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  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/02—Ethene
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  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/04—Monomers containing three or four carbon atoms
  • C08F210/06—Propene
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/12—Hydrolysis
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  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F8/00—Chemical modification by after-treatment
  • C08F8/14—Esterification
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
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  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/16—Hydrocarbons
  • C10L1/1625—Hydrocarbons macromolecular compounds
  • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
  • C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/1817—Compounds of uncertain formula; reaction products where mixtures of compounds are obtained
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/192—Macromolecular compounds
  • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
  • C10L1/197—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid
  • C10L1/1973—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and an acyloxy group of a saturated carboxylic or carbonic acid mono-carboxylic
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L10/00—Use of additives to fuels or fires for particular purposes
  • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M145/00—Lubricating compositions characterised by the additive being a macromolecular compound containing oxygen
  • C10M145/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M145/10—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate
  • C10M145/12—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate monocarboxylic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
  • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
  • C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2810/00—Chemical modification of a polymer
  • C08F2810/50—Chemical modification of a polymer wherein the polymer is a copolymer and the modification is taking place only on one or more of the monomers present in minority
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/08—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type
  • C10M2209/082—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to a carboxyl radical, e.g. acrylate type monocarboxylic
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/02—Pour-point; Viscosity index
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/08—Resistance to extreme temperature
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2060/00—Chemical after-treatment of the constituents of the lubricating composition

Definitions

• the present invention relates to the synthesis and the use of novel copolymers based on ethylene and/or propylene and vinyl ester(s) modified by grafting, effective for improving both the resistance to cold and the lubricity of liquid hydrocarbons, in particular middle distillates originating from the distillation of petroleum and crude oils, in particular those with a low sulphur content.
• additives which promote the filterability of motor fuels at low temperatures they are copolymers of ethylene and vinyl acetate and/or vinyl propionate (EVA or EVP), called CFPP (cold filter plugging point) additives. Their role is to modify the crystallization and more particularly to limit the size of the paraffin crystals formed at low temperature, for example lower than 5° C., with a view to passing through the filters arranged inside internal combustion engines or in heating installations.
• This type of additives widely known to a person skilled in the art, is very often added to the middle distillates of standard type, and in particular those used as Diesel fuels or as heating fuels. Additional quantities of these additives can be added to the motor fuels sold in service stations in particular to meet very cold weather specifications.
• additives such as copolymers of ethylene, vinyl acetate and branched vinyl ester such as vinyl neodecanoates (VeoVA) having a role on the CFPP have been described, in particular in US 2004/0226216.
• VeoVA vinyl neodecanoates
• additives can be added to these CFPP (EVA or EVP) additives which act either alone or in combination with these additives on the pour point of the distillates.
• EVA vinyl neodecanoates
• U.S. Pat. No. 3,275,427 describes a middle distillate of distillation cut comprised between 177 and 400° C. containing an additive constituted by 90 to 10% by weight of a copolymer of ethylene comprising from 10 to 30% by weight of vinyl acetate units of molecular weight comprised between 1,000 and 3,000 and from 10 to 90% by weight of a lauryl polyacrylate and/or lauryl polymethacrylate with a molecular mass by weight varying from 760 to 100,000. It should be noted that these polyacrylates improve the filterability temperature determined according to the standard NF EN116 without damaging the pour point temperature determined by the standard NF 60105.
• the inventors propose to add to these compositions from 10 ppm to 2% by weight of a mixture of a polymer of an olefinic ester of carboxylic acids with 3 to 5 carbon atoms with an alcohol with 14 to 30 carbon atoms and with a molecular mass by weight varying from 1,000 to 1,000,000, with a copolymer of ethylene and vinyl acetate comprising from 1 to 40, preferably from 14 to 24 vinyl acetate units of average molecular weight of 20,000 to 60,000.
• the molar ratio of the olefinic ester polymer to the copolymer of ethylene and vinyl acetate varies from 0.1:1 to 10:1.
• U.S. Pat. No. 4,153,422 proposes adding to these middle distillates from 10 ppm to 1% by weight of a mixture of a homopolymer of an olefinic ester of acrylic or methacrylic acid comprising an alkyl chain with 14 to 16 carbon atoms and with a molecular mass by weight varying from 1,000 to 200,000, with an ethylene and vinyl acetate copolymer with an average numerical molecular weight lower than 4,000.
• the molar ratio of olefinic ester homopolymer to copolymer of ethylene and vinyl acetate varies from 0.1:1 to 20:1.
• liquid hydrocarbons in particular the diesel fuels, aviation fuels and motor fuels or fuel oils for domestic applications (DFO) must have lubrication abilities for the protection of pumps, injection systems and/or all moving parts with which these products come into contact, for example in an internal combustion engine.
• DFO motor fuels or fuel oils with a sulphur content which is more and more reduced: since 1 st Jan. 2005 the sulphur level authorized in motor fuels within the European Union has been limited to 50 ppm and it must be less than 10 ppm starting from 1 st Jan. 2009.
• U.S. Pat. No. 4,609,376 recommends the use of anti-wear additives obtained from mono- and poly-carboxylic acid esters and polyhydroxylated alcohols in motor fuels containing alcohols in their composition.
• U.S. Pat. No. 2,686,713 recommends the introduction of tall oil up to 60 ppm into diesel fuels in order to prevent the formation of rust on the metal surfaces in contact with these motor fuels.
• esters or the vegetable oils themselves are introduced into these motor fuels to improve their lubricity or their anti-friction qualities.
• These include the esters derived from rapeseed, flax, soya, sunflower oils or the oils themselves (see patents EP 635 558 and EP 605 857).
• One of the major drawbacks of these esters is their low lubricity at a concentration of less than 0.5% by weight in motor fuels.
• WO 95/33805 recommends the introduction of a resistance to cold additive constituted by nitrogen-containing additives comprising one or more N—R 13 groups in which R 13 comprises 12 to 24 carbon atoms, is linear, slightly branched or alicyclic and aromatic, the nitrogen group being able to be linked by CO or CO 2 and to form carboxylates of amines or amides.
• U.S. Pat. No. 3,667,152 describes the use of tall oil acid (or TOFA, abbreviation of tall oil fatty acid) as an anti-wear additive.
• EP 915 944 describes anti-friction additives for improving the lubricant properties of diesel fuels with a low sulphur content, constituted by at least one saturated or unsaturated, C12-C24 monocarboxylic aliphatic hydrocarbon, and at least one polycyclic hydrocarbon compound chosen from the group constituted by resin acids, their derivatives (amine carboxylates, esters and nitriles).
• anti-friction additives can be used in liquid hydrocarbons in the presence of other additives, such as detergents, pro-cetane additives, demulsifiers, anti-corrosion additives, additives which improve resistance to cold, odour modifiers, and also known anti-friction additives.
• additives such as detergents, pro-cetane additives, demulsifiers, anti-corrosion additives, additives which improve resistance to cold, odour modifiers, and also known anti-friction additives.
• WO 94/00536 describes compositions improving the low temperature properties of fuel oils comprising
• EP 1116780 describes multifunctional additives which improve the cold properties and lubricity of motor fuels. These additives contain two different compounds A) 5-95% of an oil-soluble amphiphilic compound and B) 5-95% of a terpolymer of ethylene—C2-C4 vinyl ester—C8-C15 neocarboxylic vinyl ester (i.e. which contains a tertiary C). The lubricant properties are provided by the amphiphilic compound.
• U.S. Pat. No. 5,254,652 describes terpolymers of ethylene—vinyl acetate—C9 or C10 neoalkanoate vinyl ester which improve the flow properties of motor fuels at low temperatures.
• the present invention relates to copolymers which can advantageously be used as bifunctional additives which improve both the resistance to cold and the lubricity of the liquid motor fuels in which they are incorporated.
• the first purpose of the invention relates to the use of these copolymers as additives for motor fuel bases, preferably of distillate type for diesel fuels or for domestic fuel oils (DFO).
• the invention therefore relates to the use as a bifunctional lubricity and resistance to cold additive for liquid hydrocarbon compositions of at least one copolymer comprising:
• the percentage in moles of units A and/or A′ in the copolymer ranges from 79 to 99% in moles, preferably 86.7 to 90.7% in moles; the percentage in moles of units B in the polymer ranges from 0 to 19% in moles, preferably 4.6 to 12% in moles; the % in moles of units C in the polymer is close to 0 to 6.3% in moles and advantageously equal to 0% in moles; the percentage in moles of units D in the polymer is from 0.1 to 10% in moles, 0.1 to 21% in moles, preferably 0.93 to 8.6% in moles.
• said at least one copolymer is in the form of a concentrated solution in a hydrocarbon distillate, preferably at a concentration of more than 50% by weight, preferably more than 70% by weight or preferably more than 80% by weight, preferably 60 to 80% by weight.
• the hydrocarbon liquid composition is a hydrocarbon distillate containing from 0 to 5,000 ppm of sulphur, and contains 10 to 5,000 ppm of said at least one copolymer, optionally in a mixture with other additives such as detergents, dispersants, demulsifiers, anti-foam agents, biocides, reodorants, cetane improvers, anti-corrosion agents, friction modifiers, lubricity, combustion, cloud point, pour point improvers, anti-sedimentation agents and conductivity improvers, resistance to cold additives, lubricants.
• additives such as detergents, dispersants, demulsifiers, anti-foam agents, biocides, reodorants, cetane improvers, anti-corrosion agents, friction modifiers, lubricity, combustion, cloud point, pour point improvers, anti-sedimentation agents and conductivity improvers, resistance to cold additives, lubricants.
• the distillate comprises at least one hydrocarbon cut originating from the group constituted by the distillates with a boiling point comprised between 150 and 450° C., an initial crystallization temperature ICT greater than or equal to ⁇ 20° C., preferably greater than or equal to ⁇ 15° C., preferably comprised between ⁇ 15° C.
• distillates from direct distillation distillates from vacuum distillation, hydrotreated distillates, distillates originating from catalytic cracking and/or hydrocracking of vacuum distillates, distillates resulting from ARDS type conversion and/or visbreaking processes, distillates originating from the upgrading of Fischer Tropsch cuts, distillates resulting from the BTL conversion of vegetable and/or animal biomass, taken alone or in a mixture, and esters of vegetable and animal oils or their mixtures.
• the distillate comprises a C9 to C40 n-paraffin content comprised between 1 and 40% by mass.
• said copolymer, as a distillate additive for Diesel fuel comprises from 0 to 500 ppm of sulphur.
• said copolymer as a distillate additive for heating fuel oil comprises from 0 to 5,000 ppm of sulphur.
• said copolymer is intended as a distillate additive for heavy fuel oil.
• the second purpose is to provide a process for the preparation of these novel polymers via an esterification process of the vinyl ester units which have been hydrolyzed previously either in part or in total.
• the third purpose of the present invention relates to the novel copolymers of ethylene and/or propylene and vinyl ester(s) as mentioned above which are chemically modified by grafting branchings essentially derived from fatty acid(s) in particular for their use in motor fuel bases as bifunctional additives.
• the present invention relates to copolymers comprising:
• R 1 represents a C 1 -C 15 linear or branched alkyl group, preferably methyl, ethyl, and/or a C5 to C15 branched alkyl group, in which the branching is situated at any point of the alkyl radical, preferably in position 2 or 3 of the alkyl chain; among the preferred C5-C15 vinyl comonomers, there can be mentioned the pivalate, isopentanoate, isohexanoate, isononanoate, isodecanoate and/or isotridecanoate, and advantageously 2-ethyl hexanoate, neoalkanoates, in particular the neononanoate, neodecanoate and/or neoundecanoate; with m ranging from 2 to 105, preferably ranging from 16 to 71 and x ranging from 0.2 to 105,
• the percentage in moles of units A and/or A′ in the copolymer can represent from 79 to 99% in moles, preferably 86.7 to 90.7% in moles;
• the percentage in moles of units B can represent from 0 to 19% in moles, preferably 4.6 to 12% in moles;
• the percentage in moles of units C can represent from 0 to 6.3% in moles, preferably the percentage in moles of units C is close to, or even equal to 0% in moles;
• the percentage in moles of units D can represent from 0.1 to 21% in moles, preferably 0.93 to 8.6% in moles.
• the present invention also relates to the process for the preparation of the copolymers according to the invention as defined previously; this process comprises the following stages:
• R 1 is chosen from the C 1 -C 15 linear or branched alkyl groups, alone or in a mixture, and preferably comprises the methyl group and/or the ethyl group and/or a C5 to 015 branched alkyl groups, as defined previously;
• n and m being as defined previously;
• esterification reaction at least partial, and preferably total, of these hydrolyzed sites by at least one fatty acid of formula R2COOH, R2 being as defined previously and/or at least one fatty acid derivative such as an acid anhydride, acid halide, preferably acid chloride; the esterification level is preferably greater than 50%, advantageously greater than 80%, and particularly advantageously equal to 100%.
• Another process for the preparation of copolymers consists in carrying out a transesterification of a copolymer as defined in 1) with an alcohol of type R2CH 2 OH; a transesterification process is for example described in WO 94/00536.
• the starting copolymers used in stage 1) are random copolymers comprising:
• n and m being as defined previously.
• the copolymers according to the invention have an average numerical molar weight Mn measured by polystyrene standard calibration GPC, comprised in general between 4,500 and 20,000 g ⁇ mol ⁇ 1 .
• the copolymer obtained at the end of stage 2) is obtained by a stage of partial or total hydrolysis of the ester groups of the starting copolymer of ethylene and/or propylene and vinyl ester(s) described above.
• the hydrolysis rate can represent from 10 to 100% of the hydrolysable sites (units B).
• the hydrolysis can be direct or obtained by transesterification in an acid or basic medium preferably by basic methanolysis; the conversion rate of the vinyl ester groups to vinyl alcohol groups is controlled by the volume of methanolic soda solution introduced (in the case of transesterification in a basic medium).
• the hydrolysis rate of stage a) of the process the number of esters grafted on the final copolymer is therefore varied.
• the hydrolysis stage 2) is followed by at least one esterification of the vinyl alcohol groups formed in the previous stage by one or more fatty acids (stage 3) preferably converted to acid chlorides, for example using oxalyl chloride, in order to improve the esterification yield.
• stage 3 preferably converted to acid chlorides, for example using oxalyl chloride, in order to improve the esterification yield.
• fatty acid an aliphatic carboxylic acid deriving from, or contained in, animal and/or vegetable fats, oils or waxes.
• the natural fatty acids have a saturated or unsaturated, linear, branched and/or cyclic carbon-containing chain with 4 to 28 carbon atoms (generally an even number); preferably, the fatty acids are chosen from the acids having a C 8 to O 24 non-cyclic hydrocarbon chain, alone or in a mixture, such as stearic acid, oleic acid, linoleic acid, palmitic acid and/or linolenic acid, and are advantageously chosen from the fatty acids having at least one unsaturation.
• fatty acids derived from tall oil which are better known by the abbreviation TOFA (tall oil fatty acids).
• TOFAs are in general obtained by distillation of the tall oil, which is a by-product of the production of pine wood pulp by the sulphate process; they comprise a major quantity of fatty acids as defined above as well as a minor quantity of resin acids, such as abietic, dihydroabietic, tetrahydroabietic, dehydroabietic, neoabietic, pimaric, levopimaric, and/or parastrinic acids, etc.
• the grafted copolymers obtained can also contain ester functions of resin acids formed from the resin acids present in the mixture of acids used.
• stage 3 esterification of the copolymer originating from stage 2
• a grafted copolymer is obtained which is partially or preferably totally esterified.
• the copolymers according to the invention can be advantageously used as obtained at the end of stage 3) as additives for liquid hydrocarbons, motor fuels and fuel oils.
• copolymers according to the invention have good solubility in the hydrocarbons of middle distillate type, greater than that of the copolymers of ethylene and/or propylene and vinyl ester(s) of the prior art, such as EVA or EVP. This allows a significant improvement in the filterability characteristics of the motor fuels or other fuels with additives or the blocking tendency characteristics (standard IP 387) of the motor fuels and other fuels with additives.
• solubility of the copolymers according to the invention is improved with respect to that of the copolymers of EVA and/EVP when the FBT (Filter Blocking Tendency) values are measured; in practice, this better solubility of the compositions of hydrocarbons supplemented with the copolymers according to the invention allows blocking of the filters (of diameter in general equal to 1.6 ⁇ m) to be avoided.
• the improvement in solubility of the copolymers according to the invention allows hydrocarbons with additives to be obtained which retain their initial filterability characteristics at ambient temperature and remain perfectly filterable in filtration systems that can be encountered for example in the fuel systems of engines and heating installations.
• the lower viscosity of the copolymers in comparison to EVA and/or EVP makes it possible to achieve concentrated solutions of copolymer(s) according to the invention in the hydrocarbons with a reduced level of aromatic solvent without detriment to the pumpability and use of these solutions (constraints of viscosity and of rheological behaviour in the pumping or injection systems).
• copolymers according to the invention can also be used in the form of a concentrated solution in a solvent, in general in a hydrocarbon distillate, preferably at a concentration of more than 50% by weight, preferably more than 70% by weight, or advantageously at a concentration greater than or equal to 80%; concentrated solutions in a solvent, in general in a hydrocarbon distillate which are also preferred comprise 60 to 80% by weight of copolymer(s) according to the invention.
• These copolymers according to the invention or preferably their concentrated solutions as defined above are in particular used as bifunctional additives: both as filterability additives, i.e. additives making it possible to lower the cold filter plugging point (CFPP) of compositions based on liquid hydrocarbons and as additives which improve the lubricity or anti-friction additives for these compositions based on liquid hydrocarbons.
• CFPP cold filter plugging point
• compositions of liquid hydrocarbons in general originate from oil refining operations, in particular from the direct distillation of hydrocarbons but can also originate from thermal cracking, hydrocracking and/or catalytic cracking processes and visbreaking processes. They are preferably middle distillates that can be used as diesel fuels, domestic heating fuel oils (DFO), kerosene, heavy fuel oils.
• DFO domestic heating fuel oils
• kerosene heavy fuel oils.
• the liquid hydrocarbon compositions according to the invention comprise a major proportion of liquid hydrocarbons, preferably of middle distillate type, with a sulphur content preferably lower than 5,000 ppm, preferably lower than 500 ppm, and more preferably lower than 50 ppm, and a minor proportion comprising at least one copolymer according to the invention.
• the major proportion is constituted by the distillates with a boiling point comprised between 150 and 450° C., initial crystallization temperature ICT greater than or equal to ⁇ 20° C., preferably greater than or equal to ⁇ 15° C., preferably comprised between ⁇ 15° C.
• distillates according to the invention have a C9 to C40 n-paraffin content comprised between 1 and 40% by mass.
• the invention relates to a Diesel fuel comprising from 0 to 500 ppm of sulphur and comprising at least one distillate according to the invention.
• the invention relates to a heating fuel oil comprising from 0 to 5,000 ppm of sulphur and comprising at least one distillate according to the invention.
• the invention relates to a heavy fuel oil comprising at least one distillate according to the invention.
• the hydrocarbon compositions contain from 10 to 5,000 ppm by weight, preferably from 10 to 1,000 ppm of at least one copolymer according to the invention.
• the hydrocarbon compositions can also contain one or more others which are different, chosen from the detergents, anti-corrosion agents, dispersants, demulsifiers, anti-foam agents, biocides, reodorants, procetane additives, friction modifiers, combustion-promoting agents (catalytic combustion and soot promoters), agents improving the cloud point, pour point, cold filter plugging point, anti-sedimentation agents, anti-wear agents and/or conductivity modifying agents, or even one or more other additives which improve the pour point, the cold filter plugging point, and the lubricity.
• procetane additives in particular (but not limitatively) chosen from alkyl nitrates, preferably 2-ethyl hexyl nitrate, aroyl peroxides, preferably benzyl peroxide, and alkyl peroxides, preferably ter-butyl peroxide;
• anti-foam additives in particular (but not limitatively) chosen from polysiloxanes, oxyalkylated polysiloxanes, and amides of fatty acids originating from vegetable or animal oils. Examples of such additives are given in EP 861 882, EP 663 000, EP 736 590;
• detergent and/or anti-corrosion additives in particular (but not limitatively) chosen from the group constituted by amines, succinimides, alkenylsuccinimides, polyalkylamines, polyalkyl polyamines and polyetheramines. Examples of such additives are given in EP 938 535;
• lubricity additive or anti-wear agent in particular (but not limitatively) chosen from the group constituted by fatty acids and their ester or amide derivatives, in particular glycerol monooleate, and derivatives of mono- and polycyclic carboxylic acids.
• lubricity additive or anti-wear agent in particular (but not limitatively) chosen from the group constituted by 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: EP 680 506, EP 860 494, WO 98/04656, EP 915 944, FR2772 783, FR 2 772 784;
• cloud point additives in particular (but not limitatively) chosen from the group constituted by terpolymers of long chain olefin/(meth)acrylic ester/maleimide, and polymers of fumaric/maleic acid esters.
• examples of such additives are given in EP 71 513, EP 100 248, FR 2 528 051, FR 2 528 051, FR 2 528 423, EP1 12 195, EP 1 727 58, EP 271 385, EP 291 367;
• anti-sedimentation or dispersant additives in particular (but not limitatively) chosen from the group constituted by copolymers of (meth)acrylic acid/alkyl(meth)acrylate amidified by a polyamine, polyamine alkenylsuccinimides, derivatives of phthalic acid and a double chain fatty amine; alkyl phenol resins.
• examples of such additives are given in EP 261 959, EP593 331, EP 674 689, EP 327 423, EP 512 889, EP 832 172, US2005/0223631; U.S. Pat. No. 5,998,530; WO 93/14178;
• multifunctional cold operability additives chosen from the group constituted by the polymers based on olefin and alkenyl nitrate as described in EP 573 490;
• lubricants such as fatty acids, TOFAs, their derivatives such as esters, in particular.
• additives are in general added in a quantity ranging from 10 to 1,000 ppm (each).
• the bifunctional additives according to the invention can be added to the hydrocarbon compositions within the refinery, and/or be incorporated downstream of the refinery, optionally in a mixture with other additives, in the form of a package of additives.
• D1 is a TOFA (mixture of acids derived from tall oil, containing from 2 to 3% by weight of resin acids and a mixture of C8 to C24, but mostly C18, fatty acids; its concentration of saturated and/or unsaturated C14-C18 fatty acids can vary from 80 to 90%).
• the copolymer grafted with D1 can also comprise resin acid ester functions formed from the resin acids present in the mixture of acids derived from tall oil.
• D2 to D4 are mixtures of saturated and unsaturated C14 to C18 fatty acids the molar composition of which in fatty acids is shown in detail in Table 1 below.
• the FBT filter blocking tendency
• the test involves jointly subjecting a steel sphere in contact with a stationary metal plate to a pressure corresponding to a weight of 200 g and an alternating movement of 1 mm at a frequency of 50 Hz.
• the lubricity is expressed by the average value of the diameters of the wear scar of the sphere on the plate.
• a small diameter generally less than 400 ⁇ m
• a large wear diameter greater than 400 ⁇ m
• the grafted polymer solutions are stabilized with an antioxidant, butylated hydroxytoluene or 2,6-di-tert-butyl-4-methylphenol (BHT) at a concentration of 0.05% to 0.1% with respect to D1.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Combustion & Propulsion (AREA)
• Emergency Medicine (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
• Lubricants (AREA)
• Graft Or Block Polymers (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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