EP1746147B1 - Copolymères à base d'oléfines et d'esters d'acides carboxyliques éthylèniquement insaturés pour abaiser le point de trouble des combustibles et des lubrifiants - Google Patents

Copolymères à base d'oléfines et d'esters d'acides carboxyliques éthylèniquement insaturés pour abaiser le point de trouble des combustibles et des lubrifiants Download PDF

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EP1746147B1
EP1746147B1 EP06117661.6A EP06117661A EP1746147B1 EP 1746147 B1 EP1746147 B1 EP 1746147B1 EP 06117661 A EP06117661 A EP 06117661A EP 1746147 B1 EP1746147 B1 EP 1746147B1
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carbon atoms
alkyl
tert
monomer
alkene
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German (de)
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EP1746147A1 (fr
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Wolfgang Ahlers
Marcus Guzmann
Lidcay Herrera Taboada
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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, 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
    • 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
    • C10L1/146—Macromolecular compounds according to different macromolecular groups, mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—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
    • C10L1/1966—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 poly-carboxylic
    • 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
    • C10M145/16—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 polycarboxylic
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1625—Hydrocarbons macromolecular compounds
    • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
    • C10L1/1641—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
    • 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
    • C10M2205/028—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers containing aliphatic monomers having more than four carbon atoms
    • 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
    • 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
    • C10M2209/086—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 polycarboxylic, e.g. maleic acid
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/011—Cloud point
    • 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
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; 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
    • C10N2070/00—Specific manufacturing methods for lubricant compositions
    • C10N2070/02—Concentrating of additives

Definitions

  • the invention relates to the use of copolymers which, in addition to ethylenically unsaturated esters of dicarboxylic acids in copolymerized form contain at least one olefin and optionally the anhydride of an ethylenically unsaturated dicarboxylic acid in order to lower the CP value of fuel oils and lubricants.
  • the invention relates to such copolymers and with these copolymers additiv convinced fuel oils and lubricants and additive packages containing such copolymers.
  • Paraffinic wax-containing mineral oils such as middle distillates, e.g. Diesel and fuel oils show a significant deterioration of the flow properties when the temperature is lowered.
  • the reason for this lies in the crystallization of longer-chain paraffins occurring from the temperature of the cloud point, which form large, platelet-shaped wax crystals.
  • These wax crystals have a sponge-like structure and lead to the inclusion of other fuel constituents in the crystal composite. The appearance of these crystals quickly leads to the bonding of fuel filters both in tanks and in motor vehicles. At temperatures below the pour point (PP), finally, no more flow of fuel takes place.
  • CP Cloud Point
  • WAT Wax Appearance Temperature
  • CPD CP point depressants
  • the WO 01/04238 describes the use of copolymers of C 14 C 16 ⁇ -olefins and maleic imides or of terpolymers of ethylene, vinyl acetate and isobutene as CPD.
  • the stated dosing rates are 500 ppm and are therefore very high.
  • the EP-A-0214786 describes the use of copolymers which contain polymerized in addition to ⁇ -olefins with an alcohol esterified maleic anhydride, as a cold flow improver for fuels, eg for lowering the CP and the CFPP value.
  • additives that more effectively decrease the CP value of fuel oils and lubricants, for example, by achieving the same effect as the additives of the prior art at lower dosage rates.
  • the additives should have an improved formability and with other additives, which are usually added to the fuel oils and lubricants, not enter negative interactions. In particular, they should not adversely affect the effect of CFPP additives.
  • this object could be solved by the unexpected observation that copolymers, the esters of ethylenically unsaturated dicarboxylic acids, at least one olefin and optionally the anhydride of an ethylenically unsaturated Containing dicarboxylic acid copolymerized, effectively lowering the CP value of fuel oils and lubricants.
  • C 1 -C 48 -hydrocarbyl is a hydrocarbon radical having 1 to 48 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl, alkatrienyl, Alkatetraenyl or alkynyl.
  • C 1 -C 48 -hydrocarbyl is C 1 -C 48 -alkyl.
  • C 8 -C 40 -hydrocarbyl is a hydrocarbon radical having 8 to 40 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl, alkatrienyl, Alkatetraenyl or alkynyl.
  • C 8 -C 40 -hydrocarbyl is C 8 -C 40 -alkyl.
  • C 8 -C 48 -hydrocarbyl is a hydrocarbon radical having 8 to 48 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl, alkatrienyl, Alkatetraenyl or alkynyl.
  • C 8 -C 48 -hydrocarbyl is C 8 -C 48 -alkyl.
  • C 1 -C 4 -hydrocarbyl is a hydrocarbon radical having 1 to 4 carbon atoms. It is preferably an aliphatic hydrocarbon radical, such as alkyl, alkenyl, alkadienyl or alkynyl.
  • C 1 -C 4 -hydrocarbyl is C 1 -C 4 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert-butyl.
  • C 1 -C 10 -hydrocarbyl is a hydrocarbon radical having 1 to 10 carbon atoms. Preference is given to an aliphatic hydrocarbon radical, such as alkyl, C 2 -C 10 -alkenyl, C 4 -C 10 -alkadienyl, C 6 -C 10 -alkatrienyl, C 8 -C 10 -alkatetraenyl or alkynyl.
  • C 1 -C 10 -hydrocarbyl is C 1 -C 10 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl , Octyl, 2-ethylhexyl, neo-octyl, nonyl, neononyl, decyl, 2-propylheptyl, neodecyl and their constitutional isomers.
  • alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl, heptyl , Octyl, 2-e
  • C 1 -C 40 -alkyl represents a linear or branched alkyl radical having 1 to 40 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, neopentyl, hexyl , Heptyl, octyl, 2-ethylhexyl, neooctyl, nonyl, neononyl, decyl, 2-propylheptyl, neodecyl, undecyl, neoundecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, hencosy
  • C 1 -C 48 -alkyl is a linear or branched alkyl radical having 1 to 48 carbon atoms. Examples of these are, in addition to the abovementioned C 1 -C 40 -alkyl radicals, the higher homologues having 41 to 48 carbon atoms and the associated constitutional isomers.
  • C 8 -C 30 -alkyl represents a linear or branched alkyl radical having 8 to 30 carbon atoms. Examples of these are octyl, 2-ethylhexyl, neooctyl, nonyl, neononyl, decyl, 2-propylheptyl, neodecyl, undecyl, neoundecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, hencosyl, docosyl, tricosyl , Tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl and squalyl and the associated constitutional isomers.
  • C 8 -C 40 alkyl represents a linear or branched alkyl radical having 8 to 40 carbon atoms, such as octyl, 2-ethylhexyl, neooctyl, nonyl, neononyl, decyl, 2-propylheptyl, neodecyl, undecyl, neoundecyl, dodecyl, tridecyl, tetradecyl , Pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, hencosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, squalyl, their constitutional isomers, higher homologues having from 31 to 40 carbon atoms
  • C 6 -C 40 -alkyl represents a linear or branched alkyl radical having 6 to 40 carbon atoms. Examples include, in addition to the aforementioned C 8 -C 40 -alkyl radicals hexyl and heptyl and the associated constitution isomers.
  • C 8 -C 48 alkyl represents a linear or branched alkyl radical having 8 to 48 carbon atoms. Examples of these are, in addition to the aforementioned C 8 -C 40 -alkyl radicals, the higher homologues having 41 to 48 carbon atoms and the associated constitutional isomers.
  • C 10 -C 26 -alkyl represents a linear or branched alkyl radical having 10 to 26 carbon atoms. Examples of these are decyl, 2-propylheptyl, neodecyl, undecyl, neoundecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, hencosyl, docosyl, tricosyl, tetracosyl, pentacosyl and hexacosyl and the associated constitutional isomers.
  • C 10 -C 30 -alkyl represents a linear or branched alkyl radical having 10 to 30 carbon atoms. Examples of these are, in addition to the examples mentioned for C 10 -C 26 -alkyl, heptacosyl, octacosyl, nonacosyl and squalyl, as well as the associated constitutional isomers.
  • C 10 -C 48 alkyl represents a linear or branched alkyl radical having 10 to 48 carbon atoms. Examples include, in addition to the examples mentioned for C 10 -C 30 -alkyl, the higher homologues having 31 to 48 carbon atoms and the associated constitutional isomers.
  • C 14 -C 38 alkyl represents a linear or branched alkyl radical having 14 to 38 carbon atoms. Examples of these are tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, hencosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, squalyl, their constitutional isomers, higher homologues having 31 to 38 carbon atoms and the associated constitutional isomers.
  • C 18 -C 26 -alkyl represents a linear or branched alkyl radical having 18 to 26 carbon atoms. Examples of these are octadecyl, nonadecyl, eicosyl, hencosyl, docosyl, tricosyl, tetracosyl, pentacosyl and hexacosyl and the associated constitutional isomers.
  • C 18 -C 28 -alkyl represents a linear or branched alkyl radical having 18 to 28 carbon atoms. Examples include, in addition to the aforementioned examples of C 18 -C 26 -alkyl heptacosyl and octacosyl and the associated constitution isomers.
  • C 16 -C 28 -alkyl is a linear or branched alkyl radical having 16 to 28 carbon atoms. Examples of these are, in addition to the aforementioned examples of C 18 -C 28 -alkyl radicals, hexadecenyl and heptadecenyl and the associated constitutional isomers.
  • C 2 -C 40 alkenyl is a monounsaturated linear or branched hydrocarbon radical having 2 to 40 carbon atoms. Examples of these are ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, hencosenyl, docosenyl, tricosenyl, tetracosenyl, pentacosenyl , Hexacosenyl, heptacosenyl, octacosenyl, nonaco
  • C 4 -C 40 -alkadienyl is a diunsaturated linear or branched hydrocarbon radical having 4 to 40 carbon atoms.
  • the olefinic double bonds may be conjugated or isolated. Examples include butadienyl, pentadienyl, hexadienyl, heptadienyl, octadienyl, nonadienyl, decadienyl, undecadienyl, dodecadienyl, tridecadienyl, Tetradecadienyl, Pentadecadienyl, Hexadecadienyl, heptadecadienyl, octadecadienyl, Nonadecadienyl, Eicosadienyl, Hencosadienyl, Docosadienyl, Tricosadienyl, Tetracosadienyl, Pentacosadieny
  • C 6 -C 40 -alkatrienyl is a triunsaturated linear or branched hydrocarbon radical having 6 to 40 carbon atoms.
  • the olefinic double bonds may be conjugated or isolated. Examples include hexatrienyl heptatrienyl, octatrienyl, nonatrienyl, decatrienyl, Undecatrienyl, dodecatrienyl, tridecatrienyl, tetradecatrienyl, Pentadecatrienyl, Hexadecatrienyl, heptadecatrienyl, octadecatrienyl, Nonadecatrienyl, eicosatrienyl, Hencosatrienyl, Docosatrienyl, Tricosatrienyl, Tetracosatrienyl, Pentacosatrienyl, Hexacosatrienyl, Heptacosatrienyl, Octacosatrienyl, Nonaco
  • C 8 -C 40 -alkatetraenyl is a quadruply unsaturated linear or branched hydrocarbon radical having 8 to 40 carbon atoms.
  • the olefinic double bonds may be conjugated or isolated. Examples include Octatetraenyl, Nonatetraenyl, Decatetraenyl, Undecatetraenyl, Dodecatetraenyl, Tridecatetraenyl, Tetradecatetraenyl, Pentadecatetraenyl, hexadecatetraenyl, Heptadecatetraenyl, Octadecatetraenyl, Nonadecatetraenyl, eicosatetraenyl, Hencosatetraenyl, Docosatetraenyl, Tricosatetraenyl, Tetracosatetraenyl, Pentacosatetraenyl, Hexacosatetraenyl, Heptacosatetraenyl, Octacosatetraenyl,
  • the ethylenically unsaturated hydrocarbons having 2 to 50 carbon atoms are preferably aliphatic hydrocarbons having one or more CC double bonds, such as alkenes, alkadienes or alkatrienes.
  • they are C 2 -C 50 -alkenes, ie aliphatic hydrocarbons having a CC double bond and having 2 to 50 carbon atoms.
  • the CC double bond in the alkenes can be arranged both internally and terminally.
  • C 2 -C 50 -alkene is a monounsaturated aliphatic linear or branched hydrocarbon having 2 to 50 carbon atoms.
  • Examples of these are E-then, propene, 1- and 2-butene, isobutene, 1- and 2-pentene, 1-, 2- and 3-hexene, 1-, 2- and 3-heptene, 1-, 2- , 3- and 4-octene, 1-, 2-, 3- and 4-nonene, 1-, 2-, 3-, 4- and 5-decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene , Octadecene, nonadecene, eicosene, hencoses, docoses, tricosene, tetracoses, pentacoses, hexacoses, heptacoses, octa
  • constitutional isomers of said alkenes are oligomers and polymers of ⁇ -, ⁇ -, ⁇ -, ⁇ -, etc.
  • C 3 -C 8 -olefins such as propene, 1- or 2-butene, isobutene, 1- or 2- Pentene, 2-methylbutene, 1-, 2- or 3-hexene, 1-, 2- or 3-heptene or 1-, 2-, 3- or 4-octene.
  • C 18 -C 28 -alkene is a monounsaturated aliphatic linear or branched hydrocarbon having 18 to 28 carbon atoms. Examples of these are octadecene, nonadecene, eicosene, hencoses, docoses, tricosene, tetracoses, pentacoses, hexacoses, heptacoses, octacoses and constitutional isomers thereof.
  • C 18 -C 30 -alkene is a monounsaturated aliphatic linear or branched hydrocarbon having 18 to 30 carbon atoms. Examples of these, in addition to the previously mentioned C 18 -C 28 alkenes, are nonacoses, squalene and constitutional isomers thereof.
  • C 8 -C 30 -alkene is a monounsaturated aliphatic linear or branched hydrocarbon having 8 to 30 carbon atoms. Examples thereof include, in addition to the aforementioned C 18 -C 30 alkenes, octene, nonene, decene, undecene, dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene and constitutional isomers thereof.
  • C 16 -C 26 -alkene is a monounsaturated aliphatic linear or branched hydrocarbon having 16 to 26 carbon atoms. Examples of these are hexadecene, heptadecene, octadecene, nonadecene, eicosene, hencoses, docoses, tricosene, tetracoses, pentacoses, hexacoses and constitutional isomers thereof.
  • C 20 -C 24 -alkene represents a monounsaturated aliphatic linear or branched hydrocarbon having 20 to 24 carbon atoms. Examples of these are eicosene, hencoses, docoses, tricos, tetracoses and constitutional isomers thereof.
  • C 10 -C 14 -alkene is a monounsaturated aliphatic linear or branched hydrocarbon having 10 to 14 carbon atoms. Examples of these are decene, undecene, dodecene, tridecene, tetradecene and constitutional isomers thereof.
  • C 12 -C 40 -alkene is a monounsaturated aliphatic linear or branched hydrocarbon having 12 to 40 carbon atoms.
  • Examples of these are dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene, octadecene, nonadecene, eicosene, hencoses, docoses, tricosene, tetracoses, pentacoses, hexacoses, heptacoses, octacoses, nonacoses, squalene, constitutional isomers thereof, the higher homologues with 31 to 40 carbon atoms and the associated constitutional isomers.
  • C 12 -C 50 -alkene is a monounsaturated aliphatic linear or branched hydrocarbon having 12 to 50 carbon atoms. Examples include, in addition to the aforementioned C 12 -C 40 alkenes, the higher homologues with 41 to 50 carbon atoms and the associated constitutional isomers.
  • C 10 -C 50 -alkene represents a monounsaturated aliphatic linear or branched hydrocarbon having 10 to 50 carbon atoms. Examples include, in addition to the aforementioned C 12 -C 50 alkenes 1-, 2-, 3-, 4- and 5-decene and undecene and the associated constitutional isomers.
  • C 6 -C 50 -alkene represents a monounsaturated aliphatic linear or branched hydrocarbon having 6 to 50 carbon atoms. Examples of these are, in addition to the aforementioned C 10 -C 50 -alkenes, 1-, 2- and 3-hexene, 1-, 2- and 3-heptene, 1-, 2-, 3- and 4-octene, 1-, 2-, 3- and 4-nonene and the associated constitutional isomers.
  • C 30 -C 50 -alkene represents a monounsaturated aliphatic linear or branched hydrocarbon having 30 to 50 carbon atoms.
  • C 35 -C 45 -alkene is a monounsaturated aliphatic linear or branched hydrocarbon having from 35 to 45 carbon atoms.
  • hydrocarbyl radicals for example the alkyl, alkenyl, alkadienyl, alkatrienyl and alkatetraenyl radicals, or the unsaturated hydrocarbons, for example the alkenes, may be unsubstituted or monosubstituted or polysubstituted.
  • Suitable substituents are, for example, OH, C 1 -C 4 -alkoxy, NR 15 R 16 (R 15 and R 16 are each independently H or C 1 -C 4 -alkyl) or carbonyl (COR 15 ). Preferably, however, they are unsubstituted.
  • C 1 -C 4 alkoxy is a via an oxygen atom bonded C 1 -C 4 alkyl radical. Examples of these are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, 2-butoxy, isobutoxy and tert-butoxy.
  • C 18 -C 26 -alcohol represents a linear or branched saturated or unsaturated aliphatic hydrocarbon having 18 to 26 carbon atoms, which is substituted by one or more, preferably a hydroxy group.
  • Examples of these are octadecanol, nonadecanol, eicosanol, octadecenol, nonadecenol, eicosenol, octadecadienol, nonadecadienol, eicosadienol, octadecatrienol, nonadecatrienol, eicosatrienol, positional and constitutional isomers thereof, the higher homologues having 21 to 26 carbon atoms and the associated positional and constitutional isomers.
  • C 16 -C 26 -alcohol represents a linear or branched saturated or unsaturated aliphatic hydrocarbon having 16 to 26 carbon atoms, which is substituted by one or more, preferably a hydroxy group.
  • Examples include, in addition to the aforementioned C 18 -C 26 alcohols, hexadecanol, heptadecanol, hexadecenol, heptadecenol, hexadecadienol, heptadecadienol and the associated positional and constitutional isomers.
  • C 16 -C 28 -Alcohol is a linear or branched saturated or unsaturated aliphatic hydrocarbon having 16 to 28 carbon atoms, which is substituted by one or more, preferably a hydroxy group.
  • Examples include, in addition to the aforementioned C 16 -C 26 alcohols, the higher homologues having 27 or 28 carbon atoms and the associated position and constitution isomers.
  • C 10 -C 26 -alcohol represents a linear or branched saturated or unsaturated aliphatic hydrocarbon having 10 to 26 carbon atoms, which is substituted by one or more, preferably a hydroxy group.
  • Examples of these are, in addition to the abovementioned C 18 -C 26 -alcohols, decanol, 2-propylheptanol, undecanol, dodecanol, tridecanol, isotridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, Decenol, undecenol, dodecenol, tridecenol, isotridecenol, tetradecenol, pentadecenol, hexadecanol, heptadecenol, decadienol, undecadienol, dodecadienol, tride
  • C 10 -C 30 -Alcohol is a linear or branched saturated or unsaturated aliphatic hydrocarbon having 10 to 30 carbon atoms, which is substituted by one or more, preferably a hydroxy group.
  • Examples include, in addition to the aforementioned C 10 -C 26 alcohols, the higher homologues having 27 to 30 carbon atoms and the associated position and constitution isomers.
  • C 8 -C 30 -alcohol represents a linear or branched saturated or unsaturated aliphatic hydrocarbon having 8 to 30 carbon atoms, which is substituted by one or more, preferably a hydroxy group.
  • Examples include, in addition to the aforementioned C 10 -C 30 alcohols octanol, 2-ethylhexanol, nonanol, neononyl alcohol, octenol, 2-ethylhexenol, Nonenol and the associated position and constitution isomers.
  • C 6 -C 30 -alcohol represents a linear or branched saturated or unsaturated aliphatic hydrocarbon having 6 to 30 carbon atoms which is substituted by one or more, preferably a hydroxy group.
  • Examples include, in addition to the aforementioned C 8 -C 30 alcohols hexanol and heptanol and the associated position and constitution isomers.
  • C 6 -C 40 -Alcohol is a linear or branched aliphatic hydrocarbon having 6 to 40 carbon atoms, which is substituted by one or more, preferably a hydroxy group.
  • Examples include, in addition to the aforementioned C 6 -C 30 alcohols, the higher homologues having 31 to 40 carbon atoms and the associated position and constitution isomers.
  • suitable and preferred copolymers in particular suitable and preferred monomers M1, M2, M3 and M4, which are the basis of the copolymers, their use and compositions containing them, are taken either alone or in combination with one another.
  • M2 and M3 preferably differ by the number of Carbon atoms, the difference preferably being at least 6 carbon atoms. Most preferably, M3 contains a greater number of carbon atoms than M2. In particular, M3 contains at least 6 more carbon atoms than M2.
  • the copolymer contains the monomers M1, M2, M4 and optionally M3 in copolymerized random.
  • the molar fraction of the monomer M3 is lower than that of the monomer M2.
  • Monomer M1 is a monoester of maleic acid.
  • the copolymer used according to the invention may comprise in copolymerized form as monomer M1 monoesters of maleic acid derived from various alcohols.
  • R 5 is H.
  • R 6 is preferably C 6 -C 40 -alkyl, more preferably C 8 -C 30 -alkyl and in particular C 10 -C 30 -alkyl, for example C 10 -C 26 -alkyl or C 18 -C 26 - alkyl.
  • the alcohol component of the ester monomer M1 (R 6 ) is particularly preferably derived from longer-chain alcohols, for example from C 6 -C 40 -alcohols, preferably from C 8 -C 30 -alcohols and especially from C 10 -C 30 -alcohols ,
  • C 10 -C 26 alcohols or C 18 -C 26 alcohols can also be derived from mixtures of such alcohols, for example mixtures obtained from industrial processes, such as fatty alcohols or alcohols from hydroformylation processes.
  • the molar ratio of copolymerized M1 to copolymerized M4 is specifically 4: 1 to 2: 1.
  • R 1 and R 3 are H, while R 2 is COOR 5 and R 4 is COOR 6 , ie, M1 is a maleic monoester.
  • ester monomers M1 are the monoesters of maleic acid with hexanol, heptanol, octanol, 2-ethylhexanol, nonanol, decanol, 2-propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosanol, Hencosanol, Docosanol, Tricosanol, Tetracosanol, Pentacosanol, hexacosanol, heptacosanol, octacosanol, nonacosanol, squalanol, positional and constitutional isomers thereof, and higher homologues and associated position and constitutional isomers thereof,
  • preferred ester monomers M1 are the monoesters of maleic acid with C 6 -C 40 -alcohols, particularly preferably with C 8 -C 30 -alcohols and in particular with C 10 -C 30 -alcohols, for example with C 10 -C 26 Alcohols or with C 18 -C 26 alcohols.
  • M2 and M3 differ by at least 6 carbon atoms, with M3 being particularly preferred as the longer-chain monomer. Accordingly, M3 in such a terpolymer most preferably contains at least 6 carbon atoms more than M2.
  • R 9 and R 13 are C 8 -C 48 -alkyl, particularly preferably C 10 -C 48 -alkyl, in particular C 14 -C 38 -alkyl, for example C 16 -C 28 -alkyl.
  • R 9 and R 13 differ by at least 6 carbon atoms, it being preferred that R 13 is the longer-chain radical, ie that R 13 contains at least 6 more carbon atoms than R 9 .
  • R 10 , R 11 , R 12 , R 14 , R 16 and R 16 may be the same or different and are H or methyl. It is preferred that at least one and in particular at least two of the radicals R 10 , R 11 or R 12 in monomer M 2 or at least one and in particular at least two of the radicals R 14 , R 15 or R 16 in monomer M 3 stand for H. Specifically, all three radicals R 10 , R 11 and R 12 in monomer M2 or all three radicals R 14 , R 15 and R 16 in monomer M3 for H.
  • the monomers M2 and M3 are preferably longer-chain linear or branched alkenes, for example C 10 -C 50 -alkenes and in particular C 12 -C 50 -alkenes, for example C 12 -C 40 -alkylenes or C 18 - C 40 alkenes, for example C 18 -C 30 alkenes.
  • the double bond can be arranged both terminally ( ⁇ -olefin) and internally ( ⁇ -olefin, etc.).
  • the alkenes may also be oligomers or polymers of alkenes, for example of C 2 -C 8 -alkenes, such as ethylene, propylene, 1- or 2-butene, isobutene, pentene, hexene or heptene, or in particular of C 3 -C 8 alkenes.
  • C 2 -C 8 -alkenes such as ethylene, propylene, 1- or 2-butene, isobutene, pentene, hexene or heptene, or in particular of C 3 -C 8 alkenes.
  • the monomers M2 and M3 are alkenes having the C-C double bond in the ⁇ - or ⁇ -position (relative to the main chain of the molecule) and in particular in the ⁇ -position (terminal alkenes, ⁇ -alkenes).
  • the monomers M2 and M3 may also be alkene mixtures, for example mixtures obtained from industrial processes. This is the case in particular when the olefins used are olefin oligomers or polymers, such as polypropylene, polybutene or polyisobutene.
  • M2 is preferably a C 8 -C 30 alkene or a mixture of such alkenes, for example a mixture of C 16 -C 26 alkenes or preferably of C 20 -C 24 alkenes.
  • M2 is preferably a C 8 -C 18 alkyne and M 3 is preferably a C 18 -C 40 alkene different therefrom, preferably at least 6 more carbon atoms contains as M2, or an alkene mixture, this alkene not or in only minor amounts, for example in a proportion of at most 10 wt .-%, preferably of at most 5 wt .-% and in particular of at most 2 wt .-%, based to the total weight of the alkene mixture, and differs by at least 6 carbon atoms thereof, for example an alkene mixture of C 18 -C 50 alkenes or of C 18 -C 40 alkenes.
  • the copolymer may contain, as M 2, a C 10 -C 14 alkene and as M 3 a C 18 -C 28 alkene mixture or a C 30 -C 50 alkene mixture, for example a C 35 -C 45 alkene mixture in copolymerized form.
  • alkene mixtures are mixtures such as those resulting from oligomerization or polymerization processes of alkenes, such as ethylene, propene, n-butene or isobutene, for example polypropene, polybutene or, in particular, polyisobutene having an M n of, for example, 500, 550 or 600.
  • Alkenes such as ethylene, propene, n-butene or isobutene, are formed, for example polypropene, polybutene or, in particular, polyisobutene having an M n of, for example, 500, 550 or 600.
  • copolymers used according to the invention are preferably obtainable by, preferably free-radical, polymerization, in particular solution polymerization, of the monomers M1, M2, M4 and optionally M3.
  • di-tert-butyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxyisononanoate, tert-amyl peroxypivalate or dibenzoyl peroxide or mixtures thereof are particularly suitable.
  • azo compound azobisisobutyronitrile ("AIBN") is exemplified.
  • AIBN azobisisobutyronitrile
  • the free-radical initiators are metered in amounts customary for polymerizations.
  • the copolymer used according to the invention it is also possible to use a precursor of the monomer M1 in the polymerization process and to carry out a functionalization reaction to the desired monoester only after polymerization has taken place.
  • M1 is a maleic acid monoester
  • maleic anhydride in the polymerization reaction and to convert this copolymerized monomer into the corresponding monoester in a manner known per se by reaction with the desired alcohol only after polymerization has taken place.
  • esterification reactions of polymerized maleic anhydride are known and, for example, in EP-A-0214786 which is incorporated herein by reference in its entirety.
  • the copolymer In order for the copolymer to contain the monomer M4, it is possible, for example, to carry out the esterification of the maleic anhydride in such a way that a portion of the anhydride used and copolymerized remains unchanged.
  • the proportion of unreacted anhydride, i. the ratio of M1 and M4 can be e.g. regulate the reaction time and / or the reaction temperature via the amount of the alcohol used, the esterification catalyst optionally used.
  • suitable reaction conditions can be determined for example by simple preliminary tests.
  • esters with shorter-chain alcohols e.g. the methyl or ethyl esters of maleic acid
  • the copolymers of the invention obtainable by the polymerization process are preferably composed essentially of the above-defined monomers M1, M2, M4 and optionally M3 M4.
  • M1, M2, M4 monomers M1 or as monomer M4
  • it may contain, if appropriate, small amounts of maleic acid hydrolytically removed from the anhydride, e.g. caused by traces of water.
  • Low proportions means that the copolymer contains at most 2 mol%, preferably at most 1 mol%, more preferably at most 0.5 mol%, in particular at most 0.1%, of the acid, based on the other monomers.
  • the copolymer may also contain minor amounts of other compounds, e.g. Regulator, included.
  • the copolymers are used to lower the CP of fuel oils.
  • copolymers used according to the invention are used alone or in combination with other coadditives in amounts such that they have an effect as CP depressants in the additized fuel oil or lubricant.
  • a fuel oil composition comprising a major weight fraction of a middle distillate fuel boiling in the range of about 120-500 ° C and a minor proportion by weight of at least one copolymer of the invention.
  • lubricant compositions containing a greater weight fraction of a conventional lubricant and a smaller proportion by weight of at least one copolymer of the invention.
  • Fuel oils are preferably fuels. Suitable fuels are gasolines and middle distillates, with middle distillates being preferred. Suitable middle distillates are, for example, diesel fuels, heating oil or kerosene, with diesel fuel and heating oil being particularly preferred.
  • the fuel oils are, for example, low-sulfur or high-sulfur petroleum refines or stone or lignite distillates, which usually have a boiling range of 150 to 400 ° C.
  • the fuel oils may be standard fuel oil according to DIN 51603-1, which has a sulfur content of 0.005 to 0.2 wt .-%, or it is low sulfur fuel oils with a sulfur content of 0 to 0.005 wt .-% ,
  • heating oil is especially called heating oil for domestic oil firing systems or fuel oil EL.
  • the quality requirements for such heating oils are specified, for example, in DIN 51603-1 (see also Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A12, page 617 ff., To which reference is hereby expressly made).
  • the 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 even beyond. But you can do that too so-called "ultra low sulfur diesel” or "City diesel", characterized by a 95% point of, for example, a maximum of 345 ° C and a maximum sulfur content of 0.005 wt .-% or by a 95% point of, for example, 285 ° C and a maximum sulfur content of 0.001% by weight.
  • those available from coal gasification or gas liquefaction (GTL) or biomass to liquid (BTL) fuels are also suitable. Also suitable are mixtures of the abovementioned diesel fuels with regenerative fuels, such as biodiesel.
  • the additive used according to the invention for the addition of low sulfur diesel fuels that is with a sulfur content of less than 0.05 wt .-%, preferably less than 0.02 wt .-%, in particular less than 0.005 wt. % and especially less than 0.001% by weight of sulfur or for the addition of heating oil with a low sulfur content, for example with a sulfur content of at most 0.2% by weight, preferably of at most 0.05% by weight, more preferably of at most 0.005 wt .-%, used.
  • Such fuel oil compositions may further comprise as fuel component biodiesel (from animal and / or vegetable production) in proportions of 0-30% by weight.
  • Preferred fuel oils are selected from diesel fuels, kerosene and fuel oil, which diesel fuel may be obtainable by refining, coal gasification, gas liquefaction or biomass liquefaction, may be a mixture of such products and optionally mixed with regenerative fuels.
  • diesel fuel may be obtainable by refining, coal gasification, gas liquefaction or biomass liquefaction, may be a mixture of such products and optionally mixed with regenerative fuels.
  • Such fuel oil compositions are preferred in which the sulfur content of the mixture is at most 500 ppm.
  • the copolymer used in the present invention is preferably used in a proportion based on the total amount of the fuel oil composition, which in itself has a substantially sufficient influence on the CP value of the fuel oil compositions.
  • the additive is added in an amount of from 0.001 to 1% by weight, more preferably from 0.005 to 0.1% by weight, and especially from 0.01 to 0.05% by weight, based on the total amount of the fuel oil composition, used.
  • copolymers used according to the invention can be used in combination with other conventional cold flow improvers and / or further lubricating and fuel oil additives.
  • copolymers used according to the invention can be added to the fuel oil compositions individually or as a mixture of such copolymers and optionally in combination with other additives known per se.
  • Suitable additives which may be included in fuel oil compositions in addition to the copolymers used in the invention, especially for diesel fuels and heating oils include detergents, corrosion inhibitors, dehazers, demulsifiers, antifoams, antioxidants, metal deactivators, multifunctional stabilizers, cetane improvers, combustion improvers, dyes, Markers, solubilizers, antistatic agents, lubricity improvers, and other additives which improve the cold properties of the fuel, such as nucleators, flow improvers (“MDFI"), paraffin dispersants (“WASA”) and the combination of the last two additives (“WAFI”) (cf. Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A16, p. 719 ff; or the patents cited at the outset for flow improvers).
  • MDFI flow improvers
  • WASA paraffin dispersants
  • WAFI last two additives
  • the monomer is preferably selected from alkenylcarboxylic esters, (meth) acrylic esters and olefins.
  • Suitable olefins are, for example, those having 3 to 10 carbon atoms and having 1 to 3, preferably 1 or 2, in particular having one, carbon-carbon double bond. In the latter case, the carbon-carbon double bond can be arranged both terminally ( ⁇ -olefins) and internally.
  • ⁇ -olefins more preferably ⁇ -olefins having 3 to 6 carbon atoms, such as propene, 1-butene, 1-pentene and 1-hexene.
  • Suitable (meth) acrylic esters are, for example, esters of (meth) acrylic acid with C 1 -C 10 -alkanols, in particular with methanol, ethanol, propanol, isopropanol, n-butanol, sec-butanol, isobutanol, tert-butanol, pentanol, hexanol, Heptanol, octanol, 2-ethylhexanol, nonanol and decanol.
  • Suitable alkenylcarboxylic esters are, for example, the vinyl and propenyl esters of carboxylic acids having 2 to 20 carbon atoms, the hydrocarbon radical of which may be linear or branched. Preferred among these are the vinyl esters.
  • carboxylic acids having a branched hydrocarbon radical preferred are those whose branching is in the ⁇ -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 radical of the carboxylic acid is linear.
  • alkenylcarboxylic esters examples include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, with vinyl esters being preferred.
  • a particularly preferred alkenyl carboxylic acid ester is vinyl acetate.
  • the ethylenically unsaturated monomer is selected from alkenylcarboxylic esters.
  • copolymers which contain two or more mutually different alkenylcarboxylic acid esters in copolymerized form, these differing in the alkenyl function and / or in the carboxylic acid group. Also suitable are copolymers which, in addition to the alkenylcarboxylic 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 from 1 to 50 mol%, particularly preferably from 10 to 50 mol% and in particular from 5 to 20 mol%, based on the total copolymer.
  • the copolymer a) preferably has a number-average molecular weight M n of from 1,000 to 20,000, more preferably from 1,000 to 10,000 and in particular from 1,000 to 6,000.
  • Preferred comb polymers are obtainable, for example, by the copolymerization of maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with an ⁇ -olefin or an unsaturated ester, such as vinyl acetate, and subsequent esterification of 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. Also mixtures of comb polymers are suitable.
  • Comb polymers may also be polyfumarates or polymaleinates.
  • homopolymers and copolymers of vinyl ethers are suitable comb polymers.
  • Preferred polyoxyalkylene compounds of the formula III in which both R 19 and R 20 are R 21 are polyethylene glycols and polypropylene glycols having a number average molecular weight of 100 to 5000.
  • Preferred polyoxyalkylenes of the formula III in which one of the radicals R 19 is R 21 and the other is R 21 -CO- are polyoxyalkylene esters of fatty acids having 10 to 30 carbon atoms, such as stearic acid or behenic acid.
  • Preferred polyoxyalkylene compounds in which both R 19 and R 20 are R 21 -CO- are diesters of fatty acids having 10 to 30 carbon atoms, preferably stearic or behenic acid.
  • the polar nitrogen compounds d), suitably oil-soluble, may be both ionic and non-ionic and preferably have at least one, more preferably at least 2, substituents of the formula> NR 22 , wherein R 22 is a C 8 -C 40 hydrocarbon radical.
  • the nitrogen substituents may also be quaternized, that is in cationic form.
  • An example of such nitrogen compounds are ammonium salts and / or amides obtainable by reacting at least one amine substituted with at least one hydrocarbyl 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 octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologs.
  • Suitable secondary amines are, for example, dioctadecylamine and methylbehenylamine.
  • amine mixtures in particular industrially available amine mixtures, 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".
  • Suitable acids 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 by long-chain hydrocarbon radicals.
  • polar nitrogen compounds are ring systems bearing at least two substituents of the formula -A-NR 23 R 24 wherein A is a linear or branched aliphatic hydrocarbon group optionally substituted by one or more groups selected from O, S , NR 35 and CO, is interrupted, and R 23 and R 24 are a C 9 -C 40 -hydrocarbon radical, which is optionally interrupted by one or more groups selected from O, S, NR 35 and CO, and / or substituted by one or more substituents selected from OH, SH and NR 35 R 36 , wherein R 35 is C 1 -C 40 alkyl optionally substituted by one or more moieties selected from CO, NR 35 , O and S, interrupted, and / or substituted by one or more radicals selected from NR 37 R 38 , OR 37 , SR 37 , COR 37 , COOR 37 , CONR 37 R 38 , aryl or heterocyclyl, wherein R 37 and R 38 each una depending on one another, are
  • A is 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 either homocyclic, heterocyclic, condensed polycyclic or non-condensed polycyclic systems.
  • the ring system is carbo- or heteroaromatic, in particular carboaromatic.
  • polycyclic ring systems examples include condensed benzoic structures, such as naphthalene, anthracene, phenanthrene and pyrene, condensed nonbenzoids Structures such as azulene, indene, hydrindene and fluorene, uncondensed polycycles such as diphenyl, heterocycles such as quinoline, indole, dihydroindole, benzofuran, coumarin, isocoumarin, benzothiophene, carbazole, diphenylene oxide and diphenylene sulfide, non-aromatic or partially saturated ring systems such as decalin , and three-dimensional structures such as a-pinene, camphene, bornylene, norboman, norbornene, bicyclooctane and bicyclooctene.
  • condensed benzoic structures such as naphthalene, anthracene, phenanthrene and pyrene
  • Suitable polar nitrogen compounds are condensates of long-chain primary or secondary amines with carboxyl group-containing polymers.
  • Suitable polar nitrogen compounds are also in the DE-A-198 48 621 , of the DE-A-196 22 052 or the EP-B-398 101 described, to which reference is hereby made.
  • a and B are alkyl, alkenyl or two substituted hydrocarbon radicals or together with the carbon atoms to which they are attached form an aromatic or cycloaliphatic ring system.
  • Suitable poly (meth) acrylic esters f) are both homo- and copolymers of acrylic and methacrylic acid esters. Preferred are copolymers of at least two mutually different (meth) acrylic acid esters, which differ with respect to the fused alcohol. Optionally, the copolymer contains a further, different of which olefinically unsaturated monomer copolymerized. The weight-average molecular weight of the polymer is preferably 50,000 to 500,000 g / mol.
  • a particularly preferred polymer is a copolymer of methacrylic acid and methacrylic acid esters of saturated C 14 and C 15 alcohols wherein the acid groups are neutralized with hydrogenated tallamine.
  • Suitable poly (meth) acrylic esters are, for example, in WO 00/44857 which is incorporated herein by reference in its entirety.
  • the fuel oil composition preferably comprises at least one of the abovementioned conventional cold flow improvers and in particular at least one of the cold flow improvers of group a). These cold flow improvers are used in particular for lowering the CFPP value of fuel oil compositions additized therewith.
  • an additive package which contains at least one copolymer and at least one further additive, preferably selected from the above co-additives and optionally at least one diluent.
  • the additive package preferably contains at least one of the abovementioned conventional cold flow improvers and in particular at least one of the cold flow improvers of group a).
  • Suitable diluents are, for example, fractions obtained in petroleum processing, such as kerosene, naphtha or bright stock.
  • aromatic are suitable and aliphatic hydrocarbons and alkoxyalkanols.
  • middle distillates, especially in diesel fuels and heating oils preferably used diluents are naphtha, kerosene, diesel fuels, aromatic hydrocarbons such as Solvent Naphtha heavy, Solvesso ® or Shellsol ®, and mixtures of these solvents and diluents.
  • the copolymer is present in the additive packages preferably in an amount of from 0.1 to 99% by weight, more preferably from 1 to 90% by weight and in particular from 10 to 80% by weight, based on the total weight of the additive package ,
  • copolymers used according to the invention show improved performance compared to conventional cold flow improvers.
  • they lower the CP value of fuel oils additized therewith more effectively than comparable additives of the prior art.
  • Another advantage is that they have no negative impact on other additives contained in fuel oils, especially on cold flow improvers and especially on those that are intended to lower the CFPP value.
  • a total of four different copolymers according to the invention were prepared by solution polymerization and polymer-analogous reaction.
  • the content of the individual comonomers was determined by IR spectroscopy. To determine the molar masses, the K value was determined.
  • the Cloud Point was determined according to ASTM D 2500 and the Cold Filter Plugging Point (CFPP) according to DIN EN116.
  • CP of additized fuel oils copolymer Dosing rate [ppm] CP [° C] (H ⁇ 1) Dosing rate [ppm] CP [° C] (H ⁇ 2) Dosing rate [ppm] CP [° C] (H ⁇ 3) - - 2.9 - 0.1 - 3 1 100 2.6 100 -0.1 500 2.4 500 -0.8 2 100 2.6 100 -0.7 100 2.1 500 1.8 500 -0.7 500 1.4 3 100 2.2 100 -0.8 100 1.9 500 1.7 500 -1.3 500 1.3 4 100 2.4 100 -0.6 500 2.0 500 -0.9 500 1.8 copolymer Dosing rate [ppm] CP [° C] (DK1) Dosing rate [ppm] CP [° C] (DK2) - - -7 - -7.2 1 100 -9 100 -8.3 500 -9.2 500 -8.9

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Claims (5)

  1. Utilisation d'un copolymère, qui est composé de monomères comprenant M1, M2, M4 et éventuellement M3, M1 présentant la structure générale suivante :
    Figure imgb0017
     dans laquelle
    R1 et R3 représentent H ;
    R2 représente -COOR5 ;
    R4 représente -COOR6 ;
    R5 représente H ; et
    R6 représente hydrocarbyle en C6-C40 ; et
    M2 et M3 présentent les structures générales suivantes :
    Figure imgb0018
    Figure imgb0019
     dans lesquelles
    R9 et R13 sont identiques ou différents et représentent hydrocarbyle en C8-C48 ; et
    R10, R11, R12, R14, R15 et R16 sont identiques ou différents et représentent H ou méthyle,
    à condition que M2 et M3 ne soient pas identiques ; et
    M4 présente la structure générale suivante :
    Figure imgb0020
     dans laquelle
    R7 et R8 représentent H,
    le rapport molaire entre M1 copolymérisé et M4 copolymérisé étant de 4:1 à 1:1 ;
    pour abaisser la valeur CP d'huiles combustibles et de lubrifiants.
  2. Utilisation selon la revendication 1, dans laquelle le rapport molaire entre M1 copolymérisé et M4 copolymérisé est de 4:1 à 2:1.
  3. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle le copolymère contient sous forme copolymérisée statiquement les monomères M1, M2, M4 et éventuellement M3.
  4. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle les monomères M1, M2, M3 et M4 sont contenus dans le copolymère en les proportions molaires suivantes :
    M1 + M4 : 0,1 à 0,7
    M2 : 0,05 à 0,7
    M3 : 0 à 0,7,
    M1 et M4 étant contenus en un rapport molaire de 1:0 à 1:1 ; et
    la somme des proportions molaires de M2 et M3 étant de 0,3 à 0,9.
  5. Utilisation selon l'une quelconque des revendications précédentes, dans laquelle le monomère M1 est un monoester de l'acide maléique qui dérive d'alcools en C6-C40.
EP06117661.6A 2005-07-22 2006-07-21 Copolymères à base d'oléfines et d'esters d'acides carboxyliques éthylèniquement insaturés pour abaiser le point de trouble des combustibles et des lubrifiants Not-in-force EP1746147B1 (fr)

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EP06117661.6A EP1746147B1 (fr) 2005-07-22 2006-07-21 Copolymères à base d'oléfines et d'esters d'acides carboxyliques éthylèniquement insaturés pour abaiser le point de trouble des combustibles et des lubrifiants

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ES2437073T3 (es) 2009-04-07 2014-01-08 Basf Se Mezcla de compuestos de nitrógeno solubles en aceite polares y compuestos alifáticos solubles en aceite para la reducción del punto de enturbiamiento en combustibles destilados medios
US8790424B2 (en) 2011-03-30 2014-07-29 Basf Se Copolymer and use thereof for improving the cold flow properties of middle distillate fuels
WO2012130824A1 (fr) 2011-03-30 2012-10-04 Basf Se Copolymérisat et son utilisation pour améliorer les propriétés de fluidité à froid de carburants de distillat moyen
MY180330A (en) * 2014-01-29 2020-11-28 Basf Se Use of polycarboxylic-acid-based additives for fuels
WO2017089212A1 (fr) 2015-11-27 2017-06-01 Basf Se Copolymères comprenant des α-oléfines et esters d'acide dicarboxylique oléfinique, leur préparation et leur utilisation comme abaisseurs de point d'écoulement pour des huiles brutes, des huiles minérales ou des produits d'huile minérale
EP3481920B1 (fr) 2016-07-05 2021-08-11 Basf Se Utilisation d'additfs anticorrosivs pour des carburants et des lubrifiants
EP3481921B1 (fr) * 2016-07-07 2023-04-26 Basf Se Copolymère en tant qu'additifs pour carburants et lubrifiants
WO2018054892A1 (fr) 2016-09-21 2018-03-29 Basf Se Terpolymères d'anhydride de l'acide maléique, d'acrylates et d'alpha-oléfines, en particulier destinés à être utilisés comme agent d'amélioration de l'écoulement de pétrole
WO2018104071A1 (fr) 2016-12-07 2018-06-14 Basf Se Compositions aqueuses d'inhibiteurs de paraffine
CN108730770A (zh) 2017-04-13 2018-11-02 通用电气公司 用于油的防蜡剂以及用防蜡剂来减少油产生蜡沉积的方法
WO2023025636A1 (fr) 2021-08-27 2023-03-02 Basf Se Dispersions aqueuses d'inhibiteurs de paraffine

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