 vinyl alkyl esters. The alkyl radical of the vinyl alkyl ester is linear or branched, acyclic.

[0056] Examples of alkyl vinyl ester monomers include vinyl dodecanoate, vinyl tetradecanoate, and vinyl 2-ethylhexanoate.

[0057] When the group X of the monomer of formula (IA) is the group -CO-O-, it being understood that the group -CO-O- is linked to the vinyl carbon by the carbon atom, the monomer of formula (IA) is typically chosen from C 12 to C 22 alkyl acrylates and methacrylates. According to a particular embodiment, the monomer of formula (IA) is chosen from C 12 to C 14 alkyl acrylates and methacrylates. According to another particular embodiment, the monomer of formula (IA) is chosen from C 18 to C 22 alkyl acrylates and methacrylates.

[0058] Among the alkyl (meth)acrylates which may be used as monomers in the manufacture of the copolymer employed in the invention, mention may be made in particular, by way of non-limiting examples:, n-dodecyl acrylate, n-dodecyl methacrylate, lauryl acrylate, stearyl acrylate, octadecyl acrylate, behenyl acrylate, C 12 to C 14 alkyl acrylates and C 12 to C 14 alkyl methacrylates. It is particularly preferred to use C 12 to C 14 alkyl acrylates and C 12 to C 14 alkyl methacrylates and also C 18 to C 22 alkyl acrylates and C 18 to C 22 alkyl methacrylates.

[0059] The monomers of formula (IIA) are vinyl monomers bearing an R group as described above.

[0060] Mention may be made, as a particularly preferred monomer of formula (IIA), of 1-vinylimidazole (or N-vinylimidazole).

[0061] It is understood that it would not be a departure from the invention if the copolymer used in the invention were obtained from monomers other than those of formula (IA) and (IIA) above, insofar as the final copolymer corresponds to a polymer comprising units of formula (I) and units of formula (II) as defined above. For example, it would not be a departure from the invention if the polymer were obtained by polymerization of different monomers, followed by post-functionalization. For example, the units of formula (I) can be obtained from acrylic acid, by transesterification reaction.

[0062] The copolymer used in the invention can be prepared by any known polymerization process. The various polymerization and crosslinking techniques and conditions are widely described in the literature and fall within the general knowledge of those skilled in the art.

[0063] In the case of a statistical copolymer, one can proceed in particular by classical radical polymerization: one generally proceeds by mixing the different monomers in an appropriate solvent, and the copolymerization is initiated by means of a radical polymerization agent.

[0064] In the case of a block copolymer, it is possible to proceed in particular by controlled sequenced polymerization. Such polymerization is advantageously chosen from controlled radical polymerization; for example, by atom transfer radical polymerization (ATRP); nitroxide-mediated radical polymerization (NMP); degenerative transfer processes such as degenerative iodine transfer polymerization (ITRP) or reversible addition-fragmentation chain transfer radical polymerization (RAFT);ATRP-derived polymerizations such as polymerizations using initiators for continuous activator regeneration (ICAR) or using activators regenerated by electron transfer (ARGET);

[0065] The copolymer used in the invention advantageously has a weight-average molar mass (M w ) of between 1,000 and 50,000 g.mol -1< , more preferably between 1,000 and 20,000 g.mol -1< , even more preferably between 3,000 and 15,000 g.mol -1< .

[0066] The copolymer according to the invention advantageously has a number-average molar mass (Mn) of between 1,000 and 50,000 g.mol -1< , more preferably between 1,000 and 20,000 g.mol -1< , even more preferably between 2,000 and 10,000 g.mol -1< .

[0067] Number and weight average molar masses are measured by size exclusion chromatography (SEC).

[0068] The additive composition according to the invention comprises from 0.1 to 30% by weight of copolymer as described above, preferably from 1 to 20% by weight, more preferably from 2 to 10% by weight relative to the total weight of the additive composition.

[0069] The additive composition according to the invention also comprises at least one cold flow additive (CFI) chosen from copolymers of ethylene and unsaturated ester(s).

[0070] Preferably, the cold-thinning additive is chosen from copolymers of ethylene and vinyl and / or acrylic ester(s), such as ethylene / vinyl acetate (EVA), ethylene / vinyl propionate (EVP), ethylene / vinyl ethanoate (EVE), ethylene / methyl methacrylate (EMMA), and ethylene / alkyl fumarate copolymers described, for example, in documents US3048479, US3627838, US3790359, US3961961 and EP261957. Mention may also be made of terpolymers of ethylene, vinyl acetate and another vinyl ester, for example vinyl neodecanoate.

[0071] According to a preferred embodiment, the cold flow additive (CFI) is chosen from copolymers of ethylene and vinyl ester(s), preferably from ethylene / vinyl acetate copolymers (EVA), ethylene / vinyl propionate copolymers (EVP) and terpolymers of ethylene, vinyl acetate and another vinyl ester; more preferably still ethylene / vinyl acetate copolymers and their blends with a terpolymer of ethylene, vinyl acetate and another vinyl ester, such as in particular vinyl neodecanoate.

[0072] The additive composition according to the invention may advantageously comprise from 50 to 90% by weight of cold flow additive (CFI) as described above, preferably from 60 to 90% by weight, more preferably from 70 to 90% by weight relative to the total weight of the additive composition.

[0073] The additive composition according to the invention also comprises from 1 to 50% by weight of at least one anti-sedimentation additive and / or paraffin dispersant relative to the total weight of the additive composition.

[0074] The anti-sedimentation additive and / or paraffin dispersant (WASA) may be, in particular, but not limited to, chosen from the group consisting of (meth)acrylic acid / alkyl (meth)acrylate copolymers amidated with a polyamine, condensation products of one or more carboxylic acids with one or more polyamines, polyamine alkenylsuccinimides, phthalamic acid and double-chain fatty amine derivatives; optionally grafted alkylphenol resins, modified alkylphenol-aldehyde resins. Examples of such additives are given in the following documents: EP261959, EP593331, EP674689, EP327423, EP512889, EP832172; US2005 / 0223631; US5998530; WO93 / 14178; WO2012 / 085865.

[0075] The particularly preferred anti-settling and / or paraffin dispersant additive (WASA) is selected from alkylphenol resins and alkylphenol resins grafted for example with functional groups such as polyamines.

[0076] The additive composition according to the invention may advantageously comprise from 2 to 30% by weight of anti-sedimentation additive and / or paraffin dispersant as described above, preferably from 5 to 20% by weight relative to the total weight of the additive composition.

[0077] The additive composition according to the invention may also comprise one or more other additives commonly used in fuels or combustibles, different from the copolymer, the cold resistance additive, and the anti-sedimentation additive described above.

[0078] The additive composition may typically comprise one or more other additives selected from detergents, anti-corrosion agents, dispersants, demulsifiers, biocides, reodorants, procetane additives, friction modifiers, lubricity additives or smoothness additives, combustion aids (catalytic combustion and soot promoters), anti-wear agents and / or conductivity modifying agents.

[0079] Among these additives, we can cite in particular: a) procetane additives, in particular (but not limited to) chosen from alkyl nitrates, preferably 2-ethylhexyl nitrate, aryl peroxides, preferably benzyl peroxide, and alkyl peroxides, preferably tert-butyl peroxide; b) anti-foam additives, in particular (but not limited to) chosen from polysiloxanes, oxyalkylated polysiloxanes, and fatty acid amides derived from vegetable or animal oils. Examples of such additives are given in EP861882, EP663000, EP736590; (c) 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 WO2012 / 004300.It is also advantageous to use block copolymers formed from at least one polar unit and one apolar unit, such as for example those described in patent application FR 1761700 in the name of the Applicant; d) lubrication 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 polycyclic carboxylic acid derivatives. Examples of such additives are given in the following documents: EP680506, EP860494, WO98 / 04656, EP915944, FR2772783, FR2772784. Use

[0080] The present invention also relates to the use, for improving the cold resistance properties of a fuel or combustible composition, of the additive composition according to the invention.

[0081] Said fuel or combustible composition may be a composition chosen from diesel fuels, biodiesels, type B diesel fuels x containing x% (v / v) of esters of vegetable or animal oils or fatty acids, hydrogenated vegetable oils, and fuel oils such as domestic fuel oils, x being a number strictly greater than 0 and less than or equal to 100.

[0082] The fuel or combustible composition is as described below and advantageously comprises at least one hydrocarbon fraction from one or more sources chosen from the group consisting of mineral sources, preferably petroleum, animal, vegetable and synthetic sources.

[0083] Advantageously, said additive composition is used to improve the low temperature flow properties of the fuel or combustible during its storage and / or use at low temperature, by lowering its filterability limit 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 filterability limit temperature (TLF, measured according to standard NF EN 116).

[0084] The additive composition according to the invention can be used to delay or prevent the sedimentation of paraffin crystals and more particularly of n-alkanes, preferably n-alkanes containing at least 12 carbon atoms, more preferably at least 20 carbon atoms. Fuel or combustible composition:

[0085] The invention also relates to a fuel or combustible composition, comprising: (1) at least one hydrocarbon fraction from one or more sources selected from the group consisting of mineral, animal, vegetable and synthetic sources, and (2) at least one additive composition according to the invention, and in which said fuel or combustible composition contains: the copolymer(s) in a content ranging from 0.0001 to 0.01% by weight relative to the total weight of the composition; the cold-thinning additive(s) in a content ranging from 0.0005 to 0.2% by weight relative to the total weight of the fuel or combustible composition; the anti-sedimentation and / or paraffin dispersant(s) additive(s) in a content ranging from 0.0001 to 0.1% by weight relative to the total weight of the fuel or combustible composition.

[0086] Mineral sources are preferably petroleum.

[0087] The fuel or combustible composition according to the invention advantageously comprises the copolymer(s) in a content ranging from 0.0002 to 0.005% by weight relative to the total weight of the fuel or combustible composition.

[0088] The fuel or combustible composition according to the invention advantageously comprises the cold-thinning additive or additives in a content ranging from 0.001 to 0.1% by weight, more preferably from 0.0015 to 0.05% by weight relative to the total weight of the fuel or combustible composition.

[0089] The fuel or combustible composition according to the invention advantageously comprises the anti-sedimentation and / or dispersant additive(s) of paraffins in a content ranging from 0.0005 to 0.05% by weight, more preferably from 0.001 to 0.02% by weight, relative to the total weight of the fuel or combustible composition.

[0090] The fuels or combustibles may be chosen from liquid hydrocarbon fuels or combustibles, alone or in a mixture. The liquid hydrocarbon fuels or combustibles include in particular middle distillates with a boiling temperature between 100 and 500°C.These distillates may, for example, be chosen from distillates obtained by direct distillation of crude hydrocarbons, vacuum distillates, hydrotreated distillates, distillates resulting from catalytic cracking and / or hydrocracking of vacuum distillates, distillates resulting from ARDS (atmospheric residue desulfurization) and / or visbreaking conversion processes, distillates resulting from the recovery of Fischer Tropsch cuts, distillates resulting from BTL (biomass to liquid) conversion of plant and / or animal biomass, taken alone or in combination, and / or biodiesels of animal and / or plant origin and / or oils and / or esters of plant and / or animal oils.

[0091] The sulfur content of the fuels or combustibles is preferably less than 5000 ppm, more preferably less than 500 ppm, and even more preferably less than 50 ppm, or even less than 10 ppm, and advantageously sulfur-free.

[0092] The fuel or combustible is preferably chosen from diesel, biodiesel, Bx type diesel and fuel oils, preferably domestic fuel oils (DFO).

[0093] Type B x diesel fuel for diesel engines (compression engines) is a diesel fuel that contains x% (v / v) of vegetable or animal oil esters (including used cooking oils) transformed by a chemical process called transesterification, which reacts this oil with an alcohol to obtain fatty acid esters (FAE). With methanol and ethanol, fatty acid methyl esters (FAME) and fatty acid ethyl esters (FAE) are obtained respectively. The letter "B" followed by a number indicates the percentage of FAE contained in the diesel fuel, x being a number strictly greater than 0 and less than or equal to 100. Thus, a B 99 contains 99% FAE and 1% middle distillates of fossil origin, B 20, 20% FAE and 80% middle distillates of fossil origin, etc.We therefore distinguish between type B 0 diesel fuels which do not contain oxygenated compounds, and type Bx diesel fuels which contain x% (v / v) of vegetable or animal oil esters or fatty acids, most often methyl esters (EMHV or EMAG). When EAG is used alone in engines, the fuel is referred to as B100.

[0094] The fuel or combustible may also contain hydrogenated vegetable oils, known to those skilled in the art as HVO (from the English “hydrogenated vegetable oil”) or HDRD (from the English “hydrogenation-derived renewable diesel”).

[0095] According to a particular development, the fuel or combustible is chosen from diesel, biodiesel and B x type diesel, hydrogenated vegetable oils (HVO), and their mixtures.

[0096] The fuel composition or combustible may also contain one or more additional additives, other than the copolymers, the cold-thinning additive and the anti-sedimentation additive described above. Such additives may be chosen in particular from detergents, anti-corrosion agents, dispersants, demulsifiers, anti-foam agents, biocides, reodorants, procetane additives, friction modifiers, lubricity additives or smoothness additives, combustion aid agents (catalytic combustion and soot promoters), anti-wear agents and / or conductivity modifying agents.

[0097] These additional additives may generally be present in an amount ranging from 0.005 to 0.1% by weight, relative to the weight of the fuel or combustible composition (each).

[0098] The invention also relates to a method for improving the cold resistance properties of a fuel or combustible composition, consisting of adding an additive composition as described above.

[0099] The following examples are given as illustrations of the invention, and should not be interpreted in such a way as to limit its scope. EXAMPLES Example 1 : Synthesis of different polymers

[0100] The various polymers were synthesized by radical solution polymerization. In a typical example, the monomers were solubilized in a solvent chosen from toluene or dioxane, and the transfer agent was added to the mixture. The system was degassed under nitrogen flow for 40 minutes and then heated to 70°C. Once at this temperature, the initiator was added to start the polymerization. The reaction was left for 6 hours. The system was then opened to air and allowed to cool to room temperature. The polymer formed was recovered by vacuum drying.

[0101] The recovered polymer was characterized by NMR spectroscopy and gas chromatography (GPC) to determine the composition and molar mass of the copolymer, respectively.

[0102] The characteristics of the polymers synthesized according to the above procedure are listed in Table I below: Tableau I Polymer type Monomer of formula (I) Monomer of formula (II) MW (g.mol -1< ) M n (g.mol -1< ) Homopolymer C12 / C14 alkyl acrylate - 7750 4920 Statistical copolymer 1 C12 / C14 alkyl acrylate N-vinylimidazole 20 mol% 8100 5700 80% mol Statistical copolymer 2 C12 / C14 alkyl acrylate N-vinylimidazole 10 mol% 10230 6220 90% mol Example 2 : Evaluation of cold resistance performance

[0103] A G composition of diesel-type fuel which is particularly difficult to process, and whose characteristics are detailed in Table II below: Table II Characteristic Method Value Density at 15°C ISO 12185 836.8 kg / m 3< Cloud Point (CTP)° EN 23015 -9°C Filterability Limit Temperature (FLT) IN 116 -11°C Pour point (PTE) ASTM D 7346 -15°C Paraffin content 18.8% by weight C16+ n-paraffin content 8.51% by weight Distillation profile D86 ISO 3405 Initial point 172°C Point at 5% vol. 194°C Point at 10% vol. 203°C Point at 20% vol. 219°C Point at 30% vol. 234°C Point at 40% vol. 250°C Point at 50% vol. 263°C Point at 60% vol. 276°C Point at 70% vol. 290°C Point at 80% vol. 307°C Point at 90% vol. 327°C Point at 95% vol. 346°C Full stop 363°C has been added with various ingredients.

[0104] In particular, two compositions G1 and G2 were prepared. Composition G1 comprises: MDFI A additive; WASA 1 additive.

[0105] The G2 composition includes: MDFI A additive; WASA 2 additive.

[0106] The compositions of the additives are shown in Table III below, the contents indicated being in percentage by weight relative to the total weight of the additive: Tableau III Additive MDFI A WASA 1 WASA 2 Solvesso 150 Solvent 28 28 28 Ethylene / vinyl acetate copolymer 61 20 20 Ethylene / vinyl acetate / 2-ethylhexyl acrylate terpolymer 10 - - Homopolymer as defined in Example 1 - 10 - statistical copolymer 1 - - 10 alkylphenol resin grafted with a tallow triamine - 32 32 alpha-olefin / stearyl acrylate / maleic anhydride terpolymer amidated with a tallow amine - 10 10

[0107] Thus, composition G1 comprises a comparative additive composition. Composition G1 is therefore a comparative composition. Composition G2 comprises an additive composition according to the invention. Composition G2 is therefore a composition according to the invention.

[0108] For composition G1, 170 ppm of WASA 1 additive was added. Two rates of MDFI A additive are tested at 100 and 150 ppm.

[0109] For composition G2, 170 ppm of WASA 2 additive was added. Two rates of MDFI A additive were tested at 100 and 150 ppm.

[0110] The performance of the additive compositions was tested, by evaluating their ability to lower the filterability limit temperature (TFL) of the G1 and G2 additive diesel compositions.

[0111] The results obtained are presented below. The TLFs of compositions G1 and G2 were measured in accordance with EN 116.

[0112] The TLF results are obtained by adding each of the additives defined above, depending on the MDFI A additive rate, the WASA 1, WASA 2 additive rate respectively, being constant (170 ppm).

[0113] The TLF target to be achieved is set at -28°C.

[0114] The additive composition according to the invention makes it possible to achieve the target TLF of -28°C with an MDFI A additive level of only 100 ppm. This same TLF of -28°C is achieved with the comparative additive composition with a 50% higher level, i.e. 150 ppm.

[0115] Thus, the use of the additive composition according to the invention makes it possible to reduce the treatment rate by 33%, compared to the comparative composition. Furthermore, at the same treatment rate, the additive composition according to the invention makes it possible to obtain better cold resistance performance. Example 3 : Evaluation of cold resistance performance

[0116] A G' composition of diesel fuel which is particularly difficult to process, and whose characteristics are detailed in Table IV below: Table IV Characteristic Method Value Density at 15°C ISO 12185 831.1 kg / m 3< Cloud Point (CTP)° EN 23015 -6°C ? Filterability Limit Temperature (FLT) IN 116 -6°C Pour point (PTE) ASTM D 7346 -12°C Paraffin content 13% by weight C16+ n-paraffin content 6% by weight Distillation profile D86 ISO 3405 Initial point 167°C Point at 5% vol. 192°C Point at 10% vol. 205°C Point at 20% vol. 225°C Point at 30% vol. 243°C Point at 40% vol. 260°C Point at 50% vol. 276°C Point at 60% vol. 291°C Point at 70% vol. 305°C Point at 80% vol. 319°C Point at 90% vol. 335°C Point at 95% vol. 349°C Full stop 355°C has been added with various ingredients.

[0117] In particular, three compositions G'1, G'2 and G'3 were prepared.

[0118] Composition G'1 includes: the MDFI B additive, in Solvesso 150 solvent (28% by weight relative to the weight of the additive), marketed by the company Total Additifs Carburants Spéciaux, which comprises 65% by weight of an ethylene / vinyl acetate (EVA) copolymer, and 7% by weight of an alpha-olefin / stearyl acrylate / maleic anhydride terpolymer amidated with a tallow amine.

[0119] Composition G'2 includes: the MDFI B additive as described above; the WASA 1 additive as described in example 2.

[0120] Composition G'3 includes: the MDFI B additive as described above; the WASA 2 additive as described in example 2.

[0121] Thus, compositions G'1 and G'2 comprise a comparative additive composition. Compositions G'1 and G'2 are therefore comparative compositions. Composition G'3 comprises an additive composition according to the invention. Composition G'3 is therefore a composition according to the invention.

[0122] For each of the compositions G'1, G'2 and G'3, two rates of MDFI B additive are tested: 400 and 600 ppm.

[0123] For composition G'2, 200 ppm of WASA 1 additive was added.

[0124] For composition G'3, 200 ppm of WASA 2 additive was added.

[0125] The performance of the additive compositions was tested by evaluating their ability to lower the filterability limit temperature (FLT) of the additive diesel compositions G'1, G'2 and G'3. The FLTs of compositions G'1, G'2 and G'3 were measured in accordance with EN 116.

[0126] The results obtained are presented in Table V below: Tableau V Compositions TLF (°C) G'1 TLF (°C) G'2 TLF (°C) G'3 G'1 MDFI B 400 ppm -18°C - - G'1 MDFI B 600 ppm -25°C - - G'2 MDFI B 400 ppm - -20°C - G'2 MDFI B 600 ppm - -23°C - G'3 MDFI B 400 ppm - - -24°C G'3 MDFI B 600 ppm - - -27°C

[0127] The results clearly show that the composition of additives according to the invention leads to a significant lowering of the TLF.

Claims

1. Composition of additives comprising: - at least one copolymer comprising: - at least one unit having the following formula (I): in which R1 represents a hydrogen atom or a methyl group, X represents -O-CO-, or -CO-O- or -NH-CO- or -CO-NH-, and R2 represents a C12-C22 linear or branched acyclic alkyl radical, said copolymer containing from 70 to 95% in moles of units having the formula (I) relative to the total number of moles of the copolymer; and - at least one unit having the following formula (II): in which R is chosen from the following cycles: a substituted or non-substituted imidazole cycle, a substituted or non-substituted triazole cycle, a substituted or non-substituted pyrrolidone cycle, said copolymer containing from 5 to 30% in moles of units having the formula (II) relative to the total number of moles of the copolymer; and wherein the copolymer is present in a content ranging from 0.1 to 30% by weight relative to the total weight of the composition of additives; - at least one cold flow improver chosen from the copolymers of ethylene and of unsaturated ester(s); - from 1 to 50% by weight of at least one anti-settling additive and / or paraffin dispersant relative to the total weight of the composition of additives.

2. Composition according to claim 1, characterised in that the group R is a substituted or non-substituted imidazole cycle.

3. Composition according to claims 1 or 2, characterised in that said copolymer contains only units having the formula (I) and units having the formula (II).

4. Composition according to any one of the previous claims, characterised in that said copolymer is a statistical copolymer, or a block copolymer, and preferably said copolymer is a statistical copolymer.

5. Composition according to any one of the previous claims, characterised in that it comprises from 1 to 20% by weight of said copolymer, more preferably from 2 to 10% by weight relative to the total weight of the composition of additives.

6. Composition according to any one of the previous claims, characterised in that it comprises from 50 to 90% by weight of said cold flow improver, preferably from 60 to 90% by weight, more preferably from 70 to 90% by weight relative to the total weight of the composition of additives.

7. Composition according to any one of the previous claims, characterised in that it comprises from 2 to 30% by weight of said anti-settling additive and / or of said paraffin dispersant, more preferably from 5 to 20% by weight relative to the total weight of the composition of additives.

8. Composition according to any one of the previous claims, characterised in that the cold flow improver is chosen from the copolymers of ethylene and of vinyl and / or acrylic ester(s), preferably from the copolymers of ethylene and of vinyl ester(s), more preferably from the ethylene / vinyl acetate copolymers, the ethylene / vinyl propionate copolymers and the terpolymers of ethylene, of vinyl acetate and of another vinyl ester, even more preferably the ethylene / vinyl acetate copolymers and their mixtures with a terpolymer of ethylene, of vinyl acetate and of another vinyl ester, in particular such as vinyl neodecanoate.

9. Composition according to any one of the previous claims, characterised in that the anti-settling additive is chosen from the group consisting of the (meth)acrylic acid / alkyl (meth)acrylate copolymers amidified by a polyamine, the polyamine alkenylsuccinimides, the derivatives of phthalamic acid and of two-chain fatty amine, the products of condensation of one or more carboxylic acids with one or more polyamines, modified alkylphenol-aldehyde resins and optionally grafted alkylphenol resins, preferably the alkylphenol resins and the grafted alkylphenol resins.

10. Use, to improve the cold resistance properties of a fuel or combustible composition, of the composition of additives as defined in any one of the previous claims.

11. Use according to the previous claim, characterised in that the fuel or combustible composition is chosen from the diesel fuels, the biodiesels, the diesel fuels of the Bx type containing x% (v / v) of esters of vegetable or animal oils or of fatty acids, the hydrogenated vegetable oils, and the fuel oils such as the heating oils.

12. Use according to claims 10 or 11 to lower the cold filter plugging point measured according to the standard NF EN 116 and / or the pour point measured according to the standard ASTM D 7346, and / or to delay or prevent the settling of crystals, and preferably to lower the cold filter plugging point measured according to the standard NF EN 116.

13. Fuel or combustible composition, comprising: (1) at least one cut of hydrocarbons coming from one or more sources chosen from the group consisting of the mineral, animal, plant and synthetic sources, and (2) at least one composition of additives as defined in any one of claims 1 to 9; and wherein said fuel or combustible composition contains: - the copolymer in a concentration ranging from 0.0001 to 0.01% by weight relative to the total weight of the fuel or combustible composition; - the cold flow improver(s) in a concentration ranging from 0.0005 to 0.2% by weight relative to the total weight of the fuel or combustible composition; - the anti-settling additive and / or paraffin dispersant(s) in a concentration ranging from 0.0001 to 0.1% by weight relative to the total weight of the fuel or combustible composition.

14. Composition according to the previous claim, characterised in that it contains the copolymer(s) in a concentration ranging from 0.0002 to 0.005% by weight relative to the total weight of the composition.

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