WO2017016909A1 - Corrosion inhibitors for fuels and lubricants - Google Patents

Corrosion inhibitors for fuels and lubricants Download PDF

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Publication number
WO2017016909A1
WO2017016909A1 PCT/EP2016/067001 EP2016067001W WO2017016909A1 WO 2017016909 A1 WO2017016909 A1 WO 2017016909A1 EP 2016067001 W EP2016067001 W EP 2016067001W WO 2017016909 A1 WO2017016909 A1 WO 2017016909A1
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acid
use according
fuels
substituted
radicals
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PCT/EP2016/067001
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German (de)
French (fr)
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Jochen Mezger
Markus Hansch
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Basf Se
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Priority to DE212016000150.7U priority Critical patent/DE212016000150U1/en
Publication of WO2017016909A1 publication Critical patent/WO2017016909A1/en

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    • 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
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/68—Esters
    • C10M129/76—Esters containing free hydroxy or carboxyl groups
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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
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/19—Esters ester radical containing compounds; ester ethers; carbonic acid esters
    • C10L1/1905—Esters ester radical containing compounds; ester ethers; carbonic acid esters of di- or polycarboxylic acids
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    • C10L1/192—Macromolecular compounds
    • C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
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    • C10L1/00—Liquid carbonaceous fuels
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    • 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
    • C10L1/224—Amides; Imides carboxylic acid amides, imides
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    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/234—Macromolecular compounds
    • C10L1/238—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C10L1/2383—Polyamines or polyimines, or derivatives thereof (poly)amines and imines; derivatives thereof (substituted by a macromolecular group containing 30C)
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    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2406—Organic compounds containing sulfur, selenium and/or tellurium mercaptans; hydrocarbon sulfides
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    • C10L1/2462—Organic compounds containing sulfur, selenium and/or tellurium macromolecular compounds
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    • 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
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    • C10L2200/00—Components of fuel compositions
    • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
    • C10L2200/0204—Metals or alloys
    • C10L2200/0209—Group I metals: Li, Na, K, Rb, Cs, Fr, Cu, Ag, Au
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    • C10L2200/02—Inorganic or organic compounds containing atoms other than C, H or O, e.g. organic compounds containing heteroatoms or metal organic complexes
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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
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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
    • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
    • C10L2200/0446—Diesel
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    • 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
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    • C10L2270/00—Specifically adapted fuels
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/287—Partial esters
    • C10M2207/288—Partial esters containing free carboxyl groups
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    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
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    • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2215/08—Amides
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    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/085—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing carboxyl groups; Derivatives thereof
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    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
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    • 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

Definitions

  • the present invention relates to new uses of corrosion inhibitors in fuels and lubricants.
  • Corrosion inhibitors are common additives in fuels and lubricants, often based on acid-containing structures, e.g. Dimer fatty acids.
  • a disadvantage of these corrosion inhibitors is that they tend to precipitate, especially in the presence of calcium ions, and as a result their corrosion-inhibiting action is reduced.
  • the deposits formed by these precipitates may also affect the operation of engines, engine components or parts of the fuel system.
  • EP 235868 describes corrosion-inhibiting mixtures of hydrocarbon-substituted succinic acid derivatives, which are connected to one another via ring structures, and long-chain substituted polyamines.
  • the diester of polyisobutene-substituted succinic acid and pentaerythritol and its effect on steel, aluminum and brass is described.
  • This reaction product has no free carboxylic acid groups.
  • monoesters of polyvalent succinic acid derivatives are described.
  • From WO 2010/42378 are substituted with a hydrocarbon radical-containing additives having at least two carboxyl groups, which show an anticorrosive effect.
  • the carboxyl groups may be present as free acid groups or as anhydrides.
  • succinic acid derivatives substituted with polyolefins e.g. Polyisobutene succinic acid or polyisobutene succinic anhydride.
  • WO 2004/02681 1 discloses succinic hemiacamides which act as corrosion inhibitors and show good calcium compatibility.
  • R 1 and R 2 may each independently be hydrogen, C 1 - to C 20 -alkyl or C 3 - to C 200 -alkenyl, where the alkyl or alkenyl radicals are each straight-chain or branched, substituted by heteroatom-containing radicals or unsubstituted and optionally may be interrupted by heteroatoms,
  • R 3 is an n-linked, 3 to 30 carbon atoms alkylene, cycloalkylene or arylene radical, which may be straight-chain or branched, substituted or unsubstituted and optionally interrupted by heteroatoms,
  • n is a positive integer from 3 to 10
  • X may each independently be oxygen (O), sulfur (S) or unsubstituted or substituted nitrogen (NR 4 ), and
  • R 4 is hydrogen or C 1 -C 4 -alkyl, as corrosion inhibitors in fuels or lubricants, preferably in fuels, particularly preferably in fuels having a content of alkali and / or alkaline earth metals and / or zinc of at least 0.1 Gew.ppm have.
  • the compounds of formula (I) 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, more 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.
  • the compounds of the formula (I) are used in fuels which have a content of alkali metals and / or alkaline earth metals and / or zinc of at least 1 ppm by weight, more preferably at least 2 ppm by weight and very particularly preferably at least 3 ppm by weight.
  • alkali metals and / or alkaline earth metals and / or zinc exhibit their corrosion-inhibiting action even in the presence of 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 obtained, for example, by mixing with alkali and / or alkaline earth metal-containing lubricants, for example in the fuel pump.
  • alkali metals and / or alkaline earth metals may originate from unsatisfactorily or insufficiently desalted fuel additives, for example carrier oils.
  • a source of zinc for example, anti-wear additives.
  • alkali metals are sodium and potassium, in particular sodium.
  • alkaline earth metals are particularly magnesium and calcium, especially calcium.
  • the corrosion inhibitors of the formula (I) are still active in the presence of calcium and show no precipitations.
  • alkali and / or alkaline earth metals and / or zinc in each case relate to individual metal species.
  • R 1 and R 2 can each independently be hydrogen, C 1 - to C 20 -alkyl or C 3 - to C 20 -alkenyl, where the alkyl or alkenyl radicals are each straight-chain or branched, substituted by heteroatom-containing radicals or unsubstituted and optionally of Heteroatoms be interrupted,
  • R 1 and R 2 is hydrogen.
  • heteroatoms are understood oxygen, sulfur and substituted or unsubstituted nitrogen, preferably oxygen and substituted or unsubstituted nitrogen, and more preferably oxygen.
  • the C 1 - to C 20 -alkyl or C 3 - to C 20 -alkenyl radicals are not interrupted by heteroatoms, but are pure hydrocarbon radicals.
  • the alkenyl radicals have 3 to 200 carbon atoms, preferably 6 to 180, particularly preferably 8 to 150, very particularly preferably 12 to 100 and in particular 16 to 80.
  • Preferred alkenyl radicals are those which are prepared by the oligo- or polymerization of propene, 1-butene, 2-butene and / or isobutene, more preferably 1-butene, 2-butene and / or isobutene and very particularly preferably isobutene. Butene are available.
  • the alkenyl radicals are dodecenyl, hexadecenyl or polyisobutene radicals.
  • the alkyl radicals have 1 to 200 carbon atoms, preferably 12 to 180, particularly preferably 14 to 150, very particularly preferably 16 to 100 and in particular 18 to 80.
  • alkyl radicals are methyl, ethyl, n-propyl, n-propyl, n-butyl, n-octyl, n-hexyl, n-heptyl, n-octyl, n-butyl, n-butyl, n-butyl, n-butyl, n-butyl, n-butyl, n-butyl Decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl and those which are obtainable by oligo- or polymerization of ethene.
  • the alkenyl radicals are preferred over the alkyl radicals.
  • R 3 is an n-bonded, 3 to 30, preferably 3 to 20, particularly preferably 3 to 12, most preferably 3 to 6 and in particular 3 or 4 carbon atoms, alkylene, cycloalkylene or arylene radical, which each straight-chain or branched, substituted or unsubstituted and may optionally be interrupted by heteroatoms.
  • R 3 is preferably an alkylene radical which may optionally be interrupted by heteroatoms.
  • Preferred heteroatoms are oxygen atoms, in one embodiment, R 3 is an n-bonded alkylene radical having one or more, preferably one ether group.
  • the radical R 3 may be substituted in one embodiment by groups -XH, preferably by hydroxy groups.
  • the radicals R 3 are radicals which are formed by mental abstraction of n-hydroxy groups from an at least n-valent, preferably from an exactly n-valent polyol.
  • n is a positive integer from 3 to 10, preferably 3 to 6, particularly preferably 3 to 5, very particularly preferably 3 or 4 and in particular 3.
  • polyols examples include trimethylolbutane, trimethylolpropane, trimethylolethane, pentaerythritol, glycerol, ditrimethylolpropane, dipentaerythritol, sugar alcohols such as sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabitol (lyxite), xylitol, dulcitol (galactitol) ), Maltitol or isomalt.
  • sugar alcohols such as sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabitol (lyxite), xylitol, dulcitol (galactitol) ), Maltitol or isomalt.
  • the polyols may also carry additional functionalities such as ether functions (-O-), carboxyl functions (-COOH), Ci-C4-Alkyloxycarbonylfunktionen (ester groups), where C1-C4-AI- kyl in this document methyl, ethyl, / soPropyl, n-propyl, n-butyl, / sobutyl, seA "-butyl or fe -butyl, amino functions (-NH 2), mono- or di-C 1 -C 4 -alkylamino functions
  • Such functionalized polyols are ditrimethylolpropane, dipentaerythritol, polyglycerol 3, polyglycerol-4, dimethylolpropionic acid, dimethylolbutyric acid, trimethylolacetic acid, hydroxypivalic acid, sugar acids such as gluconic acid, glucaric acid, glucuronic acid, galacturonic acid or mucic acid (galact
  • Preferred polyols are trimethylolpropane, pentaerythritol, glycerol, ditrimethylolpropane, dipentaerythritol, polyglycerol-3 and polyglycerol-4, the latter being formally polyethers of glycerol of the formula HO - (- CH 2 -CHOH-CH 2 -O) x -H, where x is predominantly 3 or 4, respectively.
  • X can each independently be oxygen (O), sulfur (S) or unsubstituted or substituted nitrogen (NR 4 ), preferably oxygen (O) or unsubstituted or substituted nitrogen (NR 4 ) and more preferably oxygen.
  • X is oxygen
  • the radical R 4 in formula (I) is hydrogen or C 1 -C 4 -alkyl, preferably hydrogen or methyl and particularly preferably hydrogen.
  • Ci-C4-alkyl it is methyl, ethyl, / soPropyl, n-propyl, n-butyl, / soButyl, sea 'butyl or tert-butyl.
  • the compounds of the formula (I) are preferably obtainable by reacting a succinic acid derivative with an at least n-valent, preferably precisely n-valent polyol, amino alcohol or polyamine, preferably an exactly n-valent polyol.
  • the hydroxyl groups of the polyol are reacted on average at least 50%, preferably at least 66%, more preferably at least 75% and most preferably at least 85%. Full conversion of the hydroxy groups is not required.
  • reaction mixture obtained also contains those of the formula (II)
  • R 1 , R 2 , R 3 and n have the above meanings
  • q / n 0.5, preferably> 0.66, particularly preferably> 0.75, very particularly preferably> 0.85 and in particular 0.9.
  • the proportion of compounds of the formula (I) in the reaction mixture is at least 50% by weight, preferably at least 60, particularly preferably at least 70 and very particularly preferably at least 80% by weight.
  • the proportion of compounds of the formula (II) in the reaction mixture can be up to 50, preferably up to 40, particularly preferably up to 30, very particularly preferably up to 20 and in particular up to 15% by weight.
  • the proportion of compounds of the formula (I) and of the formula (II) in total in the reaction mixture is at least 80, preferably at least 85, particularly preferably at least 90, very particularly preferably at least 95 and in particular at least 97% by weight.
  • reaction mixture may contain oligomeric and polymeric polyesters as well as cyclic esters.
  • the formation of such by-products can preferably be counteracted by selecting the stoichiometry of succinic acid derivative: n-valent polyol in the range from 0.5 ⁇ n: 1 to n: 1, preferably from 0.66 ⁇ n: 1 to n: 1, more preferably from 0.75 * n: 1 to 0.99 ⁇ n: 1, most preferably from 0.8 * n: 1 to 0.98 ⁇ n: 1, in particular from 0.85 xn : 1 to 0.97 ⁇ n: 1, and specifically from 0.9 ⁇ n: 1 to 0.95 ⁇ n: 1.
  • the reaction is preferably conducted so that not more than half of the carboxyl groups of the succinic acid derivative used are reacted, preferably up to 49 mol%, more preferably up to 48 mol% and most preferably up to 47 mol%.
  • the succinic acid derivative is preferably dodecenylsuccinic acid, hexadecylsuccinic acid, eicosenylsuccinic acid or polyisobutene-substituted succinic acid derivatives, it being possible for the polyisobutene radical to have an average molecular weight of 300 to 2000, preferably 400 to 1500 and more preferably 500 to 1200 g / mol.
  • the use according to the invention relates to the inhibition of the corrosion of iron, steel and / or non-ferrous metal surfaces.
  • non-ferrous metals copper and its alloys are preferred.
  • the corrosion of steel surfaces is inhibited.
  • the compounds of the formula (I) are added to fuels having the above-specified content of alkali and / or alkaline earth metals and / or zinc, generally in amounts of 1 to 60, preferably 10 to 40, ppm by weight.
  • these are primarily conventional detergent additives, carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors other than those of the formula (I), demulsifiers, dehazers, antifoams, cetane number improvers, combustion improvers, antioxidants or Stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and / or solvents.
  • the usual detergent additives are preferably amphiphilic substances which have at least one hydrophobic hydrocarbon radical having a number-average molecular weight (M n ) of from 85 to 20 000 and at least one polar group selected from: (Da) mono- or polyamino groups having up to 6 nitrogen atoms, wherein at least one nitrogen atom has basic properties;
  • Polyamino groups wherein at least one nitrogen atom has basic properties, or terminated by carbamate groups;
  • the hydrophobic hydrocarbon radical in the above detergent additives which provides sufficient solubility in the fuel has a number average molecular weight (M n ) of from 85 to 20,000, preferably from 1 13 to 10,000, more preferably from 300 to 5,000, more preferably from 300 up to 3,000, more preferably from 500 to 2,500 and especially from 700 to 2,500, especially from 800 to 1,500.
  • M n number average molecular weight
  • hydrophobic hydrocarbon radical in particular in combination with the polar, in particular polypropenyl, polybutenyl and polyisobutenyl radicals having a number average molecular weight M n of preferably in each case from 300 to 5,000, particularly preferably from 300 to 3,000, more preferably from 500 to 2,500, even more preferably from 700 to 2,500 and in particular from 800 to 1,500 into consideration.
  • M n number average molecular weight of n of preferably in each case from 300 to 5,000, particularly preferably from 300 to 3,000, more preferably from 500 to 2,500, even more preferably from 700 to 2,500 and in particular from 800 to 1,500 into consideration.
  • Such additives based on highly reactive polyisobutene which may contain from the polyisobutene, which may contain up to 20% by weight of n-butene units,
  • monoamines or polyamines such as dimethyl-aminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine can be prepared, are known in particular from EP-A 244 616.
  • the preparation route is afforded by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to carbonyl - or carboxyl compound and subsequent amination under reductive (hydrogenating) conditions.
  • amines such as. As ammonia, monoamines or the above polyamines, are used.
  • Corresponding additives based on polypropene are described in particular in WO-A 94/24231.
  • these reaction products are mixtures of pure nitropolyisobutenes (for example ⁇ , ⁇ -dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (for example ⁇ -nitro- ⁇ -hydroxy-polyisobutene).
  • Hydroxyl groups in combination with mono- or polyamino groups cf.
  • Carboxyl groups or their alkali metal or alkaline earth metal salts (Dd) containing additives are preferably copolymers of C2 to C 4 o-olefins with maleic anhydride having a total molecular weight of 500 to 20,000, their carboxyl groups wholly or partly to the alkali metal or alkaline earth metal salts and a remaining radical of the carboxyl groups are reacted with alcohols or amines.
  • Such additives are known in particular from EP-A 307 815.
  • Such additives are mainly used to prevent valve seat wear and can, as described in WO-A 87/01 126, be used with advantage in combination with conventional fuel detergents such as poly (iso) -butene amines or polyetheramines.
  • Sulfonic acid groups or their alkali metal or alkaline earth metal salts (De) containing additives are preferably alkali metal or alkaline earth metal salts of a Sulfobernsteinklakylesters, as described in particular in EP-A 639 632.
  • Such additives are primarily for preventing valve seat wear and can be used to advantage in combination with conventional fuel detergents such as poly (iso) buteneamines or polyetheramines.
  • Polyoxy-C2-C4-alkylene (Df) containing additives are preferably polyether or polyetheramines which by reaction of C2 to C6o-alkanols, C6 to C3o-alkanediols, mono- or D1-C2 to C3o-alkylamines, C to C3o-alkylcyclo-hexanols or C to C30-alkyl- kylphenolen with 1 to 30 moles of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyether amines, by subsequent reductive amination with ammonia, monoamines or polyamines are available , Such products are described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4,877,416.
  • polyethers such products also meet carrier oil properties.
  • Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and Polyisobutenolbutoxylate and propoxylates and the corresponding reaction products with ammonia.
  • Carboxyl ester groups (Dg) -containing additives are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, especially those having a minimum viscosity of 2 mm 2 / s at 100 ° C, as described in particular in DE-A 38 38 918 are described.
  • mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable ester alcohols or polyols are long-chain representatives having, for example, 6 to 24 C atoms.
  • esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of iso-octanol, iso-nonanol, iso-decanol and of isotridecanol. Such products also meet carrier oil properties.
  • the groups having hydroxyl and / or amino and / or amido and / or imido groups are, for example, carboxylic acid groups, acid amides of monoamines, acid amides of diioder polyamines which, in addition to the amide function, still have free amine groups, succinic acid groups. red derivatives with an acid and an amide function, carboximides with monoamines, carboximides with di- or polyamines which, in addition to the imide function, still have free amine groups, or diimides which are formed by reacting di- or polyamines with two succinic acid derivatives.
  • Such fuel additives are well known and described, for example, in documents (1) and (2).
  • reaction products of alkyl- or alkenyl-substituted succinic acids or derivatives thereof with amines and particularly preferably to the reaction products of polyisobutenyl-substituted succinic acids or derivatives thereof with amines.
  • reaction products with aliphatic polyamines polyalkyleneimines
  • ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine which have an imide structure.
  • Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated moieties containing (di) additives are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine ,
  • Such "polyisobutene-Mannich bases" are described in particular in EP-A 831 141.
  • One or more of said detergent additives may be added to the fuel in such an amount that the metering rate of these detergent additives is preferably from 25 to 2500 ppm by weight, in particular from 75 to 1500 ppm by weight, especially from 150 to 1000% by weight . ppm. B2) carrier oils
  • Co-used carrier oils may be mineral or synthetic.
  • Suitable mineral carrier oils are fractions obtained in petroleum processing, such as bright stock or base oils with viscosities such as from class SN 500 to 2000, but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. It is also useful as a "hydrocrack oil” known and obtained in the refining of mineral oil fraction (Vakuumdestillatites with a boiling range of about 360 to 500 ° C, available from high pressure catalytically hydrogenated and isomerized and dewaxed natural mineral oil). Also suitable are mixtures of the abovementioned mineral carrier oils.
  • suitable synthetic carrier oils are polyolefins (polyalphaolefins or polyinteralolefins), (poly) esters, poly) alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-initiated polyethers, alkylphenol-initiated 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 prepared by reacting C 2 - to C 6 -alkanols, C 6 - to C 3 0 -alkanediols, mono- or C 1 - to C 2 - Alkylaminen, Cr to C3o-alkyl-cyclohexanols or Cr to C30-alkylphenols with 1 to 30 moles of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by subsequent reductive amination with ammonia , Monoamines or polyamines are available.
  • Such products are described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4,877,416.
  • polyetheramines polyC 2 to C 6 alkylene oxide amines or functional derivatives thereof can be used. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate 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, as described in particular in DE-A 38 38 918.
  • mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable ester alcohols or polyols are long-chain representatives having, for example, 6 to 24 carbon atoms.
  • suitable representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and of isotridecanol, eg. B. di- (n- or isotridecyl) phthalate.
  • 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 C3 to C6 alkylene oxide units, for.
  • suitable starter alcohols are long-chain alkanols or long-chain alkyl-substituted phenols, where the long-chain alkyl radical is in particular a straight-chain or branched C 6 - to C 18 -alkyl radical.
  • Specific examples include tridecanol and nonylphenol.
  • Particularly preferred alcohol-started polyethers are the reaction products (polyetherification products) of monohydric C6- to Cis-aliphatic alcohols with C3- to C6-alkylene oxides.
  • monohydric aliphatic C6-C18-alcohols are hexanol, heptanol, octanol, 2-ethyl-hexanol, nonyl alcohol, decanol, 3-propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol and their constitution and position isomers.
  • the alcohols can be used both in the form of pure isomers and in the form of technical mixtures.
  • a particularly preferred alcohol is tridecanol.
  • C3 to C6 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.
  • Particularly important Preferred among these are 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.
  • butylene oxide is used.
  • Further suitable synthetic carrier oils are alkoxylated alkylphenols, as described in DE-A 10 102 913.
  • carrier oils are synthetic carrier oils, the alkohol-based 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 from 1 to 1000 ppm by weight, more preferably from 10 to 500 ppm by weight and in particular from 20 to 100 ppm by weight.
  • Suitable cold flow improvers are in principle all organic compounds which are able to improve the flow behavior of middle distillate fuels or diesel fuels in the cold. Conveniently, they must have sufficient oil solubility. In particular, this is the usually used for middle distillates of fossil origin, ie for conventional mineral diesel fuels, used cold flow improvers ("middle distillate flow improvers", "MDFI"). However, it is also possible to use organic compounds which, when used in conventional diesel fuels, have in part or predominantly the properties of a wax anti-settling additive ("WASA"). Also, they can act partly or predominantly as nucleators. However, it is also possible to use mixtures of organic compounds which are active as MDFI and / or which act as WASA and / or as nucleators.
  • WASA wax anti-settling additive
  • the cold flow improver is selected from:
  • Suitable C 2 - to C 4 -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 1 or 2, in particular a carbon-carbon double pelitati. In the latter case, 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, above all, ethylene.
  • the at least one further ethylenically unsaturated monomer is preferably selected from carboxylic alkenyl esters, (meth) acrylic esters and further olefins.
  • further olefins are polymerized in, these are preferably higher molecular weight than the abovementioned C 2 - to C 4 -olefin base monomers. If, for example, ethylene or propene is used as the olefin basic monomer, suitable further olefins are, in particular, C 10 -C 40 -olefins. Other olefins are polymerized in most cases only when monomers with carboxylic acid ester functions are used.
  • Suitable (meth) acrylic esters are, for example, esters of (meth) acrylic acid with C 2 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 alkenyl esters are, for example, C2 to C-u-alkenyl esters, e.g. the vinyl and propenyl esters, of carboxylic acids having 2 to 21 carbon atoms, whose hydrocarbon radical may be linear or branched. Preferred among these are the vinyl esters.
  • carboxylic acids having a branched hydrocarbon radical preferred are those whose branch 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.
  • carboxylic 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, the vinyl esters being preferred.
  • a particularly preferred carboxylic acid alkenyl ester is vinyl acetate; typical resulting copolymers of group (K1) are the most commonly used ethylene-vinyl acetate copolymers ("EVA").
  • Suitable copolymers of the class (K1) are also those which contain two or more different carboxylic acid alkenyl esters in copolymerized form, these being in the Alken- nylfunktion and / or in the carboxylic acid group differ. Also suitable are copolymers which, in addition to the carboxylic acid alkenyl ester (s), contain at least one olefin and / or at least one (meth) acrylic acid ester in copolymerized form.
  • terpolymers of a C2 to C4o- ⁇ -olefin, a Cr to C2o-alkyl ester of an ethylenically unsaturated monocarboxylic acid having 3 to 15 carbon atoms and a C2 to C-alkenyl ester of a saturated monocarboxylic acid having 2 to 21 carbon atoms are copolymers of the Class (K1) suitable.
  • Such terpolymers are described in WO 2005/054314.
  • a typical such terpolymer is made up 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 from 1 to 50% by weight, in particular from 10 to 45% by weight and especially from 20 to 40% by weight .-%, based on the total copolymer, copolymerized.
  • the majority by weight of the monomer units in the copolymers of class (K1) thus usually comes from the C2 to C4o-based olefins.
  • the copolymers of class (K1) 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 available with at least 10 carbon atoms.
  • Further 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 may also be polyfumarates or polymaleinates.
  • homo- and copolymers of vinyl ethers are suitable comb polymers.
  • Comb polymers suitable as component of class (K2) are, for example, those described in WO 2004/035715 and in "Comb-Like Polymers, Structure and Properties", N.A. Plate and V.P. Shibaev, J. Poly. Be. Macromolecular Revs. 8, pages 1 17 to 253 (1974). "Mixtures of comb polymers are also suitable.
  • Polyoxyalkylenes suitable as component of class (K3) are, for example, polyoxyalkylene esters, polyoxyalkylene ethers, mixed polyoxyalkylene ester ethers and mixtures thereof. These polyoxyalkylene compounds preferably comprise at least one, preferably at least two, linear alkyl groups each having from 10 to 30 carbon atoms and a polyoxyalkylene group having a number average molecular weight of up to 5,000. Such polyoxyalkylene compounds are described, for example, in EP-A 061 895 and in US Pat. No. 4,491,455 described. Particular polyoxyalkylene compounds are based on polyethylene glycols and polypropylene glycols having a number average molecular weight of 100 to 5,000. Polyoxyalkylene mono- and diesters of fatty acids having 10 to 30 carbon atoms, such as stearic acid or behenic acid, are furthermore suitable.
  • Polar nitrogen compounds suitable as a component of class (K4) may be of both ionic and nonionic nature, and preferably have at least one, especially at least two, tertiary nitrogen substituent of the general formula> NR 7 , wherein R 7 is Cs to C 40 Hydrocarbon residue stands.
  • the nitrogen substituents may also be quaternized, ie in cationic form. Examples 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 contain at least one linear Cs to C4o-alkyl radical.
  • Primary amines suitable for the preparation of said polar nitrogen compounds are, for example, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologues
  • suitable secondary amines for this purpose 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 U-Mannesmann's Encyclopedia of Industrial Chemistry, 6th edition, in the 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.
  • the component of class (K4) is an oil-soluble reaction product of at least one tertiary amino group-containing poly (C 2 - to C 20 -carboxylic acids) with primary or secondary amines.
  • the poly (C 2 - to C 20 -carboxylic acids) which have at least one tertiary amino group and are based on this reaction product preferably contain at least 3 carboxyl groups, in particular 3 to 12, especially 3 to 5, carboxyl groups.
  • the carboxylic acid units in the polycarboxylic acids preferably have 2 to 10 carbon atoms, in particular they are acetic acid units.
  • the carboxylic acid units are suitably linked to the polycarboxylic acids, usually via one or more carbon and / or nitrogen atoms. Preferably, they are attached to tertiary nitrogen atoms, which are connected in the case of several nitrogen atoms via hydrocarbon chains.
  • the component of the class (K4) is preferably an oil-soluble reaction product based on poly (C 2 - to C 20 -carboxylic acids) having the general formula IIa or IIb and having at least one tertiary amino group H00C-o "OOH
  • 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 general formula IIa or IIb, is an amide, an amide ammonium salt or an ammonium salt in which no, one or more carboxylic acid groups are 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 ethylene, 2-methyl-1,3-propylene, 1, 5-pentylene, 2-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene ( Hexamethylene) and in particular 1, 2-ethylene.
  • the variable A comprises 2 to 4, in particular 2 or 3 carbon atoms.
  • C 1 to C 12 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 in particular methylene.
  • the variable B 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 the component (K4) are usually monoamines, in particular aliphatic monoamines. These primary and secondary amines may be selected from a variety of amines bearing hydrocarbon radicals, optionally linked together.
  • amines which are the oil-soluble reaction products of component (K4) are secondary amines and have the general formula HN (R 8 ) 2 , in which the two variables R 8 are each independently straight-chain or branched C 10 - to C 30 -alkyl radicals, in particular C to C24 alkyl radicals. These longer-chain alkyl radicals are preferably straight-chain or only slightly branched.
  • the abovementioned secondary amines are derived, with regard to their longer-chain alkyl radicals, from naturally occurring fatty acids or from their derivatives.
  • the two radicals R 8 are the same.
  • the abovementioned secondary amines can be bound to the polycarboxylic acids by means of amide structures or in the form of the ammonium salts, and only one part can be present as amide structures and another part as ammonium salts. Preferably, only a few or no free acid groups are present. Preferably, the oil-soluble reaction products of component (K4) are completely 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 in particular Ditaigfettamin.
  • a particularly preferred component (K4) is the reaction product of 1 mole of ethylenediaminetetraacetic acid and 4 moles of hydrogenated dithiol fatty amine.
  • component (K4) include 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 diethfamine, the latter being hydrogenated or unhydrogenated may be, and the reaction product of 1 mole of a Alkenylspirobislactons with 2 moles of a dialkylamine, for example, Ditaigfettamin and / or Taigfettamin, the latter two may be hydrogenated or unhydrogenated, called.
  • N, N-dialkylammonium salts of 2-N ', N'-dialkylamidobenzoates for example the reaction product of 1 mole of phthalic anhydride and 2 moles of diethfamine, the latter being hydrogenated or unhydrogenated may be, and the reaction product of 1 mole of a Alkenylspirobislactons with 2 moles of a dialkylamine, for example, Ditai
  • Sulfocarboxylic acids, sulfonic acids or their derivatives which are suitable as cold flow improvers of the component of the 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 sulfonate with alkyl-substituted ammonium cations, as described in EP-A 261 957 are described.
  • suitable poly (meth) acrylic acid esters 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.
  • 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.
  • a particularly preferred polymer is a copolymer of methacrylic acid and methacrylic acid esters of saturated Cu and Cis alcohols, wherein the acid groups with hydrogenated tallamine are neutralized.
  • Suitable poly (meth) acrylic esters are described, for example, in WO 00/44857.
  • the middle distillate fuel or diesel fuel is the cold flow improver or the mixture of various cold flow improvers in a total amount of preferably 10 to 5000 ppm by weight, more preferably from 20 to 2000 ppm by weight, more preferably from 50 to 1000 wt. ppm and in particular from 100 to 700 ppm by weight, eg from 200 to 500 ppm by weight, added.
  • Suitable lubricity improvers are usually based on fatty acids or fatty acid esters. Typical examples are tall oil fatty acid, as described for example in WO 98/004656, and glycerol monooleate.
  • the reaction products of natural or synthetic oils, for example triglycerides, and alkanolamines described in US Pat. No. 6,743,266 B2 are also suitable as such lubricity improvers.
  • Suitable corrosion inhibitors are e.g. Succinic esters, especially with polyols, fatty acid derivatives, e.g. Oleic acid esters, oligomerized fatty acids, substituted ethanolamines and products sold under the trade name RC 4801 (Rhein Chemie Mannheim, Germany), Irgacor® L12 (BASF SE) or HiTEC 536 (Ethyl Corporation).
  • RC 4801 Rhein Chemie Mannheim, Germany
  • Irgacor® L12 BASF SE
  • HiTEC 536 Ethyl Corporation
  • Suitable demulsifiers are e.g. the alkali or alkaline earth salts of alkyl-substituted phenol and naphthalene sulfonates and the alkali or alkaline earth salts of fatty acids, as well as neutral compounds such as alcohol alkoxylates, e.g. Alcohol ethoxylates, phenol alkoxylates, e.g. tert-butyl phenol ethoxylate or tert-pentyl phenol ethoxylate, fatty acids, alkyl phenols, condensation points of ethylene oxide (EO) and propylene oxide (PO), e.g. also in the form of EO / PO block copolymers, polyethyleneimines or else polysiloxanes.
  • EO ethylene oxide
  • PO propylene oxide
  • Suitable dehazers are e.g. alkoxylated phenol-formaldehyde condensates, such as the NALCO 7D07 (Nalco) and TOLAD 2683 (Porrolite) products available under the tradename.
  • alkoxylated phenol-formaldehyde condensates such as the NALCO 7D07 (Nalco) and TOLAD 2683 (Porrolite) products available under the tradename.
  • antifoam Suitable anti-foaming agents are, for example, polyether-modified polysiloxanes, such as, for example, the products available under the trade name TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc).
  • TEGOPREN 5851 Goldschmidt
  • Q 25907 Low Corning
  • RHODOSIL Rasterosol
  • Suitable cetane number improvers are e.g. aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate, and peroxides such as di-tert-butyl peroxide.
  • aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate
  • peroxides such as di-tert-butyl peroxide.
  • Suitable antioxidants are e.g. 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.
  • B1 Metal deactivators
  • Suitable metal deactivators are e.g. Salicylic acid derivatives such as N, N'-disalicylidene-1,2-propanediamine.
  • Suitable ones are e.g. nonpolar organic solvents such as aromatic and aliphatic hydrocarbons, for example toluene, xylenes, "white spirit” and products marketed under the trade name SHELLSOL (Royal Dutch / Shell Group) and EXXSOL (ExxonMobil), as well as polar organic solvents.
  • nonpolar organic solvents such as aromatic and aliphatic hydrocarbons, for example toluene, xylenes, "white spirit” and products marketed under the trade name SHELLSOL (Royal Dutch / Shell Group) and EXXSOL (ExxonMobil), as well as polar organic solvents.
  • alcohols such as 2-ethylhexanol, decanol and isotridecanol.
  • solvents usually arrive together with the aforementioned additives and co-additives which they are intended to dissolve or dilute for better handling into the diesel fuel.
  • C) fuels such as 2-ethylhe
  • Middle distillate fuels such as diesel fuels or fuel oils
  • these may 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 wt .-% or by a 95% point of for example, 285 ° C and a maximum sulfur content of 0.001 wt .-%.
  • Fuels or diesel fuels are also those obtainable by coal gasification or gas-to-liquid (GTL) fuels or by biomass to liquid (BT L) fuels. Also suitable are mixtures of the abovementioned middle distillate fuels or diesel fuels with regenerative fuels, such as biodiesel or bioethanol.
  • 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 wt .-%, in particular from 3 to 10 wt .-%, based on the total amount of middle distillate fossil, vegetable or animal origin and biofuel.
  • Biofuel oils are generally based on fatty acid esters, preferably substantially on alkyl esters of fatty acids derived from vegetable and / or animal oils and / or fats.
  • Alkyl esters are usually lower alkyl esters, especially C 1 to C 4 alkyl esters, understood by transesterification of occurring in vegetable and / or animal oils and / or fats glycerides, especially triglycerides, by means of lower alcohols, for example ethanol or especially methanol ( "FAME”) are available.
  • Typical lower alkyl esters based on vegetable and / or animal oils and / or fats which are used as biofuel oil or components thereof include, for example, sunflower methyl ester, palm oil methyl ester ("PME”), soybean oil methyl ester (“SME”) and in particular rapeseed oil methyl ester (“RME”).
  • 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 as 0.005 wt .-% and especially less than 0.001 wt .-% sulfur.
  • gasoline fuels are all commercially available gasoline fuel compositions into consideration.
  • a typical representative here is the market-standard basic fuel of Eurosuper according to EN 228. Furthermore, gasoline compositions of the specification according to WO 00/47698 are also possible fields of use for the present invention. The following examples are intended to illustrate the present invention without limiting it. Examples
  • Tetrapropenylsuccinic anhydride (CAS 26544-38-7) having a saponification number of 332.6 mg KOH / g from Aldrich.
  • Polyglycerol-3 (CAS 25618-55-7) with an OH number of 1 173 mg KOH / g from Solvay. Trimethylolpropane from BASF.
  • Polyisobutenyl succinic anhydride (PIBSA): Prepared from maleic anhydride and polyisobutene with a mean molecular weight MN of about 1000 in a known manner. For the following preparation examples according to the invention 2 different grades were used: "PIBSA 1" with a saponification number of 87 mg KOH / g and a Bismalein istsgrad of 1 1, 6%. "PIBSA 2" with a saponification number of 1 12.5 mg KOH / g and a bis-maleination level of 31, 8%.
  • tetrapropenyl succinic anhydride (215.8 g) was added dropwise to a solution of polyglycerol-3 (170 g) in Solvent Naphtha ND (385.8 g) at 80 ° C.
  • the reaction mixture was stirred for 6 h at temperatures between 80 ° C and 130 ° C, wherein the temperature was successively increased by 10 ° C after every 1 h.
  • the product was obtained as a 50% solution in Solvent Naphtha ND.
  • the fuel used was commercial Otto EO CEC RF-12-09 from Garrmann and additized with an additive package of polyisobutenamine, carrier oil, dehazer and solvent.
  • To formulate the corrosion inhibitors indicated in Table 2 were added and subjected to a corrosion test according to ASTM D 665 B.
  • FIG. 1 shows from left to right Shell Helix® (without additive) or mixed with in each case 2 ml of corrosion inhibitor from Synthesis Example 1, Synthesis Example 2 and Synthesis Example 3. The contents of the beakers remain clear.

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Abstract

The invention relates to novel uses of corrosion inhibitors in fuels and lubricants.

Description

Korrosionsinhibitoren für Kraft- und Schmierstoffe Beschreibung  Corrosion inhibitors for fuels and lubricants Description
Die vorliegende Erfindung betrifft neue Verwendungen von Korrosionsinhibitoren in Kraft- und Schmierstoffen. The present invention relates to new uses of corrosion inhibitors in fuels and lubricants.
Korrosionsinhibitoren sind gängige Additive in Kraft- und Schmierstoffen, die oftmals auf säure- gruppenhaltigen Strukturen beruhen, z.B. Dimerfettsäuren. Corrosion inhibitors are common additives in fuels and lubricants, often based on acid-containing structures, e.g. Dimer fatty acids.
Nachteilig an diesen Korrosionsinhibitoren ist, daß sie insbesondere in Gegenwart von Calcium- lonen zu Ausfällungen neigen und dadurch ihre korrosionsinhibierende Wirkung vermindert wird. Die durch diese Ausfällungen gebildeten Ablagerungen können darüber hinaus die Funkti- onsweise von Motoren, Motorbestandteilen oder Teilen des Kraftstoff Systems beeinträchtigen. A disadvantage of these corrosion inhibitors is that they tend to precipitate, especially in the presence of calcium ions, and as a result their corrosion-inhibiting action is reduced. The deposits formed by these precipitates may also affect the operation of engines, engine components or parts of the fuel system.
Es bestand daher die Aufgabe, Korrosionsinhibitoren zur Verfügung zu stellen, die eine erhöhte Verträglichkeit gegen Calcium-Ionen zeigen und dabei ihre Wirkung als Korrosionsinhibitor behalten. It was therefore an object to provide corrosion inhibitors are available, which show an increased compatibility with calcium ions and thereby retain their effect as a corrosion inhibitor.
Die Aufgabe wird gelöst durch die anspruchsgemäße Verwendung. The problem is solved by the claimed use.
Aus US 31 17091 sind Umsetzungsprodukte von Ce - C15 - alkyl- und alkenylsubstituierten Bernsteinsäurederivaten mit Diolen bekannt und deren Verwendung zur korrosionsverhindern- der und -vermindernder Zusatz in Kraftstoffen gegenüber Eisen- und Stahloberflächen. US 3291736 beschreibt die gleichen Verbindungen für Schmierstoffe. Reaction products of Ce - C15 - alkyl- and alkenyl-substituted succinic acid derivatives with diols are known from US Pat. No. 3,191,091 and their use for corrosion-inhibiting and reducing addition in fuels to iron and steel surfaces. US 3291736 describes the same compounds for lubricants.
EP 235868 beschreibt korrosionsinhibierende Mischungen aus kohlenwasserstoffsubstituierten Bernsteinsäurederivaten, die über Ringstrukturen miteinander verbunden sind und langkettig substituierten Polyaminen. Beispielhaft wird der Diester aus Polyisobuten-substituierter Bernsteinsäure und Pentaerythrit und dessen Wirkung auf Stahl, Aluminium und Messing beschrieben. Dieses Umsetzungsprodukt weist keine freien Carbonsäuregruppen auf. Weiterhin werden Monoester von mehrwertigen Bernsteinsäurederivaten beschrieben. Aus WO 2010/42378 sind mit einem Kohlenwasserstoffrest substituierte Additive mit mindestens zwei Carboxylgruppen bekannt, die eine antikorrosive Wirkung zeigen. Die Carboxylgrup- pen können dabei als freie Säuregruppen oder als Anhydride vorliegen. EP 235868 describes corrosion-inhibiting mixtures of hydrocarbon-substituted succinic acid derivatives, which are connected to one another via ring structures, and long-chain substituted polyamines. By way of example, the diester of polyisobutene-substituted succinic acid and pentaerythritol and its effect on steel, aluminum and brass is described. This reaction product has no free carboxylic acid groups. Furthermore, monoesters of polyvalent succinic acid derivatives are described. From WO 2010/42378 are substituted with a hydrocarbon radical-containing additives having at least two carboxyl groups, which show an anticorrosive effect. The carboxyl groups may be present as free acid groups or as anhydrides.
Dabei handelt es sich um mit Polyolefinen substitutierte Bernsteinsäurederivate, z.B. Polyisobu- tenbernsteinsäure oder Polyisobutenbernsteinsäureanhydrid. These are succinic acid derivatives substituted with polyolefins, e.g. Polyisobutene succinic acid or polyisobutene succinic anhydride.
Aus keiner dieser Schriften geht hervor, daß die erfindungsgemäßen Korrosionsinhibitoren eine erhöhte Verträglichkeit gegen Calcium-Ionen aufweisen. Aus WO 2004/ 02681 1 sind Bernsteinsäurehalbamide bekannt, die als Korrosionsinhibitoren wirken und eine gute Calciumverträglichkeit zeigen. None of these documents shows that the corrosion inhibitors according to the invention have an increased compatibility with calcium ions. WO 2004/02681 1 discloses succinic hemiacamides which act as corrosion inhibitors and show good calcium compatibility.
Jedoch gibt diese Schrift keinen Hinweis auf die anspruchsgemäßen Verbindungen. However, this document gives no indication of the claimed compounds.
A) Korrosionsinhibitoren A) corrosion inhibitors
Demgemäß ist Gegenstand der Erfindung die Verwendung von Verbindungen der Formel (I) Accordingly, the subject of the invention is the use of compounds of the formula (I)
Figure imgf000003_0001
worin
Figure imgf000003_0001
wherein
R1 und R2, jeweils unabhängig voneinander Wasserstoff, d- bis C2oo-Alkyl oder C3- bis C200-AI- kenyl sein können, wobei die Alkyl- oder Alkenylreste jeweils geradkettig oder verzweigt, mit Heteroatom-haltigen Resten substituiert oder unsubstituiert und optional von Heteroatomen unterbrochen sein können, R 1 and R 2 may each independently be hydrogen, C 1 - to C 20 -alkyl or C 3 - to C 200 -alkenyl, where the alkyl or alkenyl radicals are each straight-chain or branched, substituted by heteroatom-containing radicals or unsubstituted and optionally may be interrupted by heteroatoms,
mit der Maßgabe, daß einer der Reste R1 und R2 Wasserstoff ist, with the proviso that one of R 1 and R 2 is hydrogen,
R3 ein n-bindiger, 3 bis 30 Kohlenstoffatome aufweisender Alkylen, Cycloalkylen oder Arylenrest ist, der jeweils geradkettig oder verzweigt, substituiert oder unsubstituiert und optional von Heteroatomen unterbrochen sein kann, R 3 is an n-linked, 3 to 30 carbon atoms alkylene, cycloalkylene or arylene radical, which may be straight-chain or branched, substituted or unsubstituted and optionally interrupted by heteroatoms,
n eine positive ganze Zahl von 3 bis 10, n is a positive integer from 3 to 10,
X jeweils unabhängig voneinander Sauerstoff (O), Schwefel (S) oder unsubstituierter oder substituierter Stickstoff (NR4) sein können und X may each independently be oxygen (O), sulfur (S) or unsubstituted or substituted nitrogen (NR 4 ), and
R4 Wasserstoff oder Ci-C4-Alkyl bedeuten, als Korrosionsinhibitoren in Kraft- oder Schmierstoffen, bevorzugt in Kraftstoffen, besonders be- vorzugt in Kraftstoffen, die einen Gehalt an Alkali- und/oder Erdalkalimetallen und/oder Zink von mindestens 0,1 Gew.ppm aufweisen. R 4 is hydrogen or C 1 -C 4 -alkyl, as corrosion inhibitors in fuels or lubricants, preferably in fuels, particularly preferably in fuels having a content of alkali and / or alkaline earth metals and / or zinc of at least 0.1 Gew.ppm have.
Die Verbindungen der Formel (I) zeigen einen besonderen Vorteil in Kraft- oder Schmierstoffen, besonders in Kraftstoffen, die einen Gehalt an Alkali- und/oder Erdalkalimetallen und/oder Zink von mindestens 0,1 Gew.ppm aufweisen, besonders bevorzugt mindestens 0,2 Gew.ppm, ganz besonders bevorzugt mindestens 0,3 Gew.ppm und insbesondere mindestens 0,5 Gew.ppm. The compounds of formula (I) 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, more 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.
Mit besonderem Vorteil werden die Verbindungen der Formel (I) verwendet in Kraftstoffen, die einen Gehalt an Alkali- und/oder Erdalkalimetallen und/oder Zink von mindestens 1 Gew.ppm aufweisen, besonders bevorzugt mindestens 2 Gew.ppm und ganz besonders bevorzugt mindestens 3 Gew.ppm. With particular advantage, the compounds of the formula (I) are used in fuels which have a content of alkali metals and / or alkaline earth metals and / or zinc of at least 1 ppm by weight, more preferably at least 2 ppm by weight and very particularly preferably at least 3 ppm by weight.
Es stellt einen Vorteil der Korrosionsinhibitoren der Formel (I) dar, daß sie ihre korrosionsinhi- bierende Wirkung auch in Gegenwart von Alkali- und/oder Erdalkalimetallen und/oder Zink zeigen, bevorzugt auch in Gegenwart von Erdalkalimetallen. Der Gehalt an Alkali- und/oder Erdalkalimetallen in Kraftstoffen rührt beispielsweise her durch Vermischung mit Alkali- und/oder Erdalkalimetallen-haltigen Schmierstoffen, beispielsweise in der Kraftstoffpumpe. Ferner können Alkali- und/oder Erdalkalimetalle aus nicht oder unzureichend entsalzten Kraftstoffadditiven stammen, beispielsweise Trägerölen. Durch das Einschleppen von Alkali- und/oder Erdalkalimetallen in die Kraftstoffe können die oben genannten Nachteile hervorgerufen werden. Eine Quelle für Zink sind beispielsweise anti-wear Additive. It is an advantage of the corrosion inhibitors of the formula (I) that they exhibit their corrosion-inhibiting action even in the presence of 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 obtained, for example, by mixing with alkali and / or alkaline earth metal-containing lubricants, for example in the fuel pump. Furthermore, alkali metals and / or alkaline earth metals may originate from unsatisfactorily or insufficiently desalted fuel additives, for example carrier oils. By entraining alkali and / or alkaline earth metals in the fuels, the above-mentioned disadvantages can be caused. A source of zinc, for example, anti-wear additives.
Als Alkalimetalle zu nennen sind besonders Natrium und Kalium, insbesondere Natrium. Particular examples of alkali metals are sodium and potassium, in particular sodium.
Als Erdalkalimetalle zu nennen sind besonders Magnesium und Calcium, insbesondere Calcium. As alkaline earth metals are particularly magnesium and calcium, especially calcium.
Ferner ist Zink hervorzuheben Furthermore, zinc should be emphasized
Mit besonderem Vorteil sind die Korrosionsinhibitoren der Formel (I) auch in Gegenwart von Calcium noch aktiv und zeigen keine Ausfällungen. With particular advantage, the corrosion inhibitors of the formula (I) are still active in the presence of calcium and show no precipitations.
Die angegebenen Mengen an Alkali- und/oder Erdalkalimetallen und/oder Zink beziehen sich dabei jeweils auf einzelne Metallspezies. The stated amounts of alkali and / or alkaline earth metals and / or zinc in each case relate to individual metal species.
In der obigen Formel (I) haben die angegebenen Reste folgende Bedeutung: In the above formula (I), the radicals indicated have the following meanings:
R1 und R2 können jeweils unabhängig voneinander Wasserstoff, d- bis C2oo-Alkyl oder C3- bis C2oo-Alkenyl sein, wobei die Alkyl- oder Alkenylreste jeweils geradkettig oder verzweigt, mit He- teroatom-haltigen Resten substituiert oder unsubstituiert und optional von Heteroatomen unterbrochen sein, R 1 and R 2 can each independently be hydrogen, C 1 - to C 20 -alkyl or C 3 - to C 20 -alkenyl, where the alkyl or alkenyl radicals are each straight-chain or branched, substituted by heteroatom-containing radicals or unsubstituted and optionally of Heteroatoms be interrupted,
mit der Maßgabe, daß einer der Reste R1 und R2 Wasserstoff ist. Als Heteroatome werden dabei Sauerstoff, Schwefel und substituierter oder unsubstituierter Stickstoff verstanden, bevorzugt Sauerstoff und substituierter oder unsubstituierter Stickstoff und besonders bevorzugt Sauerstoff. In einer bevorzugten Ausführungsform sind die d- bis C2oo-Alkyl- oder C3- bis C2oo-Alkenylreste nicht durch Heteroatome unterbrochen, sondern es handelt sich um reine Kohlenwasserstoffreste. Die Alkenylreste weisen 3 bis 200 Kohlenstoffatome auf, bevorzugt 6 bis 180, besonders bevorzugt 8 bis 150, ganz besonders bevorzugt 12 bis 100 und insbesondere 16 bis 80. with the proviso that one of R 1 and R 2 is hydrogen. As heteroatoms are understood oxygen, sulfur and substituted or unsubstituted nitrogen, preferably oxygen and substituted or unsubstituted nitrogen, and more preferably oxygen. In a preferred embodiment, the C 1 - to C 20 -alkyl or C 3 - to C 20 -alkenyl radicals are not interrupted by heteroatoms, but are pure hydrocarbon radicals. The alkenyl radicals have 3 to 200 carbon atoms, preferably 6 to 180, particularly preferably 8 to 150, very particularly preferably 12 to 100 and in particular 16 to 80.
Bevorzugte Alkenylreste sind solche, die durch Oligo- oder Polymerisation von Propen, 1 -Buten, 2-Buten und/oder iso-Buten, besonders bevorzugt 1 -Buten, 2-Buten und/oder iso-Buten und ganz besonders bevorzugt von iso-Buten erhältlich sind. Preferred alkenyl radicals are those which are prepared by the oligo- or polymerization of propene, 1-butene, 2-butene and / or isobutene, more preferably 1-butene, 2-butene and / or isobutene and very particularly preferably isobutene. Butene are available.
In einer bevorzugten Ausführungsform handelt es sich bei den Alkenylresten um Dodecenyl-, Hexadecenyl- oder Polyisobutenreste. Die Alkylreste weisen 1 bis 200 Kohlenstoffatome auf, bevorzugt 12 bis 180, besonders bevorzugt 14 bis 150, ganz besonders bevorzugt 16 bis 100 und insbesondere 18 bis 80. In a preferred embodiment, the alkenyl radicals are dodecenyl, hexadecenyl or polyisobutene radicals. The alkyl radicals have 1 to 200 carbon atoms, preferably 12 to 180, particularly preferably 14 to 150, very particularly preferably 16 to 100 and in particular 18 to 80.
Beispiele für die Alkylreste sind Methyl, Ethyl, /so-Propyl, n-Propyl, n-Butyl, /so-Butyl, seA"-Butyl, fe -Butyl, n-Hexyl, n-Heptyl, n-Octyl, n-Decyl, n-Dodecyl, n-Tetradecyl, n-Hexadecyl, n-Octade- cyl, n-Eicosyl sowie solche, die durch Oligo- oder Polymerisation von Ethen erhältlich sind. Examples of the alkyl radicals are methyl, ethyl, n-propyl, n-propyl, n-butyl, n-octyl, n-hexyl, n-heptyl, n-octyl, n-butyl, n-butyl, n-butyl, n-butyl, n-butyl, n-butyl Decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl, n-eicosyl and those which are obtainable by oligo- or polymerization of ethene.
Die Alkenylreste sind gegenüber den Alkylresten bevorzugt. The alkenyl radicals are preferred over the alkyl radicals.
In der Formel (I) stellt R3 einen n-bindigen, 3 bis 30, bevorzugt 3 bis 20, besonders bevorzugt 3 bis 12, ganz besonders bevorzugt 3 bis 6 und insbesondere 3 oder 4 Kohlenstoffatome aufweisenden Alkylen, Cycloalkylen oder Arylenrest dar, der jeweils geradkettig oder verzweigt, substituiert oder unsubstituiert und optional von Heteroatomen unterbrochen sein kann. Bevorzugt handelt es sich bei R3 um einen Alkylenrest, der optional von Heteroatomen unterbrochen sein kann. Bevorzugte Heteroatome sind Sauerstoffatome, in einer Ausführungsform handelt es sich bei R3 um einen n-bindigen Alkylenrest, der eine oder mehrere, bevorzugt eine Ethergruppe aufweist. In the formula (I), R 3 is an n-bonded, 3 to 30, preferably 3 to 20, particularly preferably 3 to 12, most preferably 3 to 6 and in particular 3 or 4 carbon atoms, alkylene, cycloalkylene or arylene radical, which each straight-chain or branched, substituted or unsubstituted and may optionally be interrupted by heteroatoms. R 3 is preferably an alkylene radical which may optionally be interrupted by heteroatoms. Preferred heteroatoms are oxygen atoms, in one embodiment, R 3 is an n-bonded alkylene radical having one or more, preferably one ether group.
Der Rest R3 kann in einer Ausführungsform substituiert sein durch Gruppen -XH, bevorzugt durch Hydroxygruppen. The radical R 3 may be substituted in one embodiment by groups -XH, preferably by hydroxy groups.
In einer bevorzugten Ausführungsform handelt es sich bei den Resten R3 um solche Reste, die durch gedankliche Abstraktion von n Hydroxygruppen aus einem mindestens n-wertigen, bevorzugt aus einem genau n-wertigen Polyol entstehen. n ist darin eine positive ganze Zahl von 3 bis 10, bevorzugt 3 bis 6, besonders bevorzugt 3 bis 5, ganz besonders bevorzugt 3 oder 4 und insbesondere 3. Beispiele für derartige Polyole sind Trimethylolbutan, Trimethylolpropan, Trimethylolethan, Pen- taerythrit, Glycerin, Ditrimethylolpropan, Dipentaerythrit, Zuckeralkohole wie Sorbit, Mannit, Digly- cerol, Threit, Erythrit, Adonit (Ribit), Arabit (Lyxit), Xylit, Dulcit (Galactit), Maltit oder Isomalt. Die Polyole können auch noch zusätzliche Funktionalitäten tragen wie z.B. Etherfunktionen (-0-), Carboxylfunktionen (-COOH), Ci-C4-Alkyloxycarbonylfunktionen (Estergruppen), wobei C1-C4-AI- kyl in dieser Schrift Methyl, Ethyl, /soPropyl, n-Propyl, n-Butyl, /soButyl, seA"-Butyl oder fe -Butyl bedeutet, Aminofunktionen (-NH2), Mono- oder Di-Ci-C4-Alkylaminofunktionen. Beispiele für solche funktionalisierten Polyole sind Ditrimethylolpropan, Dipentaerythrit, Polyglycerol-3, Polyglycerol-4, Dimethylolpropionsäure, Dimethylolbuttersäure, Trimethylolessigsäure, Hydroxypivalin- säure, Zuckersäuren wie Gluconsäure, Glucarsäure, Glucuronsäure, Galacturonsäure oder Schleimsäure (Galactarsäure), Diethanolamin, Triethanolamin oder N-Methyl-Diethanolamin. In a preferred embodiment, the radicals R 3 are radicals which are formed by mental abstraction of n-hydroxy groups from an at least n-valent, preferably from an exactly n-valent polyol. n is a positive integer from 3 to 10, preferably 3 to 6, particularly preferably 3 to 5, very particularly preferably 3 or 4 and in particular 3. Examples of such polyols are trimethylolbutane, trimethylolpropane, trimethylolethane, pentaerythritol, glycerol, ditrimethylolpropane, dipentaerythritol, sugar alcohols such as sorbitol, mannitol, diglycerol, threitol, erythritol, adonite (ribitol), arabitol (lyxite), xylitol, dulcitol (galactitol) ), Maltitol or isomalt. The polyols may also carry additional functionalities such as ether functions (-O-), carboxyl functions (-COOH), Ci-C4-Alkyloxycarbonylfunktionen (ester groups), where C1-C4-AI- kyl in this document methyl, ethyl, / soPropyl, n-propyl, n-butyl, / sobutyl, seA "-butyl or fe -butyl, amino functions (-NH 2), mono- or di-C 1 -C 4 -alkylamino functions Examples of such functionalized polyols are ditrimethylolpropane, dipentaerythritol, polyglycerol 3, polyglycerol-4, dimethylolpropionic acid, dimethylolbutyric acid, trimethylolacetic acid, hydroxypivalic acid, sugar acids such as gluconic acid, glucaric acid, glucuronic acid, galacturonic acid or mucic acid (galactaric acid), diethanolamine, triethanolamine or N-methyl-diethanolamine.
Bevorzugte Polyole sind Trimethylolpropan, Pentaerythrit, Glycerin, Ditrimethylolpropan, Dipentaerythrit, Polyglycerol-3 und Polyglycerol-4, wobei es sich bei letzteren formal um Polyether von Glycerin der Formel HO-(-CH2-CHOH-CH2-0)x-H handelt, worin x überwiegend 3 bzw. 4 bedeuten. Preferred polyols are trimethylolpropane, pentaerythritol, glycerol, ditrimethylolpropane, dipentaerythritol, polyglycerol-3 and polyglycerol-4, the latter being formally polyethers of glycerol of the formula HO - (- CH 2 -CHOH-CH 2 -O) x -H, where x is predominantly 3 or 4, respectively.
X können jeweils unabhängig voneinander Sauerstoff (O), Schwefel (S) oder unsubstituierter oder substituierter Stickstoff (NR4) sein, bevorzugt Sauerstoff (O) oder unsubstituierter oder substituierter Stickstoff (NR4) und besonders bevorzugt Sauerstoff. X can each independently be oxygen (O), sulfur (S) or unsubstituted or substituted nitrogen (NR 4 ), preferably oxygen (O) or unsubstituted or substituted nitrogen (NR 4 ) and more preferably oxygen.
In einer bevorzugten Ausführungsform is X Sauerstoff. In a preferred embodiment, X is oxygen.
Der Rest R4 in Formel (I) ist Wasserstoff oder Ci-C4-Alkyl, bevorzugt Wasserstoff oder Methyl und besonders bevorzugt Wasserstoff. The radical R 4 in formula (I) is hydrogen or C 1 -C 4 -alkyl, preferably hydrogen or methyl and particularly preferably hydrogen.
Ci-C4-Alkyl bedeutet dabei Methyl, Ethyl, /soPropyl, n-Propyl, n-Butyl, /soButyl, seA'-Butyl oder fert-Butyl. Bevorzugt sind die Verbindungen der Formel (I) erhältlich durch Umsetzung eines Bernsteinsäurederivats mit einem mindestens n-wertigen, bevorzugt genau n-wertigen Polyol, Aminoal- kohol oder Polyamin, bevorzugt einem genau n-wertigen Polyol. Ci-C4-alkyl it is methyl, ethyl, / soPropyl, n-propyl, n-butyl, / soButyl, sea 'butyl or tert-butyl. The compounds of the formula (I) are preferably obtainable by reacting a succinic acid derivative with an at least n-valent, preferably precisely n-valent polyol, amino alcohol or polyamine, preferably an exactly n-valent polyol.
In einer bevorzugten Ausführungsform werden die Hydroxygruppen des Polyols dabei im Mittel zu mindestens 50%, bevorzugt zu mindestens 66%, besonders bevorzugt zu mindestens 75% und ganz besonders bevorzugt zu mindestens 85% umgesetzt. Ein Vollumsatz der Hydroxygruppen ist dabei nicht erforderlich. In a preferred embodiment, the hydroxyl groups of the polyol are reacted on average at least 50%, preferably at least 66%, more preferably at least 75% and most preferably at least 85%. Full conversion of the hydroxy groups is not required.
In diesem Fall enthält das erhaltene Reaktionsgemisch neben Verbindungen der obigen Formel (I) auch solche der Formel (II) In this case, in addition to compounds of the above formula (I), the reaction mixture obtained also contains those of the formula (II)
Figure imgf000007_0001
worin
Figure imgf000007_0001
wherein
p und q unabhängig voneinander positive rationale Zahlen sind, die im statistischen Mittel auch nicht ganzzahlig sein können, p and q are, independently of each other, positive rational numbers, which can not be even in statistical terms,
mit der Maßgabe, daß p + q = n gilt, with the proviso that p + q = n,
R1, R2, R3 und n die obigen Bedeutungen haben R 1 , R 2 , R 3 and n have the above meanings
und and
q/n > 0,5, bevorzugt > 0,66, besonders bevorzugt > 0,75, ganz besonders bevorzugt > 0,85 und insbesondere ä 0,9. q / n> 0.5, preferably> 0.66, particularly preferably> 0.75, very particularly preferably> 0.85 and in particular 0.9.
Der Anteil von Verbindungen der Formel (I) im Reaktionsgemisch beträgt mindestens 50 Gew%, bevorzugt mindestens 60, besonders bevorzugt mindestens 70 und ganz besonders bevorzugt mindestens 80 Gew%. The proportion of compounds of the formula (I) in the reaction mixture is at least 50% by weight, preferably at least 60, particularly preferably at least 70 and very particularly preferably at least 80% by weight.
Der Anteil von Verbindungen der Formel (II) im Reaktionsgemisch kann bis zu 50, bevorzugt bis zu 40, besonders bevorzugt bis zu 30, ganz besonders bevorzugt bis zu 20 und insbesondere bis zu 15 Gew% betragen. Der Anteil von Verbindungen der Formel (I) und der Formel (II) in Summe im Reaktionsgemisch beträgt mindestens 80, bevorzugt mindestens 85, besonders bevorzugt mindestens 90, ganz besonders bevorzugt mindestens 95 und insbesondere mindestens 97 Gew%. The proportion of compounds of the formula (II) in the reaction mixture can be up to 50, preferably up to 40, particularly preferably up to 30, very particularly preferably up to 20 and in particular up to 15% by weight. The proportion of compounds of the formula (I) and of the formula (II) in total in the reaction mixture is at least 80, preferably at least 85, particularly preferably at least 90, very particularly preferably at least 95 and in particular at least 97% by weight.
In untergeordneten Mengen kann das Reaktionsgemisch oligomere und polymere Polyester so- wie cyclische Ester enthalten. In minor amounts, the reaction mixture may contain oligomeric and polymeric polyesters as well as cyclic esters.
Der Bildung derartiger Nebenprodukte kann man einerseits bevorzugt dadurch entgegenwirken, daß man in der Herstellung die Stöchiometrie von Bernsteinsäurederivat : n-wertigem Polyol im Bereich von 0,5 χ n : 1 bis n : 1 wählt, bevorzugt von 0,66 χ n : 1 bis n : 1 , besonders bevorzugt von 0,75 * n : 1 bis 0,99 χ n : 1 , ganz besonders bevorzugt von 0,8 * n : 1 bis 0,98 χ n : 1 , insbesondere von 0,85 x n : 1 bis 0,97 χ n : 1 und speziell von 0,9 χ n : 1 bis 0,95 χ n : 1 . On the one hand, the formation of such by-products can preferably be counteracted by selecting the stoichiometry of succinic acid derivative: n-valent polyol in the range from 0.5 χ n: 1 to n: 1, preferably from 0.66 χ n: 1 to n: 1, more preferably from 0.75 * n: 1 to 0.99 χ n: 1, most preferably from 0.8 * n: 1 to 0.98 χ n: 1, in particular from 0.85 xn : 1 to 0.97 χ n: 1, and specifically from 0.9 χ n: 1 to 0.95 χ n: 1.
Andererseits wird die Reaktion bevorzugt so geführt, daß nicht mehr als die Hälfte der Car- boxylgruppen des eingesetzten Bernsteinsäurederivats umgesetzt werden, bevorzugt bis zu 49 mol%, besonders bevorzugt bis zu 48 mol% und ganz besonders bevorzugt bis zu 47 mol%. Bei dem Bernsteinsäurederivat handelt es sich bevorzugt um Dodecenylbernsteinsäure, Hexa- decenylbernsteinsäure, Eicosenylbernsteinsäure oder um Polyisobuten-substituierte Bernsteinsäurederivate, wobei der Polyisobutenrest ein mittleres Molgewicht von 300 bis 2000, bevorzugt 400 bis 1500 und besonders bevorzugt 500 bis 1200 g/mol aufweisen kann. On the other hand, the reaction is preferably conducted so that not more than half of the carboxyl groups of the succinic acid derivative used are reacted, preferably up to 49 mol%, more preferably up to 48 mol% and most preferably up to 47 mol%. The succinic acid derivative is preferably dodecenylsuccinic acid, hexadecylsuccinic acid, eicosenylsuccinic acid or polyisobutene-substituted succinic acid derivatives, it being possible for the polyisobutene radical to have an average molecular weight of 300 to 2000, preferably 400 to 1500 and more preferably 500 to 1200 g / mol.
Die erfindungsgemäße Verwendung betrifft die Inhibierung der Korrosion von Eisen-, Stahl- und/oder Buntmetalloberflächen. Unter den Buntmetallen sind dabei Kupfer und dessen Legierungen bevorzugt. The use according to the invention relates to the inhibition of the corrosion of iron, steel and / or non-ferrous metal surfaces. Of the non-ferrous metals, copper and its alloys are preferred.
Besonders bevorzugt wird die Korrosion von Stahloberflächen inhibiert. Particularly preferably, the corrosion of steel surfaces is inhibited.
Die Verbindungen der Formel (I) werden Kraftstoffen mit dem oben spezifizierten Gehalt an Al- kali- und/oder Erdalkalimetallen und/oder Zink in der Regel in Mengen von 1 bis 60, bevorzugt 10 bis 40 Gew. ppm zugesetzt. The compounds of the formula (I) are added to fuels having the above-specified content of alkali and / or alkaline earth metals and / or zinc, generally in amounts of 1 to 60, preferably 10 to 40, ppm by weight.
B) Weitere Additive Häufig werden die Verbindungen der Formel (I) in Form von Kraftstoffadditivgemischen eingesetzt, zusammen mit üblichen Additiven: B) Further Additives Frequently, the compounds of the formula (I) are used in the form of fuel additive mixtures, together with customary additives:
Im Falle von Dieselkraftstoffen sind dies in erster Linie übliche Detergenz-Additive, Trägeröle, Kaltfließverbesserer, Schmierfähigkeitsverbesserer (Lubricity Improver), anderen Korrosionsinhi- bitoren als solchen der Formel (I), Demulgatoren, Dehazer, Antischaummittel, Cetanzahlverbes- serer, Verbrennungsverbesserer, Antioxidantien oder Stabilisatoren, Antistatika, Metallocene, Metalldeaktivatoren, Farbstoffe und/oder Lösungsmittel. In the case of diesel fuels, these are primarily conventional detergent additives, carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors other than those of the formula (I), demulsifiers, dehazers, antifoams, cetane number improvers, combustion improvers, antioxidants or Stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and / or solvents.
Im Falle von Ottokraftstoffen sind dies vor allem Schmierfähigkeitsverbesserer (Friction Modifier), anderen Korrosionsinhibitoren als solchen der Formel (I), Demulgatoren, Dehazer, Antischaummittel, Verbrennungsverbesserer, Antioxidantien oder Stabilisatoren, Antistatika, Metallocene, Metalldeaktivatoren, Farbstoffe und/oder Lösungsmittel. In the case of gasoline fuels, these are mainly friction modifiers, corrosion inhibitors other than those of the formula (I), demulsifiers, dehazers, antifoams, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and / or solvents.
Typische Beispiele geeigneter Co-Additive sind im folgenden Abschnitt aufgeführt: Typical examples of suitable co-additives are listed in the following section:
B1 ) Detergenz-Additive B1) Detergent additives
Vorzugsweise handelt es sich bei den üblichen Detergenz-Additiven um amphiphile Substanzen, die mindestens einen hydrophoben Kohlenwasserstoffrest mit einem zahlengemittelten Moleku- largewicht (Mn) von 85 bis 20.000 und mindestens eine polare Gruppierung besitzen, die ausgewählt ist unter: (Da) Mono- oder Polyaminogruppen mit bis zu 6 Stickstoffatomen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat; The usual detergent additives are preferably amphiphilic substances which have at least one hydrophobic hydrocarbon radical having a number-average molecular weight (M n ) of from 85 to 20 000 and at least one polar group selected from: (Da) mono- or polyamino groups having up to 6 nitrogen atoms, wherein at least one nitrogen atom has basic properties;
(Db) Nitrogruppen, gegebenenfalls in Kombination mit Hydroxylgruppen; (Db) nitro groups, optionally in combination with hydroxyl groups;
(De) Hydroxylgruppen in Kombination mit Mono- oder Polyaminogruppen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat; (De) hydroxyl groups in combination with mono- or polyamino groups, wherein at least one nitrogen atom has basic properties;
(Dd) Carboxylgruppen oder deren Alkalimetall- oder Erdalkalimetallsalzen; (Dd) carboxyl groups or their alkali metal or alkaline earth metal salts;
(De) Sulfonsäuregruppen oder deren Alkalimetall- oder Erdalkalimetallsalzen; (De) sulfonic acid groups or their alkali metal or alkaline earth metal salts;
(Df) Polyoxy-C2- bis C4-alkylengruppierungen, die durch Hydroxylgruppen, Mono- oder(Df) polyoxy-C2 to C4 alkylene groups represented by hydroxyl groups, mono- or
Polyaminogruppen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat, oder durch Carbamatgruppen terminiert sind; Polyamino groups, wherein at least one nitrogen atom has basic properties, or terminated by carbamate groups;
(Dg) Carbonsäureestergruppen; (Dg) carboxylic acid ester groups;
(Dh) aus Bernsteinsäureanhydrid abgeleiteten Gruppierungen mit Hydroxy- und/oder Amino- und/oder Amido- und/oder Imidogruppen; und/oder (Ie) derived from succinic anhydride moieties having hydroxy and / or amino and / or amido and / or imido groups; and or
(Di) durch Mannich-Umsetzung von substituierten Phenolen mit Aldehyden und Mono- oder Polyaminen erzeugten Gruppierungen. Der hydrophobe Kohlenwasserstoffrest in den obigen Detergenz-Additiven, welcher für die ausreichende Löslichkeit im Kraftstoff sorgt, hat ein zahlengemitteltes Molekulargewicht (Mn) von 85 bis 20.000, vorzugsweise von 1 13 bis 10.000, besonders bevorzugt von 300 bis 5.000, stärker bevorzugt von 300 bis 3.000, noch stärker bevorzugt von 500 bis 2.500 und insbesondere von 700 bis 2.500, vor allem von 800 bis 1500. Als typischer hydrophober Kohlenwasserstoffrest, insbesondere in Verbindung mit den polaren insbesondere Polypropenyl-, Polybutenyl- und Po- lyisobutenylreste mit einem zahlenmittleren Molekulargewicht Mn von vorzugsweise jeweils 300 bis 5.000, besonders bevorzugt 300 bis 3.000, stärker bevorzugt 500 bis 2.500 noch stärker bevorzugt 700 bis 2.500 und insbesondere 800 bis 1.500 in Betracht. Als Beispiele für obige Gruppen von Detergenz-Additiven seien die folgenden genannt: (Di) by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated groupings. The hydrophobic hydrocarbon radical in the above detergent additives which provides sufficient solubility in the fuel has a number average molecular weight (M n ) of from 85 to 20,000, preferably from 1 13 to 10,000, more preferably from 300 to 5,000, more preferably from 300 up to 3,000, more preferably from 500 to 2,500 and especially from 700 to 2,500, especially from 800 to 1,500. As typical hydrophobic hydrocarbon radical, in particular in combination with the polar, in particular polypropenyl, polybutenyl and polyisobutenyl radicals having a number average molecular weight M n of preferably in each case from 300 to 5,000, particularly preferably from 300 to 3,000, more preferably from 500 to 2,500, even more preferably from 700 to 2,500 and in particular from 800 to 1,500 into consideration. As examples of the above groups of detergent additives, the following are mentioned:
Mono- oder Polyaminogruppen (Da) enthaltende Additive sind vorzugsweise Polyalkenmono- o- der Polyalkenpolyamine auf Basis von Polypropen oder von hochreaktivem (d.h. mit überwiegend endständigen Doppelbindungen) oder konventionellem (d.h. mit überwiegend mittenständigen Doppelbindungen) Polybuten oder Polyisobuten mit Mn = 300 bis 5000, besonders bevorzugt 500 bis 2500 und insbesondere 700 bis 2500. Derartige Additive auf Basis von hochreaktivem Polyisobuten, welche aus dem Polyisobuten, das bis zu 20 Gew.-% n-Buten-Einheiten enthalten kann, durch Hydroformylierung und reduktive Aminierung mit Ammoniak, Monoaminen oder Polyami- nen wie Dimethyl-aminopropylamin, Ethylendiamin, Diethylentriamin, Triethylentetramin oder Tetraethylenpentamin hergestellt werden können, sind insbesondere aus der EP-A 244 616 bekannt. Geht man bei der Herstellung der Additive von Polybuten oder Polyisobuten mit überwie- gend mittenständigen Doppelbindungen (meist in der ß- und γ-Position) aus, bietet sich der Herstellweg durch Chlorierung und anschließende Aminierung oder durch Oxidation der Doppelbindung mit Luft oder Ozon zur Carbonyl- oder Carboxylverbindung und anschließende Aminierung unter reduktiven (hydrierenden) Bedingungen an. Zur Aminierung können hier Amine, wie z. B. Ammoniak, Monoamine oder die oben genannten Polyamine, eingesetzt werden. Entsprechende Additive auf Basis von Polypropen sind insbesondere in der WO-A 94/24231 beschrieben. Mono- or polyamino (Da) -containing additives are preferably polyalkylene mono- or polyalkene polyamines based on polypropene or of highly reactive (ie predominantly terminal double bonds) or conventional (ie predominantly intermediate double bonds) polybutene or polyisobutene having M n = 300 to 5000 , particularly preferably 500 to 2500 and in particular 700 to 2500. Such additives based on highly reactive polyisobutene, which may contain from the polyisobutene, which may 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, are known in particular from EP-A 244 616. If one starts with the preparation of the additives of polybutene or polyisobutene with predominantly intermediate double bonds (usually in the β and γ position), the preparation route is afforded by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to carbonyl - or carboxyl compound and subsequent amination under reductive (hydrogenating) conditions. For amination here amines, such as. As ammonia, monoamines or the above polyamines, are used. Corresponding additives based on polypropene are described in particular in WO-A 94/24231.
Weitere besondere Monoaminogruppen (Da) enthaltende Additive sind die Hydrierungsprodukte der Umsetzungsprodukte aus Polyisobutenen mit einem mittleren Polymerisationsgrad P = 5 bis 100 mit Stickoxiden oder Gemischen aus Stickoxiden und Sauerstoff, wie sie insbesondere in der WO-A 97/03946 beschrieben sind. Other particular monoamino (Da) containing additives are the hydrogenation of the reaction products of polyisobutenes having an average degree of polymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A 97/03946.
Weitere besondere Monoaminogruppen (Da) enthaltende Additive sind die aus Poly-isobutenepo- xiden durch Umsetzung mit Aminen und nachfolgender Dehydratisierung und Reduktion der Ami- noalkohole erhältlichen Verbindungen, wie sie insbesondere in der DE-A 196 20 262 beschrieben sind. Other particular monoamino (Da) -containing additives are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent dehydration and reduction of the amino alcohols, as described in particular in DE-A 196 20 262.
Nitrogruppen (Db), gegebenenfalls in Kombination mit Hydroxylgruppen, enthaltende Additive sind vorzugsweise Umsetzungsprodukte aus Polyisobutenen des mittleren Polymerisationsgrades P = 5 bis 100 oder 10 bis 100 mit Stickoxiden oder Gemischen aus Stickoxiden und Sauer- Stoff, wie sie insbesondere in der WO-A96/03367 und in der WO-A 96/03479 beschrieben sind. Diese Umsetzungsprodukte stellen in der Regel Mischungen aus reinen Nitropolyisobutenen (z. B. α,β-Dinitropolyisobuten) und gemischten Hydroxynitropolyisobutenen (z. B. a-Nitro-ß-hydroxy- polyisobuten) dar. Hydroxylgruppen in Kombination mit Mono- oder Polyaminogruppen (De) enthaltende Additive sind insbesondere Umsetzungsprodukte von Polyisobutenepoxiden, erhältlich aus vorzugsweise überwiegend endständige Doppelbindungen aufweisendem Polyisobuten mit Mn = 300 bis 5000 mit Ammoniak, Mono- oder Polyaminen, wie sie insbeson-dere in der EP-A 476 485 beschrieben sind. Nitro groups (Db), optionally in combination with hydroxyl groups, containing additives are preferably reaction products of polyisobutenes of average degree of polymerization P = 5 to 100 or 10 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A96 / 03367 and in WO-A 96/03479 are described. As a rule, these reaction products are mixtures of pure nitropolyisobutenes (for example α, β-dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (for example α-nitro-β-hydroxy-polyisobutene). Hydroxyl groups in combination with mono- or polyamino groups (cf. De) containing additives are in particular reaction products of polyisobutene, obtainable from preferably predominantly terminal double bonds having polyisobutene with M n = 300 to 5000 with ammonia, mono- or polyamines, as described in particular in EP-A 476 485.
Carboxylgruppen oder deren Alkalimetall- oder Erdalkalimetallsalze (Dd) enthaltende Additive sind vorzugsweise Copolymere von C2- bis C4o-Olefinen mit Maleinsäureanhydrid mit einer Ge- samt-Molmasse von 500 bis 20.000, deren Carboxylgruppen ganz oder teilweise zu den Alkalimetall- oder Erdalkalimetallsalzen und ein verbleibender Rest der Carboxylgruppen mit Alkoholen oder Aminen umgesetzt sind. Solche Additive sind insbesondere aus der EP-A 307 815 bekannt. Derartige Additive dienen hauptsächlich zur Verhinderung von Ventilsitzverschleiß und können, wie in der WO-A 87/01 126 beschrieben, mit Vorteil in Kombination mit üblichen Kraftstoffdeter- genzien wie Poly(iso)-butenaminen oder Polyetheraminen eingesetzt werden. Carboxyl groups or their alkali metal or alkaline earth metal salts (Dd) containing additives are preferably copolymers of C2 to C 4 o-olefins with maleic anhydride having a total molecular weight of 500 to 20,000, their carboxyl groups wholly or partly to the alkali metal or alkaline earth metal salts and a remaining radical of the carboxyl groups are reacted with alcohols or amines. Such additives are known in particular from EP-A 307 815. Such additives are mainly used to prevent valve seat wear and can, as described in WO-A 87/01 126, be used with advantage in combination with conventional fuel detergents such as poly (iso) -butene amines or polyetheramines.
Sulfonsäuregruppen oder deren Alkalimetall- oder Erdalkalimetallsalze (De) enthaltende Additive sind vorzugsweise Alkalimetall- oder Erdalkalimetallsalze eines Sulfobernsteinsäurealkylesters, wie er insbesondere in der EP-A 639 632 beschrieben ist. Derartige Additive dienen hauptsächlich zur Verhinderung von Ventilsitzverschleiß und können mit Vorteil in Kombination mit üblichen Kraftstoffdetergenzien wie Poly(iso)buten-aminen oder Polyetheraminen eingesetzt werden. Polyoxy-C2-C4-alkylengruppierungen (Df) enthaltende Additive sind vorzugsweise Polyether oder Polyetheramine, welche durch Umsetzung von C2- bis C6o-Alkanolen, C6- bis C3o-Alkandiolen, Mono- oder D1-C2- bis C3o-alkylaminen, C bis C3o-Alkylcyclo-hexanolen oder C bis C30-AI- kylphenolen mit 1 bis 30 mol Ethylenoxid und/oder Propylenoxid und/oder Butylenoxid pro Hydroxylgruppe oder Aminogruppe und, im Falle der Polyetheramine, durch anschließende reduktive Aminierung mit Ammoniak, Monoaminen oder Polyaminen erhältlich sind. Derartige Produkte werden insbesondere in der EP-A 310 875, EP-A 356 725, EP-A 700 985 und US-A 4 877 416 beschrieben. Im Falle von Polyethern erfüllen solche Produkte auch Trägeröleigenschaften. Typische Beispiele hierfür sind Tridecanol- oder Isotridecanolbutoxylate, Isononylphenolbutoxylate sowie Polyisobutenolbutoxylate und -propoxylate sowie die entsprechenden Umsetzungspro- dukte mit Ammoniak. Sulfonic acid groups or their alkali metal or alkaline earth metal salts (De) containing additives are preferably alkali metal or alkaline earth metal salts of a Sulfobernsteinsäurealkylesters, as described in particular in EP-A 639 632. Such additives are primarily for preventing valve seat wear and can be used to advantage in combination with conventional fuel detergents such as poly (iso) buteneamines or polyetheramines. Polyoxy-C2-C4-alkylene (Df) containing additives are preferably polyether or polyetheramines which by reaction of C2 to C6o-alkanols, C6 to C3o-alkanediols, mono- or D1-C2 to C3o-alkylamines, C to C3o-alkylcyclo-hexanols or C to C30-alkyl- kylphenolen with 1 to 30 moles of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyether amines, by subsequent reductive amination with ammonia, monoamines or polyamines are available , Such products are described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4,877,416. In the case of polyethers, such products also meet carrier oil properties. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and Polyisobutenolbutoxylate and propoxylates and the corresponding reaction products with ammonia.
Carbonsäureestergruppen (Dg) enthaltende Additive sind vorzugsweise Ester aus Mo-no-, Dioder Tricarbonsäuren mit langkettigen Alkanolen oder Polyolen, insbesondere solche mit einer Mindestviskosität von 2 mm2/s bei 100 °C, wie sie insbesondere in der DE-A 38 38 918 beschrie- ben sind. Als Mono-, Di- oder Tricarbonsäuren können aliphatische oder aromatische Säuren eingesetzt werden, als Esteralkohole bzw. -polyole eignen sich vor allem langkettige Vertreter mit beispielsweise 6 bis 24 C-Atomen. Typische Vertreter der Ester sind Adipate, Phthalate, iso- Phthalate, Terephthalate und Trimellitate des iso-Octanols, iso-Nonanols, iso-Decanols und des iso-Tridecanols. Derartige Produkte erfüllen auch Trägeröleigenschaften. Carboxyl ester groups (Dg) -containing additives are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, especially those having a minimum viscosity of 2 mm 2 / s at 100 ° C, as described in particular in DE-A 38 38 918 are described. As mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable ester alcohols or polyols are long-chain representatives having, for example, 6 to 24 C atoms. Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of iso-octanol, iso-nonanol, iso-decanol and of isotridecanol. Such products also meet carrier oil properties.
Aus Bernsteinsäureanhydrid abgeleitete Gruppierungen mit Hydroxy- und/oder Amino- und/oder Amido- und/oder insbesondere Imidogruppen (Dh) enthaltende Additive sind vorzugsweise entsprechende Derivate von Alkyl- oder Alkenyl-substituiertem Bernsteinsäureanhydrid und insbesondere die entsprechenden Derivate von Polyisobutenylbernsteinsäureanhydrid, welche durch Umsetzung von konventionellem oder hochreaktivem Polyisobuten mit Mn = vorzugsweise 300 bis 5000, besonders bevorzugt 300 bis 3000, stärker bevorzugt 500 bis 2500, noch stärker bevorzugt 700 bis 2500 und insbesondere 800 bis 1500, mit Maleinsäureanhydrid auf thermischem Weg in einer En-Reaktion oder über das chlorierte Polyisobuten erhältlich sind. Bei den Gruppierungen mit Hydroxy- und/oder Amino- und/oder Amido- und/oder Imidogruppen handelt es sich beispielsweise um Carbonsäuregruppen, Säureamide von Monoaminen, Säure-amide von Dioder Polyaminen, die neben der Amidfunktion noch freie Amingruppen aufweisen, Bernsteinsäu- rederivate mit einer Säure- und einer Amidfunktion, Carbonsäureimide mit Monoaminen, Carbonsäureimide mit Di- oder Polyaminen, die neben der Imidfunktion noch freie Amingruppen aufweisen, oder Diimide, die durch die Umsetzung von Di- oder Polyaminen mit zwei Bernsteinsäurederivaten gebildet werden. Derartige Kraftstoffadditive sind allgemein bekannt und beispielsweise in den Dokumenten (1 ) und (2) beschrieben. Bevorzugt handelt es sich um die Umsetzungsprodukte von Alkyl- oder Alkenyl-substituierten Bernsteinsäuren oder Derivaten davon mit Aminen und besonders bevorzugt um die Umsetzungsprodukte von Polyisobutenyl-substituierten Bernsteinsäuren oder Derivaten davon mit Aminen. Von besonderem Interesse sind hierbei Umsetzungsprodukte mit aliphatischen Polyaminen (Polyalkylenimine) wie insbesondere Ethylendia- min, Diethylentriamin, Triethylentetramin, Tetraethylenpentamin, Pentaethylenhexamin und He- xaethylenheptamin, welche eine Imidstruktur aufweisen. Derivatives derived from succinic anhydride with hydroxyl and / or amino and / or amido and / or imido (Dh) containing additives are preferably corresponding derivatives of alkyl- or alkenyl-substituted succinic anhydride and in particular the corresponding derivatives of polyisobutenyl succinic anhydride, which by reaction of conventional or highly reactive polyisobutene having M n = preferably 300 to 5000, more preferably 300 to 3000, more preferably 500 to 2500, even more preferably 700 to 2500 and especially 800 to 1500, with maleic anhydride by thermal means in an ene reaction or via the chlorinated polyisobutene are available. The groups having hydroxyl and / or amino and / or amido and / or imido groups are, for example, carboxylic acid groups, acid amides of monoamines, acid amides of diioder polyamines which, in addition to the amide function, still have free amine groups, succinic acid groups. red derivatives with an acid and an amide function, carboximides with monoamines, carboximides with di- or polyamines which, in addition to the imide function, still have free amine groups, or diimides which are formed by reacting di- or polyamines with two succinic acid derivatives. Such fuel additives are well known and described, for example, in documents (1) and (2). Preference is given to the reaction products of alkyl- or alkenyl-substituted succinic acids or derivatives thereof with amines and particularly preferably to the reaction products of polyisobutenyl-substituted succinic acids or derivatives thereof with amines. Of particular interest here are reaction products with aliphatic polyamines (polyalkyleneimines), in particular ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine, which have an imide structure.
Durch Mannich-Umsetzung von substituierten Phenolen mit Aldehyden und Mono- oder Polyaminen erzeugte Gruppierungen (Di) enthaltende Additive sind vorzugsweise Umsetzungsprodukte von Polyisobuten-substituierten Phenolen mit Formaldehyd und Mono- oder Polyaminen wie Ethylendiamin, Diethylentriamin, Triethylentetramin, Tetra-ethylenpentamin oder Dimethylami- nopropylamin. Die Polyisobutenyl-substituierten Phenole können aus konventionellem oder hochreaktivem Polyisobuten mit Mn = 300 bis 5000 stammen. Derartige "Polyisobuten-Mannichbasen" sind insbesondere in der EP-A 831 141 beschrieben. By Mannich reaction of substituted phenols with aldehydes and mono- or polyamines generated moieties containing (di) additives are preferably reaction products of polyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine , The polyisobutenyl-substituted phenols may be derived from conventional or highly reactive polyisobutene having M n = 300 to 5,000. Such "polyisobutene-Mannich bases" are described in particular in EP-A 831 141.
Dem Kraftstoff können ein oder mehrere der genannten Detergenz-Additive in solch einer Menge zugegeben werden, dass die Dosierrate an diesen Detergenz-Additiven vozugsweise 25 bis 2500 Gew.-ppm, insbesondere 75 bis 1500 Gew.-ppm, vor allem 150 bis 1000 Gew.-ppm, beträgt. B2) Trägeröle One or more of said detergent additives may be added to the fuel in such an amount that the metering rate of these detergent additives is preferably from 25 to 2500 ppm by weight, in particular from 75 to 1500 ppm by weight, especially from 150 to 1000% by weight . ppm. B2) carrier oils
Mitverwendete Trägeröle können mineralischer oder synthetischer Natur sein. Geeignete mineralische Trägeröle sind bei der Erdölverarbeitung anfallende Fraktionen, wie Brightstock oder Grundöle mit Viskositäten wie beispielsweise aus der Klasse SN 500 bis 2000, aber auch aroma- tische Kohlenwasserstoffe, paraffinische Kohlenwasserstoffe und Alkoxyalkanole. Brauchbar ist ebenfalls eine als "hydrocrack oil" bekannte und bei der Raffination von Mineralöl anfallende Fraktion (Vakuumdestillatschnitt mit einem Siedebereich von etwa 360 bis 500 °C, erhältlich aus unter Hochdruck katalytisch hydriertem und isomerisiertem sowie entparaffiniertem natürlichen Mineralöl). Ebenfalls geeignet sind Mischungen oben genannter mineralischer Trägeröle. Co-used carrier oils may be mineral or synthetic. Suitable mineral carrier oils are fractions obtained in petroleum processing, such as bright stock or base oils with viscosities such as from class SN 500 to 2000, but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyalkanols. It is also useful as a "hydrocrack oil" known and obtained in the refining of mineral oil fraction (Vakuumdestillatschnitt with a boiling range of about 360 to 500 ° C, available from high pressure catalytically hydrogenated and isomerized and dewaxed natural mineral oil). Also suitable are mixtures of the abovementioned mineral carrier oils.
Beispiele für geeignete synthetische Trägeröle sind Polyolefine (Polyalphaolefine oder Polyinter- nalolefine), (Poly)ester, Poly)alkoxylate, Polyether, aliphatische Polyetheramine, alkylphenolgestartete Polyether, alkylphenolgestartete Polyetheramine und Carbonsäureester langkettiger Alkanole. Examples of suitable synthetic carrier oils are polyolefins (polyalphaolefins or polyinteralolefins), (poly) esters, poly) alkoxylates, polyethers, aliphatic polyetheramines, alkylphenol-initiated polyethers, alkylphenol-initiated polyetheramines and carboxylic acid esters of long-chain alkanols.
Beispiele für geeignete Polyolefine sind Olefinpolymerisate mit Mn = 400 bis 1800, vor allem auf Polybuten- oder Polyisobuten-Basis (hydriert oder nicht hydriert). Beispiele für geeignete Polyether oder Polyetheramine sind vorzugsweise Polyoxy-C2- bis C4- alkylengruppierungen enthaltende Verbindungen, welche durch Umsetzung von C2- bis C6o-Alka- nolen, C6- bis C3o-Alkandiolen, Mono- oder D1-C2- bis C3o-alkylaminen, Cr bis C3o-Alkyl-cyclohe- xanolen oder Cr bis C3o-Alkylphenolen mit 1 bis 30 mol Ethylenoxid und/ oder Propylenoxid und/oder Butylenoxid pro Hydroxylgruppe oder Amino-gruppe und, im Falle der Polyetheramine, durch anschließende reduktive Aminierung mit Ammoniak, Monoaminen oder Polyaminen erhältlich sind. Derartige Produkte werden insbesondere in der EP-A 310 875, EP-A 356 725, EP-A 700 985 und der US-A 4,877,416 beschrieben. Beispielsweise können als Polyetheramine Poly- C2- bis C6-Alkylenoxidamine oder funktionelle Derivate davon verwendet werden. Typische Beispiele hierfür sind Tridecanol- oder Isotridecanolbutoxylate, Isononylphenolbutoxylate sowie Po- lyisobutenolbutoxylate und -propoxylate sowie die entsprechenden Umsetzungsprodukte mit Ammoniak. Beispiele für Carbonsäureester langkettiger Alkanole sind insbesondere Ester aus Mono-, Dioder Tricarbonsäuren mit langkettigen Alkanolen oder Polyolen, wie sie insbesondere in der DE- A 38 38 918 beschrieben sind. Als Mono-, Di- oder Tricarbonsäuren können aliphatische oder aromatische Säuren eingesetzt werden, als Esteralkohole bzw. -polyole eignen sich vor allem langkettige Vertreter mit beispielsweise 6 bis 24 Kohlenstoffatomen. Typische Vertreter der Ester sind Adipate, Phthalate, iso-Phthalate, Terephthalate und Trimellitate des Isooctanols, Isonona- nols, Isodecanols und des Iso-tridecanols, z. B. Di-(n- oder lsotridecyl)phthalat. Examples of suitable polyolefins are olefin polymers having M n = 400 to 1800, especially based on polybutene or polyisobutene (hydrogenated or non-hydrogenated). Examples of suitable polyethers or polyetheramines are preferably compounds containing polyoxy-C 2 - to C 4 -alkylene groups which are prepared by reacting C 2 - to C 6 -alkanols, C 6 - to C 3 0 -alkanediols, mono- or C 1 - to C 2 - Alkylaminen, Cr to C3o-alkyl-cyclohexanols or Cr to C30-alkylphenols with 1 to 30 moles of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, by subsequent reductive amination with ammonia , Monoamines or polyamines are available. Such products are described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4,877,416. For example, as polyetheramines, polyC 2 to C 6 alkylene oxide amines or functional derivatives thereof can be used. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and polyisobutenol butoxylates and propoxylates and the corresponding reaction products with ammonia. Examples of carboxylic acid esters of long-chain alkanols are, in particular, esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, as described in particular in DE-A 38 38 918. As mono-, di- or tricarboxylic acids it is possible to use aliphatic or aromatic acids, especially suitable ester alcohols or polyols are long-chain representatives having, for example, 6 to 24 carbon atoms. Typical representatives of the esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and of isotridecanol, eg. B. di- (n- or isotridecyl) phthalate.
Weitere geeignete Trägerölsysteme sind beispielsweise in der DE-A 38 26 608, DE-A 41 42 241 , DE-A 43 09 074, EP-A 452 328 und der EP-A 548 617 beschrieben. Further suitable carrier oil systems are described, for example, in DE-A 38 26 608, DE-A 41 42 241, DE-A 43 09 074, EP-A 452 328 and EP-A 548 617.
Beispiele für besonders geeignete synthetische Trägeröle sind alkoholgestartete Polyether mit etwa 5 bis 35, vorzugsweise etwa 5 bis 30, besonders bevorzugt 10 bis 30 und insbesondere 15 bis 30 C3- bis C6-Alkylenoxideinheiten, z. B. Propylenoxid-, n-Butylenoxid- und Isobutylenoxid- Einheiten oder Gemischen davon, pro Alkoholmolekül. Nichtlimitierende Beispiele für geeignete Starteralkohole sind langkettige Alkanole oder mit langkettigem Alkyl-substituierte Phenole, wobei der langkettige Alkylrest insbesondere für einen geradkettigen oder verzweigten C6- bis C18- Alkylrest steht. Als besondere Beispiele sind zu nennen Tridecanol und Nonylphenol. Besonders bevorzugte alkoholgestartete Polyether sind die Umsetzungsprodukte (Polyveretherungspro- dukte) von einwertigen aliphatischen C6- bis Cis-Alkoholen mit C3- bis C6-Alkylenoxiden. Beispiele für einwertige aliphatische C6-Ci8-Alkohole sind Hexanol, Heptanol, Octanol, 2-Ethyl-hexanol, Nonylalkohol, Decanol, 3-Propylheptanol, Undecanol, Dodecanol, Tridecanol, Tetradecanol, Pentadecanol, Hexadecanol, Octadecanol und deren Konstitutions- und Stellungsisomere. Die Alkohole können sowohl in Form der reinen Isomere als auch in Form technischer Gemische eingesetzt werden. Ein besonders bevorzugter Alkohol ist Tridecanol. Beispiele für C3- bis C6- Alkylenoxide sind Propylenoxid, wie 1 ,2-Propylen-oxid, Butylenoxid, wie 1 ,2-Butylenoxid, 2,3- Butylenoxid, Isobutylenoxid oder Tetrahydrofuran, Pentylenoxid und Hexylenoxid. Besonders be- vorzugt sind hierunter C3- bis C4-Alkylenoxide, d.h. Propylenoxid wie 1 ,2-Propylenoxid und Buty- lenoxid wie 1 ,2-Buty-lenoxid, 2,3-Butylenoxid und Isobutylenoxid. Speziell verwendet man Buty- lenoxid. Weitere geeignete synthetische Trägeröle sind alkoxylierte Alkylphenole, wie sie in der DE-A 10 102 913 beschrieben sind. 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 C3 to C6 alkylene oxide units, for. As propylene oxide, n-butylene oxide and isobutylene oxide units or mixtures thereof, per alcohol molecule. Nonlimiting examples of suitable starter alcohols are long-chain alkanols or long-chain alkyl-substituted phenols, where the long-chain alkyl radical is in particular a straight-chain or branched C 6 - to C 18 -alkyl radical. Specific examples include tridecanol and nonylphenol. Particularly preferred alcohol-started polyethers are the reaction products (polyetherification products) of monohydric C6- to Cis-aliphatic alcohols with C3- to C6-alkylene oxides. Examples of monohydric aliphatic C6-C18-alcohols are hexanol, heptanol, octanol, 2-ethyl-hexanol, nonyl alcohol, decanol, 3-propylheptanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, octadecanol and their constitution and position isomers. The alcohols can be used both in the form of pure isomers and in the form of technical mixtures. A particularly preferred alcohol is tridecanol. Examples of C3 to C6 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. Particularly important Preferred among these are 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. In particular, butylene oxide is used. Further suitable synthetic carrier oils are alkoxylated alkylphenols, as described in DE-A 10 102 913.
Besondere Trägeröle sind synthetische Trägeröle, wobei die zuvor beschriebenen al-koholgestar- teten Polyether besonders bevorzugt sind. Particular carrier oils are synthetic carrier oils, the alkohol-based polyethers described above being particularly preferred.
Das Trägeröl bzw. das Gemisch verschiedener Trägeröle wird dem Kraftstoff in einer Menge von vorzugsweise 1 bis 1000 Gew.-ppm, besonders bevorzugt von 10 bis 500 Gew.-ppm und insbesondere von 20 bis 100 Gew.-ppm zugesetzt. B3) Kaltfließverbesserer The carrier oil or the mixture of different carrier oils is added to the fuel in an amount of preferably from 1 to 1000 ppm by weight, more preferably from 10 to 500 ppm by weight and in particular from 20 to 100 ppm by weight. B3) cold flow improver
Geeignete Kaltfließverbesserer sind im Prinzip alle organischen Verbindungen, welche in der Lage sind, das Fließverhalten von Mitteldestillat-Kraftstoffen bzw. Dieselkraftstoffen in der Kälte zu verbessern. Zweckmäßigerweise müssen sie eine ausreichende Öllöslichkeit aufweisen. Ins- besondere kommen hierfür die üblicherweise bei Mitteldestillaten aus fossilem Ursprung, also bei üblichen mineralischen Dieselkraftstoffen, eingesetzten Kaltfließverbesserer ("middle distillate flow improvers", "MDFI") in Betracht. Jedoch können auch organische Verbindungen verwendet werden, die beim Einsatz in üblichen Dieselkraftstoffen zum Teil oder überwiegend die Eigenschaften eines Wax Anti-Settling Additivs ("WASA") aufweisen. Auch können sie zum Teil oder überwiegend als Nukleatoren wirken. Es können aber auch Mischungen aus als MDFI wirksamen und/oder als WASA wirksamen und/oder als Nukleatoren wirksamen organischen Verbindungen eingesetzt werden. Suitable cold flow improvers are in principle all organic compounds which are able to improve the flow behavior of middle distillate fuels or diesel fuels in the cold. Conveniently, they must have sufficient oil solubility. In particular, this is the usually used for middle distillates of fossil origin, ie for conventional mineral diesel fuels, used cold flow improvers ("middle distillate flow improvers", "MDFI"). However, it is also possible to use organic compounds which, when used in conventional diesel fuels, have in part or predominantly the properties of a wax anti-settling additive ("WASA"). Also, they can act partly or predominantly as nucleators. However, it is also possible to use mixtures of organic compounds which are active as MDFI and / or which act as WASA and / or as nucleators.
Typischerweise wird der Kaltfließverbesserer ausgewählt aus: Typically, the cold flow improver is selected from:
(K1 ) Copolymeren eines C2- bis C4o-Olefins mit wenigstens einem weiteren ethyle- nisch ungesättigten Monomer; (K1) copolymers of a C2- to C4o-olefin with at least one further ethylenically unsaturated monomer;
(K2) Kammpolymeren;  (K2) comb polymers;
(K3) Polyoxyalkylenen;  (K3) polyoxyalkylenes;
(K4) polaren Stickstoffverbindungen;  (K4) polar nitrogen compounds;
(K5) Sulfocarbonsäuren oder Sulfonsäuren oder deren Derivaten; und (K5) sulfocarboxylic acids or sulfonic acids or their derivatives; and
(K6) Poly(meth)acrylsäureestern.  (K6) poly (meth) acrylic acid esters.
Es können sowohl Mischungen verschiedener Vertreter aus einer der jeweiligen Klassen (K1 ) bis (K6) als auch Mischungen von Vertretern aus verschiedenen Klassen (K1 ) bis (K6) eingesetzt werden. Geeignete C2- bis C4o-Olefin-Monomere für die Copolymeren der Klasse (K1 ) sind beispielsweise solche mit 2 bis 20, insbesondere 2 bis10 Kohlenstoffatomen sowie mit 1 bis 3, vorzugsweise mit 1 oder 2, insbesondere mit einer Kohlenstoff-Kohlenstoff-Dop-pelbindung. Im zuletzt genannten Fall kann die Kohlenstoff-Kohlenstoff-Doppelbindung sowohl terminal (a-Olefine) als auch intern angeordnet sein kann. Bevorzugt sind jedoch α-Olefine, besonders bevorzugt a-Olefine mit 2 bis 6 Kohlenstoffatomen, beispielsweise Propen, 1 -Buten, 1 -Penten, 1 -Hexen und vor allem Ethylen. Mixtures of different representatives from one of the respective classes (K1) to (K6) as well as mixtures of representatives from different classes (K1) to (K6) can be used. Suitable C 2 - to C 4 -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 1 or 2, in particular a carbon-carbon double pelbindung. In the latter case, the carbon-carbon double bond can be arranged both terminally (α-olefins) and internally. However, preference is given to α-olefins, particularly preferably α-olefins having 2 to 6 carbon atoms, for example propene, 1-butene, 1-pentene, 1-hexene and, above all, ethylene.
Bei den Copolymeren der Klasse (K1 ) ist das wenigstens eine weitere ethylenisch ungesättigte Monomer vorzugsweise ausgewählt unter Carbonsäurealkenylestern, (Meth)Acrylsäureestern und weiteren Olefinen. In the copolymers of class (K1), the at least one further ethylenically unsaturated monomer is preferably selected from carboxylic alkenyl esters, (meth) acrylic esters and further olefins.
Werden weitere Olefine mit einpolymerisiert, sind dies vorzugsweise höhermolekulare als das oben genannte C2- bis C4o-Olefin-Basismonomere. Setzt man beispielsweise als Olefin-Basismo- nomer Ethylen oder Propen ein, eignen sich als weitere Olefine insbesondere C10- bis C40-0 Olefine. Weitere Olefine werden in den meisten Fällen nur dann mit einpolymerisiert, wenn auch Monomere mit Carbonsäureester-Funktionen eingesetzt werden. If further olefins are polymerized in, these are preferably higher molecular weight than the abovementioned C 2 - to C 4 -olefin base monomers. If, for example, ethylene or propene is used as the olefin basic monomer, suitable further olefins are, in particular, C 10 -C 40 -olefins. Other olefins are polymerized in most cases only when monomers with carboxylic acid ester functions are used.
Geeignete (Meth)Acrylsäureester sind beispielsweise Ester der (Meth)Acrylsäure mit C bis C20- Alkanolen, insbesondere C bis Cio-Alkanolen, vor allem mit Methanol, Ethanol, Propanol, Isop- ropanol, n-Butanol, sec.-Butanol, Isobutanol, tert.-Butanol, Pentanol, Hexanol, Heptanol, Octanol, 2-Ethylhexanol, Nonanol und Decanol sowie Strukturisomeren hiervon. Suitable (meth) acrylic esters are, for example, esters of (meth) acrylic acid with C 2 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.
Geeignete Carbonsäurealkenylester sind beispielsweise C2- bis C-u-Alkenylester, z.B. die Vinyl- und Propenylester, von Carbonsäuren mit 2 bis 21 Kohlenstoffatomen, deren Kohlenwasserstoff- rest linear oder verzweigt sein kann. Bevorzugt sind hierunter die Vinylester. Unter den Carbonsäuren mit verzweigtem Kohlenwasserstoffrest sind solche bevorzugt, deren Verzweigung sich in der α-Position zur Carboxylgruppe befindet, wobei das α-Kohlenstoffatom besonders bevorzugt tertiär ist, d. h. die Carbonsäure eine sogenannte Neocarbonsäure ist. Vorzugsweise ist der Kohlenwasserstoffrest der Carbonsäure jedoch linear. Suitable carboxylic alkenyl esters are, for example, C2 to C-u-alkenyl esters, e.g. the vinyl and propenyl esters, of carboxylic acids having 2 to 21 carbon atoms, whose hydrocarbon radical may be linear or branched. Preferred among these are the vinyl esters. Among the carboxylic acids having a branched hydrocarbon radical, preferred are those whose branch is in the α-position to the carboxyl group, the α-carbon atom being particularly preferably tertiary, ie. H. the carboxylic acid is a so-called neocarboxylic acid. Preferably, however, the hydrocarbon radical of the carboxylic acid is linear.
Beispiele für geeignete Carbonsäurealkenylester sind Vinylacetat, Vinylpropionat, Vinylbutyrat, Vinyl-2-ethylhexanoat, Neopentansäurevinylester, Hexansäurevinylester, Neononansäurevi- nylester, Neodecansäurevinylester und die entsprechenden Propenyl-ester, wobei die Vinylester bevorzugt sind. Ein besonders bevorzugter Carbonsäurealkenylester ist Vinylacetat; typische hie- raus resultierende Copolymere der Gruppe (K1 ) sind die mit am häufigsten eingesetzten Ethylen- Vinylacetat-Copolymere ("EVA"). Examples of suitable carboxylic alkenyl esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, the vinyl esters being preferred. A particularly preferred carboxylic acid alkenyl ester is vinyl acetate; typical resulting copolymers of group (K1) are the most commonly used ethylene-vinyl acetate copolymers ("EVA").
Besonders vorteilhaft einsetzbare Ethylen-Vinylacetat-Copolymere und ihre Herstellung sind in der WO 99/29748 beschrieben.  Particularly advantageous ethylene-vinyl acetate copolymers and their preparation are described in WO 99/29748.
Als Copolymere der Klasse (K1 ) sind auch solche geeignet, die zwei oder mehrere voneinander verschiedene Carbonsäurealkenylester einpolymerisiert enthalten, wobei diese sich in der Alke- nylfunktion und/oder in der Carbonsäuregruppe unterscheiden. Ebenfalls geeignet sind Copolymere, die neben dem/den Carbonsäurealkenylester(n) wenigstens ein Olefin und/oder wenigstens ein (Meth)Acrylsäureester einpolymerisiert enthalten. Auch Terpolymere aus einem C2- bis C4o-a-Olefin, einem Cr bis C2o-Alkylester einer ethylenisch ungesättigten Monocarbonsäure mit 3 bis 15 Kohlenstoffatomen und einem C2- bis C -Alkenyles- ter einer gesättigten Monocarbonsäure mit 2 bis 21 Kohlenstoffatomen sind als Copolymere der Klasse (K1 ) geeignet. Derartige Terpolymere sind in der WO 2005/054314 beschrieben. Ein typisches derartiges Terpolymer ist aus Ethylen, Acrylsäure-2-ethylhexylester und Vinylacetat aufge- baut. Suitable copolymers of the class (K1) are also those which contain two or more different carboxylic acid alkenyl esters in copolymerized form, these being in the Alken- nylfunktion and / or in the carboxylic acid group differ. Also suitable are copolymers which, in addition to the carboxylic acid alkenyl ester (s), contain at least one olefin and / or at least one (meth) acrylic acid ester in copolymerized form. Also terpolymers of a C2 to C4o-α-olefin, a Cr to C2o-alkyl ester of an ethylenically unsaturated monocarboxylic acid having 3 to 15 carbon atoms and a C2 to C-alkenyl ester of a saturated monocarboxylic acid having 2 to 21 carbon atoms are copolymers of the Class (K1) suitable. Such terpolymers are described in WO 2005/054314. A typical such terpolymer is made up of ethylene, 2-ethylhexyl acrylate and vinyl acetate.
Das wenigstens eine oder die weiteren ethylenisch ungesättigten Monomeren sind in den Copo- lymeren der Klasse (K1 ) in einer Menge von vorzugsweise 1 bis 50 Gew.-%, insbesondere von 10 bis 45 Gew.-% und vor allem von 20 bis 40 Gew.-%, bezogen auf das Gesamtcopolymer, einpolymerisiert. Der gewichtsmäßige Hauptanteil der Monomereinheiten in den Copolymeren der Klasse (K1 ) stammt somit in der Regel aus den C2- bis C4o-Basis-Olefinen. The at least one or the other ethylenically unsaturated monomers are present in the copolymers of class (K1) in an amount of preferably from 1 to 50% by weight, in particular from 10 to 45% by weight and especially from 20 to 40% by weight .-%, based on the total copolymer, copolymerized. The majority by weight of the monomer units in the copolymers of class (K1) thus usually comes from the C2 to C4o-based olefins.
Die Copolymere der Klasse (K1 ) weisen vorzugsweise ein zahlenmittleres Molekulargewicht Mn von 1000 bis 20.000, besonders bevorzugt von 1000 bis 10.000 und insbesondere von 1000 bis 8000 auf. The copolymers of class (K1) 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.
Typische Kammpolymere der Komponente (K2) sind beispielsweise durch die Copolymerisation von Maleinsäureanhydrid oder Fumarsäure mit einem anderen ethylenisch ungesättigten Monomer, beispielsweise mit einem α-Olefin oder einem ungesättigten Ester wie Vinylacetat, und an- schließende Veresterung der Anhydrid- bzw. Säurefunktion mit einem Alkohol mit wenigstens 10 Kohlenstoffatomen erhältlich. Weitere geeignete Kammpolymere sind Copolymere von a-Ole- finen und veresterten Comonomeren, beispielsweise veresterte Copolymere von Styrol und Maleinsäureanhydrid oder veresterte Copolymere von Styrol und Fumarsäure. Geeignete Kammpolymere können auch Polyfumarate oder Polymaleinate sein. Außerdem sind Homo- und Copoly- mere von Vinylethern geeignete Kammpolymere. Als Komponente der Klasse (K2) geeignete Kammpolymere sind beispielsweise auch solche, die in der WO 2004/035715 und in "Comb-Like Polymers. Structure and Properties", N. A. Plate und V. P. Shibaev, J. Poly. Sei. Macromolecular Revs. 8, Seiten 1 17 bis 253 (1974)" beschrieben sind. Auch Gemische von Kammpolymeren sind geeignet. 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 α-olefin or an unsaturated ester such as vinyl acetate, and subsequent esterification of the anhydride or acid function with an alcohol available with at least 10 carbon atoms. Further suitable comb polymers are copolymers of α-olefins and esterified comonomers, for example esterified copolymers of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid. Suitable comb polymers may also be polyfumarates or polymaleinates. In addition, homo- and copolymers of vinyl ethers are suitable comb polymers. Comb polymers suitable as component of class (K2) are, for example, those described in WO 2004/035715 and in "Comb-Like Polymers, Structure and Properties", N.A. Plate and V.P. Shibaev, J. Poly. Be. Macromolecular Revs. 8, pages 1 17 to 253 (1974). "Mixtures of comb polymers are also suitable.
Als Komponente der Klasse (K3) geeignete Polyoxyalkylene sind beispielsweise Poly-oxyalky- lenester, Polyoxyalkylenether, gemischte Polyoxyalkylenesterether und Gemische davon. Bevorzugt enthalten diese Polyoxyalkylenverbindungen wenigstens eine, vorzugsweise wenigstens zwei lineare Alkylgruppen mit jeweils 10 bis 30 Kohlenstoffatomen und eine Polyoxyalkylen- gruppe mit einem zahlenmittleren Molekulargewicht von bis zu 5000. Derartige Polyoxyalkylenverbindungen sind beispielsweise in der EP-A 061 895 sowie in der US 4 491 455 beschrieben. Besondere Polyoxyalkylenverbindungen basieren auf Polyethylenglykolen und Polypropylengly- kolen mit einem zahlenmittleren Molekulargewicht von 100 bis 5000. Weiterhin sind Polyoxyalky- lenmono- und -diester von Fettsäuren mit 10 bis 30 Kohlenstoffatomen wie Stearinsäure oder Behensäure geeignet. Polyoxyalkylenes suitable as component of class (K3) are, for example, polyoxyalkylene esters, polyoxyalkylene ethers, mixed polyoxyalkylene ester ethers and mixtures thereof. These polyoxyalkylene compounds preferably comprise at least one, preferably at least two, linear alkyl groups each having from 10 to 30 carbon atoms and a polyoxyalkylene group having a number average molecular weight of up to 5,000. Such polyoxyalkylene compounds are described, for example, in EP-A 061 895 and in US Pat. No. 4,491,455 described. Particular polyoxyalkylene compounds are based on polyethylene glycols and polypropylene glycols having a number average molecular weight of 100 to 5,000. Polyoxyalkylene mono- and diesters of fatty acids having 10 to 30 carbon atoms, such as stearic acid or behenic acid, are furthermore suitable.
Als Komponente der Klasse (K4) geeignete polare Stickstoffverbindungen können sowohl ionischer als auch nicht ionischer Natur sein und besitzen vorzugsweise wenigstens einen, insbesondere wenigstens zwei Substituenten in Form eines tertiären Stickstoffatoms der allgemeinen Formel >NR7, worin R7 für einen Cs- bis C4o-Kohlenwas-serstoffrest steht. Die Stickstoffsubsti- tuenten können auch quaternisiert, das heißt in kationischer Form, vorliegen. Beispiele für solche Stickstoffverbindungen sind Ammoniumsalze und/oder Amide, die durch die Umsetzung wenigstens eines mit wenigstens einem Kohlenwasserstoffrest substituierten Amins mit einer Carbonsäure mit 1 bis 4 Carboxylgruppen bzw. mit einem geeignetem Derivat davon erhältlich sind. Vorzugsweise enthalten die Amine wenigstens einen linearen Cs- bis C4o-Alkylrest. Zur Herstel- lung der genannten polaren Stickstoffverbindungen geeignete primäre Amine sind beispielsweise Octylamin, Nonylamin, Decylamin, Undecylamin, Dodecylamin, Tetradecylamin und die höheren linearen Homologen, hierzu geeignete sekundäre Amine sind beispielsweise Dioctadecylamin und Methylbehenylamin. Geeignet sind hierzu auch Amingemische, insbesondere großtechnisch zugängliche Amingemische wie Fettamine oder hydrierte Tallamine, wie sie beispielsweise in U II- manns Encyclopedia of Industrial Chemistry, 6. Auflage, im Kapitel "Amines, aliphatic" beschrieben werden. Für die Umsetzung geeignete Säuren sind beispielsweise Cyclohexan-1 ,2-dicarbon- säure, Cyclohexen-1 ,2-dicarbonsäure, Cyclopentan-1 ,2-dicarbonsäure, Naphthalindicarbon- säure, Phthalsäure, Isophthalsäure, Terephthalsäure und mit langkettigen Kohlenwasserstoffresten substituierte Bernsteinsäuren. Polar nitrogen compounds suitable as a component of class (K4) may be of both ionic and nonionic nature, and preferably have at least one, especially at least two, tertiary nitrogen substituent of the general formula> NR 7 , wherein R 7 is Cs to C 40 Hydrocarbon residue stands. The nitrogen substituents may also be quaternized, ie in cationic form. Examples 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. Preferably, the amines contain at least one linear Cs to C4o-alkyl radical. Primary amines suitable for the preparation of said polar nitrogen compounds are, for example, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologues, suitable secondary amines for this purpose are, for example, dioctadecylamine and methylbehenylamine. Also suitable for this purpose are amine mixtures, in particular industrially available amine mixtures such as fatty amines or hydrogenated tallamines, as described, for example, in U-Mannesmann's Encyclopedia of Industrial Chemistry, 6th edition, in the 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.
Insbesondere ist die Komponente der Klasse (K4) ein öllösliches Umsetzungsprodukt aus mindestens eine tertiäre Aminogruppe aufweisenden Poly(C2- bis C2o-Carbon-säu-ren) mit primären oder sekundären Aminen. Die diesem Umsetzungsprodukt zugrundeliegenden mindestens eine tertiäre Aminogruppe aufweisenden Poly(C2- bis C2o-Car-bonsäuren) enthalten vorzugsweise mindestens 3 Carboxylgruppen, insbesondere 3 bis 12, vor allem 3 bis 5 Carboxylgruppen. Die Carbonsäure-Einheiten in den Polycarbonsäuren weisen vorzugsweise 2 bis 10 Kohlenstoffatome auf, insbesondere sind es Essigsäure-Einheiten. Die Carbonsäure-Einheiten sind in geeigneter Weise zu den Polycarbonsäuren verknüpft, meist über ein oder mehrere Kohlenstoff- und/oder Stickstoffatome. Vorzugsweise sind sie an tertiäre Stickstoffatome angebunden, die im Falle mehrerer Stickstoffatome über Kohlenwasserstoffketten verbunden sind. In particular, the component of class (K4) is an oil-soluble reaction product of at least one tertiary amino group-containing poly (C 2 - to C 20 -carboxylic acids) with primary or secondary amines. The poly (C 2 - to C 20 -carboxylic acids) which have at least one tertiary amino group and are based on this reaction product preferably contain at least 3 carboxyl groups, in particular 3 to 12, especially 3 to 5, carboxyl groups. The carboxylic acid units in the polycarboxylic acids preferably have 2 to 10 carbon atoms, in particular they are acetic acid units. The carboxylic acid units are suitably linked to the polycarboxylic acids, usually via one or more carbon and / or nitrogen atoms. Preferably, they are attached to tertiary nitrogen atoms, which are connected in the case of several nitrogen atoms via hydrocarbon chains.
Vorzugsweise ist die Komponente der Klasse (K4) ein öllösliches Umsetzungsprodukt auf Basis von mindestens eine tertiäre Aminogruppe aufweisenden Poly(C2- bis C2o-Carbonsäuren) der allgemeinen Formel IIa oder IIb H00C-o „ OOH The component of the class (K4) is preferably an oil-soluble reaction product based on poly (C 2 - to C 20 -carboxylic acids) having the general formula IIa or IIb and having at least one tertiary amino group H00C-o "OOH
B B B B
HOOC OOH B A B HOOC OOH B A B
HOOCB"N'B"COOH HOOC B "N ' B " COOH
i  i
B"COOH in denen die Vanable A eine geradkettige oder verzweigte C2- bis C6-Alkylengruppe oder die Gruppierung der Formel III
Figure imgf000018_0001
darstellt und die Variable B eine C bis Cig-Alkylengruppe bezeichnet. Die Verbindungen der allgemeinen Formel IIa und IIb weisen insbesondere die Eigenschaften eines WASA auf. Weiterhin ist das bevorzugte öllösliche Umsetzungsprodukt der Komponente (K4), insbesondere das der allgemeinen Formel IIa oder IIb, ein Amid, ein Amidammoniumsalz oder ein Ammoniumsalz, in dem keine, eine oder mehrere Carbonsäuregruppen in Amidgruppen übergeführt sind. B "COOH in which Vanable A is a straight-chain or branched C 2 - to C 6 -alkylene group or the grouping of formula III
Figure imgf000018_0001
and the variable B denotes a C to Cig alkylene group. The compounds of the general formula IIa and IIb have in particular the properties of a WASA. Furthermore, the preferred oil-soluble reaction product of component (K4), in particular that of general formula IIa or IIb, is an amide, an amide ammonium salt or an ammonium salt in which no, one or more carboxylic acid groups are converted into amide groups.
Geradkettige oder verzweigte C2- bis C6-Alkylengruppen der Variablen A sind beispielsweise 1 ,1 - Ethylen, 1 ,2-Propylen, 1 ,3-Propylen, 1 ,2-Butylen, 1 ,3-Butylen, 1 ,4-Bu-tylen, 2-Methyl-1 ,3-propy- len, 1 ,5-Pentylen, 2-Methyl-1 ,4-butylen, 2,2-Dimethyl-1 ,3-pro-pylen, 1 ,6-Hexylen (Hexamethylen) und insbesondere 1 ,2-Ethylen. Vorzugsweise umfasst die Variable A 2 bis 4, insbesondere 2 oder 3 Kohlenstoffatome. Cr bis Ci9-Alkylengruppen der Variablen B sind vor beispielsweise 1 ,2-Ethylen, 1 ,3-Propylen, 1 ,4-Butylen, Hexamethylen, Octamethylen, Decamethylen, Dodecamethylen, Tetradecamethy- len, Hexadecamethylen, Octadecamethylen, Nonadecamethylen und insbesondere Methylen. Vorzugsweise umfasst die Variable B 1 bis 10, insbesondere 1 bis 4 Kohlenstoffatome. Die primären und sekundären Amine als Umsetzungspartner für die Polycarbonsäuren zur Bildung der Komponente (K4) sind üblicherweise Monoamine, insbesondere aliphatische Monoa- mine. Diese primären und sekundären Amine können aus einer Vielzahl von Aminen ausgewählt sein, die - gegebenenfalls miteinander verbundene - Kohlenwasserstoffreste tragen. Meist sind diese den öllöslichen Umsetzungsprodukten der Komponente (K4) zugrundeliegenden Amine sekundären Amine und weisen die allgemeine Formel HN(R8)2 auf, in der die beiden Variablen R8 unabhängig voneinander jeweils geradkettige oder verzweigte C10- bis C3o-Alkylreste, insbesondere Cu- bis C24-Alkylreste bedeuten. Diese längerkettigen Alkylreste sind vorzugsweise geradkettig oder nur in geringem Grade verzweigt. In der Regel leiten sich die genannten sekundären Amine hinsichtlich ihrer längerkettigen Alkylreste von natürlich vorkommenden Fettsäuren bzw. von deren Derivaten ab. Vorzugsweise sind die beiden Reste R8 gleich. 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 ethylene, 2-methyl-1,3-propylene, 1, 5-pentylene, 2-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene ( Hexamethylene) and in particular 1, 2-ethylene. Preferably, the variable A comprises 2 to 4, in particular 2 or 3 carbon atoms. C 1 to C 12 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 in particular methylene. Preferably, the variable B 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 the component (K4) are usually monoamines, in particular aliphatic monoamines. These primary and secondary amines may be selected from a variety of amines bearing hydrocarbon radicals, optionally linked together. Most of these amines which are the oil-soluble reaction products of component (K4) are secondary amines and have the general formula HN (R 8 ) 2 , in which the two variables R 8 are each independently straight-chain or branched C 10 - to C 30 -alkyl radicals, in particular C to C24 alkyl radicals. These longer-chain alkyl radicals are preferably straight-chain or only slightly branched. As a rule, the abovementioned secondary amines are derived, with regard to their longer-chain alkyl radicals, from naturally occurring fatty acids or from their derivatives. Preferably, the two radicals R 8 are the same.
Die genannten sekundären Amine können mittels Amidstrukturen oder in Form der Ammoniumsalze an die Polycarbonsäuren gebunden sein, auch kann nur ein Teil als Amidstrukturen und ein anderer Teil als Ammoniumsalze vorliegen. Vorzugsweise liegen nur wenige oder keine freien Säuregruppen vor. Vorzugsweise liegen die öllöslichen Umsetzungsprodukte der Komponente (K4) vollständig in Form der Amidstrukturen vor. The abovementioned secondary amines can be bound to the polycarboxylic acids by means of amide structures or in the form of the ammonium salts, and only one part can be present as amide structures and another part as ammonium salts. Preferably, only a few or no free acid groups are present. Preferably, the oil-soluble reaction products of component (K4) are completely in the form of the amide structures.
Typische Beispiele für derartige Komponenten (K4) sind Umsetzungsprodukte der Nitrilotriessig- säure, der Ethylendiamintetraessigsäure oder der Propylen-1 ,2-diamintetra-essigsäure mit jeweils 0,5 bis 1 ,5 Mol pro Carboxylgruppe, insbesondere 0,8 bis 1 ,2 Mol pro Carboxylgruppe, Di- oleylamin, Dipalmitinamin, Dikokosfettamin, Distearylamin, Dibehenylamin oder insbesondere Ditaigfettamin. Eine besonders bevorzugte Komponente (K4) ist das Umsetzungsprodukt aus 1 Mol Ethylendiamintetraessigsäure und 4 Mol hydriertem Ditaigfettamin. 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 in particular Ditaigfettamin. A particularly preferred component (K4) is the reaction product of 1 mole of ethylenediaminetetraacetic acid and 4 moles of hydrogenated dithiol fatty amine.
Als weitere typische Beispiele für die Komponente (K4) seien die N,N-Dialkylammoni-umsalze von 2-N',N'-Dialkylamidobenzoaten, beispielsweise das Reaktionsprodukt aus 1 Mol Phthalsäu- reanhydrid und 2 Mol Ditaigfettamin, wobei letzteres hydriert oder nicht hydriert sein kann, und das Reaktionsprodukt von 1 Mol eines Alkenylspirobislactons mit 2 Mol eines Dialkylamins, beispielsweise Ditaigfettamin und/oder Taigfettamin, wobei die beiden letzteren hydriert oder nicht hydriert sein können, genannt. Other typical examples of component (K4) include 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 diethfamine, the latter being hydrogenated or unhydrogenated may be, and the reaction product of 1 mole of a Alkenylspirobislactons with 2 moles of a dialkylamine, for example, Ditaigfettamin and / or Taigfettamin, the latter two may be hydrogenated or unhydrogenated, called.
Weitere typische Strukturtypen für die Komponente der Klasse (K4) sind cyclische Verbindungen mit tertiären Aminogruppen oder Kondensate langkettiger primärer oder sekundärer Amine mit carbonsäurehaltigen Polymeren, wie sie in der WO 93/181 15 beschrieben sind. Als Kaltfließverbesserer der Komponente der Klasse (K5) geeignete Sulfocarbonsäuren, Sulfon- säuren oder deren Derivate sind beispielsweise die öllöslichen Carbonsäureamide und Carbonsäureester von ortho-Sulfobenzoesäure, in denen die Sulfonsäurefunktion als Sulfonat mit alkyl- substituierten Ammoniumkationen vorliegt, wie sie in der EP-A 261 957 beschrieben werden. Als Kaltfließverbesserer der Komponente der Klasse (K6) geeignete Poly(meth)acryl-säureester sind sowohl Homo- als auch Copolymere von Acryl- und Methacrylsäure-estern. Bevorzugt sind Copolymere von wenigstens zwei voneinander verschiedenen (Meth)Acrylsäureestern, die sich bezüglich des einkondensierten Alkohols unterscheiden. Gegebenenfalls enthält das Copolymer noch ein weiteres, davon verschiedenes olefinisch ungesättigtes Monomer einpolymerisiert. Das gewichtsmittlere Molekulargewicht des Polymers beträgt vorzugsweise 50.000 bis 500.000. Ein besonders bevorzugtes Polymer ist ein Copolymer von Methacrylsäure und Methacrylsäu- reestern von gesättigten C-u- und Cis-Alkoholen, wobei die Säuregruppen mit hydriertem Tallamin neutralisiert sind. Geeignete Poly(meth)acrylsäureester sind beispielsweise in der WO 00/44857 beschrieben. Further typical structural types for the component of the class (K4) are cyclic compounds having tertiary amino groups or condensates of long-chain primary or secondary amines with carboxylic acid-containing polymers, as described in WO 93/181 15. Sulfocarboxylic acids, sulfonic acids or their derivatives which are suitable as cold flow improvers of the component of the 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 sulfonate with alkyl-substituted ammonium cations, as described in EP-A 261 957 are described. As a cold flow improver of the component of the class (K6) suitable poly (meth) acrylic acid esters 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. A particularly preferred polymer is a copolymer of methacrylic acid and methacrylic acid esters of saturated Cu and Cis alcohols, wherein the acid groups with hydrogenated tallamine are neutralized. Suitable poly (meth) acrylic esters are described, for example, in WO 00/44857.
Dem Mitteldestillat-Kraftstoff bzw. Dieselkraftstoff wird der Kaltfließverbesserer bzw. das Ge- misch verschiedener Kaltfließverbesserer in einer Gesamtmenge von vorzugsweise 10 bis 5000 Gew.-ppm, besonders bevorzugt von 20 bis 2000 Gew.-ppm, stärker bevorzugt von 50 bis 1000 Gew.-ppm und insbesondere von 100 bis 700 Gew.-ppm, z.B. von 200 bis 500 Gew.-ppm, zugegeben. B4) Schmierfähigkeitsverbesserer The middle distillate fuel or diesel fuel is the cold flow improver or the mixture of various cold flow improvers in a total amount of preferably 10 to 5000 ppm by weight, more preferably from 20 to 2000 ppm by weight, more preferably from 50 to 1000 wt. ppm and in particular from 100 to 700 ppm by weight, eg from 200 to 500 ppm by weight, added. B4) Lubricity improver
Geeignete Schmierfähigkeitsverbesserer (Lubricity Improver bzw. Friction Modifier) basieren üblicherweise auf Fettsäuren oder Fettsäureestern. Typische Beispiele sind Tallölfettsäure, wie beispielsweise in der WO 98/004656 beschrieben, und Glycerinmonooleat. Auch die in der US 6 743 266 B2 beschriebenen Reaktionsprodukte aus natürlichen oder synthetischen Ölen, beispielsweise Triglyceriden, und Alkanolaminen sind als solche Schmierfähigkeitsverbesserer geeignet. Suitable lubricity improvers (or friction modifiers) are usually based on fatty acids or fatty acid esters. Typical examples are tall oil fatty acid, as described for example in WO 98/004656, and glycerol monooleate. The reaction products of natural or synthetic oils, for example triglycerides, and alkanolamines described in US Pat. No. 6,743,266 B2 are also suitable as such lubricity improvers.
B5) Andere Korrosionsinhibitoren als solche der Formel (I) Geeignete Korrosionsinhibitoren sind z.B. Bernsteinsäureester, vor allem mit Polyolen, Fettsäurederivate, z.B. Ölsäureester, oligomerisierte Fettsäuren, substituierte Ethanol-amine und Produkte, die unter dem Handelsnamen RC 4801 (Rhein Chemie Mannheim, Deutschland), Irgacor® L12 (BASF SE) oder HiTEC 536 (Ethyl Corporation) vertrieben werden. B6) Demulgatoren B5) Other corrosion inhibitors than those of formula (I) Suitable corrosion inhibitors are e.g. Succinic esters, especially with polyols, fatty acid derivatives, e.g. Oleic acid esters, oligomerized fatty acids, substituted ethanolamines and products sold under the trade name RC 4801 (Rhein Chemie Mannheim, Germany), Irgacor® L12 (BASF SE) or HiTEC 536 (Ethyl Corporation). B6) Demulsifiers
Geeignete Demulgatoren sind z.B. die Alkali- oder Erdalkalisalze von Alkyl-substituier-ten Phenol- und Naphthalinsulfonaten und die Alkali- oder Erdalkalisalze von Fettsäuren, außerdem neutrale Verbindungen wie Alkoholalkoxylate, z.B. Alkoholethoxylate, Phenolalkoxylate, z.B. tert- Butylphenolethoxylat oder tert-Pentylphenolethoxylat, Fettsäuren, Alkylphenole, Kondensations- produnkte von Ethylenoxid (EO) und Propylenoxid (PO), z.B. auch in Form von EO/PO-Blockco- polymeren, Polyethylenimine oder auch Polysiloxane. Suitable demulsifiers are e.g. the alkali or alkaline earth salts of alkyl-substituted phenol and naphthalene sulfonates and the alkali or alkaline earth salts of fatty acids, as well as neutral compounds such as alcohol alkoxylates, e.g. Alcohol ethoxylates, phenol alkoxylates, e.g. tert-butyl phenol ethoxylate or tert-pentyl phenol ethoxylate, fatty acids, alkyl phenols, condensation points of ethylene oxide (EO) and propylene oxide (PO), e.g. also in the form of EO / PO block copolymers, polyethyleneimines or else polysiloxanes.
B7) Dehazer B7) Dehazer
Geeignete Dehazer sind z.B. alkoxylierte Phenol-Formaldehyd-Kondensate, wie beispielsweise die unter dem Handelsnamen erhältlichen Produkte NALCO 7D07 (Nalco) und TOLAD 2683 (Pet- rolite). Suitable dehazers are e.g. alkoxylated phenol-formaldehyde condensates, such as the NALCO 7D07 (Nalco) and TOLAD 2683 (Porrolite) products available under the tradename.
B8) Antischaummittel Geeignete Antischaummittel sind z.B. Polyether-modifizierte Polysiloxane, wie beispielsweise die unter dem Handelsnamen erhältlichen Produkte TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) und RHODOSIL (Rhone Poulenc). B9) Cetanzahlverbesserer B8) antifoam Suitable anti-foaming agents are, for example, polyether-modified polysiloxanes, such as, for example, the products available under the trade name TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc). B9) Cetane number improver
Geeignete Cetanzahlverbesserer sind z.B. aliphatische Nitrate wie 2-Ethylhexylnitrat und Cyclo- hexylnitrat sowie Peroxide wie Di-tert-butylperoxid. B10) Antioxidantien Suitable cetane number improvers are e.g. aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate, and peroxides such as di-tert-butyl peroxide. B10) Antioxidants
Geeignete Antioxidantien sind z.B. substituierte Phenole, wie 2,6-Di-tert.-butylphenol und 6-Di- tert.-butyl-3-methylphenol sowie Phenylendiamine wie N,N'-Di-sec.-butyl-p-phenylendiamin. B1 1 ) Metalldeaktivatoren Suitable antioxidants are e.g. 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. B1 1) Metal deactivators
Geeignete Metalldeaktivatoren sind z.B. Salicylsäurederivate wie N,N'-Disalicyliden-1 ,2-propan- diamin. B12) Lösungsmittel Suitable metal deactivators are e.g. Salicylic acid derivatives such as N, N'-disalicylidene-1,2-propanediamine. B12) Solvent
Geeignete sind z.B. unpolare organische Lösungsmittel wie aromatische und aliphatische Kohlenwasserstoffe, beispielsweise Toluol, Xylole, "white spirit" und Produkte, die unter dem Handelsnamen SHELLSOL (Royal Dutch/Shell Group) und EXXSOL (ExxonMobil) vertrieben wer- den, sowie polare organische Lösungsmittel, bei-spielsweise Alkohole wie 2-Ethylhexanol, Deca- nol und Isotridecanol. Derartige Lösungsmittel gelangen meist zusammen mit den vorgenannten Additiven und Co-Additi-ven, die sie zur besseren Handhabung lösen oder verdünnen sollen, in den Dieselkraftstoff. C) Kraftstoffe Suitable ones are e.g. nonpolar organic solvents such as aromatic and aliphatic hydrocarbons, for example toluene, xylenes, "white spirit" and products marketed under the trade name SHELLSOL (Royal Dutch / Shell Group) and EXXSOL (ExxonMobil), as well as polar organic solvents. For example, alcohols such as 2-ethylhexanol, decanol and isotridecanol. Such solvents usually arrive together with the aforementioned additives and co-additives which they are intended to dissolve or dilute for better handling into the diesel fuel. C) fuels
Die erfindungsgemäße Verwendung betrifft im Prinzip jegliche Kraftstoffe, bevorzugt Diesel- und Ottokraftstoffe. Bei Mitteldestillat-Kraftstoffen wie Dieselkraftstoffen oder Heizölen handelt es sich vorzugsweise um Erdölraffinate, die üblicherweise einen Siedebereich von 100 bis 400°C haben. Dies sind meist Destillate mit einem 95%-Punkt bis zu 360°C oder auch darüber hinaus. Dies können aber auch so genannte "Ultra Low Sulfur Diesel" oder "City Diesel" sein, gekennzeichnet durch einen 95%-Punkt von beispielsweise maximal 345°C und einem Schwefelgehalt von maximal 0,005 Gew.-% oder durch einen 95%-Punkt von beispielsweise 285°C und einem Schwefelgehalt von maximal 0,001 Gew.-%. Neben den durch Raffination erhältlichen mineralischen Mitteldestillat- Kraftstoffen bzw. Dieselkraftstoffen sind auch solche, die durch Kohlevergasung oder Gasverflüssigung ["gas to liquid" (GTL)-Kraftstoffe] oder durch Biomasse-Verflüssigung ["biomass to liquid" ( BT L)- Kraftstoffe] erhältlich sind, geeignet. Geeignet sind auch Mischungen der vorstehend genannten Mitteldestillat-Kraftstoffe bzw. Dieselkraftstoffe mit regenerativen Kraftstoffen, wie Bio- diesel oder Bioethanol. The use according to the invention relates in principle to any fuels, preferably diesel and gasoline fuels. Middle distillate fuels, such as diesel fuels or fuel oils, are preferably petroleum raffinates, which usually have a boiling range of from 100 to 400.degree. These are mostly distillates with a 95% point up to 360 ° C or even beyond. However, these may 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 wt .-% or by a 95% point of for example, 285 ° C and a maximum sulfur content of 0.001 wt .-%. In addition to the mineral middle distillates available through refining. Fuels or diesel fuels are also those obtainable by coal gasification or gas-to-liquid (GTL) fuels or by biomass to liquid (BT L) fuels. Also suitable are mixtures of the abovementioned middle distillate fuels or diesel fuels with regenerative fuels, such as biodiesel or bioethanol.
Die Qualitäten der Heizöle und Dieselkraftstoffe sind beispielsweise in DIN 51603 und EN 590 näher festgelegt (vgl. auch Ullmann's Encyclopedia of Industrial Chemistry, 5. Auflage, Band A12, S. 617 ff.). The qualities of fuel oils and diesel fuels are specified in greater detail in, for example, DIN 51603 and EN 590 (cf., also, Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A12, page 617 et seq.).
Die erfindungsgemäße Verwendung in Mitteldestillat-Kraftstoffen aus fossilem, pflanzlichem oder tierischem Ursprung, die im wesentlichen Kohlenwasserstoffmischungen darstellen, betrifft auch Mischungen aus solchen Mitteldestillaten mit Biobrennstoffölen (Biodiesel). Derartige Mischungen werden von dem Begriff "Mitteldestillat-Kraftstoff" umfasst. Sie sind handelsüblich und enthalten meist die Biobrennstofföle in untergeordneten Mengen, typischerweise in Mengen von 1 bis 30 Gew.-% insbesondere von 3 bis 10 Gew.-%, bezogen auf die Gesamtmenge aus Mitteldestillat fossilen, pflanzlichem oder tierischen Ursprungs und Biobrennstofföl. The use according to the invention in middle distillate fuels of fossil, vegetable or animal origin, which are essentially hydrocarbon mixtures, also relates to mixtures of such middle distillates with biofuel oils (biodiesel). 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 wt .-%, in particular from 3 to 10 wt .-%, based on the total amount of middle distillate fossil, vegetable or animal origin and biofuel.
Biobrennstofföle basieren in der Regel auf Fettsäureestern, vorzugsweise im wesentlichen auf Alkylester von Fettsäuren, die sich von pflanzlichen und/oder tierischen Ölen und/oder Fetten ableiten. Unter Alkylestern werden üblicherweise Niedrigalkylester, insbesondere d- bis C4-Al- kylester, verstanden, die durch Umesterung der in pflanzlichen und/oder tierischen Ölen und/oder Fetten vorkommenden Glyceride, insbesondere Triglyceride, mittels Niedrigalkoholen, beispielsweise Ethanol oder vor allem Methanol ("FAME"), erhältlich sind. Typische Niedrigalkylester auf Basis von pflanzlichen und/oder tierischen Ölen und/oder Fetten, die als Biobrennstofföl oder Komponenten hierfür Verwendung finden, sind beispielsweise Sonnenblumenmethylester, Palmölmethylester ("PME"), Sojaölmethylester ("SME") und insbesondere Rapsölmethylester ("RME"). Besonders bevorzugt handelt es sich bei den Mitteldestillat-Kraftstoffen bzw. Dieselkraftstoffen um solche mit niedrigem Schwefelgehalt, das heißt mit einem Schwefelgehalt von weniger als 0,05 Gew.-%, vorzugsweise von weniger als 0,02 Gew.-%, insbesondere von weniger als 0,005 Gew.-% und speziell von weniger als 0,001 Gew.-% Schwefel. Als Ottokraftstoffe kommen alle handelsüblichen Ottokraftstoffzusammensetzungen in Betracht. Als typischer Vertreter soll hier der marktübliche Eurosuper Grundkraftstoff gemäß EN 228 genannt werden. Weiterhin sind auch Ottokraftstoffzusammensetzungen der Spezifikation gemäß WO 00/47698 mögliche Einsatzgebiete für die vorliegende Erfindung. Die nachfolgenden Beispiele sollen die vorliegende Erfindung erläutern, ohne sie zu beschränken. Beispiele Biofuel oils are generally based on fatty acid esters, preferably substantially on alkyl esters of fatty acids derived from vegetable and / or animal oils and / or fats. Alkyl esters are usually lower alkyl esters, especially C 1 to C 4 alkyl esters, understood by transesterification of occurring in vegetable and / or animal oils and / or fats glycerides, especially triglycerides, by means of lower alcohols, for example ethanol or especially methanol ( "FAME") are available. Typical lower alkyl esters based on vegetable and / or animal oils and / or fats which are used as biofuel oil or components thereof include, for example, sunflower methyl ester, palm oil methyl ester ("PME"), soybean oil methyl ester ("SME") and in particular rapeseed oil methyl ester ("RME"). , 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 as 0.005 wt .-% and especially less than 0.001 wt .-% sulfur. As gasoline fuels are all commercially available gasoline fuel compositions into consideration. A typical representative here is the market-standard basic fuel of Eurosuper according to EN 228. Furthermore, gasoline compositions of the specification according to WO 00/47698 are also possible fields of use for the present invention. The following examples are intended to illustrate the present invention without limiting it. Examples
Synthesebeispiele synthesis Examples
Verwendete Reagenzien: Reagents used:
Tetrapropenylbernsteinsäureanhydrid (CAS 26544-38-7) mit einer Verseifungszahl von 332,6 mg KOH/g der Firma Aldrich.  Tetrapropenylsuccinic anhydride (CAS 26544-38-7) having a saponification number of 332.6 mg KOH / g from Aldrich.
Solvent Naphtha naphthalene depleted (ND): Solvesso 150 ND der Fa. Exxon Mobil.  Solvent naphthalene depleted (ND): Solvesso 150 ND from Exxon Mobil.
Polyglycerin-3 (CAS 25618-55-7) mit einer OH-Zahl von 1 173 mg KOH/g der Firma Solvay. Trimethylolpropan der Fa. BASF. Polyglycerol-3 (CAS 25618-55-7) with an OH number of 1 173 mg KOH / g from Solvay. Trimethylolpropane from BASF.
Di(trimethylolpropan) (CAS 23235-61-2) der Fa. Aldrich.  Di (trimethylolpropane) (CAS 23235-61-2) from Aldrich.
Polyisobutenylbernsteinsäureanhydrid (PIBSA): Hergestellt aus Maleinsäureanhydrid und Poly- isobuten mit einem mittleren Molgewicht MN von ca. 1000 in bekannter Weise. Für die folgenden erfindungsgemäßen Herstellungsbeispiele wurden 2 unterschiedliche Qualitäten eingesetzt: "PIBSA 1 " mit einer Verseifungszahl von 87 mg KOH/g und einem Bismaleinierungsgrad von 1 1 ,6%. "PIBSA 2" mit einer Verseifungszahl von 1 12,5 mg KOH/g und einem Bismaleinierungsgrad von 31 ,8%.  Polyisobutenyl succinic anhydride (PIBSA): Prepared from maleic anhydride and polyisobutene with a mean molecular weight MN of about 1000 in a known manner. For the following preparation examples according to the invention 2 different grades were used: "PIBSA 1" with a saponification number of 87 mg KOH / g and a Bismaleinierungsgrad of 1 1, 6%. "PIBSA 2" with a saponification number of 1 12.5 mg KOH / g and a bis-maleination level of 31, 8%.
Synthesebeispiel 1 : Synthetic Example 1:
In einem 1 I Doppelmantelreaktor wurde zu einer Lösung von Polyglycerin-3 (170 g) in Solvent Naphtha ND (385,8 g) bei 80°C Tetrapropenylbernsteinsäureanhydrid (215,8 g) zugetropft. Das Reaktionsgemisch wurde 6 h bei Temperaturen zwischen 80°C und 130°C gerührt, wobei die Temperatur sukzessive nach jeweils 1 h um 10°C erhöht wurde. Der Reaktionsverlauf wurde mittels ATR-IR-Spektroskopie verfolgt (Verschwinden der C=0-Schwingung des Anhydrides bei 1779 cm-1, Entstehung einer Säure- bzw. Esterschwingung bei 1710 cm-1 bzw. 1739 cm-1). Das Produkt wurde als 50%ige Lösung in Solvent Naphtha ND erhalten. In a 1 liter jacketed reactor, tetrapropenyl succinic anhydride (215.8 g) was added dropwise to a solution of polyglycerol-3 (170 g) in Solvent Naphtha ND (385.8 g) at 80 ° C. The reaction mixture was stirred for 6 h at temperatures between 80 ° C and 130 ° C, wherein the temperature was successively increased by 10 ° C after every 1 h. The course of the reaction was monitored by ATR-IR spectroscopy (disappearance of the C = 0 vibration of the anhydride at 1779 cm -1 , formation of an acid or ester vibration at 1710 cm -1 and 1739 cm -1, respectively). The product was obtained as a 50% solution in Solvent Naphtha ND.
Synthesebeispiel 2: Synthetic Example 2:
In einem 1 I Doppelmantelreaktor wurde zu einer Lösung von Trimethyolpropan (55 g) in Solvent Naphtha ND (428,3 g) bei 80°C Tetrapropenylbernsteinsäureanhydrid (373,3 g) zugetropft. Das Reaktionsgemisch wurde 6 h bei Temperaturen zwischen 80°C und 130°C gerührt, wobei die Temperatur sukzessive nach jeweils 1 h um 10°C erhöht wurde. Der Reaktionsverlauf wurde mittels ATR-IR-Spektroskopie verfolgt. (Verschwinden der C=0-Schwingung des Anhydrides bei 1779 cm-1, Entstehung einer Säure- bzw. Esterschwingung bei 1709 cm-1 bzw. 1739 cm-1). Das Produkt wurde als 50%ige Lösung in Solvent Naphtha ND erhalten. Synthesebeispiel 3: In a 1 liter jacketed reactor, tetrapropenylsuccinic anhydride (373.3 g) was added dropwise to a solution of trimethyolpropane (55 g) in Solvent Naphtha ND (428.3 g) at 80 ° C. The reaction mixture was stirred for 6 h at temperatures between 80 ° C and 130 ° C, wherein the temperature was successively increased by 10 ° C after every 1 h. The course of the reaction was monitored by ATR-IR spectroscopy. (Disappearance of the C = 0 vibration of the anhydride at 1779 cm -1 , formation of an acid or ester vibration at 1709 cm -1 and 1739 cm -1, respectively). The product was obtained as a 50% solution in Solvent Naphtha ND. Synthesis Example 3:
In einem 1 I Doppelmantelreaktor wurde zu einer Lösung von Di(trimethylolpropan) (80 g) in Solvent Naphtha ND (457,3 g) bei 80°C Tetrapropenylbernsteinsäureanhydrid (377,3 g) zugetropft. Das Reaktionsgemisch wurde 5 h bei 130°C gerührt. Der Reaktionsverlauf wurde mittels ATR-IR-Spektroskopie verfolgt. (Verschwinden der C=0-Schwingung des Anhydrides bei 1779 cm-1, Entstehung einer Säure- bzw. Esterschwingung bei 1708 cm-1 bzw. 1738 cm-1). Das Produkt wurde als 50%ige Lösung in Solvent Naphtha ND erhalten. In a 1 liter jacketed reactor, tetrapropenylsuccinic anhydride (377.3 g) was added dropwise to a solution of di (trimethylolpropane) (80 g) in Solvent Naphtha ND (457.3 g) at 80 ° C. The reaction mixture was stirred at 130 ° C for 5 h. The course of the reaction was monitored by ATR-IR spectroscopy. (Disappearance of the C = 0 vibration of the anhydride at 1779 cm -1 , formation of an acid or ester vibration at 1708 cm -1 and 1738 cm -1, respectively). The product was obtained as a 50% solution in Solvent Naphtha ND.
Synthesebeispiel 4: Synthetic Example 4:
In einem 1 I Doppelmantelreaktor wurde zu einer Lösung von Trimethylolpropan (9,3 g) in Solvent Naphtha ND (47 g) bei 80°C eine Lösung von PIBSA 1 (243,7 g) in Solvent Naphtha ND (206 g) zugetropft. Das Reaktionsgemisch wurde für 7 h bei 80 °C und anschließend für 7 h bei 100 °C gerührt. Der Reaktionsverlauf wurde mittels ATR-IR-Spektroskopie verfolgt. (Verschwinden der C=0-Schwingung des Anhydrides bei 1779 cm-1, Entstehung einer Säure- bzw. Esterschwingung bei 1714 cm-1 bzw. 1738 cm-1). Das Produkt wurde als 50%ige Lösung in Solvent Naphtha ND erhalten. In a 1 liter jacketed reactor, a solution of PIBSA 1 (243.7 g) in Solvent Naphtha ND (206 g) was added dropwise to a solution of trimethylolpropane (9.3 g) in Solvent Naphtha ND (47 g) at 80 ° C. The reaction mixture was stirred at 80 ° C. for 7 h and then at 100 ° C. for 7 h. The course of the reaction was monitored by ATR-IR spectroscopy. (Disappearance of the C = 0 vibration of the anhydride at 1779 cm -1 , formation of an acid or ester vibration at 1714 cm -1 and 1738 cm -1, respectively). The product was obtained as a 50% solution in Solvent Naphtha ND.
Synthesebeispiel 5: Synthesis Example 5:
In einem 1 I Doppelmantelreaktor wurde zu einer Lösung von Trimethylolpropan (9,3 g) in Solvent Naphtha ND (47,8 g) bei 80°C eine Lösung von PIBSA 2 (188,5 g) in Solvent Naphtha ND (150 g) zugetropft. Das Reaktionsgemisch wurde für 7 h bei 80 °C und anschließend für 7 h bei 100 °C gerührt. Der Reaktionsverlauf wurde mittels ATR-IR-Spektroskopie verfolgt. (Verschwinden der C=0-Schwingung des Anhydrides bei 1779 cm-1, Entstehung einer Säure- bzw. Esterschwingung bei 1714 cm-1 bzw. 1738 cm-1). Das Produkt wurde als 50%ige Lösung in Solvent Naphtha ND erhalten. Anwendungsbeispiele In a 1 liter jacketed reactor, to a solution of trimethylolpropane (9.3 g) in Solvent Naphtha ND (47.8 g) at 80 ° C was added a solution of PIBSA 2 (188.5 g) in Solvent Naphtha ND (150 g). dropwise. The reaction mixture was stirred at 80 ° C. for 7 h and then at 100 ° C. for 7 h. The course of the reaction was monitored by ATR-IR spectroscopy. (Disappearance of the C = 0 vibration of the anhydride at 1779 cm -1 , formation of an acid or ester vibration at 1714 cm -1 and 1738 cm -1, respectively). The product was obtained as a 50% solution in Solvent Naphtha ND. applications
Als Kraftstoff wurde handelsüblicher Ottokraftstoff EO CEC RF-12-09 der Firma Haltermann eingesetzt und mit einem Additivpaket aus Polyisobutenamin, Trägeröl, Dehazer und Lösungsmittel additiviert. Zur Formulierung wurden die in der Tabelle 2 angegebenen Korrosionsinhibitoren zugesetzt und einem Korrosionstest nach ASTM D 665 B unterworfen. The fuel used was commercial Otto EO CEC RF-12-09 from Haltermann and additized with an additive package of polyisobutenamine, carrier oil, dehazer and solvent. To formulate the corrosion inhibitors indicated in Table 2 were added and subjected to a corrosion test according to ASTM D 665 B.
Figure imgf000025_0001
Figure imgf000025_0001
Die Bewertung erfolgte folgendermaßen: The evaluation was carried out as follows:
A 100% rostfrei A 100% rustproof
B++ 0,1 % oder weniger der gesamten Oberfläche verrostet  B ++ 0.1% or less of the entire surface rusted
B+ 0,1 % bis 5% der gesamten Oberfläche verrostet  B + 0.1% to 5% of the total surface rusted
B 5 % bis 25% der gesamten Oberfläche verrostet  B 5% to 25% of the entire surface rusted
C 25 % bis 50% der gesamten Oberfläche verrostet C 25% to 50% of the entire surface rusted
D 50 % bis 75% der gesamten Oberfläche verrostet  D 50% to 75% of the total surface rusted
E 75 % bis 100% der gesamten Oberfläche verrostet Tabelle 2 E 75% to 100% of the entire surface rusted Table 2
Figure imgf000026_0001
Figure imgf000026_0001
Calciumverträglichkeitstest: Calcium compatibility test:
100 ml Motorenöl (Shell Helix®, Figur 1 und 2, jeweils Becherglas ganz links, mit einem Ca- Gehalt von 1500 ppm, Mg-Gehalt 1 100 ppm und Zn-Gehalt 1300 ppm) wurden im Becherglas auf 70°C erhitzt und anschließend 1 ml Korrosionsinhibitor zugesetzt. Sollte die Lösung noch klar sein, gibt man weitere 1 ml Inhibitor zu. Wenn sich die Lösung trübt, gilt der Test als nicht bestanden (z.B. Figur 2, rechtes Becherglas). 100 ml motor oil (Shell Helix®, Figure 1 and 2, each beaker leftmost, with a Ca content of 1500 ppm, Mg content 1 100 ppm and Zn content 1300 ppm) were heated in a beaker to 70 ° C and then Added 1 ml of corrosion inhibitor. If the solution is still clear, add another 1 ml of inhibitor. If the solution becomes cloudy, the test is considered failed (e.g., Figure 2, right beaker).
Figur 1 zeigt von links nach rechts Shell Helix® (ohne Zusatz) bzw. versetzt mit jeweils 2 ml Korrosionsinhibitor aus Synthesebeispiel 1 , Synthesebeispiel 2 und Synthesebeispiel 3. Der Inhalt der Bechergläser bleibt klar. FIG. 1 shows from left to right Shell Helix® (without additive) or mixed with in each case 2 ml of corrosion inhibitor from Synthesis Example 1, Synthesis Example 2 and Synthesis Example 3. The contents of the beakers remain clear.
Aus Figur 2, rechtes Becherglas, sieht man, daß die als Vergleich eingesetzte Dimerfettsäure (1 ml, dimere Ölsäure; CAS: 61788-89-4) eine starke Trübung zeigt und demzufolge keine Verträglichkeit mit den angegebenen Metallionen zeigt. Demgegenüber zeigen die erfindungsgemäßen Verbindungen bei guter Korrosionsinhibierung zusätzlich eine gute Verträglichkeit gegenüber Metallionen. From Figure 2, right beaker, it can be seen that the dimer fatty acid used as a comparison (1 ml, dimeric oleic acid, CAS: 61788-89-4) shows a strong turbidity and therefore shows no compatibility with the indicated metal ions. In contrast, the compounds of the invention with good corrosion inhibition additionally show good compatibility with metal ions.

Claims

Patentansprüche  claims
1. Verwendung von Verbindungen der Formel (I) 1. Use of compounds of the formula (I)
Figure imgf000027_0001
worin
Figure imgf000027_0001
wherein
R1 und R2 jeweils unabhängig voneinander Wasserstoff, d- bis C2oo-Alkyl oder C3- bisR 1 and R 2 are each independently hydrogen, C 1 to C 20 alkyl or C 3 to
C2oo-Alkenyl sein können, wobei die Alkyl- oder Alkenylreste jeweils geradkettig oder verzweigt, mit Heteroatom-haltigen Resten substituiert oder unsubstituiert und optional von Heteroatomen unterbrochen sein können, C2-alkenyl, where the alkyl or alkenyl radicals may each be straight-chain or branched, substituted by heteroatom-containing radicals or unsubstituted and optionally interrupted by heteroatoms,
mit der Maßgabe, daß einer der Reste R1 und R2 Wasserstoff ist, with the proviso that one of R 1 and R 2 is hydrogen,
R3 ein n-bindiger, 3 bis 30 Kohlenstoffatome aufweisender Alkylen, Cycloalkylen oderR 3 is an n-bonded, having 3 to 30 carbon atoms alkylene, cycloalkylene or
Arylenrest ist, der jeweils geradkettig oder verzweigt, substituiert oder unsubstituiert und optional von Heteroatomen unterbrochen sein kann, Arylene radical which can be straight-chain or branched, substituted or unsubstituted and optionally interrupted by heteroatoms,
n eine positive ganze Zahl von 3 bis 10,  n is a positive integer from 3 to 10,
X jeweils unabhängig voneinander Sauerstoff (O), Schwefel (S) oder unsubstituierter o- der substituierter Stickstoff (NR4) sein können und X may each independently be oxygen (O), sulfur (S) or unsubstituted or substituted nitrogen (NR 4 ), and
R4 Wasserstoff oder C1-C4- Alkyl bedeuten, als Korrosionsinhibitoren in Kraft- oder Schmierstoffen bevorzugt in Kraftstoffen, besonders bevorzugt in Kraftstoffen, die einen Gehalt an Alkali- und/oder Erdalkalimetallen und/oder Zink von mindestens 0,1 Gew.ppm aufweisen. R 4 is hydrogen or C 1 -C 4 -alkyl, as corrosion inhibitors in fuels or lubricants preferably in fuels, more preferably in fuels having a content of alkali and / or alkaline earth metals and / or zinc of at least 0.1 ppm by weight ,
2. Verwendung gemäß Anspruch 1 , dadurch gekennzeichnet, daß die Alkali- und/oder Erdalkalimetalle und/oder Zink ausgewählt sind aus der Gruppe bestehend aus Natrium, Zink, Magnesium und Calcium. Verwendung gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß es sich bei den Alkenylresten in R1 und R2 um solche handelt, die durch Oligo- oder Polymerisation von Propen, 1 -Buten, 2-Buten und/oder iso-Buten erhältlich sind. 2. Use according to claim 1, characterized in that the alkali and / or alkaline earth metals and / or zinc are selected from the group consisting of sodium, zinc, magnesium and calcium. Use according to one of the preceding claims, characterized in that the alkenyl radicals in R 1 and R 2 are those which are obtainable by oligo- or polymerization of propene, 1-butene, 2-butene and / or isobutene ,
Verwendung gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß es sich bei den Resten R3 um solche Reste handelt, die durch gedankliche Abstraktion von n Hydroxygruppen aus einem mindestens n-wertigen Polyol entstehen. Use according to one of the preceding claims, characterized in that the radicals R 3 are radicals which are formed by mental abstraction of n-hydroxy groups from an at least n-valent polyol.
Verwendung gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß X Sauerstoff bedeutet. Use according to any one of the preceding claims, characterized in that X represents oxygen.
Verwendung gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß die Verbindungen der Formel (I) im Gemisch mit solchen der Formel (II) vorliegen Use according to one of the preceding claims, characterized in that the compounds of the formula (I) are present in a mixture with those of the formula (II)
Figure imgf000028_0001
worin
Figure imgf000028_0001
wherein
p und q unabhängig voneinander positive rationale Zahlen sind, die im statistischen Mittel auch nicht ganzzahlig sein können, p and q are, independently of each other, positive rational numbers, which can not be even in statistical terms,
mit der Maßgabe, daß p + q = n gilt, with the proviso that p + q = n,
R1, R2, R3 und n die Bedeutungen aus den vorstehenden Ansprüchen haben R 1 , R 2 , R 3 and n have the meanings of the preceding claims
und and
q/n > 0,5 ist. q / n> 0.5.
Verwendung gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß Verbindungen der Formel (I) erhältlich sind durch Umsetzung eines Bernsteinsäurederivats mit einem Polyol. Use according to any one of the preceding claims, characterized in that compounds of formula (I) are obtainable by reacting a succinic acid derivative with a polyol.
Verwendung gemäß Anspruch 7, dadurch gekennzeichnet, daß das Bernsteinsäurederivat ausgewählt ist aus der Gruppe bestehend aus Dodecenylbernsteinsäure, Hexadece- nylbernsteinsäure, Eicosenylbernsteinsäure und Polyisobuten-substituierte Bernsteinsäurederivaten, wobei der Polyisobutenrest ein mittleres Molgewicht von 300 bis 2000 aufweist. Use according to Claim 7, characterized in that the succinic acid derivative is selected from the group consisting of dodecenylsuccinic acid, hexadecylsuccinic acid, eicosenylsuccinic acid and polyisobutene-substituted succinic acid derivatives, the polyisobutene radical having an average molecular weight of from 300 to 2,000.
9. Verwendung gemäß Anspruch 4, 7 oder 8, dadurch gekennzeichnet, daß das Diol ausgewählt ist aus der Gruppe bestehend aus Trimethylolbutan, Trimethylolpropan, Trime- thylolethan, Pentaerythrit, Glycerin, Ditrimethylolpropan, Dipentaerythrit, Sorbit, Mannit, Diglycerol, Threit, Erythrit, Adonit (Ribit), Arabit (Lyxit), Xylit, Dulcit (Galactit), Maltit, Iso- malt, Ditrimethylolpropan, Dipentaerythrit, Polyglycerol-3, Polyglycerol-4, Dimethylolp- ropionsäure, Dimethylolbuttersäure, Trimethylolessigsäure, Hydroxypivalinsäure, Glu- consäure, Glucarsäure, Glucuronsäure, Galacturonsäure, Galactarsäure, Diethanolamin, Triethanolamin und N-Methyl-Diethanolamin. 10. Verwendung gemäß einem der vorstehenden Ansprüche zur Inhibierung der Korrosion von Eisen-, Stahl- und/oder Buntmetalloberflächen. 9. Use according to claim 4, 7 or 8, characterized in that the diol is selected from the group consisting of trimethylolbutane, trimethylolpropane, trimethylolethane, pentaerythritol, glycerol, ditrimethylolpropane, dipentaerythritol, sorbitol, mannitol, diglycerol, threitol, erythritol, Adonite (ribitol), arabitol (lyxite), xylitol, dulcitol (galactitol), maltitol, isomalt, ditrimethylolpropane, dipentaerythritol, polyglycerol-3, polyglycerol-4, dimethylolpropionic acid, dimethylolbutyric acid, trimethylolacetic acid, hydroxypivalic acid, gluconic acid, glucaric acid , Glucuronic acid, galacturonic acid, galactaric acid, diethanolamine, triethanolamine and N-methyl-diethanolamine. 10. Use according to one of the preceding claims for inhibiting the corrosion of iron, steel and / or non-ferrous metal surfaces.
1 1. Verwendung gemäß einem der vorstehenden Ansprüche, dadurch gekennzeichnet, daß es sich bei dem Kraftstoff um einen Diesel- oder Ottokraftstoff handelt. 1 1. Use according to any one of the preceding claims, characterized in that it is the fuel is a diesel or gasoline fuel.
PCT/EP2016/067001 2015-07-24 2016-07-18 Corrosion inhibitors for fuels and lubricants WO2017016909A1 (en)

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