AU2012277805A1 - Quaternized nitrogen compounds and use thereof as additives in fuels and lubricants - Google Patents

Abstract

The invention relates to novel quaternized nitrogen compounds, to the production thereof, and to the use thereof as fuel additives and lubricant additives, such as in particular detergent additives, additive packages that contain said compounds, and fuels and lubricants to which said additive packages have been added. The invention further relates to the use of said quaternized nitrogen compounds as a fuel addition for reducing or preventing deposits in the injection systems of direct-injection diesel engines, in particular in common-rail injection systems, for reducing the fuel consumption of direct-injection diesel engines, in particular diesel engines having common-rail injection systems, and for minimizing the power loss in direct-injection diesel engines, in particular in diesel engines having common-rail injection systems.

Description

I Quaternized nitrogen compounds and use thereof as additives In fuels and lubricants The present invention relates to novel quatemized nitrogen compounds, to the preparation thereof and to the use thereof as a fuel and lubricant additive, more 5 particularly as a detergent additive, to additive packages which comprise these compounds; and to fuels and lubricants thus additized. The present invention further relates to the use of these quaternized nitrogen compounds as a fuel additive for reducing or preventing deposits in the injection systems of direct-Injection diesel engines, especially in common-rai injection systems, for reducing the fuel consumption 10 of direct-injection diesel engines, especially of diesel engines with common-rail injection systems, and for minimizing power loss in direct-injection diesel engines, especialy in diesel engines with common-rail injection systems, State of the art 15 in direct-injection diesel engines, the fuel is injected and distributed ultrafinely (nebulized) by a multihole injection nozzle which reaches directly into the combustion chamber of the engine, instead of being introduced into a prechamber or swirl chamber as in the case of the conventional (chamber) diesel engine. The advantage of the 20 direct-injection diesel engines lies in their high performance for diesel engines and nevertheless low fuel consumption. Moreover, these engines achieve a very high torque even at low speeds. At present, essentially three methods are being used to inject the fuel directly into the 25 combustion charnber of the diesel engine: the conventional distributor injection pump, the pump-nozzle system (unit-injector system or unit-pump system) and the common rail system. In the common-rail system, the diesel fuel is conveyed by a pump with pressures up to 30 2000 bar into a high-pressure line, the common rail. Proceeding from the common rail, branch lines run to the different injectors which inject the fuel directly into the combustion chamber. The ful pressure is always applied to the common rail, which enables multiple injection or a specific injection form, In the other injection systems, in contrast, only smaller variation in the injection is possible. The injection in the common M/51 320-PCT 2 rail is divided essentially into three groups; (1,) pre-injection, by which essentially softer combustion is achieved, such that harsh combustion noises ("nailing") are reduced and the engine seems to run quietly; (2.) main injection, which is responsible especially for a good torque profile: and (3.) post-injection, which especially ensures a low NO- value. 5 in this post-injection, the fuel is generally not combusted, but instead evaporated by residual heat in the cylinder. The exhaust gas/fuel mixture formed is transported to the exhaust gas system, where the fuel, in the presence of suitable catalysts, acts as a reducing agent for the nitrogen oxides NO. 10 The variable, cyinder-individual injection in the common-ral injection system can positively influence the pollutant emission of the engine, for example the emission of nitrogen oxides (NO,), carbon monoxide (GO) and especially of particuiates (soot). This makes it possible, for example, that engines equipped with common-rali injection systems can meet the Euro 4 standard theoretically even without additional particulate 15 filters, In modern common-rail diesel engines, under particular conditions, for example when biodiese-containing fuels or fuels with metal impurities such as zinc compounds, copper compounds, lead compounds and other metal compounds are used, deposits 20 can form on the injector orifices, which adversely affect the injection performance of the fuel and hence impair the performance of the engine, ,e, especially reduce the power, but in some cases also worsen the combustion. The formation of deposits is enhanced further by further developments in the injector construction, especially by the change in the geometry of the nozzles (narrower, conical orifices with rounded outlet). For lasting 25 optimal functioning of engine and injectors, such deposits in the nozzle orifices must be prevented or reduced by suitable fuel additives, In the injection systems of modem diesel engines, deposits cause significant performance problems, It is common knowledge that such deposits in the spray 30 channels can lead to a decrease in the fuel flow and hence to power loss Deposits at the inector tip, in contrast, impair the optimal formation of fuel spray mist and, as a result, cause worsened combustion and associated higher emissions and increased fuel consumption. In contrast to these conventional "extemal' deposition phenomena, intemar deposits (referred to collectively as internal diesel injector deposits (IDID)) in M/51320-PCT 3 particular parts of the injectors, such as at the nozzle needIe, at the control piston, at the valve piston, at the valve seat, in the control unit and in the guides of these components, also increasingly cause performance problems, Conventional additives exhibit inadequate action against these DIDs. 5 US 4,248,719 describes quatemized ammonium salts which are prepared by reacting an alkenylsuccinimide with a monocarboxylic ester and find use as dispersants in lubricant oils for prevention of sludge formation, More particularly, for example, the reaction of polyisobutylsuccinic anhydride (PIBSA) with NN-dimethylaminopropylarine (DMAPA) and quaternization with methyli salicylate is described. However, use in fuels, 10 more particularly diesel fueis, is not proposed therein. The use of PIBSA with low bismaleation levels of < 20% is not described therein. US 4,171,959 describes quaternized arnmonium salts of hydrocarbyl-substituted succinimides, which are suitable as detergent additives for gasoline fuel compositions. 15 For quaternization, preference is given to using alkyl halides, Also mentioned are organic C-CQhydrocarby carboxylates and suifonates. Consequently, the quaternized ammonium salts provided according to the teaching therein have, as a counterion, either a halide or a Q-C-hydrocarbyl carboxylate or a CrCrhydrocarbyl suifonate group, The use of PIBSA with low bismaieation levels of < 20% is likewise not 20 described therein EP-A-2 033 945 discloses cold flow improvers which are prepared by quaternizing specific tertiary monoamines bearing at least one C 5 -0 40 -alkyi radical with a CCr4-alkyl ester of specific carboxylic acids, Examples of such carboxylic esters are dimethyl 25 oxalate, dimethyl maleate, dimethyl phthalate and dimethyl fumarate. Applications other than that of improving the CFPP value of middle distillates are not demonstrated in EP-A-2 033 945. WO 2006/135881 describes quaternized ammonium salts prepared by condensation of 30 a hydrocarbyl-substituted acylating agent and of an oxygen or nitrogen atom-containing compound with a tertiary amino group, and subsequent quatemization by means of hydrocarbyl epoxide in the presence of stoichiometric amounts of an acid, especialy acetic acid. Further quaternizing agents claimed in WO 2006/135881 are dialkyl M/51 320-PCT 4 sulfates, benzyi halides and hydrocarbyI-substituted carbonates, and dimethyl sulfate, benzyl chloride and dimethyl carbonate have been studied experimentally. The quaternizing agents used with preference in WO 2006/135881, however, have 5 serious disadvantages such as: toxicity or carcinogenicity (for example in the case of direthyl sulfate and alkylene oxides and benzyl halides), no residue-free combustion (for example in the case of dimethyl sulfate and alkyl haides), and inadequate reactivity which leads to incomplete quatemization or uneconomio reaction conditions (long reaction times, high reaction temperatures, excess of quaternizing agent; for 10 example in the case of dimethyl carbonate), It was therefore an object of the present invention to provide improved quaternized fuel additives, especially based on hydrocarbyl-substituted polycarboxylic acid compounds, which no longer have the disadvantages of the prior art mentioned. 15 Brief description of the invention: It has now been found that, surprisingly, the above object is achieved by providing specific quaternized nitrogen compounds and fuel and lubricant compositions additized 20 therewith. Surprisingly, the inventive additives thus prepared are superior in several ways to the prior art additives prepared in a conventional manner: they have low toxicity (caused by the specific selection of the quaternizing agent, bum ashlessly, exhibit a high content of 25 quaternized product, and allow an economic reaction regime in the preparation thereof, and surprisingly have improved handling properties, such as especially improved solublity, such as especially in diesel performance additive packages, At the same time, the inventive additives exhibit improved action with regard to prevention of deposits in diesel enqnes, as especially illustrated by the use examples appended. 30 M/51320-PCT 5 Detailed descripion of the invention: Al) Specific embodiments 5 The present invention relates especially to the following specific embodiments 1. A fuel or lubricant composition, especially fuel composition, comprising, in a majority of a customary fuel or lubricant, a proportion (especialy an effective amount) of at least one reaction product comprising a quaternized nitrogen compound (or a 10 fraction thereof which comprises a quatemized nitrogen compound and is obtained from the reaction product by purification), said reaction product being obtainable by a. reacting a high molecular weight hydrocarbylsubstituted polycarboxylic acid compound with a compound comprising at least one oxygen or nitrogen group reactive (especially capable of addition or condensation) with the polycarboxylic acid, 15 and comprising at least one quaternizable amino group, to obtain a quaternizable hydrocarbyl-substituted polycarboxylic acid compound (by addition or condensation), and b. subsequent reaction thereof with a quaternizing agent which converts the at least one hereafter quatemnizable, for example tertiary, amino group to a 20 quaternary ammonium group, said quatemizing agent being the alkyl ester of a cycloaromatic or cycloatiphatic mono- or polycarboxylic acid (especially of a mono- or dicarboxylic acid) or of an aliphatic polycarboxylic acid especiallyy dicarboxylic acid). 2. A fuel or lubricant composition., especially fuel composition, comprising, in a 25 majority of a customary fuel or lubricant, a proportion (especially an effective amount) of at least one reaction product comprising a quatemized nitrogen compound (or a fraction thereof which comprises a quatemnized nitrogen compound and is obtained from the reaction product by purification), said reaction product being obtainable by reacting a quaternizable high molecular weight hydrocarbyt-substituted polycarboxylic 30 acid compound comprising at least one quatemizable amino group with a quatemizing agent which converts the at least one hereafter quaternizable, for example tertiary, amino group to a quaternary ammonium group, M/51320-POT 6 said quaternizing agent being the akyi ester of a cycloaromatic or cycloaliphatic mono or polycarboxylic acid especiallyy of a mono- or dicarboxylic acid) or of an alphatic polycarboxylic acid (especially dicarboxylic acid). 5 3. The fuel composition according to either of the preceding claims, wherein about 1.1 to about 2.0 or about 1.25 to about 2.0 equivalents, for example 13, 1.4, 1.5, 1.6, 1,7, 1.8 or 1.9 equivalents, of quaternizing agent are used per equivalent of quaterizable tertiary nitrogen atom. By increasing the proportion of quaternizing agent within the range claimed, distinct improvements in product yields can be achieved, 10 4. The fuel composition according to any of the preceding claims, wherein the hydrocarbyi-substituted polycarboxylic acid compound is a polyisobutenylsuccinic acid or an anhydride thereof, said acid having a bismaleation level of equal to or less than about 20% or equal to or less than about 15%, for example 15, 14, 13, 12, 11, 10, 9, 8, 15 7, 6, 5, 4, 3, 2, 1 or 0,1%, Lower levels of bismaleation can contribute to a distinct improvement in the solubility of the additive and/or compatibility of the constituents in the formulation of additive packages. 20 5. The fuel or lubricant composition, especially fuel composition, according to any of the preceding embodiments, wherein the quaternizing agent is a compound of the general formula 1 25

R

1 0C(O)R 2 (1) in which R, is a low molecular weight hydrocarbyl radical, such as alkyl or alkenyl radical, especialy a lower alkyl radical, such as especially methyl or ethyl, and 30 R2 is an optionally substituted monocyclic hydrocarbyl radical, especially an aryl or cycloalkyl or cycloalkenyl radical, especially aryl such as phenyt where the substituent is selected from OH, NH 2 , NO 2 , C(O)OR& and ROC(O)-, in which R 1 is as defined above and R9 is H or Ri, where the substituent is especially OH. More particularly, the quaternizing agent is a phthalate or a salicylate, such as dimethyl phthalate or methyl 35 salicylate. M/51320-PCT 7 6. The fuel or ubdcant composition, especially fuel composition, according to any of the preceding embodiments, wherein the quaternizing agent is a compound of the general formula 2 5 RiOC(O)-A-C(O)OR. (2) in which R, and R 1 , are each independently a low molecular weight hydrocarbyl radical, such as 10 an alkyl or alkenyl radical, especially a lower alkyl radical and A is hydrocarbylene (such as especially C-rC7-alkyiene or CrC7-alkenylene). 7. The fuel or lubricant composition, especially fuel composition, according to any of the preceding embodiments, wherein the quaternized nitrogen compound has a 15 number-average molecular weight in the range from 400 to 5000, especially 800 to 3000 or 900 to 1500, 8. The fuel or lubricant composition, especially fuel composition, according to any of the preceding embodiments, wherein the quaternizing agent is selected from 20 alkyl salicylates, dialkyl phthalates and dialky oxalates; particular mention should be made of alkyl salicylates, especially lower alkyl salicylates, such as methyl, ethyl and n propyl saicyiates, 9- The fuel or lubricant composition, especially fuel composition, according to 25 embodiment 1, wherein the compound which is reactive (capable of addition or condensation) with the polycarboxylic acid and comprises an oxygen or nitrogen group and at least one quaternizabie amino group is selected from a. hydroxyaikyi-substituted mono- or polyamines having at least one quaternizable primary, secondary or tertiary amino group; 30 b. straight-chain or branched, cyclic, heterocyclic, aromatic or nonaromatic polyamines having at east one primary or secondary amino group and having at least one quaternizable primary, secondary or tertiary amino group; c, piperazines, and particular mention should be made of group a. M/51320-PCT a 10. The fuel or lubricant composition according to embodiment 9, wherein the compound which is reactive, especially capable of addition or condensation, with the polycarboxylic acid and comprises an oxygen or nitrogen group and at least one 5 quaternizable amino group is selected from a. hydroxyalkyl-substituted primary, secondary or tertiary monoamines and hydroxyalkyl-substituted primary, secondary or tertiary diamines, b. straight-chain or branched aliphatic diamines having two primary amino groups; di- or polyamines having at least one primary and at least one secondary 10 amino group; di- or polyanines having at least one primary and at least one tertiary amino group;, aromatic carbocyclic diamines having two primary amino groups; aromatic heterocyclic polyamines having two primary amino groups; aromatic or nonaromatic heterocycles having one primary and one tertiary amino group; and particular mention should be made of group a. 15 11. The fuei composition according to any of the preceding embodiments, selected from diesel fuels, biodiesel fuels, gasoline fuels and alkanoi-containing gasoline fuels, 20 12. The fusi or lubricant composition, especially fuel composition, according to any of the preceding embodiments, wherein the hydrocarby-substituted polycarboxylic acid compound is a polyisobutenylsuccinic acid or an anhydride (PIBSA) thereof, said acid having a low bismaleation level, especially 10% or less than 10%, for example 2 to 9 or 3 to 7%. More particularly, such PIBSAs are derived from HR-PIB with an Mn in 25 the range from about 400 to 3000. More particularly, the above compositions are fuel compositions, in particular diesel fuels, 30 13. The reaction product obtainable by a process as defined in any of the preceding embodiments, especially according to embodiment 3, 4, 5, 6 and in particular embodiment 8, 9 or 10, or quaternized nitrogen compound obtained from the reaction product by partial or full purification. M/51 320-PCT 9 in a particular configuration (A) of the invention, quaternized reaction products which are prepared proceeding from polyisobutenylsuccinic acid or an anhydride thereof are provided, this compound having a bismaleation level of equal to or less than about 20% or equal to or less than about 15%, for example 15, 14, 13, 12, 11, 10, 9, 8, 7, 6, 5, 4, 5 3, 2, 1, or 0.1%, This polyisobutenyisuccinic acid compound is reacted (especially by addition or condensation) with a compound comprising at least one oxygen or nitrogen group reactive (addable or condensable) with the polyisobutenylsuccinic acid compound and containing at least one quaternizable amino group, and then quaternized. 10 In a particular configuration (B) of the invention, quatemized reaction products which are obtained by quaternization using an excess of quaternizing agent are provided. More particularly, about 1. 1 to about 2.0 or about 1.25 to about 2.0 equivalents, for example 1.3, 1A, 1.5, 1.6, 1.7, 1.8 or 1.9, equivalents of quaternizing agent are used 15 per equivalent of quatemizable tertiary nitrogen atoms. Particularly useful quaten[zing agents are those of the formula (1), especially the lower alkyl esters of salicylic acid, such as methyl salicylate, ethyl salicylate, n and V-propyl salicylate., and n, I- or tert butyl salicylate. 20 In a further particular configuration (C), configurations (A) and (B) are combined, i,e. the quaternizable compounds prepared from the above polyisobutenylsuccinic acid compounds according to configuration (A) are quaternized according to configuration (B). 25 14. A process for preparing a quaternized nitrogen compound according to embodiment 13, comprising the reaction of a quaternizable hydrocarbyksubstituted polycarboxylic acid compound comprising at least one tertiary quaternizable amino group with a quaternizing agent which converts the at least one tertiary amino group to a quaternary 30 ammonium group, said quaternizing agent being the alkyl ester of a cycloaromatic or cycloaliphatic mono or polycarboxylic acid (especially of a rnono- or dicarboxylic acid) or of an aliphatic polycarboxylic acid (especially dicarboxylic acid), M/51 320-PCT 10 15. The use of a reaction product or of a quaternized nitrogen compound according to embodiment 13 or of a compound prepared according to embodiment 14 as a fuel additive or lubricant additive, especially fuel additive, especially diesel fuel additive. 5 16. The use according to embodiment 15 as an additive for reducing the fuel consumption of direct-injection diesel engines, especially of diesel engines with commorraili injection systems, as determined, for example, in an XUD9 test to CEC-F 23-01, and/or for minimizing power loss in direct-injection diesel engines, especially in 10 diesel engines with common-rail injection systems, as determined, for example, in a DW1 0 test based on CEC-F-098-08, 17. The use according to embodiment 15 as a gasoline fuel additive for reducing the level of deposits in the intake system of a gasoline engine, such as especially DISI 15 (direct injection spark ignition) and PF (port fuel injector) engines, 18. The use according to embodiment 15 as a diesel fuel additive, especially as a cold flow improver, as a wax antisettling addItive (WASA) or as an additive for reducing the level of and/or preventing deposits in the intake systems, such as especially the 20 intemal diesel injector deposits (IDDs), and/or valve sticking in direct-injection diesel engines, especially in common-rail injection systems. 19. An additive concentrate comprising, in combination with further diesel. fuel or gasoline fuel additives, especially diesel fuel additives, at least one quaternized 25 nitrogen compound as defined in embodiment 13 or prepared according to embodiment 14. A2) General definitions 30 A "condensation" or "condensation reacion" in the context of the present ivention describes the reaction of two molecules with elimination of a relatively small molecule, especially of a water molecule. When such an elimination is not detectable analytically, more particularly not detectable in stoichiometric amounts, and the tvo molecules react M/51320-PCT 11 nevertheless, for example with addition, the reaction in question of the two molecules is "without condensation". In the absence of statements to the contrary, the following general conditions apply: 5

"

4 Hydrocarbyr' can be interpreted widely and comprises both long-chain and short chain, straight-chain and branched hydrocarbon radicals, which may optionally additionally comprise heteroatoms, for example 0, N, NH, S, in the chain thereof. 10 "Long-chain" or "high molecular weight' hydrocarbyl radicals have a number-average molecular weight (M) of 85 to 20 000, for example 113 to 10 000, or 200 to 10 000 or 350 to 5000, for example 350 to 3000, 500 to 2500, 700 to 2500, or 800 to 1500. More particularly, they are formed essentially from C especially C0, monomer units such as ethylene, propylene, n- or isobutylene or mixtures thereof, where the different 15 monomers may be copolymerized in random distribution or as blocks. Such long-chain hydrocarbyl radicals are also referred to as polyalkylene radicals or poly-Cw2r or poly

C

24 -alkylene radicals. Suitable long-chain hydrocarbyl radicals and the preparation thereof are also described, for example, in WO 2006/135881 and the literature cited therein. 20 Examples of particularly useful poiyalkylene radicals are polyisobuteny radicals derived from "high-reactivity" polyisobutenes (HR-PIB) which are notable for a high content of terminal double bonds (cf, for example, also Rath et al, Lubrication Science (1999), 11-2, 175-185). Terminal double bonds are alpha-olefinic double bonds of the 25 type Polymer which are also referred to collectively as vinylidene double bonds. Suitable high 30 reactivity polyisobutenes are, for example, polyisobutenes which have a proportion of vinylidene double bonds of greater than 70 mol%, especially greater than 80 mol% or greater than 85 mol%. Preference is given especially to polyisobutenes which have homogeneous polymer structures, Homogeneous polymer structures are possessed M/51320-PCT 12 especially by those polyisobutenes formed from isobutene units to an extent of at least 85% by weight, preferably to an extent of at least 90% by weight and more preferably to an extent of at least 95% by weight Such high-reactivity polyisobutenes preferably have a number-average molecular weight within the abovementioned range. in 5 addition, the high-reactivity polyisobutenes may have a polydispersity in the range from 1.05 to 7, especially of about 11 to 2.5, for example of less than 1.9 or less than 1.5. Polydispersity is understood to mean the quotient of weight-average molecular weight Mw divided by the number-average molecular weight Mn. 10 Particularly suitable high-reactivity polyisobutenes are, for example, the Glissopal brands from BASF SE, especialy Gissopa 5 1000 (Mn =1000), Giissopal V 33 (Mn = 550), GlissopaP 1300 (Mn = 1300) and Giissopalo 2300 (Mn = 2300), and mixtures thereof. Other number-average molecular weights can be established in a manner known in principle by mixing polyisobutenes of different number-average 15 molecular weights or by extractive enrichment of polyisobutenes of particular molecular weight ranges, PIBSA is prepared in a manner known in principle by reacting PIB with maleic anhydride (MAA), in principle forming a rmxture of PIBSA and bismaleated PIBSA (BM 20 PIBSA, of. scheme 1, below), which is generally not separated but used as such in further reactions. The ratio of the two components to one another can be reported via the "b 1 smaleation lever (BML). The BML is known per se (see also US 5,883,196). The BML can also be determined by the following formula: 25 BML = 100% x t(wt-%(BM PISSA))/(wt-%(BM PIBSA)+wt-%(PIBSA))] where wt-% (X) represents the proportion by weight of component X (X = PIBSA or BM PIBSA) in the reaction product of PI8 with MSA, 30 Scheme I N/51 320-PCT 13 P 0 +N PIB MSA PIBSA BM PBSA Hydrocarbyi-substituted polycarboxylic acid compound with a "low bismaleation level" 5 especially corresponding polyisobutenylsuccinic acids or anhydrides thereof (also referred to overall as PIBSA) are known from the prior art. Especially advantageous are bismaleation levels of 20% or less, or 15% or less, for example 14, 13, 12 or 10%; or 10% or less, for example 2-9, 3-8, 4-7, 5 or 6%, The controlled preparation thereof is described, for example, in US 5,883,196. Suitable for preparation Thereof are especially 10 the above high-reactivity polyisobutenes with an Mn in the range from about 500 to 2500, for example 550 to 3000, 1000 to 2000 or 1000 to 1500 A nonlimiting example of a corresponding PIBSA is Glissopal* SA, derived from HR-PiB (Mn = 1000), with a bismaleation level of 9%. 15 "Shor-ch&ain hydrocarbyl" or "low molecular weight hydrocarby" is especially straight chain or branched alkyl or alkenyl, optionally interrupted by one or more, for example 2, 3 or 4, heteroatom groups such as -O- or -NH-, or optionally mono- or polysubstituted, for example di-, tri- or tetrasubstituted. 20 "AlkyP or "lower alkyl" represents especially saturated, straight-chain or branched hydrocarbon radicals having 1 to 4, 1 to 6, 1 to 8, or 1 to 10 or 1 to 20, carbon atoms, for example methyl, ethyl, n-propy, 1-methylethyl, n-butyl, 1-methypropy. 2 methylpropy, 1,i-dimethylethy, n-pentyt 1-methylbutyl, 2-methybutyt 3-methylbutyl, 25 2,2-dimethylpropy, i-ethylpropyl, n-hexyl 1,1 -dimethylpropyl, 1,2-dimethylpropyl, 1 methylpenty, 2-rnethylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethyibutyl, 1,2 dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dirnethylbuty, 3,3-direthylbutyl, 1-ethybuty, 2-ethylbuty, 1,1,2-trimethylpropy, -1,2,2-trimethylpropy. 1-ethyl-I methylpropyl and 1-ethyl-2-methylpropyl; and also n-heptyi, n-octyl, n-nonyl and n 30 decyl, and the singly or multiply branched analogs thereof. M/5 1320-PCT 14 "HydroxyalkyP represents especially the mono- or polyhydoxylated, especially monohydroxyrated, analogs of the above akyl radicals, for example the monohydroxylated analogs of the above straight-chain or branched alkyl radicals, for 5 example the linear hydroxyalkyl groups with a primary hydroxyl group, such as hydroxymethyl 2-hydroxyethyt 3-hydroxypropyl 4 -hydroxybutylt "Alkeny" represents mono- or polyunsaturated, especially monounsaturated, straght chain or branched hydrocarbon radicals having 2 to 4, 2 to 6, 2 to 8, 2 to 10 or 2 or to 10 20 carbon atoms and a double bond in any position, for example 2-Ce-afkenyJ such as ethenyl, 1-propenyt 2-propenyI, 1 -methyletheny, 1-buteny, 2-butenyl, 3-butenyl, 1 methyl-1-propeny, 2-methyl- 1-propeny, 1-methyl-2-propenyl, 2-methyb2-propeny 1 penteny, 2-penteny!, 3-pentenyt 4-pentenyl, 1-methy-Ibutenyl, 2-methyl.1-butenyl 3 methykli-butenyl, 1-rnethyl-2-butenyl, 2-methyk2-buteny 3-rmethy-2-bute nyl, 1-methyl 15 3-butenyi, 2 -methyk3-buteny 3 -methyl-3-butenyl, 1,1-dimethyl-2-propenyf, 1,2 dimethyl1--propeny, 1,2-ditethyl2-propenyi,1-ethyl-i-propeny, 1-ethyk2-propenyl,

I

hexenyl, 2-hexeny, 3-hexeny, 4-hexenyt 5-hexenyt 1-methyl-1-pentenyl, 2-methyl-1 pentenyi, 3-methyl-i-penteny, 4-nethyl-I-pentenyl, 1 -methyl-2-penteny, 2-methyl-2 pentenyl, 3-methyb-2-penteny 4 -methyl-2-penteny% 1-methyl-3-penteny, 2-methy4l 20 pentenyl, 3-methyI-Spentenyi 4-rnethy-3-penteny -methyl4-penteny 2-methy-4 pentenyl, 3-methy-4-pentenyi, 4-methy14-pentenyl, 1,1 -di methyi-2-butenyt 1,1 -dimethyk3-buteny 1,2-dimethyk1-buteny., 1,2-dimethyv2-butenyl, 1,2-dimethy-3 butenyt 1,3-dimethyl-1-buteny, I, 3-dimethyl-2-buteny% 1,3-dimethyl-3-butenyl, 2,2 dim ethy['3-b uteny', 2,3-dim ethyl-1 -butenyl, 2,3-dimethyl-2-buteny, 2,3-dimethyl-3 25 butenyl, 3,3-dirmethyl-1 -butenyl 3,3-dimethy.2-butenyr 1-ethyl-1 -butenyl, I-ethyk2 butenyl, 1 -ethyl-3-butenyt 2-ethyi-I-butenyl, 2-ethyl-2-butenyl, 2 -ethyi-3-butenyl, 1,1,2 trimethyl-2-propeny 1-ethyl-m-rethyl-2-oropenyl, 1 -ethy-2-methy-I-propenyl and I-ethyl-2-methyl-2-propenyt 30 "Alkylene" represents straight-chain or mono- or polybranched hydrocarbon bridge groups having I to 10 carbon atoms, for example C--alkylene groups selected from

-CH

2 - -(C:H2), ~(CH). -CH2-CH(CH)-,

-CH(CH)CH

-

, (CH 2 ), -(CH2) 2

-CH(CH

3 ) -CH2-CH(CH 3 )-CH, (CH 2 )- -(CH)-,

-(CH

2

)

6 , -(CH2)-, -CH(CH3)-CH 2 -CHrCH(CH)~ or -CH(CH-)-CHCHrCHrCH(CH )~ or C1-C0akylene groups selected from -CM- M/51320-PCT 15 (CH}2-, -(CH2h=, -CHrCH(CH3), ~CH(CH)-CHr, -(CH 2

)

4 -, -(CH 2 $)CH(CH), -CH2

CH(CH

3 )-CH t. "Aikenylene" represents the mono- or polyunsaturated, especially monounsaturated, 5 analogs of the above alkylene groups having 2 to 10 carbon atoms, especially C2-C7 alkenyyenes or O 2- C,-akenylenes, such as -CH=CH-, -CH=CH-CH), -CHrCH=CH-, -CH=CH-CH-2CHr2, -CH 2

-CH=CH-CH

2 -, -CH2CH2-CH=CH-, -CH(CH )-CH=CH-,

-CH

2

-C(CH

3 },)=CH-. 10 "Cyclic hydrocarbyl radicals" comprise especially: - cycloalkyl: carbocyclic radicals having 3 to 20 carbon atoms, for example C-Ce cycloalkyl such as cyclopropyt cyclobutyl, cyclopenty, cydlohexyl, cycloheptyl, cyclooctyl, cycononyl. cyclodecyl, cycloundecyl and cyclododecyl; preference is given to cyclopenty, cycohexy, cycloheptyt and also to cyclopropylmethyi, cydopropylethyl, 15 cyclobutylmethyi, cyclobutylethyl, cyclopentylmethyl, cycliopentylethy], cyclohexyimethyl, or C 3 -C7-cycloalkyl such as cyclopropyl, cyclobuty, cyclopentyl, cydohexyl, cycloheptyl, cyclopropylm ethyl, cyclopropylethyl, cyclobutylrmethyl, cyclopentylethyl, cyclohexylmethyl, where the bond to the rest of the molecule may be via any suitable carbon atom. 20 - cycloalkenyl: monocyclic, monounsaturated hydrocarbon groups having 5 to 8, preferably up to 6, carbon ring members, such as cyclopenten-1-yl, cyclopenten-3>yl, cyclohexen-1-yl, cyclohexen-3-yi and cyoiohexen-4-yl; - aryt mono- or polycyclic, preferably mono- or bicyclic, optionally substituted aromatic radicals having 6 to 20, for example 6 to 10, ring carbon atoms, for example 25 pheny, biphenyl, naphthyl such as 1- or 2-naphthyl, tetrahydronaphthyt, fluorenyl, indenyl and phenanthrenylt These aryl radicals may optionaly bear 1, 2, 3, 4, 5 or 6 identical or different substituents. "Substituents" for radicals specified herein are especially, unless stated otherwise, 30 selected from keto groups, -COOM, -COO-alkyl, -OH, -SH, -CN, amino, -NO 2 , alkyl, or alkenyl groups. The term "about" in the context of a stated figure or of a value range denotes deviations from the specifically disclosed values, These are usually customary deviations. These M/51320-PCT 16 may differ, for example, by ± 10% to ± 0.1% from the specific values. Typically, such deviations are about ± 8% to ± 1% or 5%, ± 4%, ± 3% or ±.2%. A$) Polycarboxylic acid compounds and hydrocarbyF-substituted polycarboxylic acid 5 compounds: The polycarboxylic acid compounds used are aliphatic di- or polybasic (for example tri or tetrabasic), especially from di-, tri- or tetracarboxylic acids and analogs thereof, such as anhydrides or lower aikyl enters (partially or completely esterified), and is optionally 10 substituted by one or more (for example 2 or 3), especially a long-chain alkyl radical and/or a high molecular weight hydrocarbyl radical, especially a polyalkylene radical Examples are CrCw polycarboxylic acids, such as the dicarboxylic acids malonic acid, succinic add, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebadic acid, and the branched analogs thereof; and the tricarboxylic acid ctric acid; 15 and anhydrides or lower alkyl esters thereof of. The polycarboxylic acid compounds can also be obtained from the corresponding monounsaturated acids and addition of at least one long-chain alkyl radical and/or high molecular weight hydrocarbyl radical. Examples of suitable monounsaturated acids are fumaric acid, maleic add, itaconic acid. 20 The hydrophobic 'long-chain" or "high molecular weight" hydrocarbyl radical which ensures sufficient solubility of the quaternized product in the fuel has a number average molecular weight (Ma) of 85 to 20 000, for example 113 to 10 000, or 200 to 10 000 or 350 to 5000, for example 350 to 3000, 500 to 2500, 700 to 2500, or 800 to 25 1500, Typical hydrophobic hydrocarbyl radicals include polypropenyl, polybutenyl and poiyisobutenyl radicals, for example with a number-average molecular weight M of 3500 to 5000, 350 to 3000, 500 to 2500, 700 to 2500 and 800 to 1500. Suitable hydrocarbyl-substituted compounds are described, for example, in 30 DE 43 19 672 and WO 2008/138836., Suitable hydrocarbyl-substituted polycarboxyic acid compounds also comprise polymeric, especially dimeric, forms of such hydrocarbyksubstituted polycarboxylic acid compounds. Dimeric forms comprise, for example, two acid anhydride groups which M/51320-PCT 17 can be reacted independently with the quaterizable nitrogen Compound In the preparation process according to the invention. A4) Quatemizing agents: 5 Useful quatemizing agents are in principle ai! alkyl esters which are suitable as such and are those of a cycloaromafio or cycloaliphatic mono- or polycarboxyic acid (especially of a mono- or dicarboxyic acid) or of an aliphatic polycatboxyic acid (especialy dicarboxylic acid). 10 In a particular embodiment, however, the at least one quaternizable tertiary nitrogen atom is quaternized with at least one quatemizing agent selected from a) compounds of the general formula 1 15

R

1 0C(Q)R 2 (1) in which 20 R, is a lower eikyl radical and R2 is an optionally substituted monocycic aryl or cycoalkyi radical, where the subsfituent is selected from OH, NH 2 , NOr C(O)OR, and R 3 OC(O)> in which RIa is as defined above for R, and Rs is H or R 1 ; 25 and b) compounds of the general formula 2 RtOC(Q)-A-C(O)OR* (2) 30 in which

R

1 and Ria are each independently a lower alkyl radical and A Is hydrocarbylene (such as alkylene or alkenylene). Particularly suitable compounds of the formula I are those in which M/51 320-PCT 18

R

1 is a Cl, C- or Cralkyl radical and

R

2 is a substituted phenyl radical, where the substituent is HO- or anj ester radical of the formula RiOC(O)- which is in the para, meta or especially ortho position to the R10C(O)- radical on the aromatic ring, 5 Especially suitable quaternizing agents are the lower alkyl esters of sailcylic acid, such as methyl salicylate, ethyl saficylate, n- and i-propyl salicylate, and n-, or tert-buty saliloylate, 10 A5) Quatemized or quatemizable nitrogen compounds: The quaternizable nitrogen compounds reactive wIth the polycarboxylic acid compound are selected from a, hydroxyalkyl-substituted mono- or polyamines having at least one 15 quatemized (e.g. chcline) or quaternizable primary, secondary or tertiary amino group; b. straight-chain or branched, cyclic, heterocyclic, aromatic or nonaromatic polyarnines having at least one primary or secondary (anhydride-reactive) amino group and having at least one quatemized or quatemizable primary, secondary or 20 tertiary amino group; c. piperazines, The quaternizable nitrogen compound is especially selected from di hydroxyaikylsubstituted primary, secondary, tertiary or quaternary 25 monoamines and hydroxyalkyl-substituted primary, secondary, tertiary or quaternary diamines; e- straight-chain or branched aliphatic diamines having two primary amino groups; di- or polyamines having at least one primary and at least one secondary amino group; di- or polyamines having at least one primary and at least one 30 tertiary amino group; di- or polyarnines having at least one primary and at least one quatemary amino group; aromatic carbocyclic diamines having two primary amino groups; aromatic heterocyclic polyamrines having two primary amino groups; aromatic or nonaromatic heterocycles having one primary and one tertiary arino group. M/51320-PCT 19 Examples of suitable "hydroxyalkyl-substtuted mono- or polyamines" are those provided with at least one hydroxyaikyl substituted, for example 1, 2, 3, 4, 5 or 6 hydroxyakyl substituted. Examples of "hydroxyalkyl-substituted monoamines" include: N-hydroxyalkyl monoamines, N,N-dihydroxyalkyl monca mines and N,N,N-trihydroxyalkyl monoamines, where the hydroxyalkyl groups are the same or different and are also as defined above, Hydroxyalkyl is especially 2-hydroxyethyl, 3-hydroxypropyl or 4-hydroxybutyl 10 For example, the following "hydroxyalkyksubstituted polyamines" and especially "hydroxyakylsubstituted diamines" may be mentioned: (N-hydroxyakyI)alkylene diarnines, N, N-dihydroxyalkyla Ikylened iamines, where the hydroxyalkyl groups are the same or different and are also as defined above. Hydroxyalkyl is especially 2 15 hydroxyethyl, 3-hydroxypropyl or 4-hydroxybuty; alkylene is especially ethylene, propylene or butylene. Suitable "dlamines" are alkylenediamines, and the N-alkyksubstituted analogs thereof., such as N-monoaikyiated alkylenediamines and the NN- or N,N-dialkylated 20 alkylenediamines. Alkylene is especially straight-chain or branched Cw or alkylene as defined above. Alkyl is especially 0 1 4 -alkyl as defined above, Examples are especially ethylenediamine, 1,2-propylenediamine, 1,3-propylenediamine, 1,4 butylenediamine and isomers thereof, pentanediamine and isomers thereof, hexanediamine and isomers thereof, heptanediamine and isomers thereof, and singly 25 or multiply, for example singly or doubly, C1-C, 4 alkylated, for example methylated, derivatives of the aforementioned diamine compounds such as 3-dimethylarino1 propylamine (DMAPA), N,N-diethylaminopropylamine and N,N-dimethylamino ethylamine. 30 Suitable straight-chain "polyamines" are, for example, dialkylenetriamine, trialkylenetetramine, tetraalkyienepentamine, pen taalkylenehexam ine, and the N-alkyk substituted analogs thereof, such as N-monoalkylated and the N:N- or N,N-dlialkylated alkylenepolyamines. Alkylene is especially straight-chain or branched COt- or C.4. alkylene as defined above. Aikyl is especially C 4 -aiky as defined above. M/51320-PCT 20 Examples are especially diethylenetriamine, triethylenetetramine tetraethylenepentam ne, pentaethylenehexam ine , dipropylenetla mine, trpropylenetetramneI tetrapropyIenepentamIne, pentapropylenehexamine 5 dibutylenetriarine, tributylenetetramine, tetrabutylenepentamine pentabutylenehexaine; and the NN-diaikyi derivatives thereof, especially the NN-d C14-alkyl derivatives thereof. Examples include: N.N-dimethyidimethylenetriamine N,N-diethyldimethylenetTiamine, NN-dipropyidimethylenetriamine, N, N dimethyldiethylene-1,2-riamine, NN-diethyidiethylene-1,2-riamine,

NN

10 dipropyld ethylene-1.,2-triamine, N,N-dimethyidipropylene-1I,3-triamine (i.e, DMAPAPA), N,N-diethyldipropylene-1,3-riamine, N,N-dipropyidipropylene-1,3driamine, N, N dimethyidibutylene-1,4-ramine, N,N-diethyidibutylene-1,4-triamine, N, N dipropyidibutylen e- 1,4riamine, N, N-dimethyldipentylene-1,5-riamine,

NN

diethyidipentyiene -1,5-triamine, N,N-dipropyldipentylerne-1, 4riamine, N, 15 dimethyldihexylene -1A6-riamine, N,N-diethyldihexylene-1 I,6-triamlne and N,N dipropyldihexylene-1.,6-triamine. "Aromatic carbocyclic diamines" having two primary amino groups are the diamino substituted derivatives of benzene, biphenyl, naphthalene, tetrahydronaphthalene, 20 fluorene, mdene and phenanthrene. "Aromatic or nonaromatic heterocyclic polyamines" having two primary amino groups are the derivatives, substituted by two amino groups, of the following heterocycles: 25 - 5- or 6-membered, saturated or monounsaturated heterocycles comprising one to two nitrogen atoms and/or one oxygen or sulfur atom or one or two oxygen and/or sulfur atoms as ring members, for example tetrahydrofuran, pyrrolidine, isoxazolidine, isothiazolidine, pyrazolidine, oxazolidine, thiazolidine, imidazolidine, pyrrolime, piperidine, piperidinyl, 1,3-dioxane, tetrehydropyran, hexahydropyridazine, 30 hexahydropyrimidine, piperazine; - 5-membered aromatic heterocycles comprising, in addition to carbon atoms, two or three nitrogen atoms or one or two nitrogen atoms and one sulfur or oxygen atom as ring members, for example furan, thiane, pyrrole, pyrazole., oxazole, thiazoie, imdazoie 35 and 1,3,4Ariazole; isoxazoie, isothiazole, thiadiazole, oxadiazole; M/5 I 320-PCT 21 - 6-membered heterocycles comprising, in addition to carbon atoms, one or two, or one, two or three, nitrogen atoms as ring members, for example pyridinyi, pyridazine, pyriniidine, pyrazinyi, 1,2,4-triazbne, 1 3S4riazin-2-yL 5 "Aromatic or nonaromatic heterocycles having one primary and one tertiary amino group" are, for example, the abovementioned N-heterocycles which are aminoalkyiated on at least one ring nitrogen atom, and especially bear an amino-C-alkyl group. 10 "Aromatic or nonaromatic heterocycies having a tertiary amino group and a hydroxyalkyl group' are, for example, the abovementioned N-heterocycles which are hydroxyalkylated on at least one ring nitrogen atom, and especially bear a hydroxy-C, 4 -alkyi group. 15 Mention should be made especially of the following groups of individual classes of quatemizable nitrogen compounds: M/51320-PCT 22 Group 1: NAME FORMULA Diamines with pfimaiy second nitrge am Ethytenediamine H2N .NH 2 N H 2 1 2Propytened m e N M1 1 Propyienediam ne

H

2 N ,NH 2 Isomeric butylenediamines, for example S5-Pentylenediami~ne

H

2 N t~' yNH 2

H

2 N NH somerko pentanaedIaminea, for example 2 H 2 N N H somerc heixanedamines, for example H. someric heptanediamnes, for example H NH 2 and pwth a sonrecn nitrogen ton Diethylenekramne (DETA) Dipropylenetriamine (DPTA), 3,HNH minobis(NN-dimethyprpyamine)

_-NH

2 H Triethy enetei~ramine (TETA) 2N N NN H z

~NH

2 H N N Tetraethylenepentamine (TEPA) H N N N H H NH Pentetyl neea He H N N H H M/51"I320-PCT 23 N-Met hy amino- -propy niN HNH H t slhexamethyrenetrtamne NNH

NH

2 Aoinaus~ls, H.2 Diaminobenzenes for example

H

2 N N Group 2: NAME He~cyNs FORMUL A 1 Amilnopropy) midazore

H

2 N N N 4

(

3 Aninopropy )morpholneI N-N NH2 2 -(l-Ppmziny )ethyamrne (AEP) 2 !L--- IN NI, "/ N-Methylpperazine / N Aines with' terry second'nitro atom H N- N

NH

2 3 t n y (OMAPA J H 2 N M/51320-PCT 24 NN4) ethylaqmjnopropy am ne N N,- meT~f hylami noethyIam r ireHN Group 3: NA -- - NAME FORMULA Alcohols with a primary and secondary amine IEthanolami~ne 2 OH 3-Hydroxy1-propy~aii HnsA O H2 Dthanan mine HO OH H Disopropanciamine N -OH H N -H Alcots tertiary amine OH Triethanoamine (2 1 2'NJtotr ethanol ) i HN 0OH 3-Hyd roxyp ropyj,,)m d.azo eH > -N M/51I320-POT 25 H /OH Tris(hydroxymethyl )amne ~-N \--OH 3-DImethyamino-1 -propano 34DYethylamin-c HpropanoiO N 2-Dimethylamino-I -ethanol N 40iethlarnino-Ibutanol HO N N AG) Preparation of Inventive additives: 5 a) Reaction with oxygen or nitrogen group The hydrocarbyl-substituted polycarboxylio acid compound can be reacted with the quatemizable nitrogen compound according to the present invention under thermaly 10 controlled conditions, such that there is essentially no condensation reaction. More particularly, no formation of water of reaction is observed in that case, More particularly, such a reaction is effected at a temperature in the range from 10 to 8*C, especially 20 to 60*0 or 30 to 50*C, The reaction time may be in the range from a few minutes or a few hours, for example about 1 minute up to about 10 hours. The reaction 15 can be effected at a pressure of about QA to 2 atm, but especially at approximately standard pressure. For example, an inert gas atmosphere, for example nitrogen, is appropriate, More particularly, the reaction can also be effected at elevated temperatures which 20 promote condensation, for example in the range from 90 to 100"C or 100 to 170*C, M/51320-PCT 26 The reaction time may be in the region of a few minutes or a few hours, for example about I minute up to about 10 hours, The reaction can be effected at pressure at about 0. 1 to 2 atm, but especially at about standard pressure S The reactants are initially charged especialy in about equimolar amounts; optionally, a small molar excess of the polycarboxylic acid compound, for example a 0.05- to 0.5 fold, for example a 0.1- to 0.3-fold, excess, is desirable. If required, the reactants can be initially charged in a suitable inert organic aliphatic or aromatic solvent or a mixture thereof. Typical examples are, for example, solvents of the Solvesso series, toluene or 10 xylene. The solvent can also serve, for example, to remove water of condensation azeotropically from the reaction mixture. More particularly, however, the reactions are performed without solvent, The reaction product thus formed can theoretically be purfied further, or the solvent 15 can be removed. Usually, however, this is not absolutely necessary, such that the reaction step can be transferred without further purification into the next synthesis step, the quaternmization. b) Quaternization 20 The quaternization in reaction step (b) is then carried out in a manner known per se. To perform the quaternization, the reaction product or reaction mixture from stage a) is admixed wIth at least one compound of the above formula I or 2, especially in the 25 stoichiometric amounts required to achieve the desired quaternization. It is possible to use, for example, 0.1 to 2.0, 0.2 to 1,5 or 0.5 to 1.25 equivalents, of quatemnizing agent per equivalent of quaternizabte tertiary nitrogen atom, More particularly, however, approximately equimolar proportions of the compound are used to quatermize a tertiary amine group, Correspondingly higher use amounts are required to quaternize a 30 secondary or primary amine group, in a further variant, the quaternizing agent is added in excess, for example 1.1 to 2.0, 1.25 to 2 or 1,25 to 1.75 equivalents of quaternizing agent per equivalent of quaternizable tertiary nitrogen atom, Typical working temperatures here are in the range from 50 to 180"C, for example from 35 90 to 160*C or 100 to 140*C, The reaction time may be in the range of a few minutes M/51320-PCT 27 or a few hours, for example about 10 minutes up to about 24 hours, The reaction can be effected at a pressure of about 0.1 to 20 bar, for example I to 10 or 1,5 to 3 bar, but especially at about standard pressure. 5 If required, the reactants can be initially charged for the quaternization in a suitable inert organic ali phatic or aromatic solvent or a mixture thereof, or a sufficient proportion of solvent from reaction step a) is still present Typical examples are, for example, solvents of the Solvesso series, toluene or xylene. The quatemization can, however, also be performed in the absence of a solvent 10 To perforni the quatemization, the addition of catalytically active amounts of an acid may be appropriate. Preference is given to aliphatic monocarboxylic adds, for example CIrCemonocarboxyilc acids such as especially lauric acid, isononanoic acid or neodecanoic acid. The quaternization can also be performed in the presence of a 15 Lewis acid, The quaternizaton can, however, also be performed in the absence of any acid. c) Workup of the reaction mixture 20 The reaction end product thus formed can theoretically be purified further, or the solvent can be removed, in order to improve the further processabiiity of the products, however, it is also possible to add solvent after the reaction, for example solvents from the SoIvesso series, 2-ethylhexanoi, or essentially aliphatic solvents. Usually, however, this is not absolutely necessary, and so the reaction product is usable without further 25 purification as an additive, optionally after blending with further additive components (see below). B) Further additive components 30 The fuel additized with the inventive quaternized additive is a gasoline fuel or especially a middle distillate fuel, in particular a diesel fuel, The fuel may comprise further customary additives to improve efficacy and/or suppress wear. M/51 320-PCT 28 In the case of dIesel fuels, these are primarily customary detergent additives, carrier ost, cold flow improvers, lubricity mprovers, corrosion inhibitors, denuisifers, dehazers, antifoams, cetane number improvers, combustion improvers, antioxidants or 5 stabilizers, antistats, metallocenes, metal deactivators, dyes and/or solvents, In the case of gasoline fueis, these are in particular lubricity improvers (friction modifiers), corrosion inhibitors, demulsifiers, dehazers, antifoams, combustion improvers, antioxidants or stablizers, antistats, metallocenes, metal deactivators, dyes 10 and/or solvents. Typical examples of suitable coadditives are listed in the following section: 81) Detergent additives 15 The customary deterrent additives are preferably amphiphfHIc substances which possess at least one hydrophobic hydrocarbon radical with a number-average molecular weight (Mn) of 85 to 20 000 and at least one polar moiety selected from: 20 (Da) mono- or polyamino groups having up to 6 nitrogen atoms, at least one nitrogen atom having basic properties; (Db) nitro groups, optionally in combination with hydroxyl groups; 25 (Dc) hydroxyl groups in combination with mono- or polyamino groups, at least one nitrogen atom having basic properties; (Dd) carboxyl groups or their aIkali metal or alkaline earth metal salts; 30 (De) sulfonic acid groups or their aikali metal or alkaline earth metal saits; (Df) polyoxy-C to C-alkylene moieties terminated by hydroxyl groups, mono- or poiyamino groups, at least one nitrogen atom having basic properties, or by carbamate groups; M/51320-PCT 29 (Dg) carboxylic ester groups; (Dh) moleties derived from succinic anhydride and having hydroxyl and/or amino 5 and/or amido andfor imido groups; and/or (D) moieties obtained by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines, 10 The hydrophobic hydrocarbon radical in the above detergent additives, which ensures the adequate solubliity in the fuel, has a number-average molecular weight (M,) of 85 to 20 000, preferably of 113 to 10 000, more preferably of 300 to 5000, even more preferably of 300 to 3000, even more especially preferably of 500 to 2500 and especially of 700 to 2500, in particular of 800 to 1500. As typical hydrophobic 15 hydrocarbon radicals, especially in conjunction with the polar especially polypropenyi, polybutenyi and polyisobutenyl radicals with a number-average molecular weight M) of preferably in each case 300 to 5000, more preferably 300 to 3000, even more preferably 500 to 2500, even more especially preferably 700 to 2500 and especially 800 to 1500 into consideration. 20 Examples of the above groups of detergent additives include the allowing; Additives comprising mono- or polyamino groups (Da) are preferably polyalkenemono. or polyalkenepolyamines based on polypropene or on high-reactivity (i.e. having: 25 predominantly terminal double bonds) or conventional (i.e, having predominantly internal double bonds) poiybulene or polyisobutene having M, = 300 to 5000, more preferably 500 to 2500 and especially 700 to 2500, Such additives based on high reactivity polyisobutene, which can be prepared from the polyisob.utene which may comprise up to 20% by weight of n-butene units by hydroformylation and reductive 30 amination with ammonia, monoarmines or polyamines such as dimethylaminopropylami ne, ethylenediamine, diethylenetriamine, triethylenetetramne or tetraethylenepentamijne are known especially from EP-A 244 616. When polybutene or polyisobutene having predominantly internal double bonds (usually in the 8 and V positions) are used as starting materials in the preparation of the additives, a possible M151320-PCT 30 preparative route is by chlorination and subsequent amination or by oxidation of the double bond with air or ozone to give the carbonyl or carboxyl compound and subsequent amination under reductive (hydrogenating) conditions, The amines used here for the amination may be, for example, ammonia, monoamines or the 5 abovementioned polyamines, Corresponding additives based on polypropene are described in particular in WO-A 94,24231. Further particular additives comprising monoamino groups (Da) are the hydrogenation products of the reaction products of polyisobutenes having an average degree of 10 polymerization P = 5 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A 97/03946. Further particular additives comprising monoamine groups (Da) are the compounds obtainable from polyisobutene epoxides by reaction with amines and subsequent 15 dehydration and reduction of the amino alcohols, as described in particular in DE-A 19620 262, Additives comprising nitro groups (Db), optionafly in combination with hydroxyl groups, are preferably reaction products of polylsobutenes having an average degree of 20 polymerization P =5 to 100 or 10 to 100 with nitrogen oxides or mixtures of nitrogen oxides and oxygen, as described in particular in WO-A 96/03367 and in WO-A 96/03479. These reaction products are genera ly mixtures of pure nitropolyisobutenes (e.g. or-dinitropolyisobutene) and mixed hydroxynitropolyisobutenes (e.g, a-nitro hydroxypo lyisobutene) 25 Additives comprising hydroxy groups in combination with mono- or polyamino groups (Dc) are in particular reaction products of polyisobutene epoxides obtainable from polyisobutene having preferably predominantly terminal double bonds and M, = 300 to 5000, with ammonia or mono- or polyarnines, as described in particular in EP-A 30 476 485. Additives comprising carboxyl groups or their alkali metal or alkaline earth metal salts (Dd) are preferably copolymers of C 2 - to COA-olefins with maleic anhydride which have a total molar mass of 500 to 20 000 and some or all of whose carboxyl groups have been M/51320-PCT 31 converted to the alkali metal or alkaline earth metal salts and any remainder of the carboxyl groups has been reacted with alcohols or amines. Such additives are disclosed in particular by EP-A 307 815. Such additives serve mainly to prevent valve seat wear and can, as described in WO-A 87/01126, advantageously be used in 5 combination with customary fuel detergents such as poly(iso)buteneamines or polyetherarnines. Additives comprising sulfonic acid groups or their alkali metal or alkaline earth metal salts (De) are preferably alkali metal or alkaline earth metal salts of an alkyl 10 sulfosuccinate, as described in particular in EP-A 639 632. Such additives serve mainly to prevent valve seat wear and can be used advantageously in combination with customary fuel detergents such as poiy(iso)butenasmines or polyetheramines. Additives comprising polyoxy-CC 4 -alkylene moieties (Df) are preferably polyethers or 15 polyetheramines which are obtainable by reaction of Cr to Cw-alkanols, Ce- to Cw alkanedials, mono- or di-Cr to Cr-alkylamines, C- to C-alkyicyclohexanols or Ce- to C03-alkylphenols within 1 to 30 moi 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 20 polyamines, Such products are described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4 877 416. in the case of polyethers, such products also have carrier oil properties, Typical examples of these are tridecanol butoxylates, isotridecanol butoxylates, isononylphenol butoxylates and polyisobutenol butoxylates and propoxyates and also the corresponding reaction products with ammonia. 25 Additives comprising carboxylic ester groups (Dg) are preferably esters of mono-, di- or tricarboxylic acids with long-chain alkanols or polyols, in particular those having a minimum viscosity of 2 mmIs at I 00CO, as described in particular in DE-A 38 38 918. The mono-, di- or tricarboxylic acids used may be aliphatic or aromatic acids, and 30 particularly suitable ester alcohols or ester poiyols are long-chain representatives having, for example, 6 to 24 carbon atoms. Typical representatives of the esters are adipates, phthalates, isophthalates, terephtha[ates and trimellitates of isooctanol, of isononanol, of isodecanol and of isotridecanol. Such products also have carrier oil properties. M/51320-PCT 32 Additives comprising moieties derived from succinic anhydride and having hydroxyl and/or amino and/or amido and/or especially Imido groups (0h) are preferably corresponding derivatives of alkyl- or alkenyksubsttuted succinic anhydride and S especially the corresponding derivatives of polyisobutenyisucciniC anhydride which are obtainable by reacting conventional or high-reactivity polyisobutene having M= preferably 300 to 5000, more preferably 300 to 3000, even more preferably 500 to 2500, even more especially preferably 700 to 2500 and especially 800 to 1500, with maleic anhydride by a thermal route in an ene reaction or via the chlorinated 10 polyisobutene. The moieties having hydroxyl and/or amino and/or amido and/or imido groups are, for example, carboxyl-c acid groups, acid amides of monoarnines, acid amides of di- or polyamines which, in addition to the amide function, also have free amine groups, succinic acid derivatives having an acid and an amide function, carboximides with monoamines, carboximides with di- or polyamines which, in addition 15 to the imide function, also have free amine groups, or diimides which are formed by the reaction of di- or polyamines with two succinic acid derivatives. in the presence of imido moieties D(h), the further detergent additive in the context of the present invention is, however, used only up to a maximum of 100% of the weight of compounds with betaine structure. Such fuel additives are common knowledge and are described, 20 for example, in documents (1) and (2). They are preferably the reaction products of alky- or alkenyi-subsmtuted succinic acids or derivatives thereof with mines and more preferably the reaction products of polyisobutenyi-substitute succinic acids or derivatives thereof with mines. Of particular interest in this context are reaction products with aliphatic polyamines (poiyalkyleneimines) such as especially 25 ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethyienehexamine and hexaethyleneheptanine, which have an imide structure. Additives comprising moieties (Di) obtained by Mannich reaction of substituted phenols with aldehydes and mono- or polyamines are preferably reaction products of 30 poyisobutene-substituted phenols with formaldehyde and mono- or polyamines such as ethylenediamine, diethyienetriamine, triethylenetetramine, tetraethyienepentamine or dimethylaminopropyjamine The polyisobutenyi-substtuted phenols may stem from conventional or high-reactivity polyisobutene having Mn = 300 to 5000, Such "polyisobutene Man nich bases" are described in particular in EPA 831 141, M/51320-PCT 33 One or more of the detergent additives mentioned can be added to the fuel in such an amount that the dosage of these detergent additives is preferably 25 to 2500 ppm by weight, especially 75 to 1500 ppm by weight, in particular 150 to 1000 ppm by weight. B2) Carrier oils Carrier oils additionally used may be of mineral or synthetic nature, Sutable mineral carrier oils are the fractions obtained in crude oil processing, such as brightstock or 10 base oils having viscosities, for example, from the SN 500 to 2000 class; but also aromatic hydrocarbons, paraffinic hydrocarbons and alkoxyaikanols., Likewise useful is a fraction which is obtained in the refining of mineral oil and is known as "hydrocrack oil (vacuum distillate cut having a boiling range from about 360 to 500"C, obtainable from natural mineral oil which has been catalytically hydrogenated and isomerized 15 under high pressure and also deparaffinized), Likewise suitable are mixtures of the abovementioned mineral carrier oils. Examples of suitable synthetic carrier oils are polyolefins (polyalphaoiefins or polyintemaiolefins), (poly)esters, (poly)alkoxylates, polyethers, aliphatic pofyether 20 amines, alkylphenol-started polyethers, alkylphenoi-started polyetheramines and carboxylic esters of long-chain alkanols. Examples of suitable polyolefins are olefin polymers having M, = 400 to 1800, in particular based on polybutene or polyisobutene (hydrogenated or unhydrogenated). 25 Examples of suitable polyethers or polyetheramines are preferably compounds comprising po yoxy-C2- to Cralkylene moieties which are obtainable by reacting C2 to Ce-alkanos, Ce- to Cao-aikanedois, mono- or di-C- to Cwalkylamines, Ce- to Co alkyicyclohexanols or Cs to Ca:i-alkyphenois with I to 30 mol of ethylene oxide and/or 30 propylene oxide and/or butylene oxide per hydroxyl group or amino group, and, in the case of the polyetheramines, by subsequent reductive anination with ammonia, monoamines or polyaminesa Such products are described in particular in EP-A 310 875, EP-A 356 725, EP-A 700 985 and US-A 4,877,416. For example, the polyetheramines used may be poly-C2 to Cr-aikylene oxide amines or functional NI/51320-PCT 34 derivatives thereof, Typical examples thereof are tridecano butoxylates or isotridecanol butoxylates, isononylphenol butoxylates and also PolyiSobutenol butoxylates and propoxylates, and also the corresponding reaction products with ammonia. 5 Examples of carboxylic esters of long-chain alkanols are in particular esters of mono-, di- or tricarboxylic acids with long-chain aikanols or polyois, as described in particular in DE-A 38 38 918. The mono-, di- or tricarboxyic acids used may be aliphatic or aromatic acids: suitable ester alcohols or polyols are in particular long-chain representatives having, for example, 6 to 24 carbon atoms. Typical representatives of 10 the esters are adipates, phthalates, isophthalates, terephthalates and trimeilitates of isOoctano, isononanol, isodecanol and isotridecanol, for example di(n- or isotridecyl) phthalatei Further suitable carrier oil systems are described, for example, in DE-A 38 26 608, 15 DE-A 41 42 241, DE-A 43 09 074, EP-A 452 328 and EP-A 548 617 Examples of particularly suitable synthetic carrier oils are alcohol-started polyethers having about 5 to 35, preferably about 5 to 30, more preferably 10 to 30 and especially 15 to 30 C- to Cr-alkylene oxide units, for example selected from propylene oxide, n 20 butylene oxide and isobutylene oxide units, or mixtures thereof, per alcohol molecule. Nonlimiting examples of suitable starter alcohols are iong-chain alkanols or phenols substituted by long-chain alkyl in which the long-chain alkyl radical is in particular a straight-chain or branched Ce to C08-alkyl radical, Particular examples include trIdecanol and nonylphenol. Particularly preferred alcohokstarted polyethers are the 25 reaction products (polyetherification products) of monohydric aliphatic C- to C, alcohols with Ca- to C-alkylene oxides. Examples of monohydric aiiphatic 3-Cr alcohols are hexanol, heptanol, octanot, 2-ethylhexanol nonyl alcohol, decanol, 3 propyiheptanol undecanoi, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanoi, octadecanol and the constitutional and positional isomers thereof. The 30 alcohols can be used either in the form of the pure isomers or in the form of technical grade mixtures. A particularly preferred alcohol is tridecanolt Examples of C- to C alikylene 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. Particular preference among these is given to C> M/51320-PCT 35 to Cealkylene oxides, i.e. propylene oxide such as 1 1 2 -propylene oxide and butylene oxide such as 1,2-butylene oxide, 2 ,3-butylene oxide and isobutylene oxide, Especially butylene oxide is used. o Further suitable synthetic carrier oils are alkoxylated alkylphenols, as described in DE-A 10 102 913. Particular carrier oils are synthetic carrier oils, particular preference being given to the above-desoibed alcohol-started polyethers, 10 The carrier oil or the mixture of different carrier oils is added to the fuel in an amount of preferably i to 1000 ppm by weight, more preferably of 10 to 500 ppm by weight and especially of 20 to 100 ppm by weight. 15 B3) Cold flow improvers Suitable cold flow improvers are in principle all organic compounds which are capable of improving the flow performance of middle distillate fuels or diesel fuels under cold conditions. For the intended purpose, they must have sufficient oil solubility. in 20 particular, useful cold flow improvers for this purpose are the cold flow improvers (middle distillate flow improver, MDis) typically used in the case of middle distilfates of fossil origin, i.e. in the case of customary mineral diesel fuels. However, it is also possible to use organic compounds which partly or Predominantly have the properties of a wax antisettling additive (WASA) when used in customary diesel fuels. They can 25 also act partly or predoninanly as nucleators, It is, though, also possible to use mixtures of organic compounds effective as MODFis and/or effective as WASAs and/or effective as nucleators, The cold flow Improver is typically selected from 30 (KI) copolyrners of a Cz- to ,colefin with at least one further ethylenically unsaturated monomer; (K2) comb polyrners; (K3) polyoxyalkylenes; (K4) polar nitrogen compounds; M/51320-PCT 36 S(5) suifocarboxylic acids or sulfonic acids or derivatives thereof and (K6) poly(meth)acrylic esters.. It is possible to use either mixtures of different representatives from one of the 5 particular classes (K1) to (K6) or mixtures of representatives from different classes (K1) to (K6). Suitable C2- to 04,Colefin monomers for the copolymers of class (K1) are, for example, those having 2 to 20 and especaly 2 to 10 carbon atoms, and I to 3 and preferably I 10 or 2 carbon-carbon double bonds, especially having one carbon-carbon double bond. in the latter case, the carbon-carbon double bond may be arranged either terminally (a olefins) or internally. However, preference is given to a-olefins, more preferably a olefins having 2 to 6 carbon atoms, for example propene, 1-butene, 1-pentene, 1 hexene and in particular ethylene. 15 In the copolymers of class (K1), the at least one further ethylenically unsaturated monomer is preferably selected from alkenyl carboxylates, (meth)acrylic esters and further olefins, 20 When further olefins are also copolymerized, they are preferably higher in molecular weight than the abovementioned C2- to Carotefin base monomer, When, for example, the olefin base monomer used is ethylene or propene, suitable further olefins are in particular Cz& to C4a-olefins, Further olefins are in most cases only additionally copolymerized when monomers with carboxylic ester functions are also used. 25 Suitable (meth)acrylic esters are, for example, esters of (meth)acrylic acid with C- to Cr-aikanols, especially C- to C-alkanols, in particular with methanol, ethanol, propanot, isopropanol, n-butanol, sec-butanol, isobutanol. tert-butano, pentanoi, hexanol, heptanol, octane, 2-ethylhexanol, nonanol and decano!, and structural 30 isomers thereof. Suitable alkenyl carboxylates are, for example, C- to Cwaikenyl 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. Among these, preference is given to M/51320-PCT the vinyl esters. Among the carboxylic acids with a branched hydrocarbon radical, preference is given to those whose branch is in the a-position to the carboxyl group, the o-carbon atom more preferably being tertiary, i.e. the carboxylic acid being a so called neocarboxylic acid. However, the hydrocarbon radical of the carboxylic acid is 5 preferably linear. Examples of suitable alkenyl carboxylates are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexancate, vinyl neopentanoate, vinyl hexanoate, vinyl neononanoate, vinyl neodecanoate and the corresponding propenyl esters, preference 10 being given to the vinyl esters, A particularly preferred alkenyl carboxylate is vinyl acetate; typical copolymers of group (KI) resulting therefrom are ethylene-vinyl acetate copolymers ("EVAs"), which are some of the most frequently used, Ethylene-vinyl acetate copolymers usable particularly advantageously and their preparation are described in WO 99/29748. 15 Suitable copolymers of class (K1) are also those which comprise two or more different alkenyl carboxylates in copolymerized form, which differ in the alkenyl function and/or in the carboxylic acid group. Likewise suitable are copolymers which, as weil as the alkenyl carboxylatess, comprise at least one olefin and/or at least one (meth)acrylic 20 ester in copolymerized form. Terpolymers of a C2- to Cjirc-olefin, a Cr to C&ralky ester of an ethylenically unsaturated monocarboxylic acid having 3 to 15 carbon atoms and a 02- to Cwalkenyl ester of a saturated monocarboxylic acid having 2 to 21 carbon atoms are also suitable 25 as copolymers of class (K1). Terpolymers of this kind are described in WO 200&/054314. A typical terpolymer of this kind is formed from ethylene, 2-ethylhexyl acrylate and vinyl acetate. The at least one or the further ethylenically unsaturated monomer(s) are copolymerized 30 in the copolymers of class (KI) in an amount of preferably I to 50% by weight, especially 10 to 45% by weight and in particular 20 to 40% by weight, based on the overall copolymer. The main proportion In terms of weight of the monomer units in the copolymers of class (KI) therefore originates generally from the C2 to C4 base olefins. M/5 1 3.20-PCT $8 The copolymers of class (KI) preferably have a number-average molecular weight M, of 1000 to 20 000, more preferably 1000 to 10 000 and in particular 1000 to 8000. Typical comb polymers of component (K2) are, for example, obtainable by the 5 copolymerization of maleic anhydride or fumaric acid with another ethylenically unsaturated monomer, for example with an a-ofefin 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. Further suitable comb polymers are copolymers of a-olefins and esterified cornonomers, for example esterified copolymers 10 of styrene and maleic anhydride or esterified copolymers of styrene and fumaric acid., Suitable comb polymers may also be polyfumarates or polymaleates. Homo- and copolymers of vinyl ethers are also suitable comb polymers. Comb polymers suitable as components of class (K2) are, for example, also those described in WO 2004/035715 and in "Comb-Like Polymers. Structure and Properties", N. A, Plate and 15 V. P. Shibaev, J. Poly, Sa. Macronolecular Revs. 8, pages 117 to 253 (1974)". Mixtures of comb polymers are also suitable, Polyoxyalkylenes suitable as components of class (K3) are, for example, polyoxyaikylene esters, pofyoxyalkylene ethers, mixed polyoxyalkylene ester/ethers 20 and mixtures thereof. These polyoxyalkylene compounds preferably comprise at least one linear alkyl group, 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 described, for example, in EP-A 061 895 and also in US 4,491,455. Particular polyoxyakylene compounds are based 25 on polyethylene glycols and polypropylene glycols having a number-average molecular weight of 100 to 5000, Additionally suitable are polyoxyafkylene mono- and diesters of fatty acids having 10 to 30 carbon atoms, such as stearic acid or behenic acid. Polar nitrogen compounds suitable as components of class (K4) may be either ionic or 30 nonionic and preferably have at least one substituent, in particular at least two substituents, in the form of a tertiary nitrogen atom of the general formula >NRI in which R 7 is a G - to Crhydrocarbon radical The nitrogen substituents may also be quaternized, Le. be in cationic form, An example of such nitrogen compounds is that of ammoniurn salts and/or amides which are obtainable by the reaction of at least one M/51320-PCT 39 amine substituted by at least one hydrocarbon radical with a carboxylic acid having 1 to 4 carboxyl groups or with a suitable derivative thereof. The amines preferably comprise at least one linear C8- to C40-akyl radical. Primary amines suitable for preparing the polar nitrogen compounds mentioned are, for example, octylamine, nonylamine, 5 decylamine, undecylamine, dodecylamine, tetradecylamine and the higher linear homologs, Secondary marines suitable for this purpose are, for example, dioctadecylamine and methylbehenylamine, Also suitable for this purpose are amine mixtures, in Particular amine mixtures obtainable on the industrial scale, such as fatty marines or hydrogenated tallamines, as described, for example, in Ullmann's 10 Encyclopedia of Industrial Chemistry., 6th Edition, NAmines aliphatic" chapter. Adds suitable for the reaction are, for example, cyclohexane1 24icarboxylic acid, cydlohexene-1,2-dicarboxylic acid, cyclopentane-1 ,2-dicarboxylic acid, naphthalenedicarboxylic acid, phthalic acid, isophthaic acid, terephthatic acid, and succinic acids substituted by long-chain hydrocarbon radicals, 15 in particular, the component of class (K4) is an oi-soluble reaction product of poly(C to Cw-carboxylic acids) having at least one tertiary amino group with primary or secondary amines. The poly(Cr to C 20 -carboxylic acids) which have at least one tertary amino group and form the basis of this reaction product comprise preferably at 20 least 3 carboxyl groups, especially 3 to 12 and in particular 3 to 5 carboxyl groups. The carboxylic acid units in the polycarboxylic acids have preferably 2 to 10 carbon atoms, and are especially acetic acid units. The carboxylic acid units are suitably bonded to the polycarboxylic acids, usually via one or more carbon and/or nitrogen atoms. They are preferably attached to tertiary nitrogen atoms which, in the case of a plurality of 25 nitrogen atoms, are bonded via hydrocarbon chains. The component of class (K4) is preferably an oil-soluble reaction product based on poly(C- to Cw-carboxylic acids) which have at least one tertiary amino group and are of the general formula la or lib 30 HOOC'B B'COOH HOOC, NA A, COOH B A .

M53-a MJS513 2 0 -P CT 40 BaB HOOC' 'N' W',COOH C COOH ~(lib) in which the variable A is a straightchain or branched C02 to Cralkylene group or the moiety of the formula ill HOOC'B'N'C12CF2 CH2-CHfC and the variable B is a Ce. to Ci-alkylene group. The compounds of the general formulae Fla and tb especially have the properties of a WASA. 10 Moreover, the preferred oil-soluble reaction product of component (K4), especially that of the general formula Ila or Ib, is an amide, an amide-ammonium salt or an ammonium salt in which no, one or more carboxyllc acid groups have been converted to aide groups, 15 Straight-chain or branched C2- to Ce-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-methyi I 4-butylene, 2,2-dimethyl-1,3 propylene, 1 &hexylene (hexamethylene) and in paricular 1 ,2-ethylene. The variable A 20 comprises preferably 2 to 4 and especially 2 or 3 carbon atoms C- to Ciralkylene groups of the variable B are, for example, 1,2-ethylene, 1,3-propylene, i4-butylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, tetradecamethylene, hexadecamethylene, ociadecamethylene, 25 nonadecamethylene and especially methylene. The variable 8 comprises preferably 1 to 10 and especially I to 4 carbon atoms, The primary and secondary anines as a reaction partner for the polycarboxylic acids to form component (K4) are typically monoamines, especially aliphatic monoamines. 30 These primary and secondary amines may be selected from a multitude of marines which bear hydrocarbon radicals which may optionally be bonded to one another. M/51320-PCT 41 These parent amines of the oil-soluble reaction products of component (K4) are usually secondary amines and have the general formula HN(R% 2 in which the two variables RA are each independently straight-chain or branched Ce- to C ralkyl radicals, especally 5 01W to C4-alky radicals. These relatively long-chain alkyl radicals are preferably straight-chain or only slightly branched. In general, the secondary amines mentioned, with regard to their relatively long-chain alkyl radicals, derive from naturally occurring fatty acid and from derivatives thereof. The two R radicaIs are preferably identical 10 The secondary amines mentioned may be bonded to the polycarboxylic acids by means of amide structures or in the form of the ammonium salts it is also possible for only a portion to be present as aide structures and another portion as ammoniurn salts. Preferably only few, if any, free acid groups are present. The oil-soluble reaction products of component (K4) are preferably present completely in the form of the amide 15 structures. Typical examples of such components (K4) are reaction products of nitrilotracetic acid, of ethylenediamineetraacetic acid or of propylene-1,2-diaminetetraacetic acid with in each case 0,5 to 1,5 mol per carboxyl group, especialy 0.8 to 1.2 moi per carboxyl 20 group, of dioieylamine, dipalmitinamine, dicoconut fatty amine, distearyiamine, dibehenylamine or especially ditalow fatty amine. A particularly preferred component (K4) is the reaction product of I mol of ethyienediaminetetraacetic acid and 4 mol of hydrogenated ditallow fatty amine. 25 Further typical examples of component (K4) include the N,N-dialkylammonium salts of 2-ttN'-dialkylamidobenzoates, for example the reaction product of I mo of phthalic anhydride and 2 mol of ditailow fatty amine, the latter being hydrogenated or unhydrogenated, and the reaction product of I mol of an alkenylspirobislactone with 2 mol of a diaikylamine, for example ditallow fatty amine and/or tallow fatty amine, the 30 last two being hydrogenated or unhydrogenated Further typical structure types for the component of class (K4) are cyclic compounds with tertiary anino groups or condensates of long-chain primary or secondary amines with carboxylic acid-containing polymers, as described in WO 93/18115. MA/51320-PCT 42 Sulfocarboxylic acids, sulfonic acids or derivatives thereof which are suitable as cold flow improvers of class (K5) are, for example, the oil-soluble carboxamides and carboxyic esters of ortho-sufobenzoic acid, in which the sulfonic acid function is 5 present as a sulfonate with alkyksubstituted ammonium cations, as described in EP-A 261 957. Poiy(meth)acryli esters suitable as cold fiow improvers of class (K6) are either homo or copolyrners of acrylic and methacrylic esters. Preference is given to copolymers of at 10 least two different (rneth)acrylic esters which differ with regard to the esterified alcohoL The copolymer optionaHy comprises another different olefinically unsaturated monomer in copolymerized form. The weight-average molecular weight of the polymer is preferably 50 000 to 500 000. A particularly preferred polymer is a copolymer of methacrylic acid and methacrylic esters of saturated Cu and CQs alcohols, the acid 15 groups having been neutralized with hydrogenated tallamine. Suitable poly(meth)acrylic esters are described, for example, in WO 00/44857, The cold flow improver or the mixture of different cold flow improvers is added to the middle distillate fuel or diesel fuel in a total amount of preferably 10 to 5000 ppm by 20 weight, more preferably of 20 to 2000 ppm by weight, even more preferably of 50 to 1000 ppm by weight and especially of 100 to 700 ppm by weight, for example of 200 to 500 ppm by weight. B4) Lubricity improvers 25 Suitable lubricity improvers or friction modifiers are based typically on fatty acids or fatty acid esters. Typical examples are tal ol fatty acid, as described, for example, in WO 98/004666, and glyceryl monooleate. The reaction products, described in US 6 743 266 82, of natural or synthetic oils, for example triglycerides, and alkanolamines 30 are also suitable as such lubricity improvers. M/51320-PCT 43 B5) Corrosion inhibitors Suitable corrosion inhibitors are, for example, succinic esters, in particular with polyols, fatty acid dedvatives, for example oleic esters, oigomerized fatty acids, substituted 5 ethanolamines, and products sold under the trade name RC 4801 (Rhein Chemie Mannheim, Germany) or HiTEC 536 (Ethyl Corporation), B6) Demulsifiers 10 Suitable demulsifiers are, for example, the alkali metal or alkaline earth metal salts of alkyl-substituted phenol- and naphthalenesulfonates and the alkali metal or alkaline earth rmetal salts of fatty acids, and also neutral compounds such as alcohol alkoxylates, e.g. alcohol ethoxylates, phenol alkoxylates, e~g. tert-butyipheno ethoxylate or tert-pentylphenoi ethoxylate, fatty acds, alkylphenols, condensation 15 products of ethylene oxide (EO) and propylene oxide (PO), for example including in the form of EC/PO block copolymers, polyethyleneimines or else polysiloxanes. 87) Dehazers 20 Suitable dehazers are, for example, alkoxylated phenol-formaldehyde condensates, for example the products available under the trade names NALCO 7D7 (Nalco) and TOLAD 2683 (Petrolite). 88) Antifoams 25 Suitable antifoams are, for example, polyether-modified polysiloxanes, for example the products available under the trade arnes TEGOPREN 5851 (Goldschmidt), Q 25907 (Dow Coming) and RHODOSIL (Rhone Poulenc). 30 89) Cetane number improvers Suitable cetane number improvers are, for example, aliphatic nItrates such as 2-ethyl hexyl nitrate and cyciohexyl nitrate and peroxides such as di-tert-buty peroxide. M/51320-PCT 44 B10) Antioxidants Suitable antioxidants are, for example substituted phenols, such as 2,6-di-tert~ butylphenol and 6-di-tert-butyl-3methylphenl*, and also phenylenediamines such as 5 Nt'-d-ser-butyi-p-pheryienediamine, 11) Metal deactivators Suitable metal deactivators are, for example, salicylic acid derivatives such as 10 N, KdisaIicyidene-1,2-propanediamine. 812) Solvents Suitable solvents are, for example, nonpolar organic solvents such as aromatic and 15 aliphatic hydrocarbons, for exam ple toluene, xylenes, white spirit and products sold under the trade names SHELLSOL (Royal Dutch/Shel Group) and EXXSOL (ExxonMobil), and also polar organic solvents, for example, alcohols such as 2-ethylhexanol, decanol and isotridecanol. Such solvents are usually added to the diesel fuel together with the aforementioned additives and coaddfives, which they are 20 intended to dissolve or dilute for better handling. C) Fuels The inventive additive is outstandingly suitable as a fuel additive and can be used in 25 principle in any fuels. It brings about a whole series of advantageous effects in the operation of internal combustion engines with fuels. Preference is given to using the inventive quatemized additive in middle distillate fuels, especially diesel Fuels. The present invention therefore also provides fuels, especially middle distillate fuels, 30 with a content of the inventive quatemized additive whiich is effective as an additive for achieving advantageous effects in the operation of internal combustion engines, for example of diesel engines, especially of direct-injection diesel engines, in particular of diesel engines with common-rail injection systems, This effective content (dosage) is generally 10 to 5000 ppm by weight, preferably 20 to 1500 ppm by weight, especially M/51320-PCT 45 25 to 1000 ppm by weight, in particular 30 to 750 ppm by weight, based in each case on the total amount of fuel. Middle distillate fuels such as diesel fuels or heating oils are preferably mineral oil 5 raffinates which typically have a boiling range from 100 to 400

T

C, These are usually distillates having a 95% point up to 360*C or even higher. These may also be so-called "ultra low sulfur diesel" or "city diesel", characterized by a 95% point of, for example, not more than 345"C and a sulfur content of not more than 0-005% by weight or by a 95% point of, for example, 285T and a sulfur content of not more than 0.001 % by 10 weight. In additon to the mineral middle distillate fuels or diesel fuels obtainable by refining, those obtainable by coal gasification or gas liquefaction jgas to liquid" (QTL) fuels] or by biomass liquefaction ["biomass to liquidN (BTL) fueis] are also suitable. Also suitable are mixtures of the aforementioned middle distillate fuels or diesel fuels with renewable fuels, such as biodiesel or bioethanol 15 The qualities of the heating olIs and diesel fuels are laid down in detail, for example, in DIN 51603 and EN 590 (of. also Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Volume A12, p. 817 ff), 20 in addition to the use thereof in the abovementioned middle distillate fuels of fossil, vegetable or animal origin, which are essentially hydrocarbon mixtures, the inventive quaterized additive can also be used in mixtures of such middle distillates with biofuel oils (biodiesel). Such mixtures are also encompassed by the term "middle distillate fuel" in the context of the present invention. They are commercially available and usually 25 comprise the biofuel oilsn minor amounts, typically in amounts of I to 30% by weight, especially of 3 to 10% by weight, based on the total amount of middle distillate of fossil, vegetable or animal origin and biofuel ol. Biofuel ols are generally based on fatty acid esters, preferably essentially on alkyl 30 esters of fatty acids which derive from vegetable and'or animal oils and/or fats. Alkyl esters are typically understood to mean lower alkyl esters, especially CrC4-alkyl esters, which are obtainable by transesterifying the glycerides which occur in vegetable and/or animal oils and/or fats, especially triglycerides, by means of lower alcohols, for example ethanol or in particular methanol ("FAME"). Typical lower alkyl esters based M/51320-PCT 46 on vegetable and/or animal oils and/or fats, which ftnd use as a biofuel oi or components thereof, are, for example, sunflower methyl ester, palm oil methyl ester ("PME")i soya 6l methyl ester ("sME") and especially rapeseed oil methy ester ("RME"). 5 The middle distillate fuels or diesel fuels are more preferably those having a low sulfur content, i.e., having a sulfur content of less than 0.05% by weight, preferably of less than 0.02% by weight, more particularly of less than 0,005% by weight and especialy of less than 0,001% by weight of sulfur, 10 Useful gasoline fuels include all commercial gasoline fuel compositions. One typical representative which shall be mentioned here is the Eurosuper base fuel to EN 228, which is customary on the market. In addition, gasoline fuel compositions of the specification according to WO 00/47698 are also possible fields of use for the present 15 invention. The inventive quaternized additive is especially suitable as a fuel additive in fuel compositions, especially in diesel f uels, for overcoming the problems outlined at the outset in direct-injection diesel engines, in particular In those with common-rail direction 20 systems. The invention is now illustrated in detail by the working examples which follow. The test methods described herein are not restricted to the specific working examples, but are part of the general disclosure of the description and can be employed generally in the 25 context of the present invention, Experimentali section: A. General test methods 30 Engine test b1) XUD9 test - determination of flow restriction The procedure was according to the standard stipulations of CEC F-23-01, M/51320-PCT 47 b2) DW10 - keep clean test To examine the influence of the inventive compounds on the performance of direct ijection diesel engines, the power loss was determined on the basis of the official test method CEC F-098-08. The power loss is a diect measure of formation of deposits in the injectors, The keep clean test is based on CEC test procedure F-098-08 Issue 5, The same test setup and engine type (PEUGEOT DW1 0) as in the CEC procedure are used, 10 Special features of the test used: a) Injectors in the tests, cleaned injectors were used. The cleaning time in an ultrasound bath in 15 water at 60*C + 10% Superdecontamine (Intersciences, Brussels) was 4 h. b) Test run times the test perod was 12 h without shutdown phases. The one-hour test cycle (see table below) from CEC F-098-08 was rnr through 12 times, 20 tg D E'gine Load TOrUe Charge air nues) (rpm) (%) (Nm) temperature +1-20 +/-15 downstream of charge run cooler 1 2 1750 (20) 462 12 7 30,00 (60) 2123 5 2 1750 (20) 62 45 4 1 40 180) 50 2 150 ) 45 6 1 400t10 606-s 2 1250 (10) 25 M/51320-PCT 48 2 ~ 1250 ---- 14000 1 50 for range to be expected see CEC-096-08 target value c) Power determination The initial power

(P

0 o, KC [kW) is calculated from the measured torque at ful load 4 0 0 0 /min directly after the test has started and the engine has warmed up The procedure is described in Issue 5 of the test procedure CEC F-98-0& The same test setup and the PEUGEOT DVV 10 engine type are used, 10 The final power (Pe, KC) is determined in the 12th cycle in stage 12, (see table above). Here too, the operating point is full load 4 000/mir, Pa, KC [kW} is calculated from the measured torque, 15 The power loss in KC is calculated as flows: power loss, KC [%] = (1 - PmKC / PctKC) x 100 The fuel used was a commercial diesel fuel from Haltermann (RF-06-03)- To 20 synthetically induce the formation of deposits at the injectors, 1 ppm of zinc was added thereto in the form of a zinc neodecenoate solution. B. Preparation examples: 25 Reactants used: PIBSA: Prepared from maleic anhydride and PSB 1000 in a known manner. For the inventive preparation examples and comparative examples which follow, qualities with hydrolysis numbers in the region of 84-95 mg KOH/p were used, DMAPA was used 30 with the particular PIBSA quality in a molar ratio of 1:1 according to the hydrolysis number. The PBSA quaiies used had bismaleation levels (BML) of less than 15%, M/51320-PCT 49 DMAPA: M 102.18 methyl salicytate: M = 152.14 dimethyl phthalate: M = 194.19 5 dimethyl oxalate: M 11809 dimethyl sulfate: M 126.13 dimethyl carbonate MN 90.08 Preparation example 1: Synthesis of an inventive quatemized succinimide 10 (PIBSADJMAPAdimethyi phthalate) Polyisobutylenesuccinic anhydride (1659 g) is dissolved in Solvent Naphtha Heavy (SNH, Eron Mobi4 CAS64742-955) (1220 g), and 3-dimethylamino-1-propylamine (DMAPA; 153 g) is added, The reaction solution is stirred at 170*C for 8 h, in the 15 course of which water of condensation formed is distiled off continuously. This affords the PIBSA-DMAPA succinimide as a solution in Solvent Naphtha Heavy (TBN 0.557 mmnolJg), A portion of this solution of the PI;BSA-DMAPA succinimide (181 g) is added to 20 dimethyl phthalate (19A g), and the resulting reaction solution is stirred at 120*C for 11 h and then at 150*C for 241h. After cooling to room temperature, the product obtained is the ammonium carboxylate as a solution in Solvent Naphtha Heavy. 1H NMR analysis confirms the quatemization. 25 Preparation example 2: Synthesis of an inventive quatemtzed succinimide (PBSADMAPA/methyl salicylate) Polyisobutylenesuccinic anhydride (PIBSA; 2198 g) is heated to 110*C, and 3 dimethylarino-i-propylamine (DMAPA; 182 g) is added within 40 min, in the course of 30 which the reaction mixture heats up to 140"C. The reaction mixture is heated to 170"C and held at this temperature for 3 h, in the course of which 28 g of distillate are collected. This affords the PIBSA-DMAPA succinimide as a viscous ol (TBN 0,735 mrnmog). M/51320-PCT 50 A mixture of this PIBSA-DMAPA succinimide (284,5 g), methyl salicylate (65,5 g) (i.e. about 2 equivalents of methyl salicylate per equivalent of tertiary amino group) and 3,3,5-trimethyiheptanoic acid (from BASF) (0-75 g) is heated to 140-150* and the reaction mixture is stirred at this temperature for 6 h, After cooling to room temperature, 5 the product obtained is the ammonium salicylate as a viscous otIL 'H NMR analysis confirms the quaternization. By adding Pilot 900 oil, Petrochem Carless Ltd., the active ingredient content of the solution is adjusted to 50% by weight, Preparation example 3: Synthesis of an inventive quatemized suocinimide 10 (PIlSA/DMAPNdimetfiyl oxalate) Polyisobutylenesuccinic anhydride (PIBSA; 2198 g) is heated to 110C, and 3 dimethylamino-1-propylanine (DMAPA; 182 g) is added within 40 min, in the course of which the reaction mixture heats up to 1404C. The reaction mixture is heated to 170'C 15 and held at this temperature for 3 h, in the course of which 28 g of distillate are collected, This affords the PIBSA-DMAPA succinimide as a viscous oil (TBN 0.735 mmol/q). A mixture of this PISSA-DMAPA succinimide (211 g), dimethyl oxalate (34.5 g) and 20 iauric acid (4.9 g) is heated to 120*C and then stirred at this temperature for 4 h. Excess dimethyi oxalate is removed on a rotary evaporator under reduced pressure (p = 5 mbar) at 120"C, The product obtained is the ammonium methyl oxalate as a viscous oil, 1 H NMR analysis confirms the quaternization, 25 For comparison with the prior art, Examples 2 and 4 from WO 2006/135881 were worked up. Preparation example 4: Synthesis of a known quaternized succinimide (comparative example) (Example 2 from WO 2006/135881) 30 A solution of PIBSA (420.2 g) in Pilot 900 oil, Petrochem Carless Ltd., (51,3 g) is initially charged and heated to 1 10C, DMAPA (31.4 g) is metered in within 50 minutes, in the course of which a slightly exothermic reaction is observed. Within 80 minutes, the reaction mixture is heated to 1504C and the mixture is then kept at this temperature M/51 320-PCT 51 for h, in the course of which the water of reaction which forms is distifled off. After coohng to room temperature, the PIBSA-DMAPA succinimide is obtained as a solution in Pilot 900 oil (TBN 0.62 mnmo/g), 5 A portion of the PIBSA-DMAPA succinimide thus obtained as a solution in Pilot 900 oil Petrochern Carless Ltd, (354 g) is initally charged and heated to 90"C. Dirnethyl sulfate (26,3 g) is metered in, in the course of which the reaction temperature rises to 11.2C. Subsequently, the reaction mixture is stirred at I00C for 3 h. After cooling to room temperature, the quaternized PIBSA-DMAPA succinimide is obtained as a 10 soluton in Piot 900 oi .H NMR confirmed the quaternization. The output was adjusted to an active ingredient content of 50% by weight by adding Pilot 900 oil Preparation example 5: Synthesis of a known quatemized succinimide (comparative example) (Example 4 from WO 2006/135881) 15 A solution of PIBSA (420.2 g) in Rlot 900 oil, Petrochem Can'ess Ltd,, (5.3 g) is initially charged and heated to I lOT DMAPA (31.4 g) is metered in within 50 minutes, in the course of which a slightly exothermic reaction is observed, Within 80 minutes, the reaction mixture is heated to 150* and the mixture is then kept at this temperature 20 for 3 h, in the course of which the water of reaction which forms is distbIed off, After cooling to room temperature, the PIBSA-DMAPA succinimide is obtained as a solution in Pilot 900 oil (TBN 0.62 mmoi/g). A portion of the PIBSA-DMAPA succinimide thus obtained as a solution in Pilot 900 oil, 25 Petrochem Cariess Ltd., (130 g), dimethyl carbonate (20 g) and methanol (17.4) are charged into an autoclave and inertized with nitrogen, and a starting pressure of 1,3 bar is established. Subsequently, the reaction mixture is stirred under autogenous pressure first at 90o"C for 1 h, then at 140"C for 24 h. After cooling to room temperature, the autoclave is decompressed and the contents are rinsed out completely with a little 30 toluene as a solvent. All low-boiling constituents are subsequently removed on a rotary evaporator under reduced pressure to obtain the quaternized PIBSA-DMAPA succinimide as a solution in Pilot 900 oil. 1 H NMR analysis confirmed the partial quatemization, The output is adjusted to an active ingredient content of 50% by weight by adding Pilot 900 oil. M/51320-PCT 52 C. Use examples: in the use examples which follow, the additives are used either as a pure substance 5 (as synthesized in the above preparation examples) or in the form of an additive package! M1: Additive according to preparation example 2 (inventive, quaternized with methyl salicylate) 10 M2: Additive according to preparation example 4 (comparative, quatemized with dimethyl sulfate) M3: Additive according to preparation example 5 (comparative, quatemized with dimethyl carbonate) 15 Use example 1: determination of the additive action on the formation of deposits in diesel engine injection nozzles a) XUD9 Tests 20 Fuel used: RF-06-03 (reference diesel, Haltermann Products, Hamburg) The results are compiled in table 1: Table 1: XUD9 tests . Name Osagiccording to Flow restriction preparation example 0.1 mm needle [mg/kg Strokse % #1 1, according to 30 10. 7 preparation example 2 #2 M2, according to 30 48,5 preparation example 4 #3 M, according to 30 20,8 Preparation example 5 25 M/51320-PCT 53 It was found that the inventive additive M1, with the same dosage, has an improved effect compared to the prior art (M2, M3), b) DW0I test To study the influence of the inventive compound on the performance of direct-injection diesel engines, the power loss was determined based on the official test method CEC F-098-08 as described above. The power loss is a direct measure of formation of deposits in the injectors. A conventional direct-injection diesel engine with a common 10 rai system was used, The fuel used was a commercial diesel fuel from Haltermann (RE-s063). To syntheticaly induce the formation of deposits at the injectors, I ppm by weight of zinc in the form of a zinc didodecanoate solution was added thereto. 15 The table below shows the results of the determinations of the relative power loss at 4000 rpm after 12 hours of sustained operation without interruption. The value P gives the power after 10 minutes and the value Ped the power at the end of the measurement: 20 The test results are shown in table 2, Table 2: Results of the DW1 0 test Addi ive Dose Tie p ' -[m }_[h] KW [K Pwe loss 0 12 9943+4J+ 5.0% M1 according to preparation example 2 160 12 98,7 97.4 1,32% M2. according to preparation 10 12 9 981 0% example 4 1 -160 '12 k.. 157 954 0 example 4 M3, according to prelparatin-- ---- example 5 1160 12 98.1 95,7 2,4% 25 it was found that the inventive additive M1 has an improved effect compared to the base value and has an improved effect at least compared to example M3. M/51320-POT 54 Use example 2: Determination of the solubity properties To determine the solubility properties, the following additive packages were produced and tested: M 4 (inventive) Substance Content [ppm] Additive acc. to preparation example 2 160.0 Dehazer, commercial 30 Antifoam, silicone-based, commercial 6'00 Sovent Naphtha Heavy ______I 1Tota 249.00 M 5 (comparative, dimethyl sulfate) Substance Content [ppm] Additive aco, to preparation example 4 160.00 Dehazer, commercial 3 0 Antfoam, s ii icone- based, commercial Solvent Naphtha Heavy 420,00 Total590 10 M 6 (comparative, dimethyl carbonate) Substance Content [ppm] ddtive acc. to preparation example 5 160.00 Dehazer (commercial) 3.0 Antifoam, silicone-based commercial 60 Solvent Naphtha Heavy 150M Total 319-00 The result of the solubdty tests is compiled in the table below. The minimum amount of solvent (Solvent Naphtha Heavy) needed to obtain a homogeneous, clear diesel M/51320-PCT 55 performance package at room temperature with otherwise identical amounts of active substance, Pilot 900, antifoam and dehazer is reported. Tabie 3: Determination of the solvent requirement 5 Additive Additive Miim u m m u to package solvent needed for a L homogeneous package PBSADMAPA-mide-methyl saMc ate M4 32% PIBSADMAPA-Fmide-dimethy! sulfate M5 71% PIBSA-DMAPA-Imideadimethy, carbonate me 47% It was found that surprisingy, the additive according to preparation example 2 has the best solubility properties, Le, requires the east solvent, 10 Reference is made explicidtly to the discosure of the publations cited herein, M/1 320-PCT

Claims (12)

1. A fuel composition comprising, in a majority of a customary fuel, a proportion of at least one reaction product comprising a quaternized nitrogen compound, or a 5 fraction thereof which comprises a quaternized nitrogen compound and is obtained from the reaction product by purification, said reaction product being obtainable by al) reacting a hydrocarbyl-substituted polycarboxylic acid compound with a compound comprising at least one oxygen or nitrogen group reactive, 10 especially capable of addition or condensation, with the polycarboxylic acid, and comprising at least one quaternizable amino group, to obtain a quaternizable hydrocarbyl-substituted polycarboxylic acid compound, and a2) subsequent reaction thereof with a quaternizing agent which converts the at least one quaternizable amino group to a quaternary ammonium group, said 15 quaternizing agent being the alkyl ester of a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid, especially of a mono- or dicarboxylic acid, or of an aliphatic polycarboxylic acid; or b) reacting a quaternizable hydrocarbyl-substituted polycarboxylic acid 20 compound comprising at least one quaternizable amino group with a quaternizing agent which converts the at least one quaternizable amino group to a quaternary ammonium group, said quaternizing agent being the alkyl ester of a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid, especially of a mono- or 25 dicarboxylic acid, or of an aliphatic polycarboxylic acid wherein about 1.1 to about 2.0 or about 1.25 to about 2.0 equivalents of quaternizing agent are used per equivalent of quaternizable tertiary nitrogen atom; and/or 30 the hydrocarbyl-substituted polycarboxylic acid compound is a polyisobutenylsuccinic acid or an anhydride thereof, said acid having a bismaleation level of 2 to 20% by weight or 2 to 15% by weight, based in each case on the reaction product. M/51320-PCT 57

2. The fuel composition according to any of the preceding claims, wherein the quaternizing agent is a compound of the general formula 1 R10C(O)R 2 (1) 5 in which R 1 is a lower alkyl radical and R 2 is an optionally substituted monocyclic aryl or cycloalkyl radical, where the substituent is selected from OH, NH 2 , NO 2 , C(O)OR 3 , and R 1 OC(O)-, in which R, 10 is as defined above and R 3 is H or R 1 .

3. The fuel composition according to either of the preceding claims, wherein the quaternizing agent is a compound of the general formula 2 15 R1OC(O)-A-C(O)OR 1 , (2) in which R 1 and Ri. are each independently a lower alkyl radical and A is hydrocarbylene. 20

4. The fuel composition according to any of the preceding claims, wherein the quaternized nitrogen compound has a number-average molecular weight in the range from 500 to 5000, 800 to 3000 or 900 to 1500. 25

5. The fuel composition according to any of the preceding claims, wherein the quaternizing agent is selected from alkyl salicylates, dialkyl phthalates and dialkyl oxalates.

6. The fuel composition according to claim 1, wherein the compound which is 30 reactive, especially capable of addition or condensation, with the polycarboxylic acid and comprises an oxygen or nitrogen group and at least one quaternizable amino group is selected from a) hydroxyalkyl-substituted mono- or polyamines having at least one quaternizable primary, secondary or tertiary amino group; M/51320-PCT PF 0000071427 SE/Ab 58 b) straight-chain or branched, cyclic, heterocyclic, aromatic or nonaromatic polyamines having at least one primary or secondary amino group and having at least one quaternizable primary, secondary or tertiary amino group; c) piperazines.

7. The fuel composition according to claim 6, wherein the compound which is reactive, especially capable of addition or condensation, with the polycarboxylic acid and comprises an oxygen or nitrogen group and at least one quaternizable 10 amino group is selected from a) hydroxyalkyl-substituted primary, secondary or tertiary monoamines and hydroxyalkyl-substituted primary, secondary or tertiary diamines, b) straight-chain or branched aliphatic diamines having two primary amino groups; di- or polyamines having at least one primary and at least one 15 secondary amino group; di- or polyamines having at least one primary and at least one tertiary amino group; aromatic carbocyclic diamines having two primary amino groups; aromatic heterocyclic polyamines having two primary amino groups; aromatic or nonaromatic heterocycles having one primary and one tertiary amino group. 20

8. The fuel composition according to any of the preceding claims, selected from diesel fuels, biodiesel fuels, gasoline fuels and alkanol-containing gasoline fuels.

9., The use of a reaction product obtainable by a process as defined in any of the 25 preceding claims or of quaternized nitrogen compound obtained from the reaction product; or of a quaternized nitrogen compound prepared by a process comprising the reaction of a quaternizable hydrocarbyl-substituted polycarboxylic acid compound comprising at least one tertiary quaternizable amino group with a quaternizing agent which converts the at least one tertiary amino group to a 30 quaternary ammonium group, said quaternizing agent being the alkyl ester of a cycloaromatic or cycloaliphatic mono- or polycarboxylic acid, especially of a mono- or dicarboxylic acid, or of an aliphatic polycarboxylic acid; as a fuel additive. M/51320-PCT 59

10. The use according to claim 8 or 9 as an additive for reducing the fuel consumption of direct-injection diesel engines, or diesel engines with common rail injection systems, and/or for minimizing power loss in direct-injection diesel engines, or in diesel engines with common-rail injection systems.

11. The use according to claim 8 or 9 as a gasoline fuel additive for reducing the level of deposits in the intake system of a gasoline engine, or DISI (direct injection spark ignition) and PFI (port fuel injector) engines. 10

12. The use according to claim 8 or 9 as a diesel fuel additive, as a cold flow improver, as a wax antisettling additive (WASA) or as an additive for reducing the level of and/or preventing deposits in the intake systems, the internal diesel injector deposits (IDIDs), and/or valve sticking in direct-injection diesel engines, or in common-rail injection systems. M/51320-PCT