EP3844250A1

EP3844250A1 - Use of specific copolymers for improving the cold properties of fuels or combustibles

Info

Publication number: EP3844250A1
Application number: EP19755939.6A
Authority: EP
Inventors: Ana Maria CENACCHI-PEREIRA; Julie Prevost
Original assignee: Total Marketing Services SA
Current assignee: TotalEnergies Onetech SAS
Priority date: 2018-08-28
Filing date: 2019-08-23
Publication date: 2021-07-07
Anticipated expiration: 2039-08-23
Also published as: FR3085384B1; US20210348073A1; PL3844250T3; WO2020043618A1; FR3085384A1; EP3844250B1

Abstract

The subject matter of the present invention is the use, for improving the cold-resistance properties of a fuel or combustible composition, of one or more copolymers comprising: - at least one unit of formula (I): in which R1 is a hydrogen atom or a methyl group; X is -O-CO-, or -CO-O- or -NH-CO- or -CO-NH-; R2 is a C6 to C24 alkyl group; and at least one unit of formula (II): in which R is a substituted or unsubstituted imidazole ring. The invention also relates to compositions of additives containing such a polymer, and also fuel or combustible compositions to which such polymers have been added, preferably in combination with a cold flow improver (CFI) additive or a paraffin anti-settling additive (WASA).

Description

Use of specific copolymers to improve the cold properties of fuels

The present invention relates to the use of particular copolymers to improve the cold-keeping properties of fuels and combustibles during their storage and / or their use at low temperature.

The present invention also relates to additive compositions (or “additive packages”) containing these copolymers, as well as fuel and fuel compositions additivated with such copolymers, preferably in combination with at least one cold-thinning additive. (CFI) and / or at least one paraffin anti-sedimentation additive (WASA). PRIOR STATE OF THE ART

Fuels or combustibles containing paraffinic compounds, in particular compounds containing n-alkyl, iso-alkyl or n-alkenyl groups such as paraffinic waxes, are known to exhibit deteriorated flow properties at low temperature, typically below 0 ° C. In particular, it is known that the middle distillates obtained by distillation from crude oils of petroleum origin such as diesel or heating oil, contain different amounts of n-alkanes or n-paraffins depending on their origin. These compounds tend to crystallize at low temperatures, clogging hoses, pipes, pumps and filters, for example in the fuel circuits of motor vehicles. In winter or under conditions of use of fuels or fuels at a temperature below 0 ° C, the crystallization phenomenon of these compounds can lead to a decrease in the flow properties of fuels or fuels and, consequently, cause difficulties during their transport, their storage and / or their use. The cold operability of fuels is a very important property, in particular for ensuring the starting of cold engines. If paraffins are crystallized at the bottom of the tank, they can be entrained at start-up in the fuel circuit and clog in particular the filters and prefilters placed upstream of the injection systems (pump and injectors). Likewise, for the storage of domestic heating oils, if paraffins precipitate at the bottom of the tank, they can be entrained and obstruct the pipes upstream of the pump and the boiler supply system (nozzle and filter).

These problems are well known in the field of fuels and fuels, and numerous additives or mixtures of additives have been proposed and marketed to reduce the size of the paraffin crystals and / or change their shape and / or prevent them from forming. The smallest possible crystal size is preferred since it minimizes the risk of clogging or clogging of the filters.

The usual flow improving agents known as cold flow improvers (in English "cold flow improvers" or CFI) are generally co-and ter-polymers of ethylene and of vinyl ester (s) and / or acrylic (s), used alone or as a mixture. These cold thinning additives (CFI), intended to lower the Filterability Limit Temperature (TLF) and the pour point (PE), inhibit the growth of crystals at low temperature by promoting the dispersion of paraffin crystals; these are, for example, polymers of ethylene and vinyl acetate and / or vinyl propionate (EVA or EVP), also commonly known as TLF additives. This type of additive, widely known to those skilled in the art, is systematically added to conventional medium distillates at the end of the refinery. These additive distillates are used as fuel for diesel engines or as heating fuel. Additional quantities of these additives can be added to the fuels sold in service stations, in particular to satisfy the so-called “Great Cold” specifications.

To improve both the TLF and the pour point of distillates, it is known to add additives to these CFI additives. additional or “boosters” with the function of acting in combination with CFI additives in order to increase their effectiveness. The prior art abundantly describes such combinations of additives.

By way of example, mention may be made of US Pat. No. 3,274,427 describing an average distillate for a distillation cut between 177 and 400 ° C. containing an additive consisting of 90 to 10% by mass of an ethylene copolymer comprising from 10 to 30% of vinyl acetate units with a molar mass of between 1000 and 3000 g. mol ¹ and from 10 to 90% by mass of a lauryl polyacrylate and / or of a lauryl polymethacrylate of molar mass by weight varying from 760 to 100,000 g. mol ¹ .

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

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

Patent application WO 2016/128379 describes the use, as a cold-keeping additive of 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, b-unsaturated acrylate or alkyl methacrylate monomers,

(ii) a block B consisting of a chain of structural units derived from one or more a, b-unsaturated monomers containing at least one aromatic nucleus.

This additive is particularly useful as a TLF booster in association with a cold fluidizing additive (CFI).

In addition to improving the flow of the fuel or combustible composition, another object of the cold-keeping additives is to ensure the dispersion of the paraffin crystals, so as to delay or prevent the sedimentation of such crystals and of avoid the formation of a layer rich in paraffins at the bottom of containers, tanks or storage tanks; these paraffin dispersant additives are called anti-sedimentation additives or WASA (acronym of the English term "Wax Anti-Settling Additive").

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

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

This need is particularly important for fuels or fuels comprising one or more paraffinic compounds, for example compounds containing n-alkyl, iso-alkyl or n-alkenyl groups exhibiting a tendency to crystallize at low temperature.

In particular, the distillates used in fuels and fuels are increasingly produced from more complex refining operations than those resulting from direct petroleum distillation, and can originate in particular from cracking, hydrocracking, catalytic cracking and visbreaking processes. With the growing demand for diesel fuels, the refiner tends to introduce into these fuels cuts that are more difficult to use, such as the heavier cuts resulting from cracking and visbreaking processes which are rich in long chain paraffins.

In addition, synthetic distillates from processing gas such as those from the Fischer Tropsch process, as well as distillates resulting from the treatment of biomass of plant or animal origin, such as in particular NexBTL and distillates comprising esters of vegetable or animal oils have appeared on the market, and constitute a new range of products which can be used as a basis for formulating domestic fuels and fuel oils. These products also include hydrocarbons with long paraffinic chains.

In addition, we have seen the arrival of new crude oils on the market, much richer in paraffins than those commonly refined and whose filterability temperature of distillates from direct distillation was hardly improved by conventional filterability additives in the same way than those previously cited.

It was found that the cold-keeping properties of the distillates obtained by combining the old bases and these new sources was hardly improved by the addition of conventional filterability additives, inter alia due to the significant presence of long-chain paraffins and the complex distribution of paraffins in their composition. It has been noted in fact in these new distillate combinations, discontinuous paraffin distributions, in the presence of which the known filterability additives are not always sufficiently effective.

There is therefore a need to adapt the cold-keeping additives to these new types of bases for fuels and fuels, considered to be particularly difficult to treat.

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

Thus, the aim of the present invention is to propose new additives and concentrates containing them which can advantageously be used as additives to improve the cold-resistance properties, in particular the cold-flow properties of these fuels or combustibles, during storage and / or their use at low temperature, typically less than 0 ° C.

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

Finally, another object of the invention is to provide a fuel or fuel composition having improved cold-holding properties, in particular at temperatures below 0 ° C, preferably below -5 ° C.

OBJECT OF THE INVENTION

The Applicants have now discovered that particular copolymers, as described below, have unexpected properties for improving the cold behavior of fuel and fuel compositions, including those which are particularly difficult to treat.

The present invention thus relates to the use, to improve the cold-keeping properties of a fuel or fuel composition, of one or more copolymers comprising:

- at least one motif of formula (I) below:

in which

Ri represents a hydrogen atom or a methyl group,

X represents -O-CO-, or -CO-O- or -NH-CO- or -CO-NH-, and

R2 represents a C1 to C24 alkyl group; and

- at least one motif of formula (II) below:

wherein R represents a substituted or unsubstituted imidazole ring.

According to a preferred embodiment, the polymer defined above is used as an additive called "TLF booster", that is to say in combination with a flow improvement additive or cold fluidizing additive (in English "cold flow improvers ”or CFI) which it improves performance.

The subject of the invention is also an additive composition comprising such a copolymer in combination with at least one cold-keeping additive different from the copolymers according to the invention, as well as an additive concentrate containing such a composition. The cold-keeping additive is preferably chosen from copolymers and terpolymers of ethylene and of vinyl ester (s) and / or acrylic (s), alone or as a mixture.

The invention also has for its object and a fuel or fuel composition, comprising:

(1) at least one cut of hydrocarbons from one or more sources chosen from the group consisting of mineral (preferably petroleum), animal, vegetable and synthetic sources, and

(2) at least one copolymer as defined above.

According to a preferred embodiment, said composition also comprises at least one cold-keeping additive different from the copolymers according to the invention defined above.

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

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

. .. ".

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

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

The copolymer:

The invention uses a copolymer, comprising at least one unit of formula (I) below:

in which

Ri represents a hydrogen atom or a methyl group,

X represents -O-CO-, or -CO-O- or -NH-CO- or -CO-NH-, and

R2 represents a C1 to C24 alkyl radical.

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. 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-.

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-

According to a particularly preferred embodiment, the group X is a group -CO-O-, X being linked to the vinyl carbon by the carbon atom.

The group R ₂ of formula (I) is a C 1 to C 24 alkyl radical. This alkyl radical can be linear or branched, cyclic or acyclic. This alkyl radical can comprise a linear or branched part and a cyclic part.

According to a first embodiment, the group R ₂ of formula (I) is a linear or branched acyclic alkyl radical in C to C 1 4, preferably in Cs to C 1 4, more preferably still in C 1 2 to C 1 4.

Mention may be made, for example, without limitation, of alkyl groups such as octyl, decyl, dodecyl, ethyl-2-hexyl, isooctyl, isodecyl and isododecyl, alkyl groups containing C 1 4.

According to a particularly preferred embodiment, the group X is a group -CO-O-, X being connected to the vinyl carbon by the carbon atom, and the group R2 is a linear or branched Cs to C 1 acyclic alkyl radical 4, preferably in Cio to C 1 4, and more preferably still in C 1 2 to C 1 4.

The patterns according to this embodiment correspond to those derived from monomers chosen from acrylates and methacrylates alkyl group having a alklyle Cs to C _4, preferably Cio to C 14, more preferably still C12 to Ci _4.

According to a second embodiment, the group R2 of formula (I) is a linear or branched acyclic alkyl radical in C14 to C24, preferably in C1 to C22, more preferably still in Cis to C22.

According to a particularly preferred embodiment, the group X is a group -CO-O-, X being linked to the vinyl carbon by the carbon atom, and the group R2 is an acyclic linear or branched C14 to C24 alkyl radical, preferably in CI _Ô to C22, more preferably still in Cis to C22.

The units according to this embodiment correspond to those derived from monomers selected from acrylates and alkyl methacrylates having a alklyle group C14 to C24, preferably CI _O to C 22, more preferably still C22 to Cis.

The copolymer used in the present invention also comprises at least one unit of formula (II) below:

in which

R represents a substituted or unsubstituted imidazole ring.

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

According to one embodiment, the units of formula (II) come from one or more vinyl monomers carrying an R group as described above.

As an example of a particularly preferred monomer, mention may be made of l-vinylimidazole (or N-vinylimidazole):

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

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

The copolymer according to the invention advantageously contains from 50 to 99 mol% of units of formula (I), preferably from 60 to

95% by moles, more preferably from 70 to 90% by moles, and better still from 75 to 90% by moles.

The copolymer according to the invention advantageously contains from 1 to 50 mol% of units of formula (II), preferably from 5 to 40 mol%, more preferably from 10 to 30 mol%, and better still from 10 to 25 % in moles.

Preferably, the copolymer used in the present invention contains only units of formula (I) and units of formula (II).

The copolymer used in the present invention can be obtained by copolymerization of:

at least one monomer corresponding to the following formula (IA):

in which

Ri, X and R ₂ are as defined above, the preferred variants of Ri, X and R ₂ according to formula (I) described above being also preferred variants of formula (IA), and

at least one monomer corresponding to the following formula (IIA): in which R is as defined above, the preferred variants of R according to formula (II) described above also being preferred variants of formula (IIA)

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 vinyl alkyl esters having a C 1 to C 24 alkyl group, and more preferably from vinyl alkyl esters having a C 1 2 to C 1 4 or C 1 to C 22 alkyl group. The alkyl radical of the vinyl ester is linear or branched, cyclic or acyclic, preferably acyclic.

Among the vinyl ester alkyl monomers that may be mentioned, by way of nonlimiting example, vinyl octanoate, vinyl decanoate, vinyl dodecanoate, vinyl tetradecanoate, vinyl 2-ethylhexanoate.

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 alkyl acrylates and methacrylates having a C 1 to C 24 alkyl group, and more preferably from alkyl acrylates and methacrylates having a C 1 to C 14 or C 1 to C 22 alkyl group .

Among the alkyl (meth) acrylates which may be used as monomers in the manufacture of the copolymer of the invention, mention may be made of C to C 24 alkyl acrylates and C to C 24 alkyl methacrylates , and in particular, by way of nonlimiting examples: n-octyl acrylate, n-octyl methacrylate, n-decyl acrylate, n-decyl methacrylate, n-dodecyl acrylate, n-dodecyl methacrylate, acrylate ethyl-2-hexyl, ethyl-2-hexyl methacrylate, isooctyl acrylate, isooctyl methacrylate, isodecyl acrylate, isodecyl methacrylate, C 1 alkyl acrylates 2 to C 1 4 and C 1 to C 1 4 alkyl methacrylates, C 1 to C 22 alkyl acrylates and C 1 to C 22 alkyl methacrylates. Particular preference is given to using C 12 -C 14 alkyl acrylates and C 1 2 -C 14 alkyl methacrylates.

The monomers of formula (IIA) are vinyl monomers carrying an R group as described above.

As a particularly preferred monomer of formula (IIA), mention may be made of 1-vinylimidazole (or N-vinylimidazole) of formula:

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

The polymer according to the invention can be prepared according to any known method of polymerization. The various techniques and conditions of polymerization and crosslinking are widely described in literature and fall within the general knowledge of those skilled in the art.

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

In the case of a block copolymer, one can proceed in particular by sequenced and controlled polymerization. Such a polymerization is advantageously chosen from controlled radical polymerization; for example, by atomic transfer radical polymerization (ATRP in English "Atom Transfer Radical Polymerization"); radical polymerization with nitroxide (NMP in English "Nitroxide-mediated polymerization"); degenerative transfer processes (in English "degenerative transfer processes") such as degenerative iodine transfer polymerization (in English "ITRP- iodine transfer radical polymerization") or radical polymerization by reversible chain transfer by addition-fragmentation ( RAFT in English "Reversible Addition-Fragmentation Chain Transfer"); polymerizations derived from ATRP such as polymerizations using initiators for continuous regeneration of the activator (ICAR - Initiators for continuous activator regeneration) or using activators regenerated by electron transfer (ARGET in English "activators regenerated by electron transfer ”).

The copolymer according to the invention advantageously has a weight-average molar mass (Mw) of between 1,000 and 50,000 g. mol · ¹ , more preferably between 1,000 and 20,000, even more preferably between 3,000 and 15,000 g. mol ¹ .

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

The number and weight average molar masses are measured by size exclusion chromatography (SEC in English “Size Exclusion Chromatography”).

Use:

The copolymer described above is used to improve the cold-keeping properties of a fuel or fuel composition, in particular, of a composition chosen from gas oils, biodiesels, gas oils of type B _x and fuel oils , preferably, domestic fuel oils (FOD).

The fuel or fuel composition is as described below and advantageously comprises at least one section of hydrocarbons obtained from one or more sources chosen from the group consisting of mineral sources, preferably petroleum, animal sources , vegetable and synthetic.

Advantageously, said copolymer is used to improve the flow properties at low temperature of the fuel or fuel during its storage and / or its use at low temperature, by lowering its limit filterability temperature (or TLF, measured according to the NF standard). EN 1 16) and / or its pour point (or PE, measured according to standard ASTM D 7346) and / or by delaying or preventing the sedimentation of crystals, and preferably by lowering its limit filterability temperature (TLF, measured according to standard NF EN 1 16).

The copolymer according to the invention can be used to delay or prevent the sedimentation of paraffin crystals and more particularly of n-alkanes, preferably, the n-alkanes containing at least 12 carbon atoms, more preferably at least 20 carbon atoms , even more preferably preferably at least 24.

According to a preferred embodiment, the copolymer according to the invention is used as a TLF booster additive, that is to say in combination with at least one flow-improving additive or cold-thinning additive (in English "cold flow" improvers "or CFI). The cold fluidizing 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.

In this embodiment, the copolymer according to the invention is used to amplify the fluidizing effect of the cold fluidizing additive, in particular by lowering the limit filterability temperature (TLF) and / or the pour point, and / or by delaying or preventing the sedimentation of crystals, such as those containing paraffins.

This effect is usually called the “TLF booster” effect insofar as the presence of the copolymer according to the invention improves the fluidizing nature of the CFI additive. This improvement is reflected, in particular, by a significant drop in the TLF of the fuel composition or fuel additivated with this combination compared to the same fuel composition or fuel additivated only with the additive CFI, at the same treatment rate. Generally, a significant drop in TLF results in a decrease of at least 3 ° C in TLF according to standard NF EN 1 16.

According to a particularly preferred embodiment, the copolymer is used to amplify the fluidizing (flow) effect of the cold fluidizing additive (CFI) by improving the Limit of Filterability (TLF) of the fuel or fuel, the TLF being measured according to standard NF EN 1 16.

The copolymer can be added to the fuels or combustibles within the refinery, and / or be incorporated downstream of the refinery, possibly, in mixture with other additives, in the form of an additive concentrate, also called according to the use "additive package".

The copolymer is advantageously used in fuel or fuel at a content of at least 0.0001% by weight, relative to the total weight of the fuel or fuel composition.

Preferably, the content of said copolymer ranges from 0.0001 to 0.01% by weight, preferably from 0.0002 to 0.005% by weight, and better still from 0.0003 to 0.003% by weight, relative to the total weight of the fuel or fuel composition.

The additive composition: The subject of the invention is also an additive composition comprising a copolymer as described above, and one or more additive (s) for cold resistance different from the copolymers comprising formula (I) and units of formula (II) as described above.

According to a preferred embodiment, the cold-keeping additive (s) are chosen from cold-thinning additives (s), anti-sedimentation additives and / or paraffin dispersants, and mixtures of these additives .

The cold-thinning additives (CFI) can in particular be chosen from copolymers and terpolymers of ethylene and of vinyl ester (s) and / or acrylic (s), alone or as a mixture. By way of example, mention may be made of copolymers of ethylene and of an unsaturated ester, such as ethylene / vinyl acetate (EVA), ethylene / vinyl propionate (EVP), ethylene / vinyl ethanoate (EVE) copolymers. , ethylene / methyl methacrylate (EMMA), and ethylene / alkyl fumarate 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.

According to a preferred embodiment, the composition contains at least one cold-thinning additive (CFI) chosen from copolymers of ethylene and of vinyl ester (s), alone or as a mixture, in particular ethylene / vinyl acetate (EVA), ethylene vinyl propionate copolymers (TEU) and terpolymers of ethylene, vinyl acetate and another vinyl ester; more preferably ethylene / vinyl acetate copolymers (EVA) and their mixtures with a terpolymer of ethylene, vinyl acetate and another vinyl ester, such as in particular vinyl neodecanoate. In this embodiment, the weight ratio between the content of copolymer (s) according to the invention on the one hand, and the content of copolymer (s) of ethylene and of vinyl ester (s) of on the other hand, is advantageously included in the range from 0.01: 100 to 20: 100, preferably from 0.1: 100 to 10: 100, and better still from 0.5:

100 to 5: 100. A particularly preferred weight ratio is 1: 100 ± 10%.

The anti-sedimentation additives and / or paraffin dispersants (WASA) can be in particular, but not limited to, chosen from the group consisting of (meth) acrylic acid / alkyl (meth) acrylate copolymers amidified by a polyamine, polyamine alkenyl succinimides, phthalamic acid derivatives and double chain fatty amines; optionally grafted alkylphenol resins. Examples of such additives are given in the following documents: EP261959, EP59333 1, EP674689, EP327423, EP5 12889, EP832172; US2005 / 022363 1; US5998530; W093 / 14178.

The particularly preferred anti-sedimentation additives and / or paraffin dispersants (WASA) are chosen from alkylphenol resins and alkylphenol resins grafted, for example, by functional groups such as polyamines.

The additive composition can also comprise one or more other additives commonly used in fuels or combustibles, different from the copolymer according to the invention and the cold-keeping additives described above.

The additive composition can typically include one or more other additives chosen from detergents, anti-corrosion agents, dispersants, demulsifiers, biocides, reodorants, procetane additives, friction modifiers, lubricant additives or oiliness additives, combustion aid agents (catalytic combustion and soot promoters), antiwear agents and / or agents modifying conductivity.

Among these additives, there may be mentioned in particular:

a) 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;

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, alkenyl succinimides, polyalkylamines, polyalkyl polyamines, polyetheramines, quaternary ammonium salts and triazole derivatives; examples of such additives are given in the following documents: EP0938535, US2012 / 00101 12 and W02012 / 004300. It is also advantageously possible to use block copolymers formed from at least one polar unit and one apolar unit, such as for example those described in patent application FR 1761700 in the name of the Applicant;

d) lubricant additives or anti-wear agents, in particular

(but not limited to) chosen from the group consisting of fatty acids and their ester or amide derivatives, in particular glycerol monooleate, and derivatives of mono- and polycyclic carboxylic acids. Examples of such additives are given in the following documents: EP680506, EP860494, WO98 / 04656, EP915944, FR2772783, FR2772784.

The additive composition can advantageously comprise from 0.1 to 50% by weight of copolymer as described above, relative to the total weight of the additive composition.

The present invention also relates to an additive concentrate comprising an additive composition as described above, in admixture with an organic liquid. The organic liquid is advantageously inert with respect to the constituents of the additive composition, and miscible with fuels or combustibles, in particular those from one or more sources chosen from the group consisting of mineral sources, preferably petroleum, animal, vegetable and synthetic.

The organic liquid is preferably chosen from aromatic hydrocarbon solvents such as the solvent sold under the name "SOLVESSO", alcohols, ethers and other oxygenated compounds, and paraffinic solvents such as hexane, pentane or isoparaffins, only or mixed. The fuel or fuel composition:

The invention also relates to a fuel or fuel composition, comprising:

(1) at least one cut of hydrocarbons from one or more sources chosen from the group consisting of mineral, animal, plant and synthetic sources, and

(2) at least one copolymer as defined above.

The mineral sources are preferably petroleum.

The fuel or fuel composition according to the invention advantageously comprises said copolymer (s) in a content of at least 0.0001% by weight, relative to the total weight of the fuel or fuel composition. Preferably, the content of copolymer (s) ranges from 0.0001 to 0.01% by weight, preferably from 0.0002 to 0.005% by weight, and better still from 0.0003 to 0.003% by weight, relative the total weight of the fuel or fuel composition.

According to a preferred embodiment, said composition also comprises at least one cold-keeping additive, chosen from cold-thinning additives (CEI) and anti-sedimentation additives and / or paraffin dispersants (WASA), different (s) copolymers according to the invention comprising units of formula (I) and units of formula (II). Such additives are advantageously chosen from those described above.

In this embodiment, the composition contains advantageously at least 20 ppm, preferably at least 50 ppm, advantageously between 20 and 5000 ppm, more preferably between 50 and 1000 ppm in total of cold-keeping additive (s).

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

The sulfur content of fuels is preferably less than 5000 ppm, preferably less than 500 ppm, and more preferably less than 50 ppm, or even less than 10 ppm, and advantageously without sulfur.

The fuel or fuel is preferably chosen from gas oils, biodiesel, type B _x gas oils and fuel oils, preferably domestic fuel oils (FOD).

By type B _x diesel for diesel engine (compression engine) is meant a diesel fuel which contains x% (v / v) of vegetable or animal oil esters (including used cooking oils) transformed by a process chemical called transesterification reacting this oil with an alcohol in order to obtain fatty acid esters (EAG). With methanol and ethanol, methyl esters of fatty acids (EMAG) and ethyl esters of fatty acids (EEAG) are obtained respectively. The letter "B" followed by a number x ranging from 0 to 100, which indicates the percentage of EAG contained in diesel. Thus, a B99 contains 99% of EAG and 1% of middle distillates of fossil origin, B20, 20% of EAG and 80% of middle distillates of fossil origin, etc. We therefore distinguish diesel fuels of type Bo which do not contain oxygenated compounds, diesel fuels of type Bx which contain x% (v / v) of vegetable or animal oil esters or fatty acids, most often methyl esters (EMHV or EMAG). When the EAG is used alone in engines, the fuel is designated by the term B 100.

The fuel or combustible can also contain hydrogenated vegetable oils, known to a person skilled in the art under the name HVO (from the English “hydrogenated vegetable oil”) or HDRD (from the English “hydrogenation-derived renewable diesel”) .

According to a particular development, the fuel or fuel is chosen from gas oils, biodiesel and gas oils of type B _x , hydrogenated vegetable oils (HVO), and their mixtures.

The fuel or combustible composition can also contain one or more additional additives, different from the copolymers and cold-keeping additives described above. Such additives can in particular be chosen from detergents, anti-corrosion agents, dispersants, demulsifiers, anti-foaming agents, biocides, reodorants, procetane additives, friction modifiers, lubricant additives or additives oiliness, combustion aid agents (catalytic combustion and soot promoters), antiwear agents and / or agents modifying conductivity.

These additional additives can generally be present in an amount ranging from 50 to 1000 ppm (each).

According to another embodiment of the invention, a method for improving the cold-keeping properties of a fuel or combustible composition comprises the successive steps of:

a) determination of an additive composition (s) most suitable for the fuel composition or fuel to be treated as well as treatment rate necessary to reach a given specification relating to the cold-keeping properties for the specific fuel or fuel composition, said additive composition (s) comprising at least one copolymer according to the invention and, optionally, at least one additive cold resistance, chosen from cold-thinning additives and paraffin dispersants and / or anti-sedimentation additives, different from the copolymers comprising units of formula (I) and units of formula (II);

b) treatment of the fuel or combustible composition with the quantity determined in step a) of said additive composition (s).

The process for improving the cold resistance properties is typically intended for a fuel or combustible composition as described above.

Step a) is carried out according to any known process and is part of current practice in the field of additivation of fuels or combustibles. This step involves defining a characteristic representative of the cold-keeping properties of the fuel or fuel, for example the characteristics of flow at low temperature, setting the target value and then determining the improvement which is required to reach the specification.

For example, a specification relating to the resistance to cold can be a European specification for Great Cold defining, in particular, a maximum TLF according to standard NF EN 1 16. The determination of the quantity of composition of additive (s) to be added to the composition of fuel or combustible to reach the specification will be carried out typically by comparison with the composition of fuel or combustible without said composition of additive (s).

The amount of copolymer necessary to treat the composition of fuel or combustible can vary according to the nature and the origin of the fuel or combustible, in particular according to the rate and the nature of the paraffinic compounds which it contains. The nature and origin of the fuel or combustible can therefore also be a factor to take into account for step a).

The process for improving the cold resistance properties may also include an additional step after step b) of verifying the target reached and / or of adjusting the treatment rate with the additive composition (s).

The examples below are given by way of illustration of the invention, and should not be interpreted so as to limit the scope thereof.

EXAMPLES

Example 1: Synthesis of various polymers Starting compounds:

- Monomer 1: C 1 2 / C 1 4 alkyl acrylate (A 12/14) (CAS 2156-

97-0 and 21643-42-5)

Monomer 2: 1 -vinylimidazole (NVI) (CAS 1072-63-5)

Initiator: 2,2’-Azobis- (2-methylpropionitrile) (AIBN) (CAS 78-67-1)

- Transfer agent: Butanethiol (CAS 109-79-5)

Control agent: Trithiocarbonate (CAS 558484-21 -2)

- Solvent: 1,4-Dioxane (CAS 123 -91 - 1)

Protocol for the synthesis of a C 1 2 / C 1 4 alkyl acrylate and N-vinylimidazole random copolymer with an 80/20 molar ratio:

8.84 g (35.4 mmol) of C 1 2 / C 1 4 alkyl acrylate, 0.832 g (8.84 mmol) of 1-vinylimidazole, 0.146 g (1.62 mmol) of butanethiol and 15, 23g (14.7 mL) of 1,4-Dioxane are introduced into a 25 mL flask equipped with a nitrogen inlet and outlet. The mixture is then stirred and degassed with a stream of nitrogen for 30 minutes. In parallel, a solution of AIBN (0.097g; 0.57 mmol) in 1,4-Dioxane (1 mL) is also prepared and degassed for 30 minutes. The flask containing the reaction medium is heated and once the target temperature is reached (70 ° C), the initiator solution is introduced to start the polymerization. The reaction is left for 6 h at 70 ° C. At the end of the reaction, the heating is switched off and the medium is exposed to air in order to stop the polymerization. The solvent is then evaporated under vacuum in order to recover the polymer.

The statistical polymers of the various examples, the characteristics of which appear in Table I below, were synthesized according to this protocol. The quantity and nature of the monomers have been adapted in each case.

Protocol for the synthesis of an alkyl acrylate block copolymer

C 1 2 / C 1 4 and N-vinylimidazole with an 80/20 molar ratio

Summary of block 1:

8.5 g (34 mmol) of C 1 2 / C 1 4 alkyl acrylate, 0.329 g (0.94 mmol) of trithiocarbonate and 9.0 g of 1,4-Dioxane are introduced into a 25 ml flask equipped with a nitrogen inlet and outlet. The mixture is then stirred and degassed with a stream of nitrogen for 30 minutes. In parallel, a solution of AIBN (0.0 l 5 g; 0.094 mmol) in 1,4-Dioxane (1 mL) is also prepared and degassed for 30 minutes. The flask containing the reaction medium is heated and once the target temperature is reached (70 ° C), the initiator solution is introduced to start the polymerization. The reaction is left at 70 ° C. until the conversion into C 1 2 / C 1 4 alkyl acrylate is greater than 95%.

Summary of block 2:

0.795 g (8.46 mmol) of 1-vinylimidazole are introduced into the reaction medium resulting from the synthesis of block 1, and the mixture is stirred and degassed with a stream of nitrogen for 30 minutes. In parallel, a new solution of AIBN (0.0 l 5g; 0.094 mmol) is prepared in 1,4-Dioxane and degassed for 30 minutes. The AIBN solution is then added to the reaction medium to restart the polymerization. The reaction is left for 6 h at 70 ° C. In end of reaction, the heating is switched off and the medium is exposed to air in order to stop the polymerization. The solvent is then evaporated under vacuum in order to recover the polymer. The block copolymers of the various examples, the characteristics of which appear in Table I below, were synthesized according to this protocol. The amount of the monomers was adapted in each case. The polymers were characterized by steric exclusion chromatography (SEC in English “Size Exclusion Chromatography”), in order to determine the composition and the molar mass of each copolymer. The characteristics of the polymers synthesized according to the protocols described above are collated in Table I below:

EXAMPLE 2 Evaluation of the Cold Resistance Performance The polymers described in Example 1 were tested as cold resistance additives in a fuel composition G of the diesel fuel type which is particularly difficult to process, and the characteristics of which are detailed in the table. II below: The diesel fuel composition G was added with a package containing the following two standard commercial cold-thinning additives (CFI additives), in Solvesso 150 solvent:

- 0.5% by weight of additive CP7956C sold by the company Total Additives Special Fuels, and which is an ethylene / vinyl acetate (EVA) copolymer;

- 0.5% by weight of Dodiflow additive D4134 sold by the company Clariant, and which is an ethylene / vinyl acetate / vinyl neodecanoate terpolymer.

This package was incorporated into the diesel composition G at a content of 300 ppm by weight of active material (ie 150 ppm by weight of each additive) relative to the total weight of the diesel composition.

There was thus obtained the composition of diesel fuel additive G l. This has a filterability limit temperature (TLF, standard EN 1 16) of -6 ° C.

The performance as cold-keeping additives of each of the polymers of Example 1 was tested, by evaluating their ability to lower the limit filterability temperature (TFL) of the composition of diesel fuel additive G l.

Each polymer was added at a content of 3 ppm by weight (0.0003% by weight) to the composition G l, to give the gas oil G2, the TLF of which was then measured, in accordance with standard EN 1 16.

The results obtained are shown in Table III below:

The above results show that the use of the copolymers according to the invention leads to a significant reduction in the TLF, ranging from 7 to 9 points for random copolymers, and from 5 to 6 points for block copolymers.

Claims

1. Use, to improve the cold-keeping properties of a fuel or fuel composition, of one or more copolymers comprising:

- at least one motif of formula (I) below:

in which

Ri represents a hydrogen atom or a methyl group,

X represents -O-CO-, or -CO-O- or -NH-CO- or -CO-NH-, and

R2 represents a C1 to C24 alkyl group; and

- at least one motif of formula (II) below:

wherein R represents a substituted or unsubstituted imidazole ring.

2. Use according to claim 1, characterized in that 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 l carbon atom, and preferably the group X of formula (I) is the group -CO-O-.

3. Use according to any one of claims 1 to 2, characterized in that the group R2 of formula (I) is a linear or branched Cs to C 24, preferably C 8 to C 1 acyclic alkyl radical. or in Ci6 to C 22, more preferably still in C 1 2 to C 1 4 or C is to C22 and better still C is to C22.

4. Use according to any one of the preceding claims, characterized in that the unit of formula (II) is N-vinylimidazole.

5. Use according to any one of the preceding claims, characterized in that said copolymer contains from 1 to 50 mol% of units of formula (II), preferably from 5 to 40 mol%, more preferably from 10 to 30 % in moles, and better still from 10 to 25% in moles.

6. Use according to any one of the preceding claims, characterized in that said copolymer contains only units of formula (I) and units of formula (II).

7. Use according to any one of the preceding claims, characterized in that said copolymer is a random copolymer, or a block copolymer, and preferably said copolymer is a random copolymer.

8. Use of a copolymer according to any one of the preceding claims, for lowering the filterability limit temperature measured according to standard NF EN 1 16 and / or the pour point measured according to standard ASTM D 7346, and / or to delay or prevent the sedimentation of crystals, and preferably to lower the filterability limit temperature measured according to standard NF EN 1 16.

9. Use according to any one of the preceding claims, characterized in that said copolymer is used in combination with at least one cold-thinning additive, preferably chosen from copolymers and terpolymers of ethylene and vinyl ester (s) (s) and / or acrylic (s), alone or as a mixture.

10. Composition of additives comprising a copolymer as defined in any one of claims 1 to 7, and one or more additive (s) for cold resistance different from the copolymers comprising units of formula (I) and units of formula (II), preferably chosen from cold-thinning additives, anti-sedimentation additives and / or paraffin dispersants, and mixtures of these additives.

1 1. Additive composition according to the preceding claim, characterized in that it contains at least one cold-thinning additive chosen from copolymers of ethylene and of vinyl ester (s), alone or as a mixture; preferably chosen from ethylene / vinyl acetate (EVA) copolymers, ethylene / vinyl propionate (EVP) copolymers and terpolymers of ethylene, vinyl acetate and another vinyl ester; more preferably chosen from ethylene / vinyl acetate copolymers (EVA) and their mixtures with a terpolymer of ethylene, vinyl acetate and another vinyl ester, such as in particular vinyl neodecanoate.

12. Additive composition according to the preceding claim, characterized in that the weight ratio between the content of copolymer (s) according to the invention on the one hand, and the content of copolymer (s) of ethylene and of ester (s) vinyl (s) on the other hand, is in the range from 0.01: 100 to 20: 100, preferably from 0.1: 100 to 10: 100, and more preferably from 0.5: 100 to 5: 100.

13. Fuel composition, comprising:

(2) at least one copolymer as defined in any one of claims 1 to 7.

14. Composition according to the preceding claim, characterized in that it contains the copolymer (s) in a content of at least 0.0001% by weight, preferably in a content ranging from 0.0001 to 0.01 % by weight, preferably from 0.0002 to 0.005% by weight, and better still from 0.0003 to 0.003% by weight, relative to the total weight of the composition.

15. Composition according to one of claims 13 and 14, characterized in that it further comprises at least one cold-thinning additive chosen from ethylene copolymers and vinyl ester (s), alone or as a mixture; preferably chosen from ethylene / vinyl acetate (EVA) copolymers, ethylene / vinyl propionate (EVP) copolymers and terpolymers of ethylene, vinyl acetate and another vinyl ester; more preferably chosen from ethylene / vinyl acetate (EVA) copolymers and their mixtures with a terpolymer of ethylene, vinyl acetate and another vinyl ester, such as in particular vinyl neodecanoate.