EP2812418B1 - Imidazolium salts as additives for fuels and combustibles - Google Patents

Imidazolium salts as additives for fuels and combustibles Download PDF

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EP2812418B1
EP2812418B1 EP13702810.6A EP13702810A EP2812418B1 EP 2812418 B1 EP2812418 B1 EP 2812418B1 EP 13702810 A EP13702810 A EP 13702810A EP 2812418 B1 EP2812418 B1 EP 2812418B1
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oils
fuels
fuel
imidazolium
variables
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French (fr)
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EP2812418A1 (en
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Maxim Peretolchin
Ludwig Völkel
Harald BÖHNKE
Markus Hansch
Boris GASPAR
Christian Seitz
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/22—Organic compounds containing nitrogen
    • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/04—Use of additives to fuels or fires for particular purposes for minimising corrosion or incrustation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/06—Use of additives to fuels or fires for particular purposes for facilitating soot removal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/08—Use of additives to fuels or fires for particular purposes for improving lubricity; for reducing wear
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/14—Use of additives to fuels or fires for particular purposes for improving low temperature properties
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L10/00—Use of additives to fuels or fires for particular purposes
    • C10L10/18—Use of additives to fuels or fires for particular purposes use of detergents or dispersants for purposes not provided for in groups C10L10/02 - C10L10/16
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/18—Organic compounds containing oxygen
    • C10L1/188—Carboxylic acids; metal salts thereof
    • C10L1/1881—Carboxylic acids; metal salts thereof carboxylic group attached to an aliphatic carbon atom
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
    • C10L1/2431—Organic compounds containing sulfur, selenium and/or tellurium sulfur bond to oxygen, e.g. sulfones, sulfoxides
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/10—Liquid carbonaceous fuels containing additives
    • C10L1/14—Organic compounds
    • C10L1/26—Organic compounds containing phosphorus
    • C10L1/2633—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond)
    • C10L1/2641—Organic compounds containing phosphorus phosphorus bond to oxygen (no P. C. bond) oxygen bonds only
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0407—Specifically defined hydrocarbon fractions as obtained from, e.g. a distillation column
    • C10L2200/0438—Middle or heavy distillates, heating oil, gasoil, marine fuels, residua
    • C10L2200/0446—Diesel

Definitions

  • the present invention relates to the use of imidazolium salts as additives for fuels, in particular as detergent additives for diesel fuels, especially for those diesel fuels which are burned in direct-injection diesel engines, in particular in common-rail injection systems. Furthermore, the present invention relates to an additive concentrate and a fuel or fuel composition containing such imidazolium salts. Furthermore, the present invention relates to novel imidazolium salts and their use in industrial fluids.
  • direct-injection diesel engines the fuel is injected through a directly into the combustion chamber-reaching multi-hole injection nozzle of the engine and finely distributed (nebulized), instead of being introduced as in the classic (chamber) diesel engine in a vortex or vortex chamber.
  • the advantage of direct-injection diesel engines lies in their high performance for diesel engines and yet low consumption. In addition, these engines achieve a very high torque even at low speeds.
  • the diesel fuel is pumped by a pump with pressures up to 2000 bar into a high-pressure line, the common rail.
  • spur lines run to the various injectors, which inject the fuel directly into the combustion chamber.
  • the full pressure is always applied to the common rail, which allows a multiple injection or a special injection form. In the other injection systems, however, only a smaller variation of the injection is possible.
  • Injection in the common rail is essentially subdivided into three groups: (1) preinjection, which substantially achieves softer combustion, so that hard combustion noises ("nails") are reduced and engine running appears quiet; (2.) main injection, which is responsible in particular for a good torque curve; and (3.) post-injection, which provides in particular for a low NO x value.
  • preinjection which substantially achieves softer combustion, so that hard combustion noises ("nails") are reduced and engine running appears quiet
  • main injection which is responsible in particular for a good torque curve
  • post-injection which provides in particular for a low NO x value.
  • the fuel is not burned in the rule, but evaporated by residual heat in the cylinder.
  • the resulting exhaust gas / fuel mixture is transported to the exhaust system, where the fuel in the presence of suitable catalysts acts as a reducing agent for the nitrogen oxides NO x .
  • deposits can form under certain conditions, for example when using biodiesel successionn fuels or fuels with metal impurities such as zinc compounds, copper compounds, lead compounds and other metal compounds at the injector Negatively affecting the injection behavior of the fuel and thereby impairing the performance of the engine, ie In particular, reduce the power, but in part also deteriorate the combustion.
  • the formation of deposits is further enhanced by structural developments of the injectors, in particular by the change in the geometry of the nozzles (narrower, conical openings with rounded outlet). For a permanently optimal functioning of engine and injectors such deposits must be prevented or reduced in the nozzle openings by suitable fuel additives.
  • the international application WO 2012/004300 (1) describes acid-free quaternized nitrogen compounds as fuel additives obtained by adding a compound containing at least one anhydride-reactive oxygen or nitrogen-containing group and additionally at least one quaternizable amino group to a polycarboxylic acid anhydride compound followed by quaternization with an epoxide in the absence of free acid are available.
  • Polyamines having at least one primary or secondary amino group and at least one tertiary amino group are particularly suitable as compounds with an anhydride-reactive oxygen or nitrogen-containing group and additionally a quaternizable amino group.
  • Suitable polycarboxylic acid anhydrides are, in particular, dicarboxylic acids, such as succinic acid, having a longer-chain hydrocarbyl substituent.
  • Such a quaternized nitrogen compound is, for example, the reaction product of polyisobutenyl succinic anhydride obtained at 40 ° C with 3- (dimethylamino) propylamine, which is a polyisobutenylsuccinic acid hemiamide and which is then quaternized with styrene oxide in the absence of free acid at 70 ° C.
  • acid-free quaternized nitrogen compounds are particularly useful as fuel additives to reduce or prevent deposits in injection systems of direct injection diesel engines, particularly in common rail injection systems, to reduce fuel consumption of direct injection diesel engines, particularly diesel engines with common rail injection systems, and / or to minimize the power loss in direct injection diesel engines, especially in diesel engines with common rail injection systems.
  • the international application PCT / EP2011 / 071683 (2) describes polytetrahydrobenzoxazines and bistetrahydrobenzoxazines as fuel additives which are obtainable by successively in a first reaction step a C 1 to C 20 -alkylenediamine having two primary amino functions, for example 1,2-ethylenediamine, having a C 1 to C 12 aldehyde, z. B.
  • the bistetrahydrobenzoxazine thus obtained is heated to a temperature of 125 to 280 ° C for at least 10 minutes.
  • Such Polytetrahydrobenzoxazine and Bistetrahy-drobenzoxazine are particularly useful as fuel additive for reducing or preventing deposits in injection systems of direct-injection diesel engines, especially in common-rail injection systems, to reduce the fuel consumption of direct-injection diesel engines, especially diesel engines with common-rail injection systems, and / or to minimize the power loss in direct injection diesel engines, especially in diesel engines with common rail injection systems.
  • Imidazolium salts of type (I) include - in addition to, for example, open-chain quaternary ammonium salts, pyridinium salts, pyridazinium salts, pyrimidinium salts, pyrazinium salts, pyrazolium salts, pyrazolinium salts, imidazolinium salts, thiazolium salts, triazolium salts.
  • Ionic liquids often contain an organic compound as a cation (organic cation). Depending on the valency of the anion, the ionic liquid may contain other cations, such as metal cations, in addition to the organic cation
  • Imidazolium salts of type (I) are known in their use as detergents or dispersants in lubricant formulations. That's how it describes WO 2010/101801 A1 (3) oil-soluble ionic detergents as additive components in lubricating oils for internal combustion engines; Examples include, in addition to open-chain ionic systems and quaternized pyridinium detergents, quaternized imidazolium phenates, imidazolium chlorides, and imidazolium salicylates.
  • ionic liquids such as pyridinium salts are described as additives for controlling deposit formation on the inner surfaces of internal combustion engines.
  • such additives are added to the lubricating oil rather than the fuel used to operate these engines.
  • the disclosed WO 2010/096168 A1 explicitly no imidazolium salts as such additives.
  • the US 4 108 858 discloses high molecular weight N-hydrocarbyl substituted quaternized ammonium salts having a molecular weight of 350 to 3000 carbon atoms for the hydrocarbyl group as detergents and dispersants for fuels such as gasoline and diesel fuels and lubricating oils.
  • high molecular weight N-hydrocarbyl-substituted quaternized ammonium salts in addition to open-chain systems, salts of piperidines, piperazines, morpholines and pyridines are mentioned.
  • polybutene or polypropylene radicals may be considered as longer-chain hydrocarbyl radicals.
  • the imidazolium salts (I) are used as detergent additives for diesel fuels.
  • the imidazolium salts (I) are used as a wax anti-settling additive (WASA) for middle distillate fuels, in particular diesel fuels.
  • WASA wax anti-settling additive
  • the imidazolium salts (I) are used as lubricity improvers for fuels and fuels, in particular as friction modifiers for gasoline fuels and as lubricity additives for middle distillate fuels or diesel fuels.
  • Preferred organic radicals for the variables R 1 to R 5 in the imidazolium salts of the general formula (I) are C 1 - to C 20 -alkyl radicals, in particular C 1 - to C 12 -alkyl radicals, especially C 1 - to C 8 -alkyl radicals, for example, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl,
  • Suitable organic radicals having 1 to 20 carbon atoms for the variables R 1 to R 5 in the imidazolium salts of the general formula (I) are also C 3 - to C 12 -cycloalkyl radicals, in particular C 5 - to C 7 -cycloalkyl radicals, for example cyclopentyl, 2 Methyl-1-cyclopentyl, 3-methyl-1-cyclopentyl, cyclohexyl, 2-methyl-1-cyclohexyl, 3-methyl-1-cyclohexyl, 4-methyl-1-cyclohexyl.
  • Suitable organic radicals having 1 to 20 carbon atoms for the variables R 1 to R 5 in the imidazolium salts of the general formula (I) are also C 2 - to C 20 -alkenyl radicals, in particular C 3 - to C 8 -alkenyl radicals, for example vinyl, 2 Propenyl (allyl), 3-butenyl, cis-2-butenyl, trans-2-butenyl.
  • Suitable organic radicals having 1 to 20 carbon atoms for the variables R 1 to R 5 in the imidazolium salts of the general formula (I) are furthermore also C 3 - to C 12 -cycloalkenyl radicals, in particular C 5 - to C 7 -cyclocoylcyl radicals, for example Cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl.
  • aryl or heteroaryl radicals having 3 to 20, in particular 5 to 10, carbon atoms for example phenyl, 2-methylphenyl (2-tolyl), 3-methylphenyl (3-tolyl), 4-methylphenyl (4-tolyl), 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,3- Dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 4-phenylphenyl, 1-naphthyl, 2-naphthyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl.
  • the organic radicals having 1 to 3000 carbon atoms for the variables R 1 to R 5 may be synthetically produced radicals or-especially in the case of alkyl and alkenyl radicals-radicals based on naturally occurring compounds.
  • the latter are derived, in particular, from naturally occurring glycerides or fatty acids, for example from stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid or tallow fatty acid.
  • Such radicals based on naturally occurring compounds often represent mixtures of different, mostly homologous alkyl or alkenyl radicals.
  • Suitable organic radicals for the variables R1 to R5 in the imidazolium salts of the general formula (I) are furthermore preferably polyisobutyl radicals having from 30 to 250 carbon atoms.
  • Such polyisobutyl radicals have certain number-average molecular weights M n of from 900 to 3000, very particularly preferably from 900 to 1100, determined by gel permeation chromatography.
  • the polyisobutyl radicals may be attached directly or through a methylene group (-CH 2 -) to the imidazolium ring.
  • imidazolium salts of the general formula (I) are used, in which the variables R 1 and R 3 have the meanings of an organic radical listed above and the variables R 2, R 4 and R 5 are hydrogen.
  • imidazolium salts of the general formula (I) are used, in which the variables R 1 and R 3 independently of one another for C 1 - to C 20 -alkyl groups, C 2 - to C 20 -alkenyl groups and / or polyisobutyl radicals with a number average molecular weight (M n ) of 900 to 3000 and the variables R2, R4 and R5 are each hydrogen.
  • These C 1 - to C 20 -alkyl groups are pure hydrocarbon radicals.
  • typical Examples of such pure C 1 -C 20 -hydrocarbon radicals are the 2-ethylhexyl and the tallow fatty alkyl radical.
  • anion X an alkyl carbonate, a pseudohalide, a carboxylate or the tricyanomethamide anion.
  • the charge n of the anion X depends on its nature and may be 1, 2 or 3. Most often, n is 1 or 2, especially 1.
  • imidazolium salts (I) are 1,3-dimethylimidazolium acetate, 1,3-diethylimidazolium acetate, 1-ethyl-3-methylimidazolium acetate, 1-propyl-3-methylimidazolium acetate, 1-butyl-3-yl methylimidazolium acetate, 1-pentyl-3-methylimidazolium acetate, 1-hexyl-3-methylimidazolium acetate, 1-octyl-3-methylimidazolium acetate, 1- (2-ethylhexyl) -3-methylimidazolium acetate, 1, 3-di (2-ethylhexyl) imidazolium acetate, 1-decyl-3-methylimidazolium acetate, 1- (2-propylheptyl) -3-methylimidazolium acetate, 1,3,4,5-tetramethylimidazolium a
  • Typical individual examples of imidazolium salts (I) with polyisobutenyl radicals are 1-polyisobutyl-3-methylimidazolium acetate, 1-polyisobutyl-3-ethylimidazolium acetate, 1-polyisobutyl-3-propylimidazolium acetate, 1-polyisobutyl-3-butylimidazolium acetate, 1-Polyisobutyl-3- (2-ethylhexyl) imidazolium acetate, 1,3-di (polyisobutyl) imidazolium acetate, 1-polyisobutyl-3-methylimidazolium methylcarbonate, 1-polyisobutyl-3-ethylimidazolium methylcarbonate, 1-polyisobutyl 3-propylimidazolium methylcarbonate, 1-polyisobutyl-3-butylimidazolium methylcarbon
  • Imidazolium salts of type (I) with low molecular weight radicals are marketed commercially under the name Basionics TM by BASF SE.
  • imidazolium salts of type (I) is familiar to the person skilled in the art.
  • a typical synthetic route is imidazole formation from 1 mole of a 1,2-dicarbonyl compound, 1 mole of an appropriately substituted primary amine, 1 mole of ammonia, and 1 mole of an aldehyde, N-alkylation with a suitable alkylating agent, and then exchange if desired, the anion from.
  • a low molecular weight primary alkylamine or alkenylamine e.g.
  • an N-alkyl-4,5-diphenylimidazole or an N-alkylimidazole or an N-polyisobutyl-4,5-diphenylimidazole or a N-polyisobutylimidazole forth and alkylates the unsubstituted second nitrogen atom with an epoxide such as ethylene oxide, propylene oxide, butylene oxide or styrene oxide in the presence of acetic acid or with a dialkyl carbonate, wherein the imidazolium salt then an acetate anion or an alkyl carbonate anion having.
  • an epoxide such as ethylene oxide, propylene oxide, butylene oxide or styrene oxide
  • the imidazolium salt then an acetate anion or an alkyl carbonate anion having.
  • a polyisobutyl radical on the unsubstituted second nitrogen atom can use with a polyisobutene as alkyl
  • imidazolium salts of type (I) having the same variables R1 and R3 it is advantageous to use 1 mole of a 1,2-dicarbonyl compound together with 2 moles of an appropriately substituted primary amine and 1 mole of an aldehyde, optionally in the presence of a suitable solvent (e.g. Acetic acid and water when an imidazolium acetate is to be obtained) in a one-step synthesis, usually at 20 to 120 ° C, in particular at 25 to 80 ° C to.
  • a suitable solvent e.g. Acetic acid and water when an imidazolium acetate is to be obtained
  • the fuel or fuel additized with one or more imidazolium salts (I) is a gasoline or, in particular, a middle distillate fuel, especially a diesel fuel.
  • the fuel or fuel may contain other conventional additives ("co-additives") to improve the effectiveness and / or wear suppression.
  • these are primarily conventional detergent additives, carrier oils, cold flow improvers, lubricity improvers, corrosion inhibitors, demulsifiers, dehazers, defoamers, cetane improvers, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and / or Solvent.
  • 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 113 to 10,000, more preferably from 300 to 5,000, more preferably from 300 to 3,000, even more preferably from 500 to 2,500 and in particular from 700 to 2,500, especially from 800 to 1,500.
  • M n number average molecular weight
  • typical hydrophobic hydrocarbon radicals are in particular polypropenyl, polybutenyl and polyisobutenyl radicals having a number average molecular weight M n of preferably from 300 to 5,000, more preferably 300 to 3,000, more preferably 500 to 2,500, even more preferably 700 to 2,500 and especially 800 to 1,500.
  • Such additives based on highly reactive polyisobutene, which from the polyisobutene, which may contain up to 20 wt .-% of n-butene units, by hydroformylation and reductive amination with ammonia, monoamines or polyamines such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine can be prepared, in particular from EP-A 244 616 known.
  • 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 US Pat DE-A 196 20 262 are described.
  • Carboxyl groups or their alkali metal or alkaline earth metal salts (Dd) containing additives are preferably copolymers of C 2 - to C 40 olefins with maleic anhydride having a total molecular weight of 500 to 20,000, the carboxyl groups wholly or partially to the alkali metal or alkaline earth metal salts and a remaining Rest of the carboxyl groups are reacted with alcohols or amines.
  • Such additives are in particular from the EP-A 307 815 known.
  • Such additives are primarily for preventing valve seat wear and can, as in the WO-A 87/01126 described, 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 is described.
  • Such additives are primarily for preventing valve seat wear and can be used with advantage in combination with conventional fuel detergents such as poly (iso) buten-amines or polyetheramines.
  • Polyoxy-C 2 -C 4 -alkylene (Df) containing additives are preferably polyether or polyetheramines, which by reaction of C 2 - to C 60 -alkanols, C 6 -C 30 alkanediols, mono- or di-C 2 - to C 30 -alkylamines, C 1 - to C 30 -alkylcyclohexanols or C 1 - to C 30 -alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, are obtainable by subsequent reductive amination with ammonia, monoamines or polyamines.
  • Such products are used in particular in the EP-A 310 875 .
  • 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.
  • Carboxylic 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 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 diamines or polyamines which, in addition to the amide function, still have free amine groups, succinic acid derivatives with a Acid and an amide, Carbon Textreimide with monoamines, Carbonklareimide with di- or polyamines, which still have free amine groups in addition to the imide function, or diimides, which are formed by the reaction of di- or polyamines with two succinic acid derivatives.
  • Such fuel additives are particularly in the US Pat. No. 4,849,572 described.
  • 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 groupings (di) -containing 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 particularly in the EP-A 831 141 described.
  • one or more of the above-mentioned detergent additives of the group (Da) to (Di) may be added in such an amount that the dosage rate of these detergent additives is preferably 25 to 2500 ppm by weight, especially 75 to 1500% by weight . ppm, especially 150 to 1000 ppm by weight.
  • Carrier oils used as co-additives may be mineral or synthetic.
  • Suitable mineral carrier oils are fractions obtained in petroleum processing, such as bright stock or base oils having 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 polyinternalolefins), (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 60 -alkanols, C 6 - to C 30 -alkanediols, mono- or di-C 2 - to C 30 -alkylamines, C 1 - to C 30 -alkyl-cyclohexanols or C 1 - to C 30 - Alkylphenols with 1 to 30 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.
  • EP-A 310 875 Such products are used in particular in the EP-A 310 875 .
  • EP-A 356 725 EP-A 700 985 and the US-A 4,877,416 described.
  • poly-C 2 -C 6 -alkylene oxide amines or functional derivatives thereof can be used as polyetheramines. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and Polyisobutenolbutoxylate 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 are described in particular in US Pat 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 carbon atoms.
  • esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and of isotridecanol, eg. B. di- (n- or isotridecyl) phthalate.
  • particularly suitable synthetic carrier oils are alcohol-started polyethers having about 5 to 35, preferably about 5 to 30, particularly preferably 10 to 30 and in particular 15 to 30 C 3 - to C 6 -alkylene oxide units, 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 aliphatic C 6 - to C 18 -alcohols with C 3 - to C 6 -alkylene oxides.
  • monohydric aliphatic C 6 -C 18 -alcohols are hexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, decanol, 2-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.
  • C 3 - to C 6 -alkylene oxides are propylene oxide, such as 1,2-propylene oxide, butylene oxide, such as 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide or tetrahydrofuran, pentylene oxide and hexylene oxide.
  • C 3 -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.
  • Suitable synthetic carrier oils are alkoxylated alkylphenols, as described in the DE-A 10 102 913 are described.
  • Particular carrier oils are synthetic carrier oils, the alcohol-initiated 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 as co-additives 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.
  • middle distillates of fossil origin ie for conventional mineral diesel fuels
  • MDFI used cold flow improvers
  • WASA wax anti-settling additive
  • the imidazolium salts (I) used according to the invention have properties in themselves as middle grade distillate fuels, in particular in diesel fuels, as WASA, which is also the subject matter of the present invention.
  • co-additives used as cold flow improvers can act partly or predominantly as nucleators.
  • Suitable C 2 to C 40 olefin monomers for the copolymers of class (K1) are, for example, those having 2 to 20, in particular 2 to 10, carbon atoms and having 1 to 3, preferably 1 or 2, in particular having a carbon-carbon double bond. In the latter case, the carbon-carbon double bond can be arranged both terminally ( ⁇ -olefins) and internally.
  • ⁇ -olefins more preferably ⁇ -olefins having 2 to 6 carbon atoms, for example propene, 1-butene, 1-pentene, 1-hexene and especially ethylene.
  • the at least one further ethylenically unsaturated monomer is preferably selected from carboxylic 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 40 olefin base monomers. If, for example, ethylene or propene is used as the olefin base 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 1 - to C 20 -alkanols, in particular C 1 - to C 10 -alkanols, especially with methanol, ethanol, propanol, isopropanol, n-butanol, sec. Butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol and decanol and structural isomers thereof.
  • Suitable carboxylic alkenyl esters are, for example, C 2 -C 14 -alkenyl esters, for example 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 with a branched hydrocarbon radical preference is given to those whose branching is in the ⁇ -position to the carboxyl group, the ⁇ -carbon atom being particularly preferably tertiary, ie the carboxylic acid being 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, with 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").
  • copolymers of class (K1) are those which contain two or more different carboxylic acid alkenyl esters in copolymerized form, these differing in the alkenyl function and / or in the carboxylic acid group. Also suitable are copolymers which, in addition to the 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 C 2 - to C 40 - ⁇ -olefin, a C 1 - to C 20 alkyl ester of an ethylenically unsaturated monocarboxylic acid having 3 to 15 carbon atoms and a C 2 - to C 14 alkenyl ester of a saturated monocarboxylic acid having 2 to 21 Carbon atoms are suitable as copolymers of class (K1).
  • Such terpolymers are in the WO 2005/054314 described.
  • a typical such terpolymer is composed of ethylene, 2-ethylhexyl acrylate and vinyl acetate.
  • the at least one or the other ethylenically unsaturated monomers are present in the copolymers of class (K1) in an amount of preferably 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) is thus usually derived from the C 2 to C 40 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 having at least 10 carbon atoms available.
  • 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.
  • homopolymers and copolymers of vinyl ethers are suitable comb polymers.
  • suitable comb polymers are, for example, those which are described in the WO 2004/035715 and in " Comb-like polymers. Structure and Properties ", NA Platé and VP Shibaev, J. Poly. Sci. Macromolecular Revs., 8, pp. 117-253 (1974 Also mixtures of comb polymers are suitable.
  • suitable polyoxyalkylenes are, for example, polyoxyalkylene esters, polyoxyalkylene ethers, mixed polyoxyalkylene ester ethers, and mixtures thereof. These polyoxyalkylene compounds preferably contain at least one, preferably at least two linear alkyl groups each having 10 to 30 carbon atoms and a polyoxyalkylene group having a number average molecular weight of up to 5000. Such polyoxyalkylene compounds are for example in the EP-A 061 895 as well as in the U.S. 4,491,455 described. Particular polyoxyalkylene compounds are based on polyethylene glycols and polypropylene glycols having a number average molecular weight of 100 to 5000. Further, polyoxyalkylene mono- and diesters of fatty acids having 10 to 30 carbon atoms such as stearic acid or behenic acid are 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 C 8 - to C 40 hydrocarbon radical stands.
  • the nitrogen substituents may also be quaternized, that is 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 preferably contain at least one linear C 8 - to C 40 -alkyl radical.
  • suitable primary amines for the preparation of said polar nitrogen compounds are octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologues
  • suitable secondary amines are, for example, dioctadecylamine and methylbehenylamine.
  • amine mixtures in particular industrially available amine mixtures such as fatty amines or hydrogenated tallamines, as described, for example, in US Pat Ullmanns 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 class (K4) is an oil-soluble reaction product based on at least one tertiary amino group-containing poly (C 2 - to C 20 -carboxylic acids) of the general formula IIa or IIb in which the variable A is a straight-chain or branched C 2 - to C 6 -alkylene group or the grouping of the formula III and the variable B denotes a C 1 - to C 19 -alkylene group.
  • the compounds of the general formula IIa and IIb have in particular the properties of a WASA.
  • the preferred oil-soluble reaction product of component (K4) in particular that of 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 -C 6 -alkylene groups of the variable A are, for example, 1,1-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4- Butylene, 2-methyl-1,3-propylene, 1,5-pentylene, 2-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene (hexamethylene) and in particular 1,2-ethylene.
  • the variable A comprises 2 to 4, in particular 2 or 3 carbon atoms.
  • C 1 - to C 19 -alkylene groups of the variables 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 can be from a variety be selected from amines carrying - optionally interconnected - hydrocarbon radicals.
  • these amines are secondary amines on which the oil-soluble reaction products of component (K4) are based 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 14 - to C 24 -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 acid or from its 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 , Dipalmitinamin, Dikokosfettamin, distearylamine, dibehenylamine or especially Ditalgfettamin.
  • a particularly preferred component (K4) is the reaction product of 1 mole of ethylenediaminetetraacetic acid and 4 moles of hydrogenated ditallow fatty amine.
  • component (K4) 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 ditallow fatty amine, the latter being hydrogenated or unhydrogenated, and the reaction product of 1 mole of a Alkenylspirobislactons with 2 moles of a dialkylamine, for example Ditalgfettamin and / or tallow fatty amine, the latter two may be hydrogenated or not hydrogenated, 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 ditallow fatty amine, the latter being hydrogenated or unhydrogenated
  • the reaction product of 1 mole of a Alkenylspirobislactons with 2 moles of a dialkylamine for example Ditalgfettamin
  • component of class (K4) are cyclic compounds with tertiary amino groups or condensates of long-chain primary or secondary amines with carboxylic acid-containing polymers, as described in US Pat WO 93/18115 are described.
  • Sulfocarboxylic acids, sulfonic acids or their derivatives which are suitable as cold flow improvers of the component of class (K5) are, for example, the oil-soluble carboxamides and carboxylic esters of ortho-sulfobenzoic acid in which the sulfonic acid function is present as a sulfonate with alkyl-substituted ammonium cations, as described in the EP-A 261 957 to be discribed.
  • 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 C 14 and C 15 alcohols wherein the acid groups are neutralized with hydrogenated tallamine.
  • Suitable poly (meth) acrylic esters are, for example, in WO 00/44857 described.
  • 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 ppm by weight and in particular from 100 to 700 ppm by weight, for example from 200 to 500 ppm by weight, added.
  • Lubricity improvers or friction modifiers which are suitable as coadditives are usually based on fatty acids or fatty acid esters. Typical examples are tall oil fatty acid, such as in the WO 98/004656 described, and glycerol monooleate. Also in the US Pat. No. 6,743,266 B2 described reaction products of natural or synthetic oils, such as triglycerides, and alkanolamines are suitable as such lubricity improvers.
  • suitable corrosion inhibitors are z.
  • succinic acid esters especially with polyols, fatty acid derivatives, eg.
  • fatty acid derivatives eg.
  • oleic acid esters oligomerized fatty acids, substituted ethanolamines, N-acylated sarcosine
  • imidazoline derivatives e.g. B. those which in the 2-position an alkyl group and the trivalent nitrogen atom, a functional organic radical (a typical imidazoline derivative is the reaction product of excess oleic acid with diethylenetriamine), and products sold under the trade name RC 4801 (Rhein Chemie Mannheim , Germany) or Hi-TEC 536 (Ethyl Corporation).
  • the said imidazoline derivatives are particularly effective as corrosion inhibitors when used in this application with one or more carboxylic acid amides having one or more carboxylic acid amide functions in the molecule and longer chain radicals on the amide nitrogens, for example with the reaction product of maleic anhydride with a long chain amine in equimolar Ratio, combined.
  • suitable demulsifiers z 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 polysiloxanes.
  • EO ethylene oxide
  • PO propylene oxide
  • Suitable co-additives Dehazer are z.
  • alkoxylated phenol-formaldehyde condensates such as the available under the trade name NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite).
  • suitable antifoams are for.
  • Polyether-modified polysiloxanes such as the TEGOP-REN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc) products available under the tradename.
  • Suitable co-additives Cetaniereverêter z As aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate and peroxides such as di-tert-butyl peroxide.
  • suitable antioxidants are, for. Substituted, d. H. sterically hindered phenols such as 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-3-methylphenol or products sold under the trade name IRGANOX® (BASF SE), e.g. B. 2,6-di-tert-butyl-4-alkoxycarbonylethyl-phenol (IRGANOX L135), and phenylenediamines such as N, N'-di-sec-butyl-p-phenylenediamine.
  • IRGANOX® 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-3-methylphenol or products sold under the trade name IRGANOX® (BASF SE)
  • IRGANOX L1305 2,6-di-tert-butyl-4-alkoxycarbonylethyl-phenol
  • phenylenediamines such
  • suitable metal deactivators z As co-additives suitable metal deactivators z.
  • salicylic acid derivatives such as N, N'-disalicylidene-1,2-propanediamine or under the trade name IRGAMET® (BASF SE) marketed products based on N-substituted triazoles and tolutriazoles.
  • non-polar organic solvents such as aromatic and aliphatic hydrocarbons, for example toluene, xylenes, "white spirit" and products sold 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 and carboxylic acid esters with longer-chain alkyl groups such as C 12 - to C 20 fatty acid methyl ester, suitable.
  • Such solvents usually get together with the imidazolium salts (I) and the abovementioned co-additives, which they are intended to dissolve or dilute for better handling, into the fuel or fuel, in particular the diesel fuel.
  • the imidazolium salts (I) to be used according to the invention are outstandingly suitable as a fuel or fuel additive and can in principle be used in any fuels and fuels. They bring about a whole series of advantageous Effects in the operation of internal combustion engines with fuels.
  • the imidazolium salts (I) to be used according to the invention are preferably used in middle distillate fuels, in particular diesel fuels.
  • the present invention is therefore also a fuel and fuel composition, in particular a middle distillate fuel composition, with an additive to achieve advantageous effects in the operation of internal combustion engines, such as diesel engines, especially direct injection diesel engines, especially diesel engines with common rail Injection systems, effective content of the inventively used imidazolium salts (I) in addition to the main amount of a conventional basic or basic fuel.
  • This effective content is generally from 10 to 5000 ppm by weight, preferably from 20 to 1500 ppm by weight, in particular from 25 to 1000 ppm by weight, especially from 30 to 750 ppm by weight, in each case based on the total amount of fuel or fuel.
  • Middle distillate fuels such as diesel fuels or fuel oils
  • mineral middle distillate mineral fuels or diesel fuels available through refining
  • those produced by coal gasification or gas liquefaction [GTL] or by biomass to liquid (BTL) fuels are also included. are available, suitable. Also suitable are mixtures of the abovementioned middle distillate fuels or diesel fuels with regenerative fuels, such as biodiesel or bioethanol.
  • the imidazolium salts (I) to be used according to the invention can be used not only for their use in the abovementioned middle distillate fuels of fossil, vegetable or animal origin, which are essentially hydrocarbon mixtures, but also in mixtures of such middle distillates with biofuel oils (biodiesel).
  • middle distillate fuel such mixtures are also encompassed by the term "middle distillate fuel”.
  • biofuel oils typically in amounts of 1 to 30 wt .-%, in particular from 3 to 10 wt .-%, based on the Total amount of middle distillate of fossil, vegetable or animal origin and biofuel oil.
  • Biofuel oils are generally based on fatty acid esters, usually substantially on alkyl esters of fatty acids derived from vegetable and / or animal oils and / or fats.
  • Alkyl esters are usually lower alkyl esters, in particular 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”).
  • PME palm oil methyl ester
  • SME soybean oil methyl ester
  • RME rapeseed oil methyl ester
  • the middle distillate fuels or diesel fuels are particularly preferably those with a low sulfur content, ie with a sulfur content of less than 0.05% by weight, preferably less than 0.02% by weight, in particular less 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.
  • petrol fuel compositions of the specification are also according to WO 00/47698 Possible fields of use for the present invention.
  • the present invention also provides an additive concentrate which, in combination with at least one further fuel and fuel additive, in particular with at least one further diesel fuel additive, contains at least one imidazolium salt (I) to be used according to the invention.
  • an additive concentrate contains 10 to 60% by weight of at least one solvent or diluent, which may be an abovementioned solvent or the fuel or fuel itself.
  • the additive concentrate according to the invention preferably also comprises at least one detergent additive from the above-mentioned group (Da) to (Di), in particular at least one detergent additive of the type (Dh), and in US Pat Rule additionally also contain at least one lubricity improver and / or a corrosion inhibitor and / or a demulsifier and / or a dehazer and / or an antifoaming agent and / or a Cetanierevertoneer and / or an antioxidant and / or a metal deactivator in each of these customary quantitative ratios.
  • the new imidazolium salts of the general formula (Ia) are suitable not only for their use as additives for fuels and fuels, in particular as detergent additives for diesel fuels, but also for improving the service properties of mineral and synthetic non-aqueous industrial fluids.
  • non-aqueous industrial fluids which may contain water in individual cases, but whose essential effect is based on non-aqueous components, lubricants, lubricants and lubricating oils in the broadest sense, especially motor oils, gear oils, axle oils, hydraulic fluids, hydraulic oils, compressor fluids, compressor oils, Circulation oils, turbine oils, transformer oils, gas engine oils, wind turbine oils, runway oils, lubricating greases, cooling lubricants, wear protection oils for chains and conveyor systems, metalworking fluids, food grade lubricants for industrial processing of foodstuffs and cooker oils for cookers, sterilizers and steam peelers.
  • lubricants, lubricants and lubricating oils in the broadest sense, especially motor oils, gear oils, axle oils, hydraulic fluids, hydraulic oils, compressor fluids, compressor oils, Circulation oils, turbine oils, transformer oils, gas engine oils, wind turbine oils, runway oils, lubricating greases, cooling lubricants, wear protection oils for chains and conveyor systems, metalworking fluids, food grade lub
  • Performance properties which are improved by the imidazolium salts (Ia) are in particular the lubricating effect, the friction wear, the service life, the corrosion protection, the antimicrobial protection, the demulsifying ability with regard to a facilitated separation of water and impurities and the filterability.
  • the test method used was the DW10 engine test, in which the powerloss was determined by injector deposits in the common-rail diesel engine based on the official test method CEC F-098-08 becomes.
  • the power loss is a direct measure of the formation of deposits in the injectors.
  • a direct injection diesel engine with common rail system was used according to test methods CEC F-098-08.
  • the fuel used was a commercial diesel fuel from Craigrmann (DF-79-07 / 5).
  • the results illustrate the relative power loss measured at 4000 rpm during a 12-hour continuous operation.
  • the value "t0" indicates the power ("power") in kW at the start of the test and the value "t12" the power in kW at the end of the test.
  • the compounds (I.1) and (I.2) are commercially available products; the compound (I.3) was prepared from N-octylimidazole by quaternization with dimethyl carbonate as a 30% by weight solution in methanol by a usual synthesis method; the compound (I.4) was prepared according to the above-mentioned synthesis instructions.
  • the additives (I.1) and (I.2) were used as pure substances and the additives (I.3) and (I.4) as solutions.
  • the indicated dosage refers to the active ingredient.
  • the additives (I.2) and (I.4) were additionally used to carry out a soiling and cleaning operation in accordance with the DW10 test.
  • the used common rail direct injection diesel engine used with the same commercial diesel fuel containing 1 ppm by weight of zinc in the form of a zinc didodecanoate solution
  • additive (I.4) was also a "keep clean" motor test according to the test method CEC F-23-01 with the PSA engine XUD-9 A driven.
  • the additive was used at a dosage of 50 ppm in a commercial diesel fuel from Craigrmann (DF-79-07 / 5).
  • the engine was operated in a separate test run with the same diesel fuel without additive.
  • the "flow restriction” at 0.1 mm “Needle elevation” in the fuel was 63% without additive and with 50 ppm by weight of additive (I.4) -32%.

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Description

Die vorliegende Erfindung betrifft die Verwendung von Imidazoliumsalzen als Additive für Kraft- und Brennstoffe, insbesondere als Detergenzadditive für Dieselkraftstoffe, vor allem für solche Dieselkraftstoffe, die in direkteinspritzenden Dieselmotoren, insbesondere in Common-Rail-Einspritzsystemen, verbrannt werden. Weiterhin betrifft die vorliegende Erfindung ein Additivkonzentrat sowie eine Kraft- oder Brennstoffzusammensetzung, die solche Imidazoliumsalze enthalten. Weiterhin betrifft die vorliegende Erfindung neue Imidazoliumsalze und der Verwendung in Industrieflüssigkeiten.The present invention relates to the use of imidazolium salts as additives for fuels, in particular as detergent additives for diesel fuels, especially for those diesel fuels which are burned in direct-injection diesel engines, in particular in common-rail injection systems. Furthermore, the present invention relates to an additive concentrate and a fuel or fuel composition containing such imidazolium salts. Furthermore, the present invention relates to novel imidazolium salts and their use in industrial fluids.

Bei direkteinspritzenden Dieselmotoren wird der Kraftstoff durch eine direkt in den Brennraum reichende Mehrloch-Einspritzdüse des Motors eingespritzt und feinst verteilt (vernebelt), anstatt wie beim klassischen (Kammer-)Dieselmotor in eine Vor- oder Wirbelkammer eingeführt zu werden. Der Vorteil der direkteinspritzenden Dieselmotoren liegt in ihrer für Dieselmotoren hohen Leistung und einem dennoch geringen Verbrauch. Außerdem erreichen diese Motoren ein sehr hohes Drehmoment schon bei niedrigen Drehzahlen.In direct-injection diesel engines, the fuel is injected through a directly into the combustion chamber-reaching multi-hole injection nozzle of the engine and finely distributed (nebulized), instead of being introduced as in the classic (chamber) diesel engine in a vortex or vortex chamber. The advantage of direct-injection diesel engines lies in their high performance for diesel engines and yet low consumption. In addition, these engines achieve a very high torque even at low speeds.

Zur Zeit werden im Wesentlichen drei Verfahren eingesetzt, um den Kraftstoff direkt in den Brennraum des Dieselmotores einzuspritzen: die konventionelle Verteilereinspritzpumpe, das Pumpe-Düse-System (Unit-Injector-System bzw. Unit-Pump-System) und das Common-Rail-System.Essentially, three methods are currently used to inject the fuel directly into the combustion chamber of the diesel engine: the conventional distributor injection pump, the unit-injector system and the common-rail system. System.

Beim Common-Rail-System wird der Dieselkraftstoff von einer Pumpe mit Drücken bis zu 2000 bar in eine Hochdruckleitung, die Common-Rail, gefördert. Ausgehend von der Common-Rail laufen Stichleitungen zu den verschiedenen Injektoren, die den Kraftstoff direkt in den Brennraum injizieren. Dabei liegt auf der Common-Rail stets der volle Druck an, was eine Mehrfacheinspritzung oder eine spezielle Einspritzform ermöglicht. Bei den anderen Injektionssystemen ist dagegen nur eine geringere Variation der Einspritzung möglich. Die Einspritzung beim Common-Rail wird im Wesentlichen in drei Gruppen unterteilt: (1.) Voreinspritzung, durch die im Wesentlichen eine weichere Verbrennung erreicht wird, so dass harte Verbrennungsgeräusche ("Nageln") vermindert werden und der Motorlauf ruhig erscheint; (2.) Haupteinspritzung, die insbesondere für einen guten Drehmomentverlauf verantwortlich ist; und (3.) Nacheinspritzung, die insbesondere für einen geringen NOx-Wert sorgt. Bei dieser Nacheinspritzung wird der Kraftstoff in der Regel nicht verbrannt, sondern durch Restwärme im Zylinder verdampft. Das dabei gebildete Abgas-/Kraftstoffgemisch wird zur Abgasanlage transportiert, wo der Kraftstoff in Gegenwart geeigneter Katalysatoren als Reduktionsmittel für die Stickoxide NOx wirkt.In the common-rail system, the diesel fuel is pumped by a pump with pressures up to 2000 bar into a high-pressure line, the common rail. Starting from the common rail, spur lines run to the various injectors, which inject the fuel directly into the combustion chamber. In this case, the full pressure is always applied to the common rail, which allows a multiple injection or a special injection form. In the other injection systems, however, only a smaller variation of the injection is possible. Injection in the common rail is essentially subdivided into three groups: (1) preinjection, which substantially achieves softer combustion, so that hard combustion noises ("nails") are reduced and engine running appears quiet; (2.) main injection, which is responsible in particular for a good torque curve; and (3.) post-injection, which provides in particular for a low NO x value. In this post injection, the fuel is not burned in the rule, but evaporated by residual heat in the cylinder. The resulting exhaust gas / fuel mixture is transported to the exhaust system, where the fuel in the presence of suitable catalysts acts as a reducing agent for the nitrogen oxides NO x .

Durch die variable, zylinderindividuelle Einspritzung kann beim Common-Rail-Einspritzsystem der Schadstoffausstoß des Motors, z.B. der Ausstoß von Stickoxiden (NOx), Kohlenmonoxid (CO) und insbesondere von Partikeln (Ruß), positiv beeinflusst werden. Dies ermöglicht beispielsweise, dass mit Common-Rail-Einspritzsystemen ausgerüstete Motoren der Euro 4-Norm theoretisch auch ohne zusätzlichen Partikelfilter genügen können.Due to the variable, cylinder-specific injection of the common-rail injection system of the pollutant emissions of the engine, such as the emission of nitrogen oxides (NO x ), carbon monoxide (CO) and in particular of particles (soot) are positively influenced. This allows, for example, that equipped with common-rail injection systems engines of Euro 4 standard can theoretically meet without additional particulate filter.

In modernen Common-Rail-Dieselmotoren können sich unter bestimmten Bedingungen, beispielsweise bei Verwendung von biodieselhaltigen Kraftstoffen oder von Kraftstoffen mit Metall-Verunreinigungen wie Zink-Verbindungen, Kupfer-Verbindungen, Blei-Verbindungen und weiteren Metallverbindungen, an den Injektoröffnungen Ablagerungen bilden, die das Einspritzverhalten des Kraftstoffs negativ beeinflussen und dadurch die Performance des Motors beeinträchtigen, d.h. insbesondere die Leistung verringern, aber zum Teil auch die Verbrennung verschlechtern. Die Bildung von Ablagerungen wird durch bauliche Weiterentwicklungen der Injektoren, insbesondere durch die Veränderung der Geometrie der Düsen (engere, konische Öffnungen mit abgerundetem Auslass) noch verstärkt. Für eine dauerhaft optimale Funktionsweise von Motor und Injektoren müssen solche Ablagerungen in den Düsenöffnungen durch geeignete Kraftstoffadditive verhindert oder reduziert werden.In modern common-rail diesel engines deposits can form under certain conditions, for example when using biodieselhaltigen fuels or fuels with metal impurities such as zinc compounds, copper compounds, lead compounds and other metal compounds at the injector Negatively affecting the injection behavior of the fuel and thereby impairing the performance of the engine, ie In particular, reduce the power, but in part also deteriorate the combustion. The formation of deposits is further enhanced by structural developments of the injectors, in particular by the change in the geometry of the nozzles (narrower, conical openings with rounded outlet). For a permanently optimal functioning of engine and injectors such deposits must be prevented or reduced in the nozzle openings by suitable fuel additives.

Die internationale Anmeldung WO 2012/004300 (1) beschreibt säurefreie quaternisierte Stickstoffverbindungen als Kraftstoffadditive, welche durch Addition einer Verbindung, die wenigstens eine mit einem Anhydrid reaktive Sauerstoff- oder Stickstoffhaltige Gruppe und zusätzlich wenigstens eine quaternisierbare Aminogruppe enthält, an eine Polycarbonsäureanhydrid-Verbindung und nachfolgende Quaternisierung mit einem Epoxid in Abwesenheit von freier Säure erhältlich sind. Als Verbindungen mit einer mit einem Anhydrid reaktiven Sauerstoff- oder Stickstoff-haltigen Gruppe und zusätzlich einer quaternisierbaren Aminogruppe eignen sich insbesondere Polyamine mit mindestens einer primären oder sekundären Aminogruppe und mindestens einer tertiären Aminogruppe. Als Polycarbonsäureanhydride kommen insbesondere Dicarbonsäuren wie Bernsteinsäure mit einem längerkettigen Hydrocarbylsubstituenten in Betracht. Eine solche quaternisierte Stickstoffverbindung ist beispielsweise das bei 40°C erhaltene Umsetzungsprodukt von Polyisobutenylsuccinanhydrid mit 3-(Dimethyl-amino)-propylamin, welches ein Polyisobutenylbernsteinsäurehalbamid darstellt und das anschließend mit Styroloxid in Abwesenheit von freier Säure bei 70°C quaternisiert wird. Derartige säurefreie quaternisierte Stickstoffverbindungen eignen sich insbesondere als Kraftstoffzusatz zur Verringerung oder Verhinderung von Ablagerungen in Einspritzsystemen von direkteinspritzenden Dieselmotoren, insbesondere in Common-Rail-Einspritzsystemen, zur Verringerung des Kraftstoffverbrauches von direkteinspritzenden Dieselmotoren, insbesondere von Dieselmotoren mit Common-Rail-Einspritzsystemen, und/oder zur Minimierung des Leistungsverlustes (powerloss) in direkteinspritzenden Dieselmotoren, insbesondere in Dieselmotoren mit Common-Rail-Einspritzsystemen.The international application WO 2012/004300 (1) describes acid-free quaternized nitrogen compounds as fuel additives obtained by adding a compound containing at least one anhydride-reactive oxygen or nitrogen-containing group and additionally at least one quaternizable amino group to a polycarboxylic acid anhydride compound followed by quaternization with an epoxide in the absence of free acid are available. Polyamines having at least one primary or secondary amino group and at least one tertiary amino group are particularly suitable as compounds with an anhydride-reactive oxygen or nitrogen-containing group and additionally a quaternizable amino group. Suitable polycarboxylic acid anhydrides are, in particular, dicarboxylic acids, such as succinic acid, having a longer-chain hydrocarbyl substituent. Such a quaternized nitrogen compound is, for example, the reaction product of polyisobutenyl succinic anhydride obtained at 40 ° C with 3- (dimethylamino) propylamine, which is a polyisobutenylsuccinic acid hemiamide and which is then quaternized with styrene oxide in the absence of free acid at 70 ° C. Such acid-free quaternized nitrogen compounds are particularly useful as fuel additives to reduce or prevent deposits in injection systems of direct injection diesel engines, particularly in common rail injection systems, to reduce fuel consumption of direct injection diesel engines, particularly diesel engines with common rail injection systems, and / or to minimize the power loss in direct injection diesel engines, especially in diesel engines with common rail injection systems.

Die internationale Anmeldung PCT/EP2011/071683 (2) beschreibt Polytetrahydrobenzoxazine und Bistetrahydrobenzoxazine als Kraftstoffadditive, welche dadurch erhältlich sind, dass man sukzessive in einem ersten Reaktionsschritt ein C1- bis C20-Alkylendiamin mit zwei primären Aminofunktionen, z.B. 1,2-Ethylendiamin, mit einem C1- bis C12-Aldehyd, z. B. Formaldehyd, und einem C1- bis C8-Alkanol bei einer Temperatur von 20 bis 80°C unter Abspaltung und Entfernung von Wasser umsetzt, wobei sowohl der Aldehyd als auch der Alkohol jeweils in mehr als der doppelten molaren Menge gegenüber dem Diamin eingesetzt werden, in einem zweiten Reaktionsschritt das so erhaltene Kondensationsprodukt mit einem Phenol, welches mindestens einen langkettigen Substituenten, z. B. einen tert.-Octyl-, n-Nonyl-, n-Dodecyl- oder Polyisobutylrest trägt, im stöchiometrischen Verhältnis zum ursprünglich eingesetzten Alkylendiamin von 1,2 : 1 bis 3 : 1 bei einer Temperatur von 30 bis 120°C umsetzt und gegebenenfalls in einem dritten Reaktionsschritt das so erhaltene Bistetrahydrobenzoxazin auf eine Temperatur von 125 bis 280°C für mindestens 10 Minuten erhitzt. Derartige Polytetrahydrobenzoxazine und Bistetrahy-drobenzoxazine eignen sich insbesondere als Kraftstoffzusatz zur Verringerung oder Verhinderung von Ablagerungen in Einspritzsystemen von direkteinspritzenden Dieselmotoren, insbesondere in Common-Rail-Einspritzsystemen, zur Verringerung des Kraftstoffverbrauches von direkteinspritzenden Dieselmotoren, insbesondere von Dieselmotoren mit Common-Rail-Einspritzsystemen, und/oder zur Minimierung des Leistungsverlustes (powerloss) in direkteinspritzenden Dieselmotoren, insbesondere in Dieselmotoren mit Common-Rail-Einspritzsystemen.The international application PCT / EP2011 / 071683 (2) describes polytetrahydrobenzoxazines and bistetrahydrobenzoxazines as fuel additives which are obtainable by successively in a first reaction step a C 1 to C 20 -alkylenediamine having two primary amino functions, for example 1,2-ethylenediamine, having a C 1 to C 12 aldehyde, z. B. formaldehyde, and a C 1 - to C 8 alkanol at a temperature of 20 to 80 ° C with elimination and removal of water, wherein both the aldehyde and the alcohol in each case in more than twice the molar amount compared to the diamine be used, in a second reaction step, the condensation product thus obtained with a phenol which contains at least one long-chain substituent, for. B. carries a tert-octyl, n-nonyl, n-dodecyl or Polyisobutylrest, in a stoichiometric ratio to the originally used alkylenediamine of 1.2: 1 to 3: 1 at a temperature of 30 to 120 ° C and reacted optionally in a third reaction step, the bistetrahydrobenzoxazine thus obtained is heated to a temperature of 125 to 280 ° C for at least 10 minutes. Such Polytetrahydrobenzoxazine and Bistetrahy-drobenzoxazine are particularly useful as fuel additive for reducing or preventing deposits in injection systems of direct-injection diesel engines, especially in common-rail injection systems, to reduce the fuel consumption of direct-injection diesel engines, especially diesel engines with common-rail injection systems, and / or to minimize the power loss in direct injection diesel engines, especially in diesel engines with common rail injection systems.

Die genannten säurefreien quaternisierten Stickstoffverbindungen und Polytetrahydrobenzoxazine bzw. Bistetrahydrobenzoxazine sind jedoch in ihren Eigenschaften als Detergenzadditive für Kraft- und Brennstoffe noch verbesserungsbedürftig. Weiterhin sollen sie auch eine verbesserte Korrosionsschutzwirkung, eine verbesserte Motorenölverträglichkeit und verbesserte Tieftemperatureigenschaften aufweisen.However, the above-mentioned acid-free quaternized nitrogen compounds and polytetrahydrobenzoxazines or bistetrahydrobenzoxazines are still in need of improvement in their properties as detergent additives for fuels and fuels. Furthermore, they should also have an improved corrosion protection effect, improved engine oil compatibility and improved low-temperature properties.

Es bestand daher die Aufgabe, verbesserte Kraft- und Brennstoffadditive bereitzustellen, welche die aufgeführten Nachteile des Standes der Technik nicht mehr aufweisen.It was therefore an object to provide improved fuel and fuel additives, which no longer have the disadvantages of the prior art.

Demgemäß wurde die Verwendung von Imidazoliumsalzen der allgemeinen Formel (I)

Figure imgb0001
in der

  • die Variablen R1 und R3 unabhängig voneinander für einen organischen Rest, stehen,
  • die Variablen R2, R4 und R5 unabhängig voneinander Wasserstoff oder einen organischen Rest bedeuten,
  • X ein Anion bezeichnet
  • ausgewählt aus der Gruppe bestehend aus Alkylcarbonaten, Pseudohalogeniden, Carboxylaten oder dem Tricyanomethamid-Anion
    und
  • n für die Zahl 1, 2 oder 3 steht,
  • wobei die organischen Reste ausgewählt sind aus der Gruppe bestehend aus Alkyl-, Cycloalkyl-, Alkenyl-, Cyclo-alkenyl-, Aryl- oder Heteroarylresten, enthaltend 1 bis 20 Kohlenstoffatome, sowie Polyisobutylresten mit 30 bis 250 Kohlenstoffatomen,
  • als Detergenzadditiv für Dieselkraftstoffe, als Wachs-Anti-Settling Additiv (WASA) für Mitteldestillatbrennstoffe, insbesondere Dieselkraftstoffe, als Schmierfähigkeitsverbesserer für Kraft- und Brennstoffe oder als Friction Modifier für Ottokraftstoffe gefunden.
Accordingly, the use of imidazolium salts of the general formula (I)
Figure imgb0001
 in the
  • the variables R1 and R3 independently of one another represent an organic radical,
  • the variables R2, R4 and R5 independently of one another denote hydrogen or an organic radical,
  • X denotes an anion
  • selected from the group consisting of alkylcarbonates, pseudohalides, carboxylates or the tricyanomethamide anion
    and
  • n is the number 1, 2 or 3,
  • wherein the organic radicals are selected from the group consisting of alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl or heteroaryl radicals containing 1 to 20 carbon atoms, and also polyisobutyl radicals having 30 to 250 carbon atoms,
  • as a detergent additive for diesel fuels, as wax anti-settling additive (WASA) for middle distillate fuels, in particular diesel fuels, as lubricity improvers for fuels and found as friction modifier for gasoline fuels.

Imidazoliumsalze des Typs (I) gehören - neben beispielsweise offenkettigen quaternären Ammonium-Salzen, Pyridinium-Salzen, Pyridazinium-Salzen, Pyrimidinium-Salzen, Pyrazinium-Salzen, Pyrazolium-Salzen, Pyrazolinium-Salzen, Imidazolinium-Salzen, Thiazolium-Salzen, Triazolium-Salzen, Pyrrolidinium-Salzen und Imidazolidinium-Salzen - zu den sogenannten ionischen Flüssigkeiten, worunter Salze (also Verbindungen aus Kationen und Anionen) verstanden werden, die bei Normaldruck einen Schmelzpunkt von kleiner als 200°C, meist sogar von kleiner als 80°C, aufweisen. Ionische Flüssigkeiten enthalten oftmals eine organische Verbindung als Kation (organisches Kation). Je nach Wertigkeit des Anions kann die ionische Flüssigkeit neben dem organischen Kation weitere Kationen wie Metallkationen enthalten.Imidazolium salts of type (I) include - in addition to, for example, open-chain quaternary ammonium salts, pyridinium salts, pyridazinium salts, pyrimidinium salts, pyrazinium salts, pyrazolium salts, pyrazolinium salts, imidazolinium salts, thiazolium salts, triazolium salts. Salts, pyrrolidinium salts and imidazolidinium salts - to the so-called ionic liquids, which are understood as meaning salts (ie compounds of cations and anions) which at normal pressure have a melting point of less than 200 ° C., usually even less than 80 ° C., exhibit. Ionic liquids often contain an organic compound as a cation (organic cation). Depending on the valency of the anion, the ionic liquid may contain other cations, such as metal cations, in addition to the organic cation.

Imidazoliumsalze des Typs (I) sind in ihrer Anwendung als Detergentien oder Dispergatoren in Schmierstoffformulierungen bekannt. So beschreibt die WO 2010/101801 A1 (3) öllösliche ionische Detergentien als Additivkomponenten in Schmierölen für Verbrennungsmotoren; als Beispiele werden neben offenkettigen ionischen Systemen und quaternisierten Pyridinium-Detergentien quaternisierte Imidazoliumphenolate, Imidazoliumchloride und Imidazoliumsalicylate genannt.Imidazolium salts of type (I) are known in their use as detergents or dispersants in lubricant formulations. That's how it describes WO 2010/101801 A1 (3) oil-soluble ionic detergents as additive components in lubricating oils for internal combustion engines; Examples include, in addition to open-chain ionic systems and quaternized pyridinium detergents, quaternized imidazolium phenates, imidazolium chlorides, and imidazolium salicylates.

In der WO 2010/096168 A1 (4) werden ionische Flüssigkeiten wie Pyridiniumsalze als Additive zur Kontrolle der Ablagerungsbildung auf den inneren Oberflächen von Verbrennungsmotoren beschrieben. Im Gegensatz zur vorliegenden Erfindung werden solche Additive jedoch dem Schmieröl und nicht dem Kraftstoff, der zum Betreiben dieser Motoren eingesetzt wird, zugesetzt. Außerdem offenbart die WO 2010/096168 A1 explizit keine Imidazoliumsalze als derartige Additive.In the WO 2010/096168 A1 (4) ionic liquids such as pyridinium salts are described as additives for controlling deposit formation on the inner surfaces of internal combustion engines. However, unlike the present invention, such additives are added to the lubricating oil rather than the fuel used to operate these engines. In addition, the disclosed WO 2010/096168 A1 explicitly no imidazolium salts as such additives.

Die US 4 108 858 (5 ) offenbart hochmolekulare N-hydrocarbylsubstituierte quaternisierte Ammoniumsalze mit einem Molekulargewicht von 350 bis 3000 Kohlenstoffatomen für die Hydrocarbylgruppe als Detergentien und Dispergatoren für Kraftstoffe wie Ottokraftstoffe und Dieselkraftstoffe und für Schmieröle. Als derartige hochmolekulare N-hydrocarbylsubstituierte quaternisierte Ammoniumsalze werden neben offenkettigen Systemen Salze von Piperidinen, Piperazinen, Morpholinen und Pyridinen genannt. Als längerkettige Hydrocarbylreste kommen beispielsweise Polybuten- oder Polypropylenreste in Betracht.The US 4 108 858 (5 ) discloses high molecular weight N-hydrocarbyl substituted quaternized ammonium salts having a molecular weight of 350 to 3000 carbon atoms for the hydrocarbyl group as detergents and dispersants for fuels such as gasoline and diesel fuels and lubricating oils. As such high molecular weight N-hydrocarbyl-substituted quaternized ammonium salts, in addition to open-chain systems, salts of piperidines, piperazines, morpholines and pyridines are mentioned. For example, polybutene or polypropylene radicals may be considered as longer-chain hydrocarbyl radicals.

In einer bevorzugten Ausführungsform der vorliegenden Erfindung werden die Imidazoliumsalze (I) als Detergenzadditive für Dieselkraftstoffe verwendet. In dieser Ausführungsform werden die Einzelverwendungen der Imidazoliumsalze (I) als Additiv zur Verringerung oder Vermeidung von Ablagerungen in Einspritzsystemen von direkteinspritzenden Dieselmotoren, insbesondere in Common-Rail-Einspritzsystemen, zur Verringerung des Kraftstoffverbrauches von direkteinspritzenden Dieselmotoren, insbesondere von Dieselmotoren mit Common-Rail-Einspritzsystemen, und/oder zur Minimierung des Leistungsverlustes (powerloss) in direkteinspritzenden Dieselmotoren, insbesondere in Dieselmotoren mit Common-Rail-Einspritzsystemen, besonders bevorzugt.In a preferred embodiment of the present invention, the imidazolium salts (I) are used as detergent additives for diesel fuels. In this embodiment, the individual uses of the imidazolium salts (I) as an additive for reducing or avoiding deposits in injection systems of direct injection diesel engines, especially in common rail injection systems, to reduce the fuel consumption of direct injection diesel engines, especially diesel engines with common rail injection systems , and / or for minimizing power loss in direct injection diesel engines, especially in diesel engines with common rail injection systems, particularly preferred.

In einer weiteren bevorzugten Ausführungsform werden die Imidazoliumsalze (I) als Wachs-Anti-Settling Additiv (WASA) für Mitteldestillatbrennstoffe, insbesondere Dieselkraftstoffe, verwendet.In a further preferred embodiment, the imidazolium salts (I) are used as a wax anti-settling additive (WASA) for middle distillate fuels, in particular diesel fuels.

In einer weiteren bevorzugten Ausführungsform werden die Imidazoliumsalze (I) als Schmierfähigkeitsverbesserer für Kraft- und Brennstoffe, insbesondere als Friction Modifier für Ottokraftstoffe sowie als Lubricity Additive für Mitteldestillatbrennstoffe bzw. Dieselkraftstoffe, verwendet.In a further preferred embodiment, the imidazolium salts (I) are used as lubricity improvers for fuels and fuels, in particular as friction modifiers for gasoline fuels and as lubricity additives for middle distillate fuels or diesel fuels.

Als organische Reste für die Variablen R1 bis R5 in den Imidazoliumsalzen der allgemeinen Formel (I) kommen vorzugsweise C1- bis C20-Alkylreste, insbesondere C1- bis C12-Alkylreste, vor allem C1- bis C8-Alkylreste, beispielsweise Methyl, Ethyl, 1-Propyl, 2-Propyl, 1-Butyl, 2-Butyl, 2-Methyl-1-propyl (Isobutyl), 2-Methyl-2-propyl (tert.-Butyl), 1-Pentyl, 2-Pentyl, 3-Pentyl, 2-Methyl-1-butyl, 3-Methyl-1-butyl, 2-Methyl-2-butyl, 3-Methyl-2-butyl, 2,2-Dimethyl-1-propyl, 1-Hexyl, 2-Hexyl, 3-Hexyl, 2-Methyl-1-pentyl, 3-Methyl-1-pentyl, 4-Methyl-1-pentyl, 2-Methyl-2-pentyl, 3-Methyl-2-pentyl, 4-Methyl-2-pentyl, 2-Methyl-3-pentyl, 3-Methyl-3-pentyl, 2,2-Dimethyl-1-butyl, 2,3-Dimethyl-1-butyl, 3,3-Dimethyl-1-butyl, 2-Ethyl-1-butyl, 2,3-Dimethyl-2-butyl, 3,3-Dimethyl-2-butyl, n-Heptyl, n-Octyl, 2-Ethylhexyl, n-Nonyl, n-Decyl, 2-Propylheptyl, n-Undecyl, n-Dodecyl, n-Tridecyl, Isotridecyl, n-Tetradecyl, n-Pentadecyl, n-Hexadecyl, n-Heptadecyl, n-Octadecyl, n-Nonadecyl, n-Icosyl, Phenylmethyl (Benzyl), Diphenylmethyl, Triphenylmethyl, 2-Phenylethyl, 3-Phenylpropyl, Cyc-Iopentylmethyl, 2-Cyclopentyl-ethyl, 3-Cyclopentylpropyl, Cyclohexylmethyl, 2-Cyclohexylethyl, 3-Cyclohexylpropyl.
Als organische Reste mit 1 bis 20 Kohlenstoffatomen für die Variablen R1 bis R5 in den Imidazoliumsalzen der allgemeinen Formel (I) eignen sich weiterhin auch C3- bis C12-Cycloalkylreste, insbesondere C5- bis C7-Cycloalkylreste, beispielsweise Cyclopentyl, 2-Methyl-1-cyclopentyl, 3-Methyl-1-cyclopentyl, Cyclohexyl, 2-Methyl-1-cyclohexyl, 3-Methyl-1-cyclohexyl, 4-Methyl-1-cyclohexyl.Preferred organic radicals for the variables R 1 to R 5 in the imidazolium salts of the general formula (I) are C 1 - to C 20 -alkyl radicals, in particular C 1 - to C 12 -alkyl radicals, especially C 1 - to C 8 -alkyl radicals, for example, methyl, ethyl, 1-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-1-propyl (isobutyl), 2-methyl-2-propyl (tert-butyl), 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl, 3-methyl-1-butyl, 2-methyl-2-butyl, 3-methyl-2-butyl, 2,2-dimethyl-1-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-1-pentyl, 3-methyl-1-pentyl, 4-methyl-1-pentyl, 2-methyl-2-pentyl, 3-methyl-2- pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2,2-dimethyl-1-butyl, 2,3-dimethyl-1-butyl, 3,3- Dimethyl-1-butyl, 2-ethyl-1-butyl, 2,3-dimethyl-2-butyl, 3,3-dimethyl-2-butyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, 2-propylheptyl, n-undecyl, n-dodecyl, n-tridecyl, isotridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, phenyl methyl (benzyl), diphenylmethyl, triphenylmethyl, 2-phenylethyl, 3-phenylpropyl, cyc-1-pentylmethyl, 2-cyclopentyl-ethyl, 3-cyclopentylpropyl, cyclohexylmethyl, 2-cyclohexylethyl, 3-cyclohexylpropyl.
Suitable organic radicals having 1 to 20 carbon atoms for the variables R 1 to R 5 in the imidazolium salts of the general formula (I) are also C 3 - to C 12 -cycloalkyl radicals, in particular C 5 - to C 7 -cycloalkyl radicals, for example cyclopentyl, 2 Methyl-1-cyclopentyl, 3-methyl-1-cyclopentyl, cyclohexyl, 2-methyl-1-cyclohexyl, 3-methyl-1-cyclohexyl, 4-methyl-1-cyclohexyl.

Als organische Reste mit 1 bis 20 Kohlenstoffatomen für die Variablen R1 bis R5 in den Imidazoliumsalzen der allgemeinen Formel (I) eignen sich weiterhin auch C2- bis C20-Alkenylreste, insbesondere C3- bis C8-Alkenylreste, beispielsweise Vinyl, 2-Propenyl (Allyl), 3-Butenyl, cis-2-Butenyl, trans-2-Butenyl.Suitable organic radicals having 1 to 20 carbon atoms for the variables R 1 to R 5 in the imidazolium salts of the general formula (I) are also C 2 - to C 20 -alkenyl radicals, in particular C 3 - to C 8 -alkenyl radicals, for example vinyl, 2 Propenyl (allyl), 3-butenyl, cis-2-butenyl, trans-2-butenyl.

Als organische Reste mit 1 bis 20 Kohlenstoffatomen für die Variablen R1 bis R5 in den Imidazoliumsalzen der allgemeinen Formel (I) eignen sich weiterhin auch C3- bis C12-Cycloalkenylrest, insbesondere C5- bis C7-Cylcoalkenylreste,, beispielsweise 3-Cyclopentenyl, 2-Cyclohexenyl, 3-Cyclohexenyl, 2,5-Cyclohexadienyl.Suitable organic radicals having 1 to 20 carbon atoms for the variables R 1 to R 5 in the imidazolium salts of the general formula (I) are furthermore also C 3 - to C 12 -cycloalkenyl radicals, in particular C 5 - to C 7 -cyclocoylcyl radicals, for example Cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl.

Als organische Reste mit 1 bis 20 Kohlenstoffatomen für die Variablen R1 bis R5 in den Imidazoliumsalzen der allgemeinen Formel (I) eignen sich weiterhin auch Aryl- oder Heteroarylreste mit 3 bis 20, insbesondere 5 bis 10 Kohlenstoffatomen, beispielsweise Phenyl, 2-Methyl-phenyl (2-Tolyl), 3-Methyl-phenyl (3-Tolyl), 4-Methyl-phenyl (4-Tolyl), 2-Ethyl-phenyl, 3-Ethyl-phenyl, 4-Ethyl-phenyl, 2,3-Dimethyl-phenyl, 2,4-Dimethyl-phenyl, 2,5-Dimethyl-phenyl, 2,6-Dimethyl-phenyl, 3,4-Dimethyl-phenyl, 3,5-Dimethyl-phenyl, 4-Phenyl-phenyl, 1-Naphthyl, 2-Naphthyl, 1-Pyrrolyl, 2-Pyrrolyl, 3-Pyrrolyl, 2-Pyridinyl, 3-Pyridinyl, 4-Pyridi-nyl.Also suitable as organic radicals having 1 to 20 carbon atoms for the variables R 1 to R 5 in the imidazolium salts of the general formula (I) are aryl or heteroaryl radicals having 3 to 20, in particular 5 to 10, carbon atoms, for example phenyl, 2-methylphenyl (2-tolyl), 3-methylphenyl (3-tolyl), 4-methylphenyl (4-tolyl), 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,3- Dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 4-phenylphenyl, 1-naphthyl, 2-naphthyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl.

Die organischen Resten mit 1 bis 3000 Kohlenstoffatomen für die Variablen R1 bis R5 können synthetisch erzeugte Reste oder - insbesondere bei Alkyl- und Alkenylresten - Reste auf Basis von natürlich vorkommenden Verbindungen sein. Letztere leiten sich vor allem von natürlich vorkommenden Glyceriden oder Fettsäuren ab, beispielsweise von Stearinsäure, Palmitinsäure, Ölsäure, Linolsäure, Linolensäure oder Talgfettsäure. Derartige Reste auf Basis natürlich vorkommender Verbindungen stellen oft Gemische verschiedener, meist homologer Alkyl- bzw. Alkenylreste dar.The organic radicals having 1 to 3000 carbon atoms for the variables R 1 to R 5 may be synthetically produced radicals or-especially in the case of alkyl and alkenyl radicals-radicals based on naturally occurring compounds. The latter are derived, in particular, from naturally occurring glycerides or fatty acids, for example from stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid or tallow fatty acid. Such radicals based on naturally occurring compounds often represent mixtures of different, mostly homologous alkyl or alkenyl radicals.

Als organische Reste für die Variablen R1 bis R5 in den Imidazoliumsalzen der allgemeinen Formel (I) kommen weiterhin vorzugsweise Polyisobutylreste mit 30 bis 250 Kohlenstoffatomen, in Betracht. Derartige Polyisobutylreste weisen durch Gelpermeationschromatographie bestimmte zahlenmittlere Molekulargewichte Mn von 900 bis 3000, ganz besonders bevorzugt von 900 bis 1100 auf. Die Polyisobutylreste können direkt oder durch eine Methylengruppe (-CH2-) an den Imidazoliumring angeknüpft sein.Suitable organic radicals for the variables R1 to R5 in the imidazolium salts of the general formula (I) are furthermore preferably polyisobutyl radicals having from 30 to 250 carbon atoms. Such polyisobutyl radicals have certain number-average molecular weights M n of from 900 to 3000, very particularly preferably from 900 to 1100, determined by gel permeation chromatography. The polyisobutyl radicals may be attached directly or through a methylene group (-CH 2 -) to the imidazolium ring.

In der Regel verwendet man Imidazoliumsalze der allgemeinen Formel (I), in der die Variablen R1 und R3 die vorstehend aufgeführten Bedeutungen eines organischen Restes haben und die Variablen R2, R4 und R5 Wasserstoff bedeuten.As a rule, imidazolium salts of the general formula (I) are used, in which the variables R 1 and R 3 have the meanings of an organic radical listed above and the variables R 2, R 4 and R 5 are hydrogen.

In einer bevorzugten Ausführungsform der vorliegenden Erfindung werden Imidazoliumsalze der allgemeinen Formel (I) verwendet, in der die Variablen R1 und R3 unabhängig voneinander für C1- bis C20-Alkylgruppen, C2- bis C20-Alkenylgruppen und/oder Polyisobutylreste mit einem zahlenmittleren Molekulargewicht (Mn) von 900 bis 3000 stehen und die Variablen R2, R4 und R5 jeweils Wasserstoff bedeuten. Dabei sind diese C1- bis C20-Alkylgruppen reine Kohlenwasserstoffreste. Typische Beispiele für derartige reine C1- bis C20-Kohlenwassserstoffreste sind der 2-Ethylhexyl- und der Talgfettalkylrest.In a preferred embodiment of the present invention imidazolium salts of the general formula (I) are used, in which the variables R 1 and R 3 independently of one another for C 1 - to C 20 -alkyl groups, C 2 - to C 20 -alkenyl groups and / or polyisobutyl radicals with a number average molecular weight (M n ) of 900 to 3000 and the variables R2, R4 and R5 are each hydrogen. These C 1 - to C 20 -alkyl groups are pure hydrocarbon radicals. typical Examples of such pure C 1 -C 20 -hydrocarbon radicals are the 2-ethylhexyl and the tallow fatty alkyl radical.

Als Anionen X in den Imidazoliumsalzen der allgemeinen Formel (I) kommen z. B. in Betracht: Carboxylate, insbesondere Formiat, Acetat, Propionat, Butyrat oder Benzoat; Mandelat; Trifluoracetat; Oleat; Stearat; Acrylat; Methacrylat; Maleinat; Hydrogencitrat;.As anions X in the imidazolium salts of the general formula (I) come z. B. into consideration: carboxylates, in particular formate, acetate, propionate, butyrate or benzoate; mandelate; trifluoroacetate; oleate; stearate; acrylate; methacrylate; maleate; Hydrogen citrate ;.

In der Regel sind die Anionen X aus der nachfolgenden Gruppe ausgewählt:

  • Pseudohalogenide, insbesondere Thiocyanat und Dicyanamid;
  • Carboxylate der Formel RaCOO-, wobei Ra für eine C1- bis C60-Alkylgruppe, eine C2-bis C60-Alkenylgruppe, eine C6- bis C60-Arylgruppe oder eine C7- bis C60-Alkyl-aryl- oder -Arylalkylgruppe, vorzugsweise für eine C1- bis C20-Alkylgruppe, eine C2- bis C20-Alkenylgruppe, eine C6- bis C20-Arylgruppe oder eine C7- bis C20-Alkylaryl- oder -Arylalkylgruppe, vor allem für eine C2- bis C8-Alkenylgruppe, eine C6- bis C12-Arylgruppe oder eine C7- bis C14-Alkylaryl- oder -Arylalkylgruppe,insbesondere für Acetat, jedoch auch für Formiat, Propionat, Butyrat, Acrylat, Methacrylat, Benzoat, Phenylacetat oder o-, m- oder p-Methylbenzoat, steht;
  • Polycarboxylate der Formel Rb(COO-)n, wobei n für die Zahl 1, 2 oder 3 steht und Rn einen n-bindigen Kohlenwasserstoffrest mit 1 bis 60, insbesondere 1 bis 20, vor allem 1 bis 14 Kohlenstoffatomen bedeutet; typische derartige Reste sind Malonat, Succinat, Glutarat, Adipat, Phthalat oder Terephthalat; weiterhin ist als Polycarboxylat-Anion auch das Oxalat-Anion -OOC-COO- geeignet.
  • Tricyanomethamid der Formel (CN)3 C-.
As a rule, the anions X are selected from the following group:
  • Pseudohalides, especially thiocyanate and dicyanamide;
  • Carboxylates of the formula R a COO -, where R a represents a C 1 - to C 60 -alkyl group, a C 2 to C 60 alkenyl group, a C 6 - to C 60 -aryl group or a C 7 - to C 60 - Alkyl-aryl or -arylalkyl group, preferably a C 1 - to C 20 -alkyl group, a C 2 - to C 20 -alkenyl group, a C 6 - to C 20 -aryl group or a C 7 - to C 20 -alkylaryl group or arylalkyl group, especially a C 2 to C 8 alkenyl group, a C 6 to C 12 aryl group or a C 7 to C 14 alkylaryl or arylalkyl group, in particular acetate, but also formate, Propionate, butyrate, acrylate, methacrylate, benzoate, phenylacetate or o-, m- or p-methylbenzoate;
  • Polycarboxylates of the formula R b (COO - ) n , where n is the number 1, 2 or 3 and R n is an n-bonded hydrocarbon radical having 1 to 60, especially 1 to 20, especially 1 to 14 carbon atoms; typical such radicals are malonate, succinate, glutarate, adipate, phthalate or terephthalate; furthermore, as the polycarboxylate anion and the oxalate anion - OOC-COO - suitable.
  • Tricyanomethamide of the formula (CN) 3 C - .

Ganz besonders bevorzugt verwendet man als Anion X ein Alkylcarbonat, ein Pseudohalogenid, ein Carboxylat oder das Tricyanomethamid-Anion.
Die Ladung n des Anions X hängt von dessen Beschaffenheit ab und kann den Wert 1, 2 oder 3 annehmen. Am häufigsten steht n für 1 oder 2, insbesondere für 1.Very particular preference is given to using as anion X an alkyl carbonate, a pseudohalide, a carboxylate or the tricyanomethamide anion.
The charge n of the anion X depends on its nature and may be 1, 2 or 3. Most often, n is 1 or 2, especially 1.

Typische Einzelbeispiele für Imidazoliumsalze (I) sind 1,3-Dimethylimidazolium-acetat, 1,3-Diethylimidazolium-acetat, 1-Ethyl-3-methylimidazolium-acetat, 1-Propyl-3-methylimidazolium-acetat, 1-Butyl-3-methylimidazolium-acetat, 1-Pentyl-3-methylimidazolium-acetat, 1-Hexyl-3-methylimidazolium-acetat, 1-Octyl-3-methylimidazolium-acetat, 1-(2-Ethylhexyl)-3-methylimidazolium-acetat, 1,3-Di(2-ethylhexyl)imidazolium-acetat, 1-Decyl-3-methylimidazolium-acetat, 1-(2-Propylheptyl)-3-methylimidazolium-acetat, 1,3,4,5-Tetramethylimidazolium-acetat, 1,3-Dimethyl-4,5-diphenylimidazolium-acetat, 1,4,5-Trimethyl-3-ethylimidazolium-acetat, 1-Methyl-3-ethyl-4,5-diphenylimidazolium-acetat, 1,3-Dimethylimidazolium-methylcarbonat, 1,3-Diethylimidazolium-methylcarbonat, 1-Ethyl-3-methylimidazolium-methylcarbonat, 1-Propyl-3-methylimidazolium-methylcarbonat, 1-Butyl-3-methylimidazolium-methylcarbonat, 1-Pentyl-3-methylimidazolium-methylcarbonat, 1-Hexyl-3-methylimidazolium-methylcarbonat, 1-Octyl-3-methylimidazolium-methylcarbonat, 1-(2-Ethylhexyl)-3-methylimidazolium-methylcarbonat, 1,3-Di(2-ethylhexyl)imidazolium- methylcarbonat, 1-Decyl-3-methylimidazolium-methylcarbonat, 1-(2-Propylheptyl)-3-methylimidazolium-methylcarbonat, 1,3,4,5-Tetramethylimidazolium-methylcarbonat, 1,3-Dimethyl-4,5-diphenylimidazolium-methylcarbonat, 1,4,5-Trimethyl-3-ethylimidazolium-methylcarbonat, 1-Methyl-3-ethyl-4,5-diphenylimidazolium-methylcarbonat,.Typical examples of imidazolium salts (I) are 1,3-dimethylimidazolium acetate, 1,3-diethylimidazolium acetate, 1-ethyl-3-methylimidazolium acetate, 1-propyl-3-methylimidazolium acetate, 1-butyl-3-yl methylimidazolium acetate, 1-pentyl-3-methylimidazolium acetate, 1-hexyl-3-methylimidazolium acetate, 1-octyl-3-methylimidazolium acetate, 1- (2-ethylhexyl) -3-methylimidazolium acetate, 1, 3-di (2-ethylhexyl) imidazolium acetate, 1-decyl-3-methylimidazolium acetate, 1- (2-propylheptyl) -3-methylimidazolium acetate, 1,3,4,5-tetramethylimidazolium acetate, 1, 3-Dimethyl-4,5-diphenylimidazolium acetate, 1,4,5-trimethyl-3-ethylimidazolium acetate, 1-methyl-3-ethyl-4,5-diphenylimidazolium acetate, 1,3-dimethylimidazolium methylcarbonate, 1.3 Diethylimidazolium methyl carbonate, 1-ethyl-3-methylimidazolium methylcarbonate, 1-propyl-3-methylimidazolium methylcarbonate, 1-butyl-3-methylimidazolium methylcarbonate, 1-pentyl-3-methylimidazolium methylcarbonate, 1-hexyl-3-methylimidazolium methylcarbonate, 1-octyl-3-methylimidazolium methylcarbonate, 1- (2-ethylhexyl) -3-methylimidazolium methylcarbonate, 1,3-di (2-ethylhexyl) imidazolium methylcarbonate, 1-decyl-3-methylimidazolium methylcarbonate, 1 (2-Propylheptyl) -3-methylimidazolium methylcarbonate, 1,3,4,5-tetramethylimidazolium methylcarbonate, 1,3-dimethyl-4,5-diphenylimidazolium methylcarbonate, 1,4,5-trimethyl-3-ethylimidazolium methyl carbonate, 1-methyl-3-ethyl-4,5-diphenylimidazolium methyl carbonate ,.

Typische Einzelbeispiele für Imidazoliumsalze (I) mit Polyisobutenylresten sind 1-Polyisobutyl-3-methylimidazolium-acetat, 1-Polyisobutyl-3-ethylimidazolium-acetat, 1-Polyisobutyl-3-propylimidazolium-acetat, 1-Polyisobutyl-3-butylimidazolium-acetat, 1-Polyisobutyl-3-(2-ethylhexyl)imidazolium-acetat, 1,3-Di(polyisobutyl)imidazolium-acetat, 1-Polyisobutyl-3-methylimidazolium-methylcarbonat, 1-Polyisobutyl-3-ethylimidazolium-methylcarbonat, 1-Polyisobutyl-3-propylimidazolium-methylcarbonat, 1-Polyisobutyl-3-butylimidazolium-methylcarbonat, 1-Polyisobutyl-3-(2-ethylhexyl)imidazolium-methylcarbonat, 1,3-Di(polyisobutyl)imidazolium-methylcarbonat, 1-Polyisobutyl-3-methylimidazolium-thiocyanat, 1-Polyisobutyl-3-ethylimidazolium-thiocyanat, 1-Polyisobutyl-3-propylimidazolium-thiocyanat, 1-Polyisobutyl-3-butylimidazolium-thiocyanat, 1-Polyisobutyl-3-(2-ethylhexyl)imidazolium-thiocyanat, 1,3-Di(polyisobutyl)-imidazolium-thiocyanat, 1-Polyisobutyl-3-methylimidazolium-tricyanomethamid, 1-Polyisobutyl-3-ethylimidazolium-tricyanomethamid, 1-Polyisobutyl-3-propylimidazolium-tricyanomethamid, 1-Polyisobutyl-3-butylimidazolium-tricyanomethamid, 1-Polyisobutyl-3-(2-ethylhexyl)imidazolium-tricyanomethamid und 1,3-Di(polyisobutyl)imidazolium-tricyanomethamid.Typical individual examples of imidazolium salts (I) with polyisobutenyl radicals are 1-polyisobutyl-3-methylimidazolium acetate, 1-polyisobutyl-3-ethylimidazolium acetate, 1-polyisobutyl-3-propylimidazolium acetate, 1-polyisobutyl-3-butylimidazolium acetate, 1-Polyisobutyl-3- (2-ethylhexyl) imidazolium acetate, 1,3-di (polyisobutyl) imidazolium acetate, 1-polyisobutyl-3-methylimidazolium methylcarbonate, 1-polyisobutyl-3-ethylimidazolium methylcarbonate, 1-polyisobutyl 3-propylimidazolium methylcarbonate, 1-polyisobutyl-3-butylimidazolium methylcarbonate, 1-polyisobutyl-3- (2-ethylhexyl) imidazolium methylcarbonate, 1,3-di (polyisobutyl) imidazolium methylcarbonate, 1-polyisobutyl-3- methylimidazolium thiocyanate, 1-polyisobutyl-3-ethylimidazolium thiocyanate, 1-polyisobutyl-3-propylimidazolium thiocyanate, 1-polyisobutyl-3-butylimidazolium thiocyanate, 1-polyisobutyl-3- (2-ethylhexyl) imidazolium thiocyanate, 1 , 3-Di (polyisobutyl) imidazolium thiocyanate, 1-polyisobutyl-3-methylimidazolium tricyanomethamide, 1-polyisobutene ethyl-3-ethylimidazolium tricyanomethamide, 1-polyisobutyl-3-propylimidazolium tricyanomethamide, 1-polyisobutyl-3-butylimidazolium tricyanomethamide, 1-polyisobutyl-3- (2-ethylhexyl) imidazolium tricyanomethamide and 1,3-di (polyisobutyl ) imidazolium tricyanomethamid.

Imidazoliumsalze des Typs (I) mit niedermolekularen Resten werden im Handel unter der Bezeichnung Basionics™ von BASF SE vertrieben.Imidazolium salts of type (I) with low molecular weight radicals are marketed commercially under the name Basionics ™ by BASF SE.

Die Herstellung der Imidazoliumsalze des Typs (I) ist dem Fachmann geläufig. Ein typischer Syntheseweg geht von der Imidazol-Bildung aus 1 Mol einer 1,2-Dicarbonylverbindung, 1 Mol eines entsprechend substituierten primären Amins, 1 Mol Ammoniak und 1 Mol eines Aldehyds aus, führt eine N-Alkylierung mit einem geeigneten Alkylierungsmittel durch und tauscht danach gewünschtenfalls das Anion aus. Beispielsweise stellt man aus Glyoxal oder Benzil, einem niedermolekularen primären Alkylamin oder Alkenylamin, z. B. einem C1- bis C13-Alkylamin, oder einem Polyisobutylamin, Ammoniak und Formaldehyd ein N-Alkyl-4,5-diphenylimidazol bzw. ein N-Alkylimidazol bzw. ein N-Polyisobutyl-4,5-diphenylimidazol bzw. ein N-Polyisobutylimidazol her und alkyliert das unsubstituierte zweite Stickstoffatom mit einem Epoxid wie Ethylenoxid, Propylenoxid, Butylenoxid oder Styroloxid in Gegenwart von Essigsäure oder mit einem Dialkylcarbonat, wobei das Imidazoliumsalz dann ein Acetat-Anion bzw. ein Alkylcarbonat-Anion aufweist. Zur Einführung eines Polyisobutylrestes am unsubstituierten zweiten Stickstoffatom kann mit ein Polyisobutenepoxid als Alkylierungsmittel einsetzen.The preparation of the imidazolium salts of type (I) is familiar to the person skilled in the art. A typical synthetic route is imidazole formation from 1 mole of a 1,2-dicarbonyl compound, 1 mole of an appropriately substituted primary amine, 1 mole of ammonia, and 1 mole of an aldehyde, N-alkylation with a suitable alkylating agent, and then exchange if desired, the anion from. For example, from glyoxal or benzil, a low molecular weight primary alkylamine or alkenylamine, e.g. As a C 1 - to C 13 alkylamine, or a polyisobutylamine, ammonia and formaldehyde, an N-alkyl-4,5-diphenylimidazole or an N-alkylimidazole or an N-polyisobutyl-4,5-diphenylimidazole or a N-polyisobutylimidazole forth and alkylates the unsubstituted second nitrogen atom with an epoxide such as ethylene oxide, propylene oxide, butylene oxide or styrene oxide in the presence of acetic acid or with a dialkyl carbonate, wherein the imidazolium salt then an acetate anion or an alkyl carbonate anion having. For introducing a polyisobutyl radical on the unsubstituted second nitrogen atom can use with a polyisobutene as alkylating agent.

Bei der Herstellung von Imidazoliumsalzen des Typs (I) mit gleichen Variablen R1 und R3 setzt man vorteilhafterweise 1 Mol einer 1,2-Dicarbonylverbindung zusammen mit 2 Mol eines entsprechend substituierten primären Amins und 1 Mol eines Aldehyds gegebenenfalls in Gegenwart eines geeigneten Lösungsmittels (beispielsweise von Essigsäure und Wasser, wenn ein Imidazoliumacetat erhalten werden soll) in einer Einstufensynthese, meist bei 20 bis 120°C, insbesondere bei 25 bis 80°C, um.In the preparation of imidazolium salts of type (I) having the same variables R1 and R3 it is advantageous to use 1 mole of a 1,2-dicarbonyl compound together with 2 moles of an appropriately substituted primary amine and 1 mole of an aldehyde, optionally in the presence of a suitable solvent (e.g. Acetic acid and water when an imidazolium acetate is to be obtained) in a one-step synthesis, usually at 20 to 120 ° C, in particular at 25 to 80 ° C to.

Der mit einem oder mehreren Imidazoliumsalzen (I) additivierte Kraft- oder Brennstoff ist ein Ottokraftstoff oder insbesondere ein Mitteldestillat-Kraftstoff, vor allem ein Dieselkraftstoff. Der Kraft- oder Brennstoff kann weitere übliche Additive ("Co-Additive") zur Wirksamkeitsverbesserung und/oder Verschleißunterdrückung enthalten.The fuel or fuel additized with one or more imidazolium salts (I) is a gasoline or, in particular, a middle distillate fuel, especially a diesel fuel. The fuel or fuel may contain other conventional additives ("co-additives") to improve the effectiveness and / or wear suppression.

Im Falle von Dieselkraftstoffen sind dies in erster Linie übliche Detergens-Additive, Trägeröle, Kaltfließverbesserer, Schmierfähigkeitsverbesserer (Lubricity Improver), Korrosionsinhibitoren, Demulgatoren, Dehazer, Antischaummittel, Cetanzahlverbesserer, 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, demulsifiers, dehazers, defoamers, cetane improvers, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and / or Solvent.

Im Falle von Ottokraftstoffen sind dies vor allem Schmierfähigkeitsverbesserer (Friction Modifier), Korrosionsinhibitoren, 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, demulsifiers, dehazers, antifoams, combustion improvers, antioxidants or stabilizers, antistatic agents, metallocenes, metal deactivators, dyes and / or solvents.

Typische Beispiele geeigneter Co-Additive sind in den nachfolgenden Abschnitten aufgeführt.Typical examples of suitable co-additives are listed in the following sections.

Bei den üblichen Detergens-Additiven handelt es sich vorzugsweise um amphiphile Substanzen, die mindestens einen hydrophoben Kohlenwasserstoffrest mit einem zahlengemittelten Molekulargewicht (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;
(Db)
Nitrogruppen, gegebenenfalls in Kombination mit Hydroxylgruppen;
(Dc)
Hydroxylgruppen in Kombination mit Mono- oder Polyaminogruppen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat;
(Dd)
Carboxylgruppen oder deren Alkalimetall- oder Erdalkalimetallsalzen;
(De)
Sulfonsäuregruppen oder deren Alkalimetall- oder Erdalkalimetallsalzen;
(Df)
Polyoxy-C2- bis C4-alkylengruppierungen, die durch Hydroxylgruppen, Mono- oder Polyaminogruppen, wobei mindestens ein Stickstoffatom basische Eigenschaften hat, oder durch Carbamatgruppen terminiert sind;
(Dg)
Carbonsäureestergruppen;
(Dh)
aus Bernsteinsäureanhydrid abgeleiteten Gruppierungen mit Hydroxy- und/oder Amino- und/oder Amido- und/oder Imidogruppen; und/oder
(Di)
durch Mannich-Umsetzung von substituierten Phenolen mit Aldehyden und Mono- oder Polyaminen erzeugten Gruppierungen.
The usual detergent additives are preferably amphiphilic substances which have at least one hydrophobic hydrocarbon radical with a number-average molecular weight (M n ) of 85 to 20,000 and at least one polar group selected from:
(There)
Mono or polyamino groups having up to 6 nitrogen atoms, at least one nitrogen atom having basic properties;
(Db)
Nitro groups, optionally in combination with hydroxyl groups;
(Dc)
Hydroxyl groups in combination with mono- or polyamino groups, wherein at least one nitrogen atom has basic properties;
(Dd)
Carboxyl groups or their alkali metal or alkaline earth metal salts;
(De)
Sulfonic acid groups or their alkali metal or alkaline earth metal salts;
(Df)
Polyoxy-C 2 - to C 4 -alkylene groups terminated by hydroxyl groups, mono- or polyamino groups, at least one nitrogen atom having basic properties, or terminated by carbamate groups;
(DG)
Carbonsäureestergruppen;
(Ie)
succinic anhydride-derived moieties having hydroxy and / or amino and / or amido and / or imido groups; and or
(Di)
Mannich reaction of substituted phenols with aldehydes and mono or polyamines generated moieties.

Der hydrophobe Kohlenwasserstoffrest in den obigen Detergens-Additiven, welcher für die ausreichende Löslichkeit im Kraft- oder Brennstoff sorgt, hat ein zahlengemitteltes Molekulargewicht (Mn) von 85 bis 20.000, vorzugsweise von 113 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 typische hydrophobe Kohlenwasserstoffreste kommen insbesondere Polypropenyl-, Polybutenyl- und Polyisobutenylreste 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.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 113 to 10,000, more preferably from 300 to 5,000, more preferably from 300 to 3,000, even more preferably from 500 to 2,500 and in particular from 700 to 2,500, especially from 800 to 1,500. As typical hydrophobic hydrocarbon radicals are in particular polypropenyl, polybutenyl and polyisobutenyl radicals having a number average molecular weight M n of preferably from 300 to 5,000, more preferably 300 to 3,000, more preferably 500 to 2,500, even more preferably 700 to 2,500 and especially 800 to 1,500.

Als Beispiele für obige Gruppen von Detergens-Additiven seien die folgenden genannt:As examples of the above groups of detergent additives, the following are mentioned:

Mono- oder Polyaminogruppen (Da) enthaltende Additive sind vorzugsweise Polyalkenmono- oder 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 Polyaminen wie Dimethylaminopropylamin, 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 überwiegend mittenständigen Doppelbindungen (meist in der β- 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 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 polyalkene 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 with M n = 300 to 5000, especially preferably 500 to 2500 and in particular 700 to 2500. Such additives based on highly reactive polyisobutene, which from the polyisobutene, which may contain up to 20 wt .-% of n-butene units, by hydroformylation and reductive amination with ammonia, monoamines or polyamines such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine can be prepared, in particular from EP-A 244 616 known. If one proceeds in the preparation of the additives of polybutene or polyisobutene with predominantly intermediate double bonds (usually in the β and γ position), the preparation route 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 at. Amines such as ammonia, monoamines or the polyamines mentioned above can be used for the amination. Corresponding additives based on polypropene are especially in the WO-A 94/24231 described.

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 special monoamine (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 are described.

Weitere besondere Monoaminogruppen (Da) enthaltende Additive sind die aus Polyisobutenepoxiden durch Umsetzung mit Aminen und nachfolgender Dehydratisierung und Reduktion der Aminoalkohole erhältlichen Verbindungen, wie sie insbesondere in der DE-A 196 20 262 beschrieben sind.Further special 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 US Pat DE-A 196 20 262 are described.

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 Sauerstoff, 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. α-Nitro-β-hydroxypolyisobuten) dar.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 the WO-A 96/03479 are described. These reaction products are generally mixtures of pure nitropolyisobutenes (eg, α, β-dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (eg, α-nitro-β-hydroxy polyisobutene).

Hydroxylgruppen in Kombination mit Mono- oder Polyaminogruppen (Dc) 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 insbesondere in der EP-A 476 485 beschrieben sind.Hydroxyl groups in combination with mono- or polyamino (Dc) -containing additives are in particular reaction products of polyisobutene epoxides obtainable from preferably predominantly terminal double bonds polyisobutene having M n = 300 to 5000 with ammonia, mono- or polyamines, as described in particular EP-A 476 485 are described.

Carboxylgruppen oder deren Alkalimetall- oder Erdalkalimetallsalze (Dd) enthaltende Additive sind vorzugsweise Copolymere von C2- bis C40-Olefinen mit Maleinsäureanhydrid mit einer Gesamt-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 87/01126 beschrieben, mit Vorteil in Kombination mit üblichen Kraftstoffdetergenzien 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 C 2 - to C 40 olefins with maleic anhydride having a total molecular weight of 500 to 20,000, the carboxyl groups wholly or partially to the alkali metal or alkaline earth metal salts and a remaining Rest of the carboxyl groups are reacted with alcohols or amines. Such additives are in particular from the EP-A 307 815 known. Such additives are primarily for preventing valve seat wear and can, as in the WO-A 87/01126 described, 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.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 is described. Such additives are primarily for preventing valve seat wear and can be used with advantage in combination with conventional fuel detergents such as poly (iso) buten-amines or polyetheramines.

Polyoxy-C2-C4-alkylengruppierungen (Df) enthaltende Additive sind vorzugsweise Polyether oder Polyetheramine, welche durch Umsetzung von C2- bis C60-Alkanolen, C6-bis C30-Alkandiolen, Mono- oder Di-C2- bis C30-alkylaminen, C1- bis C30-Alkylcyclo-hexanolen oder C1- bis C30-Alkylphenolen 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 Umsetzungsprodukte mit Ammoniak.Polyoxy-C 2 -C 4 -alkylene (Df) containing additives are preferably polyether or polyetheramines, which by reaction of C 2 - to C 60 -alkanols, C 6 -C 30 alkanediols, mono- or di-C 2 - to C 30 -alkylamines, C 1 - to C 30 -alkylcyclohexanols or C 1 - to C 30 -alkylphenols with 1 to 30 mol of ethylene oxide and / or propylene oxide and / or butylene oxide per hydroxyl group or amino group and, in the case of polyetheramines, are obtainable by subsequent reductive amination with ammonia, monoamines or polyamines. Such products are used in particular in the EP-A 310 875 . EP-A 356 725 . EP-A 700 985 and US Pat. No. 4,877,416 described. 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 Mono-, Di- oder 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 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 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.Carboxylic 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 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, Säureamide von Di- oder Polyaminen, die neben der Amidfunktion noch freie Amingruppen aufweisen, Bernsteinsäurederivate 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 insbesondere in der US-A 4 849 572 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 Ethylendiamin, Diethylentriamin, Triethylentetramin, Tetraethylenpentamin, Pentaethylenhexamin und Hexaethylenheptamin, 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 diamines or polyamines which, in addition to the amide function, still have free amine groups, succinic acid derivatives with a Acid and an amide, Carbonsäureimide with monoamines, Carbonsäureimide with di- or polyamines, which still have free amine groups in addition to the imide function, or diimides, which are formed by the reaction of di- or polyamines with two succinic acid derivatives. Such fuel additives are particularly in the US Pat. No. 4,849,572 described. Prefers these are the reaction products of alkyl- or alkenyl-substituted succinic acids or derivatives thereof with amines, and more preferably 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, Tetraethylenpentamin oder Dimethylaminopropylamin. 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 groupings (di) -containing 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 particularly in the EP-A 831 141 described.

Dem Kraftstoff können ein oder mehrere der genannten Detergens-Additive aus der Grupppe (Da) bis (Di) in solch einer Menge zugegeben werden, dass die Dosierrate an diesen Detergens-Additiven vorzugsweise 25 bis 2500 Gew.-ppm, insbesondere 75 bis 1500 Gew.-ppm, vor allem 150 bis 1000 Gew.-ppm, beträgt.To the fuel, one or more of the above-mentioned detergent additives of the group (Da) to (Di) may be added in such an amount that the dosage rate of these detergent additives is preferably 25 to 2500 ppm by weight, especially 75 to 1500% by weight . ppm, especially 150 to 1000 ppm by weight.

Als Co-Additive 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 aromatische 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.Carrier oils used as co-additives may be mineral or synthetic. Suitable mineral carrier oils are fractions obtained in petroleum processing, such as bright stock or base oils having 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 Polyinternalolefine), (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 polyinternalolefins), (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).Examples of suitable polyolefins are olefin polymers having M n = 400 to 1800, especially based on polybutene or polyisobutene (hydrogenated or non-hydrogenated).

Beispiele für geeignete Polyether oder Polyetheramine sind vorzugsweise Polyoxy-C2-bis C4-alkylengruppierungen enthaltende Verbindungen, welche durch Umsetzung von C2- bis C60-Alkanolen, C6- bis C30-Alkandiolen, Mono- oder Di-C2- bis C30-alkylaminen, C1- bis C30-Alkyl-cyclohexanolen oder C1- bis C30-Alkylphenolen 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 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 Polyisobutenolbutoxylate und -propoxylate sowie die entsprechenden Umsetzungsprodukte mit Ammoniak.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 60 -alkanols, C 6 - to C 30 -alkanediols, mono- or di-C 2 - to C 30 -alkylamines, C 1 - to C 30 -alkyl-cyclohexanols or C 1 - to C 30 - Alkylphenols with 1 to 30 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 used in particular in the EP-A 310 875 . EP-A 356 725 . EP-A 700 985 and the US-A 4,877,416 described. For example, poly-C 2 -C 6 -alkylene oxide amines or functional derivatives thereof can be used as polyetheramines. Typical examples of these are tridecanol or Isotridecanolbutoxylate, Isononylphenolbutoxylate and Polyisobutenolbutoxylate and propoxylates and the corresponding reaction products with ammonia.

Beispiele für Carbonsäureester langkettiger Alkanole sind insbesondere Ester aus Mono-, Di- oder 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, Isononanols, Isodecanols und des Iso-tridecanols, z. B. Di-(n- oder Isotridecyl)phthalat.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 are described in particular in US Pat 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 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.Other suitable carrier oil systems are for example in the DE-A 38 26 608 . DE-A 41 42 241 . DE-A 43 09 074 . EP-A 452 328 and the EP-A 548 617 described.

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 (Polyveretherungsprodukte) von einwertigen aliphatischen C6- bis C18-Alkoholen mit C3- bis C6-Alkylenoxiden. Beispiele für einwertige aliphatische C6-C18-Alkohole sind Hexanol, Heptanol, Octanol, 2-Ethylhexanol, Nonylalkohol, Decanol, 2-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-Propylenoxid, Butylenoxid, wie 1,2-Butylenoxid, 2,3-Butylenoxid, Isobutylenoxid oder Tetrahydrofuran, Pentylenoxid und Hexylenoxid. Besonders bevorzugt sind hierunter C3- bis C4-Alkylenoxide, d.h. Propylenoxid wie 1,2-Propylenoxid und Butylenoxid wie 1,2-Butylenoxid, 2,3-Butylenoxid und Isobutylenoxid. Speziell verwendet man Butylenoxid.Examples of particularly suitable synthetic carrier oils are alcohol-started polyethers having about 5 to 35, preferably about 5 to 30, particularly preferably 10 to 30 and in particular 15 to 30 C 3 - to C 6 -alkylene oxide units, for. For example, 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 aliphatic C 6 - to C 18 -alcohols with C 3 - to C 6 -alkylene oxides. Examples of monohydric aliphatic C 6 -C 18 -alcohols are hexanol, heptanol, octanol, 2-ethylhexanol, nonyl alcohol, decanol, 2-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 C 3 - to C 6 -alkylene oxides are propylene oxide, such as 1,2-propylene oxide, butylene oxide, such as 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide or tetrahydrofuran, pentylene oxide and hexylene oxide. Among these, particularly preferred are C 3 -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. Specifically, butylene oxide is used.

Weitere geeignete synthetische Trägeröle sind alkoxylierte Alkylphenole, wie sie in der DE-A 10 102 913 beschrieben sind.Other suitable synthetic carrier oils are alkoxylated alkylphenols, as described in the DE-A 10 102 913 are described.

Besondere Trägeröle sind synthetische Trägeröle, wobei die zuvor beschriebenen alkoholgestarteten Polyether besonders bevorzugt sind.Particular carrier oils are synthetic carrier oils, the alcohol-initiated 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.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.

Geeignete Kaltfließverbesserer als Co-Additive 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. Insbesondere 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. Die erfindungsgemäß verwendeten Imidazoliumsalze (I) weisen in Mitteldestillatbrennstoffen, insbesondere in Dieselkraftstoffen, selbst Eigenschaften als WASA auf, was ja auch Gegenstand der vorliegenden Erfindung ist. Auch können als Kaltfließverbesserer eingesetzte Co-Additive 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 as co-additives 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, the usually used for middle distillates of fossil origin, ie for conventional mineral diesel fuels, used cold flow improvers ("middle distillate flow improvers", "MDFI") come into consideration. 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"). The imidazolium salts (I) used according to the invention have properties in themselves as middle grade distillate fuels, in particular in diesel fuels, as WASA, which is also the subject matter of the present invention. Also, co-additives used as cold flow improvers 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:

(K1)
Copolymeren eines C2- bis C40-Olefins mit wenigstens einem weiteren ethylenisch ungesättigten Monomer;
(K2)
Kammpolymeren;
(K3)
Polyoxyalkylenen;
(K4)
polaren Stickstoffverbindungen;
(K5)
Sulfocarbonsäuren oder Sulfonsäuren oder deren Derivaten; und
(K6)
Poly(meth)acrylsäureestern.
Typically, the cold flow improver is selected from:
(K1)
Copolymers of a C 2 to C 40 olefin with at least one further ethylenically unsaturated monomer;
(K2)
Comb polymers;
(K3)
polyoxyalkylenes;
(K4)
polar nitrogen compounds;
(K5)
Sulfocarboxylic acids or sulfonic acids or their derivatives; and
(K6)
Poly (meth) acrylsäureestern.

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.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.

Geeignete C2- bis C40-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-Doppelbindung. Im zuletzt genannten Fall kann die Kohlenstoff-Kohlenstoff-Doppelbindung sowohl terminal (α-Olefine) als auch intern angeordnet sein kann. Bevorzugt sind jedoch α-Olefine, besonders bevorzugt α-Olefine mit 2 bis 6 Kohlenstoffatomen, beispielsweise Propen, 1-Buten, 1-Penten, 1-Hexen und vor allem Ethylen.Suitable C 2 to C 40 olefin monomers for the copolymers of class (K1) are, for example, those having 2 to 20, in particular 2 to 10, carbon atoms and having 1 to 3, preferably 1 or 2, in particular having a carbon-carbon double bond. In the latter case, the carbon-carbon double bond can be arranged both terminally (α-olefins) and internally. However, preferred are α-olefins, more preferably α-olefins having 2 to 6 carbon atoms, for example propene, 1-butene, 1-pentene, 1-hexene and especially 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 C40-Olefin-Basismonomere. Setzt man beispielsweise als Olefin-Basismonomer Ethylen oder Propen ein, eignen sich als weitere Olefine insbesondere C10- bis C40-α-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 40 olefin base monomers. If, for example, ethylene or propene is used as the olefin base monomer, suitable further olefins are, in particular, C 10 -C 40 -α-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 C1- bis C20-Alkanolen, insbesondere C1- bis C10-Alkanolen, vor allem mit Methanol, Ethanol, Propanol, Isopropanol, 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 1 - to C 20 -alkanols, in particular C 1 - to C 10 -alkanols, especially with methanol, ethanol, propanol, isopropanol, n-butanol, sec. Butanol, isobutanol, tert-butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol and decanol and structural isomers thereof.

Geeignete Carbonsäurealkenylester sind beispielsweise C2- bis C14-Alkenylester, z.B. die Vinyl- und Propenylester, von Carbonsäuren mit 2 bis 21 Kohlenstoffatomen, deren Kohlenwasserstoffrest 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, C 2 -C 14 -alkenyl esters, for example 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 with a branched hydrocarbon radical, preference is given to those whose branching is in the α-position to the carboxyl group, the α-carbon atom being particularly preferably tertiary, ie the carboxylic acid being 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, Neononansäurevinylester, Neodecansäurevinylester und die entsprechenden Propenyl-ester, wobei die Vinylester bevorzugt sind. Ein besonders bevorzugter Carbonsäurealkenylester ist Vinylacetat; typische hieraus resultierende Copolymere der Gruppe (K1) sind die mit am häufigsten eingesetzten Ethylen-Vinylacetat-Copolymere ("EVA"). Besonders vorteilhaft einsetzbare Ethylen-Vinylacetat-Copolymere und ihre Herstellung sind in der WO 99/29748 beschrieben.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, with 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"). Particularly advantageous ethylene-vinyl acetate copolymers and their preparation are in the WO 99/29748 described.

Als Copolymere der Klasse (K1) sind auch solche geeignet, die zwei oder mehrere voneinander verschiedene Carbonsäurealkenylester einpolymerisiert enthalten, wobei diese sich in der Alkenylfunktion 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.Also suitable as copolymers of class (K1) are those which contain two or more different carboxylic acid alkenyl esters in copolymerized form, these differing in the alkenyl function and / or in the carboxylic acid group. Also suitable are copolymers which, in addition to the carboxylic acid alkenyl ester (s), contain at least one olefin and / or at least one (meth) acrylic acid ester in copolymerized form.

Auch Terpolymere aus einem C2- bis C40-α-Olefin, einem C1- bis C20-Alkylester einer ethylenisch ungesättigten Monocarbonsäure mit 3 bis 15 Kohlenstoffatomen und einem C2- bis C14-Alkenylester 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 aufgebaut.Also, terpolymers of a C 2 - to C 40 -α-olefin, a C 1 - to C 20 alkyl ester of an ethylenically unsaturated monocarboxylic acid having 3 to 15 carbon atoms and a C 2 - to C 14 alkenyl ester of a saturated monocarboxylic acid having 2 to 21 Carbon atoms are suitable as copolymers of class (K1). Such terpolymers are in the WO 2005/054314 described. A typical such terpolymer is composed of ethylene, 2-ethylhexyl acrylate and vinyl acetate.

Das wenigstens eine oder die weiteren ethylenisch ungesättigten Monomeren sind in den Copolymeren 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 C40-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) is thus usually derived from the C 2 to C 40 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 anschließende Veresterung der Anhydrid- bzw. Säurefunktion mit einem Alkohol mit wenigstens 10 Kohlenstoffatomen erhältlich. Weitere geeignete Kammpolymere sind Copolymere von α-Olefinen 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 Copolymere 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. Platé und V. P. Shibaev, J. Poly. Sci. Macromolecular Revs. 8, Seiten 117 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 having at least 10 carbon atoms available. 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, homopolymers and copolymers of vinyl ethers are suitable comb polymers. As a component of class (K2) suitable comb polymers are, for example, those which are described in the WO 2004/035715 and in " Comb-like polymers. Structure and Properties ", NA Platé and VP Shibaev, J. Poly. Sci. Macromolecular Revs., 8, pp. 117-253 (1974 Also mixtures of comb polymers are suitable.

Als Komponente der Klasse (K3) geeignete Polyoxyalkylene sind beispielsweise Polyoxyalkylenester, 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 Polyoxyalkylengruppe 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 Polypropylenglykolen mit einem zahlenmittleren Molekulargewicht von 100 bis 5000. Weiterhin sind Polyoxyalkylenmono- und -diester von Fettsäuren mit 10 bis 30 Kohlenstoffatomen wie Stearinsäure oder Behensäure geeignet.As the component of the class (K3), suitable polyoxyalkylenes are, for example, polyoxyalkylene esters, polyoxyalkylene ethers, mixed polyoxyalkylene ester ethers, and mixtures thereof. These polyoxyalkylene compounds preferably contain at least one, preferably at least two linear alkyl groups each having 10 to 30 carbon atoms and a polyoxyalkylene group having a number average molecular weight of up to 5000. Such polyoxyalkylene compounds are for example in the EP-A 061 895 as well as in the U.S. 4,491,455 described. Particular polyoxyalkylene compounds are based on polyethylene glycols and polypropylene glycols having a number average molecular weight of 100 to 5000. Further, polyoxyalkylene mono- and diesters of fatty acids having 10 to 30 carbon atoms such as stearic acid or behenic acid are 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 C8- bis C40-Kohlenwasserstoffrest steht. Die Stickstoffsubstituenten 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 C8- bis C40-Alkylrest. Zur Herstellung 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 Ullmanns Encyclopedia of Industrial Chemistry, 6. Auflage, im Kapitel "Amines, aliphatic " beschrieben werden. Für die Umsetzung geeignete Säuren sind beispielsweise Cyclohexan-1,2-dicarbonsäure, Cyclohexen-1,2-dicarbonsäure, Cyclopentan-1,2-dicarbonsäure, Naphthalindicarbonsäure, 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 C 8 - to C 40 hydrocarbon radical stands. The nitrogen substituents may also be quaternized, that is 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 preferably contain at least one linear C 8 - to C 40 -alkyl radical. Examples of suitable primary amines for the preparation of said polar nitrogen compounds are octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologues, and suitable secondary amines 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 US Pat Ullmanns 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 C20-Carbon-säuren) mit primären oder sekundären Aminen. Die diesem Umsetzungsprodukt zugrundeliegenden mindestens eine tertiäre Aminogruppe aufweisenden Poly(C2- bis C20-Carbonsäuren) 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 C20-Carbonsäuren) der allgemeinen Formel IIa oder IIb

Figure imgb0002
Figure imgb0003
 in denen die Variable A eine geradkettige oder verzweigte C2- bis C6-Alkylengruppe oder die Gruppierung der Formel III
Figure imgb0004
 darstellt und die Variable B eine C1- bis C19-Alkylengruppe bezeichnet. Die Verbindungen der allgemeinen Formel IIa und IIb weisen insbesondere die Eigenschaften eines WASA auf.Preferably, the component of class (K4) is an oil-soluble reaction product based on at least one tertiary amino group-containing poly (C 2 - to C 20 -carboxylic acids) of the general formula IIa or IIb
Figure imgb0002
Figure imgb0003
 in which the variable A is a straight-chain or branched C 2 - to C 6 -alkylene group or the grouping of the formula III
Figure imgb0004
 and the variable B denotes a C 1 - to C 19 -alkylene group. The compounds of the general formula IIa and IIb have in particular the properties of a WASA.

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.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-Butylen, 2-Methyl-1,3-propylen, 1,5-Pentylen, 2-Methyl-1,4-butylen, 2,2-Dimethyl-1,3-propylen, 1,6-Hexylen (Hexamethylen) und insbesondere 1,2-Ethylen. Vorzugsweise umfasst die Variable A 2 bis 4, insbesondere 2 oder 3 Kohlenstoffatome.Straight-chain or branched C 2 -C 6 -alkylene groups of the variable A are, for example, 1,1-ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,3-butylene, 1,4- Butylene, 2-methyl-1,3-propylene, 1,5-pentylene, 2-methyl-1,4-butylene, 2,2-dimethyl-1,3-propylene, 1,6-hexylene (hexamethylene) and in particular 1,2-ethylene. Preferably, the variable A comprises 2 to 4, in particular 2 or 3 carbon atoms.

C1- bis C19-Alkylengruppen der Variablen B sind vor beispielsweise 1,2-Ethylen, 1,3-Propylen, 1,4-Butylen, Hexamethylen, Octamethylen, Decamethylen, Dodecamethylen, Tetradecamethylen, Hexadecamethylen, Octadecamethylen, Nonadecamethylen und insbesondere Methylen. Vorzugsweise umfasst die Variable B 1 bis 10, insbesondere 1 bis 4 Kohlenstoffatome.C 1 - to C 19 -alkylene groups of the variables 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.

Die primären und sekundären Amine als Umsetzungspartner für die Polycarbonsäuren zur Bildung der Komponente (K4) sind üblicherweise Monoamine, insbesondere aliphatische Monoamine. Diese primären und sekundären Amine können aus einer Vielzahl von Aminen ausgewählt sein, die - gegebenenfalls miteinander verbundene - Kohlenwasserstoffreste tragen.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 can be from a variety be selected from amines carrying - optionally interconnected - hydrocarbon radicals.

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 C30-Alkylreste, insbesondere C14- 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 Fettsäure bzw. von deren Derivaten ab. Vorzugsweise sind die beiden Reste R8 gleich.In most cases, these amines are secondary amines on which the oil-soluble reaction products of component (K4) are based 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 14 - to C 24 -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 acid or from its 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 Nitrilotriessigsäure, der Ethylendiamintetraessigsäure oder der Propylen-1,2-diamintetraessigsäure mit jeweils 0,5 bis 1,5 Mol pro Carboxylgruppe, insbesondere 0,8 bis 1,2 Mol pro Carboxylgruppe, Dioleylamin, Dipalmitinamin, Dikokosfettamin, Distearylamin, Dibehenylamin oder insbesondere Ditalgfettamin. Eine besonders bevorzugte Komponente (K4) ist das Umsetzungsprodukt aus 1 Mol Ethylendiamintetraessigsäure und 4 Mol hydriertem Ditalgfettamin.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 , Dipalmitinamin, Dikokosfettamin, distearylamine, dibehenylamine or especially Ditalgfettamin. A particularly preferred component (K4) is the reaction product of 1 mole of ethylenediaminetetraacetic acid and 4 moles of hydrogenated ditallow fatty amine.

Als weitere typische Beispiele für die Komponente (K4) seien die N,N-Dialkylammoniumsalze von 2-N',N'-Dialkylamidobenzoaten, beispielsweise das Reaktionsprodukt aus 1 Mol Phthalsäureanhydrid und 2 Mol Ditalgfettamin, wobei letzteres hydriert oder nicht hydriert sein kann, und das Reaktionsprodukt von 1 Mol eines Alkenylspirobislactons mit 2 Mol eines Dialkylamins, beispielsweise Ditalgfettamin und/oder Talgfettamin, wobei die beiden letzteren hydriert oder nicht hydriert sein können, genannt.Other typical examples of the 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 ditallow fatty amine, the latter being hydrogenated or unhydrogenated, and the reaction product of 1 mole of a Alkenylspirobislactons with 2 moles of a dialkylamine, for example Ditalgfettamin and / or tallow fatty amine, the latter two may be hydrogenated or not hydrogenated, 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 93/18115 beschrieben sind.Further typical structural types for the component of class (K4) are cyclic compounds with tertiary amino groups or condensates of long-chain primary or secondary amines with carboxylic acid-containing polymers, as described in US Pat WO 93/18115 are described.

Als Kaltfließverbesserer der Komponente der Klasse (K5) geeignete Sulfocarbonsäuren, Sulfonsäuren oder deren Derivate sind beispielsweise die öllöslichen Carbonsäureamide und Carbonsäureester von ortho-Sulfobenzoesäure, in denen die Sulfonsäurefunktion als Sulfonat mit alkylsubstituierten Ammoniumkationen vorliegt, wie sie in der EP-A 261 957 beschrieben werden.Sulfocarboxylic acids, sulfonic acids or their derivatives which are suitable as cold flow improvers of the component of class (K5) are, for example, the oil-soluble carboxamides and carboxylic esters of ortho-sulfobenzoic acid in which the sulfonic acid function is present as a sulfonate with alkyl-substituted ammonium cations, as described in the EP-A 261 957 to be discribed.

Als Kaltfließverbesserer der Komponente der Klasse (K6) geeignete Poly(meth)acrylsäureester sind sowohl Homo- als auch Copolymere von Acryl- und Methacrylsäureestern. 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 Methacrylsäureestern von gesättigten C14- und C15-Alkoholen, wobei die Säuregruppen mit hydriertem Tallamin neutralisiert sind. Geeignete Poly(meth)acrylsäureester sind beispielsweise in der WO 00/44857 beschrieben.As cold flow improvers 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 C 14 and C 15 alcohols wherein the acid groups are neutralized with hydrogenated tallamine. Suitable poly (meth) acrylic esters are, for example, in WO 00/44857 described.

Dem Mitteldestillat-Kraftstoff bzw. Dieselkraftstoff wird der Kaltfließverbesserer bzw. das Gemisch 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.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 ppm by weight and in particular from 100 to 700 ppm by weight, for example from 200 to 500 ppm by weight, added.

Als Co-Additive 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.Lubricity improvers or friction modifiers which are suitable as coadditives are usually based on fatty acids or fatty acid esters. Typical examples are tall oil fatty acid, such as in the WO 98/004656 described, and glycerol monooleate. Also in the US Pat. No. 6,743,266 B2 described reaction products of natural or synthetic oils, such as triglycerides, and alkanolamines are suitable as such lubricity improvers.

Als Co-Additive geeignete Korrosionsinhibitoren sind z. B. Bernsteinsäureester, vor allem mit Polyolen, Fettsäurederivate, z. B. Ölsäureester, oligomerisierte Fettsäuren, substituierte Ethanolamine, N-acyliertes Sarkosin, Imidazolin-Derivate, z. B. solche welche in der 2-Position eine Alkylgruppe und am trivalenten Stickstoffatom einen funktionellen organischen Rest tragen (ein hierfür typisches Imidazolin-Derivat ist das Umsetzungsprodukt von überschüssiger Ölsäure mit Diethylentriamin), und Produkte, die unter dem Handelsnamen RC 4801 (Rhein Chemie Mannheim, Deutschland) oder Hi-TEC 536 (Ethyl Corporation) vertrieben werden. Die genannten Imidazolin-Derivate sind als Korrosionsinhibitoren besonders wirksam, wenn sie in dieser Anwendung mit einem oder mehreren Carbonsäureamiden mit einer oder mehreren Carbonsäureamid-Funktionen im Molekül und mit längerkettigen Resten an den Amidstickstoffen, beispielsweise mit dem Umsetzungsprodukt von Maleinsäureanhydrid mit einem langkettigen Amin in äquimolarem Verhältnis, kombiniert werden.As co-additives suitable corrosion inhibitors are z. As succinic acid esters, especially with polyols, fatty acid derivatives, eg. For example, oleic acid esters, oligomerized fatty acids, substituted ethanolamines, N-acylated sarcosine, imidazoline derivatives, e.g. B. those which in the 2-position an alkyl group and the trivalent nitrogen atom, a functional organic radical (a typical imidazoline derivative is the reaction product of excess oleic acid with diethylenetriamine), and products sold under the trade name RC 4801 (Rhein Chemie Mannheim , Germany) or Hi-TEC 536 (Ethyl Corporation). The said imidazoline derivatives are particularly effective as corrosion inhibitors when used in this application with one or more carboxylic acid amides having one or more carboxylic acid amide functions in the molecule and longer chain radicals on the amide nitrogens, for example with the reaction product of maleic anhydride with a long chain amine in equimolar Ratio, combined.

Als Co-Additive geeignete Demulgatoren sind z. B. die Alkali- oder Erdalkalisalze von Alkyl-substituierten 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, Kondensationsprodunkte von Ethylenoxid (EO) und Propylenoxid (PO), z.B. auch in Form von EO/PO-Blockcopolymeren, Polyethylenimine oder auch Polysiloxane.As co-additives suitable demulsifiers z. 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 polysiloxanes.

Als Co-Additive geeignete Dehazer sind z. B. alkoxylierte Phenol-FormaldehydKondensate, wie beispielsweise die unter dem Handelsnamen erhältlichen Produkte NALCO 7D07 (Nalco) und TOLAD 2683 (Petrolite).Suitable co-additives Dehazer are z. Example, alkoxylated phenol-formaldehyde condensates, such as the available under the trade name NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite).

Als Co-Additive geeignete Antischaummittel sind z. B. Polyether-modifizierte Polysiloxane, wie beispielsweise die unter dem Handelsnamen erhältlichen Produkte TEGOP-REN 5851 (Goldschmidt), Q 25907 (Dow Corning) und RHODOSIL (Rhone Poulenc).As co-additives suitable antifoams are for. Polyether-modified polysiloxanes, such as the TEGOP-REN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc) products available under the tradename.

Als Co-Additive geeignete Cetanzahlverbesserer sind z. B. aliphatische Nitrate wie 2-Ethylhexylnitrat und Cyclohexylnitrat sowie Peroxide wie Di-tert-butylperoxid.Suitable co-additives Cetanzahlverbesserer z. As aliphatic nitrates such as 2-ethylhexyl nitrate and cyclohexyl nitrate and peroxides such as di-tert-butyl peroxide.

Als Co-Additive geeignete Antioxidantien sind z. B. substituierte, d. h. sterisch gehinderte Phenole, wie 2,6-Di-tert.-butylphenol, 2,6-Di-tert.-butyl-3-methylphenol oder unter dem Handelsnamen IRGANOX® (BASF SE) vertriebene Produkte, z. B. 2,6-Di-tert.-butyl-4-alkoxycarbonylethyl-phenol (IRGANOX L135), sowie Phenylendiamine wie N,N'-Di-sec.-butyl-p-phenylendiamin.As co-additives suitable antioxidants are, for. Substituted, d. H. sterically hindered phenols such as 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-3-methylphenol or products sold under the trade name IRGANOX® (BASF SE), e.g. B. 2,6-di-tert-butyl-4-alkoxycarbonylethyl-phenol (IRGANOX L135), and phenylenediamines such as N, N'-di-sec-butyl-p-phenylenediamine.

Als Co-Additive geeignete Metalldeaktivatoren sind z. B. Salicylsäurederivate wie N,N'-Disalicyliden-1,2-propandiamin oder unter dem Handelsnamen IRGAMET® (BASF SE) vertriebene Produkte auf Basis von N-substituierten Triazolen und Tolutriazolen.As co-additives suitable metal deactivators z. As salicylic acid derivatives such as N, N'-disalicylidene-1,2-propanediamine or under the trade name IRGAMET® (BASF SE) marketed products based on N-substituted triazoles and tolutriazoles.

Als mitzuverwendende Lösungsmittel 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 werden, sowie polare organische Lösungsmittel, beispielsweise Alkohole wie 2-Ethylhexanol, Decanol und Isotridecanol sowie Carbonsäureester mit längerkettigen Alkylgruppen wie C12- bis C20-Fettsäuremethylester, geeignet. Derartige Lösungsmittel gelangen meist zusammen mit den Imidazoliumsalzen (I) und den vorgenannten Co-Additiven, die sie zur besseren Handhabung lösen oder verdünnen sollen, in den Kraft- oder Brennstoff, insbesondere den Dieselkraftstoff.As concomitant solvents are z. For example, non-polar organic solvents such as aromatic and aliphatic hydrocarbons, for example toluene, xylenes, "white spirit" and products sold 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 and carboxylic acid esters with longer-chain alkyl groups such as C 12 - to C 20 fatty acid methyl ester, suitable. Such solvents usually get together with the imidazolium salts (I) and the abovementioned co-additives, which they are intended to dissolve or dilute for better handling, into the fuel or fuel, in particular the diesel fuel.

Die erfindungsgemäß zu verwendenden Imidazoliumsalze (I) eignen sich in hervorragender Weise als Kraft- oder Brennstoffzusatz und können im Prinzip in jeglichen Kraft- und Brennstoffen eingesetzt werden. Sie bewirken eine ganze Reihe von vorteilhaften Effekten beim Betrieb von Verbrennungsmotoren mit Kraft- bzw. Brennstoffen. Bevorzugt wird die erfindungsgemäß zu verwendenden Imidazoliumsalze (I) in Mitteldestillat-Kraftstoffen, insbesondere Dieselkraftstoffen, eingesetzt.The imidazolium salts (I) to be used according to the invention are outstandingly suitable as a fuel or fuel additive and can in principle be used in any fuels and fuels. They bring about a whole series of advantageous Effects in the operation of internal combustion engines with fuels. The imidazolium salts (I) to be used according to the invention are preferably used in middle distillate fuels, in particular diesel fuels.

Gegenstand der vorliegenden Erfindung ist daher auch eine Kraft- und Brennstoffzusammensetzung, insbesondere eine Mitteldestillat-Kraftstoffzusammensetzung, mit einem als Zusatzstoff zur Erzielung von vorteilhaften Effekten beim Betrieb von Verbrennungsmotoren, beispielsweise von Dieselmotoren, insbesondere von direkteinspritzenden Dieselmotoren, vor allem von Dieselmotoren mit Common-Rail-Einspritzsystemen, wirksamen Gehalt an den erfindungsgemäß zu verwendenden Imidazoliumsalzen (I) neben der Hauptmenge eines üblichen Grundkraft- oder Grundbrennstoffes. Dieser wirksame Gehalt (Dosierrate) liegt in der Regel bei 10 bis 5000 Gew.-ppm, vorzugsweise bei 20 bis 1500 Gew.-ppm, insbesondere bei 25 bis 1000 Gew.-ppm, vor allem bei 30 bis 750 Gew.-ppm, jeweils bezogen auf die Gesamtmenge an Kraft- bzw. Brennstoff.The present invention is therefore also a fuel and fuel composition, in particular a middle distillate fuel composition, with an additive to achieve advantageous effects in the operation of internal combustion engines, such as diesel engines, especially direct injection diesel engines, especially diesel engines with common rail Injection systems, effective content of the inventively used imidazolium salts (I) in addition to the main amount of a conventional basic or basic fuel. This effective content (metering rate) is generally from 10 to 5000 ppm by weight, preferably from 20 to 1500 ppm by weight, in particular from 25 to 1000 ppm by weight, especially from 30 to 750 ppm by weight, in each case based on the total amount of fuel or fuel.

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" (BTL)-Kraftstoffe] erhältlich sind, geeignet. Geeignet sind auch Mischungen der vorstehend genannten Mitteldestillat-Kraftstoffe bzw. Dieselkraftstoffe mit regenerativen Kraftstoffen, wie Biodiesel oder Bioethanol.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 distillate mineral fuels or diesel fuels available through refining, those produced by coal gasification or gas liquefaction [GTL] or by biomass to liquid (BTL) fuels are also included. are available, suitable. 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 heating oils and diesel fuels are specified in greater detail in, for example, DIN 51603 and EN 590 (cf. Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Volume A12, p. 617 et seq .).

Die erfindungsgemäß zu verwendenden Imidazoliumsalze (I) können neben ihrer Verwendung in den oben genannten Mitteldestillat-Kraftstoffen aus fossilem, pflanzlichem oder tierischem Ursprung, die im wesentlichen Kohlenwasserstoffmischungen darstellen, auch in Mischungen aus solchen Mitteldestillaten mit Biobrennstoffölen (Biodiesel) eingesetzt werden. Derartige Mischungen werden im Sinne der vorliegenden Erfindung auch 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 imidazolium salts (I) to be used according to the invention can be used not only for their use in the abovementioned middle distillate fuels of fossil, vegetable or animal origin, which are essentially hydrocarbon mixtures, but also in mixtures of such middle distillates with biofuel oils (biodiesel). For the purposes of the present invention, such mixtures are also 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 of fossil, vegetable or animal origin and biofuel oil.

Biobrennstofföle basieren in der Regel auf Fettsäureestern, meist im Wesentlichen auf Alkylester von Fettsäuren, die sich von pflanzlichen und/oder tierischen Ölen und/oder Fetten ableiten. Unter Alkylestern werden üblicherweise Niedrigalkylester, insbesondere C1- bis C4-Alkylester, 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").Biofuel oils are generally based on fatty acid esters, usually substantially on alkyl esters of fatty acids derived from vegetable and / or animal oils and / or fats. Alkyl esters are usually lower alkyl esters, in particular 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"). ,

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.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.

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.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, petrol fuel compositions of the specification are also according to WO 00/47698 Possible fields of use for the present invention.

Gegenstand der vorliegenden Erfindung ist auch ein Additivkonzentrat, welches in Kombination mit mindestens einem weiteren Kraft- und Brennstoffadditiv, insbesondere mit mindestens einem weiterem Dieselkraftstoffadditiv, wenigstens ein erfindungsgemäß zu verwendendes Imidazoliumsalz (I) enthält. Üblicherweise enthält ein solches Additivkonzentrat 10 bis 60 Gew.-% mindestens eines Lösungs- oder Verdünnungsmittels, welches ein oben genanntes Lösungsmittel oder der Kraft- oder Brennstoff selbst sein kann. Vorzugsweise enthält das erfindungsgemäße Additivkonzentrat neben dem wenigstens einen erfindungsgemäß zu verwendendem Imidazoliumsalz (I) noch mindestens ein Detergens-Additiv aus der oben genannten Gruppe (Da) bis (Di), insbesondere mindestens ein Detergens-Additiv des Typs (Dh), sowie in der Regel zusätzlich auch noch mindestens einen Schmierfähigkeitsverbesserer und/oder eine Korrosionsinhibitor und/oder einen Demulgator und/oder einen Dehazer und/oder ein Antischaummittel und/oder einen Cetanzahlverbesserer und/oder ein Antioxidans und/oder eine Metalldeaktivator in dem jeweils hierfür üblichen Mengenrelationen enthalten.The present invention also provides an additive concentrate which, in combination with at least one further fuel and fuel additive, in particular with at least one further diesel fuel additive, contains at least one imidazolium salt (I) to be used according to the invention. Usually, such an additive concentrate contains 10 to 60% by weight of at least one solvent or diluent, which may be an abovementioned solvent or the fuel or fuel itself. In addition to the at least one imidazolium salt (I) to be used according to the invention, the additive concentrate according to the invention preferably also comprises at least one detergent additive from the above-mentioned group (Da) to (Di), in particular at least one detergent additive of the type (Dh), and in US Pat Rule additionally also contain at least one lubricity improver and / or a corrosion inhibitor and / or a demulsifier and / or a dehazer and / or an antifoaming agent and / or a Cetanzahlverbesserer and / or an antioxidant and / or a metal deactivator in each of these customary quantitative ratios.

Die erfindungsgemäß zu verwendenden Imidazoliumsalze (I) eignen sich insbesondere als Zusatz in Kraft- und Brennstoffzusammensetzungen, insbesondere in DieselkraftStoffen, zur Überwindung der eingangs geschilderten Probleme bei direkteinspritzenden Dieselmotoren, vor allem bei solchen mit Common-Rail-Einspritzsystemen. Da einige der beschriebenen Imidazoliumsalze neue Stoffe darstellen, sind ebenfalls Gegenstand der vorliegenden Erfindung Imidazoliumsalze der allgemeinen Formel (la)

Figure imgb0005
in der

  • eine der Variablen R1 oder R3 oder beide Variablen R1 und R3 unabhängig voneinander für einen Polyisobutylrest mit einem zahlenmittleren Molekulargewicht von 900 bis 3000 stehen,
  • die andere Variable R1 oder R3, einen Alkylrest mit 1 bis 13 Kohlenstoffatomen oder einen Alkenylrest mit 2 bis 13 Kohlenstoffatomen bedeutet,
    und
  • die Variablen R2, R4 und R5 unabhängig voneinander Wasserstoff, einen Alkylrest mit 1 bis 20 Kohlenstoffatomen oder einen Alkenylrest mit 2 bis 20 Kohlenstoffatomen bedeuten,
  • X ein Anion bezeichnet und
  • n für die Zahl 1, 2 oder 3 steht,
  • wobei die genannten Variablen R1 bis R5, X und n die oben genannten zutreffenden Einzelbedeutungen und Vorzugsbereiche aufweisen.
The imidazolium salts (I) to be used according to the invention are particularly suitable as additives in fuel and fuel compositions, in particular in diesel fuels, to overcome the problems described above in direct-injection diesel engines, especially in those with common-rail injection systems. Since some of the described imidazolium salts are novel substances, the present invention likewise provides imidazolium salts of the general formula (Ia)
Figure imgb0005
 in the
  • one of the variables R 1 or R 3 or both variables R 1 and R 3 independently of one another represent a polyisobutyl radical having a number-average molecular weight of from 900 to 3000,
  • the other variable R 1 or R 3, an alkyl radical having 1 to 13 carbon atoms or an alkenyl radical having 2 to 13 carbon atoms,
    and
  • the variables R 2, R 4 and R 5, independently of one another, denote hydrogen, an alkyl radical having 1 to 20 carbon atoms or an alkenyl radical having 2 to 20 carbon atoms,
  • X denotes an anion and
  • n is the number 1, 2 or 3,
  • wherein said variables R1 to R5, X and n have the above-mentioned respective individual meanings and preferred ranges.

Die neuen Imidazoliumsalze der allgemeinen Formel (la) eignen sich neben ihrer Verwendungsmöglichkeit als Additive für Kraft- und Brennstoffe, insbesondere als Detergenzadditive für Dieselkraftstoffe, auch zur Verbesserung der Gebrauchseigenschaften von mineralischen und synthetischen nicht-wässrigen Industrieflüssigkeiten. Unter nicht-wässrigen Industrieflüssigkeiten, die im Einzelfall Wasseranteile enthalten können, deren wesentliche Wirkung jedoch auf nicht-wässrigen Komponenten beruht, sollen hier Schmierstoffe, Schmiermittel und Schmieröle im weitesten Sinne, insbesondere Motorenöle, Getriebeöle, Achsöle, Hydraulikflüssigkeiten, Hydrauliköle, Kompressorenflüssigkeiten, Kompressorenöle, Umlauföle,Turbinenöle, Transformatorenöle, Gasmotorenöle, Windturbinenöle, Bettbahnöle, Schmierfette, Kühlschmierstoffe, Verschleißschutzöle für Ketten und Fördersysteme, Metallbearbeitungsflüssigkeiten, lebensmittelverträgliche Schmierstoffe für die industrielle Verarbeitung von Lebensmitteln sowie Kocheröle für Dauerkocher, Sterilisatoren und Dampfschäler, verstanden werden. Gebrauchseigenschaften, die durch die Imidazoliumsalze (la) verbessert werden, sind insbesondere die Schmierwirkung, der Reibungsverschleiss, die Lebensdauer, der Korrosionsschutz, der antimikrobielle Schutz, das Demulgiervermögen hinsichlich eines erleichterten Abtrennens von Wasser und Verunreinigungen sowie die Filtrierbarkeit.The new imidazolium salts of the general formula (Ia) are suitable not only for their use as additives for fuels and fuels, in particular as detergent additives for diesel fuels, but also for improving the service properties of mineral and synthetic non-aqueous industrial fluids. Among non-aqueous industrial fluids, which may contain water in individual cases, but whose essential effect is based on non-aqueous components, lubricants, lubricants and lubricating oils in the broadest sense, especially motor oils, gear oils, axle oils, hydraulic fluids, hydraulic oils, compressor fluids, compressor oils, Circulation oils, turbine oils, transformer oils, gas engine oils, wind turbine oils, runway oils, lubricating greases, cooling lubricants, wear protection oils for chains and conveyor systems, metalworking fluids, food grade lubricants for industrial processing of foodstuffs and cooker oils for cookers, sterilizers and steam peelers. Performance properties which are improved by the imidazolium salts (Ia) are in particular the lubricating effect, the friction wear, the service life, the corrosion protection, the antimicrobial protection, the demulsifying ability with regard to a facilitated separation of water and impurities and the filterability.

Die Erfindung wird nun anhand der folgenden Ausführungsbeispiele näher beschrieben:The invention will now be described in more detail with reference to the following exemplary embodiments:

BeispieleExamples Herstellung von 1,3-Di(2-ethylhexyl)imidazolium-acetatPreparation of 1,3-di (2-ethylhexyl) imidazolium acetate

300,3 g (3,0 mol) einer 30 gew.-%igen wässrigen Formaldehyd-Lösung, 435,3 g (3,0 mol) Glyoxal und 180,2 g (3,0 mol) wasserfreie Essigsäure wurden im Kolben vorgelegt und unter Rühren bei Raumtemperatur langsam mit 791,3 g (6,0 mol) 98 gew.-%igem 2-Ethylhexylamin versetzt. Dabei stieg die Temperatur der Reaktionsmischung rasch auf 38°C an und wurde durch Eisbadkühlung bis zum Zugabeende des Amins dort gehalten. Anschließend wurde 5 Stunden bei 80°C nachgerührt. Nach Abtrennung der oberen wässrigen Phase wurden 1038,4 g 1,3-(2-Ethylhexyl)imidazolium-acetat erhalten.300.3 g (3.0 mol) of a 30 wt.% Aqueous formaldehyde solution, 435.3 g (3.0 mol) of glyoxal and 180.2 g (3.0 mol) of anhydrous acetic acid were placed in the flask and slowly added with stirring at room temperature with 791.3 g (6.0 mol) of 98 wt .-% 2-ethylhexylamine. The temperature of the reaction mixture rose rapidly to 38 ° C and was kept there by Eisbadkühlung until the end of the addition of the amine. The mixture was then stirred at 80 ° C for 5 hours. After separation of the upper aqueous phase, 1038.4 g of 1,3- (2-ethylhexyl) imidazolium acetate were obtained.

Herstellung von 1,3-Di(polyisobutyl)imidazolium-acetatPreparation of 1,3-di (polyisobutyl) imidazolium acetate

Analog zur oben beschriebenen Herstellung von 1,3-Di(2-ethylhexyl)imidazolium-acetat wurde aus 3,0 mol 30 gew.-%iger wässrigen Formaldehyd-Lösung, 3,0 mol Glyoxal, 3,0 mol wasserfreie Essigsäure und 6,0 mol Polyisobutylamin C4H9-(C4H8)x-CH2NH2 mit x = 17-18 (Handelsprodukt Kerocom® PIBA der BASF SE) 1,3-Di(polyisobutyl)imidazolium-acetat erhalten.Analogously to the preparation of 1,3-di (2-ethylhexyl) imidazolium acetate described above, 3.0 mol of 30% strength by weight aqueous formaldehyde solution, 3.0 mol of glyoxal, 3.0 mol of anhydrous acetic acid and 6 , 0 mol of polyisobutylamine C 4 H 9 - (C 4 H 8 ) x -CH 2 NH 2 with x = 17-18 (commercial product Kerocom® PIBA from BASF SE) obtained 1,3-di (polyisobutyl) imidazolium acetate.

Anwendungsbeispieleapplications

Zur Untersuchung des Einflusses der Additive auf die Performance von direkteinspritzenden Dieselmotoren wurde als Testmethode der DW10-Motorentest verwendet, bei dem der Leistungsverlust ("powerloss") durch Injektorablagerungen im Common Rail-Dieselmotor in Anlehnung an die offizielle Testmethode CEC F-098-08 bestimmt wird. Der Leistungsverlust ist ein direktes Maß für Bildung von Ablagerungen in den Injektoren.To test the influence of additives on the performance of direct-injection diesel engines, the test method used was the DW10 engine test, in which the powerloss was determined by injector deposits in the common-rail diesel engine based on the official test method CEC F-098-08 becomes. The power loss is a direct measure of the formation of deposits in the injectors.

Verwendet wurde ein direkteinspritzender Dieselmotor mit Common-Rail-System gemäß Testmethoden CEC F-098-08. Als Kraftstoff wurde ein handelsüblicher Dieselkraftstoff der Fa. Haltermann (DF-79-07/5) eingesetzt. Diesem wurden zur künstlichen Anregung der Bildung von Ablagerungen an den Injektoren 1 Gew.-ppm Zink in Form einer Zink-Didodecanoatlösung zugesetzt. Die Ergebnisse veranschaulichen den relativen Leistungsverlust bei 4000 rpm gemessen während eines 12-stündigen Dauerbetriebs. Der Wert "t0" gibt dabei die Leistung ("power") in kW bei Testbeginn und der Wert "t12" die Leistung in kW bei Testende an.A direct injection diesel engine with common rail system was used according to test methods CEC F-098-08. The fuel used was a commercial diesel fuel from Haltermann (DF-79-07 / 5). To this was added 1 wt ppm zinc in the form of a zinc didodecanoate solution to artificially stimulate the formation of deposits on the injectors. The results illustrate the relative power loss measured at 4000 rpm during a 12-hour continuous operation. The value "t0" indicates the power ("power") in kW at the start of the test and the value "t12" the power in kW at the end of the test.

Als erfindungsgemäß zu verwendende Additive wurden folgende Imidazoliumsalze eingesetzt:

(I.1)
1-Ethyl-3-methylimidazolium-acetat
(I.2)
1-Butyl-3-methylimidazolium-acetat
(I.3)
1-Octyl-3-methylimidazolium-methylcarbonat
(I.4)
1,3-Di(2eEthylhexyl)imidazolium-acetat
As additives to be used according to the invention, the following imidazolium salts were used:
(I.1)
1-ethyl-3-methylimidazolium acetate
(I.2)
1-butyl-3-methylimidazolium acetate
(I.3)
1-octyl-3-methylimidazolium methyl carbonate
(I.4)
1,3-di (2eEthylhexyl) imidazolium acetate

Die Verbindungen (I.1) und (I.2) sind handelsübliche Produkte; die Verbindung (I.3) wurde aus N-Octylimidazol durch Quaternisierung mit Dimethylcarbonat als 30 gew.-%ige Lösung in Methanol nach einer üblichen Synthesemethode hergestellt; die Verbindung (I.4) wurde gemäß oben angegebener Synthesevorschrift hergestellt.The compounds (I.1) and (I.2) are commercially available products; the compound (I.3) was prepared from N-octylimidazole by quaternization with dimethyl carbonate as a 30% by weight solution in methanol by a usual synthesis method; the compound (I.4) was prepared according to the above-mentioned synthesis instructions.

In den durchgeführten Testläufen wurden die Additive (I.1) und (I.2) als Reinsubstanzen und die Additive (I.3) und (I.4) als Lösungen eingesetzt. Die angegebenen Dosierung beziehen sich auf den aktiven Wirkstoff.In the test runs carried out, the additives (I.1) and (I.2) were used as pure substances and the additives (I.3) and (I.4) as solutions. The indicated dosage refers to the active ingredient.

Die Ergebnisse der Power- bzw. Powerloss-Bestimmungen der DW10-Motorentestläufe sind in der folgenden Tabelle zusammengefasst: Additiv Dosierung [Gew.-ppm] t0 [kW] t12 [kW] powerloss [%] ohne   0 93,9 88,8 -5,4 (I.1) 100 98,9 98,0 -0,9 (I.2) 100 97,1 97,0 -0,1 (I.2)  30 95,2 94,4 -0,8 (I.3) ..33 96,9 97,2 +0,3 (I.4)  50 95,8 95,1 -0,7 The results of the power and powerloss determinations of the DW10 engine test runs are summarized in the following table: additive Dosage [ppm by weight] t0 [kW] t12 [kW] powerloss [%] without 0 93.9 88.8 -5.4 (I.1) 100 98.9 98.0 -0.9 (I.2) 100 97.1 97.0 -0.1 (I.2) 30 95.2 94.4 -0.8 (I.3) ..33 96.9 97.2 +0.3 (I.4) 50 95.8 95.1 -0.7

Mit den Additiven (I.2) und (I.4) wurde zusätzlich ein Verschmutzungs- und Reinigungslauf gemäß DW10-Test durchgeführt. Dazu wurde zuerst der verwendete direkteinspritzende Dieselmotor mit Common-Rail-System mit dem gleichen handelsüblichen Dieselkraftstoff (mit einem Gehalt an 1 Gew.-ppm Zink in Form einer Zink-Didodecanoatlösung) für 12 Stunden ohne Detergens-Additiv betrieben, wobei der Wert t für die Leistung im Experiment mit (I.2) zuerst sukzessive von 96,2 kW auf 89,8 kW fiel. Nach Zugabe von 30 Gew.-ppm des Additivs (I.2) und weiterem Betrieb für 5 Stunden stieg der Wert t für die Leistung wieder auf 95,7 kW an, wobei der größte Sprung für t innerhalb der ersten beiden Stunden nach Zugabe von (I.2) erfolgte (nach 1 Stunde t = 91,4 kW, nach 2 Stunden t = 94,5 kW).The additives (I.2) and (I.4) were additionally used to carry out a soiling and cleaning operation in accordance with the DW10 test. For this purpose, the used common rail direct injection diesel engine used with the same commercial diesel fuel (containing 1 ppm by weight of zinc in the form of a zinc didodecanoate solution) was first operated for 12 hours without detergent additive, wherein the value t for the power in the experiment with (I.2) first fell successively from 96.2 kW to 89.8 kW. After adding 30 ppm by weight of the additive (I.2) and continuing to operate for 5 hours, the value t for the power returned to 95.7 kW, with the largest jump for t within the first two hours after the addition of (I.2) took place (after 1 hour t = 91.4 kW, after 2 hours t = 94.5 kW).

In Experiment mit Additive (I.4) fiel die Leistung von 98,4 kW auf 93,9 kW in den ersten 13 Stunden Betrieb ohne Additive. Nach Zugabe von 50 Gew.-ppm des Additivs (I.4) und weiterem Betrieb für 12 Stunden stieg der Wert t für die Leistung wieder auf 96,3 kW an, wobei der größte Sprung in Leistung innerhalb der ersten beiden Stunden nach Zugabe von (I.4) erfolgte (nach weiterer Absenkung des Wertes nach Kraftstoffwechsel zu 92,8kW stieg Leistung nach eine Stunde wieder auf t = 94,5 kW, nach 2 Stunden dann auf t = 95,5 kW).In the experiment with additives (I.4), the power dropped from 98.4 kW to 93.9 kW in the first 13 hours of operation without additives. After adding 50 ppm by weight of the additive (I.4) and continued operation for 12 hours, the value of t for the power returned to 96.3 kW, with the largest jump in power within the first two hours after the addition of (I.4) took place (after further lowering of the value after fuel change to 92.8 kW, power rose again after one hour to t = 94.5 kW, after 2 hours then to t = 95.5 kW).

Mit dem Additiv (I.4) wurde auch ein "keep clean"-Motortest gemäß der Testmethode CEC F-23-01 mit dem PSA-Motor XUD-9 A gefahren. Das Additiv wurde mit einer Dosierung von 50 ppm in einem handelsüblichen Dieselkraftstoff der Fa. Haltermann (DF-79-07/5) eingesetzt. Zum Vergleich wurde der Motor in einem separaten Prüflauf mit dem gleichen Dieselkraftstoff ohne Additiv betrieben. Die "Flow restriction" bei 0,1 mm "Needle elevation" im Kraftstoff betrug ohne Additiv 63% und mit 50 Gew.-ppm Additiv (I.4) -32%.With the additive (I.4) was also a "keep clean" motor test according to the test method CEC F-23-01 with the PSA engine XUD-9 A driven. The additive was used at a dosage of 50 ppm in a commercial diesel fuel from Haltermann (DF-79-07 / 5). For comparison, the engine was operated in a separate test run with the same diesel fuel without additive. The "flow restriction" at 0.1 mm "Needle elevation" in the fuel was 63% without additive and with 50 ppm by weight of additive (I.4) -32%.

Claims (9)

  1. The use of imidazolium salts of the general formula (I)
    Figure imgb0008
     in which the variables R1 and R3 are each independently an organic radical,
    the variables R2, R4 and R5 are each independently hydrogen or an organic radical,
    X is an anion,
    selected from the group consisting of alkyl-carbonates, pseudohalides, carboxylates or the tricyanomethamide anion and
    n is the number 1, 2 or 3,
    where the organic radicals are selected from the group consisting of alkyl, cycloalkyl, alkenyl, cycloalkyl, aryl or heteroaryl radicals comprising 1 to 20 carbon atoms, and polyisobutene radicals having 30 to 250 carbon atoms,
    as detergent additive for diesel fuels, as wax antisettling additive (WASA) for middle distillate fuels, especially diesel fuels, as lubricity improver for fuels, or as friction modifier for gasoline fuels.
  2. The use of imidazolium salts (I) according to claim 1 as an additive for reducing or preventing deposits in injection systems of direct injection diesel engines, for reducing the fuel consumption of direct injection diesel engines, and/or for minimizing power loss in direct injection diesel engines.
  3. The use of imidazolium salts (I) according to claim 1 as an additive for reducing or preventing deposits in injection systems in common rail injection systems, for reducing the fuel consumption of diesel engines with common rail injection systems, and/or for minimizing power loss in diesel engines with common rail injection systems.
  4. The use of imidazolium salts (I) according to claims 1 to 4, in which the variables R1 and R3 are each independently C1- to C20-alkyl groups, C2- to C20-alkenyl groups and/or polyisobutyl radicals having a number-average molecular weight of 900 to 3000 and the variables R2, R4 and R5 are each hydrogen.
  5. An additive concentrate comprising, in combination with at least one further fuel additive, especially with at least one further diesel fuel additive, at least one imidazolium salt (I) according to claim 1 or 4.
  6. A fuel composition comprising 10 to 5000 wt.ppm of at least one imidazolium salt (I) according to claim 1 or 4.
  7. An imidazolium salt of the general formula (Ia)
    Figure imgb0009
     in which one of the variables R1 and R3 is or both variables R1 and R3 are independently a polyisobutyl radical having a number-average molecular weight of 900 to 3000 and the variables R2, R4 and R5 are each independently hydrogen, an alkyl radical having 1 to 20 carbon atoms or an alkenyl radical having 2 to 20 carbon atoms,
    the other variable R1 or R3 is an alkyl radical having 1 to 13 carbon atoms or an alkenyl radical having 2 to 13 carbon atoms,
    X is an anion and
    n is the number 1, 2 or 3.
  8. The use of imidazolium salts of the general formula (Ia) according to claim 7 for improving lubricity, frictional wear, lifetime, corrosion protection, antimicrobial protection, demulsification capacity with regard to easier removal of water and impurities and filterability of lubricants, lubricant compositions and lubricant oils, metalworking fluids, food-compatible lubricants for the industrial processing of foods, and boiler oils for industrial cookers, sterilizers and steam peelers.
  9. The use according to Claim 8, wherein the lubricants, lubricant compositions and lubricant oils are selected from the group consisting of motor oils, transmission oils, axle oils, hydraulic fluids, hydraulic oils, compressor fluids, compressor oils, circulation oils, turbine oils, transformer oils, gas motor oils, wind turbine oils, slideway oils, lubricant greases, cooling lubricants, antiwear oils for chains and conveyor systems.
EP13702810.6A 2012-02-10 2013-02-07 Imidazolium salts as additives for fuels and combustibles Active EP2812418B1 (en)

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