ES2711361T3 - Imidazolium salts as additives for fuels and fuels - Google Patents

Abstract

Use of imidazolium salts of the general formula (I) ** Formula ** in which the variables R1 and R3 independently of each other represent an organic residue, the variables R2, R4 and R5 independently of each other mean hydrogen or an organic residue, X designates an anion, selected from the group consisting of alkyl carbonates, pseudohalides, carboxylates or the tricianometamide anion and n represents the numbers 1, 2 or 3, wherein the organic residues are selected from the group consisting of alkyl residues, cycloalkyl, alkenyl, cyclo-alkenyl, aryl or heteroaryl, containing from 1 to 20 carbon atoms, as well as polyisobutyl residues with from 30 to 250 carbon atoms, as a detergent additive for diesel fuels, as a Wachs-Anti-Settling additive (WASA) (wax anti-settling) for medium distillate fuels, mainly diesel fuels, as lubricant capacity enhancers for fuels and fuels or as friction modifier for gasoline fuels.

Description

DESCRIPTION

Imidazolium salts as additives for fuels and fuels

The present invention relates to the use of imidazolium salts as additives for fuels and fuels, mainly as detergent additives for diesel fuels, in particular for those diesel fuels that combustion in direct injection diesel engines, mainly in common rail injection systems. The present invention also relates to an additive concentrate and a fuel or fuel composition containing said imidazolium salts. The present invention also relates to new imidazolium salts and for use in industrial liquids.

In direct injection diesel engines, the fuel is injected and distributed in an ultrafine form (nebulized) by a multi-hole injection nozzle that directly reaches the combustion chamber of the engine, instead of being introduced into a pre-chamber or action chamber. swirl as in the case of the conventional diesel engine (camera) The advantage of diesel engines direct injection lies in its high performance for diesel engines and, however, in the low fuel consumption. In addition, these engines achieve a very high torque even at low speeds.

At present, essentially three methods are used for fuel injection directly into the combustion chamber of the diesel engine: the conventional distributor injection pump, the pump-pump system (unit injector system or unit pump system), and the system of common rail.

In the common rail system, the diesel fuel is transported by a pump with pressures of up to 2000 bar (200000 kPa) to a high-pressure duct, the common rail. Coming from the common rail, the bypass pipes run to the different injectors that inject the fuel directly into the combustion chamber. The fuel pressure is always adjusted to the common rail, which allows a multiple injection or a specific injection method. In the other injection systems, on the other hand, only a smaller variation in the injection is possible. The injection in the common rail is essentially divided into three groups: (1.) pre-injection, by which essentially a smoother combustion is achieved, in such a way that noises of rough combustion ("of nails") are reduced and the engine seems run in silence; (2.) main injection, which is mainly responsible for a good torque; and (3) post-injection, which particularly provides a low NOx value. In this post-injection, as a rule the fuel is not combusted, but vaporized by residual heat in the cylinder. The exhaust gas / fuel mixture formed in such a case is transported to the exhaust gas system, where the fuel, in the presence of suitable catalysts, acts as a reducing agent for NOx nitrogen oxides.

By means of the variable individual injection of the cylinder, in the system of injection of common rail can influence positively in the emission of pollutants of the engine, for example, the emission of oxides of nitrogen (NOx), carbon monoxide (CO) and mainly of particles (hollm) This makes it possible, for example, that motors equipped with common rail injection systems can theoretically satisfy the Euro 4 standard, even without additional filters for particles.

In modern common-rail diesel engines, under certain conditions, for example, when fuels containing biodiesel or fuels with metal impurities, such as zinc compounds, copper compounds, lead compounds and other metal compounds, are used, they can deposits are formed on the holes of the injector, which adversely affects the injection performance of the fuel and, therefore, impairs the performance of the engine, that is, it mainly reduces the power, but in part it also worsens the combustion. The formation of deposits is further intensified by additional developments in the construction of the injectors, mainly by the change in the geometry of the nozzles (conical orifices, narrower, with rounded outlets). For optimal long-term operation of the engine and injectors, these deposits in the nozzle orifices should be avoided or reduced by suitable fuel additives.

The international application WO 2012/004300 (1) describes quaternized, acid-free quaternized nitrogen compounds as fuel additives, which can be obtained by the addition of a compound containing at least one group containing oxygen or reactive nitrogen with an anhydride and, in addition, at least one quaternizable amino group in a polycarboxylic antidrid compound and the subsequent quaternization with an epoxide in the absence of free acid. As compounds having an oxygen or nitrogen-containing group, reactive with a dioxide and, furthermore, a quaternizable amino group, polyamines having at least one primary or secondary amino group and at least one tertiary amino group are suitable. As polycarboxylic anhydrides, dicarboxylic acids such as succinic acid with a longer chain hydrocarbyl substituent are mainly considered. Said quaternized nitrogen compound is, for example, the reaction product, obtained at 40 ° C, of polyisobutenylsuccic antisense with 3- (dimethylamino) propylamine, which is a polyisobutenylsuccinic semiamide and which is subsequently quaternized with styrene oxide in the absence of acid free at 70 ° C. Said acid-free quaternized nitrogen compounds are mainly suitable as a fuel additive to reduce or avoid deposits in injection systems of direct injection diesel engines, mainly in common rail injection systems, to reduce the fuel consumption of engines. direct injection diesel, mainly diesel engines with common rail injection systems, and / or to reduce to the minimum the power loss in direct injection diesel engines, mainly in diesel engines with common rail injection systems .

The international patent application PCT / EP2011 / 071683 (2) describes polytetrahydrobenzoxazines and bistetrahydrobenzoxazines as fuel additives, which can be obtained, in a first reaction step, by reacting successively an alkylene diamine of Ci to C20 having two functions of primary amino, for example, 1,2-ethylenediamine, with an aldehudo of Ci to C12, for example, formaldehyde, and an alkanol of Ci to Ca at a temperature of 20 to 80 ° C with detachment and removal of water, in which case both the aldehudo, as well as alcohol are used in more than twice the molar quantity in relation to the diamine; in a second reaction step, the condensation product obtained in this way is reacted with a phenol containing at least one long-chain substituent, for example, a ter-octyl, n-nonyl, n-dodecyl residue. or polyisobutyl, in stoichiometric ratio with respect to the alkylene diamine originally used from 1.2: 1 to 3: 1, at a temperature of 30 to 120 ° C and optionally, the bistetrahydrobenzoxazine thus obtained is heated in a third reaction step to a Temperature from 125 to 280 ° C for at least 10 minutes. Said polytetrahydrobenzoxazines and bistetrahydrobenzoxazines are mainly suitable as a fuel additive to reduce or avoid deposits in the injection systems of direct injection diesel engines, mainly in common rail injection systems, to reduce the fuel consumption of direct injection diesel engines, mainly diesel engines with common rail injection systems, and / or to reduce to the minimum the power loss in direct injection diesel engines, mainly in diesel engines with common rail injection systems.

However, the quaternized nitrogen-free compounds of aforementioned acid and polytetrahydrobenzoxazines or bistetrahydrobenzoxazines still need improvement in terms of their properties as detergent additives for fuels and fuels. In addition, they should also have an improved anticorrosive effect, improved motor oil compatibility and improved low temperature properties.

Therefore, one goal was to provide improved additives for fuel and fuel that no longer have the detailed drawbacks of the state of the art.

Accordingly, the use of imidazolium salts of the general formula (1)

in which

the variables R1 and R3 independently of each other represent an organic waste,

the variables R2, R4 and R5 independently of each other mean hydrogen or an organic residue, X designates an anion

selected from the group consisting of alkyl carbonates, pseudohalides, carboxylates or the anion of tricyometamide

Y

n represents the number 1, 2 or 3,

where the organic residues are selected from the group consisting of alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl or heteroaryl residues, containing 1 to 20 carbon atoms, as well as polyisobutyl residues with 30 to 250 carbon atoms,

as a detergent additive for diesel fuels, as an anti-settling wax additive (WASA) for medium distillation fuels, mainly diesel fuels as lubricant property improvers for fuels and fuels or as a friction modifier for gasoline.

The imidazolium salts of type (I) belong - together with, for example, quaternary ammonium salts, pyridinium salts, pyridazinium salts, pyrimidinium salts, pyrazinium salts, pyrazolium salts, pyrazinium salts, imidazolinium salts, thiazolium salts, triazolium salts, pyrrolidinium salts and imidazolidinium salts - to the so-called Ionic liquids, by which salts (dedr, compounds of cations and anions) are understood that, under normal pressure, have a melting point of less than 200 ° C, generally even of less than 80 ° C. Ionic ions frequently contain an organic compound as a cation (organic cation). Depending on the Valencia of the anion, in addition to the organic cation, the ionic liquid may contain other cations, such as metal cations.

Imidazolium salts of type (I) are known in their application as dispersing detergents in lubricating formulations. This way, publication WO 2010/101801 A1 (3) discloses oil-soluble ionic detergents as additive components in lubricating oils for combustion engines; Examples which may be mentioned are, in addition to the open-chain ion systems and quaternized pyridinium detergents, quaternized imidazolium phenolates, imidazolium chlorides and imidazolium salicylates.

In the publication WO 2010/096168 A1 (4) ionic liquids are described as pyridinium salts as additives for the control of the formation of deposits on the internal surfaces of combustion engines. However, unlike the present invention, such additives are added to the lubricating oil and not to the fuel, which is used to operate these engines. In addition, publication WO 2010/096168 A1 does not explicitly disclose imidazolium salts as additives of this type.

Publication US 4108858 (5) discloses quaternized ammonium salts, substituted with N-hydrocarbyl, of high molecular weight, with a molecular weight of 350 to 3000 carbon atoms for the hydrocarbyl group as detergents and dispersants for fuels such as gasolines and diesel fuels and lubricating oils. As quaternized ammonium salts, substituted with N-hydrocarbyl, high molecular weight are mentioned, in addition to open chain systems, salts of piperidines, piperazines, morpholines and pyridines. Longer chain hydrocarbon residues are considered, for example, polybutene or polypropylene residues.

In a preferred embodiment of the present invention, the imidazolium salts (I) are used as detergent additives for diesel fuels. In this embodiment, particularly preferred are the individual uses of the imidazolium (I) salts as an additive to reduce or prevent deposits in injection systems of direct injection diesel engines, mainly common rail injection system, to decrease the fuel consumption of direct injection diesel engines, mainly diesel engines with common rail injection systems and / or to minimize the power loss in direct injection diesel engines, mainly in diesel engines with rail injection systems common.

In another preferred embodiment, the imidazolium salts (I) are used as wax anti-settling additive (WASA) for medium distillation fuels, mainly diesel fuels.

In another preferred embodiment, the imidazolium salts (I) are used as lubrication capacity enhancers for fuels and fuels, mainly as friction modifiers for gasoline, as well as additives for the lubrication property for fuels and distillation fuels half.

As organic residues for the variables R1 to R5 in the imidazolium salts of the general formula (I), preference is preferably given to C1 to C20 alkyl residues, in particular C1 to C12 alkyl residues, in particular C1 to C alkyl residues. Ca, 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, npentadecyl, n-hexadecyl , n-heptadecyl, n-octadecyl, n-nonadecyl, n-icosyl, phenylmethyl (benzyl), diphenylmethyl, triphenylmethyl, 2-phenylethyl, 3-phenylpropyl, cyclopentylmethyl, 2-cyclopentyloethyl, 3-cyclopentylpropyl, cyclohexylmethyl, 2-cyclohexylethyl, 3-cyclohexylpropyl.

As organic residues with 1 to 20 carbon atoms for the variables R1 to R5 in the imidazolium salts of the general formula (I), C3 to C12 cycloalkyl radicals, in particular C5 to C7 cycloalkyl residues, are also suitable. , for example, cyclopentyl, 2-methyl-1-cyclopentyl, 3-methyl-1-cyclopentyl, cyclohexyl, 2-methyl-1-cyclohexyl, 3-methyl-1-cyclohexyl, 4-methyl-1-cyclohexyl.

As organic residues with 1 to 20 carbon atoms for the variables R1 to R5 in the imidazolium salts of the general formula (I), alkenyl residues from C2 to C20 are also suitable, mainly alkenyl residues from C3 to C ⁸ , for example, vinyl, 2-propenyl (allyl), 3-butenyl, cis-2-butenyl, trans-2-butenyl.

As organic residues with 1 to 20 carbon atoms for the variables R1 to R5 in the imidazolium salts of the general formula (I), cycloalkyl residues from C3 to C12, especially C5 alkenyl cyclic residues, are also suitable. C7, for example, 3-cyclopentenyl, 2-cyclohexenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl.

Organic residues having 1 to 20 carbon atoms for the variables R1 to R5 in the imidazolium salts of the general formula (I) are also suitable, in addition, aryl or heteroaryl residues with 3 to 20, mainly 5 to 10 atoms carbon, for example, phenyl, 2-methyl-phenyl (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 residues with 1 to 3000 carbon atoms for the variables R1 to R5 can be synthetically generated waste or - mainly in the case of alkyl and alkenyl residues - residues based on naturally occurring compounds. The latter are derived, first of all, from naturally occurring glycerides or fatty acids, for example, from stearic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid or tallow fatty acid. Residues of this type based on naturally occurring compounds often represent mixtures of different alkyl and alkenyl residues, generally homologous.

Organic residues for the variables R1 to R5 in the imidazolium salts of the general formula (I) are preferably also polyisobutyl residues with from 30 to 250 carbon atoms. Polyisobutyl residues of this type have average molecular weights of number Mn, determined by gel permeation chromatography, from 900 to 3000, very particularly preferably from 900 to 1100. The polyisobutyl residues can be attached directly or by means of a group methylene (-CH2-) to the imidazolium ring.

In general, imidazolium salts of the general formula (I) are used, in which the variables R1 and R3 have the meanings stated above of an organic residue and the variables R2, R4 and R5 mean hydrogen.

In a preferred embodiment of the present invention, imidazolium salts of the general formula (I) are used in which the variables R1 and R3 independently of each other represent alkyl groups of C1 to C20, alkenyl groups of C2 to C20 and / or polyisobutyl residues with a number average molecular weight (Mn) of 900 to 3000 and the variables R2, R4 and R5 respectively mean hydrogen. In such a case, these C1 to C20 alkyl groups are pure hydrocarbon residues. Typical examples of pure C1 to C20 hydrocarbon residues of this type are the 2-ethylhexyl residue and tallow fatty alkyl.

As X anions in the imidazolium salts of the general formula (I) are considered, for example: carboxylates, mainly formate, acetate, propionate, butyrate or benzoate; mandelato; trifluoroacetate; oleate; stearate; acrylate; methacrylate; malenate hydrogen citrate.

As a rule, the X anions are selected from the following group:

• pseudohalides, mainly thiocyanate and dicyanamide;

• carboxylates of RaCOO formula ', in which Ra represents an alkyl group of C1 to C60, an alkenyl group of C2 to C60, an aryl group of C ⁶ to C60 or an alkyl-aryl or aryl-alkyl C7 C60, preferably an alkyl group of C1 to C20, an alkenyl group of C2 to C20, an aryl group of C ⁶ to C20 or an alkyl aryl group or aryl alkyl C7 to C20, primarily an alkenyl group of C2 at C ⁸ , an aryl group of C ⁶ to C 12 or an alkyl-aryl or aryl-C ⁷ to C ¹⁴ alkyl group, mainly represents acetate, but also formate, butyrate, acrylate, methacrylate, benzoate, phenylacetate or o-, m- or p-methylbenzoate;

• polycarboxylates of the formula Rb (COO-) n, in which n represents the number 1, 2 or 3 and Rn means an n-valent hydrocarbon residue with 1 to 60, mainly 1 to 20, first of all 1 to 14 atoms of carbon; typical residues of this type are malonate, succinate, glutarate, adipate, phthalate or terephthalate; In addition, the oxalate anion -OOC-COO is also suitable as the polycarboxylate anion.

• tricianometamide of the formula (CN) 3 C-.

Very particularly preferred, as anion X, an alkyl carbonate, a pseudohalide, a carboxylate or the anion of trichometamide is used. The charge n of the anion X depends on its nature and can adopt the value 1,2 or 3. In the most frequent way, n represents 1 or 2, mainly 1.

Typical particular 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-ethyl acetate, -butyl-3-methylimidazolium, 1-pentyl-3-methylimidazolium acetate, 1-hexyl-3-methylimidazolium acetate, 1-octyl-3-methylimidazolium acetate, 1- (2-ethylhexyl) -3-methylimidazolium acetate, acetate of 1,3-di (2-ethylhexyl) imidazolium, 1-decyl-3-methylimidazolium acetate, 1- (2-propylheptyl) -3-methylimidazolium acetate, 1,3,4,5-tetramethylimidazolium acetate, acetate of 1,3-dimethyl-4,5-diphenylimidazolium, 1,4,5-trimethyl-3-ethylimidazolium acetate, 1-methyl-3-ethyl-4,5-diphenylimidazolium acetate, 1,3-dimethylimidazolium methylcarbonate, methylcarbonate 1 , 3-diethylimidazolium, 1-ethyl-3-methylimidazolium methylcarbonate, 1-propyl-3-methylimidazolium methylcarbonate, 1-butyl-3-methylimidazolium methylcarbonate, 1-pentyl-3-methylimidazolium methylcarbonate, methylcarbonate 1-hexyl-3-methylimidazolium, 1-octyl-3-methylimidazolium methylcarbonate, 1- (2-ethylhexyl) -3-methylimidazolium methylcarbonate, 1,3-di (2-ethylhexyl) imidazolium methylcarbonate, methylcarbonate 1- decyl-3-methylimidazolium, 1- (2-propylheptyl) -3-methylimidazolium methylcarbonate, 1,3,4,5-tetramethylimidazolium methylcarbonate, 1,3-dimethyl-4,5-diphenylimidazolium methylcarbonate, 1,4-methylcarbonate, 5-trimethyl-3-ethylimidazolium, 1-methyl-3-ethyl-4,5-diphenylimidazolium methylcarbonate.

Typical examples typical for imidazolium (I) salts with polyisobutenyl residues are 1-polyisobutyl-3-methylimidazolium acetate, 1-polyisobutyl-3-ethylimidazolium acetate, 1-polyisobutyl-3-propylimidazolium acetate, 1-polyisobutyl acetate -3-butylimidazolium, 1-polyisobutyl-3- (2-ethylhexyl) imidazolium acetate, 1,3-di (polyisobutyl) imidazolium acetate, 1-polyisobutyl-3-methylimidazolium methylcarbonate, 1-polyisobutyl-3-methylcarbonate ethylimidazolium, 1-polyisobutyl-3-propylimidazolium methyl carbonate, 1-polyisobutyl-3-butylimidazolium methylcarbonate, 1-polyisobutyl-3- (2-ethylhexyl) imidazolium methylcarbonate, 1,3-di (polyisobutyl) imidazolium methylcarbonate, thiocyanate of 1-polyisobutyl-3-methylimidazolium, 1-polyisobutyl-3-ethylimidazolium thiocyanate, 1-polyisobutyl-3-propylimidazolium thiocyanate, 1-polyisobutyl-3-butylimidazolium thiocyanate, 1-polyisobutyl-3- (2-thiocyanate) ethylhexyl) imidazolium, 1,3-di (polyisobutyl) imidazolium thiocyanate, 1-polyisobutyl-3-methylimidazoliotricianometamide, 1-polyisobutyl-3-ethylimidazoliotricianometamide, 1-polyisobutyl-3-propylimidazoletrotrianediomide, 1-polyisobutyl-3-butylimidazoletrotrianediomide, 1-polyisobutyl-3- (2-ethylhexyl) imidazoliumtriatromethylamide and 1,3-di (polyisobutyl) imidazoliotricianometamide.

Imidazolium salts of type (I) with low molecular weight residues are commercially available under the trade name Basionics ™ from BASF SE.

The preparation of the imidazolium salts of type (I) is common to the person skilled in the art. A typical synthesis route starts from the formation of imidazole from 1 mole of a 1,2-dicarbonyl compound, 1 mole of a correspondingly substituted primary amine, 1 mole of ammonia and 1 mole of an aldehyde; an N-alkylation is performed with a suitable alkylation medium and the anion is then exchanged, if desired. For example, starting from glyoxal or benzyl, an alkylamine or a primary low molecular weight alkylamine, for example, an alkylamine of C1 to C13, or a polyisobutylamine, ammonia and formaldehyde, an N-alkyl-4,5-diphenylimidazole is formed or an N-alkylimidazole or an N-polyisobutyl-4,5-diphenylimidazole or an N-polyisobutylimidazole and the second nitrogen atom is alkylated or unsubstituted with an epoxide, such as an ethylene oxide, propylene oxide, butylene oxide or styrene oxide in the presence of acetic acid or with a dialkyl carbonate, in which case the imidazolium salts then have an acetate anion or an alkyl-carbonate anion. To introduce a polyisobutyl residue in the second atom of unsubstituted nitrogen, a polyisobutene epoxide can be used as alkylating agents.

In preparing the imidazolium salts of type (I) with identical R1 and R3 variables, 1 mol of a 1,2-dicarbonyl compound is advantageously reacted together with 2 mol of a correspondingly substituted primary amine and 1 mol of a optionally aldehyde in the presence of a suitable solvent (for example, of acetic acid and water, if an imidazolium acetate is to be obtained) in a one-stage synthesis, generally at 20 to 120 ° C, mainly at 25 to 80 ° C.

The fuel or fuel to which one or more imidazolium salts (I) is added is a gasoline or a medium distillation fuel, especially a diesel fuel. The fuel or fuel may contain other customary additives ("co-additives") for the improvement of the effectiveness and / or the suppression of wear.

In the case of diesel fuels, these are, in the first place, common detergent additives, carrier oils, flow improvers, lubrication capacity improvers (Lubricity Improver), corrosion inhibitors, demulsifiers, defoamers, defoamers, improvers, number of cetane, combustion improvers, antioxidants or stabilizers, antistatic, metallocenes, metal deactivators, dyes and / or solvents.

In the case of gasoline fuels, these are first of all lubrication capacity enhancers (Friction Modifier), corrosion inhibitors, demulsifiers, defoamers, defoamers, combustion improvers, antioxidants or stabilizers, antistatic, metallocenes, metal deactivators, dyes and / or solvents.

Typical examples of suitable co-additives are listed in the following sections.

The usual detergent additives are preferably amphiphilic substances possessing at least one hydrophobic hydrocarbyl residue with an average molecular weight of number (Mn) of 85 to 20,000 and at least one polar group selected from:

(Da) mono- or polyamino groups up to 6 nitrogen atoms, in which case at least one nitrogen atom has basic properties;

(Db) nitro groups, optionally in combination with hydroxyl groups;

(Dc) hydroxyl groups in combination with mono- or polyamino groups, in which case at least one nitrogen atom has basic properties;

(Dd) carboxyl groups or their alkali metal or alkaline earth metal salts;

(De) sulphonic acid groups or their alkali metal or alkaline earth metal salts;

(Df) polyoxyalkylene groups of C2 to C4, which are terminated by hydroxyl groups, mono- or polyamino groups, in which case at least one nitrogen atom has basic properties, or terminated by carbamate groups, (Dg) groups of esters of carboxylic acid;

(Dh) groups derived from succinic acid antidrid with hydroxyl and / or amino and / or amide and / or imido groups; and / or (Di) groups generated by Mannich reaction of phenols substituted with aldetands and mono- or polyamines. The hydrophobic hydrocarbyl residue in the above detergent additives, which causes sufficient solubility in the fuel or fuel, has an average molecular weight of number (Mn) of 85 to 20,000, preferably 113 to 10,000, particularly preferably 300 to 5,000, much more preferable from 300 to 3,000, even much more preferable from 500 to 2,500 and mainly from 700 to 2,500, above all from 800 to 1,500. Typical hydrocarbon hydrocarbon residues are mainly polypropenyl, polybutenyl and polyisobutenyl with a number average molecular weight Mn, respectively, preferably from 300 to 5,000, particularly preferably from 300 to 3,000, much more preferably from 500 to 2,500, still much more preferable from 700 to 2,500 and especially from 800 to 1,500.

As examples of the above groups of detergent additives, the following may be mentioned:

Additives containing mono- or polyamino (Da) are preferably polyalkenmono- or polyalkenpolyamines based on polypropene or polybutene or polyisobutene highly reactive (ie, with predominantly terminal double bonds) or conventional (ie, with predominantly internal double bonds) with Mn = 300 to 5000, particularly preferably 500 to 2500 and especially 700 to 2500. Additives of this type based on highly reactive polyisobutene, which can be prepared from polyisobutene, which can contain up to 20% by weight of units of n -butene, by hydroformylation and reductive amination with ammonia, monoamines or polyamines such as dimethylaminopropylamine, ethylenediamine, diethylenetriamine, triethylenetetramine or tetraethylenepentamine, are known mainly from the publication EP-A 244616. If when preparing the additives are part of polybutene or polyisobutene with links preponderantly internal doubles (usually in the p ^{and y} position), p The preparation route is prepared by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to obtain carbonyl or a carboxyl compound, and subsequent amination under reductive (hydrogenating) conditions. For amination, here amines such as ammonia, monoamines or the aforementioned polyamines can be used. The corresponding additives based on polypropylene are described mainly in the publication WO-A 94/24231.

Other additives containing particular groups of monoamino (Da) are the hydrogenation products of the reaction products of polyisobutenes with a degree of polymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen oxide and oxygen, as described above. describe mainly in publication WO-A 97/03946. Other additives containing particular groups of monoamino (Da) are the compounds obtainable by reaction with amines and subsequent dehydration and reduction of the aminoalcohols, as described mainly in the publication DE-A 19620262.

The additives containing nitro groups (Db), optionally in combination with hydroxyl groups, are preferably reaction products of polyisobutenes of the average degree of polymerization P = 5a 100 or 10a 100 with nitrogen oxides or mixtures of nitrogen oxide and oxygen, as they are described mainly in the publication WO-A96 / 03367 and in the publication WO-A 96/03479. These reaction products generally represent mixtures of pure nitropolyisobutene (for example, a, p-dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (for example, a-nitro-p-hydroxy polyisobutene).

The additives containing hydroxyl groups in combination with mono- or polyamino groups (Dc) are mainly polyisobutene epoxide reaction products which can be obtained preferably from a polyisobutene having predominantly terminal double bonds with Mn = 300 to 5000 with ammonia , mono- or polyamines, as described mainly in the publication EP-A 476485.

The additives containing carboxyl groups or their alkali metal or alkaline earth metal (Dd) salts are preferably copolymers of C2 to C40 olefins with maleic acid antidepressant, with a total molecular mass of 500 to 20,000, whose carboxyl groups have become total or partially in the alkali metal or alkaline earth metal salts and a remaining residue of the carboxyl groups have been reacted with alcohols or amines. Such additives are mainly known from EP-A 307 815. Additives of this type serve mainly to prevent wear of the valve seat and can be used advantageously, as described in publication WO-A 87/01126, in combination with common fuel detergents, such as poly (iso) -butenesamines or polyetheramines.

The additives containing sulphonic acid groups or their alkali metal or alkaline earth metal (De) salts are preferably alkali metal or alkaline earth metal salts of a sulfosuccinic acid ester, such as described mainly in EP-A 639632 Additives of this type serve mainly to prevent the wear of the valve seat and can be advantageously used in combination with conventional fuel detergents, such as poly (iso) buten amines or polyetheramines.

Additives containing groups of polyoxyalkylene C2-C4 (Df) are preferably polyethers or polyetheramines which are obtainable by reaction of C2 to C60 alkanols, alkanediols C ⁶ to C30, mono- or di- (C2 to C3O) -amines, alkyl (from C1 to C3o) -cyclohexanols or alkyl (from C1 to C3o) -phenols 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 the polyetheramines by subsequent reductive amination with ammonia, monoamines or polyamines. Products of this type are mainly described in EP-A 310875, EP-A 356725, EP-A 700985 and US-A-4877416. In the case of polyethers, such products also fulfill the properties of carrier oil. Typical examples of these are tridecanol or isotridecanol butoxylates, isononyl phenol butoxylates and butoxylates and polyisobutenol propoxylates, as well as the corresponding reaction products with ammonia.

The additives containing carboxylic acid ester groups (Dg) are preferably mono-, di- or tricarboxylic acid esters with long chain alkanols or polyols, especially those with a minimum viscosity of 2 mm2 / s at 100 ° C, such as they are described mainly in the publication DE-A 3838918. As mono-, di or tricarboxylic acids, aliphatic or aromatic acids can be used, as alcohols or ester polyols are suitable above all for long-chain representatives, for example, with 6 to 24 atoms of C. Typical representatives of the esters are adipates, terephthalates, isophthalates, terephthalates and trimellitates of iso-octanol, iso-nonanol, iso-decanol and iso-tridecanol. Products of this type also fulfill the properties of carrier oil.

The additives containing groups derived from succinic acid anhydride with hydroxyl and / or amino and / or amide and / or imide, in particular, (Dh) are preferably corresponding derivatives of succinic acid anhydride substituted with alkyl or alkenyl and especially the derivatives corresponding to the polyisobutenyl-succinic acid anhydride which can be obtained by conventional polyisobutene reaction or highly reactive with Mn = preferably 300 to 5000, particularly preferably 300 to 3000, much more preferably 500 to 2500, still much more preferred 700 to 2500 and mainly 800 to 1500, with maleic acid antidepressant by a thermal route in an ene reaction or by chlorinated polyisobutene. Groups with hydroxyl and / or amino and / or amide and / or imide groups are, for example, carboxylic acid groups, acid amides of monoamines, acid amides of di- or polyamines which, in addition to the amide function, also have groups of free amino acids, succinic acid derivatives with an acid function and an amide function, carboximides with monoamines, carboxamides with di- or polyamines which, in addition to the imide function, also have free amino groups, or diimides which are formed by the reaction of di- or polyamines with two succinic acid derivatives. Fuel additives of this type are mainly described in US-A 4 849 572. Preferably they are the reaction products of succidic acids substituted with alkyl or alkenyl, or derivatives thereof, with amines and, particularly preferably, are the reaction products of succinic acids substituted with polyisobutenyl or derivatives thereof with amines. In this case, the reaction products with aliphatic polyamines (polyalkyleneimines), such as ethylene diamine, diethylenetriamine, triethylene tetramine, tetraethylenepentamine, pentaethylenehexamine and hexaethyleneheptamine, which have an imide structure, are of particular interest.

Additives containing groups generated by the Mannich reaction of phenols substituted with aldehydes and mono- or polyamines (Di) are preferably reaction products of phenols substituted with polyisobutene with formaldehyde and mono- or polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine or dimethylaminopropylamine. The polyisobutenyl-substituted phenols can come from conventional polyisobutene or highly reactive with Mn = 300 to 5000. This type of "Mannich-polyisobutene bases" is described mainly in EP-A 831 141.

To the fuel one or more of the aforementioned detergent additives of the groups (Da) to (Di) can be added in an amount such that the dose of these detergent additives is preferably 25 to 2500 ppm by weight, mainly 75 to 1500 ppm by weight , first of all 150 to 1000 ppm by weight.

The carrier oils used together as co-additives can be mineral or synthetic in nature. Suitable mineral carrier oils are fractions obtained in the treatment of petroleum, such as a heavy lubricant base (Brightstock) or base oils having viscosities such as, for example, class SN 500 to 2000, but also aromatic hydrocarbons, parafamous hydrocarbons and alkoxyalkanols. Equally useful is a fraction obtained during the refining of mineral oil, known as "hydrocrack oil" (hydro fractionation oil) (cutting of vacuum distillate with a range of boiling points of approximately 360 to 500 ° C, which can be obtained from natural mineral oil that has been catalytically hydrogenated at high pressure and isomerized and also deparaffinized). Mixtures of mineral carrier oils mentioned above are also suitable.

Examples of suitable synthetic carrier oils are polyolefins (polyalphaolefins or poly-enol olefins), (poly) esters, (poly) alkoxylates, polyethers, aliphatic polyetheramines, polyethers initiated with alkylphenol, polyetheramines initiated with alkylphenol and esters of carboxylic acid and long chain alkanols.

Examples of suitable polyolefins are olefin polymers with Mn = 400 to 1800, primarily based on polybutene or polyisobutene (hydrogenated or non-hydrogenated).

Examples of suitable polyethers or polyetheramines are preferably compounds containing polyoxyalkylene groups of C2 to C4, which are obtainable by reaction of C2 to C60 alkanols, alkanediols C ⁶ to C30, mono- or di- (C2 to C30) - amines, alkyl (from C1 to C30) -cyclohexanols or alkyl (from C1 to C30) -phenols with 1 to 30 moles of ethylene oxide and / or of propylene oxide and / or of butylene oxide by hydroxyl group or amino group and, in the case of the polyetheramines, by subsequent reductive amination with ammonia, monoamines or polyamines. Products of this type are mainly described in EP-A 310875, EP-A 356725, EP-A 700985 and US-A 4,877,416. For example, as polyetheramines amines polyalkylene oxide C2 can be used to C ⁶ or functional derivatives thereof. Typical examples of these are tridecanol or isotridecanol butoxylates, isononylphenol butoxylates, as well as butoxylates and polyisobutenol propoxylates, as well as the corresponding reaction products with ammonia.

Examples of carboxylic acid esters with long-chain alkanols are mainly mono-, di- or tricarboxylic acid esters with long-chain alkanols or polyols, such as are described mainly in DE-A 38 38 918. As mono-, di- or tri-carboxylic acids aliphatic or aromatic acids may be used; Examples of suitable alcohols or ester polyols are long chain representatives having, for example, 6 to 24 carbon atoms. Typical singers of esters are adipates, phthalates, isophthalates, terephthalates and trimellitates of isooctanol, isononanol, isodecanol and iso-tridecanol, for example, di- (n- or isotridecyl) phthalate.

Other suitable carrier oil systems are described, for example, in DE-A 3826608, DE-A 4142241, DE-A 4309074, EP-A 452328 and EP-A 548617.

Examples of particularly suitable synthetic carrier oils are alcohol-initiated polyethers having about 5 to 35, preferably about 5 to 30, particularly preferably 10 to 30, and most preferably 15 to 30 units of alkylene oxide of C ³ to C ⁶ , per example, units of propylene oxide, n-butylene oxide and isobutylene oxide units or mixtures thereof, per alcohol molecule. Nonlimiting examples of suitable initiators are alcohols long - chain alkanols or phenols substituted by long - chain alkyl, in which case the residue mainly long chain alkyl represents an alkyl of C ⁶ to C18 straight or branched chain. As particular examples, tridecanol and nonylphenol may be mentioned. Polyethers initiated with alcohol, particularly preferred are reaction products (products of poly esterification) of alcohols of C ⁶ to C18 aliphatic monotndricos with alkylene oxides C3 to ^C6. Examples of monomeric 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 also in the form of technical mixtures. A particularly preferred alcohol is tridecanol. Examples of alkylene oxide of 3 to C ⁶ are propylene oxide, and 1,2-propylene oxide, butylene oxide, and 1,2-butylene oxide, 2,3-butylene oxide, isobutylene oxide or tetrahydrofuran , pentylene oxide and hexylene oxide. Among these, particularly preferred are alkylene oxides of C3 to C4, ie propylene oxide such as 1,2-propylene oxide and butylene oxide such as 1,2-butylene oxide, 2,3-butylene oxide and isobutylene. Especially butylene oxide is used.

Other suitable synthetic carrier oils are alkoxylated alkylphenols, as described in DE-A 10102913.

Particular carrier oils are synthetic carrier oils, in which case the alcohol-initiated polyethers that have been previously described are particularly preferred.

The carrier oil or the mixture of different carrier oils are added to the fuel in an amount preferably of 1 to 1000 ppm by weight, particularly preferably of 10 to 500 ppm by weight and mainly of 20 to 100 ppm by weight.

Fno flow improvers that are suitable as co-additives are, theoretically, all organic compounds that are capable of improving the flow behavior of diesel fuels and diesel fuels of medium distillation in the fno. Conveniently, these have to have a sufficient solubility in oil. Mainly the flow improvers are taken into consideration in this case in middle distillates of fossil origin, that is to say in case of usual diesel fuel fuels ("middle distillate flow improvers", "MDFI"). However, organic compounds can also be used which, when used in conventional diesel fuels, present in part or predominantly the properties of a wax anti-settling additive ("WASA"). The imidazolium salts (I) used according to the invention present in medium distillation fuels, mainly in diesel fuels, themselves properties such as WASA, which, of course, is also the object of the present invention. The co-additives used as flow enhancers can also act partially or preponderantly as nucleating agents. But mixtures of organic compounds effective as MDFI and / or effective as WASA and / or effective as nucleating agents can also be used.

The flow improver in fno is normally selected from:

(K1) copolymers of an olefin of C ² to C ⁴⁰ with at least one other ethylenically unsaturated monomer;

(K2) comb pointers;

(K3) polyoxyalkylenes;

(K4) polar nitrogen compounds;

(K5) sulfocarboxylic acids or sulphonic acids or their derivatives; Y

(K6) poly (meth) acrylic esters.

It is possible to use mixtures of different representatives of one of the respective classes (K1) to (K6), as well as mixtures of representatives of the different classes (K1) to (K6).

Suitable monomers of C ² to C ⁴⁰ olefin for copolymers of class (K1) are, for example, those having 2 to 20, mainly 2 to 10 carbon atoms, and having 1 to 3, preferably 1 or 2 , mainly a carbon-carbon double bond. In the aforementioned case, the carbon-carbon double bond can be arranged both terminally (α-olefins), as well as internally. However, α-olefins are preferred, particularly preferably α-olefins with 2 to 6 carbon atoms, for example, propene, 1-butene, 1-pentene, 1-hexene and primarily ethylene.

The copolymers of class (K1) the at least one other ethylenically unsaturated monomer is preferably selected from alkemic esters of carboxylic acid, (meth) acrylic esters and other olefins.

When the other olefins are also copolymerized, they are preferably of higher molecular weight than the aforementioned C ² to C ⁴⁰ olefin base monomers. When ethylene or propene is used, for example, as the olefin-based monomer, like other olefins, C ¹⁰ to C ⁴⁰ α-olefins are suitable. In most cases the other olefins are copolymerized only if monomers with carboxylic acid ester functions are also used.

Suitable (meth) acrylic acid esters are, for example, esters of (meth) acrylic acid with C ¹ to C ²⁰ alkanols, mainly C ¹ - to C ¹⁰ alkanols, primarily with methanol, ethanol, propanol, isopropanol, n-butanol, sec.-butanol, isobutanol, tert.-butanol, pentanol, hexanol, heptanol, octanol, 2-ethylhexanol, nonanol and decanol, as well as structural isomers thereof.

Esters alquemlicos of carboxylic acid are, for example, esters of alkenyl C ² to C ^14, for example, vinyl esters and propenyl, of carboxylic acids with 2 to 21 carbon atoms, the hydrocarbyl residue may be linear or branched . Among these, vinyl esters are preferred. Among the carboxylic acids with branched hydrocarbyl residue are preferred those whose branching is in the position a with respect to the carboxyl group, in which case the carbon atom a is, particularly preferably, tertiary; that is, the carboxylic acid which is a so-called neocarboxylic acid. Preferably, however, the hydrocarbon residue of the carboxylic acid is linear.

Examples of alkemic esters of carboxylic acid are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl-2-ethyl hexanoate, vinylic ester of neopentanoic acid, vinylic ester of hexanoic acid, vimic acid ester of neononanoic acid and the corresponding propellant esters , in which case the viml esters are preferred. A particularly preferred alkemic ester of carboxylic acid is vinyl acetate; Typical copolymers resulting therefrom, belonging to the group (K1), are the ethylene-vinyl acetate copolymers ("EVA") that are used most frequently. Ethylene-vinyl acetate copolymers which can be used in a particularly advantageous manner and their preparation are described in WO 99/29748.

Also suitable as copolymers of class (K1) are those containing two or more alkemic esters of carboxylic acid, different from one another, in copolymerized form, in which case they differ in the alkenyl function and / or in the acid group. carboxylic Also suitable are copolymers which contain, in copolymerized form, in addition to the alkemic esters of carboxylic acid, at least one olefin and / or at least one (meth) acrylic acid ester.

Also suitable as copolymers of class (K1) are 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 an ester alkemic acid from C ² to C ¹⁴ of a saturated monocarboxylic acid having 2 to 21 carbon atoms. Terpolymers of this type are described in WO 2005/054314. A typical terpolymer of this type is composed of ethylene, acrylic acid 2-ethylhexyl ester and vinyl acetate.

At least one or the other ethylenically unsaturated monomers are copolymerized in the copolymers of class (K1) in an amount preferably of 1 to 50% by weight, in particular 10 to 45% by weight and, above all, 20 to 40% by weight , with respect to the total copolymer. The main percentage fraction of the units of The monomer in the co-polymers of the class (K1) therefore comes, as a rule, from the base olefins of C ² to C ⁴⁰ .

The copolymers of class (K1) preferably have an average molecular weight of Mn number from 1000 to ^{2 0} . ^{0 0 0} , particularly preferably from ^{1 00 0} to ^{1 0 .0 0 0} and mainly from ^{1 00 0} to 8000.

Typical comb polymers of the component (K2) can be obtained, for example, by the copolymerization of the antidepressant of maleic acid or fumaric acid with another ethylenically unsaturated monomer, for example, with an aolefin or an unsaturated ester such as vinyl acetate, and subsequent esterification of the antidrug or acid function with an alcohol having at least 10 carbon atoms. Other suitable comb polymers are copolymers of α-olefins and esterified comonomers, for example, esterified copolymers of styrene and maleic acid antidepressant or esterified copolymers of styrene and fumaric acid. Suitable comb polymers can also be polyamine or polymaleate. In addition, vinyl ether homo- and copolymers are suitable comb polymers. Suitable comb polymers as a component of class (K2) are also those which are described, for example, in WO 2004/035715 and in "Comb-Like Polymers. Structure and properties", NA Plate and VP Shibaev, J. Poly. Sci. Macromolecular Revs. ⁸ , pages 117 to 253 (1974). "Mixtures of comb polymers are also suitable.

Polyoxyalkylenes suitable as a component of class (K3) are, for example, polyoxyalkylene esters, polyoxyalkylene ethers, polyoxyalkylene mixed esters-esters and mixtures thereof. These polyoxyalkylene compounds preferably contain at least one, preferably at least two linear alkyl groups having respectively 10 to 30 carbon atoms and a polyoxyalkylene group having an average number molecular weight of up to 5000. Polyoxyalkylene compounds of this type they are described, for example, in EP-A 061 895 and in the publication US 4491 455. Particular polyoxyalkylene compounds are based on polyethylene glycols and polypropylene glycols having a number average molecular weight of 100 to 5000. In addition, monosteres are suitable and polyoxyalkylene diesters of fatty acids having 10 to 30 carbon atoms, such as stearic acid or behenic acid.

Polar nitrogen compounds suitable as a component of class (K4) can be both ionic and non-ionic in nature and preferably have at least one, especially at least two substituents in the form of a tertiary nitrogen atom of the general formula> NR7 , in which R7 represents a hydrocarbyl residue from Ca to C ⁴⁰ . Nitrogen substituents may also be present in quaternized form, ie in cationic form. Examples of such nitrogen compounds are ammonium salts and / or amides which can be obtained by reaction of at least one amine substituted with at least one hydrocarbyl residue with a carboxylic acid having 14 carboxyl groups, or with a suitable derivative thereof. The amines preferably contain at least one linear alkyl residue of Ca to C ⁴⁰ . Primary amines suitable for the preparation of the mentioned polar nitrogen compounds are, for example, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologs; Suitable secondary amines for this are, for example, dioctadecylamine and methylbehenylamine. Mixtures of amines, especially mixtures of amines accessible on an industrial scale, such as hydrogenated fatty amines or tallowamines as described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, 6th edition, in the chapter "Amines, aliphatic" are also suitable for this purpose. " 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 acids. Succimics substituted with long chain hydrocarbyl residues.

The component of class (A4) is mainly an oil-soluble reaction product of poly (C ² to C ²⁰ carboxylic acids), which have at least one tertiary amino group, with primary or secondary amines. Poly (carboxylic acids of C ² to C ²⁰ ) having at least one tertiary amino group, which are the basis for this reaction product, preferably contain at least 3 carboxyl groups, in particular 3 to 12, in particular 3 to 5 carboxyl groups . The carboxylic acid units in the carboxylic polyacids preferably have 2 to 10 carbon atoms, mainly acetic acid units. The carboxylic acid units are suitably linked with the carboxylic polyacids, generally by means of one or more carbon atoms and / or nitrogen. They are preferably linked to tertiary nitrogen atoms that are bound by hydrocarbyl chains in case of several nitrogen atoms.

The component of class (K4) is preferably an oil-soluble reaction product based on a poly (C ² to C ²⁰ carboxylic acid) having at least one tertiary amino group of the general formulas IIa or IIb

HOOC_ "XO OH

? ?

hooc q. n ^ n ^ cooh

BAB {lla)

in which the variable A represents a straight or branched chain C ² to C ⁶ alkylene group or the group of the formula III

and the variable B designates an alkylene group of C1 to C19. The compounds of the general formula IIa and IIb have mainly the properties of a WASA.

In addition, the reaction product, soluble in oil, of the component (K4), especially that of the general formula IIa or IIb, is an amide, an amide-ammonium salt or an ammonium salt in which none, one or more carboxylic acid groups have been converted to amide groups.

Alkylene groups of C2 to Ca, straight chain or branched, of 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 mainly 1,2-ethylene. The variable A preferably comprises 2 to 4, mainly 2 or 3 carbon atoms.

The C1 to C19 alkylene groups of the variable B are, for example, 1,2-ethylene, 1,3-propylene, 1,4-butylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, octadecamethylene, nonadecamethylene and mainly methylene. The variable B preferably comprises 1 to 10, mainly 1 to 4 carbon atoms.

The primary and secondary amines as reactants for the carboxylic polyacids for the formation of the component (K4) are usually monoamines, mainly aliphatic monoamines. These primary and secondary amines can be selected from a large number of amines having hydrocarbyl residues, optionally linked between

Generally, these amines which serve as the basis for the oil-soluble reaction products of the component (K4) are secondary amines have the general formula HN (R8) 2, in which the two variables R8 independently of each other mean residues of C10 to C30 alkyl, straight or branched chain, mainly C14 to C24 alkyl residues. These longer chain alkyl residues are preferably straight chain or branched only slightly. As a rule, the secondary amines mentioned are derived, with respect to their longer chain alkyl residues, from fatty acids of natural origin or their derivatives. Preferably, the residues R8 are the same.

The secondary amines mentioned can be linked by means of amide structures or in the form of the ammonium salts to the carboxylic poly acids; even only one part can also be presented as amide structures and another part as ammonium salts. Preferably, only a few acid groups or none are present. The reaction products, soluble in oil, of component (K4) are preferably completely in the form of amide structures.

Typical examples of components (K4) of this type are reaction products of nitrilotriacetic acid, of ethylenediaminetetraacetic acid or of propylene-1,2-diamintetraacetic acid, respectively, with 0.5 to 1.5 moles per carboxyl group, in particular 0.8. to 1.2 moles per carboxyl group, of dioleilamine, dipalmitinamine, dicocoamine, distearylamine, dibehenylamine or mainly diseboamine. A particularly preferred component (K4) is the reaction product of 1 mole of ethylenediaminetetraacetic acid and 4 moles of hydrogenated diseboamine.

As other typical examples for the component (K4) there can be mentioned the N, N-dialkylammonium salts of 2-N ', N'-dialkylamidobenzoates, for example, the reaction product of 1 mole of phthalic acid anhydride and 2 moles of diseboamine, in which case the latter may be hydrogenated or non-hydrogenated, and the reaction product of 1 mol of an alkenyl pyrrolbislactone with 2 mol of a dialkylamine, for example, diseboamine and / or tallowamine, in which case the latter two may be hydrogenated or not hydrogenated.

Other types of structure typical for the component of class (K4) are cyclic compounds with tertiary or condensed amino groups of primary or secondary long chain amines with polymers containing carboxylic acid, as described in publication WO 93/18115.

Sulfocarboxylic acids, sulphonic acids or their derivatives, suitable as fining flux enhancers of the component of class (K5) are, for example, the oil-soluble carboxamides and the carboxylic esters of the ortho-sulfobenzoic acid in which the sulfonic acid function is present as a sulfonate with alkyl-substituted ammonium cations, as described in EP-A 261 957.

Poly (meth) acrylates suitable as fining flux improvers of the component of class (K6) are both homo-, as well as copolymers of acrylates and methacrylates. Preferred are copolymers of at least two (meth) acrylates different from each other, which differ from the esterified alcohol. The copolymer optionally contains, in addition, another olefinically unsaturated monomer in copolymerized form. The number average molecular weight of the polymer is preferably 50,000 to 500,000. A particularly preferred polymer is a copolymer of methacrylic acid and methacrylate of saturated C ¹⁴ -C ¹⁵ alcohols, where the acid groups are neutralized with hydrogenated tallowamine. Suitable poly (meth) acrylates are described, for example, in publication WO 00/44857.

To the medium distillate fuel or to the diesel fuel is added the flow improver or the mixture of different flow improvers in a total amount preferably from 10 to 5000 ppm by weight, particularly preferably from 20 to 2000 ppm by weight. weight, much more preferably from 50 to 1000 ppm by weight and mainly from 100 to 700 ppm by weight, for example, from 200 to 500 ppm by weight.

Lubricating capacity improvers suitable as co-additives (Lubricity Improver bzw.Friction Modifier) are usually based on fatty acids or fatty acid esters. Typical examples are tallow fatty acid as described, for example, in WO 98/004656, and glyceryl monooleate. As such lubrication capability enhancers are also suitable reaction products from natural or synthetic oils, for example, triglycerides and alkanolamines which are described in US 6743266 B2.

Corrosion inhibitors suitable as co-additives are, for example, esters of succid acid, primarily with polyols, fatty acid derivatives, for example, oleates, oligomerized fatty acids, substituted ethanolamines, N-acylated sarcosine, imidazoline derivatives, example, those having an alkyl group in position 2 and an organic functional residue in the trivalent nitrogen atom (a typical imidazoline derivative is the reaction product of excess oleic acid with diethylenetriamine), and products sold under the name commercial RC 4801 (Rhein Chemie Mannheim, Germany) or Hi-TEC 536 (Ethyl Corporation). The aforementioned imidazoline derivatives are particularly effective as corrosion inhibitors when combined in this application with one or more carboxamides having one or more carboxamide functions in the molecule and with longer chain residues in the amide nitrogens, for example , with the reaction product of the maleic anhydride with a long chain amine in equimolar proportion.

Suitable demulsifiers as co-additives are, for example, the alkali metal or alkaline earth metal salts of phenol- and naphthalene sulfonates substituted with alkyl and the alkali metal or alkaline earth metal salts of fatty acids, furthermore neutral compounds such as alcohol alkoxylates, for example , alcohol ethoxylates, phenol alkoxylates, for example, tert-butylphenol ethoxylate or tert.-pentylphenol ethoxylate, fatty acids, alkylphenols, condensation products of ethylene oxide (EO) and propylene oxide (PO), for example , even in the form of EO / PO block copolymers, polyethylene imines or also polysiloxanes.

Suitable demisters as co-additives are, for example, phenol-formaldehyde alkoxylates, such as, for example, the products available under the tradenames NALCO 7D07 (Nalco) and TOLAD 2683 (Petrolite).

Antifoams suitable as co-additives are, for example, polysiloxanes modified with polyether as, for example, the products available under the tradenames TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Corning) and RHODOSIL (Rhone Poulenc).

Cetane number improvers suitable as co-additives are, for example, aliphatic nitrates such as 2-ethylhexyl nitrates and cyclohexyl nitrate, as well as peroxides such as di-tert-butyl peroxide.

Antioxidants suitable as co-additives are, for example, substituted phenols, ie sterically hindered such as 2,6-diter.-butylphenol, 2,6-di-tert.-butyl-3-methylphenol or the products sold under the trade name IRGANOX® (BASF SE), for example, 2,6-di-tert.-butyl-4-alkoxycarbonylethylphenol (IRGANOX L135), and phenylenediamines such as N, N'-dissect.-butyl-p-phenylenediamine.

Metal deactivators suitable as co-additives are, for example, derivatives of salidic acid such as N, N'-disaliciliden-1,2-propanediamine or the products sold under the trade name IRGAMET® (BASF SE) based on triazoles and tolutriazoles N-substituted.

Suitable solvents for use together are, for example, apolar organic solvents such as aromatic and aliphatic hydrocarbons, for example, toluene, xylenes, "white spirit" and products sold under the tradename SHELLSOL (Royal Dutch / Shell Group) and EXXSOL ( ExxonMobil), as well as polar organic solvents, for example, alcohols such as 2-ethylhexanol, decanol and isotridecanol, as well as esters of carboxylic acid with longer chain alkyl groups, such as medical esters of fatty acid of C ¹² to C ²⁰ . Solvents of this type generally pass to the fuel or fuel, mainly diesel fuel, with the imidazolium salts (I) and the aforementioned co-additives which, for better handling, must be dissolved or diluted.

The imidazolium salts (I) to be used according to the invention are excellently suitable as an additive to a fuel or a fuel and can be used theoretically in any fuel or fuel. These cause a whole series of advantageous effects during the operation of combustion engines with fuel are fuels. The imidazolium salts (1) to be used according to the invention are preferably used in medium distillation fuels, mainly diesel fuels.

Therefore, it is also an object of the present invention a combustible fuel composition, mainly a medium distillation fuel composition, with an effective content of imidazolium salts (I) to be used according to the invention as an additive to achieve advantageous effects during the operation of combustion engines, for example, diesel engines, mainly direct injection diesel engines, especially diesel engines with common rail injection systems, in addition to the main amount of a fuel or usual base fuel. This effective content (dose) 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, each case with respect to the total amount of fuel or fuel.

Medium distillation fuels, such as diesel fuels or heating oils, are preferably refined from petroleum which usually have a range of boiling points of 100 to 400 ° C. These are generally distilled with a point at 95% up to 360 ° C or even higher. But these can also be called "Ultra Low Sulfur Diesel" (ultra low sulfur diesel) or "City Diesel", characterized by a point at 95%, for example, maximum 345 ° C and a maximum sulfur content of 0.005. % by weight or by a point at 95%, for example, 285 ° C and a sulfur content of maximum 0.001% by weight. In addition to medium distillation fuels, minerals, or diesel fuels, which can be obtained by distillation, those that can be obtained by gasifying gas or liquefying gas ["gas to liquid" fuels (g Tl)] or liquefaction are also suitable. of biomass [fuels of "biomass to liquid" (BTL)]. Also suitable are mixtures of the medium distillation fuels, or diesel fuels, mentioned above with renewable fuels such as biodiesel or bioethanol.

The qualities of heating oils and diesel fuels are laid down in detail, for example, in DIN 51603 and EN 590 (see also Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, volume A12, page 617 et seq.).

The imidazolium salts (I) to be used according to the invention can be used, in addition to their use in the aforementioned medium distillation fuels of fossil, vegetable or animal origin which essentially represent mixtures of fuels, also in mixtures of said middle distillates with oils biofuels (biodiesel). Mixtures of this type are also included in the context of the present invention under the term "medium distillation fuel". These are customary in commerce and generally contain the biofuel oils in lower amounts, usually in amounts of 1 to 30% by weight, mainly from 3 to 10% by weight, with respect to the total amount of middle distillate of fossil, vegetable or animal origin. and biofuel oils.

The biofuel oils are generally based on fatty acid esters, generally alkyl esters of fatty acids that are derived from vegetable and / or vegetable oils and / or fats. Alkyl esters are usually understood as lower alkyl esters, especially C1 to C4 alkyl esters, which can be obtained by transesterification of the glycerides which exist in vegetable and / or animal oils and / or fats, mainly triglycerides, by means of alcohols. lower, for example, ethanol or especially methanol ("FAME"). Typical lower alkyl esters based on vegetable oils and / or fats and / or animals that are used as biofuel oil or components thereof are, for example, methyl sunflower ester, palm oil methyl ester ("PME"), methyl ester of soybean oil ("SME") and mainly methane oil of rapeseed oil ("RME"). The middle distillate fuels or diesel fuels are very preferably those having a low sulfur content, ie having a sulfur content of less than 0.05% by weight, preferably less than 0.02% by weight, very mainly less than 0.005% by weight and especially less than 0.001% by weight of sulfur.

Useful gasoline fuels include all commercial gasoline fuel compositions. A typical representative mentioned here is the Eurosuper base fuel according to EN 228, which is common in the market. In addition, the gasoline compositions of the specification according to publication WO 00/47698 are also possible fields of application for the present invention.

Also an object of the present invention is an additive concentrate which, in combination with at least one other fuel and fuel additive, mainly with at least one other diesel fuel additive, contains at least one imidazolium salt (I) to be used according to the invention. . An additive concentrate of this type usually contains 10 to 60% by weight of at least one solvent or diluent which can be a solvent mentioned above or the fuel or fuel itself. Preferably, the additive concentrate according to the invention contains, in addition to at least one imidazolium salt (I) to be used according to the invention, in addition to at least one detergent additive of the aforementioned groups (Da) to (Di), in particular at least a detergent additive of the type (Dh), as well as, as a rule, additionally also at least one lubrication capacity improver and / or a corrosion inhibitor and / or a demulsifier and / or a disinfectant and / or an antifoam and / or a number improver cetane and / or an antioxidant and / or a metal deactivator in the respectively usual quantity ratios for these.

The imidazolium salts (I) to be used according to the invention are suitable mainly as an additive in fuel or fuel compositions, mainly in diesel fuels, to overcome the problems initially exposed in direct injection diesel engines, especially in those with injection systems. of common rail (Common-Rail). Since some of the imidazolium salts described represent novel substances, the imidazolium salts of the general formula (I) are also the subject of the present invention.

in which

one of the variables R1 or R3 or both variables R1 and R3 independently of each other represent a polyisobutyl residue with an average molecular weight of 900 to 3000,

the other variables R1 or R3 mean an alkyl residue with 1 to 13 carbon atoms or an alkenyl residue with 2 to 13 carbon atoms,

Y

the variables R2, R4 and R5 independently of each other mean hydrogen, an alkyl residue with 1 to 20 carbon atoms or an alkenyl residue with 2 to 20 carbon atoms,

X designates an anion and

n represents the number 1, 2 or 3,

in which case the aforementioned variables R1 to R5, X and n have the relevant particular meanings in preferred ranges mentioned above.

The new imidazolium salts of the general formula (la) are suitable, besides their possibility of use as additives for fuels and fuels, mainly as detergent additives for diesel fuels, also for the improvement of the consumption properties of mineral industrial liquids and non-aqueous synthetics. For non-aqueous industrial fluids which may contain fractions of water in a particular case, but whose essential effect is not based on non-aqueous components, the lubricating materials, lubricating agents and lubricating oils in the broadest sense, especially oils, should be understood here engine, transmission oils, axle oils, hydraulic fluids, hydraulic oils, compressor fluids, compressor oils, circulating oils, turbine oils, transformer oils, gas engine oils, wind turbine oils, oils for slip, lubricating greases, cooling lubricant materials, anti-wear oils for chains and conveyor systems, liquids for metal treatment, lubricants compatible with foods for the industrial treatment of food, as well as cooking oils for stoves, stabilizers and steam peelers . The properties of use that are improved by means of the imidazolium salts (la) are mainly the lubricating effect, the friction wear, the useful life, the anticorrosive protection, the antimicrobial protection, the demulsifying capacity with respect to an easier separation of water and impurities, as well as the filtering capacity.

The invention will now be described by means of the following exemplary embodiments:

Examples

Preparation of 1,3-di (2-ethylhexyl) imidazolium acetate

300.3 g (3.0 mol) of a 30% by weight aqueous solution of formaldehyde, 435.3 g (3.0 mol) of glyoxal and 180.2 g (3.0 mol) of anhydrous acetic acid are added. They were initially charged into a flask and mixed slowly, with stirring at room temperature, with 791.3 g (6.0 moles) of 98% by weight 2-ethylhexylamine. In this, the temperature of the reaction mixture rose rapidly to 38 ° C and was kept there by means of a cooling with ice bath until the end of the addition of the sheet. Then, it continued to stir for 5 hours at 80 ° C. After removing the upper aqueous phase, 1038.4 g of 1,3- (2-ethylhexyl) imidazolium acetate were obtained.

Preparation of 1,3-di (polyisobutyl) imidazolium acetate

In a manner analogous to the above-described preparation of 1,3-di (2-ethylhexyl) imidazolium acetate, from 3.0 moles of an aqueous solution of formaldehyde at 30% by weight, 3.0 moles of glyoxal, , 0 moles of anhydrous acetic acid and 6.0 moles of polyisobutylamine C ⁴ Hg- (C ⁴ H ⁸ ) x-CH ² NH ² with x = 17-18 (commercial product Kerocom® PIBA of BASF SE) acetate was obtained of 1,3-di (polyisobutyl) imidazolium.

Application examples

To investigate the influence of the additives on the performance of direct injection diesel engines, the DW 10 engine test was used as a test procedure in which the power loss is determined by deposits in the sector in the Common Rail diesel engine in accordance with the official test procedure CEC F-098-08.

The loss of power 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 the CEC F-098-08 test procedures. A commercial diesel fuel of the company Haltermann (DF-79-07 / 5) was used as fuel. To artificially induce the formation of deposits in the injectors, 1 ppm of zinc was added in the form of a solution of zinc didodecanoate. The results illustrate the relative power loss at 4000 rpm, measured during a sustained operation for 12 hours. The value "t0" indicates the power ("power") in kW at the beginning of the test and the value "t12" indicates the power in kW at the end of the test.

As additives to be used according to the invention, the following imidazolium salts were used:

(1.1) 1-ethyl-3-methylimidazolium acetate

(1.2) 1-butyl-3-methylimidazolium acetate

(1.3) 1-octyl-3-methylimidazolium methylcarbonate

(1.4) 1,3-di (2-ethylhexyl) imidazolium acetate

Compounds (I.1) and (I.2) are commercial products; the compound (I.3) was prepared from N-octylimidazole by quaternization with dimethyl carbonate in the form of a 30% by weight solution in methanol according to a usual synthesis procedure; the compound (I.4) was prepared according to the synthesis instruction indicated above.

In the tests carried out, the additives (I.1) and (I.2) were used as pure substances, the additives (I.3) and (I.4) were used in the form of solutions. The indicated doses refer to the active ingredient. The results of the power or power loss determinations of the DW10 motor test operations are compiled in the following table:

___

With the additives (I.2) and (I.4) an additional fouling and cleaning operation was carried out according to the DW10 test. For this purpose, the direct injection diesel engine was first operated with a common rail system that was used with the same commercially available diesel fuel (with a content of 1 ppm of zinc in the form of zinc didodecanoate solution) for 12 hours. hours without detergent additive, in which case the value t for the power in the experiment with (I.2) first fell gradually from 96.2 kW to 89.8. After adding 30 ppm by weight of the additive (I.2) and continuing to operate for 5 hours, the t value for the power returned to increase to 95.7 kW, in which case the largest jump for t was made during the first two hours after adding (I.2) (after 1 hour t = 91.4 kW, after 2 hours t = 94.5 kW).

In the experiment with the additive (I.4), the power fell from 98.4 kW to 93.9 kW in the first 13 hours of operation without additive. After adding 50 ppm by weight of the additive (I.4) and continuing to operate for 12 hours, the t value for the power returned to increase to 96.3 kW, in which case the largest jump in power was made during the first two hours after adding (I.4) (after continuing to decrease the value after the change in fuel to 92.8kW, the power returned to increase after one hour at = 94.5 kW, after 2 hours at = 95.5 kW).

With the additive (I.4) a "keep clean" engine test was also used according to the CEC F-23-01 test procedure with the PSA XUD-9A engine. The additive was used with a 50 ppm dose in a commercial diesel fuel of the Haltermann company (DF-79-07 / 5). In comparison, the engine was operated in a separate test operation with the same diesel fuel without additive. The "Flow restriction" at 0.1 mm of "Needle elevation" in the fuel without additive amounted to 63% and with 50 ppm by weight of additive (I.4) to -32 %.

Claims (9)

1. Use of imidazolium salts of the general formula (I)

in which the variables R1 and R3 independently of each other represent an organic waste, the variables R2, R4 and R5 independently of each other means hydrogen or an organic residue, X denotes an anion, selected from the group consisting of alkyl carbonates, pseudohalides, carboxylates or the anion tricianometamide Y n represents the numbers 1, 2 or 3, wherein the organic residues are selected from the group consisting of alkyl, cycloalkyl, alkenyl, cycloalkenyl, aryl or heteroaryl residues, containing from 1 to 20 carbon atoms, as well as polyisobutyl residues with from 30 to 250 atoms of carbon, as a detergent additive for diesel fuels, as a Wachs-Anti-Settling additive (WASA) for medium distillate fuels, mainly diesel fuels, as lubrication capacity improvers for fuels and fuels or as a friction modifier for fuels of gas. 2. Use of imidazolium salts (I) according to claim 1 as an additive to reduce or avoid deposits in injection systems of direct injection diesel engines, to reduce the fuel consumption of direct injection diesel engines and / or to reduce the minimum loss of power (powerloss) in direct injection diesel engines. 3. Use of imidazolium salts (I) according to claim 1 as an additive to reduce or avoid deposits in injection systems in common rail injection system, to reduce the fuel consumption of diesel engines with fuel injection system. Common-Rail injection, and / or to minimize the power loss in diesel engines with common-rail injection system. 4. Use of imidazolium salts (I) according to claims 1 to 4, in which the variables R1 and R3, independently of each other, represent alkyl groups of C1 to C20, alkenyl groups of C2 to C20 and / or residues of polyisobutyl with a number average molecular weight of 900 to 3000 and the variables R2, R4 and R5 mean in each case hydrogen. 5. Additive concentrate containing, in combination with at least one other fuel or fuel additive, especially with at least one other diesel fuel additive, at least one imidazolium salt (I) according to claims 1 or 4. 6. Fuel composition or fuel containing from 10 to 5000 ppm by weight of at least one imidazolium salt (I) according to claims 1 or 4. 7. Imidazolium salts of the general formula (la)

wherein one of the variables R1 or R3 or both variables R1 and R3 independently of each other represent a polyisobutyl residue with a number average molecular weight of 900 to 3000 and the variables R2, R4 and R5 independently of each other mean hydrogen, a alkyl residue with 1 to 20 carbon atoms or an alkenyl residue with 2 to 20 carbon atoms, the other variables R1 or R3 means an alkyl residue with 1 to 13 carbon atoms or an alkenyl residue with 2 to 13 carbon atoms, X designates an anion and n represents the numbers 1, 2 or 3. 8. Use of imidazolium salts of the general formula (Ia) according to claim 7 to improve the lubricating effect, the frictional wear, the service life, the anticorrosion protection, the antimicrobial protection, the demulsifying capacity as for a further separation. easy water and impurities, as well as the filtration capacity of lubricating materials, lubricating agents and lubricating oils, metal treatment fluids, lubricants compatible with foods for the industrial treatment of food, as well as cooking oils for stoves, sterilizers and steam peelers. 9. Use according to claim 8, characterized in that the lubricating materials, lubricating agents and lubricating oils are selected from the group consisting of motor oils, transmission oils, axle oils, hydraulic fluids, hydraulic oils, compressor fluids, compressor oils, circulating oils, turbine oils, transformer oils, gas engine oils, wind turbine oils, slip oils, lubricating greases, lubricating materials for cooling and oils for antiwear protection for chains and conveyor systems.