Classifications

• • 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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