EP3940043A1 - Inhibiteurs de corrosion pour carburants et lubrifiants - Google Patents

Inhibiteurs de corrosion pour carburants et lubrifiants Download PDF

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EP3940043A1
EP3940043A1 EP21177666.1A EP21177666A EP3940043A1 EP 3940043 A1 EP3940043 A1 EP 3940043A1 EP 21177666 A EP21177666 A EP 21177666A EP 3940043 A1 EP3940043 A1 EP 3940043A1
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fuels
acid
component
use according
anhydride
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EP3940043B1 (fr
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Ivette Garcia Castro
Jochen Mezger
Maxim Peretolchin
Aaron FLORES-FIGUEROA
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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
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • 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
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/16—Hydrocarbons
    • C10L1/1625—Hydrocarbons macromolecular compounds
    • C10L1/1633—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds
    • C10L1/1641—Hydrocarbons macromolecular compounds homo- or copolymers obtained by reactions only involving carbon-to carbon unsaturated bonds from compounds containing aliphatic monomers
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/222—Organic compounds containing nitrogen containing at least one carbon-to-nitrogen single bond
    • C10L1/2222—(cyclo)aliphatic amines; polyamines (no macromolecular substituent 30C); quaternair ammonium compounds; carbamates
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0415—Light distillates, e.g. LPG, naphtha
    • C10L2200/0423—Gasoline
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/043—Kerosene, jet fuel
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
    • C10L2200/0446—Diesel
    • 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
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • C10L2200/0476—Biodiesel, i.e. defined lower alkyl esters of fatty acids first generation biodiesel
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    • 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
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/023—Specifically adapted fuels for internal combustion engines for gasoline engines
    • 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
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine
    • 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
    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/02—Amines, e.g. polyalkylene polyamines; Quaternary amines
    • 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
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • 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
    • C10N2030/12—Inhibition of corrosion, e.g. anti-rust agents or anti-corrosives
    • 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
    • C10N2030/70—Soluble oils
    • 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

Definitions

  • the present invention relates to new uses of corrosion inhibitors in fuels and lubricants.
  • Corrosion inhibitors are common additives in fuels and lubricants, which are often based on structures containing acid groups, e.g. dimeric fatty acids.
  • a disadvantage of these corrosion inhibitors is that they tend to precipitate, particularly in the presence of metal ions, especially calcium ions, and their corrosion-inhibiting effect is reduced as a result.
  • the deposits formed by these precipitations can also impair the functioning of engines, engine components or parts of the fuel system, in particular the injection system, specifically the injection pumps or injectors.
  • injection system is understood to mean the part of the fuel system in motor vehicles from the fuel pump up to and including the injector outlet.
  • fuel system is understood to mean the components of motor vehicles that are in contact with the respective fuel, preferably the area from the tank up to and including the injector outlet.
  • the compounds according to the invention act against corrosion not only in the injection system but also in the rest of the fuel system, here in particular against corrosion in fuel filters and fuel pumps.
  • WO 2015/113681 describes copolymers of ethylenically unsaturated mono- or dicarboxylic acid or derivatives thereof and ⁇ -olefins having from at least 12 up to and including 30 carbon atoms as additives in fuels or lubricants.
  • WO 2015/114029 describes copolymers of ethylenically unsaturated mono- or dicarboxylic acid or derivatives thereof and ⁇ -olefins having from at least 12 up to and including 30 carbon atoms, and optionally other monomers, as corrosion inhibitors in fuels or lubricants.
  • WO 2018/007375 describes the use of terpolymers of C20-C24 olefin, maleic anhydride and lauryl acrylate in fuels to remove and/or prevent deposits in the fuel system and/or injection system of direct injection diesel and/or gasoline engines.
  • the object was therefore to provide corrosion inhibitors which show increased compatibility with calcium ions and good compatibility and formulatability in fuel additive packages while retaining their effect as corrosion inhibitors.
  • the polymers described show a particular advantage in fuels or lubricants, especially in fuels containing alkali and/or alkaline earth metals and/or zinc of at least 0.1 ppm by weight, particularly preferably at least 0.2 ppm by weight, very particularly preferably at least 0.3 ppm by weight and in particular at least 0.5 ppm by weight.
  • alkali metals and/or alkaline earth metals and/or zinc preferably also in the presence of alkaline earth metals.
  • the content of alkali metals and/or alkaline earth metals in fuels is due, for example, to mixing with lubricants containing alkali metals and/or alkaline earth metals, for example in the fuel pump.
  • alkali metals and/or alkaline earth metals can come from fuel additives that have not been desalinated or have been insufficiently desalinated, for example carrier oils.
  • the disadvantages mentioned above can be caused by the entrainment of alkali metals and/or alkaline earth metals in the fuels.
  • One source of zinc is, for example, anti-wear additives.
  • Alkali metals which should be mentioned are, in particular, sodium and potassium, in particular sodium.
  • alkaline earth metals especially magnesium and calcium, especially calcium.
  • the polymers described are still active even in the presence of calcium and show no precipitation.
  • alkali and/or alkaline earth metals and/or zinc relate in each case to individual metal species.
  • the monomer (A) is at least one, preferably one to three, particularly preferably one or two and very particularly preferably exactly one ethylenically unsaturated, preferably ⁇ , ⁇ -ethylenically unsaturated mono- or dicarboxylic acid or derivatives thereof, preferably a dicarboxylic acid or derivatives thereof, particularly preferably the anhydride of a dicarboxylic acid, very particularly preferably maleic anhydride.
  • the derivatives are preferably anhydrides in monomeric form or di-C 1 -C 4 -alkyl esters, particularly preferably anhydrides in monomeric form.
  • C 1 -C 4 -alkyl is understood as meaning methyl, ethyl, isopropyl , n-propyl, n-butyl, isobutyl , sec- butyl and tert -butyl, preferably methyl and ethyl, particularly preferably methyl.
  • the ⁇ , ⁇ -ethylenically unsaturated mono- or dicarboxylic acid is a mono- or dicarboxylic acid or its derivatives in which the carboxyl group or, in the case of dicarboxylic acids, at least one carboxyl group, preferably both carboxyl groups, are conjugated with the ethylenically unsaturated double bond.
  • Examples of ethylenically unsaturated mono- or dicarboxylic acids that are not ⁇ , ⁇ -ethylenically unsaturated are cis-5-norbornene-endo-2,3-dicarboxylic acid anhydride, exo-3,6-epoxy-1,2,3,6- tetrahydrophthalic anhydride and cis-4-cyclohexene-1,2-dicarboxylic anhydride.
  • ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids are acrylic acid, methacrylic acid, crotonic acid and ethylacrylic acid, preferably acrylic acid and methacrylic acid, referred to in this document for short as (meth)acrylic acid, and particularly preferably acrylic acid.
  • Particularly preferred derivatives of ⁇ , ⁇ -ethylenically unsaturated monocarboxylic acids are methyl acrylate, ethyl acrylate, n-butyl acrylate and methyl methacrylate.
  • dicarboxylic acids examples include maleic acid, fumaric acid, itaconic acid (2-methylenebutanedioic acid), citraconic acid (2-methylmaleic acid), glutaconic acid (pent-2-ene-1,5-dicarboxylic acid), 2,3-dimethylmaleic acid, 2-methylfumaric acid, 2,3 -dimethylfumaric acid, methylenemalonic acid and tetrahydrophthalic acid, preferably maleic acid and fumaric acid and particularly preferably maleic acid and derivatives thereof.
  • the monomer (A) is maleic anhydride.
  • the monomer (B) is at least one, preferably one to four, particularly preferably one to three, very particularly preferably one or two and in particular precisely one ⁇ -olefin having from at least 12 up to and including 30 carbon atoms.
  • the ⁇ -olefins (B) preferably have at least 14, particularly preferably at least 16 and very particularly preferably at least 18 carbon atoms.
  • the ⁇ -olefins (B) preferably have up to and including 28, particularly preferably up to and including 26 and very particularly preferably up to and including 24 carbon atoms.
  • the ⁇ -olefins can preferably be linear or branched, preferably linear, 1-alkenes.
  • Examples thereof are 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonodecene, 1-eicosene, 1-docosene, 1-tetracosene, 1-hexacosene , Of which 1-octadecene, 1-eicosene, 1-docosene and 1-tetracosene, and mixtures thereof are preferred.
  • ⁇ -olefin (B) are those olefins which are oligomers or polymers of C 2 - to C 12 -olefins, preferably of C 3 - to C 10 -olefins, particularly preferably of C 4 - to C 6 olefins.
  • olefins which are oligomers or polymers of C 2 - to C 12 -olefins, preferably of C 3 - to C 10 -olefins, particularly preferably of C 4 - to C 6 olefins.
  • Examples thereof are ethene, propene, 1-butene, 2-butene, isobutene, pentene isomers and hexene isomers, preference being given to ethene, propene, 1-butene, 2-butene and isobutene.
  • ⁇ -olefins Mentioned specifically as ⁇ -olefins (B) are oligomers and polymers of propene, 1-butene, 2-butene, isobutene and mixtures thereof, especially oligomers and polymers of propene or isobutene or of mixtures of 1-butene and 2-butene.
  • the oligomers the trimers, tetramers, pentamers and hexamers and mixtures thereof are preferred.
  • the olefins (C) can be olefins with a terminal (a) double bond or those with a non-terminal double bond, preferably with an ⁇ double bond.
  • the olefin (C) is preferably an olefin having from 4 to less than 12 or more than 30 carbon atoms. If the olefin (C) is an olefin having 12 to 30 carbon atoms, this olefin (C) has no double bond in the ⁇ position.
  • Examples of aliphatic olefins (C) are 1-butene, 2-butene, isobutene, pentene isomers, hexene isomers, heptene isomers, octene isomers, nonene isomers, decene isomers, undecene isomers and mixtures thereof .
  • cycloaliphatic olefins are cyclopentene, cyclohexene, cyclooctene, cyclodecene, cyclododecene, ⁇ - or ⁇ -pinene and mixtures thereof, limonene and norbornene.
  • olefins (C) are polymers of propene, 1-butene, 2-butene or isobutene containing more than 30 carbon atoms or olefin mixtures containing such, preferably isobutene or olefin mixtures containing such, particularly preferably having an average molecular weight M w in the range from 500 to 5000 g/mol, preferably 650 to 3000, particularly preferably 800 to 1500 g/mol.
  • the oligomers or polymers containing isobutene in copolymerized form preferably have a high content of terminal ethylenic double bonds ( ⁇ -double bonds), for example at least 50 mol %, preferably at least 60 mol %, particularly preferably at least 70 mol % and most preferably at least 80 mole percent.
  • ⁇ -double bonds terminal ethylenic double bonds
  • Suitable isobutene sources for the preparation of such isobutene-containing oligomers or polymers are both pure isobutene and isobutene-containing C4 hydrocarbon streams, for example C4 raffinates, in particular "raffinate 1", C4 cuts from isobutane -Dehydrogenation, C4 cuts from steam crackers and from FCC crackers (fluid catalysed cracking), provided they are largely freed from the 1,3-butadiene contained therein.
  • a C4 hydrocarbon stream from an FCC refinery unit is also known as a "b/b" stream.
  • Suitable isobutenic C4 hydrocarbon streams are, for example, the product stream of a propylene-isobutane co-oxidation or the product stream from a metathesis unit, which are generally used after customary purification and/or concentration.
  • Suitable C4 hydrocarbon streams typically contain less than 500 ppm, preferably less than 200 ppm, butadiene.
  • the presence of 1-butene and of cis- and trans-2-butene is largely uncritical.
  • the isobutene concentration in the C4 hydrocarbon streams mentioned is in the range from 40 to 60% by weight.
  • raffinate 1 generally consists essentially of 30 to 50% by weight isobutene, 10 to 50% by weight 1-butene, 10 to 40% by weight cis- and trans-2-butene and 2 to 35% by weight butanes;
  • the unbranched butenes in raffinate 1 are generally practically inert and only the isobutene is polymerized.
  • Said isobutenic monomer mixture can contain small amounts of contaminants, such as water, carboxylic acids or mineral acids, without critical losses in yield or selectivity occurring. It is expedient to avoid accumulation of these impurities by removing such pollutants from the isobutene-containing monomer mixture, for example by adsorption on solid adsorbents such as activated carbon, molecular sieves or ion exchangers.
  • the monomer mixture preferably contains at least 5% by weight, more preferably at least 10% by weight and in particular at least 20% by weight isobutene, and preferably at most 95% by weight, especially preferably at most 90% by weight and in particular at most 80% by weight of comonomers.
  • the substance mixture of the olefins (B) and optionally (C), averaged for their amounts has at least 12 carbon atoms, preferably at least 14, particularly preferably at least 16 and very particularly preferably at least 17 carbon atoms.
  • the upper limit is less relevant and is usually no more than 60 carbon atoms, preferably no more than 55, more preferably no more than 50, most preferably no more than 45 and especially no more than 40 carbon atoms.
  • the monomer (D) is at least one, preferably one to three, particularly preferably one or two and very particularly preferably precisely one (meth)acrylic ester of alcohols which have at least 5 carbon atoms.
  • Preferred (meth)acrylic esters (D) are (meth)acrylic esters of C 5 - to C 18 -alkanols, preferably of n-pentanol, n-hexanol, n-heptanol, n-octanol, n-decanol, n-dodecanol (lauryl alcohol ), tridecanol isomer mixtures, n-tetradecanol, n-hexadecanol, heptadecanol isomer mixtures, n-octadecanol, 2-ethylhexanol or 2-propylheptanol.
  • the acrylic esters are preferred over the methacrylic esters. Dodecyl acrylate, 2-ethylhexyl acrylate and 2-propylheptyl acrylate are particularly preferred.
  • the alcohol is a mixture of alcohols containing 13 carbon atoms, particularly preferably obtainable by oligomerization of C 2 -C 6 -olefins, in particular C 3 - or C 4 -olefins, and subsequent hydroformylation.
  • the alcohol is a mixture of alcohols having 17 carbon atoms, particularly preferably one that can be obtained by hydroformylation from a C 16 olefin mixture, which in turn can be obtained by oligomerization of an olefin mixture that contains predominantly four Contains hydrocarbons containing carbon atoms.
  • this olefin mixture has from 15 to 17 carbon atoms, preferably from 15.1 to 16.9, particularly preferably from 15.2 to 16.8, very particularly preferably from 15.5 to 16.5 and in particular from 15.8 to 16.2 .
  • this alcohol has an average degree of branching, measured as the ISO index, of 2.8 to 3.7.
  • this alcohol is obtained by a process as described in WO 2009/124979 A1 , there in particular page 5, line 4 to page 16, line 29, and the examples from page 19, line 19 to page 21, line 25, which is hereby incorporated by reference into the present disclosure.
  • a C 17 -alcohol mixture having particularly advantageous performance properties can be prepared as the product of the transition metal-catalyzed oligomerization of olefins having 2 to 6 carbon atoms.
  • a C 16 -olefin mixture is first isolated from the product of the olefin oligomerization by distillation and only then is this C 16 -olefin mixture subjected to hydroformylation. It is thus possible to provide a more highly branched C 17 -alcohol mixture with particularly advantageous performance properties.
  • the incorporation ratio of the monomers (A) and (B) and (D) and optionally (C) in the copolymer obtained from reaction step (I) is generally as follows:
  • the molar ratio of (A)/((B) and (C)) (total) is generally from 10:1 to 1:10, preferably from 8:1 to 1:8, particularly preferably from 5:1 to 1 :5, very particularly preferably 3:1 to 1:3, in particular 2:1 to 1:2 and especially 1.5:1 to 1:1.5.
  • the molar incorporation ratio of maleic anhydride to monomers ((B) and (C)) (total) is about 1:1.
  • maleic anhydride in a slight excess over the ⁇ -olefin, for example 1.01-1.5:1, preferably 1.02-1.4 :1, particularly preferably 1.05-1.3:1, very particularly preferably 1.07-1.2:1 and in particular 1.1-1.15:1.
  • the molar ratio of the obligatory monomer (B) to the optional monomer (C), if present, is generally from 1:0.05 to 10, preferably from 1:0.1 to 6, particularly preferably from 1:0 .2 to 4, very particularly preferably from 1:0.3 to 2.5 and especially 1:0.5 to 1.5.
  • no optional monomer (C) is present in addition to monomer (B).
  • the proportion of one or more of the (meth)acrylic esters (D) based on the amount of the monomers (A), (B) and optionally (C) (in total) is generally 5 to 200 mol%, preferably 10 to 150 mol%, particularly preferably 15 to 100 mol%, very particularly preferably 20 to 50 mol% and in particular more than 20 to 33 mol%.
  • the copolymer consists of the monomers (A) and (B) and (D).
  • reaction step (II) the anhydride or carboxylic acid ester functionalities present in the copolymer obtained from (I) can be partially or completely hydrolyzed and/or hydrolyzed.
  • reaction step (II) anhydride functionalities are hydrolyzed and carboxylic acid ester functionalities are left substantially intact.
  • more than 90% of the anhydride and carboxylic acid ester functionalities contained remain intact after reaction step (II), preferably at least 92%, more preferably at least 94%, most preferably at least 95%, in particular at least 97% and especially at least 98 %.
  • reaction step (II) it is possible for up to 99.9% of the anhydride and carboxylic acid ester functionalities present to remain intact after reaction step (II), preferably up to 99.8%, more preferably up to 99.7%, most preferably up to 99, 5% and especially up to 99%.
  • reaction step (II) is not run through, so that 100% of the anhydride and carboxylic acid ester functionalities contained in the copolymer obtained from reaction step (I), particularly the anhydride functionalities contained, remain intact.
  • reaction step (II) it is a preferred embodiment of the present invention to go through reaction step (II) and to hydrolyze or saponify at least 10% of the anhydride and carboxylic acid ester functionalities present. Particularly preferably at least 25%, very particularly preferably at least 50%, in particular at least 75%, especially at least 85% and even at least 90% of the anhydride and carboxylic acid ester functionalities present are hydrolyzed or hydrolyzed.
  • reaction step (II) anhydride functionalities are hydrolyzed and carboxylic acid ester functionalities are left substantially intact.
  • anhydride functionalities are fully hydrolyzed, more preferably up to 99.9%, most preferably up to 99.5%, especially up to 99% and especially up to 95%.
  • Hydrolysis in reaction step (II) occurs when an anhydride, preferably the anhydride of a dicarboxylic acid, is used as the derivative of monomer (A), whereas saponification or hydrolysis can occur when an ester is used as monomer (A).
  • an anhydride preferably the anhydride of a dicarboxylic acid
  • the amount of water corresponding to the desired degree of hydrolysis, based on the anhydride functionalities present, is added and the copolymer obtained from (I) is heated in the presence of the added water.
  • more than the required equimolar amount of water can also be added, for example at least 1.05 times, preferably at least 1.1 times, particularly preferably at least 1.2 times and very particularly preferably at least 1.25 times the molar amount of water.
  • the reaction can be carried out under pressure to prevent water from escaping. Under these reaction conditions, the anhydride functionalities in the copolymer are generally reacted selectively, whereas any carboxylic acid ester functionalities present in the copolymer do not react, or at least react only to a minor extent.
  • the copolymer is reacted with an amount of strong base in the presence of water equal to the degree of saponification desired.
  • Hydroxides, oxides, carbonates or bicarbonates of alkali metals or alkaline earth metals can preferably be used as strong bases.
  • the copolymer obtained from (I) is then heated in the presence of the added water and the strong base.
  • the acids used are preferably mineral, carboxylic, sulfonic or phosphorus-containing acids with a pKa value of not more than 5, particularly preferably not more than 4.
  • acetic acid formic acid, oxalic acid, salicylic acid, substituted succinic acids, benzenesulfonic acids substituted or unsubstituted on the aromatic compound, sulfuric acid, nitric acid, hydrochloric acid or phosphoric acid; the use of acidic ion exchange resins is also conceivable.
  • the copolymer obtained from (I) is then heated in the presence of the added water and acid.
  • the copolymers obtained from step (II) still contain residues of acid anions, it may be preferable to remove these acid anions from the copolymer using an ion exchanger and preferably to exchange them for hydroxide ions or carboxylate ions, particularly preferably hydroxide ions. This is particularly the case when the acid anions contained in the copolymer are halides, contain sulfur or contain nitrogen.
  • the copolymer obtained from reaction step (II) generally has a weight-average molecular weight Mw of 0.5 to 20 kDa, preferably 0.6 to 15, particularly preferably 0.7 to 7, very particularly preferably 1 to 7 and in particular 1, 5 to 54 kDa (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standards).
  • the number-average molecular weight Mn is usually from 0.5 to 10 kDa, preferably from 0.6 to 5, particularly preferably from 0.7 to 4, very particularly preferably from 0.8 to 3 and in particular from 1 to 2 kDa (determined by gel permeation chromatography with tetrahydrofuran and polystyrene as standard).
  • the polydispersity is generally from 1 to 10, preferably from 1.1 to 8, particularly preferably from 1.2 to 7, very particularly preferably from 1.3 to 5 and in particular from 1.5 to 3.
  • the acid numbers according to DIN EN ISO 2114 (titration with KOH, potentiometric) of the copolymers after going through the reaction step (II) (based on the solids in the absence of solvent) are preferably from 5 to 100 mg KOH/g of copolymer, particularly preferably from 7 to 90 mg KOH/g and most preferably from 10 to 80 mg/g copolymer.
  • the copolymers contain a high proportion of adjacent carboxylic acid groups, as determined by measuring adjacency. For this purpose, a sample of the copolymer for a period of 30 minutes at a Tempered at a temperature of 290 °C between two Teflon foils and an FTIR spectrum recorded at a bubble-free point. The IR spectrum of Teflon is subtracted from the spectra obtained, the layer thickness is determined and the content of cyclic anhydride is determined.
  • the adjacency is at least 10%, preferably at least 15%, particularly preferably at least 20%, very particularly preferably at least 25% and in particular at least 30%.
  • the use according to the invention relates to the inhibition of the corrosion of iron, steel, magnesium, aluminum and/or non-ferrous metal surfaces and their alloys.
  • non-ferrous metals preference is given to copper, zinc and their alloys, as well as brass and bronze.
  • the corrosion of steel surfaces is particularly preferably inhibited.
  • the polymers described are added to fuels, which can optionally have the above-specified content of alkali metals and/or alkaline earth metals and/or zinc, generally in amounts of from 1 to 60 ppm by weight, preferably from 5 to 40 ppm by weight.
  • the polymers described are often used in the form of fuel additive mixtures, together with the usual additives: In the case of diesel fuels, these are primarily customary detergent additives, carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors other than the polymers described, demulsifiers, dehazers, antifoams, cetane number improvers, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators , dyes and/or solvents.
  • additives In the case of diesel fuels, these are primarily customary detergent additives, carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors other than the polymers described, demulsifiers, dehazers, antifoams, cetane number improvers, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators , dyes and/or solvents.
  • additives in additive packages containing at least one additive selected from the group consisting of detergent additives, carrier oils, cold flow improvers, lubricity improvers (lubricity improvers), corrosion inhibitors other than the polymers described, demulsifiers, dehazers, antifoams, cetane number improvers, combustion improvers, antioxidants, stabilizers, antistatic agents, Metallocenes, metal deactivators, dyes and solvents for reducing corrosion in diesel fuels, which can optionally have a content of alkali and/or alkaline earth metals and/or zinc of at least 0.1 ppm by weight.
  • additives selected from the group consisting of detergent additives, carrier oils, cold flow improvers, lubricity improvers (lubricity improvers), corrosion inhibitors other than the polymers described, demulsifiers, dehazers, antifoams, cetane number improvers, combustion improvers, antioxidants, stabilizers, antistatic agents, Metallocenes, metal de
  • lubricity improvers In the case of petrol, these are primarily lubricity improvers (friction modifiers), corrosion inhibitors other than the polymers described, demulsifiers, dehazers, antifoams, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and/or solvents.
  • lubricity improvers for reduction of corrosion in petrol, which can optionally have a content of alkali and/or alkaline earth metals and/or zinc of at least 0.1 ppm by weight.
  • detergent additives Da), (Dh) and (Di)
  • detergent additives Da and (Di)
  • more preferred are detergent additives (Da) and (Di)
  • most preferred are (Da).
  • the hydrophobic hydrocarbon residue in the above detergent additives which provides sufficient solubility in fuel, has a number average molecular weight (M n ) of 85 to 20,000, preferably 113 to 10,000, more preferably 300 to 5,000, more preferably 300 to 3,000, even more preferably from 500 to 2,500 and in particular from 700 to 2,500, especially from 800 to 1500.
  • M n number average molecular weight
  • a typical hydrophobic hydrocarbon radical, in particular in connection with the polar groups, is in particular polypropenyl, polybutenyl and polyisobutenyl radicals with a number-average molecular weight M n of preferably 300 to 5000, particularly preferably 300 to 3000, more preferably 500 to 2500, even more preferably 700 to 2500 and in particular 800 to 1500.
  • Such additives based on highly reactive polyisobutene which are obtained from the polyisobutene, which can contain up to 20% by weight of n-butene units, by hydroformylation and reductive amination with ammonia, monoamines or polyamines such as dimethyl -aminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine can be prepared, in particular from the EP-A 244 616 known.
  • the production route offers itself by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to the carbonyl or Carboxyl compound and subsequent amination under reductive (hydrogenating) conditions.
  • Amines such as e.g. B. ammonia, monoamines or the above polyamines can be used.
  • Corresponding additives based on polypropylene are in particular in the WO-A 94/24231 described.
  • Da-containing additives are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as they are in particular in DE-A 196 20 262 are described.
  • Additives containing carboxyl groups or their alkali metal or alkaline earth metal salts (Dd) are preferably copolymers of C 2 - to C 40 -olefins with maleic anhydride having a total molecular weight of 500 to 20,000, all or part of the carboxyl groups to the alkali metal or alkaline earth metal salts and one remaining Rest of the carboxyl groups are reacted with alcohols or amines.
  • Such additives are in particular from EP-A 307 815 known.
  • Such additives are mainly used to prevent valve seat wear and, as in the WO-A 87/01126 described, are used with advantage in combination with conventional fuel detergents such as poly (iso) buteneamines or polyetheramines.
  • Additives containing sulfonic acid groups or their alkali metal or alkaline earth metal salts are preferably alkali metal or alkaline earth metal salts of an alkyl sulfosuccinate, as is found in particular in EP-A 639 632 is described.
  • Such additives serve mainly to prevent valve seat wear and can be used to advantage in combination with conventional fuel detergents such as poly(iso)buteneamines or polyetheramines.
  • Additives containing polyoxy-C 2 -C 4 -alkylene groups are preferably polyethers or polyetheramines, which are obtained by reacting C 2 - to C 60 -alkanols, C 6 - to C 30 -alkanediols, mono- or di-C 2 - to C 30 -alkylamines, C 1 - to C 30 -alkylcyclohexanols or C 1 - to C 30 -alkylphenols with 1 to 30 mol of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or amino group and, in the case of the polyetheramines, are obtainable by subsequent reductive amination with ammonia, monoamines or polyamines.
  • Such products are particularly in the EP-A 310 875 , EP-A 356 725 , EP-A 700 985 and US-A 4,877,416 described.
  • polyethers such products also have carrier oil properties. Typical examples of these are tridecanol or isotridecanol butoxylates, isononylphenol butoxylates and polyisobutenol butoxylates and propoxylates and the corresponding reaction products with ammonia.
  • Additives containing carboxylic acid ester groups (Dg) are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, in particular those with a minimum viscosity of 2 mm 2 /s at 100° C., as is the case in particular in DE-A 38 38 918 are described.
  • Aliphatic or aromatic acids can be used as mono-, di- or tricarboxylic acids, and long-chain representatives having, for example, 6 to 24 carbon atoms are particularly suitable as ester alcohols or ester polyols.
  • esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol. Such products also fulfill carrier oil properties.
  • the groups with hydroxyl and/or amino and/or amido and/or imido groups are, for example, carboxylic acid groups, acid amides of monoamines, acid amides of di- or polyamines which have free amine groups in addition to the amide function, and succinic acid derivatives with an acid and an amide function, carboxylic acid imides with monoamines, carboxylic acid imides with di- or polyamines which, in addition to the imide function, also have free amine groups, or diimides which are formed by reacting di- or polyamines with two succinic acid derivatives.
  • Such fuel additives are generally known and are described, for example, in documents (1) and (2).
  • reaction products of alkyl- or alkenyl-substituted succinic acids or derivatives thereof with amines are preferably the reaction products of polyisobutenyl-substituted succinic acids or derivatives thereof with amines.
  • reaction products with aliphatic polyamines such as in particular ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine, which have an imide structure.
  • detergent additives which contain a hydrophobic hydrocarbon radical having a number average molecular weight (Mn) of 85 to 20,000 and at least one mono- or polyamino group having up to 6 nitrogen atoms have, wherein at least one nitrogen atom has basic properties.
  • Mn number average molecular weight
  • the compounds according to the invention can be combined with quaternized compounds, as described in WO 2012/004300 , there preferably page 5, line 18 to page 33, line 5, particularly preferably of preparation example 1, which is hereby expressly incorporated by reference into the present disclosure.
  • the compounds according to the invention can be combined with quaternized compounds, as described in WO 2014/195464 , there preferably page 5, line 21 to page 47, line 34, particularly preferably of preparation examples 1 to 17.
  • the compounds according to the invention can be combined with quaternized compounds, as described in WO 11/95819 A1 , there preferably page 4, line 5 to page 13, line 26, particularly preferably preparation example 2.
  • the compounds according to the invention can be combined with quaternized compounds, as described in WO 11/110860 A1 , there preferably page 4, line 7 to page 16, line 26, particularly preferably of preparation examples 8, 9, 11 and 13.
  • the compounds according to the invention can be combined with quaternized compounds, as described in WO 06/135881 A2 , there preferably page 5, line 14 to page 12, line 14, particularly preferably examples 1 to 4.
  • the compounds according to the invention can be combined with quaternized compounds, as described in WO 10/132259 A1 , there preferably page 3, line 29 to page 10, line 21, particularly preferably example 3.
  • the compounds according to the invention can be combined with quaternized compounds, as described in WO 08/060888 A2 , there preferably page 6, line 15 to page 14, line 29, particularly preferably examples 1 to 4.
  • the compounds according to the invention can be combined with quaternized compounds, as described in GB 2496514A , there preferably paragraphs [00012] to [00039], particularly preferably examples 1 to 3.
  • the compounds according to the invention can be combined with quaternized compounds, as described in WO 2013 070503 A1 , there preferably paragraphs [00011] to [00039], particularly preferably examples 1 to 5.
  • Additives containing groups (Di) produced by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine.
  • One or more of the detergent additives mentioned can be added to the fuel in such an amount that the dosing rate of these detergent additives is preferably 25 to 2500 ppm by weight, in particular 75 to 1500 ppm by weight, especially 150 to 1000 ppm by weight .-ppm, is.
  • Carrier oils used can be mineral or synthetic. Suitable mineral carrier oils are fractions obtained during petroleum processing, such as bright stock or base oils with viscosities such as from the class SN 500 to 2000, but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. A fraction known as "hydrocrack oil” and obtained in the refining of mineral oil (vacuum distillate cut with a boiling range of about 360 to 500° C., obtainable from natural mineral oil which has been catalytically hydrogenated and isomerized and dewaxed under high pressure) can also be used. Mixtures of the mineral carrier oils mentioned above are also suitable.
  • suitable synthetic carrier oils are polyolefins (polyalphaolefins or polyinternal olefins), (poly)esters, poly)alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-started polyethers, alkylphenol-started polyetheramines and carboxylic acid esters of long-chain alkanols.
  • suitable polyethers or polyetheramines are preferably compounds containing polyoxy-C 2 - to C 4 -alkylene groups, which are obtained by reacting C 2 - to C 60 -alkanols, C 6 - to C 30 -alkanediols, mono- or di-C 2 - to C 30 -alkylamines, C 1 - to C 30 -alkyl-cyclohexanols or C 1 - to C 30 -alkylphenols with 1 to 30 mol of ethylene oxide and/or propylene oxide and/or butylene oxide per hydroxyl group or amino group and, if the polyetheramines, are obtainable by subsequent reductive amination with ammonia, monoamines or polyamines.
  • Such products are particularly in the EP-A 310 875 , EP-A 356 725 , EP-A 700 985 and the US-A 4,877,416 described.
  • polyetheramines poly-C 2 - to C 6 -alkylene oxide amines or functional derivatives thereof can be used. Typical examples of these are tridecanol or isotridecanol butoxylates, isononylphenol butoxylates and polyisobutenol butoxylates and propoxylates and the corresponding reaction products with ammonia.
  • carboxylic acid esters of long-chain alkanols are, in particular, esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, such as those in particular DE-A 38 38 918 are described.
  • Aliphatic or aromatic acids can be used as mono-, di- or tricarboxylic acids, and long-chain representatives having, for example, 6 to 24 carbon atoms are particularly suitable as ester alcohols or ester polyols.
  • esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and isotridecanol, e.g. B. di-(n- or isotridecyl)phthalate.
  • Examples of particularly suitable synthetic carrier oils are alcohol-started polyethers having about 5 to 35, preferably about 5 to 30, particularly preferably 10 to 30 and in particular 15 to 30 C 3 - to C 6 -alkylene oxide units, z. B. propylene oxide, n-butylene oxide and isobutylene oxide units or mixtures thereof, per alcohol molecule.
  • suitable starter alcohols are long-chain alkanols or phenols substituted with long-chain alkyl, where the long-chain alkyl radical is in particular a straight-chain or branched C 6 - to C 18 -alkyl radical.
  • Particular examples include tridecanol and nonylphenol.
  • Particularly preferred alcohol-started polyethers are the reaction products (polyetherification products) of monohydric aliphatic C 6 - to C 18 -alcohols with C 3 - to Co-alkylene oxides.
  • monohydric aliphatic C 6 -C 18 alcohols are hexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, decanol, 3-propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol and their constitutional and positional isomers.
  • the alcohols can be used either in the form of the pure isomers or in the form of technical mixtures.
  • a particularly preferred alcohol is tridecanol.
  • C 3 - to C 6 -alkylene oxides are propylene oxide, such as 1,2-propylene oxide, butylene oxide, such as 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide or tetrahydrofuran, pentylene oxide and hexylene oxide.
  • propylene oxide such as 1,2-propylene oxide
  • butylene oxide such as 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide or tetrahydrofuran
  • pentylene oxide and hexylene oxide particular preference is given to C 3 - to C 4 -alkylene oxides, ie propylene oxide such as 1,2-propylene oxide and butylene oxide such as 1,2-butylene oxide, 2,3-butylene oxide and isobutylene oxide.
  • Suitable synthetic carrier oils are alkoxylated alkyl phenols, as in the DE-A 10 102 913 are described.
  • Particular carrier oils are synthetic carrier oils, with the alcohol-started polyethers described above being particularly preferred.
  • the carrier oil or the mixture of different carrier oils is added to the fuel in an amount of preferably 1 to 1000 ppm by weight, particularly preferably 10 to 500 ppm by weight and in particular 20 to 100 ppm by weight.
  • suitable cold flow improvers are all organic compounds which are able to improve the flow behavior of middle distillate fuels or diesel fuels in the cold. Appropriately, they must have sufficient oil solubility.
  • the cold flow improvers (middle distillate flow improvers", "MDFI") usually used with middle distillates of fossil origin, ie with conventional mineral diesel fuels, come into consideration for this.
  • MDFI middle distillate flow improvers
  • WASA wax anti-settling additive
  • Suitable C 2 - to C 40 -olefin monomers for the copolymers of class (K1) are, for example, those having 2 to 20, in particular 2 to 10, carbon atoms and having 1 to 3, preferably with 1 or 2, in particular with a carbon-carbon double bond.
  • the carbon-carbon double bond can be arranged both terminally ( ⁇ -olefins) and internally.
  • ⁇ -olefins particularly preferably ⁇ -olefins having 2 to 6 carbon atoms, for example propene, 1-butene, 1-pentene, 1-hexene and especially ethylene.
  • the at least one further ethylenically unsaturated monomer is preferably selected from carboxylic acid alkenyl esters, (meth)acrylic acid esters and other olefins.
  • olefins are also polymerized, these are preferably higher molecular weight than the abovementioned C 2 - to C 40 -olefin base monomers. If, for example, ethylene or propene is used as the olefin base monomer, C 10 - to C 40 - ⁇ -olefins are particularly suitable as further olefins. In most cases, further olefins are only polymerized in if monomers with carboxylic acid ester functions are also used.
  • Suitable (meth)acrylic esters are, for example, esters of (meth)acrylic acid with C 1 - to C 20 -alkanols, in particular C 1 - to C 10 -alkanols, especially with methanol, ethanol, propanol, isopropanol, n-butanol, sec. -Butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol and decanol and structural isomers thereof.
  • Suitable carboxylic acid alkenyl esters are, for example, C 2 - to C 14 -alkenyl esters, for example the vinyl and propenyl esters, of carboxylic acids having 2 to 21 carbon atoms, the hydrocarbon radical of which can be linear or branched.
  • carboxylic acids with a branched hydrocarbon radical preference is given to those whose branching is in the ⁇ -position to the carboxyl group, the ⁇ -carbon atom particularly preferably being tertiary, ie the carboxylic acid being a so-called neocarboxylic acid.
  • the hydrocarbyl radical of the carboxylic acid is preferably linear.
  • carboxylic acid alkenyl 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, preference being given to the vinyl esters.
  • a particularly preferred carboxylic acid alkenyl ester is vinyl acetate;
  • Typical group (K1) copolymers resulting therefrom are the ethylene-vinyl acetate copolymers ("EVA”) used most frequently.
  • class (K1) copolymers are those which contain two or more different carboxylic acid alkenyl esters as copolymerized units, these differing in the alkenyl function and/or in the carboxylic acid group. Also suitable are copolymers which, in addition to the alkenyl carboxylic ester(s), contain at least one olefin and/or at least one (meth)acrylic ester as copolymerized units.
  • terpolymers of a C 2 - to C 40 - ⁇ -olefin, a C 1 - to C 20 -alkyl ester of an ethylenically unsaturated monocarboxylic acid having 3 to 15 carbon atoms and a C 2 - to C 14 -alkenyl ester of a saturated monocarboxylic acid having 2 to 21 Carbon atoms are suitable as class (K1) copolymers.
  • Such terpolymers are in the WO 2005/054314 described.
  • a typical terpolymer of this type is composed of ethylene, 2-ethylhexyl acrylate and vinyl acetate.
  • the at least one or the other ethylenically unsaturated monomers are present in the copolymers of class (K1) in an amount of preferably 1 to 50% by weight, in particular 10 to 45% by weight and above all 20 to 40% by weight. %, based on the total copolymer, polymerized.
  • the majority by weight of the monomer units in the copolymers of class (K1) thus generally comes from the C 2 - to C 40 -base olefins.
  • the class (K1) copolymers preferably have a number-average molecular weight M n of from 1000 to 20,000, particularly preferably from 1000 to 10,000 and in particular from 1000 to 8000.
  • Typical comb polymers of component (K2) are, 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 with at least 10 carbon atoms available.
  • Other suitable 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.
  • Suitable comb polymers can also be polyfumarates or polymaleates.
  • homo- and copolymers of vinyl ethers are suitable comb polymers.
  • suitable comb polymers are, for example, those in the WO 2004/035715 and in " Comb-Like Polymers. Structure and Properties", NA Plate and VP Shibaev, J. Poly. Sci. Macromolecular Revs. 8, pp. 117-253 (1974 )" are described. Mixtures of comb polymers are also suitable.
  • Polyoxyalkylenes suitable as a component of class (K3) are, for example, polyoxyalkylene esters, polyoxyalkylene ethers, mixed polyoxyalkylene ester ethers and mixtures thereof. These polyoxyalkylene compounds preferably contain at least one, preferably at least two, linear alkyl groups each having 10 to 30 carbon atoms and a polyoxyalkylene group having a number-average molecular weight of up to 5000. Such polyoxyalkylene compounds are, for example, in EP-A 061 895 as well as in the U.S. 4,491,455 described. Particular polyoxyalkylene compounds are based on polyethylene glycols and polypropylene glycols having a number-average molecular weight of 100 to 5000. Polyoxyalkylene mono- and diesters of fatty acids having 10 to 30 carbon atoms, such as stearic acid or behenic acid, are also suitable.
  • Polar nitrogen compounds suitable as a component of class (K4) can be both ionic and nonionic in nature and preferably have at least one, in particular at least two, substituents in the form of a tertiary nitrogen atom of the general formula >NR 7 , where R 7 is a C 8 - bis C 40 hydrocarbon residue.
  • the nitrogen substituents can also be quaternized, ie in cationic form. Examples of such nitrogen compounds are ammonium salts and/or amides which can be obtained by reacting at least one amine substituted by 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 - to C 40 -alkyl radical.
  • Primary amines suitable for the preparation of the polar nitrogen compounds mentioned are, for example, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologues; secondary amines suitable for this purpose are, for example, dioctadecylamine and methylbehenylamine.
  • Amine mixtures are also suitable for this purpose, in particular amine mixtures which can be obtained industrially, such as fatty amines or hydrogenated tallamines, as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, in the "Amines, aliphatic" chapter.
  • acids suitable for the reaction are 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.
  • the component of class (K4) is an oil-soluble reaction product of poly(C 2 - to C 20 -carboxylic acids) having at least one tertiary amino group with primary or secondary amines.
  • the poly(C 2 -C 20 -carboxylic acids) containing at least one tertiary amino group and on which this reaction product is based preferably contain at least 3 carboxyl groups, in particular 3 to 12, in particular 3 to 5 carboxyl groups.
  • the carboxylic acid units in the polycarboxylic acids preferably have 2 to 10 carbon atoms on, in particular there are acetic acid units.
  • the carboxylic acid units are linked in a suitable manner to form the polycarboxylic acids, usually via one or more carbon and/or nitrogen atoms. They are preferably attached to tertiary nitrogen atoms which, in the case of several nitrogen atoms, are connected via hydrocarbon chains.
  • the component of class (K4) is preferably an oil-soluble reaction product based on poly(C 2 - to C 20 -carboxylic acids) having at least one tertiary amino group and having the general formula IIa or IIb in which the variable A is a straight-chain or branched C 2 - to C 6 -alkylene group or the grouping of the formula III and the variable B denotes a C 1 to C 19 alkylene group.
  • the compounds of the general formula IIa and IIb have in particular the properties of a WASA.
  • the preferred oil-soluble reaction product of component (K4) in particular that of the general formula IIa or IIb, is an amide, an amide-ammonium salt or an ammonium salt in which none, one or more carboxylic acid groups have been converted into amide groups.
  • Straight-chain or branched C 2 - to C 6 -alkylene groups of the variable A are, for example, 1,1-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4- butylene, 2-methyl-1,3-propylene, 1,5-pentylene, 2-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene (hexamethylene) and especially 1,2-ethylene.
  • the variable A preferably comprises 2 to 4, in particular 2 or 3, carbon atoms.
  • C 1 - to C 19 -Alkylene groups of the variable B are, for example, 1,2-ethylene, 1,3-propylene, 1,4-butylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, octadecamethylene, nonadecamethylene and especially methylene .
  • the variable B preferably comprises 1 to 10, in particular 1 to 4, carbon atoms.
  • the primary and secondary amines as reaction partners for the polycarboxylic acids to form component (K4) are usually monoamines, in particular aliphatic monoamines. These primary and secondary amines can be selected from a large number of amines which carry hydrocarbon radicals, which may be bonded to one another.
  • These amines on which the oil-soluble reaction products of component (K4) are based are usually secondary amines and have the general formula HN(R 8 ) 2 , in which the two variables R 8 are each, independently of one another, straight-chain or branched C 10 - to C 30 -alkyl radicals, in particular C 14 - to C 24 -alkyl radicals. These longer-chain alkyl radicals are preferably straight-chain or only slightly branched.
  • the secondary amines mentioned are derived, with regard to their relatively long-chain alkyl radicals, from naturally occurring fatty acids or from their derivatives.
  • the two radicals R 8 are preferably the same.
  • the secondary amines mentioned can be bound to the polycarboxylic acids by means of amide structures or in the form of the ammonium salts; it is also possible for only a part to be present as amide structures and another part as ammonium salts. Preferably there are few or no free acid groups present.
  • the oil-soluble reaction products of component (K4) are preferably present entirely in the form of the amide structures.
  • Typical examples of such components (K4) are reaction products of nitrilotriacetic acid, ethylenediaminetetraacetic acid or propylene-1,2-diaminetetraacetic acid with in each case 0.5 to 1.5 mol per carboxyl group, in particular 0.8 to 1.2 mol per carboxyl group , dioleylamine, dipalmitinamine, dicoco fatty amine, distearylamine, dibehenylamine or especially ditallow fatty amine.
  • a particularly preferred component (K4) is the reaction product of 1 mole of ethylenediaminetetraacetic acid and 4 moles of hydrogenated ditallow fatty amine.
  • component (K4) are the N,N-dialkylammonium salts of 2-N',N'-dialkylamidobenzoates, for example the reaction product of 1 mole of phthalic anhydride and 2 moles of ditallow fatty amine, the latter being hydrogenated or non-hydrogenated , and the reaction product of 1 mole of an alkenylspirobislactone with 2 moles of a dialkylamine, for example ditallow fatty amine and/or tallow fatty amine, the latter two being hydrogenated or non-hydrogenated.
  • component of class (K4) are cyclic compounds with tertiary amino groups or condensates of long-chain primary or secondary amines with carboxylic acid-containing polymers, as in the WO 93/18115 are described.
  • Sulfocarboxylic acids, sulfonic acids or their derivatives suitable as cold flow improvers for the component of class (K5) are, for example, the oil-soluble carboxamides and carboxylic acid esters of ortho-sulfobenzoic acid in which the sulfonic acid function is present as a sulfonate with alkyl-substituted ammonium cations, as in EP-A 261 957 to be discribed.
  • Poly(meth)acrylic acid esters suitable as cold flow improvers of the component of class (K6) are both homo- and copolymers of acrylic and methacrylic acid esters. Copolymers of at least two different (meth)acrylic acid esters which differ in terms of the alcohol condensed in are preferred. If appropriate, the copolymer also contains another, different, olefinically unsaturated monomer as copolymerized units. 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 esters of saturated C 14 - and C 15 alcohols, wherein the acid groups are neutralized with hydrogenated tallow amine. Suitable poly (meth) acrylic acid esters are for example in WO 00/44857 described.
  • the cold flow improver or the mixture of different cold flow improvers is added to the middle distillate fuel or diesel fuel in a total amount of preferably 10 to 5000 ppm by weight, particularly preferably 20 to 2000 ppm by weight, more preferably 50 to 1000 ppm by weight and in particular from 100 to 700 ppm by weight, for example from 200 to 500 ppm by weight.
  • Suitable lubricity improvers are usually based on fatty acids or fatty acid esters. Typical examples are tall oil fatty acid, such as in WO 98/004656 described, and glycerol monooleate. Also the one in the U.S. 6,743 266 B2 reaction products described from natural or synthetic oils, for example triglycerides, and alkanolamines are suitable as such lubricity improvers.
  • Suitable corrosion inhibitors include BernsteinTexreester, in particular with polyols, fatty acid derivatives, for example ⁇ l Listereester, oligomerized fatty acids, substituted ethanol amines and products sold under the trade name RC 4801 (Rhein Chemie Mannheim, Germany), Irgacor ® L12 (BASF SE) or HiTEC 536 (Ethyl Corporation).
  • Suitable demulsifiers are, for example, the alkali metal or alkaline earth metal salts of alkyl-substituted phenol and naphthalene sulfonates and the alkali metal or alkaline earth metal salts of fatty acids, as well as neutral compounds such as alcohol alkoxylates, for example alcohol ethoxylates, phenol alkoxylates, for example tert-butylphenol ethoxylate or tert-pentylphenol ethoxylate, fatty acids, Alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), for example also in the form of EO/PO block copolymers, polyethylene imines or polysiloxanes.
  • EO ethylene oxide
  • PO propylene oxide
  • Suitable dehazers are, for example, alkoxylated phenol-formaldehyde condensates, such as the products available under the trade names NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite).
  • Suitable antifoams are, for example, polyether-modified polysiloxanes, such as the products available under the trade names TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc).
  • Suitable cetane improvers include aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate, and peroxides such as di-tert-butyl peroxide.
  • antioxidants examples include substituted phenols such as 2,6-di-tert-butylphenol and 6-di-tert-butyl-3-methylphenol and phenylenediamines such as N,N'-di-sec-butyl-p-phenylenediamine.
  • Suitable metal deactivators include salicylic acid derivatives such as N,N'-disalicylidene-1,2-propanediamine.
  • Suitable are, for example, non-polar organic solvents such as aromatic and aliphatic hydrocarbons, for example toluene, xylenes, "white spirit” and products sold under the trade names SHELLSOL (Royal Dutch/Shell Group) and EXXSOL (ExxonMobil), as well as polar organic solvents -for example alcohols such as 2-ethylhexanol, decanol and isotridecanol.
  • solvents usually get into the diesel fuel together with the aforementioned additives and co-additives, which they are supposed to dissolve or dilute for better handling.
  • the additive according to the invention is outstandingly suitable as a fuel additive and can in principle be used in any fuel. It brings about a whole range of beneficial effects when operating internal combustion engines with fuels.
  • the quaternized additive according to the invention is preferably used in middle distillate fuels, in particular diesel fuels.
  • the present invention therefore also relates to fuels, in particular middle distillate fuels, with an effective content as an additive to achieve advantageous effects in the operation of internal combustion engines, for example diesel engines, in particular direct-injection diesel engines, especially diesel engines with common-rail injection systems on the quaternized additive according to the invention.
  • This effective content (dosage rate) is generally from 10 to 5000 ppm by weight, preferably from 20 to 1500 ppm by weight, in particular from 25 to 1000 ppm by weight, in particular from 30 to 750 ppm by weight. in each case based on the total amount of fuel.
  • the use according to the invention relates to any fuel, preferably diesel and Otto fuels.
  • Middle distillate fuels such as diesel fuels or heating oils are preferably petroleum raffinates which usually have a boiling range of 100 to 400.degree. These are mostly distillates with a 95% point up to 360°C or even higher. However, this 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 maximum sulfur content 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.
  • middle distillate fuels of fossil, vegetable or animal origin which are essentially hydrocarbon mixtures
  • biofuel oils biodiesel
  • middle distillate fuel Such mixtures are encompassed by the term "middle distillate fuel”. They are commercially available and usually contain the biofuel oils in minor amounts, typically in amounts of 1 to 30% by weight, in particular 3 to 10% by weight, based on the total amount of middle distillate of fossil, vegetable or animal origin and biofuel oil.
  • Biofuel oils are typically based on fatty acid esters, preferably essentially on alkyl esters, of fatty acids derived from vegetable and/or animal oils and/or fats.
  • Alkyl esters are usually understood to mean lower alkyl esters, in particular C 1 - to C 4 -alkyl esters, which are obtained by transesterification of the glycerides occurring in vegetable and/or animal oils and/or fats, in particular triglycerides, using lower alcohols, for example ethanol or, above all, methanol (“FAME”), are available.
  • Typical lower alkyl esters based on vegetable and/or animal oils and/or fats that are used as biofuel oil or components thereof are, for example, sunflower methyl ester, palm oil methyl ester (“PME”), soybean oil methyl ester (“SME”), animal fat methyl ester (“FME”), tallow methyl ester (“TME”), methyl esters of recovered vegetable oils, recycled used cooking oils and frying fats, used vegetable oil (“UVO”), waste vegetable oil (“WVE”), used cooking oil methyl ester (“UCOME”), tall oil methyl ester and rapeseed oil methyl ester (“RME”).
  • sunflower methyl ester palm oil methyl ester
  • SME soybean oil methyl ester
  • FME animal fat methyl ester
  • TME tallow methyl ester
  • UVO used vegetable oil
  • WVE waste vegetable oil
  • UCOME used cooking oil methyl ester
  • RME tall oil methyl ester and rapeseed oil methyl ester
  • the middle distillate fuels or diesel fuels are particularly preferably those with a low sulfur content, ie 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 sulphur.
  • petrol compositions can be used as petrol.
  • the standard Eurosuper base fuel according to EN 228 should be mentioned here as a typical representative.
  • gasoline compositions are also in accordance with the specification WO 00/47698 possible areas of application for the present invention.
  • test methods mentioned below are part of the general disclosure of the application and are not limited to the specific exemplary embodiments.
  • the mass average Mw and number average molecular weight Mn of the copolymers were measured by gel permeation chromatography (GPC). GPC separation was performed using two PLge Mixed B columns (Agilent) in tetrahydrofuran at 35 °C. Calibration was carried out using a narrow-distribution polystyrene standard (PSS, Germany) with a molecular weight of 162-50400 Da. Hexylbenzene was used as a low molecular weight marker.
  • the product has a solids content of 54.3% (measured after 2 hours under vacuum at 100°C).
  • the solids content of the hydrolyzed product is 62.7% (measured after 2 hours under vacuum at 100°C).
  • a copolymer of C 20 -C 24 olefin, maleic anhydride and lauryl acrylate in a molar ratio of 0.43:0.43:0.14 was prepared as described in Synthesis Example 1 and hydrolyzed with 1.1 equivalents of deionized water (based on mol maleic anhydride).
  • the solids content of the hydrolyzed product is 57.7% (measured after 2 hours under vacuum at 100°C).
  • a copolymer of C 20 -C 24 olefin, maleic anhydride and lauryl acrylate in a molar ratio of 0.35:0.35:0.3 was prepared as described in Synthesis Example 1 and hydrolyzed with 1.1 equivalents of deionized water (based on mol maleic anhydride).
  • the solids content of the hydrolyzed product is 64.4% (measured after 2 hours under vacuum at 100°C).
  • a copolymer of C 20 -C 24 olefin, maleic anhydride and lauryl acrylate in a molar ratio of 0.4:0.4:0.2 was prepared as described in Synthesis Example 1 and hydrolyzed with 1.1 equivalents of deionized water (based on mol of maleic anhydride).
  • the solids content of the hydrolyzed product is 58.8% (measured after 2 hours under vacuum at 100°C).
  • a copolymer was prepared from C 20 -C 24 olefin, maleic anhydride and 2-ethylhexyl acrylate in a molar ratio of 0.35:0.35:0.3 and treated with 1.1 equivalents of deionized water (based on mol maleic anhydride) hydrolyzed.
  • the solids content of the hydrolyzed product is 61.2% (measured after 2 hours under vacuum at 100°C).
  • a copolymer of C 20 -C 24 olefin, maleic anhydride and 2-ethylhexyl acrylate in a molar ratio of 0.4:0.4:0.2 was prepared as described in Synthesis Example 1 and hydrolyzed with 1.1 equivalents of deionized water (based on mol maleic anhydride). .
  • the solids content of the hydrolyzed product is 58.3% (measured after 2 hours under vacuum at 100°C).
  • a copolymer of C 20 -C 24 olefin, maleic anhydride and 2-ethylhexyl acrylate in a molar ratio of 0.45:0.45:0.1 was prepared as described in Synthesis Example 1 and hydrolyzed with 1.1 equivalents of deionized water (based on mol maleic anhydride). .
  • the solids content of the hydrolyzed product is 58.3% (measured after 2 hours under vacuum at 100°C).
  • the solids content of the hydrolyzed product is 55% (measured after 2 hours under vacuum at 100°C).
  • Table 1 Polyisobutenamine* + carrier oil** [mg/kg] Solvent/ Dehazer*** [mg/kg] anti-corrosion component Rating according to NACE Formulation 1 443 47 4 mg/kg dimer fatty acid**** B/A Formulation 2 443 47 4 mg/kg Synthesis Example 1 B+ Formulation 3 443 47 4 mg/kg Synthesis Example 2 B Formulation 4 443 47 4 mg/kg Synthesis Example 3 B Formulation 5 443 47 4 mg/kg Synthesis Example 4 B+ Formulation 6 443 47 4 mg/kg reference product 1 B++ Formulation 7 443 47 4 mg/kg Synthesis Example 7 A Formulation 8 443 47 4 mg/kg Synthesis Example 6 B Formulation 9 443 47 4 mg/kg Synthesis Example 5 A * Polyisobuteneamine: commercially available polyisobuteneamine obtainable from polyisobutene having a number-average molar mass of 1000 g/mol by hydroformylation
  • 100 ml engine oil (Shell Helix ® , figure 1 and 2 , each beaker on the far left, with a Ca content of 1500 ppm, Mg content 1100 ppm and Zn content 1300 ppm) were heated to 70° C. in the beaker and then 1 ml of corrosion inhibitor was added. If the solution is still clear, add another 1 ml of inhibitor. If the solution becomes cloudy, the test is failed (e.g figure 1 and 2 , right beaker with dimer fatty acid as comparison).
  • figure 1 shows the oil, which remains clear, as the second beaker from the left, to which 2 ml of synthesis example 1 has been added.
  • 2 ml of Synthesis Example 4 was added to the oil. The oil always remains clear.
  • figure 2 shows the oil, which remains clear, as the second beaker from the left, to which 2 ml of synthesis example 2 has been added.
  • 2 ml of Synthesis Example 3 was added to the oil. The oil always remains clear.
  • Solution experiment 1 To test the solution properties, 1.600 g of the product from synthesis example 6 were placed in a 100 ml laboratory bottle at room temperature and mixed with 39.68 g of polyisobuteneamine (see Table 1), 31.2 g of a carrier oil analogous to entry 2 of Table 1 in WO 00/02978 and 7.52 g of kerosene are added.
  • Solution experiment 2 For comparison, 1.696 g of comparative product 1 were presented and 39.648 g of polyisobuteneamine (see Table 1), 31.168 g of KC 3489 and 7.488 g of kerosene were added as in solution experiment 1.

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Citations (46)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0061895A2 (fr) 1981-03-31 1982-10-06 Exxon Research And Engineering Company Additif pour améliorer l'écoulement des carburants distillés et leurs concentrats
US4491455A (en) 1982-02-10 1985-01-01 Nippon Oil And Fats Co., Ltd. Method for improving cold flow of fuel oils
WO1987001126A1 (fr) 1985-08-16 1987-02-26 The Lubrizol Corporation Produits combustibles
EP0244616A2 (fr) 1986-04-04 1987-11-11 BASF Aktiengesellschaft Polybutène et polyisobutèneamine, leur procédé de préparation et compositions de combustibles et de lubrifiants qui les contiennent
EP0261957A2 (fr) 1986-09-24 1988-03-30 Exxon Chemical Patents Inc. Compositions chimiques et usage comme additifs de combustibles
JPS63125599A (ja) * 1986-11-17 1988-05-28 Idemitsu Kosan Co Ltd 含水潤滑剤
EP0307815A1 (fr) 1987-09-15 1989-03-22 BASF Aktiengesellschaft Combustibles pour moteurs à allumage par étincelle
EP0310875A1 (fr) 1987-09-30 1989-04-12 BASF Aktiengesellschaft Combustibles contenant une polyétheramine pour moteur à allumage par étincelle
US4877416A (en) 1987-11-18 1989-10-31 Chevron Research Company Synergistic fuel compositions
DE3826608A1 (de) 1988-08-05 1990-02-08 Basf Ag Polyetheramine oder polyetheraminderivate enthaltende kraftstoffe fuer ottomotoren
DE3838918A1 (de) 1988-11-17 1990-05-23 Basf Ag Kraftstoffe fuer verbrennungsmaschinen
EP0476485A1 (fr) 1990-09-24 1992-03-25 BASF Aktiengesellschaft Polyisobutylaminoalcools et combustibles pour moteurs à combustion interne contenant ces aminoalcools à haut poids moléculaire
DE4142241A1 (de) 1991-12-20 1993-06-24 Basf Ag Kraftstoffe fuer ottomotoren
WO1993018115A1 (fr) 1992-03-03 1993-09-16 Exxon Chemical Patents Inc. Additifs pour huiles
DE4309074A1 (de) 1993-03-20 1994-09-22 Basf Ag Als Kraftstoffadditiv geeignete Mischungen
WO1994024231A1 (fr) 1993-04-22 1994-10-27 Basf Aktiengesellschaft Poly-1-n-alcenamines et compositions de carburant et de lubrifiant les contenant
EP0639632A1 (fr) 1993-08-17 1995-02-22 ÖMV Aktiengesellschaft Additif pour combustibles sans plomb pour moteurs à combustion interne à allumage par étincelle, ainsi que combustible le contenant
WO1996003479A1 (fr) 1994-07-21 1996-02-08 Basf Aktiengesellschaft Utilisation de produits de reaction de polyolefines et d'oxydes d'azote ou de melanges d'oxydes d'azote et d'oxygene en tant qu'additifs pour carburants
EP0700985A1 (fr) 1994-09-09 1996-03-13 BASF Aktiengesellschaft Combustibles, pour moteurs à allumage par etincelles, contenant des polyetheramines
WO1997003946A1 (fr) 1995-07-17 1997-02-06 Basf Aktiengesellschaft Procede de production de composes azotes organiques, de composes azotes organiques speciaux et de melanges ces composes, ainsi que leur utilisation comme additifs pour carburants et lubrifiants
DE19620262A1 (de) 1996-05-20 1997-11-27 Basf Ag Verfahren zur Herstellung von Polyalkenaminen
WO1998004656A1 (fr) 1996-07-31 1998-02-05 Elf Antar France Carburant pour moteurs diesel a faible teneur en soufre
EP0831141A1 (fr) 1996-09-05 1998-03-25 BP Chemicals (Additives) Limited Détergents pour combustibles hydrocarbures
WO1999029748A1 (fr) 1997-12-05 1999-06-17 Basf Aktiengesellschaft Procede pour produire des copolymeres d'ethylene dans des reacteurs tubulaires segmentes et utilisation de ces copolymeres comme ameliorateurs d'ecoulement
WO2000002978A1 (fr) 1998-07-09 2000-01-20 Basf Aktiengesellschaft Compositions de carburant contenant du propoxilate
WO2000044857A2 (fr) 1998-12-11 2000-08-03 Infineum Usa Lp Materiaux macromoleculaires
WO2000047698A1 (fr) 1999-02-09 2000-08-17 Basf Aktiengesellschaft Composition de carburant
DE10102913A1 (de) 2001-01-23 2002-07-25 Basf Ag Alkoxylierte Alkyphenole und deren Verwendung in Kraft- und Schmierstoffen
WO2004035715A1 (fr) 2002-10-14 2004-04-29 Basf Aktiengesellschaft Utilisation d'homopolymères d'éther vinylique hydrocarbyle pour améliorer l'effet de promoteurs d'écoulement à froid
US6743266B2 (en) 2000-03-31 2004-06-01 Texaco, Inc. Fuel additive composition for improving delivery of friction modifier
WO2005054314A2 (fr) 2003-12-04 2005-06-16 Basf Aktiengesellschaft Compositions d'huiles combustibles presentant de meilleures proprietes d'ecoulement a froid
WO2006003367A1 (fr) 2004-06-30 2006-01-12 New Transducers Limited Transducteur inertiel piezoelectrique
WO2006135881A2 (fr) 2005-06-16 2006-12-21 The Lubrizol Corporation Detergents a base de sel d'ammonium quaternaire utilisables dans des combustibles
WO2008060888A2 (fr) 2006-11-09 2008-05-22 The Lubrizol Corporation Sel d'ammonium quaternaire d'un composé amine substitué par un polyalcène
WO2009124979A1 (fr) 2008-04-10 2009-10-15 Basf Se Mélange d'alcools en c17
WO2010132259A1 (fr) 2009-05-15 2010-11-18 The Lubrizol Corporation Sels d'amide et/ou d'ester d'ammonium quaternaire
WO2011095819A1 (fr) 2010-02-05 2011-08-11 Innospec Limited Compositions de carburant
WO2011110860A1 (fr) 2010-03-10 2011-09-15 Innospec Limited Composition de carburant comprenant un additif détergent et un additif sel d'ammonium quaternaire
WO2012004300A1 (fr) 2010-07-06 2012-01-12 Basf Se Composés azotés quaternisés exempts d'acide et utilisation desdits composés comme additifs pour carburants ou pour lubrifiants
GB2496514A (en) 2011-11-11 2013-05-15 Afton Chemical Corp Fuel additive for improved performance in direct fuel injected engines
WO2013070503A1 (fr) 2011-11-11 2013-05-16 Afton Chemical Corporation Additif pour carburant pour un meilleur rendement des moteurs à injection directe du carburant
WO2014195464A1 (fr) 2013-06-07 2014-12-11 Basf Se Utilisation de composés d'azote quaternisés avec un oxyde d'alkylène et de l'acide polycarboxylique substitué par un hydrocarbyle comme additifs dans les carburants et les lubrifiants
WO2015114029A1 (fr) 2014-01-29 2015-08-06 Basf Se Inhibiteurs de corrosion pour carburants et lubrifiants
WO2015113681A1 (fr) 2014-01-29 2015-08-06 Basf Se Additifs à base d'acide polycarbonique, destinés à des carburants et à des lubrifiants
WO2017009306A1 (fr) * 2015-07-16 2017-01-19 Basf Se Inhibiteurs de corrosion pour carburants et lubrifiants
WO2018007375A1 (fr) 2016-07-07 2018-01-11 Basf Se Copolymères utilisés en tant qu'additifs pour carburants et lubrifiants

Patent Citations (49)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0061895A2 (fr) 1981-03-31 1982-10-06 Exxon Research And Engineering Company Additif pour améliorer l'écoulement des carburants distillés et leurs concentrats
US4491455A (en) 1982-02-10 1985-01-01 Nippon Oil And Fats Co., Ltd. Method for improving cold flow of fuel oils
WO1987001126A1 (fr) 1985-08-16 1987-02-26 The Lubrizol Corporation Produits combustibles
EP0244616A2 (fr) 1986-04-04 1987-11-11 BASF Aktiengesellschaft Polybutène et polyisobutèneamine, leur procédé de préparation et compositions de combustibles et de lubrifiants qui les contiennent
EP0261957A2 (fr) 1986-09-24 1988-03-30 Exxon Chemical Patents Inc. Compositions chimiques et usage comme additifs de combustibles
JPS63125599A (ja) * 1986-11-17 1988-05-28 Idemitsu Kosan Co Ltd 含水潤滑剤
EP0307815A1 (fr) 1987-09-15 1989-03-22 BASF Aktiengesellschaft Combustibles pour moteurs à allumage par étincelle
EP0310875A1 (fr) 1987-09-30 1989-04-12 BASF Aktiengesellschaft Combustibles contenant une polyétheramine pour moteur à allumage par étincelle
EP0452328A1 (fr) 1987-11-18 1991-10-23 Chevron Res & Tech Compositions de carburant synergiques.
US4877416A (en) 1987-11-18 1989-10-31 Chevron Research Company Synergistic fuel compositions
DE3826608A1 (de) 1988-08-05 1990-02-08 Basf Ag Polyetheramine oder polyetheraminderivate enthaltende kraftstoffe fuer ottomotoren
EP0356725A1 (fr) 1988-08-05 1990-03-07 BASF Aktiengesellschaft Carburants pour moteurs à allumage par étincelle contenant des polyétheramines ou des dérivés de polyétheramines
DE3838918A1 (de) 1988-11-17 1990-05-23 Basf Ag Kraftstoffe fuer verbrennungsmaschinen
EP0476485A1 (fr) 1990-09-24 1992-03-25 BASF Aktiengesellschaft Polyisobutylaminoalcools et combustibles pour moteurs à combustion interne contenant ces aminoalcools à haut poids moléculaire
EP0548617A2 (fr) 1991-12-20 1993-06-30 BASF Aktiengesellschaft Carburants pour moteurs à allumage par étincelle
DE4142241A1 (de) 1991-12-20 1993-06-24 Basf Ag Kraftstoffe fuer ottomotoren
WO1993018115A1 (fr) 1992-03-03 1993-09-16 Exxon Chemical Patents Inc. Additifs pour huiles
DE4309074A1 (de) 1993-03-20 1994-09-22 Basf Ag Als Kraftstoffadditiv geeignete Mischungen
WO1994024231A1 (fr) 1993-04-22 1994-10-27 Basf Aktiengesellschaft Poly-1-n-alcenamines et compositions de carburant et de lubrifiant les contenant
EP0639632A1 (fr) 1993-08-17 1995-02-22 ÖMV Aktiengesellschaft Additif pour combustibles sans plomb pour moteurs à combustion interne à allumage par étincelle, ainsi que combustible le contenant
WO1996003479A1 (fr) 1994-07-21 1996-02-08 Basf Aktiengesellschaft Utilisation de produits de reaction de polyolefines et d'oxydes d'azote ou de melanges d'oxydes d'azote et d'oxygene en tant qu'additifs pour carburants
EP0700985A1 (fr) 1994-09-09 1996-03-13 BASF Aktiengesellschaft Combustibles, pour moteurs à allumage par etincelles, contenant des polyetheramines
WO1997003946A1 (fr) 1995-07-17 1997-02-06 Basf Aktiengesellschaft Procede de production de composes azotes organiques, de composes azotes organiques speciaux et de melanges ces composes, ainsi que leur utilisation comme additifs pour carburants et lubrifiants
DE19620262A1 (de) 1996-05-20 1997-11-27 Basf Ag Verfahren zur Herstellung von Polyalkenaminen
WO1998004656A1 (fr) 1996-07-31 1998-02-05 Elf Antar France Carburant pour moteurs diesel a faible teneur en soufre
EP0831141A1 (fr) 1996-09-05 1998-03-25 BP Chemicals (Additives) Limited Détergents pour combustibles hydrocarbures
WO1999029748A1 (fr) 1997-12-05 1999-06-17 Basf Aktiengesellschaft Procede pour produire des copolymeres d'ethylene dans des reacteurs tubulaires segmentes et utilisation de ces copolymeres comme ameliorateurs d'ecoulement
WO2000002978A1 (fr) 1998-07-09 2000-01-20 Basf Aktiengesellschaft Compositions de carburant contenant du propoxilate
WO2000044857A2 (fr) 1998-12-11 2000-08-03 Infineum Usa Lp Materiaux macromoleculaires
WO2000047698A1 (fr) 1999-02-09 2000-08-17 Basf Aktiengesellschaft Composition de carburant
US6743266B2 (en) 2000-03-31 2004-06-01 Texaco, Inc. Fuel additive composition for improving delivery of friction modifier
DE10102913A1 (de) 2001-01-23 2002-07-25 Basf Ag Alkoxylierte Alkyphenole und deren Verwendung in Kraft- und Schmierstoffen
WO2004035715A1 (fr) 2002-10-14 2004-04-29 Basf Aktiengesellschaft Utilisation d'homopolymères d'éther vinylique hydrocarbyle pour améliorer l'effet de promoteurs d'écoulement à froid
WO2005054314A2 (fr) 2003-12-04 2005-06-16 Basf Aktiengesellschaft Compositions d'huiles combustibles presentant de meilleures proprietes d'ecoulement a froid
WO2006003367A1 (fr) 2004-06-30 2006-01-12 New Transducers Limited Transducteur inertiel piezoelectrique
WO2006135881A2 (fr) 2005-06-16 2006-12-21 The Lubrizol Corporation Detergents a base de sel d'ammonium quaternaire utilisables dans des combustibles
WO2008060888A2 (fr) 2006-11-09 2008-05-22 The Lubrizol Corporation Sel d'ammonium quaternaire d'un composé amine substitué par un polyalcène
WO2009124979A1 (fr) 2008-04-10 2009-10-15 Basf Se Mélange d'alcools en c17
WO2010132259A1 (fr) 2009-05-15 2010-11-18 The Lubrizol Corporation Sels d'amide et/ou d'ester d'ammonium quaternaire
WO2011095819A1 (fr) 2010-02-05 2011-08-11 Innospec Limited Compositions de carburant
WO2011110860A1 (fr) 2010-03-10 2011-09-15 Innospec Limited Composition de carburant comprenant un additif détergent et un additif sel d'ammonium quaternaire
WO2012004300A1 (fr) 2010-07-06 2012-01-12 Basf Se Composés azotés quaternisés exempts d'acide et utilisation desdits composés comme additifs pour carburants ou pour lubrifiants
GB2496514A (en) 2011-11-11 2013-05-15 Afton Chemical Corp Fuel additive for improved performance in direct fuel injected engines
WO2013070503A1 (fr) 2011-11-11 2013-05-16 Afton Chemical Corporation Additif pour carburant pour un meilleur rendement des moteurs à injection directe du carburant
WO2014195464A1 (fr) 2013-06-07 2014-12-11 Basf Se Utilisation de composés d'azote quaternisés avec un oxyde d'alkylène et de l'acide polycarboxylique substitué par un hydrocarbyle comme additifs dans les carburants et les lubrifiants
WO2015114029A1 (fr) 2014-01-29 2015-08-06 Basf Se Inhibiteurs de corrosion pour carburants et lubrifiants
WO2015113681A1 (fr) 2014-01-29 2015-08-06 Basf Se Additifs à base d'acide polycarbonique, destinés à des carburants et à des lubrifiants
WO2017009306A1 (fr) * 2015-07-16 2017-01-19 Basf Se Inhibiteurs de corrosion pour carburants et lubrifiants
WO2018007375A1 (fr) 2016-07-07 2018-01-11 Basf Se Copolymères utilisés en tant qu'additifs pour carburants et lubrifiants

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
N. A. PLATEV. P. SHIBAEV: "Comb-Like Polymers. Structure and Properties", J. POLY. SCI. MACROMOLECULAR REVS., vol. 8, 1974, pages 117 - 253
ULLMANN'S ENCYCLOPEDIA OF INDUSTRIAL CHEMISTRY, vol. 5, pages 617

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