WO2004106470A1 - Compositions de combustibles presentant de meilleures proprietes d'ecoulement a froid - Google Patents

Compositions de combustibles presentant de meilleures proprietes d'ecoulement a froid Download PDF

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Publication number
WO2004106470A1
WO2004106470A1 PCT/EP2004/005735 EP2004005735W WO2004106470A1 WO 2004106470 A1 WO2004106470 A1 WO 2004106470A1 EP 2004005735 W EP2004005735 W EP 2004005735W WO 2004106470 A1 WO2004106470 A1 WO 2004106470A1
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vinyl
copolymer
fuel
hydrocarbyl
weight
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English (en)
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Wolfgang Ahlers
Andreas FECHTENKÖTTER
Frank-Olaf Mähling
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BASF SE
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BASF SE
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    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/1955—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by an alcohol, ether, aldehyde, ketonic, ketal, acetal radical
    • C—CHEMISTRY; METALLURGY
    • 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
    • C08F210/02—Ethene
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/192—Macromolecular compounds
    • C10L1/195—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/196—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof
    • C10L1/1963—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derived from monomers containing a carbon-to-carbon unsaturated bond and a carboxyl group or salts, anhydrides or esters thereof homo- or copolymers of compounds having one or more unsaturated aliphatic radicals each having one carbon bond to carbon double bond, and at least one being terminated by a carboxyl radical or of salts, anhydrides or esters thereof mono-carboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • 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 OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/236—Macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • 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
    • C10M145/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an acyloxy radical of a saturated carboxylic or carbonic acid
    • C10M145/08—Vinyl esters of a saturated carboxylic or carbonic acid
    • 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
    • C10M149/00—Lubricating compositions characterised by the additive being a macromolecular compound containing nitrogen
    • C10M149/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/022—Ethene
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/024—Propene
    • 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
    • C10M2205/00—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
    • C10M2205/026—Butene
    • 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
    • C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
    • 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
    • C10M2209/06—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an acyloxy radical of saturated carboxylic or carbonic acid
    • C10M2209/062—Vinyl esters of saturated carboxylic or carbonic acids, e.g. vinyl acetate
    • 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
    • C10M2209/084—Acrylate; Methacrylate
    • 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

Definitions

  • the invention relates to the use of copolymers which contain copolymerized special heteroatom-functionalized vinyl compounds as an additive for fuel oils and lubricants and in particular as a cold flow improver in fuel oils; the fuel oils and lubricants added with these copolymers; and additive packages containing such copolymers.
  • Mineral oils containing paraffinic waxes such as middle distillates, diesel and heating oils, show a marked deterioration in the flow properties when the temperature is lowered.
  • the reason for this is the crystallization of longer-chain paraffins, which form large, platelet-shaped wax crystals, starting from the temperature of the cloud point.
  • These wax crystals have a sponge-like structure and lead to the inclusion of other fuel components in the crystal composite.
  • the appearance of these crystals quickly leads to the sticking of fuel filters both in tanks and in motor vehicles. Finally, at temperatures below the pour point (PP), the fuel no longer flows.
  • fuel additives have been added for a long time, which often consist of combinations of nucleators for the early formation of small crystals of paraffins with the actual cold flow improvers (also known as CFI or MDFI). These in turn show similar crystallization properties as the paraffins of the fuel, but prevent their growth, so that the filter can be passed at significantly lower temperatures than the unadditized fuel.
  • CFI Cold Filter Plugging Point
  • WASA wax anti-settling additives
  • WASA wax anti-settling additives
  • Cold flow improvers are added in amounts of approximately 50 to 500 ppm, depending on the nature of the base fuel and the additive.
  • Various CFI products are known from the prior art (see, for example, US Pat. Nos. 3,038,479, 3,627,838 and 3,961, 961, EP-A-0,261, 957 or DE-A-31 41 507 and 25 15 805).
  • Common CFIs are usually polymeric Compounds, in particular ethylene-vinyl acetate (EVA) copolymers, such as, for example, the products sold by BASF AG under the trade name Keroflux.
  • EVA ethylene-vinyl acetate
  • WO-A-94/00386 describes a mixture of at least two mutually different copolymers which are composed of ethylene, an unsaturated carboxylic acid ester and, if appropriate, a vinyl alcohol or a branched olefin. These mixtures are said to be suitable as cold flow improvers.
  • a first object of the invention relates to the use of an oil-soluble copolymer which contains a vinyl compound in copolymerized form, in which the vinyl group is bonded to an sp 3 - hybridized, heteroatom-functionalized carbon atom, as an additive for fuel oils and lubricants.
  • those copolymers are used which contain the vinyl compound and any other comonomers present in copolymerized form in a random distribution.
  • vinyl compounds in which the vinyl group is bonded to an sp 3 -hybridized, heteroatom-functionalized carbon atom are understood to mean compounds which contain a single carbon-carbon double bond to which the sp 3 -hybridized carbon atom is bonded directly is, with the remaining three sub- substituents of the double bond are selected from H and CC 4 alkyl and preferably from H.
  • At least one heteroatom is bonded directly to the sp 3 -hybridized carbon atom and / or to a carbon atom which is ⁇ -, ⁇ -, ⁇ - and / or ⁇ -positioned.
  • at least one heteroatom is bonded directly to the sp 3 -hybridized carbon atom and / or to a carbon atom which is ⁇ and / or ⁇ -related to this carbon atom.
  • an sp 3 -hybridized carbon atom is understood to mean a carbon atom which is bonded to its neighboring atoms via four single bonds. It is not important whether the binding orbitals that form these single bonds are actually pure sp 3 hybrid orbitals.
  • the heteroatom can be bonded to the carbon atom carrying it via a single, double or triple bond. It goes without saying that the heteroatom can only be bonded to the vinyl group-substituted sp 3 -hybridized carbon atom via a single bond.
  • heteroatoms are understood to mean all elements other than carbon and hydrogen which, with carbon, form a covalent bond which is stable under customary ambient conditions (room temperature, air humidity, light irradiation, etc.) and polymerization conditions and do not conflict with the use of the copolymer according to the invention.
  • ambient conditions room temperature, air humidity, light irradiation, etc.
  • polymerization conditions do not conflict with the use of the copolymer according to the invention.
  • These include e.g. Si, O, S, N and P.
  • the heteroatom is preferably selected from O and N.
  • the heteroatom is particularly preferably part of one of the following functional groups: hydroxyl, alkoxy, aldehyde, keto, carboxy, oxycarbonyl, carbonate, amino, imino, amido, imido, urea, Urethane, nitrile, isonitrile, cyanate and isocyanate groups.
  • it is part of an alkoxy, carboxy or oxycarbonyl group.
  • copolymers which are essentially composed of monomers comprising the monomers M1, M2 and optionally M3, where M1, M2 and M3 have the following general formulas R
  • R 1 represents H or CC 40 -, such as CC 20 -, in particular CrC 10 -, preferably CC 4 - hydrocarbyl;
  • R 2 , R 3 , R 4 and R 5 are the same or different and represent H, CC 4 o-, such as CC 20 -, in particular C Cio-, preferably CC ⁇ -hydrocarbyl, -COOR 7 or -OCOR 7 , where R 7 is C 1 -C 40 -, such as C 1 -C 20 -, in particular CC 10 -, preferably dC ⁇ hydrocarbyl and at least one of the radicals R 2 , R 3 , R 4 and R 5 is -COOR 7 or-OCOR 7 ; and
  • R 6 represents -CR 8 R 9 R 10 , wherein R 8 represents H, CC 4 -alkyl or CC 4 -alkoxy,
  • R 11 for such as CC 2 o-, in particular C C ⁇ o-, preferably CC 6 - hydrocarbyl and
  • R 2 and R 13 are each independently H, CC 10 alkyl, C 2 -C 10 hydroxyalkyl or C 2 -C ⁇ 0 - alkoxyalkyl, wherein R 9 and R 10 may not simultaneously represent H or CrC ⁇ hydrocarbyl, and where R 9 and R 10 together with the carbon atom to which they are attached can form a 3- to 8-membered, saturated or unsaturated heterocyclic ring which can be formed by at least one group O and / or NR 12 is interrupted and which is optionally substituted by at least one CrC ⁇ alkyl group and / or CrC 10 alkoxy group.
  • radicals R 2 , R 3 , R 4 and R 5 which do not represent -COOR 7 or -OCOR 7 are preferably H or methyl, especially H.
  • R 8 preferably represents H or methyl.
  • R 9 and R 10 together with the carbon atom to which they are attached preferably form a ring as defined above.
  • R 11 preferably represents CrC 10 hydrocarbyl, particularly preferably CC 6 hydrocarbyl and in particular methyl, ethyl or propyl.
  • R 12 and R 13 are preferably H or C r C 4 alkyl.
  • R 9 and R 10 together with the carbon atom to which they are attached form, particularly preferably, a three- to six-membered heterocyclic ring having one or two oxygen ring atoms, which may have one to four d-C 4 -alkyl groups, in particular methyl groups is substituted.
  • the copolymers used according to the invention may contain the monomers M1, M2 and M3 in the following molar proportions (Mx / (M1 + M2 + M3) in the copolymer: M1: 0.6 to 0.999, preferably 0.7 to 0.95, in particular 0.8 to 0.95; M2: 0.001 to 0.2, preferably 0.015 to 0.1, in particular 0.015 to 0.08; M3: 0 to 0.2, preferably 0.02 to 0.15, in particular 0.05 to 0.15.
  • the vinyl copolymers according to the invention are preferably obtainable by, preferably free-radical, polymerization, in particular high-pressure polymerization, of the monomers M1, M2 and, if appropriate, M3, in particular of the monomers M1, M2 and M3.
  • Preferred monomers M1 are selected from ethylene, propylene and 1-butene.
  • Preferred monomers M2 are selected from monomers of the following formula:
  • M1 is preferably ethylene and / or the molar fraction of M3 is preferably greater than zero.
  • Preferred monomers M3 are selected from d-do-carboxylic acid vinyl esters or Cr C 20 hydrocarbyl (meth) acrylates.
  • a particularly preferred monomer M3 is vinyl acetate.
  • Copolymers used with preference are selected from ethylene-1-compound and ethylene / vinyl compound 1 / vinyl acetate copolymers.
  • copolymers described above are used alone or in combination with other such copolymers in amounts to show an effect as a cold flow improver in the additive fuel or lubricant.
  • the present invention also relates to a copolymer as defined above.
  • Another object of the invention relates to fuel oil compositions containing a larger proportion by weight of a middle distillate fuel boiling in the range of approximately 120-500 ° C. and a smaller proportion by weight of at least one cold flow improver as defined above.
  • Such fuel oil compositions can further comprise biodiesel (from animal and / or vegetable production) as a fuel component in proportions of 0-30% by weight.
  • Preferred fuel oil compositions are selected from diesel fuels, kerosene and heating oil, it being possible for the diesel fuel to be obtainable by refining, coal gasification or gas liquefaction, to be a mixture of such products and, if appropriate, to be mixed with regenerative fuels.
  • Such fuel oil compositions are preferred, the sulfur content of the mixture being at most 500 ppm.
  • the invention further relates to lubricant compositions containing a larger proportion by weight of a conventional lubricant and a smaller proportion by weight of at least one cold flow improver as defined above.
  • copolymers according to the invention can be used in combination with further conventional cold flow improvers and / or further lubricating and fuel oil additives.
  • a last subject of the invention also relates to additive packages comprising a copolymer according to the invention as defined above in combination with at least one further conventional lubricant and fuel oil additive.
  • the copolymers according to the invention are preferably essentially composed of the monomers M1, M2 and optionally M3 defined above. Can be due to manufacturing optionally small proportions of a compound used as a regulator (chain terminator) may be included.
  • CrC 40 hydrocarbyl is in particular C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2- Ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, no-nadecyl, eicosyl, hencosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, octacosyl, heptacosyl the higher homologues and the corresponding positional isomers.
  • CC 10 hydrocarbyl is in particular C 1 -C 10 alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl , Nonyl and decyl.
  • CC 6 hydrocarbyl stands in particular for CC 6 alkyl.
  • CrC 4 hydrocarbyl is in particular dC 4 alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.
  • dC 6 alkyl also represents pentyl, hexyl and the associated positional isomers.
  • C 2 -C 10 hydroxyalkyl represents C 2 -C 10 alkyl substituted by a hydroxy group such as 2-hydroxyethyl, 2- and 3-hydroxypropyl, 2-, 3- and 4-hydroxybutyl and the like.
  • the hydroxyl group is preferably not bound to a carbon atom which is ⁇ to a hetero atom.
  • C 2 -C 10 alkoxyalkylene is in particular C n -alkylene-OC (10 -n ) -alkyl, where n is a number from 1 to 9.
  • Examples include methoxymethylene, ethoxymethylene, propoxymethylene, methoxyethylene, ethoxyethylene, propoxyethylene, methoxypropylene, ethoxypropylene, propoxypropylene and the like.
  • dC -alkylene radicals are in particular methylene, ethylene, 1,2- or 1, 3-propylene, 1, 2-, 1, 3-, 2,3-, 2,4-, 3,4- or 1, 4-butylene ,
  • C n -alkylene radicals are in particular ethylene, 1, 2- or 1, 3-propylene, 1, 2-, 1, 3-, 2,3-, 2,4-, 3,4- or 1,4-butylene, 1, 2-, 1, 3-, 1, 4-, 2,3-, 2,4-, 2,5- 3,4-, 3,5-, 4,5- or 1, 5-pentylene and like.
  • Suitable monomers M 1 include: mono-alkenes with a non-terminal or preferably terminal double bond, in particular ethylene, propylene, 1-butene, 1- Pentene, 1-hexene, 1-heptene, 1-octene, 1-nonen and 1-decene as well as the higher monounsaturated homologues with up to 40 carbon atoms.
  • Examples of preferred vinyl compounds M2 are:
  • 3-vinyltetrahydropyran the methyl-3-vinyltetrahydropyrane, the dimethyl-3-vinyltetrahydropyrane, the trimethyl-3-vinyltetrahydropyrane, 4-vinyl-1, 3-dioxane, the methyl-4-vinyl-1, 3-dioxane, the dimethyl-4-vinyl-1, 3-dioxanes, the trimethyl-4-vinyl-1, 3-dioxanes,
  • 2-vinyl-1, 4-dioxane the methyl-2-vinyl-1, 4-dioxanes, the dimethyl-2-vinyl-1, 4-dioxanes, the trimethyl-2-vinyl-1, 4-dioxanes .
  • C ⁇ -C 20 -carboxylic acid vinyl esters especially the vinyl esters of formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, oenanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, ceric acid, behenic acid, behenic acid and melissic acid; and dC 20 alkyl acrylates and d-do alkyl methacrylates, in which dC 20 alkyl represents methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, do
  • the copolymers according to the invention also have a number average molecular weight M n in the range from about 1000 to 20,000, particularly preferably from 1,000 to 10,000 and in particular from 1,000 to 6,000.
  • the copolymers can also have a weight average molecular weight M w of 1000 to
  • Particularly preferred copolymers are built up from the monomers ethylene, vinyl compound 1 (1 -vinylethylene glycol diacetate; VV1) and optionally vinyl acetate (VAC). Based on the polymer, the weight fraction of the monomers is:
  • VAC 0-42% by weight, preferably approximately 0 to 35% by weight, particularly preferably approximately 2.5 to 34% and in particular approximately 7 to 34% by weight
  • the viscosity of such copolymers is approximately 5-25000 or 10 to 1000 mm 2 / s, in particular approximately 10 to 1000 or 20 to 800 mm 2 / s, in each case at a temperature of approximately 120 ° C. ,
  • copolymers according to the invention are prepared by processes known per se, preferably according to the state of the art (see, for example, Ullmann's Encyclopedia of Industrial Chemistry 5th edition, keyword: Waxes, Vol. A 28, p. 146 ff., VCH Weinheim, Ba sei, Cambridge, New York, Tokyo, 1996) known methods for direct radical high-pressure copolymerization of unsaturated compounds.
  • the copolymers are preferably produced in stirred high-pressure autoclaves or in high-pressure tube reactors or combinations of the two.
  • the ratio length / diameter predominates in the range from 5: 1 to 30: 1, preferably 10: 1 to 20: 1.
  • Suitable pressure conditions for the polymerization are 1000 to 3000 bar, preferably 1500 to 2000 bar.
  • the reaction temperatures are e.g. in the range from 160 to 320 ° C, preferably in the range from 200 to 280 ° C.
  • An aliphatic aldehyde or an aliphatic ketone of the general formula I is used, for example, as a regulator for adjusting the molecular weight of the copolymers
  • radicals R a and R are the same or different and selected from
  • cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cycloctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; cyclopentyl are preferred,
  • R a and R b can also be covalently bonded to one another to form a 4- to 13-membered ring.
  • R a and R b can together form the following alkylene groups: - (CH 2 ) 4 -, - (CH 2 ) 5 -, - (CH 2 ) 6 , - (CH 2 ) 7 -, -CH (CH 3 ) -CH 2 -CH 2 -CH (CH 3 ) - or - CH (CH 3 ) -CH 2 -CH 2 -CH 2 -CH (CH 3 ) -.
  • the use of propionaldehyde or ethyl methyl ketone as a regulator is very particularly preferred.
  • Suitable regulators are unbranched aliphatic hydrocarbons, such as propane or branched aliphatic hydrocarbons with tertiary H atoms, such as isobutane, isopentane, isooctane or isododecane (2,2,4,6,6-pentamethylheptane). Higher oiefines such as propylene can be used as further additional regulators.
  • the amount of regulator used corresponds to the amounts customary for the high-pressure polymerization process.
  • radical initiators such as organic peroxides, oxygen or azo compounds
  • radical initiators can be used as starters for the radical polymerization. Mixtures of several radical initiators are also suitable.
  • radical initiators e.g. one or more peroxides, selected from the following commercially available substances:
  • Di-tert-butyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxyisononanoate or dibenzoyl peroxide or mixtures thereof are particularly suitable as peroxides.
  • AIBN Azobisisobutyronitrile
  • the radical initiators are dosed in amounts customary for polymerizations.
  • the copolymers according to the invention are prepared by mixing the monomers M1, M2 and optionally M3 in the presence of the regulator at a temperature in the range from about 20 to 50 ° C, e.g. of 30 ° C, preferably continuously through a stirred autoclave which operates at a pressure in the range of about 1500 to 2000 bar, e.g. of about 1700 bar.
  • a suitable solvent such as. Isododecane
  • the temperature in the reactor is increased to the desired reaction temperature, e.g. kept at 200 to 250 ° C.
  • the polymer obtained after the relaxation of the reaction mixture is then isolated in a conventional manner.
  • Modifications of this driving style are of course possible and can be carried out by the expert without undue effort.
  • the comonomers and the regulator can be metered into the reaction mixture separately, and the reaction temperature can be varied during the process, to name just a few examples.
  • fuel oil compositions are preferably understood to mean fuels.
  • Suitable fuels are petrol and middle distillates, such as diesel fuels, heating oil or kerosene, with diesel fuel and heating oil being particularly preferred.
  • the heating oils are, for example, low-sulfur or high-sulfur petroleum refinates or hard or lignite distillates, which usually have a boiling range of 150 to 400 ° C.
  • the heating oils are preferably low-sulfur heating oils, for example those with a sulfur content of at most 0.1% by weight, preferably at most 0.05% by weight, particularly preferably at most 0.005% by weight, and in particular of at most 0.001% by weight.
  • Examples of heating oil include heating oil for domestic oil firing systems or heating oil EL.
  • the quality requirements for such heating oils are specified, for example, in DIN 51-603-1 (see also Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, vol. A12, p. 617 ff., To which express reference is hereby made).
  • Diesel fuels are, for example, petroleum raffinates, which usually have a boiling range of 100 to 400 ° C. These are mostly distillates with a 95% point up to 360 ° C or beyond. However, these can also be so-called “ultra low sulfur diesel” or “city diesel”, characterized by a 95% point of, for example, a maximum of 345 ° C. and a sulfur content of a maximum of 0.005% by weight or by a 95% point of, for example, 285 ° C. and a maximum sulfur content of 0.001% by weight.
  • diesel fuels obtainable by refining
  • those which are obtainable by coal gasification or gas liquefaction (“gas to liquid” (GTL) fuels) are suitable.
  • GTL gas to liquid
  • the additive according to the invention is particularly preferred for the additization of diesel fuels with a low sulfur content, that is to say with a sulfur content of less than 0.05% by weight, preferably less than 0.02% by weight, in particular less than 0.005% by weight. % and especially less than 0.001% by weight sulfur or for the additive of heating oil with a low sulfur content, for example with a sulfur content of at most 0.1% by weight, preferably at most 0.05% by weight, particularly preferably at most 0.005 % By weight, and in particular of at most 0.001% by weight, is used.
  • the additive according to the invention is preferably used in a proportion, based on the total amount of the fuel oil composition, which in itself has an essentially sufficient influence on the cold flow properties of the fuel oil compositions.
  • the additive is particularly preferably used in an amount of 0.001 to 1% by weight, in particular 0.01 to 0.1% by weight, based on the total amount of the fuel oil composition.
  • the copolymers according to the invention are usually used as cold flow improvers in an amount which has the effect that the CFPP value (determined according to DIN EN116) of the additive fuel is at least 1 degree Celsius, for example 1 to 30, 1 to 25, 3 to 15 or 5 to 10 degrees Celsius drops.
  • the correspondingly determined CFPP value of the fuel to be additized can vary over a wide range depending on the composition of the base fuel used and the type and amount of any co-additives (such as conventional cold flow improvers) added and is, for example, in the range from about 0 to -35, -5 to -28 or -8 to -28 degrees Celsius. d) Co-additives
  • copolymers according to the invention can be added to the fuel oil compositions individually or as a mixture of such copolymers and, if appropriate, in combination with other additives known per se.
  • Suitable additives which can be contained in the fuel oils according to the invention in addition to the copolymer according to the invention, in particular for diesel fuels and heating oils include detergents, corrosion inhibitors, dehazers, demulsifiers, antifoam ("antifoam”), antioxidants, metal deactivators, multifunctional stabilizers, cetane number improvers, combustion improvers, Dyes, markers, solubilizers, antistatic agents, lubricity improvers, and further additives which improve the cold properties of the fuel, such as nucleators, other conventional flow improvers (“MDFI"), paraffin dispersants (“WASA”) and the combination of the last two additives mentioned (“WAFI ”) (see also Ullmann's Encyclopedia of Industrial Chemistr, 5th edition, Vol. A16, pp. 719 ff; or the patents cited at the beginning for flow improvements).
  • detergents corrosion inhibitors, dehazers, demulsifiers, antifoam (“antifoam”), antioxidants, metal deactivators
  • the monomer is preferably selected from alkenyl carboxylic acid esters, (meth) acrylic acid esters and olefins.
  • Suitable olefins are, for example, those with 3 to 10 carbon atoms and with 1 to 3, preferably with 1 or 2, in particular with one, carbon-carbon double bond. In the latter case, the carbon-carbon double bond can be arranged both terminally ( ⁇ -olefins) and internally.
  • ⁇ -olefins are preferred, particularly preferably ⁇ -olefins having 3 to 6 carbon atoms, such as propene, 1-butene, 1-pentene and 1-hexene.
  • Suitable (meth) acrylic acid esters are, for example, esters of (meth) acrylic acid with dC 10 alkanols, in particular with methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol , 2-ethylhexanol, nanol and decanol.
  • Suitable alkenyl carboxylic acid esters are, for example, the vinyl and propenyl esters of carboxylic acids having 2 to 20 carbon atoms, the hydrocarbon radical of which can be linear or branched. Among these, the vinyl esters are preferred.
  • Preferred carboxylic acids with a branched hydrocarbon radical are those whose branch is in the a position to the carboxyl group, the ⁇ carbon atom being particularly preferably tertiary, ie. H. the carboxylic acid is a so-called neocarboxylic acid.
  • the hydrocarbon residue of the carboxylic acid is preferably linear.
  • alkenyl carboxylic acid esters examples include vinyl acetate, vinyl propionate, vinyl butirate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononate, vinyl neodecanoate and the corresponding propenyl esters, with the vinyl esters being preferred.
  • a particularly preferred alkenyl carboxylic acid ester is vinyl acetate.
  • the ethylenically unsaturated monomer is particularly preferably selected from alkenyl carboxylic acid esters.
  • Copolymers which contain two or more different alkenyl carboxylic acid esters in copolymerized form are also suitable, these differing in the alkenyl function and / or in the carboxylic acid group. Also suitable are copolymers which, in addition to the alkenyl carboxylic acid ester (s), contain at least one olefin and / or at least one (meth) acrylic acid ester in copolymerized form.
  • the ethylenically unsaturated monomer is copolymerized in the copolymer in an amount of preferably 1 to 50 mol%, particularly preferably 10 to 50 mol% and in particular 5 to 20 mol%, based on the total copolymer.
  • the copolymer a) preferably has a number average molecular weight M n from 1000 to 20,000, particularly preferably from 1000 to 10,000 and in particular from 1000 to 6000.
  • Comb polymers b) are, for example, those described in "Comb-Like Polymers. Structure and Properties", NA Plate and VP Shibaev, J. Poly. Be. Macromolecular Revs. 8, pages 117 to 253 (1974). Of the compounds described there, comb polymers of the formula II are suitable, for example
  • D represents R 17 , COOR 17 , OCOR 17 , R 18 , OCOR 17 or OR 17 ,
  • E represents H, CH 3 , D or R 18 ,
  • G represents H or D
  • J represents H, R 18 , COOR 17 , R 18 COOR 17 , aryl or heterocyclyl,
  • K represents H, COOR 18 , OCOR 18 , OR 18 or COOH
  • L represents H, R 18 COOR 18 , COOR 18 , OCOR 18 , COOH or aryl, where
  • R 17 represents a hydrocarbon radical with at least 10 carbon atoms, preferably with 10 to 30 carbon atoms,
  • R 18 stands for a hydrocarbon radical with at least one carbon atom, preferably with 1 to 30 carbon atoms, m stands for a mole fraction in the range from 1.0 to 0.4 and n stands for a mole fraction in the range from 0 to 0.6.
  • Preferred comb polymers are obtainable, for example, by copolymerizing maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with a ⁇ -olefin or an unsaturated ester such as vinyl acetate, and then esterifying the anhydride or acid function with an alcohol having at least 10 carbon atoms.
  • Further preferred comb polymers are copolymers of ⁇ -olefins and esterified comonomers, for example esterified copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid. Mixtures of comb polymers are also suitable.
  • Comb polymers can also be polyfumarates or polymaleates. Homopolymers and copolymers of vinyl ether are also suitable comb polymers.
  • Suitable polyoxyalkylenes c) are, for example, polyoxyalkylene esters, ethers, esters / ethers and mixtures thereof.
  • the polyoxyalkylene compounds preferably contain at least one, particularly preferably at least two linear alkyl groups with 10 to 30 carbon atoms and a polyoxyalkylene group with a molecular weight of up to 5000.
  • the alkyl group of the polyoxyalkylene radical preferably contains 1 to 4 carbon atoms.
  • polyoxyalkylene compounds are described, for example, in EP-A-0 061 895 and in US 4,491,455, to which reference is hereby made in full.
  • Preferred polyoxyalkylene esters, ethers and esters / ethers have the general formula III
  • R 19 and R 20 each independently represent R 21 , R 21 CO-, R 21 -O-CO (CH 2 ) 2 - or R 21 -O- CO (CH 2 ) z -CO-, where R 21 is linear CC 3 o-alkyl, y stands for a number from 1 to 4, x stands for a number from 2 to 200, and z stands for a number from 1 to 4.
  • Preferred polyoxyalkylene compounds of the formula III in which both R 19 and R 20 are R 21 , are polyethylene glycols and polypropylene glycols with a number average molecular weight of 100 to 5000.
  • Preferred polyoxyalkylene compounds in which both R 19 and R 20 represent a radical R 21 -CO- are diesters of fatty acids having 10 to 30 carbon atoms, preferably stearic or behenic acid.
  • the polar nitrogen compounds d), which are suitably oil-soluble, can be both ionic and non-ionic and preferably have at least one, particularly preferably at least 2, substituents of the formula> NR 22 , where R 22 is a C 8 -C 40 -
  • the nitrogen substituents can also be quaternized, that is to say in cationic form.
  • An example of such nitrogen compounds are ammonium salts and / or amides, which can be obtained by reacting at least one A ins substituted with at least one hydrocarbon radical with a carboxylic acid having 1 to 4 carboxyl groups or with a suitable derivative thereof.
  • the amines preferably contain at least one linear C 8 -C 40 alkyl radical.
  • Suitable primary amines are, for example, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologues.
  • Suitable secondary amines are, for example, diocadecylamine and methylbehenylamine.
  • Amine mixtures in particular amine mixtures which are commercially available, such as fatty amines or hydrogenated tallamines, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, 2000 electronic release, chapter "Amines, aliphatic", are also suitable.
  • Acids suitable for the reaction are, for example, cyclohexane-1,2-dicarboxylic acid, cyclohexene-1,2-dicarboxylic acid, cyclopentane-1,2-dicarboxylic acid, naphthalenedicarboxylic acid, phthalic acid, isophthalic acid, terephthalic acid and succinic acids substituted with long-chain hydrocarbon radicals.
  • polar nitrogen compounds are ring systems which carry at least two substituents of the formula -A-NR 23 R 24 , in which A stands for a linear or branched aliphatic hydrocarbon group, which may be replaced by one or more groups which are selected from O, S , NR 35 and CO, is interrupted, and R 23 and R 24 stand for a C 9 -C 40 hydrocarbon radical which is optionally interrupted by one or more groups which are selected from O, S, NR 35 and CO, and / or by one or more substituents which are selected from OH, SH and NR 35 R 36 , where R 35 is d-do-alkyl, which is optionally by one or more groupings which are selected from CO, NR 35 , O and S, interrupted, and / or by one or more radicals which are selected from NR 37 R 38 , OR 37 , SR 37 , COR 37 , COOR 37 , CONR 37 R 38 , aryl or heterocyclyl, where R 37 and R 38 each independently
  • A is preferably a methylene or polymethylene group having 2 to 20 methylene units.
  • suitable radicals R 23 and R 24 are 2-hydroxyethyl, 3-hydroxypropyl, 4-hydroxybutyl, 2-ketopropyl, ethoxyethyl and propoxypropyl.
  • the cyclic system can be both homocyclic, heterocyclic, condensed polycyclic or uncondensed polycyclic systems.
  • the ring system is preferably carbo- or heteroaromatic, in particular carboaromatic.
  • polycyclic ring systems examples include condensed benzoid structures such as naphthalene, anthracene, phenanthrene and pyrene, condensed nonbenzoic structures such as azulene, indene, hydrindenes and fluorene, uncondensed polycycles such as diphenyl, heterocycles such as quinoline, indole, dihydroindole, Benzofuran, coumarin, isocoumarin, benzthiophene, carbazole, diphenylene oxide and diphenylene sulfide, non-aromatic or partially saturated ring systems such as decalin, and three-dimensional structures such as ⁇ -pinene, camphene, bornylene, norbonane, norbonen, bicyclooctane and bicyclooctene.
  • suitable polar nitrogen compounds are condensates of long-chain primary or secondary amines with polymers containing carboxyl groups.
  • Suitable polar nitrogen compounds are e.g. also described in DE-A-198 48 621, DE-A-196 22 052 or EP-B-398 101, to which reference is hereby made.
  • Suitable sulfocarboxylic acids / sulfonic acids or their derivatives e) are, for example, those of the general formula IV
  • Y is SO 3 - (NR 25 3 R 26 ) + , SO 3 - (NHR 25 2 R 26 ) + , SO 3 - (NH 2 R 25 R 26 ), SO 3 ' (NH 3 R 26 ) or SO 2 NR 25 R 26 stands,
  • R 26 and R 27 are alkyl, alkoxyalkyl or polyalkoxyalkyl with at least 10 carbon atoms in the main chain
  • R 28 is C 2 -C 5 alkylene
  • a and B are alkyl, alkenyl or two substituted hydrocarbon radicals stand or together with the carbon atoms to which they are attached form an aromatic or cycloaliphatic ring system.
  • Suitable poly (meth) acrylic acid esters f) are both homo- and copolymers of acrylic and methacrylic acid esters. Copolymers of at least two mutually different (meth) acrylic acid esters, which differ with respect to the condensed alcohol, are preferred. If necessary, the copolymer contains another, different olefinically unsaturated monomer copolymerized.
  • the weight average molecular weight of the polymer is preferably 50,000 to 500,000.
  • a particularly preferred polymer is a copolymer of methacrylic acid and methacrylic acid esters of saturated C 4 and C 15 alcohols, the acid groups being neutralized with hydrogenated tallamine.
  • Suitable poly (meth) acrylic acid esters are described, for example, in WO 00/44857, to which reference is hereby made in full.
  • alkylphenol-aldehyde resins such as those e.g. are known from EP-A-0857776, 1088045, 0311452 or WO-A-92/07047 and DE-A-3328739.
  • the subject of the present application is an additive concentrate containing an inventive copolymer as defined above and at least one diluent and, if appropriate, at least one further additive, in particular selected from the above co-additives.
  • Suitable diluents are, for example, fractions obtained in petroleum processing, such as kerosene, naphtha or brightstock. Aromatic and aliphatic hydrocarbons and alkoxyalkanols are also suitable. In the case of middle distillates, particularly preferred diluents for diesel fuels and heating oils, naphtha, kerosene, diesel fuels, aromatic hydrocarbons such as heavy solvent naphtha, Solvesso ® or Shellsol ® and mixtures of these solvents and diluents.
  • the copolymer according to the invention is preferably present in the concentrates in an amount of 0.1 to 80% by weight, particularly preferably 1 to 70% by weight and in particular 20 to 60% by weight, based on the total weight of the concentrate. in front.
  • a total of six different copolymers according to the invention were produced by high-pressure polymerization of ethylene, vinyl compound 1 (W1) and vinyl acetate (VAC).
  • Ethylene, VV1 and VAC were polymerized with the addition of propionaldehyde as a regulator in a high-pressure autoclave, as described in the literature (M. Buback et al., Chem. Ing. Tech. 1994, 66, 510).
  • a mixture of 11, 850 kg / h ethylene, 5.557 kg / h vinyl acetate, 1, 349 kg / h vinyl compound 1 and 1, 231 kg / h propionaldehyde was continuously at a temperature of 30 ° C by a pressure of 1700 bar held 11 stirred autoclaves.
  • Vinyl acetate in the intermediate pressure range at 260 bar, the vinyl compound in the high pressure zone at 1700 bar at the preheater inlet and the propionaldehyde in the intermediate pressure range were metered in.
  • the temperature in the autoclave reactor was kept at 220 ° C.
  • the polymer obtained in a quantity of 4.2 kg / h after the expansion of the reaction mixture corresponds to a total conversion of all starting materials of approx. 22%. It contains 67% by weight of ethylene, 25% by weight of vinyl acetate and 8% by weight of vinyl compound 1.
  • the viscosity is 60 mm 2 / s at 120 ° C.
  • the content of ethylene, VV1 and VAC in the copolymers obtained was determined by NMR spectroscopy.
  • the viscosities were determined according to Ubbelohde DIN 51562.
  • VV1 vinyl compound 1
  • PA propionaldehyde (modifier / regulator)
  • MDFI A ethylene-vinyl acetate-based polymer blend (Keroflux ES 6100, BASF AG)
  • MDFI B ethylene-vinyl acetate-based polymer blend (Keroflux ES 6103, BASF AG)
  • MDFI C ethylene-vinyl acetate-based polymer blend (Keroflux ES 6204, BASF AG )
  • MDFI D Ethylene-vinyl acetate-based polymer mixture (Keroflux ES 6310, BASF AG)
  • MDFI E Comparison sample: ethylene-vinyl acetate copolymer
  • MDFI F Comparison sample: ethylene-vinyl acetate copolymer
  • MDFI G Comparison sample: ethylene-vinyl acetate copolymer
  • Table 3 The determined CFPP values (in ° C) of the additive middle distillate fuels are summarized in Table 3.

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Abstract

L'invention concerne l'utilisation de copolymères contenant des composés vinyle spéciaux à fonction hétéroatome, intégrés au polymère, en tant qu'additifs pour des huiles combustibles et des lubrifiants, notamment en tant qu'agents d'écoulement à froid. L'invention concerne également des huiles combustibles et des lubrifiants additionnés de tels copolymères, ainsi que des ensembles d'additifs contenant de tels copolymères.
PCT/EP2004/005735 2003-05-27 2004-05-27 Compositions de combustibles presentant de meilleures proprietes d'ecoulement a froid Ceased WO2004106470A1 (fr)

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WO2005121194A1 (fr) * 2004-06-10 2005-12-22 The Nippon Synthetic Chemical Industry Co., Ltd. Copolymère éthylène/alcohol de vinyle et objet moulé à partir de celui-ci
WO2006035516A1 (fr) * 2004-09-28 2006-04-06 The Nippon Synthetic Chemical Industry Co., Ltd. Formulation de copolymère éthylène/alcool vinylique et structure multicouche comprenant ledit copolymère
US7915341B2 (en) 2004-06-10 2011-03-29 The Nippon Synthetic Chemical Industry Co., Ltd. Ethylene-vinyl alcohol copolymer and molded article thereof
US10131776B2 (en) 2009-09-25 2018-11-20 Evonik Oil Additives Gmbh Composition to improve cold flow properties of fuel oils

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DE102006016588A1 (de) * 2006-04-06 2007-10-18 Rohmax Additives Gmbh Kraftstoffzusammensetzungen umfassend nachwachsende Rohstoffe

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WO2005121194A1 (fr) * 2004-06-10 2005-12-22 The Nippon Synthetic Chemical Industry Co., Ltd. Copolymère éthylène/alcohol de vinyle et objet moulé à partir de celui-ci
US7915341B2 (en) 2004-06-10 2011-03-29 The Nippon Synthetic Chemical Industry Co., Ltd. Ethylene-vinyl alcohol copolymer and molded article thereof
WO2006035516A1 (fr) * 2004-09-28 2006-04-06 The Nippon Synthetic Chemical Industry Co., Ltd. Formulation de copolymère éthylène/alcool vinylique et structure multicouche comprenant ledit copolymère
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US10131776B2 (en) 2009-09-25 2018-11-20 Evonik Oil Additives Gmbh Composition to improve cold flow properties of fuel oils

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